CN109467539A - A kind of preparation method and purification process of the compound containing at least one cyclic ligand structure - Google Patents

A kind of preparation method and purification process of the compound containing at least one cyclic ligand structure Download PDF

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CN109467539A
CN109467539A CN201811283004.XA CN201811283004A CN109467539A CN 109467539 A CN109467539 A CN 109467539A CN 201811283004 A CN201811283004 A CN 201811283004A CN 109467539 A CN109467539 A CN 109467539A
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compound
lithium
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ligand
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蒋玉贵
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Suzhou Lithium Fixing New Energy Technology Co., Ltd.
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蒋玉贵
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Priority to CN201911019182.6A priority patent/CN110627742B/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/15—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/36—Seven-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/02—Five-membered rings
    • C07D339/06—Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates
    • 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 System
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages
    • 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 System
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/025—Silicon compounds without C-silicon linkages
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

The invention discloses the preparation method and purification process of a kind of compound containing at least one cyclic ligand structure, the compound of the cyclic ligand structure contains the cyclic ligand of 1-2 kind different structure, that is, contains LaCyclic ligand and/or contain LbCyclic ligand, wherein contain LaCyclic ligand in contain sulfonyl (- SO2), one in sulfinyl (- SO-) or carbonyl (C=O).The compound can be separately as the electrolyte lithium salt of lithium ion battery, it is dissolved in the electrolyte solution that organic solvent is used to prepare lithium ion battery, or, the compound and lithium salts are dissolved in the electrolyte solution that organic solvent prepares lithium ion battery, the electrolyte solution can be obviously improved the internal resistance of lithium ion battery and have effect to the cycle performance of battery.

Description

A kind of preparation method and purifying of the compound containing at least one cyclic ligand structure Method
Technical field
The invention belongs to lithium ion battery technical field of electrolyte more particularly to a kind of chemical combination containing cyclic ligand structure The preparation method and purification process of object.
Background technique
Lithium ion battery is a kind of secondary cell, and by lithium ion, movement carrys out work between a positive electrode and a negative electrode.Lithium ion Battery has the characteristics that specific energy is high, specific power is big, has extended cycle life, and is mainly used in 3C number class consumption electronic product at present Field and new energy power vehicle and energy storage field.Disappear as the requirement of new-energy automobile course continuation mileage is continuously improved with digital class The size of expense electronic product is increasingly miniaturized, and high-energy density chemical conversion is the Main Trends of The Development of current lithium ion battery, and mentions High-lithium ion battery operating voltage is the effective way for improving battery energy density.
The raising of lithium ion battery operating voltage, although can be improved battery energy density, at the same time, battery work The raising for making voltage will also tend to the performance of deterioration battery.Because, on the one hand, the crystal structure of anode is in high voltage condition Under it is unstable, during charge and discharge, the crystal structure of anode can recurring structure collapse, so as to cause the evil of performance Change；On the other hand, under high voltages, positive electrode surface is under high oxidation state, and activity is higher, is easy catalytic electrolysis liquid oxidation point Solution, the decomposition product of electrolyte are easy to deposit in positive electrode surface, the deintercalation channel of lithium ion are blocked, to deteriorate cell performance Energy.
Electrolyte is the key factor for influencing battery comprehensive performance, and particularly, the additive in electrolyte is to each of battery The performance of item performance is even more important.Therefore, the lithium-ion-power cell using ternary nickel cobalt manganese material as anode is given full play to Performance, the matching of electrolyte is crucial.
It is negative electrode material that current commercialized lithium ion battery, which mostly uses greatly graphitized carbon material, due to the work of graphite material Make that voltage is lower, the output voltage of battery is high when using as negative electrode material, but since lithium intercalated graphite reactivity is very high, The inevasible side reaction existed with electrolyte.(EC) solvent of ethylene carbonate used in electrolyte is in battery initial charge When can restore to form one layer of SEI passivating film in graphite surface, prevent lithium intercalated graphite reacted with the further of electrode solution.Simultaneously SEI film can allow lithium ion to pass through, and enable the normal charge and discharge of lithium ion battery.
For example, disclosing a kind of lithium-ion battery electrolytes additive, electrolysis in Chinese patent application 2017113114786 Liquid, lithium ion battery, belong to technical field of lithium ion.Thermostabilization is selected in lithium ion battery additive provided by the invention Property is good, and at the low component of membrane impedance, wherein ethylene carbonate, sulfuric acid vinyl ester can be improved lithium-ion electric under low temperature and ultralow temperature The conductivity of liquid is solved, three (trimethyl silane) borates can protect anode, improve the high-temperature behavior of battery.Added with the addition The lithium ion battery of the electrolyte preparation of agent can take into account performance under low temperature, the condition of high temperature, discharge and hold in -20 DEG C of low temperature environments Amount reaches the 85% of initial capacity, and battery discharge capacity in -40 DEG C of low temperature environments reaches the 75% of initial capacity, in high temperature 55 DEG C storage 28d battery capacity keep 85%.But EC at film be not sufficiently stable, during circulating battery exist rupture, regeneration Long process, therefore there is the disadvantages of circulation is bad, and impedance increases greatly, and high-temperature behavior is poor in battery.
Addition film for additive can improve the passivating film on negative electrode of lithium ion battery surface, ethylene carbonate in the electrolytic solution (VC) and fluorinated ethylene carbonate (FEC) is widely applied in lithium ion battery.These additives can be before EC It is reduced film forming, the passivating film of formation is more stable compared with EC film forming during circulating battery, so that so that battery is kept longer makes Use the service life.
Such as a kind of lithium ion battery containing fluorinated ethylene carbonate is disclosed in Chinese patent application 2015105013623 Electrolyte, including nonaqueous solvents, lithium salts and additive, it is characterised in that: the additive includes fluorinated ethylene carbonate, cyanophenyl Compound and cyclic annular phosphorus compound, cyclic annular phosphorus compound used in the present invention can be in positive table in the case where being greater than 4.35V high voltage Ring-opening polymerization occurs for face, forms oxidative resistance and the good protective film of lithium ion permeability in positive electrode surface, reduces electrolysis Cathode material structure is stablized in decomposition of the liquid under high potential, and internal resistance of the battery in cyclic process can be effectively suppressed and increase, promoted Discharge capacity of the cell improves cycle performance；The protective film that cyclic annular phosphorus compound is formed simultaneously has good thermal stability, can have Effect inhibits high temperature caused by fluorinated ethylene carbonate under hot conditions to produce gas.The thicker and high resilience research shows that VC forms a film, it is excellent Point is that battery room temperature and high temperature cyclic performance are excellent, the disadvantage is that the internal resistance of cell is bigger, is unfavorable for low temperature and high current charge-discharge. Compared with VC, for FEC film forming than relatively thin, the impedance comparison of formation is small, but unstable under high temperature, is easy to decompose.
Based on above-mentioned deficiency and defect, the compound of cyclic ligand structure is developed and is applied to lithium ion battery Electrolyte field, the fewer predominantly double oxalic acid boric acid of the compound reported at present containing at least one cyclic ligand structure The technology of preparing of lithium, method of reporting that there are two main classes both at home and abroad:
For example, Chinese patent application 201310125304.6 discloses a kind of preparation method of biethyl diacid lithium borate, packet It includes: lithium carbonate or lithium hydroxide being configured to slurry, are continuously passed through CO2, reaction generation LiHCO3, then with ethanedioic acid solution carry out Mixing, obtains LiHC2O4With ethanedioic acid mixed solution, then mixed with boric acid solution, react biethyl diacid lithium borate is molten Liquid.
For another example, Chinese patent application 200710164241.X discloses a kind of preparation method of di-oxalate lithium borate, comprising: By Li2CO3、LiOH·H2O、Li2C2O4And CH3One or more of COOLi, boric acid, diboron trioxide, metaboric acid, inclined boron The heating of the solution of one or more of sour lithium and pyroboric acid and one or more of oxalic acid, oxalic acid hydrogen lithium and lithium oxalate, obtains To the solution containing di-oxalate lithium borate.
But method disclosed above not can avoid product deliquesce, hydrolysis the problem of, the moisture and impurity content of product is high, Method route is complicated, leads to that product yield is low, manufacturing cost is high.If problem above is unresolved, the big of them will be hindered Sizable application especially hinders it to become the mainstream electrolyte of the new energy such as lithium ion battery, supercapacitor.
Therefore based on above-mentioned deficiency and defect, the application is intended to disclose a kind of containing at least one cyclic ligand structure The purification process of the preparation method sum of compound makes it in fields such as lithium ion batteries there is important industrial application to be worth, The compound moisture and impurity content of the purification process preparation of preparation method sum disclosed in the present application are few, method route is simple, lead It causes that product yield is high, manufacturing cost the, the large-scale production of high-volume and application may be implemented.
Summary of the invention
In view of the foregoing deficiencies of prior art, the object of the present invention is to provide a kind of changes containing cyclic ligand structure Close object with and preparation method thereof and purification process, meet field of lithium ion battery and its purity, impurity content, cost etc. wanted It asks.For the purpose for realizing foregoing invention, the present invention uses the method with low water content, drying, improves product Yield reduces the cost of product, by preferred starting material and preparation method, purification process, keeps reaction system in low water Content, drying regime obtain high-purity product, and improve simple, at low cost, the suitable industrialized production of yield, method, fit Together in the application in field of lithium ion battery.
The present invention provides one kind to contain cyclic ligand structure compound I to solve the above-mentioned problems, the compound Structure and substituent group are defined as follows described.
The preparation side of the present invention also provides a kind of to solve the above-mentioned problems compound I containing cyclic ligand structure Method in the compound I, contains only the cyclic ligand of 1~2 kind of different structure, that is, contains LaCyclic ligand, and/or, contain Lb's Cyclic ligand, wherein containing LaCyclic ligand in contain sulfonyl (- SO2), in sulfinyl (- SO-) or carbonyl (C=O) One；The structure of the compound I is as follows:
m1、m2、m3、m4Respectively 0 or 1；
n1For one in 1,2,3, n2For one in 0,1,2,3；
n3For one in 0,1,2,3,4；
n4For one in 0,1,2,3,4；
One in boron, phosphorus, carbon, nitrogen, aluminium or silicon of A；
A, b, c, d, e and f are respectively 0 or 1；And a, b, c one and only one be 1, d, e, f are 0, or at most only Having one is 1；
A ', b ', c ', d ', e ' and f ' are respectively 0 or 1；And a ', b ', c ' are 0, or at most only one is 1, D ', e ', f ' are 0, or at most only one is 1；
LaAnd LbRespectively saturation or unsaturated, halogen atom or not halogen atom, containing linear chain or branched chain, containing hetero atom or Without heteroatomic C1-C20Alkyl, C6-C20Aryl, C3-C20One in fatty ring group or heterocycle structure；Or LaAnd LbRespectively It is not present or is not present simultaneously, is i.e. LaOr LbThe functional group of two sides is separately or concurrently connected directly, LaAnd LbChange in the absence of simultaneously The structure for closing object I is as follows；
The compound I, when A is boron, 2 × n1+2×n2+n3+n4=4；When A is phosphorus, 2 × n1+2×n2+n3+n4 =6 or 4；When A is carbon, 2 × n1+2×n2+n3+n4=3；When A is nitrogen, 2 × n1+2×n2+n3+n4=2；When A is aluminium, 2 ×n1+2×n2+n3+n4=4；When A is silicon, 2 × n1+2×n2+n3+n4=3；
(1) preparation method of compound I:
The preparation method is that:
(1) contain LaLigand compound a and/or contain LbLigand compound b, and compound II and contain lithium reagent and/or contain Fluorine reagent, which reacts, is made compound I；
In some specific embodiments, the preparation method comprises the following steps:
In a specific embodiment, reaction equation are as follows:
Or, (2) prepare intermediate 1 first by compound II and at least one containing lithium reagent, the reagent containing M,
Then, intermediate 1 is directly reacted with ligand compound a and/or ligand compound b is made compound I；
Alternatively, intermediate 1 and ligand compound a and/or ligand compound b and fluorine-containing reagent, containing in lithium reagent at least Compound I is made in a kind of react；
In some specific embodiments, the preparation method comprises the following steps:
In a specific embodiment, reaction equation are as follows:
Or, (3) are reacted by compound II with ligand compound a and/or ligand compound b first prepares intermediate 2,
Compound I is made in intermediate 2 and at least one react containing lithium reagent, fluorine-containing reagent；
In some specific embodiments, the preparation method comprises the following steps:
In a specific embodiment, reaction equation are as follows:
Or, (4) first by compound II and ligand compound a and/or ligand compound b with containing lithium reagent, the reagent containing M At least one prepares intermediate 3；Then,
Compound I is made in intermediate 3 and fluorine-containing reagent, at least one react containing lithium reagent；
In some specific embodiments, the preparation method comprises the following steps:
In a specific embodiment, reaction equation are as follows:
Wherein, reaction temperature is -50-100 DEG C in above-mentioned preparation method (1)-(4), and reaction pressure is -0.05-1MPa (table Pressure), the reaction time is 0.5-24 hours.
Contain lithium reagent described in above-mentioned preparation method (1)-(4), is selected from LiOH, Li2CO3、Li2O, lithium halide, simple substance Li、LiHCO3, carbon number be 1~10 carboxylic acid lithium, carbon number be 1~10 Sulfonic Lithium, LiXO3、LiXO4、Li2SO4、LiNO3、 Li3PO4Or in LiH or above-mentioned equivalent (including presoma and hydrate, solvent complex object, halogenation hydride-complex) It is one or more of；
Fluorine-containing reagent described in above-mentioned preparation method (1)-(4) is the fluoride or hydrofluoride, anhydrous fluorination of metal Hydrogen, hydrofluoric acid, NH4F、NH4HF2, anhydrous hydrogen fluoride or hydrofluoric acid organic amine salt, fluorine gas or sulfur tetrafluoride or compound II One or more of equivalent (including presoma and hydrate, solvent complex object, halogenation hydride-complex).
Reagent containing M described in above-mentioned preparation method (1)-(4) is halide, the M of the hydroxide of M, the alkoxide of M, M Oxide, the hydride of M or equivalent (including presoma and the hydrate, solvent complex object, halogenation of compound II One or more of hydride-complex).
Ligand compound a and ligand compound b and the molar ratio of compound II are respectively in above-mentioned preparation method (1)-(4) 0.1-10:1.
Preferably, above-mentioned preparation method (1)-(4) carry out in a solvent, and the solvent is selected from methanol, ethyl alcohol, acetone, four Hydrogen furans, ethyl acetate, dimethyl carbonate, diethyl carbonate, ether, acetonitrile, dioxane, n,N-Dimethylformamide, two At least one of methyl sulfoxide and water；
Above-mentioned preparation method (1)-(4) carry out in the presence of a catalyst, and catalyst is selected from 4 bromide, tetraethyl One of ammonium bromide, 4-propyl bromide, 18- crown ether -6 and 15- crown ether -5 are a variety of；
The dosage of the catalyst is compound II, by mole being calculated as 0.01%-20%.
Wherein, described to contain LaLigand compound a structural formula it is as follows,
A, b, c, d, e and f are respectively 0 or 1；And a, b, c one and only one be 1, d, e, f can be 0, or most Mostly only one is 1；
LaFor saturation or unsaturated, halogen atom or not halogen atom, containing linear chain or branched chain, containing hetero atom or be free of miscellaneous original The C of son1-C20Alkyl, C6-C20Aryl, C3-C20Fatty ring group or heterocycle structure；Or LaIt is not present, i.e. LaThe functional group of two sides It is connected directly.
Z1Selected from following two situation:
(a) work as LaIt is not present, seven conditions of a=1, b=0, c=0, d=1, e=0, f=0 while when meeting, contains LaMatch Body compound a is respectively carboxylic acid halides (Z1=halogen), aldehyde (Z1=H), cyclic acid anhydride (Z1=O- (CO)-(CO) -), nitration mixture acid anhydride (Z1= O-CO-R or O-SO2- R or O-SO-R), ester (Z1=OR), silicon ester (Z1=OSiR3、Z1=OSiHR2Or OSiXR2、Z1= OSiH2R or OSiX2R、Z1=OSiH3Or OSiX3One of)；Or
(b) work as LaIt is not present, when seven conditions of a=1, b=0, c=0, d=1, e=0, f=0 do not meet simultaneously, contains La's Ligand compound a is carboxylic acid halides (Z1=halogen), aldehyde (Z1=H), cyclic acid anhydride (Z1=O- (CO)a-(SO2)b-(SO)c-La- (SO)f-(SO2)e-(CO)d), nitration mixture acid anhydride (Z1=O-CO-R or O-SO2- R or O-SO-R), ester (Z1=OR), silicon ester (Z1= OSiR3、Z1=OSiHR2Or OSiXR2、Z1=OSiH2R or OSiX2R、Z1=OSiH3Or OSiX3), acid (Z1=OH), salt (Z1= OMIOr ONH4One of)；
Containing LaLigand compound a in Z2For halogen, H, O- (CO)a-(SO2)b-(SO)c-La-(SO)f-(SO2)e- (CO)d, O-CO-R or O-SO2- R or O-SO-R, OR, OSiR3、OSiHR2Or OSiXR2、OSiH2R or OSiX2R、OSiH3Or OSiX3、OH、OMI、ONH4One of；
Wherein, R is the C of linear chain or branched chain1-C20Alkyl；
Wherein, MIFor metallic element；Preferably, the metallic element be alkali metal, alkaline-earth metal and chromium, manganese, iron, One of cobalt, nickel, copper, zinc, titanium, aluminium, lead.
Preferably, described to contain LaLigand compound a in Z1Selected from following two situation:
(a) work as LaIt is not present, seven conditions of a=1, b=0, c=0, d=1, e=0, f=0 while when meeting, contains LaMatch Body compound a is respectively carboxylic acid halides (Z1=Z2=halogen), aldehyde (Z1=Z2=H), cyclic acid anhydride (Z1=Z2=O- (CO)-(CO) -), Nitration mixture acid anhydride (Z1=Z2=O-CO-R or O-SO2- R or O-SO-R), ester (Z1=Z2=OR), silicon ester (Z1=Z2=OSiR3、Z1= Z2=OSiHR2Or OSiXR2、Z1=Z2=OSiH2R or OSiX2R、Z1=Z2=OSiH3Or OSiX3One of)；Or
(b) work as LaIt is not present, when seven conditions of a=1, b=0, c=0, d=1, e=0, f=0 do not meet simultaneously, contains La's Ligand compound a is respectively carboxylic acid halides (Z1=Z2=halogen), aldehyde (Z1=Z2=H), cyclic acid anhydride (Z1=O- (CO)a-(SO2)b- (SO)c-La-(SO)f-(SO2)e-(CO)d), acid nitration mixture acid anhydride (Z1=Z2=O-CO-R or O-SO2- R or O-SO-R), ester (Z1 =Z2=OR), silicon ester (Z1=Z2=OSiR3、Z1=Z2=OSiHR2Or OSiXR2、Z1=Z2=OSiH2R or OSiX2R、Z1= Z2=OSiH3Or OSiX3), acid (Z1=Z2=OH), acid salt (Z1=Z2=OMIOr ONH4One of)；
Wherein, R is the C of linear chain or branched chain1-C20Alkyl；
Wherein, MIFor metallic element；Preferably, the metallic element be alkali metal, alkaline-earth metal and chromium, manganese, iron, One of cobalt, nickel, copper, zinc, titanium, aluminium, lead.
It is described to contain LbLigand compound b structural formula it is as follows,
A ', b ', c ', d ', e ' and f ' are respectively 0 or 1；And a ', b ', c ' are 0, or at most only one is 1, D ', e ', f ' are 0, or at most only one is 1；
LbFor saturation or unsaturated, halogen atom or not halogen atom, containing linear chain or branched chain, containing hetero atom or be free of miscellaneous original The C of son1-C20Alkyl, C6-C20Aryl, C3-C20Fatty ring group or heterocycle structure；Or LbIt is not present, i.e. LbThe functional group of two sides It is connected directly；
Z1' and Z2' it is respectively selected from halogen, H, O- (CO)a-(SO2)b-(SO)c-La-(SO)f-(SO2)e-(CO)d-)、O-CO- R or O-SO2- R or O-SO-R, OR, OSiR3、OSiHR2Or OSiXR2、OSiH2R or OSiX2R、OSiH3Or OSiX3、OH、OMI’、 ONH4One of；
Wherein, R is the C of linear chain or branched chain1-C20Alkyl；
Wherein, MI' it is metallic element；Preferably, the metallic element be alkali metal, alkaline-earth metal and chromium, manganese, iron, One of cobalt, nickel, copper, zinc, titanium, aluminium, lead；
Compound that the compound II structure is as follows or its equivalent (including it is presoma and hydrate, molten Agent complex compound, halogenation hydride-complex):
Wherein, MIISelected from metallic element, NH4 +One of；Preferably, the metallic element is alkali metal, alkaline-earth metal And one of chromium, manganese, iron, cobalt, nickel, copper, zinc, titanium, aluminium, lead；
RIIFor the C of linear chain or branched chain1-C20Alkyl, alternatively, the C of silicon atoms1-C20Alkyl；
X is halogen；
j1、j2、j3、j4、j5One in respectively 0,1,2,3,4,5；
When A is boron, j1+j2+j3+j4+j5=3；When A is phosphorus, j1+j2+j3+j4+j5=5 or 3；When A is carbon, j1+ j2+j3+j4+j5=4；When A is nitrogen, j1+j2+j3+j4+j5=3；When A is aluminium, j1+j2+j3+j4+j5=3；When A is silicon, j1+j2+j3+j4+j5=4.
The structure of the intermediate 1, intermediate 2 and intermediate 3 is as follows:
M is respectively selected from metallic element, NH in intermediate 1 and intermediate 34 +, organic amine salt cation, organophosphorated salt cation Or H+One of；Preferably, the metallic element be alkali metal, alkaline-earth metal and chromium, manganese, iron, cobalt, nickel, copper, zinc, titanium, One of aluminium, lead；
Wherein, the organic group in the organic amine salt cation or organophosphorated salt cation is respectively selected from identical or not The C of same, saturation or unsaturated, halogen atom or not halogen atom, linear chain or branched chain1-C20Alkyl, C6-C20Aryl, C6-C20Rouge One of fat ring group or heterocycle；The organic group and nitrogen-atoms or phosphorus atoms form the cyclic annular of one or more and tie Structure, the cyclic structure be saturation or unsaturated, halogen atom or not halogen atom, containing hetero atom or without heteroatomic C6-C20Aryl, C3-C20Fatty ring group or heterocycle；
N in intermediate 1 and intermediate 3 is respectively one in 1,2,3,4.
E in intermediate 2 and intermediate 3 is selected from X, OH, ORII、OMIIOne of；
A, b, c, d, e and f in intermediate 2 and intermediate 3 are respectively 0 or 1；And a, b, c one and only one be 1, D, e, f can be 0, or at most only one is 1；A ', b ', c ', d ', e ' and f ' are respectively 0 or 1；And a ', b ', c ' It is all 0, or at most only one is 1, d ', e ', f ' are 0, or at most only one is 1；m1、m2、m3、m4Respectively 0 Or 1；n1For one in 1,2,3, n2For one in 0,1,2,3；n3For one in 0,1,2,3,4；n4It is 0,1,2,3,4 In one；n1' for one in 1,2,3, n2' for one in 0,1,2,3；n3' for one in 0,1,2,3,4；n4' be 0, one in 1,2,3,4；
RIIFor the C of linear chain or branched chain1-C20Alkyl, alternatively, the C of silicon atoms1-C20Alkyl；MIISelected from metallic element, NH4 +One of alkyl；Preferably, the metallic element be alkali metal, alkaline-earth metal and chromium, manganese, iron, cobalt, nickel, copper, zinc, One of titanium, aluminium, lead；
j1′、j2′、j3′、j4′、j5One in ' respectively 0,1,2,3,4,5；
When A is boron, j1′+j2′+j3′+j4′+j5'=4；When A is phosphorus, j1′+j2′+j3′+j4′+j5'=6 or 4；Work as A When for carbon, j1′+j2′+j3′+j4′+j5'=3；When A is nitrogen, j1′+j2′+j3′+j4′+j5'=2；When A is aluminium, j1′+j2′+ j3′+j4′+j5'=4；When A is silicon, j1′+j2′+j3′+j4′+j5'=3；
Preferably, above-mentioned LaGroup or LbThe structure of group includes at least:
The structural formula of compound I includes being not limited to:
Above-mentioned preparation method can be carried out by following technique:
(1) based on the preparation process of electrolytic tank electrolysis:
The progress of hydrogen fluoride electrolyzer reaction method can be used in above-mentioned preparation method (1)-(4)；
Hydrogen fluoride electrolyzer reaction method are as follows: the raw material in preparation method described in claim 1 is added in electrolytic cell It is reacted in dry conditions；
The hydrogen fluoride electrolyzer reaction technique, is reacted under the dry condition in electrolytic cell.
Hydrogen fluoride is removed water through electrolysis method in electrolytic cell, so that electrolytic cell reaches drying condition, electrolytic cell is keeping 0~25V Decomposition voltage or be not added under conditions of decomposition voltage reacted.
(2) preparation process based on the mixing of the mixing apparatus such as ball mill, sand mill, batch mixer or mixing machine:
Above-mentioned preparation method (1)-(4) can be used first to mix and carry out high temperature solid-state preprocess method afterwards and be prepared.
The mixing is mixed in the mixing apparatus such as ball mill, sand mill, kneader, batch mixer or mixing machine；
The mixing temperature is -50-100 DEG C, and incorporation time is 0.5-24 hours.
The described high temperature solid-state pretreatment is the raw material that will mix as in heating equipment, and heating heating is allowed to carry out Reaction；
The heating equipment is Muffle furnace or microwave heating or infrared heating；
The heating temperature is 0-800 DEG C, and heating treatment time is 1-24 hours.
(3) based on the preparation process for using Special dewatering substance:
Contain L described in above-mentioned preparation method (1)-(4)aLigand compound a or contain LbLigand compound b reaction when, Special dewatering substance is added；
The Special dewatering substance is selected from SiHX3、SiH2X2、Si(-OR)4、SiX4、COX2、AlX3、BX3、SO2X2、 SOX2、PX5、PX3、P2O5Or POX3One of or it is a variety of；X is halogen.
(4) based on the preparation process of Protective substances:
Ligand compound a or ligand compound b described in above-mentioned preparation method (1)-(4) reacts to form tool with Protective substances There are the pure substance or mixture of protecting group；
After ligand compound a or ligand compound b participates in reaction, protecting group is removed by hydrolysis process；
The Protective substances are one of compound R OH of hydroxyl or phenolic group or a variety of；
Wherein, the R in Protective substances is the protecting group that carbon number is 1~20, selected from saturated or unsaturated alkyl, whole halogen Change or partially halogenated alkyl, aromatic ring yl and fatty ring group；
Ligand compound a or ligand compound b is one of following structure or more after reacting with above-mentioned Protective substances Kind.
(2) a kind of purification process of above compound I:
The purification process includes: in dry conditions, to purge condition using dry Sealing Arrangement, or in dry gas Under, it is recrystallized using crude product of the organic solvent to above compound I, is crystallized under cryogenic, filtered, it is dry, it obtains To the fine work of target compound.
The organic solvent is selected from methanol, ethyl alcohol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, carbonic acid diethyl One of ester, ether, acetonitrile, dioxane, n,N-Dimethylformamide, dimethyl sulfoxide and water are a variety of.
(3) a kind of method that electrolyte is prepared using above compound I:
Compound I can be separately as the electrolyte lithium salt of lithium ion battery, and being dissolved in organic solvent can be used for preparing lithium ion The electrolyte solution of battery；The concentration of the compound I is 0.1~5.0mol/L；
Or, being dissolved in organic solvent can be used for preparing the electrolyte solution of lithium ion battery by compound I and lithium salts；It is described The concentration of lithium salts and compound I are respectively 0.1-5.0mol/L；
The organic solvent is selected from ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, propene carbonate, carbonic acid diformazan One of ester, chlorocarbonic acid vinyl acetate and fluorinated ethylene carbonate are a variety of.
The lithium salts is selected from lithium hexafluoro phosphate, LiBF4, double fluorine sulfimide lithiums, bis trifluoromethyl sulfimide One of lithium and trifluoromethanesulfonic acid lithium are a variety of；
Contain cyclic ligand structure compound I as described above the present invention also provides a kind of.
1, the preparation method of this application provides a kind of compound I containing at least one cyclic ligand structure and purifying side Method meets requirement of the field of lithium ion battery to its purity, impurity content, cost etc..Have the advantages that low water content, drying Method, improve the yield of product, reduce the cost of product, by preferred starting material, preparation method and purification process, It keeps reaction system in low water content, drying regime, obtains the product of high-purity, and improve that yield, method be simple, cost Low, suitable industrialized production, is suitable for the application in field of lithium ion battery；
2, the present invention used in part contain LaLigand compound a and/or contain LbLigand compound b itself have The property of low water content, in addition, using hydrogen fluoride electrolytic cell method, or using the method for Special dewatering substance, cause to react The moisture content of system substantially reduces, and deliquescence or hydrolysis so as to avoid product improve the yield and purity of reaction.The party Method significantly simplifies the preparation method process of product, reduces process units requirement, improves production efficiency；
3, the application conversion ratio of the extent of reaction and starting material in order to better improve in implementation process, has used Mixed method in the mixing apparatus such as ball mill, sand mill, batch mixer, kneader and mixing machine causes the extent of reaction more abundant, Improve the yield and purity of reaction；
4, the application has used Protective substances side in order to avoid the destruction to sensitive group in ligand in implementation process Method can largely avoid the side reaction of product from occurring, improve the yield and purity of reaction using Protective substances method；
5, the by-product and impurity generated in preparation and purification method reaction process provided by the present application is easily purified and divides From impurity simplifies product without the practical application standard that can reach high-purity by complicated method of purification in product Preparation flow makes product yield high, and product purity is high, is able to satisfy in the yield and quality of large-scale application and needs.
Specific embodiment
By partial, non-limiting specific embodiment, for the present invention to be described in more detail, still, the present invention is not limited In embodiment below, merely illustrated the principles of the invention described in embodiment and specification；That is, it is as described below only It is only example is preferably implemented in a part of the invention, interest field of the invention cannot be limited with this, for the art Those of ordinary skill for, under the premise of not departing from spirit of that invention, principle and range, the present invention can also make various changes Change, improvements and modifications, these improved additional features can individually or form exists in any combination, these variations improve Within the scope of also should be regarded as claimed invention of the invention with retouching.
Below with reference to embodiment, invention is further described in detail, but must not be construed to these embodiments to this The limitation of invention protection scope.The present invention can be realized by any mode described in summary of the invention.
Every impurity content in product carries out analytical control using following methods:
Chloride ion content carries out analysis test using spectrophotometry, and content of fluoride ion is surveyed using fluoride ion electrode analysis Examination, sulfate radical content carry out analysis test using spectrophotometry, and water content uses the analysis test of karl Fischer Moisture Meter, gold Belong to content and carries out analysis test using inductively-coupled plasma spectrometer.
The pressure value mentioned in present patent application, if referring both to gauge pressure without specified otherwise.
Yield, with the percent ratio of actual product quality and theoretical product quality, theoretical product quality, with anti- Not excessive raw material in equation is answered to be calculated.
Purity is calculated by minusing, i.e., the summation that each impurity content in product is subtracted by 100% carries out It calculates.
Ball mill is that Wuxi new thirty years of age of mechanical equipment Co., Ltd produces, model ZM.
Glove box is that German Braun company produces, model LABstar.
Basic embodiment:
The preparation and test of electrolyte:
1, prepared by electrolyte: configuring electrolyte in glove box, is full of 99.99% nitrogen in glove box, in glove box Moisture is controlled in≤5ppm, and temperature is room temperature.The dicyandiamide solution that mass ratio is EC:DMC:DEC=3:3:4 is uniformly mixed, it is close Envelope, is put into refrigerator after it is cooled to 8 DEG C, is transferred in glove box, LiPF is then added in two batches6It is sufficiently mixed, obtains Lithium salts molar concentration is the nonaqueous electrolytic solution A of the lithium ion battery of 1mol/L, and it is uniform that compound I is added into nonaqueous electrolytic solution A After mixing, the nonaqueous electrolytic solution B of the lithium salts of this patent containing 0.01mol/L is made and is electrolysed to get to nonaqueous lithium ion battery Liquid.
2, the preparation of lithium ion cell positive: by NCA material, conductive agent SuperP, bonding agent PCDF in mass ratio 96: 2.0:2.0 is uniformly mixed the lithium ion battery anode glue size that certain viscosity is made, and is coated in current collector aluminum foil, coating weight is 0.0194g/cm2, it is cold-pressed after being dried at 85 DEG C；Then trimming, cut-parts, slitting are carried out, after slitting under vacuum conditions 85 DEG C dry 4 hours, and the lithium ion cell positive met the requirements is made in soldering polar ear.
3, the preparation of lithium ion battery negative electrode: by artificial graphite and conductive agent SuperP, thickener CMC, bonding agent Slurry is made in SBR (SBR emulsion) ratio of 90:2.0:2.0:6.0 in mass ratio, be coated on copper foil of affluxion body and It is dried at 85 DEG C, coating weight 0.0089g/cm2；It carries out trimming, cut out item, slitting, 110 DEG C of drying under vacuum conditions after slitting 4 hours, the negative electrode of lithium ion battery met the requirements was made in soldering polar ear.
4, the preparation of lithium ion battery: the lithium ion cell positive, cathode pole piece and isolation that will be prepared according to preceding method Film is made by laminating method with a thickness of 4.2mm, broadband 34mm, and length is the lithium ion battery of 82mm, the vacuum at 75 DEG C Baking 10 hours, injects foregoing nonaqueous lithium ion battery electrolyte.After standing 24 hours, with the perseverance of 0.1C (160mA) Then constant-current charge drops to 0.05C (80mA) to 4.2V with 4.2C constant-voltage charge to electric current；Then with 0.1C (160mA) It is discharged to 3.0V, is repeated 2 times charge and discharge, battery is finally charged to by 3.8V with 0.1C (160mA) again, completes battery production.
Initial coulomb efficiency test: the test condition of initial coulomb efficiency in a specific embodiment are as follows: at 25 DEG C, adopt With lithium ion battery with 0.1C, 4.4V, the cut-off of 0.02C constant-current constant-voltage charging, the mode that 0.1C is discharged to 2.75V cut-off tested.
Cycle performance test: the test condition of the cycle performance of embodiment in this embodiment are as follows: at 25 DEG C, adopt With lithium ion battery with 0.1C, 4.4V, the cut-off of 0.02C constant-current constant-voltage charging, then at different temperatures, 0.2C electric discharge or 2C are put Electricity to the mode that 2.75V ends is tested, and one cycle, 100 times or 300 times circulation cut-offs, after calculating circulation are once counted in charge and discharge Capacity retention ratio.
Embodiment 1: the preparation and purification method of compound I
Compound I isLigand compound a isLigand compound b isCompound II is
Under agitation, ligand compound a and ligand compound b, compound II are added into the dry reactor of 1L With reaction dissolvent ethyl alcohol, the molar ratio of ligand compound a, ligand compound b and compound II are respectively 1:1, and reaction temperature is 50 DEG C, reaction pressure is 0.2MPa (gauge pressure), and the reaction time is 2 hours.It is down to room temperature after the reaction was completed.Insoluble matter is filtered off, Filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, compound I crude product is prepared, compound I crude yield is 99.6%, crude product purity is 99.2%.
It is recrystallized using etoh solvent, is then dried, fine work purity is 99.99% after recrystallization, is prepared pure Changing two step gross production rates (referred to as gross production rate, the same below) is 99.0%.Chloride ion content < 12ppm in product, content of fluoride ion < 12ppm, sulfate radical content < 12ppm, water content < 12ppm, tenor < 12ppm, other impurities < 12ppm.
The preparation and test of electrolyte:
Anode for the present embodiment 1 is NCA nickel cobalt aluminium ternary material, and cathode is artificial graphite, solvent EC, DMC, DEC, solvent ratios 3:3:4, lithium salts LiPF6Concentration is 1M, and additive is the compound I of the present embodiment 1, additive ratio Example is 0.006M.The initial coulomb efficiency of battery is 90.5%, and 300 weeks capacity remain 56.5%, and -40 DEG C of 0.2C electric discharges are 49.5%.2C multiplying power discharging is 89.5%, 60 DEG C circulation 100 weeks be 29.5%, 60 DEG C of thickness swellings are 1.85%, 60 DEG C 7 Its capacity retention ratio is 88.5%, and 60 DEG C of 7 days capacity recovery rates are 97.5%, does not analyse lithium under the conditions of 0 DEG C.
Embodiment 2: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, compound a, compound II and reaction dissolvent methanol are added into the dry reactor of 1L, matches The molar ratio of body compound a and compound II are 1:1, and reaction temperature is 50 DEG C, and reaction pressure is 0MPa (gauge pressure), reaction time It is 24 hours, is reacted using ball mill method, be down to room temperature after the reaction was completed, filters off insoluble matter, filtrate decompression rotation Evaporation of solvent, condensing crystallizing is dry, and compound I crude product is prepared, and compound I crude yield is 99.6%, and crude product is pure Degree is 99.3%.
Recrystallization solvent is methanol, other reaction conditions are same as Example 1.Gained fine work purity is 99.99%, total yield Rate is 99.1%.Chloride ion content < 8ppm in product, content of fluoride ion < 8ppm, sulfate radical content < 8ppm, water content < 8ppm, tenor < 8ppm, other impurities < 8ppm.
The preparation and test condition of electrolyte, solvent EC, DMC, methyl ethyl carbonate, lithium salts are LiBF4, lithium salts Concentration is 0.1~5.0mol/L, with embodiment 1.The initial coulomb efficiency of battery is 90.0%, and capacity remains within 300 weeks 56.0%, -40 DEG C of 0.2C electric discharges are 49.0%.2C multiplying power discharging be 89.0%, 60 DEG C circulation 100 weeks be 29.0%, 60 DEG C of thickness Spending expansion rate is 1.9%, and 60 DEG C of 7 days capacity retention ratios are 88.0%, and 60 DEG C of 7 days capacity recovery rates are 97%, under the conditions of 0 DEG C not Analyse lithium.
Embodiment 3: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II isIntermediate
1 is
Under agitation, LiF, compound II and reaction dissolvent acetone are added into the dry reactor of 1L.LiF and change The molar ratio for closing object II is 1:1, and reaction temperature is 20 DEG C, and reaction pressure is 1MPa (gauge pressure), and the reaction time is 2 hours, is used Hydrogen fluoride electrolytic cell method is reacted.It is down to room temperature after the reaction was completed, filters off insoluble matter, filtrate decompression rotary evaporation removes Solvent, condensing crystallizing is dry, and 1 crude product of intermediate is prepared；Then ligand compound a is added into the dry reactor of 1L Under the same reaction conditions with intermediate 1, prepare compound I crude product, gross production rate 99.2% are reacted, crude product purity is 90%.
Recrystallization solvent is acetone, other reaction conditions are same as Example 1.Gained fine work purity is 99.95%, total yield Rate is 99.0%.Chloride ion content < 15ppm in product, content of fluoride ion < 15ppm, sulfate radical content < 15ppm, moisture content contain Measure < 15ppm, tenor < 15ppm, other impurities < 15ppm.
The preparation and test condition of electrolyte, solvent EC, DMC, propene carbonate, with embodiment 1.The library for the first time of battery Logical sequence efficiency is 91.0%, and 300 weeks capacity remain 55.0%, and -40 DEG C of 0.2C electric discharges are 48.0%.2C multiplying power discharging is 88.0%, 60 DEG C circulation 100 weeks be 28.0%, 60 DEG C of thickness swellings are 2.0%, and 60 DEG C of 7 days capacity retention ratios are 87.0%, 60 DEG C of 7 days capacity recovery rates are 96%, do not analyse lithium under the conditions of 0 DEG C.
Embodiment 4: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II isIntermediate 2 is
Under agitation, ligand compound a, compound II and reaction dissolvent tetrahydro are added into the dry reactor of 1L Furans.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is 100 DEG C, and reaction pressure is 0MPa (gauge pressure), Reaction time is 0.5 hour.Using Special dewatering substance method is added, Special dewatering substance A lCl is added3, drop after the reaction was completed To room temperature.Insoluble matter is filtered off, filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, and it is thick that intermediate 2 is prepared Product；Then LiF and intermediate 2 is added under the same reaction conditions into the dry reactor of 1L, reaction prepare compound I is thick Product, gross production rate 99.6%, crude product purity are 92%.
Recrystallization solvent is tetrahydrofuran.Other reaction conditions are same as Example 1.Fine work purity is 99.99%, total yield Rate is 99.0%.Chloride ion content < 13ppm in product, content of fluoride ion < 13ppm, sulfate radical content < 13ppm, moisture content contain Measure < 13ppm, tenor < 13ppm, other impurities < 13ppm.
The preparation and test condition of electrolyte, solvent EC, DMC, chlorocarbonic acid vinyl acetate, lithium salts are double fluorine sulfimides Lithium, with embodiment 1.The initial coulomb efficiency of battery is 90.5%, and 300 weeks capacity remain 56.0%, and -40 DEG C of 0.2C electric discharges are 49.0%.2C multiplying power discharging is 89.0%, 60 DEG C circulation 100 weeks be 29.0%, 60 DEG C of thickness swellings are 1.9%, 60 DEG C 7 days Capacity retention ratio is 88.0%, and 60 DEG C of 7 days capacity recovery rates are 97%, does not analyse lithium under the conditions of 0 DEG C.
Embodiment 5: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II isIntermediate 3 is
Under agitation, ligand compound a, compound II and KF reaction dissolvent second are added into the dry reactor of 1L Acetoacetic ester.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is 0 DEG C, and reaction pressure is 0.5MPa (table Pressure), the reaction time is 4 hours, is down to room temperature after the reaction was completed.Insoluble matter is filtered off, filtrate decompression rotary evaporation removes solvent, Condensing crystallizing, it is dry, 3 crude product of intermediate is prepared；Then LiBF is added into the dry reactor of 1L4Exist with intermediate 3 Under same reaction conditions, prepare compound I crude product, gross production rate 99.6% are reacted, crude product purity is 92%.
Recrystallization solvent is ethyl acetate, other reaction conditions are same as Example 1.Fine work purity is 99.99%, total yield Rate is 99.0%.Chloride ion content < 9ppm in product, content of fluoride ion < 9ppm, sulfate radical content < 9ppm, water content < 9ppm, tenor < 9ppm, other impurities < 9ppm.
The preparation and test condition of electrolyte, solvent EC, DMC, fluorinated ethylene carbonate, lithium salts are bis trifluoromethyl sulphur Imide li, with embodiment 1.The initial coulomb efficiency of battery is 90.5%, and 300 weeks capacity remain 55.5%, -40 DEG C of 0.2C Electric discharge is 48.5%.2C multiplying power discharging is 88.5%, 60 DEG C circulation 100 weeks be 28.5%, 60 DEG C of thickness swellings are 1.8%, 60 DEG C of 7 days capacity retention ratios are 87.5%, and 60 DEG C of 7 days capacity recovery rates are 96.5%, do not analyse lithium under the conditions of 0 DEG C.
Embodiment 6: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent carbonic acid are added into the dry reactor of 1L Dimethyl ester.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is 10 DEG C, and reaction pressure is 0MPa (table Pressure), the reaction time is 12 hours, is down to room temperature after the reaction was completed, filters off insoluble matter, and filtrate decompression rotary evaporation removes molten Agent, condensing crystallizing is dry, and compound I crude product is prepared, and compound I crude yield is 99.6%, and crude product purity is 92%.
Recrystallization solvent is dimethyl carbonate, other reaction conditions are same as Example 1.Fine work purity is 99.99%, always Yield is 99.0%.Chloride ion content < 11ppm in product, content of fluoride ion < 11ppm, sulfate radical content < 11ppm, moisture content Content < 11ppm, tenor < 11ppm, other impurities < 11ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 91.0%, 300 weeks capacity 56.0% is remained, -40 DEG C of 0.2C electric discharges are 49.0%.2C multiplying power discharging be 89.0%, 60 DEG C circulation 100 weeks be 29.0%, 60 DEG C of thickness swellings are 1.9%, and 60 DEG C of 7 days capacity retention ratios are 88.0%, and 60 DEG C of 7 days capacity recovery rates are 97%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 7: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent carbonic acid are added into the dry reactor of 1L Diethylester.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is 50 DEG C, and reaction pressure is 0MPa (table Pressure), the reaction time is 2 hours, is down to room temperature after the reaction was completed, filters off insoluble matter, and filtrate decompression rotary evaporation removes solvent, Condensing crystallizing, it is dry, compound I crude product is prepared, compound I crude yield is 99.6%, and crude product purity is 92%.
Recrystallization solvent is diethyl carbonate, other reaction conditions are same as Example 1.Fine work purity is 99.995%, Gross production rate is 99.0%.Chloride ion content < 7ppm in product, content of fluoride ion < 7ppm, sulfate radical content < 7ppm, moisture content contain Measure < 7ppm, tenor < 7ppm, other impurities < 7ppm.
The concentration of the preparation and test condition of electrolyte, the compound I and lithium salts is 0.1mol/L, and lithium salts is fluoroform Sulfonic Lithium, with embodiment 1.The initial coulomb efficiency of battery is 89.0%, and 300 weeks capacity remain 56.0%, and -40 DEG C of 0.2C are put Electricity is 49.0%.2C multiplying power discharging is 89.0%, 60 DEG C circulation 100 weeks be 29.0%, 60 DEG C of thickness swellings are 1.8%, 60 DEG C of 7 days capacity retention ratios are 88.0%, and 60 DEG C of 7 days capacity recovery rates are 97%, do not analyse lithium under the conditions of 0 DEG C.
Embodiment 8: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent second are added into the dry reactor of 1L Ether.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is -20 DEG C, and reaction pressure is 0MPa (gauge pressure), instead It is 20 hours between seasonable, Protective substances method is added before starting in reaction, and Protective substances isopropanol is added, and is down to after the reaction was completed often Temperature filters off insoluble matter, and filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, and compound I crude product is prepared, and changes Closing object I crude yield is 99.7%, and crude product purity is 92%.
Recrystallization solvent is ether.Other reaction conditions are same as Example 1.Fine work purity is 99.99%, and gross production rate is 99.0%.Chloride ion content < 14ppm in product, content of fluoride ion < 14ppm, sulfate radical content < 14ppm, water content < 14ppm, tenor < 14ppm, other impurities < 14ppm.
The concentration of the preparation and test condition of electrolyte, the compound I and lithium salts is 5.0mol/L, with embodiment 1.Electricity The initial coulomb efficiency in pond is 90.0%, and 300 weeks capacity remain 55.0%, and -40 DEG C of 0.2C electric discharges are 47.0%.2C multiplying power is put Electricity is 87.0%, 60 DEG C circulation 100 weeks be 28.0%, 60 DEG C of thickness swellings are 2.1%, and 60 DEG C of 7 days capacity retention ratios are 87.0%, 60 DEG C of 7 days capacity recovery rates are 96%, do not analyse lithium under the conditions of 0 DEG C.
Embodiment 9: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent second are added into the dry reactor of 1L Nitrile.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is -30 DEG C, and reaction pressure is 0MPa (gauge pressure), instead It is 24 hours between seasonable, obtains product crude product A, product crude product A carries out HF fluorination reaction again.It is down to room temperature, mistake after the reaction was completed Insoluble matter is filtered off, filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, and compound I crude product, compound I is prepared Crude yield is 99.6%, and crude product purity is 92%.
Recrystallization solvent is acetonitrile, other reaction conditions are same as Example 1.Fine work purity is 99.99%, and gross production rate is 99.1%.Chloride ion content < 10ppm in product, content of fluoride ion < 10ppm, sulfate radical content < 10ppm, water content < 10ppm, tenor < 10ppm, other impurities < 10ppm.
The preparation and test condition of electrolyte, only use compound I, lithium salts are not used, with embodiment 1.Battery is for the first time Coulombic efficiency is 90.0%, and 300 weeks capacity remain 56.0%, and -40 DEG C of 0.2C electric discharges are 49.0%.2C multiplying power discharging is 89.0%, 60 DEG C circulation 100 weeks be 29.0%, 60 DEG C of thickness swellings are 1.9%, and 60 DEG C of 7 days capacity retention ratios are 88.0%, 60 DEG C of 7 days capacity recovery rates are 97%, do not analyse lithium under the conditions of 0 DEG C.
Embodiment 10: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent dioxy are added into the dry reactor of 1L Six rings.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is 30 DEG C, and reaction pressure is 0MPa (gauge pressure), Reaction time is 3 hours, is down to room temperature after the reaction was completed, filters off insoluble matter, and filtrate decompression rotary evaporation removes solvent, concentration Crystallization, it is dry, compound I crude product is prepared, compound I crude yield is 99.4%, and crude product purity is 92%.
Recrystallization solvent is dioxane, other reaction conditions are same as Example 1.Fine work purity is 99.99%, total yield Rate is 99.2%.Chloride ion content < 10ppm in product, content of fluoride ion < 10ppm, sulfate radical content < 10ppm, moisture content contain Measure < 10ppm, tenor < 10ppm, other impurities < 10ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.0%, 300 weeks capacity 56.0% is remained, -40 DEG C of 0.2C electric discharges are 49.0%.2C multiplying power discharging be 89.0%, 60 DEG C circulation 100 weeks be 29.0%, 60 DEG C of thickness swellings are 1.9%, and 60 DEG C of 7 days capacity retention ratios are 88.0%, and 60 DEG C of 7 days capacity recovery rates are 97%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 11: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent N, N- are added into the dry reactor of 1L Dimethylformamide.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is 40 DEG C, reaction pressure 0MPa (gauge pressure), reaction time are 2 hours, and Special dewatering substance method is added after the reaction was completed, Special dewatering substance B Cl is added3, instead It should be down to room temperature after the completion, filter off insoluble matter, filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, is prepared Compound I crude product, compound I crude yield are 99.6%, and crude product purity is 92%.
Recrystallization solvent is n,N-Dimethylformamide, other reaction conditions are same as Example 1.Fine work purity is 99.99%, gross production rate 99.0%.Chloride ion content < 14ppm in product, content of fluoride ion < 14ppm, sulfate radical content < 14ppm, water content < 14ppm, tenor < 14ppm, other impurities < 14ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.0%, 300 weeks capacity 55.0% is remained, -40 DEG C of 0.2C electric discharges are 48.0%.2C multiplying power discharging be 88.0%, 60 DEG C circulation 100 weeks be 28.0%, 60 DEG C of thickness swellings are 2.0%, and 60 DEG C of 7 days capacity retention ratios are 87.0%, and 60 DEG C of 7 days capacity recovery rates are 96%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 12: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent diformazan are added into the dry reactor of 1L Base sulfoxide.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is 10 DEG C, and reaction pressure is 0MPa (table Pressure), the reaction time is 12 hours, obtains crude product A after the reaction was completed, crude product A carries out HF fluorination reaction again, is down to after the reaction was completed Room temperature filters off insoluble matter, and filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, and compound I crude product is prepared, Compound I crude yield is 99.6%, and crude product purity is 92%.
Recrystallization solvent is dimethyl sulfoxide, other reaction conditions are same as Example 1.Fine work purity is 99.995%, Gross production rate is 99.1%.Chloride ion content < 7ppm in product, content of fluoride ion < 7ppm, sulfate radical content < 7ppm, moisture content contain Measure < 7ppm, tenor < 7ppm, other impurities < 7ppm.
The preparation and test condition of electrolyte, only use compound I, lithium salts are not used, with embodiment 1.Battery is for the first time Coulombic efficiency is 91.5%, and 300 weeks capacity remain 56.5%, and -40 DEG C of 0.2C electric discharges are 49.5%.2C multiplying power discharging is 89.5%, 60 DEG C circulation 100 weeks be 29.5%, 60 DEG C of thickness swellings are 1.8%, and 60 DEG C of 7 days capacity retention ratios are 89.0%, 60 DEG C of 7 days capacity recovery rates are 98%, do not analyse lithium under the conditions of 0 DEG C.
Embodiment 13: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent water are added into the dry reactor of 1L. The molar ratio of ligand compound a and compound II are 1.1:1, and reaction temperature is 0 DEG C, and reaction pressure is 0.1MPa (gauge pressure), instead It is 18 hours between seasonable, is down to room temperature after the reaction was completed, filter off insoluble matter, filtrate decompression rotary evaporation removes solvent, concentration Crystallization, it is dry, compound I crude product is prepared, compound I crude yield is 99.2%, and crude product purity is 90%.
Recrystallization solvent is water, other reaction conditions are same as Example 1.Fine work purity is 99.99%, and gross production rate is 99.0%.Chloride ion content < 11ppm in product, content of fluoride ion < 11ppm, sulfate radical content < 11ppm, water content < 11ppm, tenor < 11ppm, other impurities < 11ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.0%, 300 weeks capacity 53.0% is remained, -40 DEG C of 0.2C electric discharges are 46.0%.2C multiplying power discharging be 86.0%, 60 DEG C circulation 100 weeks be 26.0%, 60 DEG C of thickness swellings are 2.2%, and 60 DEG C of 7 days capacity retention ratios are 85.0%, and 60 DEG C of 7 days capacity recovery rates are 94%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 14: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent first are added into the dry reactor of 1L Alcohol.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is 20 DEG C, and reaction pressure is 0MPa (gauge pressure), instead It is 8 hours between seasonable, obtains product crude product A after the reaction was completed, product crude product A is reacted with LiOH again, is down to after the reaction was completed often Temperature filters off insoluble matter, and filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, and compound I crude product is prepared, and changes Closing object I crude yield is 99.2%, and crude product purity is 90%.
Recrystallization solvent is methanol, other reaction conditions are same as Example 1.Fine work purity is 99.99%, and gross production rate is 99.0%.Chloride ion content < 12ppm in product, content of fluoride ion < 12ppm, sulfate radical content < 12ppm, water content < 12ppm, tenor < 12ppm, other impurities < 12ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.0%, 300 weeks capacity 54.0% is remained, -40 DEG C of 0.2C electric discharges are 47.0%.2C multiplying power discharging be 87.0%, 60 DEG C circulation 100 weeks be 27.0%, 60 DEG C of thickness swellings are 2.1%, and 60 DEG C of 7 days capacity retention ratios are 86.0%, and 60 DEG C of 7 days capacity recovery rates are 95%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 15: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent second are added into the dry reactor of 1L Alcohol.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is -50 DEG C, and reaction pressure is -0.09MPa (table Pressure), the reaction time is 24 hours, obtains product crude product after the reaction was completed, and product crude product carries out HF fluorination reaction again, and reaction is completed After be down to room temperature, filter off insoluble matter, filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, and compound is prepared I crude product, compound I crude product crude yield are 99.2%, and crude product purity is 90%.
Recrystallization solvent is ethyl alcohol, other reaction conditions are same as Example 1.Fine work purity is 99.99%, and gross production rate is 99.0%.Chloride ion content < 9ppm in product, content of fluoride ion < 9ppm, sulfate radical content < 9ppm, water content < 9ppm, tenor < 9ppm, other impurities < 9ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.0%, 300 weeks capacity 55.0% is remained, -40 DEG C of 0.2C electric discharges are 48.0%.2C multiplying power discharging be 898.0%, 60 DEG C circulation 100 weeks be 28.0%, 60 DEG C of thickness swellings are 2.0%, and 60 DEG C of 7 days capacity retention ratios are 87.0%, and 60 DEG C of 7 days capacity recovery rates are 96%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 16: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent third are added into the dry reactor of 1L Ketone.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is -20 DEG C, and reaction pressure is 0MPa (gauge pressure), instead It is 20 hours between seasonable, obtains product crude product after the reaction was completed, product crude product carries out HF fluorination reaction again, then reacts with LiOH, It is down to room temperature after the reaction was completed, filters off insoluble matter, filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, is prepared into To compound I crude product.Compound I crude yield is 99.2%, and crude product purity is 90%.
Recrystallization solvent is acetone, other reaction conditions are same as Example 1.Fine work purity is 99.99%, and gross production rate is 99.0%.Chloride ion content < 11ppm in product, content of fluoride ion < 11ppm, sulfate radical content < 11ppm, water content < 11ppm, tenor < 11ppm, other impurities < 11ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 91.0%, 300 weeks capacity 54.0% is remained, -40 DEG C of 0.2C electric discharges are 47.0%.2C multiplying power discharging be 87.0%, 60 DEG C circulation 100 weeks be 27.0%, 60 DEG C of thickness swellings are 2.1%, and 60 DEG C of 7 days capacity retention ratios are 86.0%, and 60 DEG C of 7 days capacity recovery rates are 95%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 17: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent tetrahydro are added into the dry reactor of 1L Furans.The molar ratio of ligand compound a and compound II are 1.1:1, and reaction temperature is -10 DEG C, and reaction pressure is 0MPa (table Pressure), the reaction time is 20 hours, obtains product crude product after the reaction was completed, and product crude product carries out HF fluorination reaction again, and reaction is completed After be down to room temperature, filter off insoluble matter, filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, and compound is prepared I crude product.Compound I crude yield is 99.6%, and crude product purity is 92%.
Recrystallization solvent is tetrahydrofuran, other reaction conditions are same as Example 1.Fine work purity is 99.99%, total yield Rate is 99.2%.Chloride ion content < 10ppm in product, content of fluoride ion < 10ppm, sulfate radical content < 10ppm, moisture content contain Measure < 10ppm, tenor < 10ppm, other impurities < 10ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.0%, 300 weeks capacity 56.0% is remained, -40 DEG C of 0.2C electric discharges are 49.0%.2C multiplying power discharging be 89.0%, 60 DEG C circulation 100 weeks be 29.0%, 60 DEG C of thickness swellings are 1.9%, and 60 DEG C of 7 days capacity retention ratios are 88.0%, and 60 DEG C of 7 days capacity recovery rates are 97%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 18: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent acetic acid are added into the dry reactor of 1L Ethyl ester.The molar ratio of ligand compound a and compound II are 1.2:1, and reaction temperature is 10 DEG C, and reaction pressure is 0MPa (table Pressure), the reaction time is 12 hours, obtains product crude product after the reaction was completed, and product crude product carries out HF fluorination reaction again, then with LiOH Reaction, is down to room temperature after the reaction was completed, filters off insoluble matter, and filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, Compound I crude product is prepared.Compound I yield is 99.6%, and crude product purity is 92%.
Recrystallization solvent is ethyl acetate, other reaction conditions are same as Example 1.Fine work purity is 99.99%, total yield Rate is 99.0%.Chloride ion content < 10ppm in product, content of fluoride ion < 10ppm, sulfate radical content < 10ppm, moisture content contain Measure < 10ppm, tenor < 10ppm, other impurities < 10ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.0%, 300 weeks capacity 56.0% is remained, -40 DEG C of 0.2C electric discharges are 49.0%.2C multiplying power discharging be 89.0%, 60 DEG C circulation 100 weeks be 29.0%, 60 DEG C of thickness swellings are 1.9%, and 60 DEG C of 7 days capacity retention ratios are 88.0%, and 60 DEG C of 7 days capacity recovery rates are 97%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 19: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent carbonic acid are added into the dry reactor of 1L Dimethyl ester.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is 0 DEG C, and reaction pressure is 0MPa (gauge pressure), Reaction time is 18 hours, obtains product crude product after the reaction was completed, and product crude product is reacted with LiF again, is down to after the reaction was completed often Temperature filters off insoluble matter, and filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, and compound I crude product is prepared.Change Closing object I crude yield is 99.6%, and crude product purity is 92%.
Recrystallization solvent is dimethyl carbonate, other reaction conditions are same as Example 1.Fine work purity is 99.99%, always Yield is 99.1%.Chloride ion content < 10ppm in product, content of fluoride ion < 10ppm, sulfate radical content < 10ppm, moisture content Content < 10ppm, tenor < 10ppm, other impurities < 10ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.0%, 300 weeks capacity 56.0% is remained, -40 DEG C of 0.2C electric discharges are 49.0%.2C multiplying power discharging be 89.0%, 60 DEG C circulation 100 weeks be 29.0%, 60 DEG C of thickness swellings are 1.9%, and 60 DEG C of 7 days capacity retention ratios are 88.0%, and 60 DEG C of 7 days capacity recovery rates are 97%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 20: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent carbonic acid are added into the dry reactor of 1L Diethylester.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is 20 DEG C, and reaction pressure is 0MPa (table Pressure), the reaction time is 8 hours, obtains product crude product after the reaction was completed, and product crude product carries out HF fluorination reaction again, and reaction is completed After be down to room temperature, filter off insoluble matter, filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, and compound is prepared I crude product.Compound I crude yield is 99.6%, and crude product purity is 92%.
Recrystallization solvent is diethyl carbonate, other reaction conditions are same as Example 1.Fine work purity is 99.99%, always Yield is 99.0%.Chloride ion content < 10ppm in product, content of fluoride ion < 10ppm, sulfate radical content < 10ppm, moisture content Content < 10ppm, tenor < 10ppm, other impurities < 10ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.0%, 300 weeks capacity 56.0% is remained, -40 DEG C of 0.2C electric discharges are 49.0%.2C multiplying power discharging be 89.0%, 60 DEG C circulation 100 weeks be 29.0%, 60 DEG C of thickness swellings are 1.9%, and 60 DEG C of 7 days capacity retention ratios are 88.0%, and 60 DEG C of 7 days capacity recovery rates are 97%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 21: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent second are added into the dry reactor of 1L Ether.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is 100 DEG C, and reaction pressure is 1MPa (gauge pressure), instead It is 0.5 hour between seasonable, obtains product crude product after the reaction was completed, product crude product is reacted with LiOH again, is down to after the reaction was completed often Temperature filters off insoluble matter, and filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, and compound I crude product is prepared.Change Closing object I crude yield is 99.2%, and crude product purity is 90%.
Recrystallization solvent is ether, other reaction conditions are same as Example 1.Fine work purity is 99.99%, and gross production rate is 99.0%.Chloride ion content < 10ppm in product, content of fluoride ion < 10ppm, sulfate radical content < 10ppm, water content < 10ppm, tenor < 10ppm, other impurities < 10ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.5%, 300 weeks capacity 54.0% is remained, -40 DEG C of 0.2C electric discharges are 47.0%.2C multiplying power discharging be 87.0%, 60 DEG C circulation 100 weeks be 27.0%, 60 DEG C of thickness swellings are 2.1%, and 60 DEG C of 7 days capacity retention ratios are 86.0%, and 60 DEG C of 7 days capacity recovery rates are 95%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 22: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent second are added into the dry reactor of 1L Nitrile.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is -20 DEG C, and reaction pressure is 0MPa (gauge pressure), instead It is 20 hours between seasonable, is down to room temperature after the reaction was completed, filter off insoluble matter, filtrate decompression rotary evaporation removes solvent, concentration Crystallization, it is dry, compound I crude product is prepared.Compound I crude yield is 99.2%, and crude product purity is 90%.
Recrystallization solvent is acetonitrile, other reaction conditions are same as Example 1.Fine work purity is 99.99%, and gross production rate is 99.0%.Chloride ion content < 10ppm in product, content of fluoride ion < 10ppm, sulfate radical content < 10ppm, water content < 10ppm, tenor < 10ppm, other impurities < 10ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.5%, 300 weeks capacity 54.0% is remained, -40 DEG C of 0.2C electric discharges are 47.0%.2C multiplying power discharging be 87.0%, 60 DEG C circulation 100 weeks be 27.0%, 60 DEG C of thickness swellings are 2.1%, and 60 DEG C of 7 days capacity retention ratios are 86.0%, and 60 DEG C of 7 days capacity recovery rates are 95%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 23: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent dioxy are added into the dry reactor of 1L Six rings.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is -10 DEG C, and reaction pressure is 0MPa (gauge pressure), Reaction time is 20 hours, obtains product crude product after the reaction was completed, and product crude product is reacted with LiF again, is down to after the reaction was completed often Temperature filters off insoluble matter, and filtrate decompression rotary evaporation removes solvent, and condensing crystallizing is dry, and compound I crude product is prepared.Change Closing object I crude yield is 99.2%, and crude product purity is 90%.
Recrystallization solvent is dioxane, other reaction conditions are same as Example 1.Fine work purity is 99.99%, total yield Rate is 99.0%.Chloride ion content < 10ppm in product, content of fluoride ion < 10ppm, sulfate radical content < 10ppm, moisture content contain Measure < 10ppm, tenor < 10ppm, other impurities < 10ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.0%, 300 weeks capacity 54.0% is remained, -40 DEG C of 0.2C electric discharges are 47.0%.2C multiplying power discharging be 87.0%, 60 DEG C circulation 100 weeks be 27.0%, 60 DEG C of thickness swellings are 2.1%, and 60 DEG C of 7 days capacity retention ratios are 86.0%, and 60 DEG C of 7 days capacity recovery rates are 95%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 24: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent N, N- are added into the dry reactor of 1L Dimethylformamide.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is 10 DEG C, and reaction pressure is 0.1MPa (gauge pressure), reaction time are 12 hours, are down to room temperature after the reaction was completed, filter off insoluble matter, and filtrate decompression rotation is steamed Hair removes solvent, and condensing crystallizing is dry, and compound I crude product is prepared.Compound I crude yield is 99.2%, crude product purity It is 90%.
Recrystallization solvent is n,N-Dimethylformamide, other reaction conditions are same as Example 1.Fine work purity is 99.99%, gross production rate 99.1%.Chloride ion content < 10ppm in product, content of fluoride ion < 10ppm, sulfate radical content < 10ppm, water content < 10ppm, tenor < 10ppm, other impurities < 10ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.0%, 300 weeks capacity 54.0% is remained, -40 DEG C of 0.2C electric discharges are 47.0%.2C multiplying power discharging be 87.0%, 60 DEG C circulation 100 weeks be 27.0%, 60 DEG C of thickness swellings are 2.1%, and 60 DEG C of 7 days capacity retention ratios are 86.0%, and 60 DEG C of 7 days capacity recovery rates are 95%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 25: the preparation and purification method of compound I
Compound I isLigand compound a isLigand compound b isCompound II For
Under agitation, into the dry reactor of 1L be added ligand compound a, ligand compound b, compound II and Reaction dissolvent dimethyl sulfoxide.The molar ratio of ligand compound a and ligand compound b and compound II is respectively 1:1, reaction temperature Degree is 0 DEG C, and reaction pressure is 0MPa (gauge pressure), and the reaction time is 18 hours, obtains product crude product, product crude product after the reaction was completed It is reacted again with LiOH, is down to room temperature after the reaction was completed, filter off insoluble matter, filtrate decompression rotary evaporation removes solvent, concentration knot Crystalline substance, it is dry, compound I crude product is prepared.Compound I crude yield is 99.6%, and crude product purity is 92%.
Recrystallization solvent is dimethyl sulfoxide, other reaction conditions are same as Example 1.Fine work purity is 99.90%, always Yield is 99.0%.Chloride ion content < 10ppm in product, content of fluoride ion < 10ppm, sulfate radical content < 10ppm, moisture content Content < 10ppm, tenor < 10ppm, other impurities < 10ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.0%, 300 weeks capacity 54.0% is remained, -40 DEG C of 0.2C electric discharges are 47.0%.2C multiplying power discharging be 87.0%, 60 DEG C circulation 100 weeks be 27.0%, 60 DEG C of thickness swellings are 2.1%, and 60 DEG C of 7 days capacity retention ratios are 86.0%, and 60 DEG C of 7 days capacity recovery rates are 95%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 26: the preparation and purification method of compound I
Compound I isLigand compound a isLigand compound b isCompound II For
Under agitation, into the dry reactor of 1L be added ligand compound a, ligand compound b, compound II and Reaction dissolvent water.The molar ratio of ligand compound a and ligand compound b and compound II is respectively 1:1, reaction temperature 20 DEG C, reaction pressure is 0MPa (gauge pressure), and the reaction time is 8 hours, is down to room temperature after the reaction was completed, filters off insoluble matter, filtrate It depressurizes rotary evaporation and removes solvent, condensing crystallizing is dry, and compound I crude product is prepared.Compound I crude yield is 99.6%, crude product purity is 92%.
Recrystallization solvent is water, other reaction conditions are same as Example 1.Fine work purity is 99.99%, and gross production rate is 99.1%.Chloride ion content < 10ppm in product, content of fluoride ion < 10ppm, sulfate radical content < 10ppm, water content < 10ppm, tenor < 10ppm, other impurities < 10ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 90.0%, 300 weeks capacity 56.0% is remained, -40 DEG C of 0.2C electric discharges are 49.0%.2C multiplying power discharging be 89.0%, 60 DEG C circulation 100 weeks be 29.0%, 60 DEG C of thickness swellings are 1.9%, and 60 DEG C of 7 days capacity retention ratios are 88.0%, and 60 DEG C of 7 days capacity recovery rates are 97%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 27: the preparation and purification method of compound I
Compound I isLigand compound a isLigand compound b isCompound II is
Under agitation, into the dry reactor of 1L be added ligand compound a, ligand compound b, compound II and Reaction dissolvent methanol.The molar ratio of ligand compound a and ligand compound b and compound II is respectively 0.5:1, reaction temperature It is -50 DEG C, reaction pressure is -0.09MPa (gauge pressure), and the reaction time is 24 hours, is down to room temperature after the reaction was completed, filters off not Molten object, filtrate decompression rotary evaporation remove solvent, and condensing crystallizing is dry, and compound I crude product is prepared.Compound I crude product produces Rate is 99.6%, and crude product purity is 92%.
Recrystallization solvent is methanol, other reaction conditions are same as Example 1.Fine work purity is 99.99%, and gross production rate is 99.0%.Chloride ion content < 10ppm in product, content of fluoride ion < 10ppm, sulfate radical content < 10ppm, water content < 10ppm, tenor < 10ppm, other impurities < 10ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 92.0%, 300 weeks capacity 56.0% is remained, -40 DEG C of 0.2C electric discharges are 49.0%.2C multiplying power discharging be 89.0%, 60 DEG C circulation 100 weeks be 29.0%, 60 DEG C of thickness swellings are 1.9%, and 60 DEG C of 7 days capacity retention ratios are 88.0%, and 60 DEG C of 7 days capacity recovery rates are 97%, 0 DEG C of item Lithium is not analysed under part.
Embodiment 28: the preparation and purification method of compound I
Compound I isLigand compound a isCompound II is
Under agitation, ligand compound a, compound II and reaction dissolvent second are added into the dry reactor of 1L Alcohol.The molar ratio of ligand compound a and compound II are 1:1, and reaction temperature is -30 DEG C, and reaction pressure is -0.05MPa (table Pressure), the reaction time is 12 hours, is down to room temperature after the reaction was completed, filters off insoluble matter, and filtrate decompression rotary evaporation removes molten Agent, condensing crystallizing is dry, and compound I crude product is prepared.Compound I crude yield is 99.6%, and crude product purity is 92%.
Recrystallization solvent is ethyl alcohol, other reaction conditions are same as Example 1.Fine work purity is 99.99%, and gross production rate is 99.0%.Chloride ion content < 10ppm in product, content of fluoride ion < 10ppm, sulfate radical content < 10ppm, water content < 10ppm, tenor < 10ppm, other impurities < 10ppm.
The preparation and test condition of electrolyte, with embodiment 1.The initial coulomb efficiency of battery is 92.0%, 300 weeks capacity 56.0% is remained, -40 DEG C of 0.2C electric discharges are 49.0%.2C multiplying power discharging be 89.0%, 60 DEG C circulation 100 weeks be 29.0%, 60 DEG C of thickness swellings are 1.9%, and 60 DEG C of 7 days capacity retention ratios are 88.0%, and 60 DEG C of 7 days capacity recovery rates are 97%, 0 DEG C of item Lithium is not analysed under part.
Comparative example
Anode is NCA nickel cobalt aluminium ternary material, and cathode is artificial graphite, solvent EC, DMC, DEC, solvent ratios For 3:3:4, LiPF6Concentration is 1M, additive-free.
The initial coulomb efficiency of battery is 62.0%, and 300 weeks capacity remain 34.0%, and -40 DEG C of 0.2C electric discharges are 42.0%.
2C multiplying power discharging is 80.0%, 60 DEG C circulation 100 weeks be 12.0%, 60 DEG C of thickness swellings are 6.0%, 60 DEG C 7 Its capacity retention ratio is 74%, and 60 DEG C of 7 days capacity recovery rates are 89%, and 0 DEG C of analysis lithium situation is analysis lithium.

Claims (10)

1. a kind of preparation method of the compound I containing at least one cyclic ligand structure, it is characterised in that: the compound I Cyclic ligand containing 1-2 kind different structure contains LaCyclic ligand and/or contain LbCyclic ligand, wherein contain LaRing-type Contain sulfonyl (- SO in ligand2), sulfinyl (- SO-) or carbonyl (C=O)；The structure of compound I is as follows:
m1、m2、m3、m4Respectively 0 or 1；
n1For one in 1,2,3；
n2For one in 0,1,2,3；
n3For one in 0,1,2,3,4；
n4For one in 0,1,2,3,4；
A is selected from boron, phosphorus, carbon, nitrogen, aluminium or silicon；
A, b, c, d, e and f are respectively 0 or 1；And a, b, c one and only one be 1, d, e, f can all be 0, or at most only Having one is 1；
A ', b ', c ', d ', e ' and f ' are respectively 0 or 1；And a ', b ', c ' all be 0, or at most only one be 1, d ', e ', F ' is 0, or at most only one is 1；
LaAnd LbRespectively saturation or unsaturated, halogen atom or not halogen atom, containing linear chain or branched chain, containing hetero atom or be free of Heteroatomic C1-C20Alkyl, C6-C20Aryl, C3-C20Fatty ring group or heterocycle structure；Or LaAnd LbIt is not present respectively or together When be not present, i.e. LaOr LbThe functional group of two sides is connected directly separately or together, LaAnd LbCompound I in the absence of simultaneously Structure is as follows；
A, b, c, d, e, f, a ', b ', c ', d ', e ', f ', m1、m2、m3、m4, n1、n2、n3、n4It is defined as described above,
The compound I, when A is boron, 2 × n1+2×n2+n3+n4=4；When A is phosphorus, 2 × n1+2×n2+n3+n4=6 Or 4；When A is carbon, 2 × n1+2×n2+n3+n4=3；When A is nitrogen, 2 × n1+2×n2+n3+n4=2；When A is aluminium, 2 × n1+2×n2+n3+n4=4；When A is silicon, 2 × n1+2×n2+n3+n4=3；
The preparation method of the compound I includes:
(1) contain LaLigand compound a and/or contain LbLigand compound b, with compound II and contain lithium reagent and/or fluorine-containing examination Agent, which is reacted, is made compound I；
Or, (2) prepare intermediate 1 first by compound II and at least one containing lithium reagent, the reagent containing M, and then, intermediate 1 It is directly reacted with ligand compound a and/or ligand compound b and compound I is made；
Alternatively, intermediate 1 and ligand compound a and/or ligand compound b and fluorine-containing reagent, containing at least one of lithium reagent It reacts and compound I is made；
Or, (3) are reacted by compound II with ligand compound a and/or ligand compound b first prepares intermediate 2,
Compound I is made in intermediate 2 and at least one react containing lithium reagent, fluorine-containing reagent；
Or, (4) first by compound II and ligand compound a and/or ligand compound b with containing lithium reagent, reagent containing M at least One kind preparing intermediate 3；Then,
Compound I is made in intermediate 3 and fluorine-containing reagent, at least one react containing lithium reagent；
Wherein, described to contain LaLigand compound a structural formula it is as follows,
A, b, c, d, e and f are respectively 0 or 1；And a, b, c one and only one be 1, d, e, f can all be 0, or at most only Having one is 1；
LaFor saturation or unsaturated, halogen atom or not halogen atom, containing linear chain or branched chain, containing hetero atom or without heteroatomic C1-C20Alkyl, C6-C20Aryl, C3-C20Fatty ring group or heterocycle structure；Or LaIt is not present, i.e. LaThe functional group of two sides is direct It is connected；
Z1Selected from following two situation:
(a) work as LaIt is not present, seven conditions of a=1, b=0, c=0, d=1, e=0, f=0 while when meeting, contains LaIt is liganded Closing object a is respectively carboxylic acid halides (Z1=halogen), aldehyde (Z1=H), cyclic acid anhydride (Z1=O- (CO)-(CO) -), nitration mixture acid anhydride (Z1=O- CO-R or O-SO2- R or O-SO-R), ester (Z1=OR), silicon ester (Z1=OSiR3、Z1=OSiHR2Or OSiXR2、Z1=OSiH2R Or OSiX2R、Z1=OSiH3Or OSiX3One of)；Or
(b) work as LaIt is not present, when seven conditions of a=1, b=0, c=0, d=1, e=0, f=0 do not meet simultaneously, contains LaLigand Compound a is respectively carboxylic acid halides (Z1=halogen), aldehyde (Z1=H), cyclic acid anhydride (Z1=O- (CO)a-(SO2)b-(SO)c-La- (SO)f-(SO2)e-(CO)d), acid nitration mixture acid anhydride (Z1=O-CO-R or O-SO2- R or O-SO-R), ester (Z1=OR), silicon ester (Z1=OSiR3、Z1=OSiHR2Or OSiXR2、Z1=OSiH2R or OSiX2R、Z1=OSiH3Or OSiX3), acid (Z1=OH), acid Salt (Z1=OMIOr ONH4One of)；
Containing LaLigand compound a in Z2For halogen, H, O- (CO)a-(SO2)b-(SO)c-La-(SO)f-(SO2)e-(CO)d-、O- CO-R or O-SO2- R or O-SO-R, OR, OSiR3、OSiHR2Or OSiXR2、OSiH2R or OSiX2R、OSiH3Or OSiX3、OH、 OMI、ONH4One of；
Wherein, R is the C of linear chain or branched chain1-C20Alkyl；
Wherein, MIFor metallic element；Preferably, the metallic element be alkali metal, alkaline-earth metal and chromium, manganese, iron, cobalt, nickel, One of copper, zinc, titanium, aluminium, lead；
It is described to contain LbLigand compound b structural formula it is as follows,
A ', b ', c ', d ', e ' and f ' are respectively 0 or 1；And a ', b ', c ' all be 0, or at most only one be 1, d ', e ', F ' is 0, or at most only one is 1；
LbFor saturation or unsaturated, halogen atom or not halogen atom, containing linear chain or branched chain, containing hetero atom or without heteroatomic C1-C20Alkyl, C6-C20Aryl, C3-C20Fatty ring group or heterocycle structure or LbIt is not present, i.e. LbThe functional group of two sides is direct It is connected；
Z1' and Z2' it is respectively selected from halogen, H, O- (CO)a-(SO2)b-(SO)c-La-(SO)f-(SO2)e-(CO)d), O-CO-R or O-SO2- R or O-SO-R, OR, OSiR3、OSiHR2Or OSiXR2、OSiH2R or OSiX2R、OSiH3Or OSiX3、OH、OMI’、ONH4 One of；
Wherein, R is the C of linear chain or branched chain1-C20Alkyl；
Wherein, MI' it is metallic element；Preferably, the metallic element be alkali metal, alkaline-earth metal and chromium, manganese, iron, cobalt, nickel, One of copper, zinc, titanium, aluminium, lead；
Compound that the compound II structure is as follows or its equivalent (including presoma and hydrate, solvent network Close object, halogenation hydride-complex):
Wherein, MIISelected from metallic element, NH4 +One of；Preferably, the metallic element be alkali metal, alkaline-earth metal and One of chromium, manganese, iron, cobalt, nickel, copper, zinc, titanium, aluminium, lead；
RIIFor the C of linear chain or branched chain1-C20Alkyl, alternatively, the C of silicon atoms1-C20Alkyl；
X is halogen；
j1、j2、j3、j4、j5One in respectively 0,1,2,3,4,5；
When A is boron, j1+j2+j3+j4+j5=3；When A is phosphorus, j1+j2+j3+j4+j5=5 or 3；When A is carbon, j1+j2+j3+ j4+j5=4；When A is nitrogen, j1+j2+j3+j4+j5=3；When A is aluminium, j1+j2+j3+j4+j5=3；When A is silicon, j1+j2+ j3+j4+j5=4；
The structure of the intermediate 1, intermediate 2 and intermediate 3 is as follows:
M in intermediate 1 and intermediate 3 is respectively selected from metallic element, NH4 +, organic amine salt cation, organophosphorated salt cation or H+One of；Preferably, the metallic element be alkali metal, alkaline-earth metal and chromium, manganese, iron, cobalt, nickel, copper, zinc, titanium, One of aluminium, lead；
Wherein, the organic group in the organic amine salt cation or organophosphorated salt cation be respectively selected from it is identical or different, The C of saturation or unsaturated, halogen atom or not halogen atom, linear chain or branched chain1-C20Alkyl, C6-C20Aryl, C6-C20Aliphatic One of ring group or heterocycle；The organic group and nitrogen-atoms or phosphorus atoms form the cyclic structure of one or more, The cyclic structure be saturation or unsaturated, halogen atom or not halogen atom, containing hetero atom or be free of heteroatomic C6-C20 Aryl, C3-C20Fatty ring group or heterocycle；
N in intermediate 1 and intermediate 3 is respectively one in 1,2,3,4；
E in intermediate 2 and intermediate 3 is selected from X, OH, ORII、OMIIOne of；
A, b, c, d, e and f in intermediate 2 and intermediate 3 are respectively 0 or 1；And a, b, c one and only one be 1, d, e, f It can all be 0, or at most only one is 1；A ', b ', c ', d ', e ' and f ' are respectively 0 or 1；And a ', b ', c ' are 0, Or at most only one is 1, d ', e ', f ' they are 0, or at most only one is 1；m1、m2、m3、m4Respectively 0 or 1；n1 For one in 1,2,3, n2For one in 0,1,2,3；n3For one in 0,1,2,3,4；n4For one in 0,1,2,3,4 It is a；n1' for one in 1,2,3, n2' for one in 0,1,2,3；n3' for one in 0,1,2,3,4；n4' for 0,1,2, 3, one in 4；
L in intermediate 2 and intermediate 3aAnd LbRespectively saturation or unsaturated, halogen atom or not halogen atom, containing straight chain or Branch contains hetero atom or is free of heteroatomic C1-C20Alkyl, C6-C20Aryl, C3-C20Fatty ring group or heterocycle structure；Or La And LbIt is not present separately or together, i.e. LaOr LbThe functional group of two sides is connected directly separately or together；
RIIFor the C of linear chain or branched chain1-C20Alkyl, alternatively, the C of silicon atoms1-C20Alkyl；
MIISelected from metallic element, NH4 +One of；Preferably, the metallic element be alkali metal, alkaline-earth metal and chromium, manganese, One of iron, cobalt, nickel, copper, zinc, titanium, aluminium, lead；
X is halogen；
j1′、j2′、j3′、j4′、j5One in ' respectively 0,1,2,3,4,5；
When A is boron, j1′+j2′+j3′+j4′+j5'=4；When A is phosphorus, j1′+j2′+j3′+j4′+j5'=6 or 4；When A is carbon When, j1′+j2′+j3′+j4′+j5'=3；When A is nitrogen, j1′+j2′+j3′+j4′+j5'=2；When A is aluminium, j1′+j2′+j3′+ j4′+j5'=4；When A is silicon, j1′+j2′+j3′+j4′+j5'=3；
Described contains lithium reagent, is selected from LiOH, Li2CO3、Li2O, lithium halide, simple substance Li, LiHCO3, carbon number be 1~10 carboxylic acid Lithium, carbon number are 1~10 Sulfonic Lithium, LiXO3、LiXO4、Li2SO4、LiNO3、Li3PO4Or the equivalent of LiH or compound II One or more of (including presoma and hydrate, solvent complex object, halogenation hydride-complex)；
The fluorine-containing reagent is the fluoride or hydrofluoride, anhydrous hydrogen fluoride, hydrofluoric acid, NH of metal4F、NH4HF2, it is anhydrous Equivalent (including the presoma, Yi Jishui of the organic amine salt of hydrogen fluoride or hydrofluoric acid, fluorine gas or sulfur tetrafluoride or compound II One or more of close object, solvent complex object, halogenation hydride-complex)；
The reagent containing M is the hydroxide of M, the alkoxide of M, the halide of M, the oxide of M, the hydride of M or change Close at least one of the equivalent (including presoma and hydrate, solvent complex object, halogenation hydride-complex) of object II.
2. preparation method according to claim 1, it is characterised in that: preparation method (1)-(4) reaction temperature It is -50-100 DEG C, reaction pressure is -0.05-1MPa (gauge pressure), and the reaction time is 0.5-24 hours；
The molar ratio of ligand compound a and ligand compound b and compound II is respectively 0.1-10:1 in the method；
Preparation method (1)-(4) carry out in the presence of a catalyst, and catalyst is selected from 4 bromide, tetrem bromide Change one of ammonium, 4-propyl bromide, 18- crown ether -6 and 15- crown ether -5 or a variety of；
The dosage of the catalyst is the 0.01%-20% of compound II by mole meter.
3. preparation method according to claim 1, it is characterised in that: described contains LaLigand compound a in Z1Selected from Lower two kinds of situations:
(a) work as LaIt is not present, seven conditions of a=1, b=0, c=0, d=1, e=0, f=0 while when meeting, contains LaIt is liganded Closing object a is respectively carboxylic acid halides (Z1=Z2=halogen), aldehyde (Z1=Z2=H), cyclic acid anhydride (Z1=Z2=O- (CO)-(CO) -), nitration mixture Acid anhydride (Z1=Z2=O-CO-R or O-SO2- R or O-SO-R), ester (Z1=Z2=OR), silicon ester (Z1=Z2=OSiR3、Z1=Z2= OSiHR2Or OSiXR2、Z1=Z2=OSiH2R or OSiX2R、Z1=Z2=OSiH3Or OSiX3One of)；Or
(b) work as LaIt is not present, when seven conditions of a=1, b=0, c=0, d=1, e=0, f=0 do not meet simultaneously, contains LaLigand Compound a is respectively carboxylic acid halides (Z1=Z2=halogen), aldehyde (Z1=Z2=H), cyclic acid anhydride (Z1=O- (CO)a-(SO2)b-(SO)c- La-(SO)f-(SO2)e-(CO)d), nitration mixture acid anhydride (Z1=Z2=O-CO-R or O-SO2- R or O-SO-R), ester (Z1=Z2=OR), Silicon ester (Z1=Z2=OSiR3、Z1=Z2=OSiHR2Or OSiXR2、Z1=Z2=OSiH2R or OSiX2R、Z1=Z2=OSiH3Or OSiX3), acid (Z1=Z2=OH), acid salt (Z1=Z2=OMIOr ONH4One of)；
R is the C of linear chain or branched chain1-C20Alkyl；
MIFor metallic element；Preferably, the metallic element be alkali metal, alkaline-earth metal and chromium, manganese, iron, cobalt, nickel, copper, zinc, One of titanium, aluminium, lead.
4. preparation method according to claim 1, it is characterised in that: the LaGroup or LbThe structure of group includes:
5. preparation method according to claim 1, it is characterised in that:
It is carried out using hydrogen fluoride electrolyzer reaction method；
Hydrogen fluoride electrolyzer reaction method are as follows: the raw material in preparation method described in claim 1 is added in electrolytic cell dry It is reacted under the conditions of dry；
The hydrogen fluoride electrolyzer reaction technique, is reacted under the dry condition in electrolytic cell；
Hydrogen fluoride is removed water through electrolysis method in electrolytic cell, so that electrolytic cell reaches drying condition, electrolytic cell is in the electricity for keeping 0~25V Solution voltage or be not added under conditions of decomposition voltage is reacted.
6. preparation method according to claim 1, it is characterised in that:
Using first mixing high temperature solid-state pretreating process is carried out afterwards prepared；
The mixing is that raw material in preparation method described in claim 1 is added to ball mill, sand mill, kneader, mixing It is mixed in the mixing apparatus such as machine or mixing machine；The mixing temperature is -50-100 DEG C, and incorporation time is 0.5-24 hours；
The described high temperature solid-state pretreatment is the raw material that will mix as in heating equipment, and heating heating is allowed to be reacted； The heating equipment is Muffle furnace or microwave heating or infrared heating；
The heating temperature is 0-800 DEG C, and heating treatment time is 1-24 hours.
7. preparation method according to claim 1, it is characterised in that:
Special dewatering substance is added in reaction in ligand compound a or ligand compound b；
The Special dewatering substance is selected from SiHX3、SiH2X2、Si(-OR)4、SiX4、COX2、AlX3、BX3、SO2X2、SOX2、 PX5、PX3、P2O5Or POX3One of or it is a variety of；Wherein, X is halogen.
8. preparation method according to claim 1, it is characterised in that:
Ligand compound a or ligand compound b reacts the pure substance or mixture to be formed with protecting group with Protective substances；
After ligand compound a or ligand compound b participates in reaction, protecting group is removed by hydrolysis process；
The Protective substances are one of compound R OH of hydroxyl or phenolic group or a variety of；
Wherein, the R in Protective substances is the protecting group that carbon number is 1~20, selected from saturated or unsaturated alkyl, whole halogenation or Partially halogenated alkyl, aromatic ring yl and fatty ring group；
Ligand compound a or ligand compound b is one of following structure or a variety of after reacting with above-mentioned Protective substances；
9. a kind of purification process of the compound I of preparation method preparation according to claim 1, it is characterised in that:
The purification process include: in dry conditions, using dry Sealing Arrangement, or under the conditions of dry gas purging, Compound I crude product obtained in claim 1 is recrystallized using organic solvent, is crystallized under cryogenic, is filtered, It is dry, obtain the fine work of target compound；
The organic solvent is selected from methanol, ethyl alcohol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl carbonate, second One of ether, acetonitrile, dioxane, n,N-Dimethylformamide, dimethyl sulfoxide and water are a variety of.
10. a kind of compound I answering in lithium ion battery electrolyte of preparation method preparation according to claim 1 With, it is characterised in that: compound I can be dissolved in organic solvent and be used to prepare lithium separately as the electrolyte lithium salt of lithium ion battery The electrolyte solution of ion battery；The concentration of the compound I is 0.1-5.0mol/L；
Or, being dissolved in organic solvent can be used for preparing the electrolyte solution of lithium ion battery by compound I and lithium salts；The chemical combination The concentration of object I and lithium salts is respectively 0.1-5.0mol/L；
The lithium salts be selected from lithium hexafluoro phosphate, LiBF4, double fluorine sulfimide lithiums, bis trifluoromethyl sulfimide lithium and One of trifluoromethanesulfonic acid lithium is a variety of；
The organic solvent is selected from ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, propene carbonate, dimethyl carbonate, chlorine For one of ethylene carbonate and fluorinated ethylene carbonate or a variety of.
CN201811283004.XA 2018-10-31 2018-10-31 A kind of preparation method and purification process of the compound containing at least one cyclic ligand structure Pending CN109467539A (en)

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