CN115490723A - Chain-like halogenated phosphate and preparation method and application thereof - Google Patents

Chain-like halogenated phosphate and preparation method and application thereof Download PDF

Info

Publication number
CN115490723A
CN115490723A CN202110683234.0A CN202110683234A CN115490723A CN 115490723 A CN115490723 A CN 115490723A CN 202110683234 A CN202110683234 A CN 202110683234A CN 115490723 A CN115490723 A CN 115490723A
Authority
CN
China
Prior art keywords
group
carbon atoms
chain
halogenated
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110683234.0A
Other languages
Chinese (zh)
Inventor
时迎华
钟海敏
田培钦
洪祖川
赵文文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evergrande New Energy Technology Shenzhen Co Ltd
Original Assignee
Evergrande New Energy Technology Shenzhen Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evergrande New Energy Technology Shenzhen Co Ltd filed Critical Evergrande New Energy Technology Shenzhen Co Ltd
Priority to CN202110683234.0A priority Critical patent/CN115490723A/en
Publication of CN115490723A publication Critical patent/CN115490723A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/06Phosphorus compounds without P—C bonds
    • C07F9/08Esters of oxyacids of phosphorus
    • C07F9/09Esters of phosphoric acids
    • C07F9/14Esters of phosphoric acids containing P(=O)-halide groups
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0567Liquid materials characterised by the additives
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0017Non-aqueous electrolytes
    • H01M2300/0025Organic electrolyte
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Physics & Mathematics (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a chain-shaped halogenated phosphate ester and a preparation method and application thereof. The molecular structural formula of the chain-shaped halogenated phosphate ester is shown as the following general formula I. The chain-shaped halogenated phosphate can improve the electrochemical performance of the electrolyte, the electrolyte containing the chain-shaped halogenated phosphate can form a more stable interface film on the surface of an electrode material, and the impedance is inhibited from increasing, so that the performances of high and low temperature, circulation, storage and the like of the secondary battery are obviously improved, and the chain-shaped halogenated phosphate also has an obvious effect on inhibiting the gas generation of the battery. The chain-shaped halogenated phosphate can be used as an additive and applied to an electrolyte and a secondary battery.

Description

Chain-like halogenated phosphate and preparation method and application thereof
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to chain-shaped halogenated phosphate, a preparation method thereof, an electrolyte additive, an electrolyte and a secondary battery.
Background
The lithium ion battery is a novel high-energy secondary battery which is developed in the 90 s, and compared with other batteries, the lithium ion battery has the advantages of high energy density, small size, light weight, high discharge rate, low self-discharge rate, long cycle life and no memory effect, and is widely applied to the fields of digital products, power and energy storage.
Due to the fact that requirements for energy density of batteries in various fields are higher and higher, rapid charging is more and more trend, and battery materials are inevitably developed towards higher nickel, higher voltage and higher multiplying power. The difficulties in the industry at present mainly focus on the following aspects:
1. and (3) controlling a bulk phase structure: under the condition of higher voltage, the layered structure of the anode is changed violently due to excessive lithium removal, and the phase change and the stress are generated, so that the excessive stress can crack, pulverize or break material particles, destroy the bulk phase structure of the material and deteriorate the cycle performance. The problem can be counteracted with certain stress to a certain extent through element co-doping, so as to achieve the purpose of inhibiting the phase change of the material;
2. controlling the interface structure: the interface structure is optimized by introducing new interface coating, so that the dissolution of transition metal is inhibited, and the change of the interface structure is inhibited, thereby prolonging the cycle life;
3. inhibition of interfacial oxygen activity: oxygen evolution is often accompanied by gas evolution and transition metal dissolution. By the combined use of interface treatment and electrolyte, the gas generation at the material interface can be reduced, so that the stability of the material in a high-temperature state is improved, and the cycle and storage performance are improved.
With the continuous development of social demands, the service life, high and low temperature performance, safety performance, rate performance and the like of the lithium ion battery can not meet the requirements of power battery development. There are various ways to improve the performance of power cells, where additives play a crucial role in the electrochemical performance of the cell. To date, a large number of novel additives have been developed to improve battery performance. The additive can form a solid electrolyte interface film (SEI film and CEI film) on the surface of the electrode material, the performance of the lithium secondary battery depends on the SEI film to a great extent, the SEI film formed on the negative electrode interface inhibits the side reaction of the electrolyte on the negative electrode interface, and simultaneously prevents the electrolyte solvent from being co-inserted into the negative electrode material, thereby relieving the structural collapse of the negative electrode material and playing the role of a lithium ion channel.
In the charge and discharge of the lithium secondary battery, the positive electrode active material structurally collapses or undergoes a phase change, and at the same time, metal ions are eluted from the positive electrode and reduced at the negative electrode, deteriorating the battery performance. The high temperature may aggravate the deterioration of the battery performance. The existing research shows that the starting point of battery thermal runaway comes from the decomposition of an electrolyte interface film (SEI film), and then the electrolyte is continuously decomposed at the interface of a positive electrode material and a negative electrode material to release a large amount of heat, so that the safety problem is caused.
The development of secondary batteries is moving towards high energy density, and the development of ultra-high nickel is a development trend, but in research and practical application, the problems of serious degradation of high nickel materials, serious gas generation and low chemical stability of the high energy density secondary batteries are found to be easy to occur in the circulating process. Although the electrolyte additives such as additives for improving the stability of the electrolyte and inhibiting the gas generation of the secondary battery during the circulation process are reported in the present disclosure, it is found in research and practical application that the thermal stability of the presently disclosed additives per se and the improvement effect on the thermal stability of the electrolyte are not ideal, so that the effects of the additives related to the improvement of the stability of the electrolyte and the inhibition of the gas generation are still not ideal, and particularly, the improvement effect on the problems of severe gas generation and the reduction of chemical stability, which are easily caused during the circulation process of the secondary battery with high energy density, is not ideal. Resulting in a large amount of gas evolution during high temperature storage or cycling of the high nickel positive electrode, resulting in battery swelling and poor high temperature performance.
In view of the above, it is necessary to develop a novel additive to stabilize the structure of the positive and negative electrode materials and reduce the battery impedance, while ensuring the stability of the lithium secondary battery during high-temperature cycling and high-temperature storage.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a chain-shaped halogenated phosphate and a preparation method thereof so as to solve the technical problems that the thermal stability of the existing additive and the effects of improving the high-temperature stability of the electrolyte and inhibiting the gas generation are not ideal.
Another object of the present invention is to provide an additive, an electrolyte containing the additive, and a secondary battery containing the electrolyte, which solve the technical problems of poor high-temperature cyclability and storage performance of the conventional electrolyte due to poor thermal stability.
In order to achieve the above object, one aspect of the present invention provides a chain-like halogenated phosphate. The molecular structural formula of the chain-shaped halogenated phosphate ester is shown as the following general formula I:
Figure BDA0003122683400000021
wherein R in the general formula I 1 Any one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a chain alkoxy group having 1 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trimethylsilyl group, a trimethylsiloxy group, a halogen-containing alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, a halogenated phenyl group, a halogenated biphenyl group, a phenol group, an alkyl-containing phenol group, an alkenyl-containing phenol group, an alkynyl-containing phenol group, a nitrile-containing phenol group, a halogenated phenol group and a halogenated naphthol group;
R 2 、R 3 、R 4 、R 5 independently selected from hydrogen atom, halogen atom, aryl group with 6-10 carbon atoms, halogenated aryl group with 6-10 carbon atoms, alkyl group with 1-10 carbon atoms, halogenated alkyl group with 1-10 carbon atoms, alkenyl group with 1-10 carbon atoms, halogenated alkenyl group with 1-10 carbon atoms, alkynyl group with 1-10 carbon atoms, halogenated alkynyl group with 1-10 carbon atoms and chain with 2-10 carbon atomsAny one of a cyclic alkoxy group, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 20 carbon atoms, a trialkylsiloxy group having 3 to 20 carbon atoms, an aryl-containing silicon group, a pyridyl group, a thienyl group, a phenol group, an alkyl-containing phenol group, an alkenyl-containing phenol group, an alkynyl-containing phenol group, a nitrile-containing phenol group, a halogenated phenol group, and a halogenated naphthol group;
X 1 、X 2 independently selected from halogen atoms;
n is an integer of 0 to 10.
The phosphate group contained in the chain-shaped halogenated phosphate ester has the function of forming a film on the positive electrode, and can obviously improve the cycle stability of the positive electrode material. Other groups contained in the chain-shaped halogenated phosphate ester can play a role in film forming synergy of the phosphate group, and the stability of the positive and negative electrode interfaces of the chain-shaped halogenated phosphate ester is improved. The halogenated group and/or halogen atom contained gives the chain-like halogenated phosphate good wettability. Therefore, the chain-shaped halogenated phosphate can obviously improve the thermal stability of the electrolyte, improve the film-forming property and the wetting property of the electrolyte and endow the electrolyte with low impedance characteristic.
Further, R 1 To R 5 At least one group in (a) is a chain group, and the chain group includes a linear group or a branched group. The chain-shaped groups can adjust the membrane components and the membrane forming capability of an electrolyte interface, and can improve the membrane forming synergistic effect between the chain-shaped groups and the phosphate groups so as to improve the thermal stability of the chain-shaped halogenated phosphate.
Further, R 1 To R 5 At least one group in (b) is a chain group, and the chain group contains at least one of a halogen atom, an oxygen atom, or an unsaturated bond functional group.
Specifically, when the chain group contains an unsaturated bond functional group, the unsaturated bond functional group includes at least one of a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-oxygen double bond, a sulfur-oxygen double bond, a phosphorus-oxygen double bond, an amide, an imide, a sulfonamide, a sulfonimide, a phosphoramide, a phosphoryl imide, a carboxylate, a sulfonate, and a phosphate.
Specifically, when the chain-like group contains an unsaturated bond functional group, the position of the unsaturated bond functional group is on the inner side of the terminal group or/and the terminal group.
The chain groups can further improve the film-forming synergistic effect on the phosphate groups, improve the stability of the positive and negative electrode interfaces of the chain halogenated phosphate ester and improve the stability of the positive and negative electrode interfaces of the chain halogenated phosphate ester.
Further, R 1 To R 5 At least one group in (a) is a halogenated group, which is partially or fully substituted.
Further, X 1 、X 2 The halogen atom is at least one of fluorine, chlorine, bromine and iodine atoms.
The halogenated groups and X 1 、X 2 The represented halogen atom improves the wettability of the chain-like halophosphate.
Further, the chain-like halogenated phosphate ester includes the following molecular structural formula I 1 To structural formula I 4 At least one of:
Figure BDA0003122683400000022
wherein, the general formula I 2 To I 4 R in (1) 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 Independently selected from hydrogen atom, halogen atom, alkyl with 1-10 carbon atoms, alkenyl with 1-10 carbon atoms, alkynyl with 1-10 carbon atoms, chain alkoxy with 1-10 carbon atoms, chain alkenyloxy with 2-10 carbon atoms, chain alkynyloxy with 2-10 carbon atoms, cyclic alkoxy with 3-10 carbon atoms, cyclic alkenyloxy with 3-10 carbon atoms, trimethylsilyl, trimethylsiloxy, halogen-containing alkyl, phenyl, biphenyl, naphthyl, pyridyl, thienyl, halogenOne of substituted phenyl, halogenated biphenyl, phenol group containing alkyl, phenol group containing alkenyl, phenol group containing alkynyl, phenol group containing nitrile group, halogenated phenol group and halogenated naphthol group; m is 1 、m 2 Independently an integer of 0 to 10.
In a specific embodiment, the chain-like halophosphate comprises at least one of the compounds represented by the following formulas 1 to 32:
Figure BDA0003122683400000031
structural formula I 1 To structural formula I 4 The chain-shaped halogenated phosphate shown in the formulas 1 to 32 has more excellent anode film-forming function, wettability, low impedance and more excellent thermal stability.
In another aspect of the present invention, a method for preparing the chain-like halophosphate of the present invention is provided. The preparation method of the chain-shaped halogenated phosphate ester comprises the following steps:
will be shown in the following structural formula I A A reactant A is shown with the following structural formula I B Carrying out a first substitution reaction on the reactant B in a first non-aqueous solution to generate a chain-shaped halogenated phosphate ester product shown in the following structural formula I;
Figure BDA0003122683400000041
wherein, formula I A And R in I 1 Selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a chain alkoxy group having 1 to 10 carbon atoms a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trimethylsilyl group, a trimethylsilyloxy group, a halogen-containing alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, a halogenated phenyl group, a halogenated biphenyl group, a phenol group, an alkyl-containing phenol group, an alkenyl-containing phenol group, an alkyne-containing phenol groupAny one of a phenol group, a nitrile group-containing phenol group, a halogenated phenol group, and a halogenated naphthol group; r 2 、R 3 、R 4 、R 5 Any one of a hydrogen atom, a halogen atom, an aromatic group having 6 to 10 carbon atoms, a halogenated aromatic group having 6 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, a halogenated alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a halogenated alkynyl group having 1 to 10 carbon atoms, a chain alkoxy group having 2 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 20 carbon atoms, a trialkylsiloxy group having 3 to 20 carbon atoms, an arylsilyl group, an arylsiloxy group, a pyridyl group, a thienyl group, a phenol group having an alkyl group, a phenol group having an alkenyl group, a phenol group having an alkyne group, a phenol group having a nitrile group, a halogenated phenol group, and a halogenated naphthyl group; x 1 、X 2 、X 3 Independently selected from halogen atoms; n is an integer of 0 to 10.
The target product chain-shaped halogenated phosphate prepared by the preparation method of the chain-shaped halogenated phosphate contains functional groups such as phosphate groups and the like, so that the prepared chain-shaped halogenated phosphate has excellent film-forming performance, wetting performance and low impedance characteristic, and the thermal stability is high. In addition, the preparation method of the chain-shaped halogenated phosphate ester generates a target product through one-step reaction, the yield of the target product is high, side reactions are few, the process conditions are easy to control, and the yield and the performance of the chain-shaped halogenated phosphate ester prepared by the preparation method are stable. Meanwhile, the non-aqueous solution is used as a reaction solvent, so that the purification difficulty of the target product can be reduced.
Further, the molar ratio of the reactant A to the reactant B is 1: (1-6) in a first nonaqueous solution and carrying out a first substitution reaction.
Further, the mass ratio of the reactant a to the first non-aqueous solution is 1: (1-6).
Through the adjustment of the proportion and the concentration of the reactant A and the reactant B, the forward reaction rate of the first substitution reaction is improved, the efficiency of the first substitution reaction is improved, the reactant consumption is saved, and the synthesis cost is reduced.
Further, the temperature of the first substitution reaction is-20 to 40 ℃. The efficiency of the substitution reaction is improved by controlling and optimizing the temperature of the substitution reaction.
Specifically, the first substitution reaction includes a step of performing a former-stage substitution reaction and then performing a latter-stage substitution reaction; the former-stage substitution reaction is a substitution reaction stage of gradually adding the reactant A into a first non-aqueous solution containing the reactant B until the addition is finished and then continuing to react for 1-2 hours, and the later-stage substitution reaction is a stage of finishing the addition of the reactant A and continuing to react for 1-2 hours until the substitution reaction is finished; and the temperature of the front-stage substitution reaction is-20 to 0 ℃; the temperature of the latter stage substitution reaction is 0-40 ℃. By setting the substitution reaction into two stages, the efficiency of the first substitution reaction is improved, the generation of byproducts is reduced, and the yield of the target product is improved.
Further, reactant A comprises the following structural formula A 1 To A 3 At least one of:
Figure BDA0003122683400000042
wherein, the general formula A 1 To A 3 R in (1) 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 Independently selected from hydrogen atom, halogen atom, alkyl with 1-10 carbon atoms, alkenyl with 1-10 carbon atoms, alkynyl with 1-10 carbon atoms, chain alkoxy with 1-10 carbon atoms, chain alkenyloxy with 2-10 carbon atoms, chain alkynyloxy with 2-10 carbon atoms, cyclic alkoxy with 3-10 carbon atoms, cyclic alkenyloxy with 3-10 carbon atoms, trimethylsilyl, trimethylsiloxy, halogen-containing alkyl, phenyl, biphenyl, naphthyl, pyridyl, thienyl, halogenOne of substituted phenyl, halogenated biphenyl, phenol group containing alkyl, phenol group containing alkenyl, phenol group containing alkynyl, phenol group containing nitrile group, halogenated phenol group and halogenated naphthol group; m is 1 、m 2 Independently an integer of 0 to 10. These reactants A can form with reactant B the structure I above 2 To structural formula I 4 The chain-shaped halogenated phosphate can improve the efficiency of the second substitution reaction and the yield of the target product.
Further, the first non-aqueous solution is selected from at least one of acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N-dimethylformamide, N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous triamide, hexaethylphosphoric triamide, hexaethylphosphorous triamide, dimethyl sulfoxide, diethylsulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, N-hexane, N-heptane, cyclohexane, benzene, toluene, xylene. The non-aqueous solutions can effectively dissolve two reactants, effectively reduce the generation of byproducts and improve the yield of target products.
Further, X 1 、X 2 When the compound is independently selected from any one of chlorine, bromine and iodine atoms, the method also comprises the following steps:
the chain-shaped halogenated phosphate ester product shown in the structural formula I generated by the first substitution reaction and fluoride are subjected to a second substitution reaction in a second non-aqueous solution to generate the general formula I 1 A chain difluorophosphate product as shown;
Figure BDA0003122683400000051
the product generated by the first substitution reaction is subjected to fluorine substitution reaction, so that the generated chain difluorophosphate product has more excellent wettability, and no or few impurity elements are attached to the electrolyte, thereby improving the purity and corresponding chemical properties of the corresponding electrolyte or electrolyte.
Further, the chain halophosphate product of formula i and the fluoride are present in a molar ratio of 1: (1-6) in a second nonaqueous solution and carrying out a second substitution reaction.
Further, the mass ratio of the chain-like halophosphate product represented by structural formula I to the second non-aqueous solution is 1: (1-10).
The ratio and concentration of chain-shaped halogenated phosphate ester products and fluoride shown in the structural formula I are adjusted, so that the efficiency of the second substitution reaction is improved, the reactant consumption is saved, and the synthesis cost is reduced.
Further, the temperature of the second substitution reaction is-20 to 80 ℃. The efficiency of the substitution reaction is improved by controlling and optimizing the temperature of the substitution reaction.
Further, the fluoride is at least one selected from the group consisting of hydrogen fluoride, triethylamine hydrogen fluoride, pyridine hydrogen fluoride, potassium fluoride, sodium fluoride, magnesium fluoride, zinc fluoride, aluminum fluoride, antimony trifluoride, antimony pentafluoride, sulfur tetrafluoride, and sulfur hexafluoride. The fluorides can effectively perform substitution reaction with chain-shaped halogenated phosphate shown in a structural formula I, so that the efficiency of the second substitution reaction is improved, and the yield of a chain-shaped difluorophosphate product is improved.
Still further, the second non-aqueous solution is selected from at least one of acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N-dimethylformamide, N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous triamide, hexaethylphosphoric triamide, hexaethylphosphorous triamide, dimethyl sulfoxide, diethyl sulfoxide, methylene chloride, chloroform, diethyl ether, propyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, N-hexane, N-heptane, cyclohexane, benzene, toluene, xylene. The non-aqueous solutions can effectively dissolve two reactants, effectively reduce the generation of byproducts and improve the yield of target products.
In yet another aspect of the present invention, an electrolyte additive is provided. The electrolyte additive contains the chain-shaped halogenated phosphate ester or the chain-shaped halogenated phosphate ester prepared by the preparation method of the chain-shaped halogenated phosphate ester. Because the electrolyte additive contains the chain-shaped halogenated phosphate, the electrolyte additive can obviously improve the thermal stability of the electrolyte, and improve the film-forming property, the wetting property and the low impedance property of the electrolyte.
In yet another aspect of the present invention, an electrolyte is provided. The electrolyte comprises an additive, and the additive is the electrolyte additive. The electrolyte contains the electrolyte additive, namely the chain-shaped halogenated phosphate, so that the electrolyte has good film forming performance, wetting performance and thermal stability, can remarkably improve the high and low temperature, circulation, storage and other performances of the secondary battery, can inhibit gas generation and impedance increase of the secondary battery, and improves the safety performance and comprehensive performance of the secondary battery.
In still another aspect of the present invention, a secondary battery is provided. The secondary battery of the present invention includes the electrolyte of the present invention. Therefore, the secondary battery has good cycle performance and storage performance at high and low temperatures, reduces the occurrence of adverse phenomena such as secondary battery gas generation and impedance increase, and has high safety, good comprehensive chemical performance and longer service life.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In this application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the specification of the embodiments of the present application may not only refer to the specific content of each component, but also refer to the proportional relationship of the weight of each component, and therefore, the proportional enlargement or reduction of the content of the related components according to the specification of the embodiments of the present application is within the scope disclosed in the specification of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
In one aspect, embodiments of the present invention provide a chain halogenated phosphate. The molecular structural formula of the chain-shaped halogenated phosphate ester in the embodiment of the invention is shown as the following general formula I:
Figure BDA0003122683400000061
wherein R in the general formula I 1 Any one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a chain alkoxy group having 1 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trimethylsilyl group, a trimethylsiloxy group, a halogen-containing alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, a halogenated phenyl group, a halogenated biphenyl group, a phenol group, an alkyl-containing phenol group, an alkenyl-containing phenol group, an alkynyl-containing phenol group, a nitrile-containing phenol group, a halogenated phenol group and a halogenated naphthol group;
r in the general formula I 2 、R 3 、R 4 、R 5 Any one independently selected from a hydrogen atom, a halogen atom, an aryl group having 6 to 10 carbon atoms, a halogenated aryl group having 6 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, a halogenated alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a halogenated alkynyl group having 1 to 10 carbon atoms, a chain alkoxy group having 2 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 20 carbon atoms, a trialkylsiloxy group having 3 to 20 carbon atoms, an arylsilyl group, an arylsiloxy group, a pyridyl group, a thienyl group, a phenol group, an alkyl-containing phenol group, an alkenyl-containing phenol group, an alkynyl-containing phenol group, a nitrile-containing phenol group, a halogenated phenol group, and a halogenated naphthol group;
x in the general formula I 1 、X 2 Independently selected from halogen atoms;
n in the general formula I is an integer of 0 to 10.
The phosphate group contained in the chain-shaped halogenated phosphate ester has the film forming function of the positive electrode, and can obviously improve the cycle stability of the positive electrode material and reduce the impedance. Other groups contained in the chain-shaped halogenated phosphate ester can play a role in film forming synergy of the phosphate group, and the stability of the positive and negative electrode interfaces of the chain-shaped halogenated phosphate ester is improved. The contained halogenated groups endow the chain-shaped halogenated phosphate with good wettability. Therefore, after the chain-shaped halogenated phosphate is used in the electrolyte, the thermal stability of the electrolyte can be obviously improved, the film-forming property and the wetting property of the electrolyte are improved, and the adverse phenomena of gas generation and impedance increase can be effectively reduced.
In the examples, R in the formula I 1 To R 5 When at least one group in (b) is a chain group, the chain group includes a linear group and/or a branched group. The chain-shaped groups containing or being straight chain groups or/and branched chain groups can improve the film forming synergistic effect between the chain-shaped groups and the phosphate groups contained in the chain-shaped halogenated phosphate ester so as to improve the thermal stability of the chain-shaped halogenated phosphate ester.
In the above-mentioned R 1 To R 5 In the case where at least one group in (b) is a chain group, in an embodiment, the chain group contains at least one of a halogen atom, an oxygen atom, or an unsaturated bond functional group. In a specific embodiment, when the chain group includes an unsaturated bond functional group, the unsaturated bond functional group includes at least one of a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-oxygen double bond, a sulfur-oxygen double bond, a phosphorus-oxygen double bond, an amide, an imide, a sulfonamide, a sulfonimide, a phosphoramide, a phosphoryl imide, a carboxylate, a sulfonate, and a phosphate. Wherein R is 2 、R 3 、R 4 、R 5 When at least one of the groups is an aromatic group, the aromatic group includes, but is not limited to, at least one of phenyl, biphenyl, and naphthyl. In other embodiments, the unsaturated bond functional groups are located at the terminal group or/and inside. The chain groups can further improve the film-forming synergistic effect on the phosphate groups, improve the stability of the positive and negative electrode interfaces of the chain halogenated phosphate ester and improve the stability of the positive and negative electrode interfaces of the chain halogenated phosphate ester.
In the examples, when R is as defined above 1 To R 5 At least one group of (A) is halogenWhen substituted, the halo group is partially or fully substituted. In particular embodiments, the halogen atom in the halo group may be at least one of fluorine, chlorine, bromine, or iodine. The halogenated group can further improve the wettability of the chain-shaped halogenated phosphate ester product.
X in the general formula I 1 、X 2 Is a halogen atom to improve the wettability of the chain-like halophosphate, in example, X 1 、X 2 The halogen atom is at least one of fluorine, chlorine, bromine and iodine atoms, and in further embodiment, X is 1 、X 2 The halogen atom is fluorine, and the chain-like halogenated phosphate ester has the following structural formula I 1 The chain difluorophosphate further improves the wettability of chain halogenated phosphate, and impurity elements are not attached or are less after the chain difluorophosphate is added into electrolyte, so that the purity and the corresponding chemical performance of the corresponding electrolyte or the electrolyte are improved.
In the examples, the chain-like halophosphate comprises at least the following molecular structure formula I 1 To structural formula I 4 At least one of:
Figure BDA0003122683400000071
wherein, the general formula I 2 To I 4 R in (1) 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 Independently selected from hydrogen atom, halogen atom, alkyl with 1-10 carbon atoms, alkenyl with 1-10 carbon atoms, alkynyl with 1-10 carbon atoms, chain alkoxy with 1-10 carbon atoms, chain alkenyloxy with 2-10 carbon atoms, chain alkynyloxy with 2-10 carbon atoms, cyclic alkoxy with 3-10 carbon atoms, cyclic alkenyloxy with 3-10 carbon atoms, trimethylsilyl, trimethylsilyloxy, halogen-containing alkyl, phenyl, biphenyl, naphthyl, pyridyl, thienyl, halogenated phenyl, halogenated biphenyl, phenol group, alkyl-containing groupOne of the phenol group, the phenol group containing alkenyl, the phenol group containing alkynyl, the phenol group containing nitrile group, the halogenated phenol group and the halogenated naphthol group; m is 1 、m 2 Independently an integer of 0 to 10. The chain-shaped halogenated phosphate esters have more excellent anode film-forming function and wettability and more excellent thermal stability.
Wherein, the general formula I 2 To I 4 R in (1) 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 When at least one group in (b) is a chain group, the chain group includes a linear group and/or a branched group. The chain-shaped groups containing or being straight chain groups or/and branched chain groups can improve the film-forming synergistic effect between the chain-shaped groups and the phosphate groups contained in the chain-shaped halogenated phosphate ester so as to improve the thermal stability of the chain-shaped halogenated phosphate ester.
In the above general formula I 2 To I 4 R in (1) 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 In the case where at least one group in (b) is a chain group, in an embodiment, the chain group contains at least one of a halogen atom, an oxygen atom, or an unsaturated bond functional group. In a specific embodiment, when the chain group includes an unsaturated bond functional group, the unsaturated bond functional group includes at least one of a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-oxygen double bond, a sulfur-oxygen double bond, a phosphorus-oxygen double bond, an amide, an imide, a sulfonamide, a sulfonimide, a phosphoramide, a phosphorylimine, a carboxylate, a sulfonate, and a phosphate. In other embodiments, the unsaturated bond functional groups are located at the terminal group or/and the inner side. The chain groups can further improve the film-forming synergistic effect on the phosphate groups, improve the stability of the positive and negative electrode interfaces of the chain halogenated phosphate ester and improve the stability of the positive and negative electrode interfaces of the chain halogenated phosphate ester.
In the examples, when the above description is givenGeneral formula I 2 To I 4 R in (1) 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 When at least one of the groups is a halogenated group, the halogenated group is partially or fully substituted. In a specific embodiment, the halogen atom in the halo group may be at least one of fluorine, chlorine, bromine, or iodine. The halogenated group can further improve the wettability of the chain-shaped halogenated phosphate ester product.
Based on the groups contained in the chain-like halogenated phosphate, in a specific embodiment, the upper Wen Lianzhuang halogenated phosphate specifically contains at least one of the compounds represented by the following formulas 1 to 32:
Figure BDA0003122683400000072
Figure BDA0003122683400000081
the chain-type halophosphate represented by formula 1 to formula 32 has more excellent positive electrode film-forming function, wettability, low impedance characteristic, and more excellent thermal stability. Of course, formulae 1 through 32 are merely exemplary of the moieties of the chain halophosphate esters of formula I above, which may also be based on R as described above 1 To R 18 Other compounds within the indicated group range, and other compounds also have excellent positive electrode film-forming function, wettability and thermal stability.
On the other hand, the embodiment of the invention provides a preparation method of the chain-like halogenated phosphate ester in the embodiment of the invention. The preparation method of the chain-shaped halogenated phosphate ester comprises the following steps:
s01: will be shown in the following structural formula I A A reactant A is shown with the following structural formula I B The reactant B shown undergoes a first substitution reaction in a first non-aqueous solution to form the following structureChain-like halogenated phosphate ester products shown in a structural formula I; according to reactant A and reactant B, the chemical reaction formula (1) of the first substitution reaction is shown as follows:
Figure BDA0003122683400000082
the chain-shaped halogenated phosphate ester product shown in the structural formula I generated by the first substitution reaction is the chain-shaped halogenated phosphate ester shown in the structural formula I of the embodiment of the invention. Thus, formula I in step S01 A And R in I 1 To R 5 R contained in the chain-like halophosphate of the present invention as shown in formula I above 1 To R 5 . In particular as R 1 Any one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a chain alkoxy group having 1 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trimethylsilyl group, a trimethylsiloxy group, a halogen-containing alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, a halophenyl group, a halobiphenyl group, a phenol group containing an alkyl group, a phenol group containing an alkenyl group, a phenol group containing an alkynyl group, a phenol group containing a nitrile group, a halophenol group, and a halonaphthol group. R 2 、R 3 、R 4 、R 5 Independently selected from hydrogen atom, halogen atom, aryl group with 6-10 carbon atoms, halogenated aryl group with 6-10 carbon atoms, alkyl group with 1-10 carbon atoms, halogenated alkyl group with 1-10 carbon atoms, alkenyl group with 1-10 carbon atoms, halogenated alkenyl group with 1-10 carbon atoms, alkynyl group with 1-10 carbon atoms, halogenated alkynyl group with 1-10 carbon atoms, chain alkoxy group with 2-10 carbon atoms, chain alkenyloxy group with 2-10 carbon atoms, chain alkynyloxy group with 2-10 carbon atoms, cyclic alkoxy group with 3-10 carbon atoms, cyclic alkenyloxy group with 3-10 carbon atoms, trialkylsilyl group with 3-20 carbon atoms, trialkylsiloxy group with 3-20 carbon atoms, aryl-containing groupAny one of a silyl group, an arylsiloxy group-containing group, a pyridyl group, a thienyl group, a phenol group, an alkyl-containing phenol group, an alkenyl-containing phenol group, an alkynyl-containing phenol group, a nitrile-containing phenol group, a halogenated phenol group, and a halogenated naphthol group. n is an integer of 0 to 10.
Based on the structural formula I A The reactant A and the group R contained therein 1 The group types shown, in the examples, reactant A includes at least the following structural formula A 1 To A 3 At least one of:
Figure BDA0003122683400000091
wherein, the general formula A 1 To A 3 R in (1) 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 Independently selected from one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a chain alkoxy group having 1 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trimethylsilyl group, a trimethylsilyloxy group, a halogen-containing alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, a halogenated phenyl group, a halogenated biphenyl group, a phenol group, an alkyl-containing phenol group, an alkenyl-containing phenol group, an alkynyl-containing phenol group, a nitrile-containing phenol group, a halogenated phenol group and a halogenated naphthol group; m is 1 、m 2 Independently an integer of 0 to 10. These reactants A are capable of reacting with reactant B to form the above formula I 2 To structural formula I 4 The chain-shaped halogenated phosphate can improve the efficiency of the second substitution reaction and the yield of the target product.
In a further embodiment, when R is the above-mentioned chain halophosphate represented by structural formula I of the examples of the invention 1 To R 18 When at least one group in (b) is a chain group, the chain group includes a linear group or a branched group. The chain groups can improve the film forming synergistic effect between the chain groups and phosphate ester groups so as to improve the thermal stability of the chain halogenated phosphate ester.
Further, when the above R is 1 To R 18 When at least one group in (b) is a chain group, the chain group contains at least one of a halogen atom, an oxygen atom, or an unsaturated bond functional group. In a specific embodiment, when the chain group includes an unsaturated bond functional group, the unsaturated bond functional group includes at least one of a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-oxygen double bond, a sulfur-oxygen double bond, a phosphorus-oxygen double bond, an amide, an imide, a sulfonamide, a sulfonimide, a phosphoramide, a phosphinimine, a carboxylate, a sulfonate, and a phosphate. In other embodiments, when the chain group comprises an unsaturated functional group, the unsaturated functional group is located at the terminal group or/and the inner side. When the chain groups contain unsaturated groups, the film forming synergistic effect on the phosphate groups can be further improved, the stability of the positive and negative electrode interfaces of the chain halogenated phosphate ester is improved, and the stability of the positive and negative electrode interfaces of the chain halogenated phosphate ester is improved.
In the examples, when R is as defined above 1 To R 18 When at least one of the groups is a halogenated group, the halogenated group is partially or fully substituted. In a specific embodiment, the halogen atom in the halo group may be at least one of fluorine, chlorine, bromine, or iodine. The halogenated group can further improve the wettability of the chain-shaped halogenated phosphate ester product.
In the examples, compound a in step S01 can be prepared as follows:
structure I A The preparation method of the compound A has the following reaction formula:
Figure BDA0003122683400000092
of course, structure I A The compound A can also be prepared by other synthetic routesObtained synthetically or purchased commercially. When compound a is synthesized, in the specific example, the synthesis of compound a is illustrated by propargyl diethylene glycol, and the reaction formula of the synthetic route is shown below:
Figure BDA0003122683400000101
according to the synthesis reaction formula of the propargyl diethylene glycol, the specific preparation method comprises the following steps:
and SA1: adding 50mL of THF (tetrahydrofuran) into the reaction kettle at room temperature, then adding 7.8g (0.1 mol) of sodium propargylate, and stirring for 0.5h at 0 ℃; in a second reaction kettle, a THF solution of propylene oxide (the effective content of the propylene oxide is 4.5 g) is cooled and stirred for 0.5h at the temperature of minus 20 ℃; adding a THF solution of sodium propargyl alcohol into a THF solution of propylene oxide, stirring and keeping the temperature at-20 ℃ in the whole adding process, controlling the dropping speed to keep the temperature stable, and keeping the temperature unchanged after the THF solution of sodium allyl alcohol is added, and continuing to react for 3 hours;
and SA2: adding a THF solution of propylene oxide (the effective content of propylene oxide is 4.5 g) into a third reaction kettle, and cooling and stirring for 0.5h at the temperature of minus 20 ℃; then adding the solution in the second reaction kettle, stirring and keeping the temperature at-20 ℃ in the whole adding process, controlling the dropping speed to keep the temperature stable, and keeping the temperature unchanged after the adding is finished to continue reacting for 3-6 hours; after the reaction was completed, 2ml of water was added to the reaction vessel, the temperature was slowly raised to room temperature, the solvent THF was distilled off under normal pressure, then 50ml of DMC was added and extracted, after filtration, the DMC solution was dried over anhydrous magnesium sulfate for 12 hours, the solvent DMC was distilled off under normal pressure, and then, distillation under reduced pressure gave 13.3g of a viscous colorless liquid, with a yield of 92%. Namely propargyl diethylene glycol.
And SA3: in a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the colorless liquid, filtered with an organic filter to remove suspended matter, a small amount of the filtrate was injected with a syringe and analyzed by gas chromatography (Thermo Fisher Scientific), and the analysis result showed GC-MS (ESI) calcd for C 7 H 12 O 3 [M] + Is 144.25. 1 H NMR(400MHz,CDCl 3 )δ:5.4(br,1H),4.15(s,2H),3.70(t,2H),5.54(t,2H),3.52(m,4H),3.32(s,1H); 13 C NMR(100MHz,CDCl 3 ) 78.7,76.4,70.3,69.5,69.2,61.3,60.3. The resulting colorless liquid was confirmed to be propargyl diethylene glycol. The water content was 21ppm, the acidity was 12ppm and the chloride ion concentration was 2ppm as measured by a Karl moisture meter and a potentiometric titrator.
Formula I in step S01 B And X in I 1 、X 2 X contained in the chain-like halophosphate esters of the embodiments of the present invention as shown in formula I above 1 、X 2 Is shown in formula I B X in (1) 3 Is a halogen atom, therefore, X 1 、X 2 、X 3 Independently a halogen atom. In embodiments, the halogen atom in the halo group may be at least one of fluorine, chlorine, bromine, or iodine. Thus, in particular embodiments, formula I B The compound B may be a phosphorus trihalide such as PF 3 、PCl 3 、PBr 3 、PI 3 At least one of (1).
In the example, in the first substitution reaction system shown in chemical reaction formula (1), reactant a and reactant B are controlled in a molar ratio of 1: (1-6) further 1: (1-2) in the first nonaqueous solution. In a specific embodiment, the molar ratio of reactant a to reactant B is 1:1. 1:1.5, 1:2. 1:2.5, 1:3. 1:3.5, 1:4. 1:4.5, 1:5. 1:5.5, 1:6, etc. are typical but not limiting ratios.
In some embodiments, in the first substitution reaction system represented by chemical formula (1), the mass ratio of the reactant a to the first nonaqueous solution is controlled to be 1: (1-6). In a specific embodiment, the mass ratio of reactant a to the first non-aqueous solution is 1:1. 1:1.5, 1:2. 1:2.5, 1:3. 1:3.5, 1:4. 1:4.5, 1:5. 1:5.5, 1:6, etc. are typical but not limiting ratios.
Through the adjustment of the proportion and the concentration of the reactant A and the reactant B, the forward reaction rate of the first substitution reaction is improved, and the efficiency of the first substitution reaction is improved. Meanwhile, the reactants are completely reacted, the generation of impurities is reduced, the reactant consumption is saved, and the synthesis cost is reduced.
In the examples, the temperature of the first substitution reaction was-20 to 40 ℃. Specifically, typical but not limiting temperatures may be selected from-20 ℃, -15 ℃, -10 ℃, -5 ℃,0 ℃,5 ℃,10 ℃,15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, and the like. The efficiency of the substitution reaction is improved by temperature control and optimization of the substitution reaction.
In order to improve the efficiency of the first substitution reaction, in the embodiment, before mixing the reactant a and the reactant B, it is desirable to first dissolve the reactant a in a first non-aqueous solution to prepare a first non-aqueous solution of the reactant a; dissolving a reactant B in a first non-aqueous solution to prepare a first non-aqueous solution of the reactant B; a first non-aqueous solution of reactant A is then added to a first non-aqueous solution of reactant B to effect a first substitution reaction.
In a further embodiment, the first substitution reaction in step S01 includes a step of performing a former-stage substitution reaction and then performing a latter-stage substitution reaction; the former-stage substitution reaction is a substitution reaction stage of gradually adding the reactant A into a first non-aqueous solution containing the reactant B until the addition is finished and then continuing to react for 1-2 hours, and the latter-stage substitution reaction is a stage of finishing the addition of the reactant A and continuing to react for 1-2 hours until the substitution reaction is finished. Wherein, the temperature of the front-stage substitution reaction is-20-0 ℃, and can be typical but not limited to-20 ℃,15 ℃,10 ℃,5 ℃,0 ℃ and the like. The temperature of the latter substitution reaction is typically, but not limited to, 0 ℃ to 40 ℃, and specifically, 0 ℃,5 ℃,10 ℃,15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ and the like. The latter substitution reaction should be sufficient, e.g., until no gas is produced in the first substitution reaction. By setting the substitution reaction to two stages, the efficiency of the first substitution reaction is improved, the generation of byproducts is reduced, and the yield of the target product is improved. Meanwhile, the method is favorable for avoiding over violent reaction and absorbing the heat released by the reaction.
In an embodiment, the first non-aqueous solution is selected from at least one of acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N-dimethylformamide, N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous triamide, hexaethylphosphoric triamide, hexaethylphosphorous triamide, dimethyl sulfoxide, diethyl sulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, N-hexane, N-heptane, cyclohexane, benzene, toluene, xylene. The non-aqueous solutions can effectively dissolve two reactants, effectively reduce the generation of byproducts and improve the yield of target products. And the purification of the target product is convenient, for example, the chain-shaped halogenated phosphate with high purity is obtained by concentration and purification.
In addition, the byproduct gas generated during the first substitution reaction in step S01 may be absorbed by water to improve environmental protection or reuse of the byproduct.
After the first substitution reaction in step S01, the method further comprises a step of separating and purifying the chain-like halophosphate product represented by structural formula i, wherein the purification treatment comprises removing the first non-aqueous solution from the mixture after the first substitution reaction, and then distilling the crude product or recrystallizing and drying the crude product with the non-aqueous solution. In a specific embodiment, when the crude product has poor fluidity such as viscous wall built-up, the crude product is dissolved in a third non-aqueous solution for recrystallization, solid-liquid separation and drying treatment to obtain a pure chain halogenated phosphate product. Wherein, the drying is vacuum drying, for example, the vacuum drying temperature is 0-80 ℃, and the drying time is 2-6 h. When the crude product has good fluidity and does not have the phenomenon of viscous wall hanging, the crude product is directly subjected to reduced pressure distillation treatment to obtain a pure chain-shaped halogenated phosphate ester product. For example, the reduced pressure distillation temperature is 20-300 ℃.
In a specific embodiment, the third non-aqueous solution used for recrystallization is at least one of acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N-dimethylformamide, N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous triamide, hexaethylphosphoric triamide, hexaethylphosphorous triamide, dimethyl sulfoxide, diethylsulfoxide, methylene chloride, chloroform, diethyl ether, propyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, N-hexane, N-heptane, cyclohexane, benzene, toluene, xylene.
When the structural formula I in step S01 B X in (1) 1 、X 2 、X 3 Phosphorus trihalide independently selected from any of chlorine, bromine and iodine atoms, i.e. reactant B is at least one of chlorine, bromine and iodine, such as PCl 3 、PBr 3 、PI 3 In this case, the method for preparing the chain-like halogenated phosphate further includes the following step S02:
step S02: the chain-shaped halogenated phosphate ester product shown in the structural formula I and generated by the first substitution reaction and fluoride are subjected to a second substitution reaction in a second non-aqueous solution to generate the general formula I 1 Chain difluorophosphate ester products are shown.
Specifically, according to the chain-like halophosphate product shown in the structural formula I, the chemical reaction formula (2) of the second substitution reaction is shown, and it is noted that X in the structural formula I shown in the chemical reaction formula (2) 1 、X 2 None of which is a fluorine atom:
Figure BDA0003122683400000111
the product generated by the first substitution reaction is subjected to fluorine substitution reaction, so that the generated chain difluorophosphate product has more excellent wettability, and no or few impurity elements are attached to the electrolyte, thereby improving the purity and corresponding chemical properties of the corresponding electrolyte or electrolyte. In order to improve the efficiency of the preparation method of the chain-shaped halogenated phosphate, in the second substitution reaction shown in the chemical reaction formula (2), the chain-shaped halogenated phosphate shown in the structural formula I can also be directly used as a crude product without purification or directly added into a mixture solution after the first substitution reaction.
In the examples, the chain halophosphate product of formula i and fluoride are present in a molar ratio of 1: (1-6) in a second nonaqueous solution and carrying out a second substitution reaction. In a specific embodiment, the molar ratio of the chain halophosphate product represented by structural formula I to fluoride is 1:1. 1:1.5, 1:2. 1:2.5, 1:3. 1:3.5, 1:4. 1:4.5, 1:5. 1:5.5, 1:6, etc. are typical but not limiting ratios.
In other embodiments, the mass ratio of the chain halophosphate product of formula i to the second non-aqueous solution is 1: (1-10). In a specific embodiment, the mass ratio of the chain-like halogenated phosphate ester product to the second nonaqueous solution is 1:1. 1:2. 1:3. 1:4. 1:5. 1: 6. 1: 7. 1: 8. 1: 9. 1:10, etc. are typical but not limiting.
The efficiency of the second substitution reaction is improved by adjusting the proportion and concentration of the chain-like halogenated phosphate ester product shown in the structural formula I in the chemical reaction formula (2) and the fluoride. Meanwhile, the reactants are completely reacted, the generation of impurities is reduced, the reactant consumption is saved, and the synthesis cost is reduced.
In the examples, the temperature of the second substitution reaction was-20 to 80 ℃. Specifically, the temperature may be typically but not limited to-20 ℃, -15 ℃, -10 ℃, -5 ℃,0 ℃,5 ℃,10 ℃,15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃,60 ℃,65 ℃,70 ℃,75 ℃,80 ℃ and the like. The efficiency of the substitution reaction is improved by temperature control and optimization of the substitution reaction. The efficiency of the substitution reaction is improved by controlling and optimizing the temperature of the substitution reaction. The second substitution reaction should be sufficient based on the temperature of the substitution reaction, such as a reaction time of 3 to 12 hours, specifically 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, and the like, which are typical and not limiting.
In the examples, the fluoride is selected from Hydrogen Fluoride (HF), triethylamine hydrogen fluoride (Et) 3 N.3HF), pyridine hydrogen fluoride (Py.HF), potassium fluoride (KF), sodium fluoride (NaF), magnesium fluoride (MgF) 2 ) Zinc fluoride (ZnF) 2 ) Aluminum fluoride (AlF) 3 ) Antimony trifluoride (SbF) 3 ) Antimony pentafluoride (SbF) 5 ) Sulfur tetrafluoride (SF) 4 ) Sulfur hexafluoride (SF) 6 ) At least one of (a). The fluoride can effectively perform substitution reaction with chain-shaped halogenated phosphate shown in the structural formula I, so that the efficiency of the second substitution reaction is improved, and the yield of the chain-shaped difluorophosphate product is improved.
In an embodiment, the second non-aqueous solution is selected from at least one of acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N-dimethylformamide, N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous triamide, hexaethylphosphoric triamide, hexaethylphosphorous triamide, dimethyl sulfoxide, diethyl sulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, N-hexane, N-heptane, cyclohexane, benzene, toluene, xylene. The non-aqueous solutions can effectively dissolve two reactants, effectively reduce the generation of byproducts and improve the yield of target products.
In addition, after the second substitution reaction in step S02 is finished, the method also comprises the step of reacting the structural formula I 1 And (3) carrying out separation and purification treatment on the chain difluorophosphate product, wherein the purification treatment comprises the steps of removing a second non-aqueous solution from the mixture subjected to the second substitution reaction, and then carrying out distillation treatment on the crude product or carrying out recrystallization and drying treatment on the crude product by using the non-aqueous solution. In a specific embodiment, when the crude product has poor fluidity such as viscous wall built-up, the crude product is dissolved in a fourth non-aqueous solution for recrystallization, solid-liquid separation and drying treatment, so as to obtain a pure chain halogenated phosphate ester product. Wherein, the drying is vacuum drying, for example, the vacuum drying temperature is 0-80 ℃, and the drying time is 2-6 h. When the crude product has good fluidity and does not have the phenomenon of viscous wall hanging, the crude product is directly subjected to reduced pressure distillation treatment to obtain pure chain-shaped halogenated phosphoric acidAnd (3) an ester product. For example, the reduced pressure distillation temperature is 20-300 ℃.
In a specific embodiment, the fourth non-aqueous solution used for recrystallization is at least one of acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N-dimethylformamide, N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous triamide, hexaethylphosphoric triamide, hexaethylphosphorous triamide, dimethyl sulfoxide, diethylsulfoxide, methylene chloride, chloroform, diethyl ether, propyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, N-hexane, N-heptane, cyclohexane, benzene, toluene, xylene.
The target product chain-shaped halogenated phosphate ester prepared by the preparation method of the chain-shaped halogenated phosphate ester provided by the embodiment of the invention contains functional groups such as phosphate ester groups and the like, so that the prepared chain-shaped halogenated phosphate ester has excellent film-forming property, wetting property and low impedance characteristic, and is high in thermal stability. In addition, the preparation method of the chain-shaped halogenated phosphate generates a target product through one-step reaction, the yield of the target product is high, side reactions are few, the process conditions are easy to control, and the yield and the performance of the chain-shaped halogenated phosphate prepared by the preparation method are stable. Meanwhile, the non-aqueous solution is used as a reaction solvent, so that the purification difficulty of the target product can be reduced. In addition, the reaction efficiency can be effectively improved and the yield of the target product can be improved by adjusting the reaction conditions.
On the other hand, based on the chain-like halogenated phosphate and the preparation method thereof in the embodiment of the invention, the embodiment of the invention also provides an electrolyte additive. The electrolyte additive of the embodiment of the invention contains chain-shaped halogenated phosphate ester of the embodiment of the invention. When the embodiment of the invention contains the branched halogenated phosphate as the electrolyte additive, the water content is less than or equal to 100ppm, the acidity is less than or equal to 100ppm, and the chloride ion content is less than or equal to 50ppm. The purity is high, and the above functions of the halogenated phosphate ester in the embodiment of the invention are fully exerted. Of course, the electrolyte salt may further contain an additive thereof, that is, the electrolyte additive may contain the above chain-like halogenated phosphate alone, or may be compounded with the additive thereof to form a mixed additive. The other additives can be additives in the field of electrolyte, and the types and the proportion of the other additives to the chain halogenated phosphate can be selected according to requirements. Because the electrolyte additive contains the chain-shaped halogenated phosphate, the electrolyte additive provided by the embodiment of the invention can obviously improve the thermal stability of the electrolyte, and improve the film-forming property, the wetting property and the low-impedance property of the electrolyte.
Based on the chain-shaped halogenated phosphate ester, the preparation method thereof and the electrolyte additive, the embodiment of the invention also provides an electrolyte. The electrolyte contains the electrolyte additive, namely the chain-shaped halogenated phosphate. Therefore, the electrolyte disclosed by the embodiment of the invention has good film-forming property, wetting property and thermal stability, can remarkably improve the high and low temperature, circulation and storage properties of the secondary battery, can inhibit gas generation and impedance increase of the secondary battery, and improves the safety performance and comprehensive performance of the secondary battery.
In the embodiment, the mass concentration of the Wen Lianzhuang halophosphate in the electrolyte is typically 0.1% -5%, specifically 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, and the like, but not limited thereto, based on 100% of the total mass of the electrolyte. By controlling and adjusting the concentration of the chain-shaped halogenated phosphate in the electrolyte, on one hand, the improvement effect of the chain-shaped halogenated phosphate on the thermal stability of the electrolyte is fully exerted, the film-forming property and the wetting property of the electrolyte are improved, and the impedance increase is inhibited; on the other hand, the electrolyte can play a role of functional complementation with other components in the electrolyte, further improve the stability of the electrolyte, inhibit the gas generation phenomenon of the secondary battery, and improve the safety and the electrochemical performance of the secondary battery.
In addition, the electrolyte contains the chain halogenated phosphate, and also contains components which are necessary to the electrolyte, such as a solvent, an electrolyte lithium salt or further other components applied to the electrolyte, and the other components can play a role independently or can play a synergistic effect with the chain halogenated phosphate.
Wherein the electrolyte contains a solvent that is a non-aqueous solution, defined as a fifth non-aqueous solution, which in some embodiments may be, but is not limited to, a carbonate-based solvent, wherein the carbonate is a linear or cyclic carbonate. In some embodiments, the carbonate is a linear or cyclic carbonate. In some embodiments, the cyclic carbonate is selected from at least one of Ethylene Carbonate (EC), vinylene Carbonate (VC), vinyl Ethylene Carbonate (VEC), propylene Carbonate (PC), γ -butyrolactone; the chain carbonate is at least one selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethyl Methyl Carbonate (EMC), methyl propyl carbonate, ethyl propyl carbonate, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl propionate.
In a specific embodiment, the electrolyte lithium salt comprises LiPF 6 、LiBF 4 、LiClO 4 、LiSbF 6 、LiAsF 6 、LiTDI、LiN(SO 2 C 2 F 5 ) 2 、LiN(SO 2 CF 3 ) 2 、LiN(SO 3 C 2 F 5 ) 2 、LiN(SO 2 F) 2 、LiN(SO 2 C 6 F 5 ) 2 、LiN(SO 3 C 6 F 5 ) 2 、LiSO 3 CF 3 、LiSO 3 C 2 F 5 、LiSO 3 C 4 F 9 、LiSO 3 C 6 H 5 、LiSO 3 C 6 F 5 One or more of (a).
In particular embodiments, the other additives include, but are not limited to, one or more of 1,3-Propane Sultone (PS), 1,3-propene sultone (PES), vinyl sulfite (ES), vinyl sulfate (DTD), lithium difluorooxalate borate (LiODFB), lithium bis-oxalate borate (LiBOB).
The electrolyte may be a lithium ion battery electrolyte or a lithium metal battery electrolyte.
Based on the electrolyte, the embodiment of the invention also provides a secondary battery. The secondary battery comprises necessary components such as a positive electrode, a negative electrode and the like, and also comprises electrolyte, and the components and the electrolyte are assembled according to the assembly requirement of the lithium ion battery.
The electrolyte contained in the secondary battery is the electrolyte of the embodiment of the invention. Therefore, the secondary battery provided by the embodiment of the invention has good cycle performance and storage performance at high and low temperatures, reduces the occurrence of adverse phenomena such as gas generation and impedance increase of the secondary battery, and has high safety, good comprehensive chemical performance and longer service life.
The positive electrode included in the secondary battery may have a conventional positive electrode structure, such as including a positive electrode current collector and a positive electrode active layer bonded to the surface of the positive electrode current collector, wherein the positive electrode active layer includes components such as a positive electrode active material, a binder, a conductive agent, and a thickener (if necessary). In an embodiment, the positive active material may be selected from Li a CoO 2 (0.5<a<1.3)、Li a NiO 2 (0.5<a<1.3)、Li a MnO 2 (0.5<a<1.3)、Li a Mn 2 O 4 (0.5<a<1.3)、Li a (Ni x Co y Mn z )O 2 (0.5<a<1.3,0<x<1,0<y<1,0<z<1,x+y+z=1)、Li a Ni 1-x Co x O 2 (0.5<a<1.3,0<x<1)、Li a Co 1-x Mn x O 2 (0.5<a<1.3,0≤x<1)、Li a Ni 1-x Mn x O 2 (0.5<a<1.3,0≤x<1)、Li a (Ni x Co y Mn z )O 4 (0.5<a<1.3,0<x<2,0<y<2,0<z<2,x+y+z=2)、Li a Mn 2-x N x O 4 (0.5<a<1.3,0<x<2)、Li a Mn 2-x N x O 4 (0.5<a<1.3,0<y<2) And Li a NPO 4 (0.5<a<1.3 Any one or a mixture of two or more of); n is selected from one or more of Fe, ni, co, mn, zn, al, cr, mg, zr, mo, W, V, ti, B, F and Y. The positive electrode active material may beLi-Ni/Co/Mn oxide; further is Li a (Ni x Co y Mn z )O 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.10,0.3 and less than or equal to 0.9,0.05 and less than or equal to y<0.5,0.05≤z<0.5, and x + y + z =1; further Li (Ni) x Co y Mn z )O 2 Wherein x is more than or equal to 0.3 and less than or equal to 0.9,0.05 and less than or equal to y<0.5,0.05≤z<0.5, and x + y + z =1. In a specific embodiment, the positive electrode active material may be LiNi 0.6 Co 0.2 Mn 0.2 O 2 、LiNi 0.5 Co 0.2 Mn 0.3 O 2 、LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 1/3 Co 1/3 Mn 1/3 O 2 A mixture of one or more of them. And the mass of the positive electrode active material accounts for 88-98% of the mass of the positive electrode active slurry.
The negative electrode included in the secondary battery may have a conventional negative electrode structure, such as including a negative electrode current collector and a negative electrode active layer bonded to the surface of the negative electrode current collector, wherein the negative electrode active layer includes components such as a negative electrode active material capable of intercalating and deintercalating lithium ions, a conductive agent, a binder, and a thickener (if necessary). In an embodiment, the anode active material may be selected from at least one of carbon materials (such as crystalline carbon, amorphous carbon, carbon composite, and carbon fiber), lithium metal, alloys of lithium with other elements, and the like, which are capable of lithium ion intercalation and deintercalation. Non-limiting examples of crystalline carbon include graphite-based materials such as artificial graphite, natural graphite, graphitized coke, graphitized MCMB, graphitized MPCF, and the like. Non-limiting examples of amorphous carbon may include soft carbon (low temperature-fired carbon), hard carbon, coke, mesocarbon microbeads (MCMB), mesophase pitch-based carbon fibers (MPCF), and the like. Other elements that form alloys with lithium metal include one or more of the elements aluminum, zinc, bismuth, cadmium, antimony, silicon, lead, tin, gallium, or indium. And the mass of the negative active material accounts for 90-96% of the mass of the negative active slurry.
It should be noted that, the positive electrode current collector (or the negative electrode current collector) and the positive electrode active material layer (or the negative electrode active material layer) only provide a common positional relationship, that is, the positive electrode active slurry (or the negative electrode active slurry) is coated on the surface of the positive electrode current collector (or the negative electrode current collector) to form the positive electrode active material layer (or the negative electrode active material layer), and the present invention is not limited to the secondary battery provided in the embodiment of the present invention. Depending on the actual situation, the current collector and the active material may be changed according to the requirements for the performance of the secondary battery, for example, various ways such as filling the mixed powder of the positive electrode active material (or the negative electrode active material) and the auxiliary agent in the hollow positive electrode current collector (or the hollow negative electrode current collector).
In the examples, a solvent is further added to form the positive electrode active material slurry for the positive electrode active material and to form the negative electrode active material slurry for the negative electrode active material, and the solvent serves to disperse the electrode active material, the binder, the conductive material, and the like, and may be a nonaqueous solution or an aqueous solvent. In the case of high-purity deionized water, the conductivity of the high-purity deionized water is less than or equal to 3us/cm, and the nonaqueous solution may include N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, N-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran, etc., wherein the water content is less than or equal to 100ppm.
In an embodiment, the conductive agent for the positive electrode and the negative electrode may be selected from a graphite-based conductive agent, a carbon black-based conductive agent, a metal-based conductive agent, and a metal compound-based conductive agent. Examples of applications of the graphite-based conductive agent include artificial graphite, natural graphite, and the like. Examples of the application of the carbon black-based conductive agent include acetylene black, ketjen black (ketjen black), superconducting acetylene black (denka black), thermal black (thermal black), channel black (channel black), and the like. Examples of the use of the metal-based or metal compound-based conductive agent include tin, tin oxide, tin phosphate, titanium oxide, potassium titanate, perovskite materials such as LaSrCoO 3 Or LaSrMnO 3 And the mass of the positive and negative electrode conductive agents accounts for 0.1-6% of the mass of the positive and negative electrode active slurry respectively. When the mass ratio of the conductive agent is less than 0.1%, the electrochemical performance is deteriorated, and when the content is more than 6%, the content of the positive and negative electrode active materials is reduced, resulting in a low energy density of the battery. It should be noted that the conductive agent can improve the conductivity of the material, and any material that does not undergo chemical reaction in the battery system and is an electronic conductor can be used as the conductive agent.
In an embodiment, the binder used for the positive and negative electrodes may be at least one selected from polyvinylidene fluoride (PVDF), copolymer of polyhexafluoropropylene-polyvinylidene fluoride (HFP/PVDF), polyvinyl acetate, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, alkylated polyethylene oxide, polyvinyl ether, polymethyl methacrylate, polyethylacrylate, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyvinyl pyridine, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and the like, and the mass of the binder for the positive and negative electrodes accounts for 1% -6% of the mass of the active slurry for the positive and negative electrodes, respectively. The content of the binder is too low, the bonding strength between the positive and negative active materials and the current collector is insufficient, the content of the binder is too high, the bonding strength can be enhanced, but the content of the positive and negative active materials can be reduced, and the energy density of the battery is not favorably improved.
In the embodiment, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, or the like may be used as the negative electrode thickener, and the mass thereof accounts for 1% to 4% of the mass of the negative electrode active slurry. The thickener is not particularly limited as long as it can be used to adjust the viscosity of the anode active material slurry.
In addition, the positive electrode current collector included in the positive electrode and the negative electrode current collector included in the negative electrode may be, but not limited to, aluminum, an aluminum alloy, and the like, and the shape may be, but not limited to, foil (foil) or mesh (mesh), and the like.
A separator included in the secondary battery mainly provides an ion channel required for ion migration while isolating a positive electrode and a negative electrode from each other to prevent the positive electrode and the negative electrode from being short-circuited, and olefin polymer films (e.g., polypropylene, polyethylene/polypropylene/polyethylene, and polypropylene/polyethylene/polypropylene) or multi-layer films (multi-film), microporous films, and woven and nonwoven fabrics thereof are generally used. Specifically, a three-layer composite diaphragm can be adopted, the thickness of the diaphragm is 12-36 μm, and the porosity is 30-70%. In order to improve the thermal stability of the diaphragm, one or more layers of structurally stable resin or ceramic materials can be coated on the surface of the diaphragm.
In the embodiment, the secondary battery may be in the form of a square, a cylinder, a pouch, or the like. The secondary battery may be a lithium ion battery or a lithium metal battery. The secondary battery can be applied to conventional mobile communication tools, personal computers and other applications, and is also suitable for high-voltage, high-power and high-temperature driving systems, such as electric automobiles, electric ships, electric airplanes and the like. In addition, the secondary battery may be used in combination with an internal combustion engine, a fuel cell, a solar cell, a supercapacitor, or the like, for hybrid vehicles, electric bicycles, logistics vehicles, ships, airplanes, machine tools, and other uses of high-power, high-voltage, or high-temperature driving.
In order to clearly understand the details and operation of the above-mentioned embodiments of the present invention by those skilled in the art and to obviously embody the advanced performance of the chain-type halophosphate, the preparation method thereof, the electrolyte and the secondary battery in the embodiments of the present invention, the above-mentioned technical solutions are illustrated by a plurality of examples below.
A. Chain-like halogenated phosphate and preparation method examples thereof
Example A1
This example provides an ethyl ethylene glycol dichlorophosphate, an ethyl ethylene glycol difluorophosphate (formula 1 above), and a method for preparing the same.
The preparation method of ethylene glycol dichlorophosphate in the embodiment specifically comprises the following steps:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 90g (1 mol) of ethyl glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of ethyl glycol in methylene chloride to the POCl 3 The methylene dichloride solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the methylene dichloride solution of the ethyl glycol is added, the reaction is continued until no gas is produced in the system as the reaction end point, HCl gas produced by the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excessive POCl was distilled off at room temperature under reduced pressure 3 Obtaining viscous yellow liquid and obtaining the ethyl glycol dichlorophosphate.
The preparation method of ethyl glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and 149.8g of colorless liquid is obtained by distillation under reduced pressure at 65 ℃, wherein the yield is 86%.
In a glove box, 0.1mL of the colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the colorless liquid, filtered with an organic filter to remove suspended matter, a small amount of the filtrate was injected with a syringe, and analyzed by gas chromatography-mass spectrometry (Thermo Fisher Scientific), and the analysis result showed GC-MS (ESI) calcd for C 4 H 9 O 3 PF 2 [M] + Is 174.24. 1 H NMR(400MHz,CDCl 3 )δ:4.20(m,2H),3.72(t,2H),3.46(q,2H),1.05(t,3H); 13 C NMR(100MHz,CDCl 3 ) 69.1,66.3,64.0,15.2. The resulting colorless liquid was confirmed to be ethyl ethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 70ppm, the acidity was measured to be 62ppm, and the chloride ion concentration was measured to be 14ppm.
Example A2
This example provides trifluoroethyl ethylene glycol dichlorophosphate, trifluoroethyl ethylene glycol difluorophosphate (formula 2 above) and methods for their preparation.
The preparation method of trifluoroethylene glycol dichlorophosphate in this example is specifically as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 144g (1 mol) of trifluoroethylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of trifluoroethylene glycol in methylene chloride to POCl 3 The methylene dichloride solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, and the temperature is kept unchanged after the methylene dichloride solution of trifluoroethylene glycol is added, and the reaction is continued until the system is finishedNo gas is generated as a reaction end point, HCl gas generated by the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 Obtaining viscous yellow liquid and obtaining trifluoroethylene glycol dichlorophosphate.
The preparation method of trifluoroethylene glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and then heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 65 ℃ to obtain 198.5g with the yield of 87 percent.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the colorless liquid, filtered with an organic filter to remove suspended matter, a small amount of the filtrate was injected with a syringe and analyzed by gas chromatography (Thermo Fisher Scientific), and the analysis result showed GC-MS (ESI) calcd for C 4 H 6 O 3 PF 5 [M] + Is 228.16. 1 H NMR(400MHz,CDCl 3 )δ:4.20(m,2H),3.72(t,2H),3.89(q,2H); 13 C NMR(100MHz,CDCl 3 ) 122.8,69.7,69.1,64.0. The colorless liquid obtained was confirmed to be trifluoroethylene glycol difluorophosphate. The water content, acidity and chloride ion concentration were measured by a Karl moisture meter and a potentiometric titrator, respectively, to be 61ppm, 65ppm and 18ppm, respectively.
Example A3
This example provides a propyl ethylene glycol dichlorophosphate, a propyl ethylene glycol difluorophosphate (formula 3 above), and a method for preparing the same.
The preparation method of propylene glycol dichlorophosphate in this example is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 104g (1 mol) of propylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a methylene chloride solution of propylene glycol to POCl 3 The methylene dichloride solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the methylene dichloride solution of the propylene glycol is added, the reaction is continued until no gas is produced in the system as the reaction end point, HCl gas produced by the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 Obtaining viscous yellow liquid and obtaining the propylene glycol dichlorophosphate.
The preparation method of propylene glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and 169.3g of colorless liquid is obtained by distillation under reduced pressure at 75 ℃, wherein the yield is 90%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the colorless liquid, filtered with an organic filter to remove suspended matter, a small amount of the filtrate was injected with a syringe and analyzed by gas chromatography (Thermo Fisher Scientific), and the analysis result showed GC-MS (ESI) calcd for C 5 H 11 O 3 PF 2 [M] + Was 188.17. 1 H NMR(400MHz,CDCl 3 )δ:4.20(m,2H),3.72(t,2H),3.35(q,2H),1.49(m,2H),0.99(t,3H); 13 C NMR(100MHz,CDCl 3 ) 70.7,69.4,64.0,27.3,10.4. The colorless liquid obtained was confirmed to be propyl ethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 53ppm, the acidity was measured to be 66ppm, and the chloride ion concentration was measured to be 18ppm.
Example A4
This embodiment provides pentafluoropropylethylene glycol difluorophosphate and pentafluoropropylethylene glycol difluorophosphate (formula 4 above) and methods for preparing the same.
The preparation method of pentafluoropropylethylene glycol dicloyl phosphate in this example is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 104g (1 mol) of pentafluoropropylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of pentafluoropropylene glycol in methylene chloride to POCl 3 In the dichloromethane solution, stirring and keeping the temperature at 0 ℃ in the whole adding process, controlling the dropping speed to keep the gas production speed stable, keeping the temperature unchanged after the dichloromethane solution of the pentafluoropropylene glycol is added, continuously reacting until no gas is generated in the system, wherein the HCl gas generated in the reaction is absorbed by purified water to obtain hydrochloric acid which can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 Obtaining viscous yellow liquid and obtaining the pentafluoropropylethylene glycol dicloyl phosphate.
The preparation method of pentafluoropropylethylene glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 70 ℃ to obtain 244.8g of colorless liquid with the yield of 88 percent.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the colorless liquid, filtered with an organic filter to remove suspended matter, a small amount of the filtrate was injected with a syringe and analyzed by gas chromatography (Thermo Fisher Scientific), and the analysis result showed GC-MS (ESI) calcd for C 5 H 6 O 3 PF 7 [M] + Is 278.22. 1 H NMR(400MHz,CDCl 3 )δ:4.20(m,2H),3.72(m,2H),3.67(t,2H); 13 C NMR(100MHz,CDCl 3 ) 128.4,123.9,69.4,65.5,64.0. The resulting colorless liquid was confirmed to be pentafluoropropylethylene glycol difluorophosphate. The water content, acidity and chloride ion concentration were measured by a Karl moisture meter and a potentiometric titrator, respectively, to be 47ppm, 52ppm and 15ppm, respectively.
Example A5
This example provides allyl glycol dichlorophosphate, allyl glycol difluorophosphate (formula 5 above), and methods of making the same.
The preparation method of allyl glycol dichlorophosphate in the embodiment is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 102.1g (1 mol) of allyl glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of allyl glycol in methylene chloride to POCl 3 The methylene dichloride solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the methylene dichloride solution of the allyl glycol is added, the reaction is continued until no gas is produced in the system as the reaction end point, HCl gas produced in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid is obtained, and allyl glycol dichlorophosphate is obtained.
The preparation method of allyl glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and then heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 85 ℃ to obtain 160g, wherein the yield is 86%.
In a glove box, 0.1mL of the obtained colorless liquid is taken and addedDissolving completely in 2ml anhydrous acetonitrile, filtering with organic filter membrane to remove suspended matter, taking a small amount of filtrate, injecting sample with syringe, and analyzing by gas chromatography-mass spectrometry (Thermo Fisher Scientific), wherein the analysis result shows that GC-MS (ESI) calcd for C 5 H 9 O 3 PF 2 [M] + 186.17. 1 H NMR(400MHz,CDCl 3 )δ:6.07(m,1H),5.43(m,1H),5.31(m,1H),4.20(m,2H),4.04(d,2H),3.72(t,2H); 13 C NMR(101MHz,CDCl 3 ) 134.1,117.6,71.6,69.5,64.1. The resulting colorless liquid was confirmed to be allyl glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 51ppm, the acidity was measured to be 42ppm, and the chloride ion concentration was measured to be 16ppm.
Example A6
This example provides (2-methylallyl) ethylene glycol dichlorophosphate, (2-methylallyl) ethylene glycol difluorophosphate (formula 6 above) and a method for preparing the same.
The preparation method of (2-methylallyl) ethylene glycol di-chlorophosphate in this example is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 116g (1 mol) of 2-methyl allyl glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of 2-methyl allyl glycol in methylene chloride to POCl 3 The dichloromethane solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the dichloromethane solution of the 2-methyl allyl glycol is added, the reaction is continued until no gas is produced in the system as the reaction end point, HCl gas produced in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, and (2-methylallyl) ethylene glycol di (chlorophosphate) was obtained.
The preparation method of (2-methylallyl) ethylene glycol difluorophosphate of this example is specifically as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood for settling, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed through reduced pressure distillation at normal temperature to obtain a yellow liquid, and the mixture is distilled under reduced pressure at 85 ℃ to obtain 172g of colorless liquid, wherein the yield is 86%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the colorless liquid, filtered with an organic filter to remove suspended matter, a small amount of the filtrate was injected with a syringe and analyzed by gas chromatography (Thermo Fisher Scientific), and the analysis result showed GC-MS (ESI) calcd for C 6 H 11 O 3 PF 2 [M] + Is 200.16. 1 H NMR(400MHz,CDCl 3 )δ:5.89(m,1H),5.29(m,2H),4.20(m,2H),4.08(m,1H),3.74(m,2H),1.07(d,3H); 13 C NMR(101MHz,CDCl 3 ) 133.8,115.8,85.7,67.0,64.4,21.1. The colorless liquid obtained was confirmed to be 2-methylallyl glycol difluorophosphate. The water content was 57ppm, the acidity was 45ppm and the chloride ion concentration was 25ppm as measured by a Karl moisture meter and a potentiometric titrator.
Example A7
This example provides (2,2-dimethylallyl) ethylene glycol difluorophosphate (2,2-dimethylallyl) ethylene glycol difluorophosphate (formula 7 above) and a method for preparing the same.
The preparation method of the (2,2-dimethylallyl) ethylene glycol diphosphate in this example is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 130g (1 mol) of 2,2-dimethyl allyl glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding 2,2-dimethyl allyl glycol solution in dichloromethane to POCl 3 The methylene dichloride solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, and the methylene dichloride solution of 2,2-dimethyl allyl glycol is addedKeeping the temperature unchanged, continuously reacting until no gas is generated in the system as a reaction end point, absorbing HCl gas generated by the reaction by using purified water to obtain hydrochloric acid, and selling the hydrochloric acid as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, giving (2,2-dimethylallyl) ethylene glycol bischlorophosphate.
The preparation method of this example (2,2-dimethylallyl) ethylene glycol difluorophosphate is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood for settling, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed through reduced pressure distillation at normal temperature to obtain a yellow liquid, and the colorless liquid is obtained through reduced pressure distillation at 85 ℃ to obtain 186.4g with the yield of 87%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the colorless liquid, filtered with an organic filter to remove suspended matter, a small amount of the filtrate was injected with a syringe and analyzed by gas chromatography (Thermo Fisher Scientific), and the analysis result showed GC-MS (ESI) calcd for C 7 H 13 O 3 PF 2 [M] + Is 214.21. 1 H NMR(400MHz,CDCl 3 )δ:5.89(m,1H),5.29(m,2H),4.20(m,2H),3.72(t,2H),1.05(s,6H); 13 C NMR(101MHz,CDCl 3 ) 143.1,114.6,85.9,64.7,64.5,26.2. The colorless liquid obtained was found to be 2,2-dimethylallylethylene glycol difluorophosphate. The water content was 52ppm, the acidity was 53ppm and the chloride ion concentration was 28ppm as measured by a Karl moisture meter and a potentiometric titrator.
Example A8
This example provides an allyl diglycol dichlorophosphate, an allyl diglycol difluorophosphate (formula 8 above), and methods for their preparation.
The preparation method of allyl diglycol dichlorophosphate in the embodiment is as follows:
S1:adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 146g (1 mol) of allyl diglycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding allyl diethylene glycol solution in methylene chloride to POCl 3 The methylene dichloride solution is stirred and kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the methylene dichloride solution of the allyl diglycol is added, the reaction is continued until no gas is produced in the system, the reaction end point is reached, HCl gas produced in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid is obtained, and the allyl diglycol dichlorophosphate is obtained.
The preparation method of allyl diglycol difluorophosphate in the embodiment is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 105 ℃ to obtain 204.8g, wherein the yield is 89%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the colorless liquid, filtered with an organic filter to remove suspended matter, a small amount of the filtrate was injected with a syringe and analyzed by gas chromatography (Thermo Fisher Scientific), and the analysis result showed GC-MS (ESI) calcd for C 7 H 13 O 4 PF 2 [M] + 230.16. 1 H NMR(400MHz,CDCl 3 )δ:6.07(m,1H),5.43(d,1H),5.31(d,1H),4.20(m,2H),4.04(d,2H),3.72(t,2H),3.52(s,4H); 13 C NMR(101MHz,CDCl 3 ) 134.1,117.6,70.5,70.2,69.4,64.0. The resulting colorless liquid was confirmed to be allyl diethylene glycol difluorophosphate. By Karl moisture meter and potentialThe water content of the titrator was 42ppm, the acidity was 48ppm, and the chloride ion concentration was 22ppm.
Example A9
This example provides (2-methylallyl) diethylene glycol dichlorophosphate, (2-methylallyl) diethylene glycol difluorophosphate (formula 9 above) and a method for preparing the same.
The preparation method of (2-methylallyl) diethylene glycol dichlorophosphate in this example is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 160g (1 mol) of 2-methylallyl diethylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of 2-methylallyl diethylene glycol in methylene chloride to POCl 3 The dichloromethane solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the dichloromethane solution of the 2-methylallyl diethylene glycol is added, the reaction is continued until no gas is produced in the system, the reaction end point is reached, HCl gas produced in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, and (2-methylallyl) diethylene glycol dichlorophosphate was obtained.
The preparation method of (2-methylallyl) diethylene glycol difluorophosphate of this example is specifically as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid 222.1g is obtained by distillation under reduced pressure at 105 ℃, wherein the yield is 91%.
In a glove box, 0.1mL of the obtained colorless liquid was taken, added to 2mL of anhydrous acetonitrile to be completely dissolved, filtered by an organic filter membrane to remove suspended matters, and a small amount of the solution was takenThe filtrate was injected using a syringe and analyzed by GC-MS (ESI) calcd for C 8 H 15 O 4 PF 2 [M] + Is 244.14. 1 H NMR(400MHz,CDCl 3 )δ:5.89(m,1H),5.29(m,2H),4.20(m,2H),4.08(q,1H),3.72(t,2H),3.54(s,4H),1.07(d,3H); 13 C NMR(101MHz,CDCl 3 ) 133.8,115.8,86.0,70.7,70.5,69.4,64.1,21.1. The resulting colorless liquid was confirmed to be (2-methylallyl) diethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 53ppm, the acidity was measured to be 54ppm, and the chloride ion concentration was measured to be 22ppm.
Example A10
This example provides (2,2-dimethylallyl) diethylene glycol dichlorophosphate, (2,2-dimethylallyl) diethylene glycol difluorophosphate (formula 10 above) and a method for preparing the same.
The preparation method of this example (2,2-dimethylallyl) diethylene glycol dichlorophosphate is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 2,2-dimethylallyl diethylene glycol 174g (1 mol), and stirring for 0.5h at room temperature; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; 2,2-dimethylallyl diethylene glycol in methylene chloride was added to POCl 3 The dichloromethane solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the dichloromethane solution of 2,2-dimethyl allyl diethylene glycol is added, the reaction is continued until no gas is generated in the system, the reaction end point is reached, HCl gas generated in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, giving (2,2-dimethylallyl) diethylene glycol dichlorophosphate.
The preparation method of this example (2,2-dimethylallyl) diethylene glycol difluorophosphate is specifically as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 110 ℃ to obtain 227.2g, wherein the yield is 88%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 9 H 17 O 4 PF 2 [M] + Is 258.22. 1 H NMR(400MHz,CDCl 3 )δ:5.89(m,1H),5.29(m,1H),5.21(m,1H),4.20(m,2H),3.72(t,2H),3.52(m,4H),1.05(s,6H); 13 C NMR(101MHz,CDCl 3 ) 143.1,114.6,86.2,70.8,69.4,65.5,64.0,26.2. The colorless liquid obtained was confirmed to be (2,2-dimethylallyl) diethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 45ppm, the acidity was measured to be 44ppm, and the chloride ion concentration was measured to be 22ppm.
Example A11
This example provides allyl triethylene glycol dichlorophosphate, allyl triethylene glycol difluorophosphate (formula 11 above) and methods of making the same.
The preparation method of allyl triethylene glycol dichlorophosphate in the embodiment is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 190.2g (1 mol) of allyl triethylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding allyl triethylene glycol solution in methylene chloride to POCl 3 The methylene dichloride solution is stirred and kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the methylene dichloride solution of the allyl triethylene glycol is added, and the reaction is continued until the system is free of gasThe generation of the HCl gas is the reaction end point, the HCl gas generated in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excessive POCl was distilled off at room temperature under reduced pressure 3 Obtaining viscous yellow liquid and obtaining the allyl triethylene glycol dichlorophosphate.
The preparation method of allyl triethylene glycol difluorophosphate in the embodiment is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 125 ℃ to obtain 235.8g, wherein the yield is 86%. In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the colorless liquid, filtered with an organic filter to remove suspended matter, a small amount of the filtrate was injected with a syringe and analyzed by gas chromatography (Thermo Fisher Scientific), and the analysis result showed GC-MS (ESI) calcd for C 9 H 17 O 5 PF 2 [M] + Is 274.23. 1 H NMR(400MHz,CDCl 3 )δ:6.07(m,1H),5.43(m,1H),5.31(m,1H),4.20(q,2H),4.04(d,2H),3.72(t,2H),3.52(t,8H); 13 C NMR(101MHz,CDCl 3 ) 134.1,117.6,71.9,70.5,70.4,70.1,69.4,64.0. The resulting colorless liquid was confirmed to be allyltriethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 46ppm, the acidity was measured to be 44ppm, and the chloride ion concentration was measured to be 22ppm.
Example A12
This example provides (2-methylallyl) triethylene glycol dichlorophosphate, (2-methylallyl) triethylene glycol difluorophosphate (formula 12 above) and a method for preparing the same.
The preparation method of (2-methallyl) triethylene glycol dichlorophosphate in the embodiment is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature,then 204.3g (1 mol) of 2-methylallyl triethylene glycol is added, and the mixture is stirred for 0.5h at room temperature; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of 2-methylallyl triethylene glycol in methylene chloride to POCl 3 The dichloromethane solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the dichloromethane solution of the 2-methylallyl triethylene glycol is added, the reaction is continued until no gas is produced in the system, the reaction end point is reached, HCl gas produced in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, and (2-methylallyl) triethylene glycol dichlorophosphate was obtained.
The preparation method of (2-methylallyl) triethylene glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood for settling, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at normal temperature to obtain a yellow liquid, and 253.6g of colorless liquid is obtained by distillation under reduced pressure at 125 ℃, and the yield is 88 percent.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve it, filtered with an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 10 H 19 O 5 PF 2 [M] + Is 288.23. 1 H NMR(400MHz,CDCl 3 )δ:5.89(m,1H),5.29(m,2H),4.20(m,2H),4.08(q,1H),3.72(t,2H),3.54(m,4H),3.52(m,4H),1.07(d,3H); 13 C NMR(101MHz,CDCl 3 ) 133.8,115.8,86.0,70.8,70.7,70.4,70.1,69.4,64.0,21.1. The colorless liquid obtained was confirmed to be 2-methylallyl triethylene glycol difluorophosphate. By Karl moisture determinationThe water content was 44ppm, the acidity was 45ppm and the chloride ion concentration was 17ppm as measured by a potentiometric titrator.
Example A13
This example provides (2,2-dimethylallyl) triethylene glycol dichlorophosphate, (2,2-dimethylallyl) triethylene glycol difluorophosphate (formula 13 above) and methods of making the same.
The preparation method of triethylene glycol dichlorophosphate (2,2-dimethylallyl) in this example is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 2,2-dimethylallyl triethylene glycol 218.3g (1 mol), and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; a solution of 2,2-dimethylallyl triethylene glycol in methylene chloride was added to POCl 3 The dichloromethane solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the dichloromethane solution of 2,2-dimethyl allyl triethylene glycol is added, the reaction is continued until no gas is generated in the system as a reaction end point, HCl gas generated in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excessive POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, giving (2,2-dimethylallyl) triethylene glycol dichlorophosphate.
The preparation method of (2,2-dimethylallyl) triethylene glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by reduced pressure distillation at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by reduced pressure distillation at 125 ℃ to obtain 272.2g with the yield of 90 percent.
In a glove box, 0.1mL of the colorless liquid obtained is taken and added into 2mL of anhydrous acetonitrileCompletely dissolving, filtering with organic filter membrane to remove suspended matter, injecting small amount of filtrate with syringe, and analyzing by gas chromatography-mass spectrometry (Thermo Fisher Scientific), GC-MS (ESI) calcd for C 11 H 21 O 5 PF 2 [M] + Is 302.24. 1 H NMR(400MHz,CDCl 3 )δ:5.89(m,1H),5.29(m,2H),4.20(q,2H),3.72(t,2H),3.52(s,8H),1.05(s,6H); 13 C NMR(101MHz,CDCl 3 ) 143.1,114.6,86.2,71.1,70.4,70.1,69.4,65.5,64.0,26.2. The colorless liquid obtained was found to be 2,2-dimethylallyl triethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 41ppm, the acidity was measured to be 42ppm, and the chloride ion concentration was measured to be 18ppm.
Example A14
This example provides a propargyl ethylene glycol dichloro phosphate, propargyl ethylene glycol difluorophosphate (formula 14 above), and methods for their preparation.
The preparation method of propargyl ethylene glycol dichloro phosphate in this example is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 100.1g (1 mol) of propargyl glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding propargylethylene glycol in dichloromethane to POCl 3 The dichloromethane solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the dichloromethane solution of propargyl glycol is added, the reaction is continued until no gas is produced in the system as the reaction end point, HCl gas produced in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 Obtaining viscous yellow liquid and obtaining the propargyl ethylene glycol dichloro phosphate.
The preparation method of propargyl ethylene glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 75 ℃ to obtain 156.6g of colorless liquid, wherein the yield is 85 percent.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 5 H 7 O 3 PF 2 [M] + Was 184.15. 1 H NMR(400MHz,CDCl 3 )δ:4.15(s,2H),4.20(m,2H),3.72(t,2H),3.32(s,1H); 13 C NMR(101MHz,CDCl 3 ) 78.7,76.4,68.2,63.1,60.0. The resulting colorless liquid was confirmed to be propargyl ethylene glycol difluorophosphate. The water content, acidity and chloride ion concentration were measured by a Karl moisture meter and a potentiometric titrator, respectively, to be 33ppm, 36ppm and 16ppm, respectively.
Example A15
This example provides (2-methylpropargyl) ethylene glycol difluorophosphate (formula 15 above) and a method for preparing the same.
The preparation method of (2-methylpropargyl) ethylene glycol diclofophosphate in this example is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 114.1g (1 mol) of 2-methyl propargyl glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of 2-methylpropargylethylene glycol in methylene chloride to POCl 3 The dichloromethane solution is added in the whole process, the stirring is carried out, the temperature is kept at 0 ℃, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the dichloromethane solution of the 2-methyl propargyl glycol is added, the reaction is continued until no gas is generated in the system, the reaction end point is reached, the HCl gas generated in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be used as industrial hydrochloric acidSelling raw materials; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 To obtain viscous yellow liquid, and obtain (2-methyl propargyl) ethylene glycol dichlorophosphate.
The preparation method of (2-methylpropargyl) ethylene glycol difluorophosphate of this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the mixture is distilled under reduced pressure at 75 ℃ to obtain 172.3g of colorless liquid, wherein the yield is 87%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 6 H 9 O 3 PF 2 [M] + Is 198.14. 1 H NMR(400MHz,CDCl 3 )δ:4.44(q,1H),4.20(m,2H),3.74(t,2H),3.56(m,1H),1.43(d,3H); 13 C NMR(101MHz,CDCl 3 ) 84.0,72.2,70.7,65.7,63.4,22.2. The colorless liquid obtained was confirmed to be 2-methylpropargyl ethylene glycol difluorophosphate. The water content, acidity and chloride ion concentration were measured by a Karl moisture meter and a potentiometric titrator, respectively, to be 32ppm, 33ppm and 15ppm, respectively.
Example A16
This example provides (2,2-dimethylpropargyl) ethylene glycol difluorophosphate (2,2-dimethylpropargyl) ethylene glycol difluorophosphate (formula 16 above) and a method for its preparation.
The preparation method of (2-methylpropargyl) ethylene glycol diclofophosphate in this example is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 128.1g (1 mol) of 2,2-dimethyl propargyl ethylene glycol, and stirring at room temperature for 0.5h; in another reaction kettleMethyl chloride 200mL and 180g POCl 3 Mixing at 0 deg.C; 2,2-Dimethylpropargylethylene glycol in dichloromethane was added to POCl 3 The dichloromethane solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the dichloromethane solution of 2,2-dimethyl propargyl glycol is added, the reaction is continued until no gas is generated in the system as the reaction end point, HCl gas generated in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 To obtain viscous yellow liquid, and obtain (2-methyl propargyl) ethylene glycol dichlorophosphate.
The preparation method of (2-methylpropargyl) ethylene glycol difluorophosphate of this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 80 ℃ to obtain 184.5g, wherein the yield is 87%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 7 H 11 O 3 PF 2 [M] + Is 212.14. 1 H NMR(400MHz,CDCl 3 )δ:4.20(m,2H),3.72(t,2H),3.56(m,1H),1.46(s,6H); 13 C NMR(101MHz,CDCl 3 ) 88.3,84.2,72.1,63.7,63.2,29.6. The colorless liquid obtained was found to be 2,2-dimethylproparganeglycol difluorophosphate. The water content was 32ppm, the acidity was 31ppm and the chloride ion concentration was 15ppm as measured by a Karl moisture meter and a potentiometric titrator.
Example A17
This example provides propargyl diethylene glycol dichlorophosphate, propargyl diethylene glycol difluorophosphate (formula 17 above) and methods of making the same.
The preparation method of propargyl diethylene glycol dichlorophosphate in the embodiment is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 144.2g (1 mol) of propargyl diethylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding propargyl diethylene glycol in dichloromethane to POCl 3 The dichloromethane solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the dichloromethane solution of the propargyl diethylene glycol is added, the reaction is continued until no gas is produced in the system as the reaction end point, HCl gas produced in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 Obtaining viscous yellow liquid and obtaining the propargyl diethylene glycol dichlorophosphate.
The preparation method of propargyl diethylene glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 105 ℃ to obtain 200.7g, wherein the yield is 88%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 7 H 11 O 4 PF 2 [M] + Is 228.13. 1 H NMR(400MHz,CDCl 3 )δ:4.20(m,2H),4.15(d,2H),3.72(t,2H),3.52(s,4H),3.32(t,1H); 13 C NMR(101MHz,CDCl 3 ) 78.7,76.4,69.4,69.2,64.0,60.3. The resulting colorless liquid was confirmed to be propargyl diethylene glycol difluorophosphate. The water content, acidity and chloride ion concentration were measured by a Karl moisture meter and a potentiometric titrator, respectively, to be 27ppm, 33ppm and 18ppm, respectively.
Example A18
This example provides (2-methylpropargyl) diethylene glycol dichlorophosphate, (2-methylpropargyl) diethylene glycol difluorophosphate (formula 18 above) and a method for preparing the same.
The preparation method of propargyl diethylene glycol dichlorophosphate in the embodiment is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 158.2g (1 mol) of 2-methyl propargyl diethylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of 2-methylpropargyldiglycol in methylene chloride to POCl 3 The dichloromethane solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the dichloromethane solution of the 2-methyl propargyl diethylene glycol is added, the reaction is continued until no gas is produced in the system as a reaction end point, HCl gas produced in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid is obtained, and propargyl diethylene glycol dichlorophosphate is obtained.
The preparation method of propargyl diethylene glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 105 ℃ to obtain 205.8g, wherein the yield is 85%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 8 H 13 O 4 PF 2 [M] + Is 242.15. 1 H NMR(400MHz,CDCl 3 )δ:4.44(q,1H),4.20(m,2H),3.72(t,2H),3.56(m,1H),3.54(m,4H),1.43(d,3H); 13 C NMR(101MHz,CDCl 3 ) 84.0,72.2,71.0,69.5,69.4,66.7,64.0,22.2. The colorless liquid obtained was confirmed to be 2-methylpropargyl diethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 35ppm, the acidity was measured to be 41ppm, and the chloride ion concentration was measured to be 18ppm.
Example A19
This example provides (2,2-dimethylpropargyl) diethylene glycol dichlorophosphate, (2,2-dimethylpropargyl) diethylene glycol difluorophosphate (formula 19 above) and a method for preparing the same.
The preparation method of this example (2,2-dimethylpropargyl) diethylene glycol dichlorophosphate is specifically as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 2,2-dimethyl propargyl diethylene glycol 172.1g (1 mol), and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding 2,2-dimethylpropargyldiglycol in dichloromethane to POCl 3 In the dichloromethane solution, stirring and keeping the temperature at 0 ℃ in the whole adding process, controlling the dropping speed to keep the gas production speed stable, keeping the temperature unchanged after the dichloromethane solution of 2,2-dimethyl propargyl diethylene glycol is added, and continuously reacting until no gas is generated in the system to be a reaction end point, absorbing HCl gas generated in the reaction by using purified water to obtain hydrochloric acid, wherein the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, giving (2,2-dimethylpropargyl) diethylene glycol dichlorophosphate.
The preparation method of diethylene glycol difluorophosphate of this example (2,2-dimethylpropargyl) is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by reduced pressure distillation at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by reduced pressure distillation at 110 ℃ to obtain 220.3g, wherein the yield is 86%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 9 H 15 O 4 PF 2 [M] + 256.22. 1 H NMR(400MHz,CDCl 3 )δ:4.20(m,2H),3.72(t,2H),3.56(m,1H),3.52(m,4H),1.46(s,6H); 13 C NMR(101MHz,CDCl 3 ) 88.3,84.5,72.1,69.8,69.4,64.2,64.0,29.6. The colorless liquid obtained was found to be 2,2-dimethylpropargyldiethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 36ppm, the acidity was measured to be 42ppm, and the chloride ion concentration was measured to be 21ppm.
Example A20
This example provides propargyl triethylene glycol dichlorophosphate, propargyl triethylene glycol difluorophosphate (formula 20 above) and methods of making the same.
The preparation method of propargyl triethylene glycol dichlorophosphate in the embodiment is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 188.2g (1 mol) of propargyl triethylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding propargyl triethylene glycol in methylene chloride solution to POCl 3 To the dichloromethane solution of (2), addingCheng Quancheng stirring and keeping the temperature at 0 ℃, controlling the dropping speed to keep the gas production speed stable, keeping the temperature unchanged after the methylene dichloride solution of propargyl triethylene glycol is added, continuously reacting until no gas is generated in the system as a reaction end point, absorbing HCl gas generated by the reaction by using purified water to obtain hydrochloric acid, and selling the hydrochloric acid as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 Obtaining viscous yellow liquid and obtaining the propargyl triethylene glycol dichlorophosphate.
The preparation method of propargyl triethylene glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by reduced pressure distillation at room temperature to obtain a yellow liquid, and the mixture is distilled under reduced pressure at 125 ℃ to obtain 236.8g of colorless liquid, wherein the yield is 87%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 9 H 15 O 5 PF 2 [M] + Is 272.23. 1 H NMR(400MHz,CDCl 3 )δ:4.20(m,2H),4.15(d,2H),3.72(t,2H),3.52(m,8H),3.32(m,1H); 13 C NMR(101MHz,CDCl 3 ) 78.7,76.4,70.4,70.1,69.5,69.4,69.2,61.0,60.3. The resulting colorless liquid was confirmed to be propargyl triethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 31ppm, the acidity was measured to be 42ppm, and the chloride ion concentration was measured to be 18ppm.
Example A21
This example provides (2-methylpropargyl) triethylene glycol dichlorophosphate, (2-methylpropargyl) triethylene glycol difluorophosphate (formula 21 above) and a method for preparing the same.
The preparation method of (2-methyl propargyl) triethylene glycol dichlorophosphate in the embodiment is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 202.3g (1 mol) of 2-methyl propargyl triethylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of 2-methylpropargyl triethylene glycol in methylene chloride to POCl 3 In the dichloromethane solution, stirring and keeping the temperature at 0 ℃ in the whole adding process, controlling the dropping speed to keep the gas production speed stable, keeping the temperature unchanged after the dichloromethane solution of 2-methyl propargyl triethylene glycol is added, continuously reacting until no gas is generated in the system, wherein the reaction end point is that HCl gas generated in the reaction is absorbed by purified water to obtain hydrochloric acid which can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excessive POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid is obtained, and (2-methyl propargyl) triethylene glycol dichlorophosphate is obtained.
The preparation method of (2-methyl propargyl) triethylene glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and then heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and 243.3g of colorless liquid is obtained by distillation under reduced pressure at 125 ℃, wherein the yield is 85%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 10 H 17 O 5 PF 2 [M] + Is 286.24. 1 H NMR(400MHz,CDCl 3 )δ:4.44(q,1H),4.20(m,2H),3.72(t,2H),3.56(m,1H),3.54(m,4H),3.52(m,4H),1.43(d,3H); 13 C NMR(101MHz,CDCl 3 ) 84.0,72.2,71.0,70.4,70.1,69.8,69.4,66.7,64.0,22.2. The colorless liquid obtained was confirmed to be 2-methylpropargyl triethylene glycol difluorophosphate. The water content was 32ppm, the acidity was 38ppm and the chloride ion concentration was 18ppm as measured by a Karl moisture meter and a potentiometric titrator.
Example A22
This example provides (2,2-dimethylpropargyl) triethylene glycol dichlorophosphate, (2,2-dimethylpropargyl) triethylene glycol difluorophosphate (formula 22 above) and a method for preparing the same.
The preparation method of (2,2-dimethylpropargyl) triethylene glycol dichlorophosphate in this example is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 216.3g (1 mol) of 2,2-dimethyl propargyl triethylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding 2,2-dimethylpropargyltriethylene glycol solution in methylene chloride to POCl 3 The dichloromethane solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the dichloromethane solution of 2,2-dimethyl propargyl triethylene glycol is added, the reaction is continued until no gas is generated in the system as the reaction end point, HCl gas generated in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, giving (2,2-dimethylpropargyl) triethylene glycol dichlorophosphate.
The preparation method of triethylene glycol difluorophosphate (2,2-dimethylpropargyl) in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by reduced pressure distillation at room temperature to obtain a yellow liquid, and the mixture is distilled under reduced pressure at 125 ℃ to obtain 261.2g of colorless liquid, wherein the yield is 87%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 11 H 19 O 5 PF 2 [M] + Is 300.24. 1 H NMR(400MHz,CDCl 3 )δ:4.20(m,2H),3.72(t,2H),3.56(m,1H),3.52(m,8H),1.46(s,6H); 13 C NMR(101MHz,CDCl 3 ) 88.3,84.5,72.1,70.4,70.1,69.4,64.2,64.0,29.6. The colorless liquid obtained was found to be 2,2-dimethylpropargyltriethylene glycol difluorophosphate. The water content, acidity and chloride ion concentration were measured by a Karl moisture meter and a potentiometric titrator, respectively, to be 41ppm, 43ppm and 19ppm, respectively.
Example A23
This example provides (4-fluorophenyl) ethylene glycol dichlorophosphate, (4-fluorophenyl) ethylene glycol difluorophosphate (formula 23 above) and a method for preparing the same.
The preparation method of (4-fluorophenyl) ethylene glycol dichlorophosphate in the embodiment is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 156.2g (1 mol) of (4-fluorophenyl) ethylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of (4-fluorophenyl) ethylene glycol in methylene chloride to POCl 3 Stirring and keeping the temperature at 0 ℃ in the whole adding process, controlling the dropping speed to keep the gas production speed stable, keeping the temperature unchanged after the dichloromethane solution of the (4-fluorophenyl) glycol is added, continuously reacting until no gas is generated in the system, wherein HCl gas generated in the reaction is absorbed by purified water to obtain hydrochloric acid which can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, and (4-fluorophenyl) ethylene glycol di-chlorophosphate was obtained.
The preparation method of (4-fluorophenyl) ethylene glycol difluorophosphate in this example is specifically as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the mixture is distilled under reduced pressure at 155 ℃ to obtain 204.1g of colorless liquid, wherein the yield is 85 percent.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve it, filtered with an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 8 H 8 O 3 PF 3 [M] + Is 240.14. 1 H NMR(400MHz,CDCl 3 )δ:7.19(m,2H),7.09(m,2H),4.51(t,2H),4.45(t,2H); 13 C NMR(101MHz,CDCl 3 ) 155.0,154.5,116.1,116.0,68.3,63.6. The resulting colorless liquid was confirmed to be (4-fluorophenyl) ethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 38ppm, the acidity was measured to be 42ppm, and the chloride ion concentration was measured to be 18ppm.
Example A24
This example provides (3,5-difluorophenyl) ethylene glycol difluorophosphate, (3,5-difluorophenyl) ethylene glycol difluorophosphate (formula 24 above) and a method for preparing the same.
The preparation method of the (3,5-difluorophenyl) ethylene glycol dichlorophosphate in this example is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 174.1g (1 mol) of (3,5-difluorophenyl) ethylene glycol, and stirring for 0.5h at room temperature; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; a solution of (3,5-difluorophenyl) ethylene glycol in methylene chloride was added to POCl 3 The dichloromethane solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, (3,5-difluorobenzene)After the methylene dichloride solution of ethylene glycol is added, keeping the temperature unchanged, continuously reacting until no gas is generated in the system, wherein the reaction end point is the reaction end point, HCl gas generated in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, and (3,5-difluorophenyl) ethylene glycol dichlorophosphate was obtained.
The preparation method of (3,5-difluorophenyl) ethylene glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the mixture is distilled under reduced pressure at 155 ℃ to obtain 221.9g of colorless liquid with the yield of 86 percent.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve it, filtered with an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 8 H 7 O 3 PF 4 [M] + Is 258.17. 1 H NMR(400MHz,CDCl 3 )δ:6.90(m,2H),6.36(m,1H),4.51(t,2H),4.45(t,2H); 13 C NMR(101MHz,CDCl 3 ) 165.1,160.6,98.1,96.3,68.3,63.6. The colorless liquid obtained was confirmed to be (3,5-difluorophenyl) ethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 35ppm, the acidity was measured to be 23ppm, and the chloride ion concentration was measured to be 16ppm.
Example A25
This example provides (pentafluorophenyl) ethylene glycol difluorophosphate (formula 25 above) and a method for its preparation.
In this example, (pentafluorophenyl) ethylene glycol dichlorophosphate is prepared as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 228.1g (1 mol) of (pentafluorophenyl) ethylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; (pentafluorophenyl) ethylene glycol in dichloromethane was added to the POCl 3 Stirring and keeping the temperature at 0 ℃ in the whole adding process, controlling the dropping speed to keep the gas production speed stable, keeping the temperature unchanged after the dichloromethane solution of the (pentafluorophenyl) glycol is added, continuously reacting until no gas is produced in the system, wherein HCl gas produced in the reaction is absorbed by purified water to obtain hydrochloric acid which can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, and (pentafluorophenyl) ethylene glycol dichlorophosphate was obtained.
The preparation method of (pentafluorophenyl) ethylene glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 155 ℃, wherein the yield is 90 percent.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 8 H 4 O 3 PF 7 [M] + Is 312.15. 1 H NMR(400MHz,CDCl 3 )δ:4.51(m,2H),4.45(m,2H); 13 C NMR(101MHz,CDCl 3 ) 144.2,142.6,134.9,131.4,68.3,63.6. The resulting colorless liquid was confirmed to be (pentafluorophenyl) ethylene glycol difluorophosphate. The water content, acidity and chlorine contents were measured by a Karl-type moisture meter and a potentiometric titrator to be 31ppm, 28ppm andthe ion concentration was 17ppm.
Example A26
This example provides (4-fluorophenyl) diethylene glycol dichlorophosphate, (4-fluorophenyl) diethylene glycol difluorophosphate (formula 26 above) and a method for preparing the same.
The preparation method of (4-fluorophenyl) diethylene glycol dichlorophosphate in the embodiment is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 200.2g (1 mol) of (4-fluorophenyl) diethylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of (4-fluorophenyl) diethylene glycol in methylene chloride to POCl 3 Stirring and keeping the temperature at 0 ℃ in the whole adding process, controlling the dropping speed to keep the gas production speed stable, keeping the temperature unchanged after the dichloromethane solution of the (4-fluorophenyl) diethylene glycol is added, continuously reacting until no gas is generated in the system, wherein HCl gas generated in the reaction is absorbed by purified water to obtain hydrochloric acid which can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, and (4-fluorophenyl) diethylene glycol dichlorophosphate was obtained.
The preparation method of (4-fluorophenyl) diethylene glycol difluorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 185 ℃ to obtain 250.1g, wherein the yield is 88%.
In a glove box, 0.1mL of the obtained colorless liquid was taken, added to 2mL of anhydrous acetonitrile to be completely dissolved, filtered by an organic filter membrane to remove suspended matters, a small amount of the filtrate was injected by a syringe, analyzed by gas chromatography-mass spectrometry (Thermo Fisher Scientific),GC-MS(ESI)calcd for C 10 H 12 O 4 PF 3 [M] + is 284.24. 1 H NMR(400MHz,CDCl 3 )δ:7.19(m,2H),7.09(m,2H),4.31(t,2H),4.20(m,2H),3.77(m,2H),3.72(m,2H); 13 C NMR(101MHz,CDCl 3 ) 155.0,154.5,116.1,116.0,69.7,69.4,69.3,64.0. The resulting colorless liquid was confirmed to be (4-fluorophenyl) diethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 28ppm, the acidity was measured to be 31ppm, and the chloride ion concentration was measured to be 18ppm.
Example A27
This example provides (3,5-difluorophenyl) diethylene glycol dichlorophosphate, (3,5-difluorophenyl) diethylene glycol difluorophosphate (formula 27 above) and methods of making the same.
The preparation method of (3,5-difluorophenyl) diethylene glycol dichlorophosphate in this example is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 218.2g (1 mol) of (3,5-difluorophenyl) diethylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; a solution of (3,5-difluorophenyl) diethylene glycol in methylene chloride was added to POCl 3 Stirring and keeping the temperature at 0 ℃ in the whole adding process, controlling the dropping speed to keep the gas production speed stable, keeping the temperature unchanged after the dichloromethane solution of (3,5-difluorophenyl) diethylene glycol is added, and continuously reacting until no gas is generated in the system to be a reaction end point, wherein HCl gas generated in the reaction is absorbed by purified water to obtain hydrochloric acid which can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, giving (3,5-difluorophenyl) diethylene glycol dichlorophosphate.
The preparation method of (3,5-difluorophenyl) diethylene glycol dichlorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood still, settled and cooled to room temperature, and then filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at normal temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 185 ℃, wherein the yield is 87%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 10 H 11 O 4 PF 4 [M] + 302.25. 1 H NMR(400MHz,CDCl 3 )δ:6.90(m,2H),6.36(m,1H),4.31(t,2H),4.20(t,2H),3.77(t,2H),3.72(m,2H); 13 C NMR(101MHz,CDCl 3 ) 165.1,160.6,98.1,96.3,69.7,69.4,69.3,64.0. The colorless liquid obtained was confirmed to be (3,5-difluorophenyl) diethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 31ppm, the acidity was measured to be 28ppm, and the chloride ion concentration was measured to be 17ppm.
Example A28
This example provides (pentafluorophenyl) diethylene glycol dichlorophosphate, (pentafluorophenyl) diethylene glycol difluorophosphate (formula 28 above) and methods of making the same.
The preparation method of (pentafluorophenyl) diethylene glycol dichlorophosphate in this example is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 272.2g (1 mol) of (pentafluorophenyl) diethylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of (pentafluorophenyl) diethylene glycol in methylene chloride to the POCl 3 Stirring and keeping the temperature at 0 ℃ in the whole adding process, controlling the dropping speed to keep the gas production speed stable, keeping the temperature unchanged after the dichloromethane solution of the (pentafluorophenyl) diethylene glycol is added, continuously reacting until no gas is produced in the system, wherein HCl gas produced in the reaction is absorbed by purified water to obtain hydrochloric acid which can be sold as an industrial raw material; after the reaction is finished, the temperature is room temperatureThe dichloromethane was removed by distillation at atmospheric pressure, and then the excess POCl was removed by distillation at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, giving (pentafluorophenyl) diethylene glycol dichlorophosphate.
The preparation method of (pentafluorophenyl) diethylene glycol dichlorophosphate in this example is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and 313.4g of colorless liquid is obtained by distillation under reduced pressure at 185 ℃, and the yield is 88%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 10 H 8 O 4 PF 7 [M] + Is 356.16. 1 H NMR(400MHz,CDCl 3 )δ:4.31(t,2H),4.20(m,2H),3.77(m,2H),3.72(m,2H); 13 C NMR(101MHz,CDCl 3 ) 144.2,142.6,134.9,131.4,69.7,69.4,69.3,64.0. The resulting colorless liquid was confirmed to be (pentafluorophenyl) diethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 35ppm, the acidity was measured to be 32ppm, and the chloride ion concentration was measured to be 17ppm.
Example A29
This example provides an acrylic acid ethylene glycol dichlorophosphate, acrylic acid ethylene glycol difluorophosphate (formula 29 above), and methods for their preparation.
The preparation method of the ethylene glycol dichloride phosphate of the embodiment is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 116.1g (1 mol) of ethylene glycol acrylate, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; dichloro of ethylene glycol acrylateAdding methane solution to POCl 3 The methylene dichloride solution is stirred and kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the methylene dichloride solution of the ethylene acrylate glycol is added, the reaction is continued until no gas is produced in the system as a reaction end point, HCl gas produced by the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 Obtaining viscous yellow liquid and obtaining the acrylic acid glycol dichlorophosphate.
The preparation method of the acrylic acid ethylene glycol difluorophosphate of the embodiment is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 85 ℃ to obtain 168.2g, wherein the yield is 84%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 5 H 7 O 4 PF 2 [M] + Is 200.21. 1 H NMR(400MHz,CDCl 3 )δ:6.41(m,1H),6.12(m,1H),5.83(m,1H),4.47(t,2H),4.31(m,2H); 13 C NMR(101MHz,CDCl 3 ) 166.5,131.3,128.2,63.8,63.0. The colorless liquid obtained was confirmed to be acrylic acid ethylene glycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 31ppm, the acidity was measured to be 35ppm, and the chloride ion concentration was measured to be 18ppm.
Example A30
This example provides a methacrylic acid ethylene glycol dichloro phosphate, methacrylic acid ethylene glycol difluorophosphate (formula 30 above), and a method for preparing the same.
The preparation method of the ethylene glycol dimethacrylate phosphate of the embodiment is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 130.1g (1 mol) of ethylene glycol methacrylate, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of ethylene glycol methacrylate in methylene chloride to the POCl 3 The methylene dichloride solution is stirred and kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the methylene dichloride solution of the ethylene glycol methacrylate is added, the reaction is continued until no gas is produced in the system, the reaction end point is reached, HCl gas produced in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 Obtaining viscous yellow liquid and obtaining the methacrylic acid ethylene glycol dichloro phosphate.
The preparation method of the methacrylic acid ethylene glycol difluorophosphate of the embodiment is as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and then heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid 184.1g is obtained by distillation under reduced pressure at 90 ℃, wherein the yield is 86%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve it, filtered with an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 6 H 9 O 4 PF 2 [M] + Is 214.13. 1 H NMR(400MHz,CDCl 3 )δ:6.48(s,1H),6.40(s,1H),4.47(t,2H),4.31(m,2H),2.01(s,3H); 13 C NMR(101MHz,CDCl 3 )δ:167.2,136.0,125.2,64.1,63.0,17.9. The colorless liquid obtained was confirmed to be methacrylic acid ethylene glycol difluorophosphate. The water content, acidity and chloride ion concentration were measured by a Karl moisture meter and a potentiometric titrator, respectively, to be 28ppm, 31ppm and 16ppm, respectively.
Example A31
This example provides (1-butenyl) ethylene glycol dichlorophosphate, (1-butenyl) ethylene glycol difluorophosphate (formula 31 above) and a method of making the same.
The preparation method of (1-butenyl) ethylene glycol dichlorophosphate in the embodiment is concretely as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 116.1g (1 mol) of 1-butylene glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a solution of 1-butenylglycol in methylene chloride to POCl 3 The dichloromethane solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the dichloromethane solution of the 1-butylene glycol is added, the reaction is continued until no gas is produced in the system, the reaction end point is reached, HCl gas produced in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 A viscous yellow liquid was obtained, and (1-butenyl) ethylene glycol diclorophosphate was obtained.
The preparation method of (1-butenyl) ethylene glycol difluorophosphate in this example is specifically as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid 172.1g is obtained by distillation under reduced pressure at 85 ℃, wherein the yield is 86%.
In a glove box, 0.1mL of the obtained colorless liquid was taken and added to 2mL of anhydrous acetonitrile to complete the reactionComplete dissolution, removal of suspended matter by filtration through an organic filter, injection of a small amount of the filtrate using a syringe, analysis by gas chromatography-Mass Spectrometry (Thermo Fisher Scientific), GC-MS (ESI) calcd for C 6 H 11 O 3 PF 2 [M] + 200.15. 1 H NMR(400MHz,CDCl 3 )δ:5.82(m,1H),5.13(d,1H),4.88(d,1H),4.20(m,2H),3.72(m,2H),3.38(m,2H),2.13(m,2H); 13 C NMR(101MHz,CDCl 3 ) 134.3,116.4,71.2,69.5,64.0,34.6. The resulting colorless liquid was confirmed to be 1-butenylglycol difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 43ppm, the acidity was measured to be 41ppm, and the chloride ion concentration was measured to be 17ppm.
Example A32
This example provides (1-butynyl) ethylene glycol dichlorophosphate, (1-butynyl) ethylene glycol difluorophosphate (formula 32 above) and a method for preparing the same.
The preparation method of (1-butynyl) ethylene glycol diclofophosphate in this example is as follows:
s1: adding 200mL of dichloromethane into the reaction kettle at room temperature, then adding 116.1g (1 mol) of 1-butynyl glycol, and stirring at room temperature for 0.5h; in another reaction kettle, 200mL of dichloromethane and 180g of POCl 3 Mixing at 0 deg.C; adding a dichloromethane solution of 1-butynyl glycol to POCl 3 The dichloromethane solution is stirred and the temperature is kept at 0 ℃ in the whole adding process, the dropping speed is controlled to keep the gas production speed stable, the temperature is kept unchanged after the dichloromethane solution of the 1-butynyl glycol is added, the reaction is continued until no gas is produced in the system as the reaction end point, the HCl gas produced in the reaction is absorbed by purified water to obtain hydrochloric acid, and the hydrochloric acid can be sold as an industrial raw material; after the reaction was completed, dichloromethane was distilled off at room temperature under normal pressure, and then excess POCl was distilled off at room temperature under reduced pressure 3 To obtain a viscous yellow liquid, and obtain (1-butynyl) ethylene glycol dichlorophosphate.
The preparation method of (1-butynyl) ethylene glycol difluorophosphate in this example is specifically as follows:
s2: and (2) adding 200mL of acetonitrile into the viscous yellow liquid obtained in the step S1, stirring at room temperature to obtain a light yellow solution, adding 150 g of KF into the solution in batches, and then heating to 60 ℃ for reaction for 3 hours. No gas is discharged in the reaction process, then the mixture is stood, settled, cooled to room temperature and filtered under normal pressure to obtain a light yellow solution, acetonitrile is removed by distillation under reduced pressure at room temperature to obtain a yellow liquid, and the colorless liquid is obtained by distillation under reduced pressure at 90 ℃ to obtain 174.3g, wherein the yield is 88%.
In a glove box, 0.1mL of the resulting colorless liquid was taken, added to 2mL of anhydrous acetonitrile to completely dissolve the liquid, filtered through an organic filter to remove suspended matter, a small amount of the filtrate was injected using a syringe, and analyzed by GC-MS (ESI) calcd for C 6 H 9 O 3 PF 2 [M] + Is 198.15. 1 H NMR(400MHz,CDCl 3 )δ:4.20(m,2H),3.72(t,2H),3.54(t,2H),3.06(m,1H),2.20(t,2H); 13 C NMR(101MHz,CDCl 3 ) 81.4,69.7,68.5,68.1,64.0,19.6. The colorless liquid obtained was confirmed to be 1-butynylglycol difluorophosphate. The water content was 42ppm, the acidity was 27ppm and the chloride ion concentration was 18ppm as measured by a Karl moisture meter and a potentiometric titrator.
B. Examples of nonaqueous electrolyte solution
This example provides a nonaqueous electrolyte.
Preparing a non-aqueous electrolyte solution:
in an argon atmosphere glove box (glove box H) 2 O、O 2 Content less than 0.1 ppm), an electrolyte solution was obtained by mixing Ethylene Carbonate (EC), ethyl Methyl Carbonate (EMC), and diethyl carbonate (DEC) at a mass ratio of 30 6 ) Reacting lithium hexafluorophosphate (LiPF) 6 ) The concentration was 1.0mol/L. Lithium difluorophosphate (LiO) is added into the nonaqueous electrolyte solution by taking the total weight of the nonaqueous electrolyte solution as 100 percent 2 PF 2 ) 1,3-Propane Sultone (PS) and vinyl sulfate (DTD) were added to make their mass fractions 1%, while Vinylene Carbonate (VC) and propenyl-1,3-sultone (PES) were added to make their mass fractions 0.5%, to give a control electrolyte sample numbered (1);
in an argon atmosphereEnclosed glove box (glove box H) 2 O、O 2 Content less than 0.1 ppm), an electrolyte solution was obtained by mixing Ethylene Carbonate (EC), ethyl Methyl Carbonate (EMC), and diethyl carbonate (DEC) at a mass ratio of 30 6 ) Reacting lithium hexafluorophosphate (LiPF) 6 ) Lithium difluorophosphate (LiO) was added to the nonaqueous electrolyte solution at a concentration of 1.0mol/L in an amount of 100% by weight based on the total weight of the nonaqueous electrolyte solution 2 PF 2 ) 1,3-Propane Sultone (PS) and vinyl sulfate (DTD) to make their mass fractions 1%, and simultaneously adding Vinylene Carbonate (VC) and propenyl-1,3-sultone (PES) to make their mass fractions 0.5%, and then adding the additives represented by formulae 1 to 32 to make their mass fractions 1%, respectively. The electrolytes (2) to (33) were obtained.
The components contained in the nonaqueous electrolytic solutions of the above nos. (1) to (33) are shown in the following table 1:
TABLE 1 Main Components of nonaqueous electrolyte
Figure BDA0003122683400000281
Figure BDA0003122683400000291
C. Secondary Battery embodiment
Example C1 (comparative example C1)
The present embodiment provides a lithium secondary battery. The lithium secondary battery is assembled as follows:
preparing a positive pole piece:
lithium nickel cobalt manganese (LiNi) 0.8 Co 0.1 Mn 0.1 O 2 NCM811 for short) as a positive electrode active material, and a positive electrode active slurry was obtained by mixing 97% by mass of the positive electrode active material +1.8% by mass of pvdf binder +1.2% by mass of super P conductive carbon black dissolved in N-methylpyrrolidone as a solvent. Then, the positive active slurry is uniformly coated on a current collector aluminum foil with the coating weight of 305g/m 2 And then drying at 80 ℃, performing cold pressing, trimming, cutting into pieces and slitting, drying for 4 hours at 80 ℃ under a vacuum condition, and welding the tabs to obtain the positive plate.
Preparing a negative pole piece:
taking artificial graphite as a negative active material, mixing a negative active slurry with 96% of the negative active material, 2% of CMC/SBR adhesive and 2% of super P conductive carbon black according to the mass ratio, adding the mixture into deionized water, and uniformly stirring to obtain the composite material, and then uniformly coating the negative active slurry on a current collector copper foil, wherein the coating weight is 215g/m 2 And then drying at 85 ℃, performing cold pressing, trimming, cutting into pieces and slitting, drying for 4 hours at 110 ℃ under a vacuum condition, and welding a tab to obtain the negative plate.
Preparing a soft package lithium ion battery:
and (3) manufacturing the positive plate, the negative plate and the PE diaphragm coated with the ceramic into a soft package battery core through a lamination process, baking the soft package battery core at 75 ℃ in vacuum for 10 hours, injecting the electrolyte with the number of (1) into the soft package battery core, standing the soft package battery core for 24 hours after the injection, and performing the working procedures of formation aging, clamping, capacity grading and the like to obtain the soft package battery with the number of (A1).
Examples C2 to C33
The present embodiment provides a lithium secondary battery. The lithium secondary battery is assembled as follows:
except that the electrolytes with the numbers of (2) to (33) are respectively used for injecting liquid into the soft package battery core in the preparation process of the soft package lithium ion battery, standing for 24 hours after the liquid injection, and carrying out the procedures of formation aging, clamping, capacity grading and the like to respectively obtain the numbers of (A2) to (A32) of the soft package battery. The rest of the process was the same as in example C1.
Lithium ion battery performance test
To maintain consistency of the experiment, the same volume of electrolyte was used for all small flexible pouch cells. And then carrying out charge and discharge tests on the prepared small soft-packaged battery cell, and carrying out the following performance tests on the assembled battery cell by using a LAND charge and discharge test system.
In the preparation process of the positive pole piece, nickel cobalt lithium manganate (LiNi) is used 0.8 Co 0.1 Mn 0.1 O 2 For shortNCM 811) ternary material as positive electrode active material soft pouch batteries were made as follows:
1 Normal temperature cycle Performance test
The battery after formation was placed in an oven at a constant temperature of 25 ℃, charged to a voltage of 4.2V using a 1C constant current and constant voltage (CC CV), and cut off to a current of 0.01C, and then discharged to a voltage of 3.0V using a 1C Constant Current (CC). After N cycles of such charge/discharge, the capacity retention rates after the first and Nth cycles were recorded to evaluate the normal temperature cycle performance.
The calculation formula of the capacity retention rate at 25 ℃ for 1C circulation N times is as follows:
the nth cycle capacity retention (%) = (nth cycle discharge capacity/first cycle discharge amount) × 100%.
2. High temperature cycle performance test
The battery after formation was placed in an oven at a constant temperature of 45 ℃, charged to a voltage of 4.2V using a 1C constant current and constant voltage (CC CV), and cut off to a current of 0.01C, and then discharged to a voltage of 3.0V using a 1C Constant Current (CC). After N cycles of such charge/discharge, the capacity retention rates after the first and Nth cycles were recorded to evaluate the high-temperature cycle properties.
The calculation formula of the capacity retention rate at 45 ℃ for 1C circulation N times is as follows:
the nth cycle capacity retention (%) = (nth cycle discharge capacity/first cycle discharge amount) × 100%.
3. Test of Room temperature storage Property
The formed battery cell is charged to a voltage of 4.2V by using a 1C constant current and constant voltage (CC CV) at normal temperature, a cutoff current is 0.01C, the battery cell is discharged to a voltage of 3.0V by using a 1C Constant Current (CC), the initial discharge capacity of the battery is measured, the battery cell is charged to a voltage of 4.2V by using a 1C constant current and constant voltage (CC CV), a cutoff current is 0.01C, the initial thickness of the battery is measured, the battery cell is stored for N days at room temperature, the thickness of the battery cell is measured, the battery cell is discharged to a voltage of 3.0V by using a 1C Constant Current (CC), the retention capacity of the battery cell is measured, the battery cell is charged to a voltage of 4.2V by using a 1C constant current and constant voltage (CC) and a cutoff current of 0.01C, and the recovery capacity is measured.
The calculation formulas of the capacity retention rate and the capacity recovery rate are as follows:
battery capacity retention (%) = retention capacity/initial capacity × 100%;
battery capacity recovery (%) = recovered capacity/initial capacity × 100%;
4.60 ℃ high temperature storage Performance test
The formed battery cell is charged to a voltage of 4.2V by using a 1C constant current and constant voltage (CC CV) at normal temperature, a cutoff current is 0.01C, then the battery cell is discharged to a voltage of 3.0V by using a 1C Constant Current (CC), the initial discharge capacity of the battery is measured, then the battery cell is charged to a voltage of 4.2V by using a 1C constant current and constant voltage (CC CV), a cutoff current is 0.01C, the initial thickness of the battery is measured, then the battery cell is stored for N days at a temperature of 60 ℃, then the thickness of the battery cell is measured, then the battery cell is discharged to a voltage of 3.0V by using a 1C Constant Current (CC), the retention capacity of the battery is measured, then the battery cell is charged to a voltage of 4.2V by using a 1C constant current and constant voltage (CC) and a cutoff current of 0.01C, and then the recovery capacity is measured.
The calculation formulas of the capacity retention rate and the capacity recovery rate are as follows:
battery capacity retention (%) = retention capacity/initial capacity × 100%;
battery capacity recovery rate (%) = recovered capacity/initial capacity × 100%;
specific data are shown in table 2.
Table 2 cell performance test results
Figure BDA0003122683400000301
Figure BDA0003122683400000311
The test results in table 2 show that the use of the chain-like halogenated phosphate ester as an additive in the embodiment of the present invention is beneficial to improving the normal temperature cycle performance, the high temperature cycle performance, the normal temperature storage performance and the high temperature storage performance of the battery, and also has the effect of inhibiting the DCIR growth in the battery storage process. Wherein, the effect of the additive containing unsaturated bonds is better than that of the additive without unsaturated bonds, and the effect of the additive containing alkynyl is better than that of the additive containing alkenyl. The halogenated phosphate group, particularly the difluorophosphate group, is beneficial to reducing impedance, other groups can improve film forming capability or improve wettability, and the comprehensive performance of the battery can be better improved through the synergistic effect of the halogenated group, particularly the difluorophosphate group, and other groups.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (11)

1. A chain-shaped halogenated phosphate ester, wherein the molecular structural formula of the chain-shaped halogenated phosphate ester is shown as the following general formula I:
Figure FDA0003122683390000011
wherein R in the general formula I 1 Any one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a chain alkoxy group having 1 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trimethylsilyl group, a trimethylsiloxy group, a halogen-containing alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, a halogenated phenyl group, a halogenated biphenyl group, a phenol group, an alkyl-containing phenol group, an alkenyl-containing phenol group, an alkynyl-containing phenol group, a nitrile-containing phenol group, a halogenated phenol group and a halogenated naphthol group;
R 2 、R 3 、R 4 、R 5 independently selected from hydrogen atom, halogenAny one of an atom, an aromatic group having 6 to 10 carbon atoms, a halogenated aromatic group having 6 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, a halogenated alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a halogenated alkynyl group having 1 to 10 carbon atoms, a chain alkoxy group having 2 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 20 carbon atoms, an arylsilyl group, a pyridyl group, a thienyl group, a phenol group, an alkyl-containing phenol group, an alkenyl-containing phenol group, an alkynyl-containing phenol group, a nitrile-containing phenol group, a halogenated phenol group, and a halogenated naphthol group;
X 1 、X 2 independently selected from halogen atoms;
n is an integer of 0 to 10.
2. The chain-like halophosphate according to claim 1, characterized in that: the R is 1 To R 5 At least one group of (a) is a chain group, the chain group including a linear group or a branched group; and/or
The R is 1 To R 5 At least one group in (b) is a chain group, and the chain group contains at least one of a halogen atom, an oxygen atom, or an unsaturated bond functional group; and/or
The R is 1 To R 5 Is a halogenated group, said halogenated group being partially or fully substituted; and/or
Said X 1 、X 2 The halogen atom is at least one of fluorine, chlorine, bromine and iodine atoms.
3. The chain-like halogenated phosphate according to claim 2, characterized in that: when the chain-like group contains an unsaturated bond functional group, the unsaturated bond functional group comprises at least one of a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-oxygen double bond, a sulfur-oxygen double bond, a phosphorus-oxygen double bond, an amide, an imide, a sulfonamide, a sulfimide, a phosphoramide, a phosphorus imide, a carboxylic ester, a sulfonic ester and a phosphate ester; and/or
When the chain-like group contains an unsaturated bond functional group, the position of the unsaturated bond functional group is on the inner side of the terminal group or/and the terminal group.
4. The chain-like halogenated phosphate according to claim 1, characterized in that: comprises the following molecular structural formula I 1 To structural formula I 4 At least one of:
Figure FDA0003122683390000021
wherein, the general formula I 2 To I 4 R in (1) 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 Independently selected from one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a chain alkoxy group having 1 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trimethylsilyl group, a trimethylsilyloxy group, a halogen-containing alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, a halogenated phenyl group, a halogenated biphenyl group, a phenol group, an alkyl-containing phenol group, an alkenyl-containing phenol group, an alkynyl-containing phenol group, a nitrile-containing phenol group, a halogenated phenol group and a halogenated naphthol group;
m 1 、m 2 independently an integer of 0 to 10.
5. The chain-like halogenated phosphate according to any one of claims 1 to 4, characterized in that: the chain-like halogenated phosphate ester comprises at least one of compounds shown as formulas 1 to 32 below:
Figure FDA0003122683390000031
Figure FDA0003122683390000041
6. a preparation method of chain-shaped halogenated phosphate ester comprises the following steps:
will be shown in the following structural formula I A A reactant A is shown with the following structural formula I B Carrying out a first substitution reaction on the reactant B in a first non-aqueous solution to generate a chain-shaped halogenated phosphate ester product shown in the following structural formula I;
Figure FDA0003122683390000042
wherein, formula I A And R in I 1 Any one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a chain alkoxy group having 1 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trimethylsilyl group, a trimethylsiloxy group, a halogen-containing alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, a halophenyl group, a halobiphenyl group, a phenol group containing an alkyl group, a phenol group containing an alkenyl group, a phenol group containing an alkynyl group, a phenol group containing a nitrile group, a halophenol group, and a halonaphthol group;
R 2 、R 3 、R 4 、R 5 independently selected from hydrogen atom, halogen atom, aryl group with 6-10 carbon atoms, halogenated aryl group with 6-10 carbon atoms and aryl group with 6-10 carbon atomsAny one of an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, a halogenated alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a halogenated alkynyl group having 1 to 10 carbon atoms, a chain alkoxy group having 2 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 20 carbon atoms, a trialkylsiloxy group having 3 to 20 carbon atoms, an aryl-containing silyl group, an aryl-containing siloxy group, a pyridyl group, a thienyl group, a phenol group, an alkyl-containing phenol group, an alkenyl-containing phenol group, an alkynyl-containing phenol group, a nitrile-containing phenol group, a halogenated phenol group, and a halogenated naphthol group;
X 1 、X 2 、X 3 independently selected from halogen atoms;
n is an integer of 0 to 10.
7. The method of claim 6, wherein: the reactant A and the reactant B are mixed according to a molar ratio of 1: (1-6) in the first non-aqueous solution and carrying out the first substitution reaction; and/or
The mass ratio of the reactant A to the first non-aqueous solution is 1: (1-6); and/or
The temperature of the first substitution reaction is-20 to 40 ℃; and/or
The reactant A comprises the following structural formula A 1 To A 3 At least one of:
Figure FDA0003122683390000051
wherein, the general formula A 1 To A 3 R in (1) 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 Independently selected from hydrogen atoms, halogen atomsOne of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, a chain alkoxy group having 1 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trimethylsilyl group, a trimethylsiloxy group, a halogen-containing alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, a halogenated phenyl group, a halogenated biphenyl group, a phenol group, an alkyl-containing phenol group, an alkenyl-containing phenol group, an alkynyl-containing phenol group, a nitrile-containing phenol group, a halogenated phenol group, and a halogenated naphthol group;
m 1 、m 2 independently an integer of 0 to 10;
and/or
The first substitution reaction comprises the steps of carrying out a front-stage substitution reaction and then carrying out a rear-stage substitution reaction; the former-stage substitution reaction is a substitution reaction stage of gradually adding the reactant A into the first non-aqueous solution containing the reactant B until the addition is finished and then continuing to react for 1-2 hours, and the later-stage substitution reaction is a stage of finishing the addition of the reactant A and continuing to react for 1-2 hours until the substitution reaction is finished; and the temperature of the front-stage substitution reaction is-20-0 ℃; the temperature of the back-stage substitution reaction is 0-40 ℃; and/or
The first non-aqueous solution is selected from at least one of acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N-dimethylformamide, N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous triamide, hexaethylphosphoric triamide, hexaethylphosphorous triamide, dimethyl sulfoxide, diethyl sulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, N-hexane, N-heptane, cyclohexane, benzene, toluene, xylene; and/or
Said X 1 、X 2 When the compound is independently selected from any one of chlorine, bromine and iodine atoms, the method also comprises the following steps:
the chain-shaped halogenated phosphate ester product which is generated by the first substitution reaction and is shown in the structural formula I and fluoride are subjected to a second substitution reaction in a second non-aqueous solution to generate the general formula I 1 A chain difluorophosphate product as shown;
Figure FDA0003122683390000061
8. the method of claim 7, wherein: the chain halogenated phosphate ester product shown in the structural formula I and the fluoride are mixed according to a molar ratio of 1: (1-6) in the second nonaqueous solution and carrying out the second substitution reaction; and/or
The mass ratio of the chain-shaped halogenated phosphate ester product shown in the structural formula I to the second non-aqueous solution is 1: (1-10); and/or
The temperature of the second substitution reaction is-20 to 80 ℃; and/or
The fluoride is at least one of hydrogen fluoride, triethylamine hydrogen fluoride, pyridine hydrogen fluoride, potassium fluoride, sodium fluoride, magnesium fluoride, zinc fluoride, aluminum fluoride, antimony trifluoride, antimony pentafluoride, sulfur tetrafluoride and sulfur hexafluoride; and/or
The second non-aqueous solution is selected from at least one of acetonitrile, propionitrile, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N-dimethylformamide, N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous triamide, hexaethylphosphoric triamide, hexaethylphosphorous triamide, dimethyl sulfoxide, diethyl sulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, N-hexane, N-heptane, cyclohexane, benzene, toluene, xylene.
9. An electrolyte additive, characterized in that: the chain-like halogenated phosphate ester according to any one of claims 1 to 5 or the chain-like halogenated phosphate ester produced by the production method according to any one of claims 6 to 8.
10. An electrolyte comprising an additive, characterized in that: the additive is the electrolyte additive of claim 9, and the mass concentration of the chain-like halogenated phosphate in the electrolyte is 0.1-5%.
11. A secondary battery, characterized in that: comprising the electrolyte of claim 10.
CN202110683234.0A 2021-06-18 2021-06-18 Chain-like halogenated phosphate and preparation method and application thereof Pending CN115490723A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110683234.0A CN115490723A (en) 2021-06-18 2021-06-18 Chain-like halogenated phosphate and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110683234.0A CN115490723A (en) 2021-06-18 2021-06-18 Chain-like halogenated phosphate and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN115490723A true CN115490723A (en) 2022-12-20

Family

ID=84464475

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110683234.0A Pending CN115490723A (en) 2021-06-18 2021-06-18 Chain-like halogenated phosphate and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115490723A (en)

Similar Documents

Publication Publication Date Title
CN111082138B (en) Electrolyte for lithium secondary battery and lithium secondary battery including the same
KR102498193B1 (en) Electrolyte for non-aqueous electrolyte battery and non-aqueous electrolyte battery using the same
KR102451966B1 (en) Electrolyte for Secondary Battery and Lithium Secondary Battery Containing the Same
EP2642579B1 (en) Non-aqueous electrolyte secondary battery
JP2019102459A (en) Electrolyte solution for nonaqueous electrolyte solution battery, and nonaqueous electrolyte battery using the same
WO2019117101A1 (en) Electrolyte solution for nonaqueous electrolyte batteries and nonaqueous electrolyte battery using same
JP2019106362A (en) Electrolyte solution for nonaqueous electrolyte battery, and nonaqueous electrolyte battery using the same
WO2014030684A1 (en) Nonaqueous electrolyte solution and electricity storage device using same
KR20140127741A (en) Additive for electrolyte of lithium battery, organic electrolytic solution comprising the same and Lithium battery using the solution
CN114583270B (en) Lithium ion battery
WO2019111983A1 (en) Electrolyte solution for nonaqueous electrolyte batteries, and nonaqueous electrolyte battery using same
KR20160109663A (en) Organic electrolytic solution and Lithium battery comprising organic electrolyte solution
KR102460822B1 (en) Electrolyte for Lithium Secondary Battery and Lithium Secondary Battery Containing the Same
KR102308599B1 (en) Electrolyte for Lithium Secondary Battery and Lithium Secondary Battery Containing the Same
CN110915052B (en) Heterocyclic sulfonyl fluoride additives for electrolyte compositions of lithium batteries
CN115010758A (en) Bisphthalic acid phosphate derivative, preparation method thereof, electrolyte and secondary battery
CN115010730A (en) Oxalato borate derivative, preparation method thereof, electrolyte and secondary battery
CN115490723A (en) Chain-like halogenated phosphate and preparation method and application thereof
KR102353962B1 (en) Electrolyte for Lithium Secondary Battery and Lithium Secondary Battery Containing the Same
KR20140073654A (en) Electrolyte for Lithium Secondary Battery and Lithium Secondary Battery Containing the Same
KR20220133684A (en) Compounds, non-aqueous electrolyte comprising thereof and lithium secondary battery comprising the same
CN115466286A (en) Chain-like halophosphite and preparation method and application thereof
CN115448945A (en) Halogenated phosphate and preparation method and application thereof
CN114600281A (en) Electrolyte additive for secondary battery, non-aqueous electrolyte for lithium secondary battery comprising same, and lithium secondary battery
CN115448946A (en) Multi-branched halogenated phosphate and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination