CN117321061A - Sodium difluoro oxalate borate, and preparation method and application thereof - Google Patents

Sodium difluoro oxalate borate, and preparation method and application thereof Download PDF

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Publication number
CN117321061A
CN117321061A CN202280033945.6A CN202280033945A CN117321061A CN 117321061 A CN117321061 A CN 117321061A CN 202280033945 A CN202280033945 A CN 202280033945A CN 117321061 A CN117321061 A CN 117321061A
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sodium
reaction
oxalic acid
hydrogen fluoride
difluoroborate
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黄起森
李斌
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CATL Sicong Novel Materials Co Ltd
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CATL Sicong Novel Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)

Abstract

The application relates to a preparation method of sodium difluoro oxalate borate. A method for preparing sodium difluoro oxalate borate, comprising the following steps: mixing anhydrous oxalic acid and triethylamine hydrogen fluoride salt to obtain oxalic acid solution of the triethylamine hydrogen fluoride salt; dissolving sodium tetrafluoroborate in an organic solvent to obtain a sodium tetrafluoroborate solution; mixing and reacting the oxalic acid solution of triethylamine hydrogen fluoride salt and the sodium tetrafluoroborate solution to obtain a reaction solution; purifying sodium difluoro oxalate borate in the reaction liquid. The method solves the problem of serious corrosion of the prior art to equipment, prolongs the service life of the equipment, and obtains higher yield and purity by optimizing the reaction conditions.

Description

Sodium difluoro oxalate borate, and preparation method and application thereof
Technical Field
The application relates to the field of chemical industry, in particular to sodium difluoro oxalate borate, a preparation method and application thereof.
Background
Sodium ion batteries using sodium difluorooxalato borate as an electrolyte salt can obtain superior cycle performance compared with conventional sodium ion batteries using sodium hexafluorophosphate as an electrolyte, and thus sodium difluorooxalato borate is popular in sodium ion secondary batteries.
At present, reports about the preparation process of sodium difluorooxalato borate are wide, but the existing preparation process has the defects. The reaction raw materials of the existing process contain hydrogen fluoride and water at the same time, so that equipment is severely corroded. For this purpose, the present invention is proposed.
Disclosure of Invention
The invention mainly aims to provide a preparation method of sodium difluoro oxalate borate, which solves the problem of serious corrosion to equipment in the prior art, prolongs the service life of the equipment, and simultaneously obtains higher yield and purity by optimizing reaction conditions.
In order to achieve the above object, the present invention provides the following technical solutions.
A method for preparing sodium difluoro oxalate borate, comprising the following steps:
mixing anhydrous oxalic acid and triethylamine hydrogen fluoride salt to obtain oxalic acid solution of the triethylamine hydrogen fluoride salt;
dissolving sodium tetrafluoroborate in an organic solvent to obtain a sodium tetrafluoroborate solution;
mixing and reacting the oxalic acid solution of triethylamine hydrogen fluoride salt and the sodium tetrafluoroborate solution to obtain a reaction solution;
purifying sodium difluoro oxalate borate in the reaction liquid.
The sodium difluorooxalate borate is prepared by adding raw materials in two steps and carrying out two reactions in the same container, and the chemical reaction mechanism is as follows.
H 2 C 2 O 4 +(C 2 H 5 ) 3 N·HF→(C 2 H 5 ) 3 N·H 2 C 2 O 4 +HF
Compared with the prior art, the preparation method provided by the invention has the following advantages:
on one hand, the reactant is changed, and three raw materials of anhydrous oxalic acid, triethylamine hydrogen fluoride salt and sodium tetrafluoroborate are used as the reactant to obtain sodium difluorooxalate borate, so that acid gas is avoided, and corrosion to equipment is reduced;
on the other hand, the anhydrous oxalic acid is solid powder in normal state, so the mass transfer efficiency is low during the reaction; firstly, adding triethylamine hydrogen fluoride salt into anhydrous oxalic acid to form oxalic acid solution, and then mixing with sodium tetrafluoroborate solution for reaction, so that all reactants are guaranteed to be in liquid-liquid reaction, and the reaction efficiency is improved;
in yet another aspect, the three reactants and the organic solvent of the present invention are anhydrous materials, so that no water is required in the whole preparation process, and corrosion of the reaction to equipment is further reduced.
In the present invention, the solution involved in the reaction is generally as homogeneous or clear as the conditions allow, and therefore, the mixing can be promoted by means of heating, stirring or the like in preparing the oxalic acid solution of triethylamine hydrogen fluoride salt and the sodium tetrafluoroborate solution.
The invention further optimizes the dosage ratio of reactants, reaction temperature, purification means and other factors to shorten the reaction time, improve the yield or purity or reduce the cost and the like, as listed below.
In some embodiments, the mixing means of the mixing reaction is: and (3) dropwise adding oxalic acid solution of triethylamine hydrogen fluoride salt into the sodium tetrafluoroborate solution.
In some embodiments, the temperature of the mixing reaction is 50 to 100 ℃, preferably 50 to 70 ℃. Too low a reaction temperature not only reduces yield and purity, but also reduces efficiency; too high a reaction temperature results in too much byproducts, which is detrimental to yield and purity. In some embodiments, the reaction is continued for 4 to 12 hours, preferably 10 to 12 hours, after the completion of the dropwise addition. The reaction yield and purity can be improved by properly extending the reaction time.
In some embodiments, the molar ratio of the organic solvent to the sodium tetrafluoroborate is from 8 to 20:1, preferably from 14 to 20:1. When the molar ratio of the organic solvent to the sodium tetrafluoroborate is in the range of 8-20:1, higher yields and purities can be obtained simultaneously, and the proportions of other reactants can be optimized for the purpose of improving the yields and purities as follows.
In some embodiments, the molar ratio of the triethylamine hydrogen fluoride salt to the anhydrous oxalic acid is 0.5 to 2:1, preferably 1 to 2:1.
In some embodiments, the molar ratio of the sodium tetrafluoroborate to the anhydrous oxalic acid is 1 to 2:1, preferably 1 to 1.2:1.
In some embodiments, the organic solvent is one or more of acetonitrile, propionitrile, acetone, 1, 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, methyl ethyl carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, and ethylene carbonate, preferably at least one of acetonitrile and dimethyl carbonate.
The organic solvents are all solvents with strong polarity, have certain solubility to sodium tetrafluoroborate and sodium difluoroborate, and are completely mutually dissolved with triethylamine hydrogen fluoride salt. When triethylamine hydrogen fluoride salt is added dropwise, oxalic acid and the triethylamine hydrogen fluoride salt in the system generate triethylamine oxalate and hydrogen fluoride, and part of hydrogen fluoride can be dissolved in a polar organic solvent.
In some embodiments, anhydrous oxalic acid and triethylamine hydrogen fluoride salt are also heated and stirred while being mixed to quickly obtain a clear solution.
In some embodiments, the method of purifying comprises: concentrating, and crystallizing at least once. Evaporating concentration, vacuum concentration under reduced pressure and other means can be adopted. Crystallization is performed by selecting a poor solvent that causes precipitation of the product under mild conditions, such as:
in some embodiments, the poor solvent used in the crystallization is a weak polar solvent, preferably one of dichloromethane, dichloroethane, chloroform, carbon tetrachloride, toluene, and cyclohexane, which can be crystallized at about zero degrees, and the operation conditions are mild, wherein dichloromethane or toluene is more preferred.
In some embodiments, the crystallization temperature is maintained at-10 to 5 ℃, and the crystallization duration is preferably more than 2 hours.
In some embodiments, the crystallization is performed more than two times, and between each two times the crystallization further comprises: the extraction is carried out by adding a polar organic solvent, preferably the same as the organic solvent in the sodium tetrafluoroborate solution, more preferably in the same amount.
In some embodiments, during the mixing reaction, further comprising: the tail gas generated by the reaction is absorbed by triethylamine.
In a second aspect the invention provides sodium difluorooxalato borate which is obtainable by the preparation process as described above.
A third aspect of the invention provides an electrolyte comprising sodium difluorooxalato borate as described above.
A fourth aspect of the present invention provides a secondary battery comprising the electrolyte described above.
A fifth aspect of the present invention provides a battery pack including the secondary battery described above.
A sixth aspect of the invention provides an electrical device comprising a secondary battery or battery pack as described above.
In summary, compared with the prior art, the invention at least achieves the following technical effects:
the problem of serious corrosion to equipment in the prior art is solved by changing the types of reactants, and the service life of the equipment is prolonged; meanwhile, higher yield and purity are obtained by optimizing the reaction conditions.
The foregoing description is only an overview of the technical solutions of the present application, and may be implemented according to the content of the specification in order to make the technical means of the present application more clearly understood, and in order to make the above-mentioned and other objects, features and advantages of the present application more clearly understood, the following detailed description of the present application will be given.
Detailed Description
Embodiments of the technical solutions of the present application will be described in detail below. The following examples are only for more clearly illustrating the technical solutions of the present application, and thus are only examples, and are not intended to limit the scope of protection of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application; the terms "comprising" and "having" and any variations thereof in the description and claims of the present application and in the foregoing description are intended to cover non-exclusive inclusions.
In the description of the embodiments of the present application, the technical terms "first," "second," etc. are used merely to distinguish between different objects and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated, a particular order or a primary or secondary relationship. In the description of the embodiments of the present application, the meaning of "plurality" is two or more unless explicitly defined otherwise.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the present application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
In the description of the embodiments of the present application, the term "and/or" is merely an association relationship describing an association object, which means that three relationships may exist, for example, a and/or B may mean: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
In the description of the embodiments of the present application, the term "plurality" refers to two or more (including two), and similarly, "plural sets" refers to two or more (including two), and "plural sheets" refers to two or more (including two).
In the description of the embodiments of the present application, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured" and the like are to be construed broadly and may be, for example, fixedly connected, detachably connected, or integrally formed; or may be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the embodiments of the present application will be understood by those of ordinary skill in the art according to the specific circumstances.
Currently, the application of power batteries is more widespread from the development of market situation. The power battery is not only applied to energy storage power supply systems such as hydraulic power, firepower, wind power and solar power stations, but also widely applied to electric vehicles such as electric bicycles, electric motorcycles, electric automobiles, and the like, and a plurality of fields such as military equipment, aerospace, and the like. With the continuous expansion of the application field of the power battery, the market demand of the power battery is also continuously expanding.
Sodium ion batteries using sodium difluorooxalato borate as an electrolyte salt can obtain superior cycle performance compared with conventional sodium ion batteries using sodium hexafluorophosphate as an electrolyte, and thus sodium difluorooxalato borate is popular in sodium ion secondary batteries. At present, reports about the preparation process of sodium difluorooxalato borate are wide, but the existing preparation process has the defects.
To this end, the invention proposes another method for preparing sodium difluorooxalato borate, which is based on the following reaction principle:
H 2 C 2 O 4 +(C 2 H 5 ) 3 N·HF→(C 2 H 5 ) 3 N·H 2 C 2 O 4 +HF
the method for preparing the sodium difluoro oxalate borate solves the problem of serious equipment corrosion caused by the prior art, prolongs the service life of equipment, and simultaneously obtains higher yield and purity by optimizing the reaction conditions.
The sodium difluoro oxalate borate disclosed by the embodiment of the application is mainly used for a sodium ion battery, and the sodium ion battery can be used in electric devices such as vehicles, ships or aircrafts, and can also be applied to mobile phones, flat plates, notebook computers, electric toys, electric tools, battery cars, ships, spacecrafts and the like. Among them, the electric toy may include fixed or mobile electric toys, such as game machines, electric car toys, electric ship toys, electric plane toys, and the like, and the spacecraft may include planes, rockets, space planes, and spacecraft, and the like.
In a first aspect of the present application, there is provided a method for preparing sodium difluorooxalato borate, comprising the steps of:
mixing anhydrous oxalic acid and triethylamine hydrogen fluoride salt to obtain oxalic acid solution of the triethylamine hydrogen fluoride salt;
dissolving sodium tetrafluoroborate in an organic solvent to obtain a sodium tetrafluoroborate solution;
mixing and reacting the oxalic acid solution of triethylamine hydrogen fluoride salt and the sodium tetrafluoroborate solution to obtain a reaction solution;
purifying sodium difluoro oxalate borate in the reaction liquid.
The raw materials used in the method can be self-made or purchased.
The solution to be involved in the reaction is usually as homogeneous or clear as the conditions allow, and therefore, in preparing the oxalic acid solution of triethylamine hydrogen fluoride salt and the sodium tetrafluoroborate solution, mixing can be promoted by means of heating, stirring, or the like.
The term "mixing" in the above-mentioned method generally means a degree of mixing, and for example, a soluble substance is clarified, and diffusion can be accelerated by heating, stirring, or the like.
The purification in the above method can be, but not limited to, centrifugation, filtration, crystallization, drying, etc. The degree of purification depends on the use of the product. Compared with the prior art, the preparation method provided by the invention has the following advantages:
on one hand, the reactant is changed, and three raw materials of anhydrous oxalic acid, triethylamine hydrogen fluoride salt and sodium tetrafluoroborate are used as the reactant to obtain sodium difluorooxalate borate, so that acid gas is avoided, and corrosion to equipment is reduced;
on the other hand, the anhydrous oxalic acid is solid powder in normal state, so the mass transfer efficiency is low during the reaction; firstly, adding triethylamine hydrogen fluoride salt into anhydrous oxalic acid to form oxalic acid solution, and then mixing with sodium tetrafluoroborate solution for reaction, so that all reactants are guaranteed to be in liquid-liquid reaction, and the reaction efficiency is improved;
in yet another aspect, the three reactants and the organic solvent of the present invention are anhydrous materials, so that no water is required in the whole preparation process, and corrosion of the reaction to equipment is further reduced.
The invention further optimizes the dosage ratio of reactants, reaction temperature, purification means and other factors to shorten the reaction time, improve the yield or purity or reduce the cost and the like, as listed below.
In some embodiments, the mixing means of the mixing reaction is: and (3) dropwise adding oxalic acid solution of triethylamine hydrogen fluoride salt into the sodium tetrafluoroborate solution.
By dripping is meant that the oxalic acid solution of triethylamine hydrogen fluoride salt is dripped into the sodium tetrafluoroborate solution at a certain speed or for a predetermined period of time so as to generate a sufficient amount of (C 2 H 5 ) 3 N·H 2 C 2 O 4 Simultaneously, the problem of excessive byproducts when the two solutions are mixed in a large quantity at one time is avoided.
In some embodiments, the temperature of the mixing reaction is 50 to 100 ℃, preferably 50 to 70 ℃. Too low a reaction temperature not only reduces yield and purity, but also reduces efficiency; too high a reaction temperature results in too much byproducts, which is detrimental to yield and purity. In some embodiments, the reaction is continued for 4 to 12 hours, preferably 10 to 12 hours, after the completion of the dropwise addition. The reaction yield and purity can be improved by properly extending the reaction time.
In general, the reaction is preferably carried out at 50 to 100℃such as 50℃and 60℃and 70℃and 80℃and 90℃and 100℃and more preferably 50 to 70 ℃.
In some embodiments, the molar ratio of the organic solvent to the sodium tetrafluoroborate is from 8 to 20:1, preferably from 14 to 20:1. When the molar ratio of organic solvent to sodium tetrafluoroborate is in the range of 8-20:1, higher yields and purities can be obtained simultaneously, such as 8:1, 9:1, 10:1, 11:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, etc.; a higher ratio range, for example 14 to 20:1, is more preferred.
Also, the proportions of the other reactants may be optimized for improved yield and purity, as follows.
In some embodiments, the molar ratio of the triethylamine hydrogen fluoride salt to the anhydrous oxalic acid is 0.5 to 2:1, e.g., 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.2:1, 1.4:1, 1.5:1, 1.7:1, 1.8:1, 2.0:1, etc., with 1 to 2:1 being preferred.
In some embodiments, the molar ratio of sodium tetrafluoroborate to anhydrous oxalic acid is 1 to 2:1, e.g., 1:1, 1.1:1, 1.2:1, 1.4:1, 1.5:1, 1.7:1, 1.8:1, 2.0:1, etc., preferably 1 to 1.2:1.
In some embodiments, the organic solvent is one or more of acetonitrile, propionitrile, acetone, 1, 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, methyl ethyl carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, and ethylene carbonate, preferably at least one of acetonitrile and dimethyl carbonate.
The organic solvents are all solvents with strong polarity, have certain solubility to sodium tetrafluoroborate and sodium difluoroborate, and are completely mutually dissolved with triethylamine hydrogen fluoride salt. When triethylamine hydrogen fluoride salt is added dropwise, oxalic acid and the triethylamine hydrogen fluoride salt in the system generate triethylamine oxalate and hydrogen fluoride, and part of hydrogen fluoride can be dissolved in a polar organic solvent.
In some embodiments, anhydrous oxalic acid and triethylamine hydrogen fluoride salt are also heated and stirred while being mixed to quickly obtain a clear solution.
In some embodiments, the method of purifying comprises: concentrating, and crystallizing at least once. Evaporating concentration, vacuum concentration under reduced pressure and other means can be adopted. Crystallization is performed by selecting a poor solvent that causes precipitation of the product under mild conditions, such as:
in some embodiments, the poor solvent used in the crystallization is a weak polar solvent, preferably one of dichloromethane, dichloroethane, chloroform, carbon tetrachloride, toluene, and cyclohexane, which can be crystallized at about zero degrees, and the operation conditions are mild, wherein dichloromethane or toluene is more preferred.
In some embodiments, the crystallization temperature is maintained at-10 to 5 ℃, and the crystallization duration is preferably more than 2 hours.
In some embodiments, the crystallization is performed more than two times, and between each two times the crystallization further comprises: the extraction is carried out by adding a polar organic solvent, preferably the same as the organic solvent in the sodium tetrafluoroborate solution, more preferably in the same amount.
The combination of extraction and crystallization can further improve the purity of the product.
If extraction is carried out and concentration is carried out, the concentration of the product can be improved, the crystallization speed is increased, and the solvent capacity is reduced. To this end, in some embodiments, each of the extractions is followed by concentration to turbidity and subsequent crystallization.
In some embodiments, during the mixing reaction, further comprising: the tail gas generated by the reaction is absorbed by triethylamine.
The tail gas refers to hydrogen fluoride, the tail gas can be absorbed to avoid pollutant emission, the forward reaction can be promoted, and the triethylamine hydrogen fluoride salt obtained after absorption can be further used for preparation of the invention, so that raw material recycling is realized.
The sodium difluorooxalate borate prepared by the preparation method provided by the schemes can be used as the electrolyte of the battery, and the electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate.
In some embodiments, the electrolyte is an electrolyte. The electrolyte comprises electrolyte salt and solvent, and sodium difluoro oxalate borate can be prepared by using the process of the invention as the electrolyte salt.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
The positive electrode and the negative electrode sheet may be combined with the above-described electrolyte to form a secondary battery.
Taking a sodium ion secondary battery as an example, the positive plate comprises a positive current collector and a positive film layer arranged on at least one surface of the positive current collector, wherein the positive film layer can comprise the following positive active materials: sodium iron composite oxide (NaFeO) 2 ) Sodium cobalt composite oxide (NaCoO) 2 ) Sodium chromium composite oxide (NaCrO) 2 ) Sodium manganese composite oxide (NaMnO) 2 ) Sodium nickel composite oxide (NaNiO) 2 ) Sodium nickel titanium composite oxide (NaNi) 1/2 Ti 1/2 O 2 ) Sodium nickel manganese composite oxide (NaNi) 1/2 Mn 1/2 O 2 ) Sodium iron manganese composite oxide (Na 2/3 Fe 1/3 Mn 2/3 O 2 ) Sodium nickel cobalt manganese composite oxide (NaNi) 1/3 Co 1/3 Mn 1/3 O 2 ) Sodium iron phosphate compound (NaFePO) 4 ) Sodium manganese phosphate compound (NaMnPO) 4 ) Sodium cobalt phosphate compound (NaCoPO) 4 ) Prussian blue type materials, polyanionic materials (phosphates, fluorophosphates, pyrophosphates, sulfates), etc., but the present application is not limited to these materials, other conventionally known materials that can be used as positive electrode active materials for sodium ion batteries may also be used herein.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining a positive electrode plate after the procedures of drying, cold pressing and the like.
The negative electrode plate comprises a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, wherein the negative electrode film layer comprises a negative electrode active material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode film layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the anode active material may employ an anode active material for a battery, which is well known in the art. As an example, the anode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like. The silicon-based material may be at least one selected from elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxide, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode active material may be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode film layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
In some embodiments, the negative electrode film layer may optionally further include other adjuvants, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode sheet may be prepared by: dispersing the above components for preparing the negative electrode sheet, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and obtaining the negative electrode plate after the procedures of drying, cold pressing and the like.
In some embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability may be used.
In some embodiments, the material of the isolating film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode sheet, the negative electrode sheet, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the secondary battery may include an outer package. The outer package may be used to encapsulate the electrode assembly and electrolyte described above.
In some embodiments, the outer package of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, or the like. The exterior package of the secondary battery may also be a pouch type pouch, for example. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
In some embodiments, the secondary batteries may be assembled into a battery pack, and the number of secondary batteries included in the battery pack may be one or more, and the specific number may be selected by one skilled in the art according to the application and capacity of the battery module.
In addition, the application also provides an electric device, which comprises at least one of the secondary battery, the battery module or the battery pack. The secondary battery, the battery module, or the battery pack may be used as a power source of the power consumption device, and may also be used as an energy storage unit of the power consumption device. The power utilization device may include mobile devices (e.g., cell phones, notebook computers, etc.), electric vehicles (e.g., electric-only vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but is not limited thereto.
As the electricity consumption device, a secondary battery or a battery pack may be selected according to the use requirements thereof.
Based on the concepts described above, the present invention provides the following examples with differences in reactant types or reaction conditions for each example.
Example 1
In the first step, a 1L autoclave lined with polytetrafluoroethylene was completely dried, 66g (0.6 mol) of sodium tetrafluoroborate was added, 288g (7 mol) of acetonitrile was then added, and after nitrogen substitution, stirring was started and the temperature was raised to 50 ℃. In addition, 45g (0.5 mol) of anhydrous oxalic acid and 80.5g (0.5 mol) of triethylamine hydrogen fluoride salt are added into a 500ml tetrafluoro reaction kettle, the mixture is stirred until the mixture is completely dissolved, a 1L high-pressure reaction kettle is heated to 70 ℃, then triethylamine hydrogen fluoride salt oxalic acid solution is slowly added dropwise, and generated tail gas is absorbed by triethylamine (the tail gas can be recycled later).
And secondly, continuously stirring the reaction kettle at 70 ℃ for 10 hours after the dripping is finished, stopping reacting, vacuum concentrating the reaction liquid at 60 ℃, stopping when the reaction liquid is not reduced, cooling to room temperature, adding an equal volume of dichloromethane, continuously cooling to-10 ℃ for 2 hours, filtering the mixture, and drying filter residues at 90 ℃ in vacuum to obtain crude sodium difluoroborate.
Thirdly, adding the dried crude sodium difluoroborate into 361g of acetonitrile, stirring for 2 hours at room temperature, filtering, concentrating the filtrate in vacuum at 60 ℃ until the filtrate is slightly turbid, cooling to room temperature, adding an equal volume of Dichloromethane (DCM), continuously cooling to-10 ℃ and maintaining for 2 hours for crystallization, filtering the mixture, and drying the filter residue at 90 ℃ under reduced pressure to obtain 74.8g of sodium difluoroborate with the purity of 99.25% and the yield of 92.8%.
Examples 2 to 3
The procedure was the same as in example 1, except that the molar amounts of sodium tetrafluoroborate were 0.5mol and 1mol, respectively.
Examples 4 to 5
The procedure was the same as in example 1, except that the molar amounts of triethylamine hydrogen fluoride salt were 0.25 and 1mol, respectively.
Examples 6 to 7
The procedure was the same as in example 1, except that the molar amounts of acetonitrile as an organic solvent were 4.8 and 12mol, respectively.
Examples 8 to 9
The procedure was as in example 1, except that the reaction times were 4 hours and 12 hours, respectively.
Examples 10 to 11
The procedure was the same as in example 1, except that the reaction temperatures were 50℃and 70℃respectively.
Example 12
The procedure was the same as in example 1 except that the organic solvent was changed to 630g (7 mol) of dimethyl carbonate.
Example 13
The procedure was as in example 1, except that the weakly polar reagent was replaced with toluene.
Comparative examples 1 to 2
The procedure was the same as in example 1, except that the molar amounts of sodium tetrafluoroborate were 0.4 and 1.2mol, respectively.
Comparative examples 3 to 4
The procedure was the same as in example 1, except that the molar amounts of triethylamine hydrogen fluoride salt were 0.2 and 1.6mol, respectively.
Comparative examples 5 to 6
The procedure was the same as in example 1, except that the molar amounts of acetonitrile as an organic solvent were 4.2 and 12.6mol, respectively.
Comparative examples 7 to 8
The procedure was as in example 1, except that the reaction times were 3 hours and 14 hours, respectively.
Comparative examples 9 to 10
The procedure was the same as in example 1, except that the reaction temperatures were 40℃and 110℃respectively.
Comparative example 11
Unlike example 1 in which triethylamine hydrogen fluoride salt oxalic acid solution and sodium tetrafluoroborate solution were mixed, the "slow dropping" was replaced with: the triethylamine hydrogen fluoride salt oxalic acid solution is all introduced into the high-pressure reaction kettle at one time.
Comparative example 12
The difference from example 1 is that the third step is different from the amount of acetonitrile added to the crude product, and the addition amounts are 288g as in the first step.
The reaction conditions and results of all the above examples and comparative examples are shown in the following table.
Note that: the number "example" in the table represents an example, and "pair" represents a comparative example.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the embodiments, and are intended to be included within the scope of the claims and description. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.

Claims (20)

1. The preparation method of the sodium difluoro oxalate borate is characterized by comprising the following steps:
mixing anhydrous oxalic acid and triethylamine hydrogen fluoride salt to obtain oxalic acid solution of the triethylamine hydrogen fluoride salt;
dissolving sodium tetrafluoroborate in an organic solvent to obtain a sodium tetrafluoroborate solution;
mixing and reacting the oxalic acid solution of triethylamine hydrogen fluoride salt and the sodium tetrafluoroborate solution to obtain a reaction solution;
purifying sodium difluoro oxalate borate in the reaction liquid.
2. The method for preparing sodium difluoroborate as claimed in claim 1, wherein the mixing mode of the mixing reaction is as follows: and (3) dropwise adding oxalic acid solution of triethylamine hydrogen fluoride salt into the sodium tetrafluoroborate solution.
3. The process for the preparation of sodium difluorooxalato borate according to claim 1 or 2, wherein the temperature of the mixing reaction is 50-100 ℃, preferably 50-70 ℃.
4. The method for preparing sodium difluoroborate according to claim 2, wherein the reaction is continued for 4 to 12 hours, preferably 10 to 12 hours after the completion of the dropwise addition.
5. The method of preparing sodium difluoroborate according to claim 1 or 2 or 4, wherein the molar ratio of the organic solvent to the sodium tetrafluoroborate is 8-20:1, preferably 14-20:1.
6. The method for producing sodium difluoroborate according to claim 1 or 2 or 4, wherein the molar ratio of the triethylamine hydrogen fluoride salt to the anhydrous oxalic acid is 0.5 to 2:1, preferably 1 to 2:1.
7. The method of preparing sodium difluoroborate according to claim 1 or 2 or 4, wherein the molar ratio of sodium tetrafluoroborate to anhydrous oxalic acid is 1-2:1, preferably 1-1.2:1.
8. The method for preparing sodium difluoroborate according to claim 1, wherein the organic solvent is one or more of acetonitrile, propionitrile, acetone, 1, 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, methyl ethyl carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, and ethylene carbonate, preferably at least one of acetonitrile and dimethyl carbonate.
9. The method for producing sodium difluorooxalato borate according to claim 1, wherein the anhydrous oxalic acid and the triethylamine hydrogen fluoride salt are further heated and stirred when mixed.
10. The method for preparing sodium difluorooxalato borate according to claim 1, wherein the purification method comprises: concentrating, and crystallizing at least once.
11. The method for preparing sodium difluoroborate as claimed in claim 10, wherein the poor solvent used in the crystallization is a weak polar solvent, and the weak polar solvent is preferably one of dichloromethane, dichloroethane, chloroform, carbon tetrachloride, toluene and cyclohexane, preferably dichloromethane or toluene.
12. The method for producing sodium difluoroborate according to claim 11, wherein the crystallization temperature is maintained at-10 to 5 ℃, and the crystallization time is preferably 2 hours or longer.
13. The method for producing sodium difluorooxalato borate according to claim 11, wherein crystallization is performed twice or more, and further comprising between each two times of crystallization: the extraction is carried out by adding a polar organic solvent, preferably the same as the organic solvent in the sodium tetrafluoroborate solution, more preferably in the same amount.
14. The method for preparing sodium difluoroborate according to claim 13, wherein the sodium difluoroborate is further concentrated to turbidity after each extraction and then subjected to the next crystallization.
15. The method for producing sodium difluoroborate according to any one of claims 1 or 2 or 4 or 8 to 14, further comprising, during the mixing reaction: the tail gas generated by the reaction is absorbed by triethylamine.
16. Sodium difluorooxalato borate, characterized in that it is obtained by the preparation process according to any one of claims 1 to 15.
17. An electrolyte comprising the sodium difluorooxalato borate of claim 16.
18. A secondary battery comprising the electrolyte of claim 17.
19. A battery pack comprising the secondary battery according to claim 18.
20. An electric device comprising the secondary battery according to claim 18 or the battery pack according to claim 19.
CN202280033945.6A 2022-06-24 2022-06-24 Sodium difluoro oxalate borate, and preparation method and application thereof Pending CN117321061A (en)

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US6849752B2 (en) * 2001-11-05 2005-02-01 Central Glass Company, Ltd. Process for synthesizing ionic metal complex
CN103483367B (en) * 2013-09-17 2016-03-23 东莞市凯欣电池材料有限公司 The preparation method of difluoro oxalic acid boric acid metal salt
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