CN117133986A - Electrolyte, gel electrolyte and preparation method thereof - Google Patents

Electrolyte, gel electrolyte and preparation method thereof Download PDF

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Publication number
CN117133986A
CN117133986A CN202311069578.8A CN202311069578A CN117133986A CN 117133986 A CN117133986 A CN 117133986A CN 202311069578 A CN202311069578 A CN 202311069578A CN 117133986 A CN117133986 A CN 117133986A
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electrolyte
lithium
phosphate
monomer
salt
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陈东
张薇
李宇航
皮智超
端木凡昌
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Dongfeng Motor Corp
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Dongfeng Motor Corp
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Priority to CN202311069578.8A priority Critical patent/CN117133986A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

The application relates to the technical field of solid-state lithium battery preparation, in particular to electrolyte, gel electrolyte and a preparation method thereof. The electrolyte comprises the following components: an organic solvent and a lithium salt; wherein the organic solvent comprises the following components: phosphate esters and fluorocarbonates; the lithium salt comprises the following components: lithium ion conductive salts and SEI film forming salts. The compatibility of the phosphate and the negative electrode is realized by adjusting solvation and interface structure; the Li+ solvation structure is regulated by adding fluorocarbonate into the phosphate solvent, the number of solvent molecules in the solvation structure is reduced, and the number of anions in the solvation structure is increased, so that the reduction resistance of the solvent is increased; and SEI film forming salt is added into the electrolyte to adjust SEI film components, so that a better SEI film is formed on the surface of the negative electrode.

Description

Electrolyte, gel electrolyte and preparation method thereof
Technical Field
The application relates to the technical field of solid-state lithium battery preparation, in particular to electrolyte, gel electrolyte and a preparation method thereof.
Background
Solid-state lithium batteries are the ultimate solution for power batteries due to their high energy density and high safety. In-situ curing is an important process for solid-state batteries, and polymerization curing is performed by heating and the like after monomer and initiator are added into the traditional carbonate electrolyte. Although the safety is greatly improved compared with that of a liquid lithium battery, inflammable carbonate is still a constituent component of a solid electrolyte, and risks such as thermal runaway, combustion, explosion and the like caused by high temperature and internal short circuit still exist. The phosphate compound has the potential of replacing carbonate compounds in the traditional electrolyte because of the characteristics of low viscosity, higher dielectric constant, low cost, incombustibility and the like. However, phosphate electrolytes are not compatible with commonly used negative electrodes such as graphite, silicon carbon, lithium metal, and the like. Although the former preliminarily solves the problem of compatibility with the negative electrode by designing the high-concentration phosphate electrolyte, the high-concentration electrolyte has high viscosity and low cost, is difficult to apply in a large scale, and still has the problems of leakage, narrow voltage window, difficulty in effectively inhibiting lithium dendrite and the like.
Disclosure of Invention
The application provides electrolyte, gel electrolyte and a preparation method thereof, which are used for solving the technical problem that the existing phosphate electrolyte is difficult to realize compatibility with a battery cathode.
In a first aspect, the present application provides an electrolyte comprising the following components: an organic solvent and a lithium salt; wherein,
the organic solvent comprises the following components: phosphate esters and fluorocarbonates; the lithium salt comprises the following components: lithium ion conductive salts and SEI film forming salts.
Optionally, the phosphate comprises at least one of: trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, and tripentyl phosphate; and/or the number of the groups of groups,
the fluorocarbonate is methyl trifluoroethyl carbonate.
Optionally, the lithium ion conductive salt is one of the following: lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate; and/or the number of the groups of groups,
the SEI film forming salt is one of the following: lithium bisoxalato borate, lithium difluorooxalato borate, lithium bisdifluorosulfonimide, and lithium bistrifluoromethylsulfonimide.
Optionally, the molar ratio of the organic solvent to the lithium salt is (6-9): 1.
Optionally, the molar ratio of the phosphate to the fluorocarbonate is (3-6): 10-13.
Optionally, the molar ratio of the lithium ion conductive salt to the SEI film-forming salt is (2-3): 2-3.
In a second aspect, the present application provides a gel electrolyte comprising: a monomer, an initiator and an electrolyte according to any one of the embodiments of the first aspect.
Optionally, the monomer is a composition of two or more acrylic compounds, and the initiator is an azo compound.
Optionally, the monomers include a first monomer and a second monomer; wherein,
the first monomer is one of the following: polyethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate,
the second monomer is one of the following: methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate;
the mol ratio of the first monomer to the second monomer is (2-3): 2-3.
In a third aspect, the present application provides a method for preparing a gel electrolyte according to any one of the embodiments of the second aspect, the method comprising:
and adding a monomer and an initiator into the electrolyte, and heating to obtain the gel electrolyte.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the electrolyte provided by the embodiment of the application, the compatibility of phosphate and a negative electrode is realized by adjusting solvation and interface structures; in the aspect of regulating solvation and interfacial structure, the fluoro-carbonate is added into the phosphate solvent to regulate Li+ solvation structure, so that the number of solvent molecules in the solvation structure is reduced, the number of anions in the solvation structure is increased, and the reduction resistance of the solvent is improved; and SEI film forming salt is added into the electrolyte to adjust SEI film components, so that a better SEI film is formed on the surface of the negative electrode. The mixed solvent and the double salt are used, so that the electrolyte is perfectly compatible with negative electrodes such as graphite, silicon carbon, lithium metal and the like, and the electrolyte has incombustible characteristics, so that the battery has extremely high safety.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a schematic flow chart of a preparation method of a gel electrolyte according to an embodiment of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present specification, the terms "include", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one (a) or the like refer to any combination of these items, including any combination of single item(s) or plural items (a). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of 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, c may be single or multiple, respectively.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
In a first aspect, the present application provides an electrolyte comprising the following components: an organic solvent and a lithium salt; wherein,
the organic solvent comprises the following components: phosphate esters and fluorocarbonates; the lithium salt comprises the following components: lithium ion conductive salts and SEI film forming salts.
In the embodiment of the application, the electrolyte realizes the compatibility of phosphate and a negative electrode under the condition of conventional low lithium salt concentration by adjusting solvation and interface structures; in the aspect of regulating solvation and interfacial structure, the fluoro-carbonate is added into the phosphate solvent to regulate Li+ solvation structure, so that the number of solvent molecules in the solvation structure is reduced, the number of anions in the solvation structure is increased, and the reduction resistance of the solvent is improved; and SEI film forming salt is added into the electrolyte to adjust SEI film components, so that a better SEI film is formed on the surface of the negative electrode.
In the electrolyte, the solvent consists of phosphate with stronger coordination ability with lithium ions and fluorocarbonate with weaker coordination ability, and the reduction stability of the electrolyte is improved by introducing a low coordination solvent into a high coordination solvent. The lithium salt consists of a lithium ion conductive salt and an SEI film-forming salt, and the solvent composition is changed to adjust the solvation structure, and meanwhile, the interface of the cathode is further optimized. The mixed solvent and the double salt are used, so that the electrolyte is perfectly compatible with negative electrodes such as graphite, silicon carbon, lithium metal and the like, and the electrolyte has incombustible characteristics, so that the battery has extremely high safety.
In some embodiments, the phosphate comprises at least one of the following: trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, and tripentyl phosphate; and/or the number of the groups of groups,
the fluorocarbonate is methyl trifluoroethyl carbonate.
In the embodiment of the application, one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate and tripentyl phosphate are selected as phosphate, and the most commonly used incombustible solvent is easy to obtain, low in price and good in incombustible characteristic, but has higher polarity and is extremely easy to coordinate with Li+; methyl trifluoroethyl carbonate is selected as fluorocarbonate, is a low-polarity solvent, has good incombustible property, can be mixed with phosphate in any proportion, and reduces the polarity of the solvent after being mixed; the most commonly used fluorocarbonates are readily available and are less expensive than other fluorocarbonates.
In some embodiments, the lithium ion conductive salt is one of: lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate; and/or the number of the groups of groups,
the SEI film forming salt is one of the following: lithium bisoxalato borate, lithium difluorooxalato borate, lithium bisdifluorosulfonimide, and lithium bistrifluoromethylsulfonimide.
In the embodiment of the application, one of lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate and lithium tetrafluoroate is selected as the lithium ion conductive salt, so that the lithium ion conductive salt is a common lithium ion conductive salt, and has wide sources and low price; one of lithium bisoxalato borate, lithium difluorooxalato borate, lithium bisdifluorosulfimide and lithium bistrifluoromethylsulfonyl imide is selected as SEI film forming salt, and an excellent SEI layer can be formed on the surface of a negative electrode after the SEI film forming salt is matched with a solvent in the system, so that the reduction decomposition of the solvent is inhibited, and the desolvation difficulty of Li < + > is reduced.
In some embodiments, the molar ratio of the organic solvent to the lithium salt is (6-9): 1.
In the embodiment of the application, the molar ratio of the organic solvent to the lithium salt is controlled, and the ratio is in the range of low-concentration lithium salt, so that the cost is low, and the large-scale application is facilitated. If the molar ratio of the organic solvent to the lithium salt is too large, the ionic conductivity of the electrolyte is insufficient to a certain extent, and the effective release of the battery capacity is affected; if the molar ratio of the organic solvent to the lithium salt is too small, the organic solvent becomes a high-concentration electrolyte to a certain extent, and the preparation cost of the electrolyte and the subsequent gel electrolyte is increased. Specifically, the molar ratio of the organic solvent to the lithium salt may be 6: 1. 7: 1. 8: 1. 9:1, etc.
In some embodiments, the molar ratio of the phosphate to the fluorocarbonate is (3-6): 10-13.
In the embodiment of the application, the molar ratio of the phosphate to the fluorocarbonate is controlled, and the compatibility and incombustibility of the cathode are balanced. If the molar ratio of the phosphate to the fluorocarbonate is too large, the polarity of the solvent is increased to some extent, and the reduction resistance of the solvent and the desolvation capacity of Li+ are reduced; if the molar ratio of the phosphate to the fluorocarbonate is too small, the incombustibility of the electrolyte is impaired to some extent, and the preparation cost of the electrolyte is increased. Specifically, the molar ratio of the phosphate to the fluorocarbonate may be 3: 13. 6: 13. 1: 2. 5: 13. 6: 11. 3:10, etc.
In some embodiments, the molar ratio of the lithium ion conductive salt to the SEI film-forming salt is (2-3): 2-3.
In the embodiment of the application, the lithium ion conductive salt and SEI film forming salt are controlled, so that the film forming quality of the negative electrode SEI film is good. If the molar ratio of the lithium ion conductive salt to the SEI film forming salt is too large, the negative electrode SEI film forming quality is poor to a certain extent, and the compatibility with a negative electrode is reduced; if the molar ratio of the lithium ion conductive salt to the SEI film-forming salt is too small, the ionic conductivity of the electrolyte is slightly reduced to a certain extent, and the preparation cost of the electrolyte is increased. Specifically, the molar ratio of the phosphate to the fluorocarbonate may be 2: 3. 3: 2. 6: 5. 6: 7. 3: 4. 1:1, etc.
In a second aspect, the present application provides a gel electrolyte comprising: a monomer, an initiator and an electrolyte according to any one of the embodiments of the first aspect.
In some embodiments, the monomer is a combination of two or more acrylic compounds and the initiator is an azo compound.
The mass fraction of the acrylic ester compound in the electrolyte is 2% -5%, and the mass fraction of the azo compound in the electrolyte is 0.1% -0.25%.
In some embodiments, the monomers include a first monomer and a second monomer; wherein,
the first monomer is one of the following: polyethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate,
the second monomer is one of the following: methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate;
the mol ratio of the first monomer to the second monomer is (2-3): 2-3.
In the embodiment of the application, one of polyethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate is selected as the first monomer, and the first monomer belongs to a polyfunctional monomer, has strong gel capability and small addition amount, but has strong gel rigidity; one of methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate is selected as the second monomer, and the second monomer belongs to a single-functionality monomer, and has weak gel capability and high flexibility.
The molar ratio of the first monomer to the second monomer is controlled, and the added amount and the rigidity and flexibility of the gel are balanced. If the molar ratio of the first monomer to the second monomer is too large, the gel has stronger rigidity to a certain extent, which is unfavorable for ion transmission and production and preparation; if the molar ratio of the first monomer to the second monomer is too small, the amount of the monomer added will be increased to some extent, and the gel will be too soft, which is disadvantageous for the maintenance of the micro-electrolyte. Specifically, the molar ratio of the phosphate to the fluorocarbonate may be 2: 3. 3: 2. 6: 5. 6: 7. 3: 4. 1:1, etc.
Further, the initiator may be one of azobisisobutyronitrile, azobisisovaleronitrile, and azobisisoheptonitrile.
In a third aspect, the present application provides a method for preparing a gel electrolyte, referring to fig. 1, for preparing a gel electrolyte according to any one of the embodiments of the second aspect, the method includes:
s1, adding a monomer and an initiator into the electrolyte, and heating to obtain the gel electrolyte.
In the embodiment of the application, the gel electrolyte formed after the double-salt mixed phosphate electrolyte is polymerized and solidified not only inherits the incombustible property of the electrolyte, but also presents gel state, avoids the risks of leakage, volatilization and the like of the electrolyte, effectively inhibits the growth of lithium dendrites, and plays the high safety advantage to the greatest extent when the gel electrolyte is used in a solid-state battery. The preparation method is simple to operate, low in cost and very suitable for large-scale production and application.
The heating temperature is 50-80 ℃, the heating time is 3-10 h, and the energy consumption and the gel curing degree are balanced. If the heating temperature is too high or the heating time is too long, the energy consumption is increased to a certain extent, and the performance of the electrode material in the battery is possibly adversely affected; if the heating temperature is too low or the heating time is too short, the electrolyte is insufficient in solidification degree to a certain extent, and the content of the remained liquid electrolyte is too high.
The preparation method of the gel electrolyte is realized based on the gel electrolyte, and specific components of the gel electrolyte can refer to the embodiment, and because the preparation method of the gel electrolyte adopts part or all of the technical schemes of the embodiment, the preparation method at least has all the beneficial effects brought by the technical schemes of the embodiment, and the description is omitted herein.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
The molar ratio of trimethyl phosphate to methyl trifluoroethyl carbonate is 3:13 as a solvent, the molar ratio of lithium hexafluorophosphate to lithium difluorooxalato borate is 5:5 as lithium salt, and the double salt mixed phosphate electrolyte is formed by fully mixing and dissolving according to the molar ratio of the solvent to the lithium salt being 8:1. Adding 5% of monomer in mass fraction, wherein the mass ratio of pentaerythritol triacrylate to propyl acrylate in the monomer is 5:5, and adding 0.2% of azodiisobutyronitrile in mass fraction. And then placing the electrolyte into heating equipment to heat for 4 hours at 80 ℃ to obtain the ultra-high safety gel electrolyte for the solid-state battery.
Example 2
The molar ratio of triethyl phosphate to methyl trifluoroethyl carbonate is 6:10 as a solvent, the molar ratio of lithium hexafluorophosphate to lithium bisoxalato borate is 6:4 as lithium salt, and the double salt mixed phosphate electrolyte is formed by fully mixing and dissolving according to the molar ratio of the solvent to the lithium salt being 8:1. 3% of monomer is added into the electrolyte, the mass ratio of pentaerythritol tetraacrylate to butyl acrylate in the monomer is 6:4, and 0.1% of azodiisobutyronitrile is added. And then placing the electrolyte into heating equipment to heat for 10 hours at 50 ℃ to obtain the ultra-high safety gel electrolyte for the solid-state battery.
Example 3
The molar ratio of trimethyl phosphate, tripropyl phosphate and methyl trifluoroethyl carbonate is 3:3:10 as a solvent, the molar ratio of lithium tetrafluoroborate to lithium bisdifluorosulfimide is 4:6 as lithium salt, and the double salt mixed phosphate electrolyte is formed by fully mixing and dissolving according to the molar ratio of the solvent to the lithium salt being 6:1. 3.5% of monomer is added into the electrolyte, the mass ratio of pentaerythritol tetraacrylate to methyl acrylate in the monomer is 5:5, and 0.15% of azodiisoheptanenitrile is added. And then placing the electrolyte into heating equipment to heat at 60 ℃ for 8 hours, thus obtaining the ultra-high safety gel electrolyte for the solid-state battery.
Comparative example 1
And taking the triethyl phosphate and the methyl trifluoroethyl carbonate as a solvent in a molar ratio of 6:10, taking lithium hexafluorophosphate as a lithium salt, and fully mixing and dissolving the lithium hexafluorophosphate and the lithium salt according to a molar ratio of 8:1 to form the double-salt mixed phosphate electrolyte. 3% of monomer is added into the electrolyte, the mass ratio of pentaerythritol tetraacrylate to butyl acrylate in the monomer is 6:4, and 0.1% of azodiisobutyronitrile is added. And then placing the electrolyte into heating equipment to heat for 10 hours at 50 ℃ to obtain the ultra-high safety gel electrolyte for the solid-state battery.
In the button cell, the gel electrolyte prepared in the methods of examples 1 to 3 was used as a battery electrolyte, and Li/graphite half cell and Li/LiNi 0.8 Co 0.1 Mn 0.1 O 2 The specific capacity and cycle performance of the full cell are shown in table 1.
Table 1 results of specific capacity and cycle performance of the battery
The compatibility of the gel electrolyte prepared by the test of the half cell and the full cell with electricity is verified by the test of the table 1, and the gel electrolyte has the advantages of ultra-high safety and good electrochemical performance, and can be applied to all-solid-state batteries; while the comparative examples do not employ the inventive solution, the battery performance is inferior to the examples.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. An electrolyte, characterized in that the electrolyte comprises the following components: an organic solvent and a lithium salt; wherein,
the organic solvent comprises the following components: phosphate esters and fluorocarbonates; the lithium salt comprises the following components: lithium ion conductive salts and SEI film forming salts.
2. The electrolyte of claim 1 wherein the phosphate comprises at least one of: trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, and tripentyl phosphate; and/or the number of the groups of groups,
the fluorocarbonate is methyl trifluoroethyl carbonate.
3. The electrolyte of claim 1, wherein the lithium ion conductive salt is one of: lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate; and/or the number of the groups of groups,
the SEI film forming salt is one of the following: lithium bisoxalato borate, lithium difluorooxalato borate, lithium bisdifluorosulfonimide, and lithium bistrifluoromethylsulfonimide.
4. The electrolyte according to any one of claims 1 to 3, wherein the molar ratio of the organic solvent to the lithium salt is (6 to 9): 1.
5. The electrolyte according to any one of claims 1 to 3, wherein the molar ratio of the phosphate to the fluorocarbonate is (3 to 6): 10 to 13.
6. The electrolyte according to any one of claims 1 to 3, wherein the molar ratio of the lithium ion conductive salt to the SEI film-forming salt is (2 to 3): 2 to 3.
7. A gel electrolyte, characterized in that the gel electrolyte comprises: a monomer, an initiator, and the electrolyte according to any one of claims 1 to 6.
8. The gel electrolyte according to claim 7, wherein the monomer is a combination of two or more kinds of acrylic acid ester compounds, and the initiator is an azo compound.
9. The gel electrolyte of claim 8, wherein the monomers comprise a first monomer and a second monomer; wherein,
the first monomer is one of the following: polyethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate,
the second monomer is one of the following: methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate;
the mol ratio of the first monomer to the second monomer is (2-3): 2-3.
10. A method for producing the gel electrolyte according to any one of claims 7 to 9, comprising:
and adding a monomer and an initiator into the electrolyte, and heating to obtain the gel electrolyte.
CN202311069578.8A 2023-08-24 2023-08-24 Electrolyte, gel electrolyte and preparation method thereof Pending CN117133986A (en)

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CN117543075A (en) * 2024-01-10 2024-02-09 四川新能源汽车创新中心有限公司 Solid electrolyte and preparation method thereof, lithium battery and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117543075A (en) * 2024-01-10 2024-02-09 四川新能源汽车创新中心有限公司 Solid electrolyte and preparation method thereof, lithium battery and preparation method thereof
CN117543075B (en) * 2024-01-10 2024-03-26 四川新能源汽车创新中心有限公司 Solid electrolyte and preparation method thereof, lithium battery and preparation method thereof

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