CN111211355A - High-voltage lithium ion battery electrolyte additive, electrolyte and battery thereof - Google Patents
High-voltage lithium ion battery electrolyte additive, electrolyte and battery thereof Download PDFInfo
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- CN111211355A CN111211355A CN202010044170.5A CN202010044170A CN111211355A CN 111211355 A CN111211355 A CN 111211355A CN 202010044170 A CN202010044170 A CN 202010044170A CN 111211355 A CN111211355 A CN 111211355A
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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
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- 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
Abstract
The invention discloses a high-voltage lithium ion battery electrolyte additive, electrolyte and a battery thereof, wherein the high-voltage lithium ion battery electrolyte additive is an acetylene silicon-based compound, silicon is used as a stable group for stabilizing an ethynyl functional group, so that the battery deterioration caused by the thorough oxidative decomposition under high voltage is avoided, and the acetylene silicon-based compound forms a high-electron conductance (RC) on the surfaces of a positive electrode and a negative electrode through electrochemical polymerization2Si) n, and Si is used as a core group, and the decomposition product can form a stable interface film on the surfaces of positive and negative electrodes at high voltage, thereby inhibiting the decomposition of the electrolyte, reducing the impedance of the battery, and improving the cycle performance of the high voltage battery. And has the advantages of small addition amount, low cost, simple synthesis and the like, and is easy to synthesizeThe method is realized and is beneficial to wide popularization and application.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-voltage lithium ion battery electrolyte additive, electrolyte and a battery thereof.
Background
The development of new energy automobiles is regarded as an important development strategy for transformation and upgrading of the automobile industry in China. In order to encourage the development of new energy vehicles, relevant ministries and governments at all levels have issued a series of new energy vehicle subsidy policies. The global new energy automobile sales volume in 2017 is about 140 thousands, the Chinese new energy automobile sales volume is about 77.7 thousands, and the percentage of the new energy automobile sales volume exceeds 50%. In 2018, more than 180 thousands of new energy automobiles are sold globally, and the Chinese market accounts for 55 percent. The global new energy automobile sales volume is expected to reach 350 million by 2020, and China becomes the largest global new energy automobile production base and sales market.
The current commercial power battery anode material is mainly a ternary material of lithium iron phosphate and nickel cobalt lithium manganate, however, the lithium iron phosphate has the problem of low specific energy, the ternary material contains more cobalt and is limited by deficient cobalt resources and high cost, the current ternary power battery has high cost, and with the continuous subsidy of governments, the development of new energy automobiles is greatly challenged, so that the development of cobalt-free anode materials with high specific energy is imperative.
The lithium nickel manganese oxide with a spinel structure is a novel high-voltage positive electrode material, the platform voltage is 4.7V (vs. Li/Li +), the theoretical specific capacity is 146.7mAh/g, the reversible specific capacity is 133mAh/g, and the energy density is as high as 650 Wh/kg.
The chemical formula of the lithium nickel manganese oxide is LiNi0.5Mn1.5O4-δThe composite material is a cobalt-free anode material, adopts Ni and Mn elements with rich resources and low cost, has the advantage of low cost, and can meet the sustainable development of new energy automobiles. Meanwhile, the spinel high-voltage lithium nickel manganese oxide has a three-dimensional lithium ion channel and good rate capability, and can meet the requirement of rapid charge and discharge of a power battery.
The plateau voltage of the lithium nickel manganese oxide reaches 4.7V, is about 40 percent higher than that of lithium iron phosphate and about 25 percent higher than that of ternary lithium manganese oxide, and the specific energy can be improved on the basis of the whole battery module. Meanwhile, the lithium nickel manganese oxide is in a complete lithium removal state in the charging process, the problem of lithium separation does not exist in the overcharging process, and the safety is high. Therefore, the lithium nickel manganese oxide is an ideal next-generation cathode material of a power battery with low cost and high specific energy.
However, under high voltage, the interface of lithium nickel manganese oxide and the electrolyte can generate side reaction, and the decomposition product of the electrolyte can form a thick dielectric layer on the surfaces of the positive electrode and the negative electrode, which causes the increase of battery impedance and the deterioration of battery cycle performance. Therefore, it is necessary to develop a high-voltage lithium ion battery electrolyte additive, an electrolyte and a battery thereof, which can form a stable interface film with high electronic conductance at the positive and negative electrode interfaces under high voltage, inhibit the decomposition of the electrolyte, reduce the impedance, and improve the cycle performance of the battery.
Disclosure of Invention
In view of the above-mentioned shortcomings, an object of the present invention is to provide an electrolyte additive for a high voltage lithium ion battery, which can form a stable interface film with high electron conductance at the positive and negative electrode interfaces under high voltage, inhibit the decomposition of the electrolyte, reduce the impedance, and improve the cycle performance of the battery.
The second purpose of the invention is to provide a high-voltage lithium ion battery electrolyte containing the high-voltage lithium ion battery electrolyte additive.
The invention also provides a high-voltage lithium ion battery containing the high-voltage lithium ion battery electrolyte.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the high voltage lithium ion battery electrolyte additive is an acetylene silicon-based compound with the following structural formula
Wherein R1, R2, R3 and R4 are respectively selected from one or more of alkyl with 1-10 carbon atoms, unsaturated alkyl, halogenated unsaturated alkyl, halogen atom, phenyl, thiophene, aldehyde group, cyano, methoxy and ethoxy. The invention provides high voltage lithiumThe electrolyte additive of the ion battery is an acetylene silicon-based compound, silicon is used as a stable group for stabilizing an ethynyl functional group, the deterioration of the battery caused by the thorough oxidative decomposition under high voltage is avoided, and the acetylene silicon-based compound forms a (RC) with high electronic conductance on the surfaces of a positive electrode and a negative electrode through electrochemical polymerization2Si)nThe decomposition product containing the alternating single-double bonds of-C can form a stable interfacial film on the surfaces of a positive electrode and a negative electrode under high voltage by using Si as a core group, so that the decomposition of the electrolyte is inhibited, the impedance of the battery can be reduced, and the cycle performance of the high-voltage battery is improved.
The ethynylsilyl compound is selected from the group consisting of triisopropylsilylacetylene, 3-methylphenyl (trimethylsilyl) acetylene, triisopropyl ((4- ((trimethylsilyl) acetylene) phenyl) acetylene) silane, trimethyl ((4- ((4- (phenylacetylene) phenyl) acetylene) silane, trimethyl ((2-nitrophenyl) acetylene) silane, trimethyl ((3-methyloxetan-3-yl) acetylene) silane, triethylsilylacetylene, trimethylsilyl silicon, (tert-butyldimethyl) acetylene, triphenylsilylacetylene, lithium trimethylsilylethynyl, bis (trimethylsilyl) acetylene, bis (trichlorosilane) acetylene, 4-ethyltrimethylsilylacetylbenzene, 1- (trimethylsilyl) propyne, ethyl 3- (trimethylsilyl) propionate, and mixtures thereof, ((4-ethynylphenyl) acetylene) triisopropylsilane, (methyldiphenylsilyl) acetylene, 1-iodo-2-trimethylsilylacetylene, 1, 3-bis [ (trimethylsilyl) ethynyl ] benzene, phenylethynyltrimethylsilane, 4- [ (trimethylsilyl) ethynyl ] morpholine, 3- (trimethylsilynyl) thiophene, (3, 5-difluorophenylethynyl) trimethylsilane, cyclopropyl (trimethylsilyl) acetylene, (4-fluorophenylacetylene) trimethylsilane, 1-triethylsilane-4-triethylsiloxane-1-butyne, 2-trimethylsilylethynyl thiophene, dimethyl [ di (phenylethynyl) ] silane, hexakis ((trimethylsilyl) ethylnyl) bezene, 4-trimethylsilylacetylbenzaldehyde, benzaldehyde, and mixtures thereof, triiso-propyl ((trimethylsilyl) ethyl) silane, 5- [ (trimethylsilyl) ethynyl ]) -1-methylimidazole, 4- [ (trimethylsilyl) ethynyl ] benzonitrile, 1- [ (trimethylsilyl) ethynyl ] -4- (trifluoromethyl) benzene, 1- [ (trimethylsilyl) acetylene ] -3, 5-dimethoxybenzene, ethynyltriethoxysilane, at least one of (pentamethyldisilyl) acetylene, 2, 5-bis [ (trimethylsilyl) ethynyl ] thiophene, (3-furanylethynyl) (trimethyl) silane, 2- [2- (trimethylsilyl) ethynyl ] -benzonitrile, p-tolyl [2- (trimethylsilyl) ethynyl ] sulfone, and 3- (triethylsilyl) -2-propynal.
The high-voltage lithium ion battery electrolyte consists of an additive, lithium salt, an organic solvent and the high-voltage lithium ion battery electrolyte additive. The addition proportion of the high-voltage lithium ion battery electrolyte additive in the high-voltage lithium ion battery electrolyte is 0.01-3% by mass percent.
In a preferred embodiment of the present invention, the organic solvent is selected from one or more of propylene carbonate, ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, dioxolane, 1, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, γ -butyrolactone, methyl acetate, ethyl acetate, dimethyl sulfoxide, and sulfolane, which are mixed in any proportion.
In a preferred embodiment of the present invention, the lithium salt is one or more of lithium tetrafluoroborate, lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, lithium tris (trifluoromethanesulfonyl) methide, lithium bis (oxalato) borate, lithium difluorooxalato borate, or lithium tetrafluorooxalato phosphate. The molar concentration range of the lithium salt in the high-voltage lithium ion battery electrolyte is 0.5-3 mol/L.
A high-voltage lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and the high-voltage lithium ion battery electrolyte. The charge cut-off voltage of the high-voltage lithium ion battery is 4.5-5V.
The invention has the beneficial effects that: the high-voltage lithium ion battery electrolyte additive provided by the invention is an acetylene silicon-based compound, silicon is used as a stable group for stabilizing an acetylene functional group, so that the deterioration of a battery caused by the thorough oxidative decomposition under high voltage is avoided, and the acetylene silicon-based compound is electrochemically polymerized on the surface shapes of a positive electrode and a negative electrodeTo have a high electronic conductance (RC)2Si) n, and Si is used as a core group, and the decomposition product can form a stable interface film on the surfaces of positive and negative electrodes at high voltage, thereby inhibiting the decomposition of the electrolyte, reducing the impedance of the battery, and improving the cycle performance of the high voltage battery. And has the advantages of small addition amount, low cost, simple synthesis and the like, is easy to realize and is beneficial to wide popularization and application.
The invention is further illustrated by the following figures and examples.
Drawings
Fig. 1 is a graph comparing the impedance of comparative example 1, comparative example 8 and example 1.
Detailed Description
Example 1:
preparing high-voltage lithium ion battery electrolyte:
ethylene carbonate, ethyl methyl carbonate and diethyl carbonate were uniformly mixed in a mass ratio of 1:1:1 in a glove box filled with argon (moisture < 10ppm, oxygen < 1ppm) to obtain a mixed solution.
Adding triisopropyl silicon-based acetylene with the mass fraction of 3% into the mixed solution, and slowly adding lithium salt LiPF6And stirring until the electrolyte is completely dissolved to obtain the high-voltage lithium ion battery electrolyte A1.
Preparing a high-voltage lithium ion battery:
reacting LiNi0.5Mn1.5O4(LNMO) is used as a positive electrode active material, carbon black is used as a conductive additive, carboxymethyl cellulose (CMC), a copolymer (SBR) of styrene and butadiene is used as a binder, the mixture is uniformly mixed in water according to the mass ratio of 92:5:1:2, then coated on an aluminum foil current collector, dried, cold-pressed, cut into round pieces with the diameter of phi 14mm, and placed in a glove box.
Graphite is used as a negative electrode active material, carbon black is used as a conductive additive, carboxymethyl cellulose (CMC) and a copolymer (SBR) of styrene and butadiene are used as a binder, the materials are uniformly mixed in water according to a mass ratio of 93:2:2:3, then the mixture is coated on a copper foil current collector, and after drying and cold pressing, the copper foil current collector is cut into round pieces with the diameter of phi 15mm, and the round pieces are placed in a glove box.
Polyethylene (PE) is used as a base film (12 mu m), and a nano aluminum oxide coating (2 mu m) is coated on the two sides of the base film to be used as a diaphragm. The positive pole piece, the diaphragm and the negative pole piece are put in sequence, the prepared high-voltage lithium ion battery electrolyte A1 is injected, and then the button cell with the model number of CR2032 is assembled after packaging.
The prepared button cell is kept stand for 24 hours at room temperature, and then a blue battery charge and discharge tester (purchased from blue electronic corporation, Wuhan city) is adopted to perform cycle test on the cell.
Example 2:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
ethylene carbonate, ethyl methyl carbonate and diethyl carbonate were uniformly mixed in a mass ratio of 1:1:1 in a glove box filled with argon (moisture < 10ppm, oxygen < 1ppm) to obtain a mixed solution.
Adding 1 percent by mass of 3-methylphenyl (trimethylsilyl) acetylene into the mixed solution, and slowly adding lithium salt LiPF6And stirring until the electrolyte is completely dissolved to obtain the high-voltage lithium ion battery electrolyte A2.
Example 3:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
ethylene carbonate, ethyl methyl carbonate and diethyl carbonate were uniformly mixed in a mass ratio of 1:1:1 in a glove box filled with argon (moisture < 10ppm, oxygen < 1ppm) to obtain a mixed solution.
Adding 0.01 percent of trimethyl ((2-nitrophenyl) acetylene) silane by mass fraction into the mixed solution, and slowly adding lithium salt LiPF6And stirring until the electrolyte is completely dissolved to obtain the high-voltage lithium ion battery electrolyte A3.
Example 4:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
ethylene carbonate, ethyl methyl carbonate and diethyl carbonate were uniformly mixed in a mass ratio of 1:1:1 in a glove box filled with argon (moisture < 10ppm, oxygen < 1ppm) to obtain a mixed solution.
Adding 2 percent by mass of triethylsilyl acetylene into the mixed solution, and slowly adding lithium salt LiPF6And stirring until the electrolyte is completely dissolved to obtain the high-voltage lithium ion battery electrolyte A4.
Example 5:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
ethylene carbonate, ethyl methyl carbonate and diethyl carbonate were uniformly mixed in a mass ratio of 1:1:1 in a glove box filled with argon (moisture < 10ppm, oxygen < 1ppm) to obtain a mixed solution.
Adding 1.5 percent of trimethylacetylene silicon by mass into the mixed solution, and then slowly adding lithium salt LiPF6And stirring until the electrolyte is completely dissolved to obtain the high-voltage lithium ion battery electrolyte A5.
Example 6:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
ethylene carbonate, ethyl methyl carbonate and diethyl carbonate were uniformly mixed in a mass ratio of 1:1:1 in a glove box filled with argon (moisture < 10ppm, oxygen < 1ppm) to obtain a mixed solution.
Adding 1 percent of triphenyl silicon acetylene by mass into the mixed solution, and then slowly adding lithium salt LiPF6And stirring until the electrolyte is completely dissolved to obtain the high-voltage lithium ion battery electrolyte A6.
Example 7:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
ethylene carbonate, ethyl methyl carbonate and diethyl carbonate were uniformly mixed in a mass ratio of 1:1:1 in a glove box filled with argon (moisture < 10ppm, oxygen < 1ppm) to obtain a mixed solution.
Adding 2 percent by mass of trimethylsilyl acetylene lithium into the mixed solution, and slowly adding lithium salt LiPF6And stirring until the electrolyte is completely dissolved to obtain the high-voltage lithium ion battery electrolyte A7.
Example 8:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
ethylene carbonate, ethyl methyl carbonate and diethyl carbonate were uniformly mixed in a mass ratio of 1:1:1 in a glove box filled with argon (moisture < 10ppm, oxygen < 1ppm) to obtain a mixed solution.
Adding 0.5 mass percent of 3- (trimethylsilyl alkynyl) thiophene into the mixed solution, and slowly adding lithium salt LiPF6And stirring until the electrolyte is completely dissolved to obtain the high-voltage lithium ion battery electrolyte A8.
Example 9:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
ethylene carbonate, ethyl methyl carbonate and diethyl carbonate were uniformly mixed in a mass ratio of 1:1:1 in a glove box filled with argon (moisture < 10ppm, oxygen < 1ppm) to obtain a mixed solution.
Adding 1.5 percent of 4- [ (trimethylsilyl) ethynyl by mass fraction into the mixed solution]Benzonitrile and then lithium salt LiPF is slowly added6And stirring until the solution is completely dissolved to obtain the lithium ion battery electrolyte A9.
Example 10:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
ethylene carbonate, ethyl methyl carbonate and diethyl carbonate were uniformly mixed in a mass ratio of 1:1:1 in a glove box filled with argon (moisture < 10ppm, oxygen < 1ppm) to obtain a mixed solution.
Adding 1 percent of ethynyltriethoxysilane by mass fraction into the mixed solution, and slowly adding lithium salt LiPF6And stirring until the solution is completely dissolved to obtain the lithium ion battery electrolyte A10.
Example 11:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
ethylene carbonate, ethyl methyl carbonate and diethyl carbonate were uniformly mixed in a mass ratio of 1:1:1 in a glove box filled with argon (moisture < 10ppm, oxygen < 1ppm) to obtain a mixed solution.
Adding 2 mass percent of 3- (triethylsilyl) -2-propynal into the mixed solution, and slowly adding lithium salt LiPF6And stirring until the solution is completely dissolved to obtain the lithium ion battery electrolyte A11.
Example 12:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
ethylene carbonate, ethyl methyl carbonate and diethyl carbonate were uniformly mixed in a mass ratio of 1:1:1 in a glove box filled with argon (moisture < 10ppm, oxygen < 1ppm) to obtain a mixed solution.
Adding 1 mass percent of p-tolyl [2- (trimethylsilyl) ethynyl group to the mixed solution]Sulfone, and slowly adding lithium salt LiPF6And stirring until the solution is completely dissolved to obtain the lithium ion battery electrolyte A12.
Comparative example 1:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
in a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, and lithium salt LiPF is slowly added6And stirring until the solution is completely dissolved to obtain the lithium ion battery electrolyte B1.
Comparative example 2:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
in a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, 0.5 percent of phenylacetylene is added, and lithium salt LiPF is slowly added6And stirring until the solution is completely dissolved to obtain the lithium ion battery electrolyte B2.
Comparative example 3:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
in an argon-filled glove box (moisture < 10ppm, oxygen < 1ppm) carbonic acid was addedUniformly mixing ethylene ester, methyl ethyl carbonate and diethyl carbonate in a mass ratio of 1:1:1, adding 1% of 4-methoxyphenylacetylene, and slowly adding lithium salt LiPF6And stirring until the solution is completely dissolved to obtain the lithium ion battery electrolyte B3.
Comparative example 4:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
in a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate, ethyl methyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, 1.5 percent of diethyl acetylenedicarboxylate is added, and lithium salt LiPF is slowly added6And stirring until the solution is completely dissolved to obtain the lithium ion battery electrolyte B4.
Comparative example 5:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
in a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, 2 percent of 3-ethynyl thiophene is added, and lithium salt LiPF is slowly added6And stirring until the solution is completely dissolved to obtain the lithium ion battery electrolyte B5.
Comparative example 6:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
in an argon-filled glove box (moisture content is less than 10ppm, oxygen content is less than 1ppm), ethylene carbonate, ethyl methyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, 2.5 percent of 3-ethynylpyridine is added, and lithium salt LiPF is slowly added6And stirring until the solution is completely dissolved to obtain the lithium ion battery electrolyte B6.
Comparative example 7:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
in an argon-filled glove box (moisture is less than 10ppm, oxygen content is less than 1ppm), ethylene carbonate, ethyl methyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, 2.5 percent of 4-ethynyl benzonitrile is added, and lithium salt LiPF is slowly added6And stirring until the solution is completely dissolved to obtain the lithium ion battery electrolyte B7.
Comparative example 8:
the difference from example 1 is the preparation of the high voltage lithium ion battery electrolyte:
in a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate, ethyl methyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, 3 percent of 4-ethynyltriphenylamine is added, and lithium salt LiPF is slowly added6And stirring until the solution is completely dissolved to obtain the lithium ion battery electrolyte B8.
Table 1 shows the results of the cell impedance tests of examples 1 to 12 and comparative examples 1 to 8.
TABLE 1
| Battery numbering | Electrolyte numbering | Additive content (%) | Impedance (omega) |
| Example 1 | A1 | 3 | 31 |
| Example 2 | A2 | 1 | 63 |
| Example 3 | A3 | 0.01 | 103 |
| Example 4 | A4 | 2 | 52 |
| Example 5 | A5 | 1.5 | 59 |
| Example 6 | A6 | 1 | 67 |
| Example 7 | A7 | 2 | 55 |
| Example 8 | A8 | 0.5 | 71 |
| Example 9 | A9 | 1.5 | 62 |
| Example 10 | A10 | 1 | 69 |
| Example 11 | A11 | 2 | 56 |
| Example 12 | A12 | 1 | 73 |
| Comparative example 1 | |
0 | 139 |
| Comparative example 2 | B2 | 0.5 | 147 |
| Comparative example 3 | B3 | 1 | 153 |
| Comparative example 4 | B4 | 1.5 | 167 |
| Comparative example 5 | B5 | 2 | 169 |
| Comparative example 6 | B6 | 2.5 | 193 |
| Comparative example 7 | B7 | 2.5 | 249 |
| Comparative example 8 | B8 | 3 | 303 |
Comparing comparative example 1 and the examples, it can be seen that the impedance of the battery using the acetylene-silicon-based compound of the present invention as an additive is significantly reduced, and as in example 1, the impedance can be reduced from 139 Ω to 31 Ω, and the effect is significant. It is understood from comparative examples 1 to 8 that the impedance of the battery was greatly increased by adding the ethynyl compound containing no silicon because, without silicon as a stabilizer, the ethynyl compound had a large oxidative decomposition at a high voltage and could not inhibit the oxidative decomposition of the electrolyte, the side reaction of the battery was serious, and the decomposition products on the surfaces of the positive and negative electrodes were large, resulting in an increase in the impedance of the battery. Referring to fig. 1, a graph comparing the impedance of comparative example 1, comparative example 8, and example 1 is shown.
Table 2 shows the results of the battery cycle performance tests of examples 1 to 12 and comparative examples 1 to 8.
TABLE 2
Comparing comparative example 1 and example, it can be seen that, when the acetylene silicon-based compound of the present invention is used as an additive, the efficiency and cycle performance of the battery are greatly improved, as in example 1, the efficiency of the battery can be increased from 98.7% to 99.4%, and the capacity retention rate after 200 weeks can be increased from 65% to 95%, which is very significant. On the other hand, it is understood from comparative examples 1 to 8 that the efficiency and cycle performance of the battery are remarkably decreased and the deterioration is more serious as the content is increased when the acetylene compound containing no silicon is added as an additive, because the acetylene compound containing no silicon does not endure a high voltage, the oxidative decomposition is serious at the high voltage and the oxidative decomposition of the electrolyte is not inhibited, and the side reaction of the battery is serious, resulting in the deterioration of the efficiency and cycle performance of the battery.
The above examples are only preferred embodiments of the present invention, and the present invention is not limited to all embodiments, and any technical solution using one of the above examples or equivalent changes made according to the above examples is within the scope of the present invention.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation. Other additives, electrolytes and batteries prepared by the same or similar methods and compositions as described in the above embodiments of the invention are within the scope of the invention.
Claims (8)
1. The high-voltage lithium ion battery electrolyte additive is characterized by being an acetylene silicon-based compound with the following structural formula
Wherein R1, R2, R3 and R4 are respectively selected from one or more of alkyl with 1-10 carbon atoms, unsaturated alkyl, halogenated unsaturated alkyl, halogen atom, phenyl, thiophene, aldehyde group, cyano, methoxy and ethoxy.
2. The high voltage lithium ion battery electrolyte additive of claim 1 wherein the acetylenic silicon based compound is selected from the group consisting of triisopropylsilylacetylene, 3-methylphenyl (trimethylsilyl) acetylene, triisopropyl ((4- ((trimethylsilyl) acetylene) phenyl) acetylene) silane, trimethyl ((4- ((4- (phenylacetylene) phenyl) acetylene) silane, trimethyl ((2-nitrophenyl) acetylene) silane, trimethyl ((3-methyloxetan-3-yl) acetylene) silane, triethylsilylacetylene, trimethylsilylsilicon, (tert-butyldimethyl) acetylene, triphenylsilylacetylene, lithium trimethylsilylethynyl, bis (trimethylsilyl) acetylene, bis (trichlorosilane) acetylene, lithium trimethylsilylethynyl, lithium bis (trimethylsilyl) acetylene, and mixtures thereof, 4-ethyltrimethylsilylacetylene benzene, 1- (trimethylsilyl) propyne, ethyl 3- (trimethylsilyl) propionate, ((4-ethynylphenyl) acetylene) triisopropylsilane, (methyldiphenylsilyl) acetylene, 1-iodo-2-trimethylsilylacetylene, 1, 3-bis [ (trimethylsilyl) ethynyl ] benzene, phenylethynyltrimethylsilane, 4- [ (trimethylsilyl) ethynyl ] morpholine, 3- (trimethylsilyl alkynyl) thiophene, (3, 5-difluorophenylethynyl) trimethylsilane, cyclopropyl (trimethylsilyl) acetylene, (4-fluorophenylacetylene) trimethylsilane, 1-triethylsilane-4-triethylsiloxane-1-butyne, 2-trimethylsilylethynyl thiophene, thionylmethane, 2-trimethylsilylethynyl, isopropylsilane-1-butyne, and mixtures thereof, Dimethyl [ bis (phenylethynyl) ] silane, hexakis ((trimethylsilyl) ethyl) bezene, 4-trimethylsilylacetylbenzaldehyde, trisiso-propyl ((trimethylsilyl) ethyl) silane, 5- [ (trimethylsilyl) ethynyl ]) -1-methylimidazole, 4- [ (trimethylsilyl) ethynyl ] benzonitrile, 1- [ (trimethylsilyl) ethynyl ] -4- (trifluoromethyl) benzene, 1- [ (trimethylsilyl) acetylene ] -3, 5-dimethoxybenzene, ethynyltriethoxysilane, (pentamethyldisilyl) acetylene, 2, 5-bis [ (trimethylsilyl) ethynyl ] thiophene, (3-furanylethynyl) (trimethyl) silane, 2- [2- (trimethylsilyl) ethynyl ] -benzonitrile, p-tolyl [2- (trimethylsilyl) ethynyl ] sulfone, At least one of 3- (triethylsilyl) -2-propynal.
3. The high-voltage lithium ion battery electrolyte is characterized by comprising an additive, a lithium salt, an organic solvent and the high-voltage lithium ion battery electrolyte additive of claim 1 or 2, wherein the addition proportion of the high-voltage lithium ion battery electrolyte additive in the high-voltage lithium ion battery electrolyte is 0.01-3% by mass percent.
4. The high-voltage lithium ion battery electrolyte as claimed in claim 3, wherein the organic solvent is selected from one or more of propylene carbonate, ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, dioxolane, 1, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, gamma-butyrolactone, methyl acetate, ethyl acetate, dimethyl sulfoxide and sulfolane.
5. The high voltage lithium ion battery electrolyte of claim 3, wherein the lithium salt is one or more of lithium tetrafluoroborate, lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methide, lithium bis (oxalato) borate, lithium difluorooxalato borate, or lithium tetrafluorooxalato phosphate.
6. The high voltage lithium ion battery electrolyte of claim 3 or 5, wherein the molar concentration of the lithium salt in the high voltage lithium ion battery electrolyte is in the range of 0.5-3 mol/L.
7. A high-voltage lithium ion battery, which is characterized by comprising a positive electrode, a negative electrode, a diaphragm and the high-voltage lithium ion battery electrolyte of any one of claims 3 to 6.
8. The high-voltage lithium ion battery according to claim 7, wherein the charge cut-off voltage is 4.5 to 5V.
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| CN111769324A (en) * | 2020-06-18 | 2020-10-13 | 合肥国轩高科动力能源有限公司 | High-voltage lithium ion battery electrolyte additive and lithium ion battery electrolyte containing additive |
| CN113948768A (en) * | 2020-07-15 | 2022-01-18 | 浙江中蓝新能源材料有限公司 | Silane additive, electrolyte containing same and lithium ion battery |
| CN114497702A (en) * | 2022-02-15 | 2022-05-13 | 苏州华赢新能源材料科技有限公司 | Trimethyl silane based compound, electrolyte and lithium ion battery |
| EP4184646A4 (en) * | 2020-07-15 | 2024-01-10 | Zhejiang Res Institute Of Chemical Industry Co Ltd | Silane additive, electrolyte and lithium ion battery containing same |
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