CN111600072A - Lithium battery electrolyte and preparation method and application thereof - Google Patents

Lithium battery electrolyte and preparation method and application thereof Download PDF

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CN111600072A
CN111600072A CN202010473642.9A CN202010473642A CN111600072A CN 111600072 A CN111600072 A CN 111600072A CN 202010473642 A CN202010473642 A CN 202010473642A CN 111600072 A CN111600072 A CN 111600072A
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electrolyte
lithium
lithium battery
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ether
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袁峰
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Xiwang New Energy Technology Kunshan Co ltd
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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
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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
    • 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
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    • 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
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    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
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    • 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
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Abstract

The invention provides a lithium battery electrolyte which is characterized by comprising lithium salt, ethylene glycol dibutyl ether, a fluorine-containing organic solvent, a high and low temperature resistant additive and an imidazolyl ionic liquid. The electrolyte of the lithium battery prepared by the invention can form a relatively stable passive film, and the passive film of the layer is inhibited from increasing along with the prolonging of the storage time, so that the storage performance and the storage life of the lithium battery are obviously improved. Meanwhile, the electrolyte has lower freezing point and high-temperature incombustibility, and simultaneously gives the electrolyte strong flame resistance, and simultaneously can enhance the quick charge performance of the battery, and can be widely applied to quick charge lithium batteries.

Description

Lithium battery electrolyte and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a lithium battery electrolyte and a preparation method and application thereof.
Background
Lithium ion batteries have witnessed the modern, briskly developed electronic technology and become an essential part of modern ubiquitous portable electronic devices. Lithium electrochemical cells, more commonly referred to as batteries (packs), are widely used in a variety of military and commercial products. Many of these products use high energy and high power batteries. Due in part to the miniaturization of portable electronic devices, it is desirable to develop smaller lithium batteries with increased power capacity and service life
In the lithium batteryIn the cell, after the metal lithium contacts the electrolyte, a passivation layer (SEI film) is formed on the surface of the lithium metal, and the passivation film prevents the metal lithium from further reacting with the electrolyte, so that the lithium battery has low self-discharge rate and long storage life. However, in some cases, such as long-term storage at normal temperature and high-temperature storage, the passive film often grows excessively, which causes severe passivation and high self-discharge rate of the battery, and causes battery failure. In order to improve the storage performance of lithium batteries, common methods such as adding a certain amount of sulfur dioxide SO into the electrolyte2Or adding transition metal macrocyclic compound, organic polymer additive, anode coating treatment and the like.
In addition, in general, most lithium ion batteries include a polyolefin-based separator, a liquid organic electrolyte (including ethylene carbonate, diethyl carbonate, and dimethyl carbonate), a lithium salt, and positive and negative electrodes. Among them, low thermal stability and flammability of the separator and the electrolyte are generally considered to be the main causes of combustion and explosion of the lithium ion battery.
Therefore, it is necessary to develop a safe and stable electrolyte for improving the storage performance of lithium batteries to meet the needs of modern people.
Disclosure of Invention
The invention aims to provide a lithium battery electrolyte, a preparation method and application thereof, which can form a relatively stable passive film, and the passive film can be inhibited from increasing along with the prolonging of storage time, so that the storage performance and the storage life of a lithium battery are obviously improved.
The technical scheme of the invention is realized as follows:
the invention provides a lithium battery electrolyte, which comprises lithium salt, ethylene glycol dibutyl ether, a fluorine-containing organic solvent, a high and low temperature resistant additive and an imidazolyl ionic liquid.
Further, the feed additive is prepared from the following raw materials in parts by weight: 5-12 parts of lithium salt, 1-3 parts of ethylene glycol dibutyl ether, 30-50 parts of a fluorine-containing organic solvent, 2-5 parts of a high-temperature and low-temperature resistant additive and 10-15 parts of an imidazolyl ionic liquid.
As a further improvement of the invention, the lithium salt is LiBF4And bis (oxalato) boronic acidLithium in a mass ratio of 1: (1-2).
As a further improvement of the invention, the fluorine-containing organic solvent is one or a mixture of several of methyl-nonafluorobutyl ether, sevoflurane, glycidyl ether hexadecafluorononyl ether and octafluoropentyl allyl ether.
As a further improvement of the invention, the high and low temperature resistant additive is dihydropyridine, laurone and fluoroethylene carbonate, and the mass ratio of the dihydropyridine to the laurone to the fluoroethylene carbonate is 1: (0.5-2): (3-7).
As a further improvement of the invention, the cation in the imidazolyl ionic liquid has the following structure shown in formula I:
Figure BDA0002515111380000031
as a further improvement of the invention, the anion in the imidazolyl ionic liquid is BF4 -Or PF6 -。
The preparation method of the ionic liquid is shown in the following references: synthesis and application of liuhongxia, xuqu, alkyl imidazole ionic liquid [ J ], journal of chinese medical industry, 2006,37 (9): 644-648.
The method comprises the following specific steps:
reacting N-methylimidazole with N-butyl bromide in N-heptane at 80 ℃ for 18h to obtain [ bmim]Br is added. The latter reacts with ammonium fluoroborate in methanol in equal molar ratio to obtain the product [ bmim]BF4。
The invention further provides a preparation method of the lithium battery electrolyte, which comprises the following steps:
s1, respectively connecting high-purity aluminum sheets for the positive electrode and the negative electrode in an anhydrous environment, and connecting a voltage-stabilized power supply for electrolysis for 10-15h to remove water in the imidazolyl ionic liquid and the fluorine-containing organic solvent;
s2, dissolving lithium salt in the imidazolyl ionic liquid obtained in the step S1, and uniformly mixing to obtain a solution A;
s3, adding ethylene glycol dibutyl ether and the high and low temperature resistant additive into the fluorine-containing organic solvent obtained in the step S1, and uniformly mixing to obtain a solution B;
and S4, mixing the solution A and the solution B at the temperature of 30-40 ℃, and homogenizing to obtain the lithium battery electrolyte.
As a further improvement of the invention, the voltage in step S1 is 3-6V.
As a further improvement of the invention, the homogenization condition in step S4 is 10000-12000r/min for homogenization for 1-2 min.
The invention further protects the application of the lithium battery electrolyte in the preparation of the fast-charging lithium ion battery.
The invention has the following beneficial effects: the lithium bis (oxalato) borate adopted by the invention has the advantages of low cost, high thermal stability, high safety and stable electrochemical property, and the LiBF is added4The ionic conductivity can be improved, the stability of the electrolyte and the positive and negative electrode interfaces is improved, and the combination of the electrolyte and the positive and negative electrode interfaces has good conductivity, high and low temperature resistance, low cost, safety and stability and synergistic effect;
the addition of the high and low temperature resistant additive is beneficial to enhancing the compatibility of the electrolyte and the carbon cathode and simultaneously enhancing the interface stability of the electrolyte and the cathode, so that the electrolyte can carry out heavy current discharge at the low temperature of-40 ℃; the interface stability of the lithium ion electrolyte and a negative electrode under the conditions of low temperature and high temperature is obtained through long-term research of an inventor; the electrolyte is ensured to have a lower freezing point and high-temperature incombustibility, and is endowed with strong flame resistance, and the quick charging performance of the battery can be enhanced;
the imidazolyl ionic liquid has the characteristics of high solubility to lithium salt, no combustion, no explosion, difficult oxidation, good thermal stability and the like, and has the advantages of wider liquid range, stronger dissolving capacity, lower vapor pressure, more proper viscosity, higher conductivity, wider electrochemical window and the like when being added into the electrolyte, so that the imidazolyl ionic liquid has wide application prospect. The application of the imidazolyl ionic liquid in the lithium battery can change the composition and structure of a passivation film to form a stable passivation film, the growth of the passivation film is inhibited along with the prolonging of the storage time, and meanwhile, the high-temperature discharge performance of the lithium battery can be obviously improved;
the electrolyte of the lithium battery prepared by the invention can form a relatively stable passive film, and the passive film of the layer is inhibited from increasing along with the prolonging of the storage time, so that the storage performance and the storage life of the lithium battery are obviously improved. Meanwhile, the electrolyte has lower freezing point and high-temperature incombustibility, and simultaneously gives the electrolyte strong flame resistance, and simultaneously can enhance the quick charge performance of the battery, and can be widely applied to quick charge lithium batteries.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
LiBF4CAS number: 14283-07-9.
Lithium bis (oxalato) borate, CAS No.: 409071-16-5.
Dihydropyridines, CAS number: 1149-23-1.
Laurone, CAS No.: 59227-89-3.
Fluoroethylene carbonate, CAS number: 114435-02-8.
Ethylene glycol dibutyl ether, CAS number: 112-48-1.
Methyl-nonafluorobutyl ether, CAS No.: 163702-07-6. The chemicals are purchased from the national medicine group.
Imidazolyl ionic liquids are all available from Reynolds Biotechnology, Inc., Guangzhou. The preparation method of the ionic liquid is shown in the following references: synthesis and application of liuhongxia, xuqu, alkyl imidazole ionic liquid [ J ], journal of chinese medical industry, 2006,37 (9): 644-648.
Figure BDA0002515111380000051
The preparation method specifically comprises the following steps:
reacting N-methylimidazole with N-butyl bromide in N-heptane at 80 ℃ for 18h to obtain [ bmim]Br is added. The latter is reacted with ammonium fluoroborate in the same molar ratio in the methanol to obtain the product[bmim]BF4。
Figure BDA0002515111380000061
The preparation method specifically comprises the following steps:
reacting N-methylimidazole with N-butyl bromide in N-heptane at 80 ℃ for 18h to obtain [ bmim]Br is added. The latter reacts with potassium hexafluorophosphate in methanol in equal molar ratio to obtain the product bmim]PF6。
Example 1
The raw materials comprise the following components in parts by weight: 5 parts of lithium salt, 1 part of ethylene glycol dibutyl ether, 30 parts of methyl-nonafluorobutyl ether, 2 parts of high and low temperature resistant additive and 10 parts of imidazolyl ionic liquid.
The lithium salt being LiBF4And lithium bis (oxalate) borate in a mass ratio of 1: 1.
the high and low temperature resistant additive is dihydropyridine, laurocapram and fluoroethylene carbonate, and the mass ratio is 1: 0.5: 3.
the structural formula of the imidazolyl ionic liquid is as follows:
Figure BDA0002515111380000062
the preparation method of the lithium battery electrolyte comprises the following steps:
s1, respectively using high-purity aluminum sheets for the positive electrode and the negative electrode in an anhydrous environment, connecting a voltage-stabilized power supply for electrolysis for 10 hours at a voltage of 3V, and removing water in the imidazolyl ionic liquid and the methyl-nonafluorobutyl ether;
s2, dissolving lithium salt in the imidazolyl ionic liquid obtained in the step S1, and uniformly mixing to obtain a solution A;
s3, adding ethylene glycol dibutyl ether and a high-temperature and low-temperature resistant additive into methyl-nonafluorobutyl ether, and uniformly mixing to obtain a solution B;
and S4, mixing the solution A and the solution B at the temperature of 30 ℃, and homogenizing at 10000r/min for 1min to obtain the lithium battery electrolyte.
Example 2
The raw materials comprise the following components in parts by weight: 12 parts of lithium salt, 3 parts of ethylene glycol dibutyl ether, 50 parts of octafluoropentyl allyl ether, 5 parts of a high and low temperature resistant additive and 15 parts of imidazolyl ionic liquid.
The lithium salt being LiBF4And lithium bis (oxalate) borate in a mass ratio of 1: 2.
the high and low temperature resistant additive is dihydropyridine, laurocapram and fluoroethylene carbonate, and the mass ratio is 1: 2: 7.
the structural formula of the imidazolyl ionic liquid is as follows:
Figure BDA0002515111380000071
the preparation method of the lithium battery electrolyte comprises the following steps:
s1, respectively using high-purity aluminum sheets for the positive electrode and the negative electrode in an anhydrous environment, connecting a voltage-stabilized power supply for electrolysis for 15 hours at a voltage of 6V, and removing water in the imidazolyl ionic liquid and octafluoropentyl allyl ether;
s2, dissolving lithium salt in the imidazolyl ionic liquid obtained in the step S1, and uniformly mixing to obtain a solution A;
s3, adding ethylene glycol dibutyl ether and a high and low temperature resistant additive into octafluoropentyl allyl ether, and uniformly mixing to obtain a solution B;
and S4, mixing the solution A and the solution B at the temperature of 40 ℃, and homogenizing at 12000r/min for 1min to obtain the lithium battery electrolyte.
Example 3
The raw materials comprise the following components in parts by weight: 6 parts of lithium salt, 2 parts of ethylene glycol dibutyl ether, 35 parts of sevoflurane, 3 parts of high and low temperature resistant additive and 11 parts of imidazolyl ionic liquid.
The lithium salt being LiBF4And lithium bis (oxalate) borate in a mass ratio of 1: 1.2.
the high and low temperature resistant additive is dihydropyridine, laurocapram and fluoroethylene carbonate, and the mass ratio is 1: 0.7: 4.
the structural formula of the imidazolyl ionic liquid is as follows:
Figure BDA0002515111380000081
the preparation method of the lithium battery electrolyte comprises the following steps:
s1, respectively using high-purity aluminum sheets for the positive electrode and the negative electrode in an anhydrous environment, connecting a voltage-stabilized power supply for electrolysis for 11 hours at a voltage of 4V, and removing water in the imidazolyl ionic liquid and the sevoflurane;
s2, dissolving lithium salt in the imidazolyl ionic liquid obtained in the step S1, and uniformly mixing to obtain a solution A;
s3, adding ethylene glycol dibutyl ether and a high and low temperature resistant additive into sevoflurane, and uniformly mixing to obtain a solution B;
and S4, mixing the solution A and the solution B at the temperature of 32 ℃, and homogenizing at 10500r/min for 1min to obtain the lithium battery electrolyte.
Example 4
The raw materials comprise the following components in parts by weight: 10 parts of lithium salt, 2.5 parts of ethylene glycol dibutyl ether, 45 parts of glycidyl ether hexadecafluorononyl ether, 4 parts of high and low temperature resistant additive and 14 parts of imidazolyl ionic liquid.
The lithium salt being LiBF4And lithium bis (oxalate) borate in a mass ratio of 1: 2.
the high and low temperature resistant additive is dihydropyridine, laurocapram and fluoroethylene carbonate, and the mass ratio is 1: 1.7: 6.
the structural formula of the imidazolyl ionic liquid is as follows:
Figure BDA0002515111380000082
the preparation method of the lithium battery electrolyte comprises the following steps:
s1, respectively using high-purity aluminum sheets for the positive electrode and the negative electrode in an anhydrous environment, connecting a voltage-stabilized power supply for electrolysis for 14 hours at a voltage of 5V, and removing water in the imidazolyl ionic liquid and glycidyl ether hexadecyl nonyl fluoride ether;
s2, dissolving lithium salt in the imidazolyl ionic liquid obtained in the step S1, and uniformly mixing to obtain a solution A;
s3, adding ethylene glycol dibutyl ether and a high and low temperature resistant additive into glycidyl ether hexadecafluorononyl ether, and uniformly mixing to obtain a solution B;
and S4, mixing the solution A and the solution B at the temperature of 38 ℃, and homogenizing for 2min at 11500r/min to obtain the lithium battery electrolyte.
Example 5
The raw materials comprise the following components in parts by weight: 7 parts of lithium salt, 2 parts of ethylene glycol dibutyl ether, 40 parts of methyl-nonafluorobutyl ether, 4 parts of high and low temperature resistant additive and 12 parts of imidazolyl ionic liquid.
The lithium salt being LiBF4And lithium bis (oxalate) borate in a mass ratio of 1: 1.5.
the high and low temperature resistant additive is dihydropyridine, laurocapram and fluoroethylene carbonate, and the mass ratio is 1: 1.2: 5.
the structural formula of the imidazolyl ionic liquid is as follows:
Figure BDA0002515111380000091
the preparation method of the lithium battery electrolyte comprises the following steps:
s1, respectively using high-purity aluminum sheets for the positive electrode and the negative electrode in an anhydrous environment, connecting a voltage-stabilized power supply for electrolysis for 12 hours at a voltage of 5V, and removing water in the imidazolyl ionic liquid and the methyl-nonafluorobutyl ether;
s2, dissolving lithium salt in the imidazolyl ionic liquid obtained in the step S1, and uniformly mixing to obtain a solution A;
s3, adding ethylene glycol dibutyl ether and the high and low temperature resistant additive into the methyl-nonafluorobutyl ether obtained in the step S1, and uniformly mixing to obtain a solution B;
and S4, mixing the solution A and the solution B at the temperature of 35 ℃, and homogenizing at 11000r/min for 2min to obtain the lithium battery electrolyte.
Comparative example 1
In contrast to example 5, the lithium salt was LiBF4Other conditions are not changed.
The raw materials comprise the following components in parts by weight: 7 parts of lithium salt, 2 parts of ethylene glycol dibutyl ether, 40 parts of methyl-nonafluorobutyl ether, 4 parts of high and low temperature resistant additive and 12 parts of imidazolyl ionic liquid.
The lithium salt being LiBF4。
The high and low temperature resistant additive is dihydropyridine, laurocapram and fluoroethylene carbonate, and the mass ratio is 1: 1.2: 5.
the structural formula of the imidazolyl ionic liquid is as follows:
Figure BDA0002515111380000101
the preparation method of the lithium battery electrolyte comprises the following steps:
s1, respectively using high-purity aluminum sheets for the positive electrode and the negative electrode in an anhydrous environment, connecting a voltage-stabilized power supply for electrolysis for 12 hours at a voltage of 5V, and removing water in the imidazolyl ionic liquid and the methyl-nonafluorobutyl ether;
s2, dissolving lithium salt in the imidazolyl ionic liquid obtained in the step S1, and uniformly mixing to obtain a solution A;
s3, adding ethylene glycol dibutyl ether and the high and low temperature resistant additive into the methyl-nonafluorobutyl ether obtained in the step S1, and uniformly mixing to obtain a solution B;
and S4, mixing the solution A and the solution B at the temperature of 35 ℃, and homogenizing at 11000r/min for 2min to obtain the lithium battery electrolyte.
Comparative example 2
Compared with example 5, the lithium salt is lithium bis (oxalato) borate, and other conditions are not changed.
The raw materials comprise the following components in parts by weight: 7 parts of lithium salt, 2 parts of ethylene glycol dibutyl ether, 40 parts of methyl-nonafluorobutyl ether, 4 parts of high and low temperature resistant additive and 12 parts of imidazolyl ionic liquid.
The lithium salt is lithium bis (oxalate) borate.
The high and low temperature resistant additive is dihydropyridine, laurocapram and fluoroethylene carbonate, and the mass ratio is 1: 1.2: 5.
the structural formula of the imidazolyl ionic liquid is as follows:
Figure BDA0002515111380000111
the preparation method of the lithium battery electrolyte comprises the following steps:
s1, respectively using high-purity aluminum sheets for the positive electrode and the negative electrode in an anhydrous environment, connecting a voltage-stabilized power supply for electrolysis for 12 hours at a voltage of 5V, and removing water in the imidazolyl ionic liquid and the methyl-nonafluorobutyl ether;
s2, dissolving lithium salt in the imidazolyl ionic liquid obtained in the step S1, and uniformly mixing to obtain a solution A;
s3, adding ethylene glycol dibutyl ether and the high and low temperature resistant additive into the methyl-nonafluorobutyl ether obtained in the step S1, and uniformly mixing to obtain a solution B;
and S4, mixing the solution A and the solution B at the temperature of 35 ℃, and homogenizing at 11000r/min for 2min to obtain the lithium battery electrolyte.
Comparative example 3
Compared with example 5, methyl-nonafluorobutyl ether was replaced by imidazolyl ionic liquid, and other conditions were not changed.
The raw materials comprise the following components in parts by weight: 7 parts of lithium salt, 2 parts of ethylene glycol dibutyl ether, 4 parts of high and low temperature resistant additive and 52 parts of imidazolyl ionic liquid.
The lithium salt being LiBF4And lithium bis (oxalate) borate in a mass ratio of 1: 1.5.
the high and low temperature resistant additive is dihydropyridine, laurocapram and fluoroethylene carbonate, and the mass ratio is 1: 1.2: 5.
the structural formula of the imidazolyl ionic liquid is as follows:
Figure BDA0002515111380000121
the preparation method of the lithium battery electrolyte comprises the following steps:
s1, respectively connecting high-purity aluminum sheets for the positive electrode and the negative electrode in an anhydrous environment, and electrolyzing for 12 hours by using a stabilized voltage power supply at a voltage of 5V to remove moisture of the imidazolyl ionic liquid;
s2, dissolving lithium salt in the imidazolyl ionic liquid (12/52 of the total volume) obtained in the step S1, and uniformly mixing to obtain a solution A;
s3, adding ethylene glycol dibutyl ether and the high and low temperature resistant additive into the imidazolyl ionic liquid (40/52 of the total volume) obtained in the step S1, and uniformly mixing to obtain a solution B;
and S4, mixing the solution A and the solution B at the temperature of 35 ℃, and homogenizing at 11000r/min for 2min to obtain the lithium battery electrolyte.
Comparative example 4
Compared with example 5, the imidazolyl ionic liquid was replaced with methyl-nonafluorobutyl ether, and other conditions were not changed.
The raw materials comprise the following components in parts by weight: 7 parts of lithium salt, 2 parts of ethylene glycol dibutyl ether, 52 parts of methyl-nonafluorobutyl ether and 4 parts of high and low temperature resistant additive.
The lithium salt being LiBF4And lithium bis (oxalate) borate in a mass ratio of 1: 1.5.
the high and low temperature resistant additive is dihydropyridine, laurocapram and fluoroethylene carbonate, and the mass ratio is 1: 1.2: 5.
the preparation method of the lithium battery electrolyte comprises the following steps:
s1, respectively using high-purity aluminum sheets for the positive electrode and the negative electrode in an anhydrous environment, connecting a voltage-stabilized power supply for electrolysis for 12 hours at a voltage of 5V, and removing water in methyl-nonafluorobutyl ether;
s2, dissolving lithium salt in the methyl-nonafluorobutyl ether (12/52 of the total volume) obtained in the step S1, and uniformly mixing to obtain a solution A;
s3, adding ethylene glycol dibutyl ether and the high and low temperature resistant additive into the methyl-nonafluorobutyl ether (40/52 of the total volume) obtained in the step S1, and uniformly mixing to obtain a solution B;
and S4, mixing the solution A and the solution B at the temperature of 35 ℃, and homogenizing at 11000r/min for 2min to obtain the lithium battery electrolyte.
Test example 1 measurement of viscosity
The viscosities of the organic electrolytes prepared in examples 1 to 5 and comparative examples 1 to 4, and a commercially available electrolyte (available from hanqian new materials co., dogguan) were measured, and some results are shown in table 1.
The viscosity was measured by using a viscometer SV-1A (A & D Company; Vibro viscometer).
TABLE 1
Group of Viscosity (cp)
Example 1 5.21
Example 2 5.02
Example 3 4.92
Example 4 5.11
Example 5 4.87
Comparative example 1 6.12
Comparative example 2 6.25
Comparative example 3 8.24
Comparative example 4 7.87
Is commercially available 7.14
As shown in table 1 above, the viscosity of the organic electrolytes prepared in examples 1 to 5 was significantly reduced compared to the viscosity of comparative examples 1 to 4 and the commercially available electrolytes. In comparative examples 3 and 4, imidazolyl ionic liquid or methyl-nonafluorobutyl ether is used as a matrix, so that the viscosity is remarkably improved.
Test example 2 Charge and discharge characteristics
1. Evaluation of Charge and discharge characteristics at Room temperature (25 ℃ C.)
The electrolytes manufactured in examples 1 to 5 and comparative examples 1 to 4, and a commercially available electrolyte (available from hanqian new materials co., ltd., dongguan), were used to prepare lithium batteries, which were charged at a constant current of about 0.5C rate at room temperature (25C) until a voltage reached 4.20V (vs.li), and then stopped at a current level of about 0.05C rate while maintaining a constant voltage of about 4.20V. Thereafter, the lithium battery was discharged at a constant current of about 0.5C rate until the voltage reached 2.80V (vs. li) (formation process, first cycle).
The lithium battery undergoing the formation process was charged at a temperature of about 25 ℃ and a constant current of about 0.5C-rate until the voltage reached 4.20V (vs. li), and then stopped at a current of about 0.05C-rate while maintaining a constant voltage of about 4.20V. Thereafter, a cycle in which the lithium battery was discharged at a constant current at a rate of about 1.5C until the voltage reached 2.80V (vs. li) was repeated until the 200 th cycle.
Some of the above charge and discharge evaluation results are shown in table 2 below. The capacity retention at the 200 th cycle is defined by the following.
Capacity retention rate ═ [ discharge capacity at 200 th cycle/discharge capacity at first cycle ] × 100%
2. Evaluation of Charge and discharge characteristics at high temperature (45 ℃ C.)
The lithium battery was charged and discharged in the same manner as the evaluation of the charge and discharge characteristics at room temperature (25 deg.c), except that the charge and discharge temperature was changed to about 45 deg.c.
Some results of the charge and discharge evaluation results are shown in table 2 below.
TABLE 2
Figure BDA0002515111380000151
As shown in Table 2, lithium batteries prepared from the electrolytes of examples 1 to 5 of the present invention exhibited improved life characteristics at room temperature (25 ℃ C.) and high temperature (45 ℃ C.), which are significantly superior to those of comparative examples 1 to 4 and commercially available electrolytes.
Test example 3 evaluation of direct Current impedance (DC IR) at high temperature (45 ℃ C.)
The direct current impedance (DC IR) of the lithium battery was measured by the following method.
Lithium batteries prepared in first cycle examples 1 to 5 and comparative examples 1 to 4, and commercially available electrolyte (available from hanqian new materials co., tokyo) lithium batteries were charged at a current of 0.5C rate at a high temperature (45C) until the voltage reached 50% of the SOC, stopped at a rate of 0.02C, maintained under the same conditions for 10 minutes, discharged at a constant current of 0.5C rate for 30 seconds, maintained under the same conditions for 30 seconds, discharged at a constant current of 0.5C rate for 30 seconds, maintained under the same conditions for 10 minutes, discharged at a constant current of 1.0C rate for 30 seconds, maintained under the same conditions for 30 seconds, discharged at a constant current level of 0.5C rate for 1 minute, maintained under the same conditions for 10 minutes, discharged at a constant current of 2.0C rate for 30 seconds, maintained under the same conditions for 30 seconds, discharged at a constant current of 0.5C rate for 2 minutes, maintained under the same conditions for 10 minutes, discharged at a constant current of 3.0C rate for 30 seconds, maintained under the same conditions for 30 seconds, discharged at a constant current of 0.5C rate for 2 minutes, and then maintained under the same conditions for 10 minutes.
The average voltage drop for each C-rate of 10 seconds is a dc voltage.
Some dc impedance values are shown in table 3 below.
TABLE 3
Group of Increase in DC impedance at high temperature (45 ℃ C.) (%)
Example 1 92
Example 2 90
Example 3 93
Example 4 88
Example 5 85
Comparative example 1 143
Comparative example 2 152
Comparative example 3 102
Comparative example 4 107
Is commercially available 110
As shown in table 3 above, lithium batteries including examples 1-5 of the present invention showed significantly lower rates of increase in dc resistance at high temperatures (45 c) as compared to lithium batteries prepared by comparative examples 1-4 and commercially available electrolytes. In comparative example 1 and comparative example 2, the lithium salt was a single LiBF, respectively4Or lithium bis (oxalato) borate, a significant increase in its DC resistance, visible LiBF4The mixture of the lithium bis (oxalato) borate and the lithium bis (oxalato) borate has a synergistic effect. The lithium bis (oxalato) borate adopted by the invention has the advantages of low cost, high thermal stability, high safety and stable electrochemical property, and the LiBF is added4Can improve the ionic conductivity, improve the stability of the electrolyte and the positive and negative electrode interfaces, and have good conductivity, high and low temperature resistance and costLow cost, safety and stability, thus having synergistic effect.
Test example 4 evaluation of stability at high temperature of 60 ℃
During the first cycle, lithium batteries prepared from the electrolytes manufactured in examples 1 to 5 and comparative examples 1 to 4, and a commercially available electrolyte (available from hanqian new materials co., dongguan) were charged at room temperature (25 ℃) and a constant current of about 0.5C rate until the voltage reached 4.20V, charged at a constant voltage of 4.20V until the current reached 0.05C, and then discharged at a constant current of 0.5C rate until the voltage reached 2.75V.
During the second cycle, the lithium battery was charged at a constant current of about 0.5C rate until the voltage reached 4.20V, charged at a constant voltage of 4.20V until the current reached 0.05C, and then discharged at a constant current of 0.2C rate until the voltage reached 2.80V.
During the third cycle, the lithium battery was charged at a constant current of about 0.5C rate until the voltage reached 4.20V, charged at a constant voltage of 4.20V until the current reached 0.05C, and then discharged at a constant current of 0.2C rate until the voltage reached 2.80V. The discharge capacity in the third cycle was regarded as a standard capacity.
During the fourth cycle, the lithium cell was charged at a rate of about 0.5C until the voltage reached 4.20V, charged at a constant voltage of 4.20V until the current reached 0.05C, stored in an oven at 60 ℃ for 60 days, and then the cell was removed and subjected to a fourth discharge cycle at a rate of 0.1C until the voltage reached 2.75V. Some charge and discharge results are shown in table 4 below. The capacity retention rate after high-temperature storage can be defined as follows.
Capacity retention after high-temperature storage [% ] is [ discharge capacity/standard capacity after high-temperature exposure in the fourth cycle ] × 100%.
(Standard Capacity is discharge Capacity in third cycle)
TABLE 4
Figure BDA0002515111380000171
Figure BDA0002515111380000181
As shown in table 4 above, lithium batteries prepared including the electrolytes of examples 1 to 5 of the present invention showed significantly increased stability at high temperatures, compared to lithium batteries manufactured in comparative examples 1 to 4 and commercial electrolytes.
Compared with the embodiment 5, the comparative examples 3 and 4 are respectively not added with methyl-nonafluorobutyl ether or imidazolyl ionic liquid, the imidazolyl ionic liquid has high solubility to lithium salt, has the characteristics of no combustion, no explosion, difficult oxidation, good thermal stability and the like, has a wider liquid range, stronger dissolving capacity, lower vapor pressure, more proper viscosity, higher conductivity, a wider electrochemical window and the like when being added into the electrolyte, can more effectively reduce the passivation phenomenon of the lithium/carbon fluoride battery and improve the storage performance of the lithium/manganese dioxide battery, and can reduce an SEI film layer formed on the surface of the anode of the passivated lithium battery under the synergistic action of the imidazolyl ionic liquid. The compact layer has electronic insulating capability and good ion conducting capability, while the loose layer has loose and porous structure and poor electronic conducting capability, and is the main reason of voltage lag at the initial discharge stage of the battery. Due to the addition of the imidazolyl ionic liquid, strong-polarity cationic groups of the imidazolyl ionic liquid can be effectively adsorbed in the SEI film layer, the ionic conductivity of the SEI film layer is enhanced due to the high conductivity of the ionic liquid, and the methyl-nonafluorobutyl ether relatively inhibits the migration of lithium ions and plays a role in inhibiting the growth of a loose layer. The two aspects act simultaneously, and the passivation phenomenon of the lithium battery is reduced.
Compared with the prior art, the lithium bis (oxalato) borate adopted by the invention has the advantages of low cost, high thermal stability, high safety and stable electrochemical property, and the LiBF is added4Can improve the ionic conductivity and the stability of the electrolyte and the positive and negative electrode interfaces, and the combination of the electrolyte and the positive and negative electrode interfaces has good conductivity and high and low temperature resistance, and the electrolyte and the positive and negative electrode interfaces have good performanceThe composition is low in cost, safe and stable, and has a synergistic effect;
the addition of the high and low temperature resistant additive is beneficial to enhancing the compatibility of the electrolyte and the carbon cathode and simultaneously enhancing the interface stability of the electrolyte and the cathode, so that the electrolyte can carry out heavy current discharge at the low temperature of-40 ℃; the interface stability of the lithium ion electrolyte and a negative electrode under the conditions of low temperature and high temperature is obtained through long-term research of an inventor; the electrolyte is ensured to have a lower freezing point and high-temperature incombustibility, and is endowed with strong flame resistance, and the quick charging performance of the battery can be enhanced;
the imidazolyl ionic liquid has the characteristics of high solubility to lithium salt, no combustion, no explosion, difficult oxidation, good thermal stability and the like, and has the advantages of wider liquid range, stronger dissolving capacity, lower vapor pressure, more proper viscosity, higher conductivity, wider electrochemical window and the like when being added into the electrolyte, so that the imidazolyl ionic liquid has wide application prospect. The application of the imidazolyl ionic liquid in the lithium battery can change the composition and structure of a passivation film to form a stable passivation film, the growth of the passivation film is inhibited along with the prolonging of the storage time, and meanwhile, the high-temperature discharge performance of the lithium battery can be obviously improved;
the electrolyte of the lithium battery prepared by the invention can form a relatively stable passive film, and the passive film of the layer is inhibited from increasing along with the prolonging of the storage time, so that the storage performance and the storage life of the lithium battery are obviously improved. Meanwhile, the electrolyte has lower freezing point and high-temperature incombustibility, and simultaneously gives the electrolyte strong flame resistance, and simultaneously can enhance the quick charge performance of the battery, and can be widely applied to quick charge lithium batteries.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The lithium battery electrolyte is characterized by comprising lithium salt, ethylene glycol dibutyl ether, a fluorine-containing organic solvent, a high and low temperature resistant additive and an imidazolyl ionic liquid.
2. The electrolyte for a lithium battery of claim 1 wherein the lithium salt is LiBF4And lithium bis (oxalate) borate in a mass ratio of 1: (1-2).
3. The lithium battery electrolyte as claimed in claim 1, wherein the fluorine-containing organic solvent is one or more selected from methyl-nonafluorobutyl ether, sevoflurane, glycidyl ether hexadecafluorononyl ether and octafluoropentyl allyl ether.
4. The electrolyte for the lithium battery as claimed in claim 1, wherein the high and low temperature resistant additives are dihydropyridine, laurone and fluoroethylene carbonate, and the mass ratio of the dihydropyridine to the laurone to the fluoroethylene carbonate is 1: (0.5-2): (3-7).
5. The electrolyte for a lithium battery as claimed in claim 1, wherein the cation in the imidazolyl ionic liquid has the following structure of formula i:
Figure FDA0002515111370000011
6. the lithium battery electrolyte as claimed in claim 1, wherein the imidazole-based ionic liquid has a BF anion4 -Or PF6 -。
7. A method of manufacturing a lithium battery electrolyte as claimed in any one of claims 1 to 6, characterized in that it comprises the following steps:
s1, respectively connecting high-purity aluminum sheets for the positive electrode and the negative electrode in an anhydrous environment, and connecting a voltage-stabilized power supply for electrolysis for 10-15h to remove water in the imidazolyl ionic liquid and the fluorine-containing organic solvent;
s2, dissolving lithium salt in the imidazolyl ionic liquid obtained in the step S1, and uniformly mixing to obtain a solution A;
s3, adding ethylene glycol dibutyl ether and the high and low temperature resistant additive into the fluorine-containing organic solvent obtained in the step S1, and uniformly mixing to obtain a solution B;
and S4, mixing the solution A and the solution B at the temperature of 30-40 ℃, and homogenizing to obtain the lithium battery electrolyte.
8. The method according to claim 7, wherein the voltage in step S1 is 3-6V.
9. The method as claimed in claim 7, wherein the homogenizing condition in step S4 is 10000-12000r/min for 1-2 min.
10. Use of the lithium battery electrolyte according to claims 1-6 for the preparation of a fast-charging lithium ion battery.
CN202010473642.9A 2020-05-29 2020-05-29 Lithium battery electrolyte and preparation method and application thereof Pending CN111600072A (en)

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