CN112086683A - Lithium ion battery electrolyte, preparation method thereof, high-voltage lithium ion battery and battery module - Google Patents
Lithium ion battery electrolyte, preparation method thereof, high-voltage lithium ion battery and battery module Download PDFInfo
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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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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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
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Abstract
The present disclosure relates to a lithium ion battery electrolyte containing a solvent, a first ionic liquid, a second ionic liquid, and a lithium salt; the first ionic liquid contains a piperidine cation and a tris (pentafluoroethyl) trifluorophosphate anion, and the second ionic liquid contains an imidazole cation and a tetracyanoborate anion. The ionic liquid disclosed by the invention has the advantages of lower viscosity, higher conductivity and higher oxidation resistance potential, and the lithium ion battery containing the electrolyte disclosed by the invention has a wider electrochemical window and good stability.
Description
Technical Field
The disclosure relates to the field of lithium ion batteries, in particular to a lithium ion battery electrolyte and a preparation method thereof, a high-voltage lithium ion battery and a battery module.
Background
LiNi0.5Mn1.5O4It is considered to be an ideal commercial battery material due to its high power and energy density, but it is slowly developed due to the limitation of the electrolyte. The main reason is that the prior electrolyte is usually high-viscosity and high-dielectric-constant cyclic carbonate, such as Ethylene Carbonate (EC) and Propylene Carbonate (PC), and low-viscosity and low-dielectric-constant chain carbonate, such as carbonic acid diesterMixtures of methyl ester (DMC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) are solvent electrolytes, and the chemical windows of these electrolytes are low. When the voltage of the battery reaches about 4.5V, the electrolyte begins to generate violent oxidative decomposition reaction, so that the interface impedance between the electrode and the electrolyte is increased, the charging and discharging efficiency of the lithium ion battery is reduced, the cycle performance is poor, and the performance of the battery is deteriorated.
The piperidine ionic liquid has the electrochemical characteristics of good ionic conductivity, wide electrochemical window and the like, and can be widely applied to the field of lithium ion batteries. However, when the piperidine ionic liquid is used as an electrolyte, the problems of high viscosity, low lithium ion concentration, low electrolyte conductivity and the like exist.
In order to overcome the above disadvantages, researchers have proposed a method of incorporating an organic solvent into an ionic liquid to reduce the viscosity of the ionic liquid and to improve the conductivity of the ionic liquid. However, when the organic solvent is added, the corresponding problem also exists, if the addition amount of the organic solvent is too small, the viscosity of the ionic liquid cannot be reduced sufficiently, and the effect of improving the conductivity is not obvious; if the addition amount of the organic solvent is large, the problems of viscosity and conductivity can be solved, but the thermal stability of the electrolyte and the oxidation resistance potential of the electrolyte are reduced, so that the safety performance of the lithium battery is reduced. The existing electrolyte containing piperidine ionic liquid cannot simultaneously have the advantages of low viscosity, high conductivity, high oxidation resistance potential and thermal stability.
Disclosure of Invention
The invention aims to solve the problems of high viscosity, low conductivity, poor stability and narrow electrochemical window of a lithium ion battery of the conventional high-voltage lithium ion battery electrolyte, and provides a lithium ion battery electrolyte, a preparation method thereof, a high-voltage lithium ion battery and a battery module.
In order to achieve the above object, a first aspect of the present disclosure provides a lithium ion battery electrolyte containing a solvent, a first ionic liquid, a second ionic liquid, and a lithium salt;
the first ionic liquid contains piperidine cation and tris (pentafluoroethyl) trifluorophosphate anion, the structure of the piperidine cation is shown as the formula (I),
the second ionic liquid contains imidazole cations and tetracyanoborate anions, and the structure of the imidazole cations is shown in a formula (II);
Alternatively, in formula (I), R0、R1、R2、R3、R4、R5And R6At least one of which is said group (CH)2)nOm(CH2)zOyCH3。
Alternatively, in formula (I), R2、R3、R4、R5And R6Are each hydrogen, R0And R1Each independently of the others halogen, C1-C10 alkyl, said group (CH)2)xOH or the group (CH)2)nOm(CH2)zOyCH3。
Alternatively, in formula (I), R0Is a group (CH)2)nOm(CH2)zOyCH3，R1Is halogen, C1-C10 alkyl or the radical (CH)2)xOH。
Alternatively, in formula (I), m is 1, and/or y is 1.
Alternatively, in the formula (II), R7、R9And R10Are each hydrogen, R8One selected from halogen, C2-C6 cyanoalkyl, C1-C12 alkyl and C1-C4 alkenyl.
Optionally, the total content of the first ionic liquid and the second ionic liquid is 3 to 80 wt%, and the content of the lithium salt is 10 to 40 wt%, based on the total weight of the electrolyte.
Optionally, the weight ratio of the first ionic liquid to the second ionic liquid is 1: (0.15-6).
Optionally, the solvent is selected from cyclic carbonates and/or chain carbonates;
the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate and vinylene carbonate; the chain carbonate is selected from one or more of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate and dipropyl carbonate.
Optionally, the lithium salt is selected from one or more of lithium bistrifluoromethanesulfonylimide, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium halides, lithium difluorophosphate, lithium monofluorophosphate and lithium fluorofluorosulfonate.
Optionally, the first ionic liquid contains at least one of the following compounds:
the second ionic liquid contains at least one of the following compounds:
in a second aspect of the present disclosure, the first ionic liquid, the second ionic liquid, the lithium salt, and the solvent are mixed under an inert atmosphere to prepare the lithium ion battery electrolyte.
Optionally, the total amount of the first ionic liquid and the second ionic liquid is 3 to 80 wt%, and the amount of the lithium salt is 10 to 40 wt%, based on the total weight of the electrolyte.
Optionally, the weight ratio of the first ionic liquid to the second ionic liquid is 1: (0.15-6).
A third aspect of the present disclosure provides a high voltage lithium ion battery comprising a positive electrode, a negative electrode, and the electrolyte provided by the first aspect of the present disclosure.
Optionally, the active material of the positive electrode is selected from LiNi0.5Mn1.5O4、LiCoPO4、Li1.2Ni0.13Co0.13Mn0.54O2And LiCoMnO4One or more of them.
A fourth aspect of the present disclosure provides a lithium ion battery module including the high voltage lithium ion battery provided by the third aspect of the present disclosure.
Through the technical scheme, the lithium ion battery electrolyte disclosed by the invention contains two different ionic liquids, wherein the first ionic liquid contains piperidine cations and tris (pentafluoroethyl) trifluorophosphate anions, and the second ionic liquid contains imidazole cations and tetracyanoborate anions. The piperidine ions disclosed by the invention have high electrochemical stability, are very stable to moisture, cannot be decomposed to generate HF, and have better thermal stability, and the imidazole ions disclosed by the invention also have wider electrochemical window and extremely low viscosity. Therefore, the piperidine ionic liquid and the imidazole ionic liquid not only make up for the defects of the piperidine ionic liquid and the imidazole ionic liquid, but also have complementary advantages, so that the lithium ion battery has low viscosity, high conductivity and wider electrochemical window. Meanwhile, tris (pentafluoroethyl) trifluorophosphate anion and tetracyanoborate anion can remarkably improve the stability of the electrolyte. The electrolyte disclosed by the invention is low in viscosity, high in conductivity and high in oxidation resistance potential, and the lithium ion battery containing the electrolyte disclosed by the invention is wide in electrochemical window and good in stability.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides in a first aspect a lithium ion battery electrolyte comprising a solvent, a first ionic liquid, a second ionic liquid, and a lithium salt;
the first ionic liquid contains piperidine cation and tris (pentafluoroethyl) trifluorophosphate anion, the structure of the piperidine cation is shown as the formula (I),
wherein R is0、R1、R2、R3、R4、R5And R6Each independently selected from hydrogen, halogen, C1-C10 alkyl, group (CH)2)xOH and a radical (CH)2)nOm(CH2)zOyCH3X is any integer from 1 to 10, n is any integer from 1 to 10, m is 0 or 1, z is any integer from 0 to 6, and y is 0 or 1;
the second ionic liquid contains imidazole cations and tetracyanoborate anions, and the structure of the imidazole cations is shown as the formula (II);
wherein R is7、R8、R9And R10Each independently selected from hydrogen, halogen, C2-C6 cyanoalkyl, C1-C12 alkyl and C1-C4 alkenyl11Is C1-C12 alkyl or C1-C4 alkenyl.
In one embodiment, in formula (I), R0、R1、R2、R3、R4、R5And R6Each independently selected from hydrogen, C1-C10 alkyl, group (CH)2)xOH and a radical (CH)2)nOm(CH2)zOyCH3X is an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, preferably 1, 2, 3, 4; n is an integer from 1 to 10, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, preferably 1, 2, 3, 4; m is 0 or 1; y is 0 or 1; z is an integer from 0 to 6, for example 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 4. Among them, the C1-C10 alkyl group is, for example, C3, C4, C6, C9 or C10 alkyl group, preferably C4 or C6 alkyl group.
In one embodiment, in formula (II), R7、R8、R9And R10Each independently selected from hydrogen, C2-C6 cyanoalkyl, C1-C12 alkyl and C1-C4 alkenyl, preferably hydrogen or C1-C12 alkyl.
Among them, the C1-C10 alkyl group in the formula (I), the C2-C6 cyanoalkyl group, the C1-C12 alkyl group and the C1-C12 alkyl group in the formula (II) are not particularly limited in kind, and may be a cyclic alkyl group or an acyclic alkyl group, or a branched alkyl group or a straight-chain alkyl group. Wherein, the C2-C6 cyanoalkyl group may include at least one of ethylnitrile, propylnitrile, isopropylnitrile, butylnitrile, and valeronitrile; the cyanoalkyl group preferably having C2 to C4 may be, for example, at least one of ethylnitrile, propylnitrile, isopropylnitrile and butylnitrile; further preferably at least one of ethylnitrile, propylnitrile and butylnitrile, and the C1-C12 alkyl group may be at least one of methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, undecane and dodecane, preferably methyl and/or butyl. Wherein the halogen can be at least one of fluorine, chlorine, bromine and iodine, and is preferably fluorine and chlorine.
The lithium ion battery electrolyte disclosed by the disclosure contains two different ionic liquids, wherein the cation of the first ionic liquid is piperidine cation, and the anion of the first ionic liquid is tris (pentafluoroethyl) trifluorophosphate anion. The piperidine ionic liquid has a wide electrochemical window, but has the problems of high viscosity and low conductivity, and the tris (pentafluoroethyl) trifluorophosphate anion is very stable to water, cannot be decomposed to generate HF, and has high electrochemical stability and thermal stability. The cation of the second ionic liquid is imidazole cation, the anion of the second ionic liquid is tetracyanoboric acid anion, the imidazole ionic liquid is small in viscosity, but the electrochemical window is narrow, and the tetracyanoboric acid anion is strong in oxidation resistance, so that the stability of the electrolyte can be further enhanced. The second ionic liquid of the disclosure has higher conductivity and lower viscosity, the conductivity can be above 13ms/cm, the viscosity is below 20mPa/S, and the electrochemical window can be as high as 5.6V. The piperidine first ionic liquid and the imidazole second ionic liquid contained in the electrolyte disclosed by the invention can complement each other in advantages, so that the electrolyte disclosed by the invention not only has lower viscosity and higher conductivity, but also has a wider electrochemical window and good thermal stability.
In one embodiment, in formula (I), R0、R1、R2、R3、R4、R5And R6At least one of which may be a group (CH)2)nOm(CH2)zOyCH3N is an integer of 1 to 10, m is 0 or 1, z is an integer of 0 to 6, and y is 0 or 1. Preferably, the group (CH)2)nOm(CH2)zOyCH3Is an ether group, a radical (CH)2)nOm(CH2)zOyCH3Wherein at least one oxygen atom, in particular m is 1, and/or y is 1; in this case, the piperidine cation is a piperidine cation containing ether bond substituent, and the introduction of the ether bond substituent can further improve the lithium ion batteryStability of the electrolyte.
Preferably, in the formula (I), R2、R3、R4、R5And R6Can be respectively hydrogen, R0And R1May each independently be halogen, C1-C10 alkyl, a group (CH)2)xOH or a group CH2)nOm(CH2)zOyCH3。
Further preferably, in the formula (I), R0May be a group (CH)2)nOm(CH2)zOyCH3，R1Is halogen, C1-C10 alkyl or a group (CH)2)xAnd (5) OH. Preferably, m is 1, and/or y is 1, so that the lithium ion battery electrolyte of the present disclosure has more excellent stability.
In one embodiment, according to the present disclosure, in formula (II), R7、R9And R10Can be respectively hydrogen, R8May be one of halogen, C2-C6 cyanoalkyl, C1-C12 alkyl and C1-C4 alkenyl, preferably C2-C4 alkyl, C2-C4 cyanoalkyl and C1-C3 alkenyl. When the imidazolium cation of the present disclosure has the above structure, the second ionic liquid has a lower viscosity, so that the conductivity of the lithium ion battery electrolyte may be further improved.
In one embodiment, in formula (I), R2、R3、R4、R5And R6Are each hydrogen, R0And R1Each independently of the others being halogen, C1-C10 alkyl, a radical (CH)2)xOH or a radical (CH)2)nOm(CH2)zOyCH3. Further, R0Is a group (CH)2)nOm(CH2)zOyCH3，R1Is halogen, C1-C10 alkyl or a group (CH)2)xAnd (5) OH. Wherein n is an integer from 1 to 10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, preferably 1, 2, 3, 4; m is 0 or 1; y is 0 or 1, z is an integer from 0 to 6, for example 0, 1, 2, 3, 4, 5 or 6, preferably 0,1. 2 and 4. Among them, the C1-C10 alkyl group is, for example, C3, C4, C6, C9 or C10 alkyl group, preferably C4 or C6 alkyl group.
According to the present disclosure, the total content of the first ionic liquid and the second ionic liquid may be 3 to 80% by weight, and the content of the lithium salt may be 10 to 40% by weight, based on the total weight of the electrolyte. Preferably, the total content of the first ionic liquid and the second ionic liquid is 20-40 wt% and the content of the lithium salt is 10-20 wt% based on the total weight of the electrolyte. Too high content of the first ionic liquid and the second ionic liquid may cause too high viscosity and poor conductivity of the electrolyte, and too low content may cause poor stability of the electrolyte. Within the preferable content range, the proportion of each component of the lithium ion battery electrolyte is proper, so that the electrochemical window of the lithium ion battery is wider, and the performance of the battery, such as the deterioration of cycle performance, caused by the decomposition of the electrolyte is avoided; meanwhile, the electrolyte has lower viscosity, higher conductivity, higher oxidation resistance potential and good stability.
According to the present disclosure, the usage ratio of the first ionic liquid to the second ionic liquid may vary within a wide range, and preferably, the weight ratio of the first ionic liquid to the second ionic liquid may be 1: (0.15-6), more preferably, the weight ratio of the first ionic liquid to the second ionic liquid is 1: (0.8-4), for example, 1: (1.1-4) or 1: (1.5-3.5). Within the preferable range, the ratio of the two ionic liquids is proper, so that the imidazole ionic liquid and the piperidine ionic liquid can fully exert respective advantages, and the electrolyte has good conductivity, a wide electrochemical window and good stability.
The solvent may be one conventionally used by those skilled in the art in light of the present disclosure, and may be selected from cyclic carbonates and/or chain carbonates, for example, and other kinds of solvents will not be described herein.
Wherein, the cyclic carbonate can be selected from one or more of ethylene carbonate, propylene carbonate and vinylene carbonate; the chain carbonate can be one or more selected from dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate and dipropyl carbonate.
According to the present disclosure, the lithium salt may be selected from one or more of lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium bistrifluorosulfonylimide (LiFSI), lithium tetrafluoroborate, lithium hexafluorophosphate, lithium halides, lithium difluorophosphate, lithium monofluorophosphate, and lithium fluorosulfonate, and other kinds of lithium salts are not described herein in detail.
According to the present disclosure, the first ionic liquid may contain at least one of the following compounds:
the second ionic liquid may contain at least one of the following compounds:
when the first ionic liquid and the second ionic liquid contain the compound, the electrolyte can have better electrochemical performance.
In a second aspect of the present disclosure, a method for preparing the lithium ion battery electrolyte provided in the first aspect of the present disclosure is provided, where the first ionic liquid, the second ionic liquid, the lithium salt, and the solvent are mixed under an inert atmosphere to prepare the lithium ion battery electrolyte. The inert gas atmosphere may be a nitrogen gas atmosphere and/or an inert gas atmosphere, such as a helium gas atmosphere, a neon gas atmosphere, an argon gas atmosphere. The method disclosed by the invention can be used for simply, conveniently and efficiently preparing the lithium ion battery electrolyte.
According to the present disclosure, the first ionic liquid and the second ionic liquid may be used in a total amount of 3 to 80% by weight, and the lithium salt may be used in an amount of 10 to 40% by weight, based on the total weight of the electrolyte, and preferably, the first ionic liquid and the second ionic liquid may be used in a total amount of 20 to 40% by weight, and the lithium salt may be used in an amount of 10 to 20% by weight, based on the total weight of the electrolyte. Within the preferable dosage range, the proportion of the two ionic liquids is proper, so that the imidazole ionic liquid and the piperidine ionic liquid can fully exert respective advantages, and the electrolyte has good conductivity, a wide electrochemical window and good stability.
According to the present disclosure, the weight ratio of the first ionic liquid to the second ionic liquid may vary within a wide range, and the weight ratio of the first ionic liquid to the second ionic liquid may be 1: (0.15-6), preferably, the weight ratio of the first ionic liquid to the second ionic liquid is 1: (0.8-4). The electrolyte can be ensured to have higher conductivity and wider electrochemical window, and also has good stability.
A third aspect of the present disclosure provides a high voltage lithium ion battery comprising a positive electrode, a negative electrode, and the electrolyte provided by the first aspect of the present disclosure. The high-voltage lithium ion battery disclosed by the invention has the advantages of higher conductivity, wider electrochemical window and thermal stability.
The positive electrode is well known to those skilled in the art and may include a positive electrode current collector and an active material coated or filled on the positive electrode current collector. The material of the positive current collector may be aluminum foil, copper foil, nickel-plated steel strip, etc., and preferably copper foil is used as the positive current collector. The active material of the positive electrode may be conventionally employed by those skilled in the art in light of the present disclosure, and may be selected from, for example, LiNi0.5Mn1.5O4、LiCoPO4、Li1.2Ni0.13Co0.13Mn0.54O2And LiCoMnO4One or more of the above materials have relatively high output voltage and cycling stability. The positive electrode may further contain a binder, optionally a conductive agent.
The composition of the negative electrode is well known to those skilled in the art, and the negative electrode may include a negative electrode current collector and an active material coated or filled on the negative electrode current collector. The material of the negative electrode current collector may be well known to those skilled in the art, and for example, may be one or more selected from the group consisting of aluminum foil, copper foil, nickel-plated steel strip, and punched steel strip. The active material of the negative electrode can be one or more of artificial graphite, natural graphite, carbon fiber, organic cracking carbon, tin alloy, silicon alloy and the like. The negative electrode may further include a binder, such as one or more of polytetrafluoroethylene, styrene-butadiene rubber, and polyvinyl alcohol. The negative electrode can also directly use metal lithium, and the metal lithium can provide large theoretical capacity and high output voltage when used as a negative electrode material.
The lithium ion battery of the present disclosure may further include a separator, which is well known to those skilled in the art, for example, a composite film formed by welding or bonding a modified polyethylene felt, an ultra-fine glass fiber felt, a modified polypropylene felt, a nylon felt and a wettable polyolefin microporous film.
The positive electrode, the negative electrode and the lithium ion battery of the present disclosure may be prepared by a method conventionally employed by those skilled in the art, and preferably, the method of preparing the positive electrode includes: and coating slurry containing a positive active substance, a positive adhesive and a positive conductive agent on the positive current collector, drying, rolling and slicing to obtain the positive electrode. Drying is generally carried out at from 50 to 160 ℃ and preferably from 80 to 150 ℃. The preparation method of the negative electrode comprises the following steps: and coating slurry containing a negative active material, a negative binder and a negative conductive agent which is selectively contained on a negative current collector, drying, rolling and slicing to obtain the negative electrode. And arranging a diaphragm between the positive electrode and the negative electrode to obtain an electrode group, accommodating the electrode group in a battery shell, injecting the electrolyte provided by the first aspect of the disclosure into the shell, and sealing the battery shell to obtain the high-voltage lithium ion battery disclosed by the disclosure.
The fourth aspect of the present disclosure provides a lithium ion battery module, which includes the high voltage lithium ion battery provided by the third aspect of the present disclosure, and the lithium ion battery module of the present disclosure has good cycle stability.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
Piperidines of examples 1 to 11 and comparative examples 1 to 5 (C)2F5)3PF3Ionic liquids and imidazoles B (CN)4Ionic liquids were purchased from merck, germany.
PP of comparative example 613-PO2F2imidazole-PO2F2Purchased from the research and development center of new materials of Shanghai organic chemistry institute (salt city), Chinese academy of sciences.
Example 1
At room temperature, based on 100 parts by weight of lithium ion battery electrolyte, 45 parts by weight of solvent (composed of dimethyl carbonate and EC ethylene carbonate in a weight ratio of 1: 2), 10 parts by weight of first ionic liquid, 30 parts by weight of second ionic liquid and 15 parts by weight of LiPF6And uniformly mixing to prepare the lithium ion battery electrolyte.
Wherein, the first ionic liquid is the following compound:
the second ionic liquid is the following compound:
example 2
A lithium ion battery electrolyte was prepared in the same manner as in example 1, except that the first ionic liquid was the following compound:
the second ionic liquid is the following compound:
example 3
A lithium ion battery electrolyte was prepared in the same manner as in example 1, except that the first ionic liquid was the following compound:
the second ionic liquid is the following compound:
example 4
A lithium ion battery electrolyte was prepared in the same manner as in example 1, except that the second ionic liquid was the following compound: .
Example 5
A lithium ion battery electrolyte was prepared in the same manner as in example 1, except that the solvent was used in an amount of 5 parts by weight, the first ionic liquid was used in an amount of 40 parts by weight, the second ionic liquid was used in an amount of 50 parts by weight, and the lithium salt was used in an amount of 5 parts by weight, based on 100 parts by weight of the lithium ion battery electrolyte.
Example 6
A lithium ion battery electrolyte was prepared in the same manner as in example 1, except that the first ionic liquid was used in an amount of 5 parts by weight and the second ionic liquid was used in an amount of 35 parts by weight, based on 100 parts by weight of the lithium ion battery electrolyte.
Example 7
A lithium ion battery electrolyte was prepared in the same manner as in example 1, except that the second ionic liquid contained the following compound:
example 8
At room temperature, based on 100 parts by weight of lithium ion battery electrolyte, uniformly mixing 40 parts by weight of solvent (composed of dimethyl carbonate and EC ethylene carbonate in a weight ratio of 1: 2), 15 parts by weight of first ionic liquid, 25 parts by weight of second ionic liquid and 20 parts by weight of lithium bis (fluorosulfonyl) imide (LiFSI) to prepare the lithium ion battery electrolyte.
Wherein, the first ionic liquid is the following compound:
the second ionic liquid contains the following compounds:
example 9
50 parts by weight of dimethyl carbonate, 10 parts by weight of first ionic liquid, 25 parts by weight of second ionic liquid and 15 parts by weight of LiPF (lithium ion power) based on 100 parts by weight of lithium ion battery electrolyte at room temperature6And uniformly mixing to prepare the lithium ion battery electrolyte.
Wherein, the first ionic liquid is the following compound:
the second ionic liquid contains the following compounds:
example 10
At room temperature, in 100 parts by weight of lithium ionBased on the cell electrolyte, 45 parts by weight of ethylene carbonate, 10 parts by weight of first ionic liquid, 25 parts by weight of second ionic liquid and 15 parts by weight of LiPF6And 5 parts by weight of lithium bis (fluorosulfonyl) imide, and mixing uniformly to prepare the lithium ion battery electrolyte.
Wherein, the first ionic liquid is the following compound:
the second ionic liquid is the following compound:
example 11
At room temperature, based on 100 parts by weight of lithium ion battery electrolyte, 50 parts by weight of solvent (composed of dimethyl carbonate and ethylene carbonate in a weight ratio of 1: 2), 10 parts by weight of first ionic liquid, 20 parts by weight of second ionic liquid and 15 parts by weight of LiPF6And 5 parts by weight of lithium bis (fluorosulfonyl) imide, and mixing uniformly to prepare the lithium ion battery electrolyte.
Wherein, the first ionic liquid is the following compound:
the second ionic liquid is the following compound:
comparative example 1
Lithium ions were prepared in the same manner as in example 1, except that the first ionic liquid
The anions in the body are:
comparative example 2
Lithium ions were prepared in the same manner as in example 1, except that the anion in the second ionic liquid was.
Comparative example 3
At room temperature, based on 100 parts by weight of lithium ion battery electrolyte, 45 parts by weight of solvent (composed of dimethyl carbonate and ethylene carbonate in a weight ratio of 1: 2), 40 parts by weight of first ionic liquid and 15 parts by weight of LiPF6And uniformly mixing to prepare the lithium ion battery electrolyte. Wherein the first ionic liquid is the same as the first ionic liquid in example 1.
Comparative example 4
At room temperature, based on 100 parts by weight of lithium ion battery electrolyte, 45 parts by weight of solvent (composed of dimethyl carbonate and ethylene carbonate in a weight ratio of 1: 2), 40 parts by weight of second ionic liquid and 15 parts by weight of LiPF6And uniformly mixing to prepare the lithium ion battery electrolyte. Wherein the second ionic liquid is the same as the second ionic liquid in example 1.
Comparative example 5
At room temperature, based on 100 parts by weight of lithium ion battery electrolyte, 85 parts by weight of solvent (composed of dimethyl carbonate and EC ethylene carbonate in a weight ratio of 1: 2) and 15 parts by weight of LiPF6And uniformly mixing to prepare the lithium ion battery electrolyte.
Comparative example 6
At room temperature, based on 100 parts by weight of lithium ion battery electrolyte, 45 parts by weight of solvent (composed of dimethyl carbonate and EC ethylene carbonate in a weight ratio of 1: 2) and 10 parts by weight of PP13-PO2F230 parts by weight of N, N-dimethylimidazoleAzole difluorophosphoric acid and 15 parts by weight of LiPF6And uniformly mixing to prepare the lithium ion battery electrolyte.
PP13-PO2F2The structure of (A) is as follows:
test examples
(1) Thermal stability of electrolyte
The thermal stability of the electrolytes of examples and comparative examples was measured under a nitrogen atmosphere and in the range of 25 ℃ to 350 ℃ using a differential scanning calorimeter according to the GB/T19466.1-2004 standard.
(2) Oxidation resistance potential of electrolyte
The measurement was carried out by cyclic voltammetry according to GB/T31484-2015 standard. The working electrode adopts a platinum electrode, the counter electrode and the reference electrode adopt lithium foils, the scanning speed is 50mV/s, and the test range is 1.0-6.0V.
(3) Conductivity of electrolyte
The conductivity of the electrolytes was measured at 25 ℃ by using a conductivity meter (using a platinum black electrode, and a KCl solution of 0.01mol/L to correct the cell constant).
(4) Viscosity of electrolyte
And (3) according to the GB/T2794 standard, measuring the electrolyte at 25 ℃ by using an automatic viscometer. The test results of the above tests are shown in table 1.
TABLE 1
| Item | Thermal stability | 25 deg. conductivity(mS/cm) | Antioxidant potential (V) | Viscosity (mPa/S) |
| Example 1 | ≥285 | 8.4 | 5.1 | 30 |
| Example 2 | ≥280 | 8.0 | 5.1 | 32 |
| Example 3 | ≥280 | 6.5 | 5.1 | 35 |
| Example 4 | ≥280 | 8.1 | 5.0 | 30 |
| Example 5 | ≥285 | 4.5 | 5.2 | 40 |
| Example 6 | ≥280 | 7.1 | 4.8 | 30 |
| Example 7 | ≥285 | 6.5 | 5.0 | 30 |
| Example 8 | ≥280 | 6.4 | 5.2 | 30 |
| Example 9 | ≥280 | 5.5 | 5.0 | 30 |
| Example 10 | ≥275 | 5.2 | 4.9 | 30 |
| Example 11 | ≥270 | 8.1 | 5.0 | 32 |
| Comparative example 1 | ≥260 | 3.5 | 4.9 | 80 |
| Comparative example 2 | ≥260 | 6.4 | 4.8 | 50 |
| Comparative example 3 | ≥295 | 3.2 | 5.2 | 85 |
| Comparative example 4 | ≥270 | 4.2 | 4.8 | 24 |
| Comparative example 5 | ≥200 | 12.0 | 4.2 | 20 |
| Comparative example 6 | ≥255 | 4.0 | 4.8 | 80 |
As can be seen from table 1, the lithium ion battery electrolyte disclosed by the present disclosure has a relatively low viscosity, a relatively high conductivity, a relatively high oxidation resistance potential, and a good stability, and the lithium ion battery containing the electrolyte disclosed by the present disclosure has a relatively wide electrochemical window.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (17)
1. The electrolyte of the lithium ion battery is characterized by comprising a solvent, a first ionic liquid, a second ionic liquid and a lithium salt;
the first ionic liquid contains piperidine cation and tris (pentafluoroethyl) trifluorophosphate anion, the structure of the piperidine cation is shown as the formula (I),
the second ionic liquid contains imidazole cations and tetracyanoborate anions, and the structure of the imidazole cations is shown in a formula (II);
2. The electrolyte of claim 1, wherein in formula (I), R is0、R1、R2、R3、R4、R5And R6At least one of which is said group (CH)2)nOm(CH2)zOyCH3。
3. The electrolyte of claim 2, wherein in formula (I), R is2、R3、R4、R5And R6Are each hydrogen, R0And R1Each independently of the others halogen, C1-C10 alkyl, said group (CH)2)xOH or the group (CH)2)nOm(CH2)zOyCH3。
4. The electrolyte of claim 3, wherein in formula (I), R is0Is a group (CH)2)nOm(CH2)zOyCH3，R1Is halogen, C1-C10 alkyl or the radical (CH)2)xOH。
5. The electrolyte of any one of claims 1 to 4, wherein in formula (I), m is 1, and/or y is 1.
6. The electrolyte of claim 1, wherein in formula (II), R7、R9And R10Are each hydrogen, R8Selected from halogen, C2-C6 cyanoalkyl, C1-C12One of alkyl and C1-C4 alkenyl.
7. The electrolyte of any one of claims 1-4 and 6, wherein the total content of the first ionic liquid and the second ionic liquid is 3-80 wt% and the content of the lithium salt is 10-40 wt%, based on the total weight of the electrolyte.
8. The electrolyte of any one of claims 1-4 and 6, wherein the weight ratio of the first ionic liquid to the second ionic liquid is 1: (0.15-6).
9. The electrolyte of any one of claims 1-4 and 6, wherein the solvent is selected from cyclic carbonates and/or chain carbonates;
the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate and vinylene carbonate; the chain carbonate is selected from one or more of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate and dipropyl carbonate.
10. The electrolyte of any one of claims 1-4 and 6, wherein the lithium salt is selected from one or more of lithium bistrifluoromethanesulfonimide, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium halides, lithium difluorophosphate, lithium monofluorophosphate, and lithium fluorofluorosulfonate.
11. The electrolyte of any one of claims 1-4 and 6, wherein the first ionic liquid comprises at least one of the following compounds:
the second ionic liquid contains at least one of the following compounds:
12. the method for preparing the electrolyte according to any one of claims 1 to 11, wherein the lithium ion battery electrolyte is prepared by mixing the first ionic liquid, the second ionic liquid, the lithium salt and the solvent under an inert atmosphere.
13. The method of claim 12, wherein the first ionic liquid and the second ionic liquid are present in a total amount of 3 to 80 wt%, and the lithium salt is present in an amount of 10 to 40 wt%, based on the total weight of the electrolyte.
14. The method of claim 12 or 13, wherein the weight ratio of the first ionic liquid to the second ionic liquid is 1: (0.15-6).
15. A high voltage lithium ion battery comprising a positive electrode, a negative electrode and the electrolyte of any one of claims 1 to 11.
16. The li-ion battery of claim 15, wherein the active material of the positive electrode is selected from the group consisting of LiNi0.5Mn1.5O4、LiCoPO4、Li1.2Ni0.13Co0.13Mn0.54O2And LiCoMnO4One or more of them.
17. A lithium ion battery module, characterized in that the battery module comprises a high voltage lithium ion battery according to claim 16.
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