CN110204473B - Double-center cationic liquid for lithium battery and preparation method thereof - Google Patents
Double-center cationic liquid for lithium battery and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of ionic liquid, and particularly relates to a double-center cationic liquid for a lithium battery and a preparation method thereof. Introduction of-CH in ionic liquid structural formula 2 ‑O‑CH 2 (OEG) contribution of Li + More efficient migration can dissolve more lithium salts, enhance the transport effect of cations, and improve the conductivity when used as the lithium battery electrolyte. Meanwhile, compared with the design of a single-side chain, the design of the double-center cation has higher chemical and thermal stability, and the double-center cation is added into organic electrolyte as an additive to prepare a nonflammable electrolyte system and improve the thermal stability of the lithium battery.
Description
Technical Field
The invention belongs to the technical field of ionic liquid, and particularly relates to a double-center cationic liquid for a lithium battery and a preparation method thereof.
Background
Ionic liquids, also known as room temperature ionic liquids or room temperature molten salts, are also known as non-aqueous ionic liquids, liquid organic salts, and the like. It is generally considered to be a liquid consisting entirely of cations and anions, and organic salts that are present as liquids at or near room temperature.
Ionic liquids have attracted considerable attention as a new type of ionizing solvent in many fields of chemistry and chemistry. In recent years, dicationic ionic liquids have attracted considerable attention for their excellent properties. The dicationic ionic liquid has the most remarkable properties of excellent thermal stability, high density, high viscosity, wider liquid range and the like. The method can be used for high-temperature organic reaction, novel high-temperature-resistant lubricants, gas chromatography stationary phases, all-solid-state dye-sensitized solar cells, potential electrolytes, catalytic synthesis, selective complexation and mercury extraction, and has wide potential application fields.
Lall et al synthesize a series of di-ammonium and poly-ammonium cation phosphate ionic liquids by anion exchange with poly-ammonium cation chlorides. Shreeve et al synthesized a coupled bipyridine ionic liquid. Armstrong et al synthesized a series of symmetric and asymmetric dicationic ionic liquids.
However, the use of conventional ionic liquids in electrolyte systems can lead to a reduction in the rate charge and discharge performance of the battery, since the ionic liquid has a higher cation diffusion coefficient than Li + Much larger, and the cation diffusion rate is higher than that of Li when the battery is charged and discharged + Fast, fast migrating cations are attached around the C cathode and further embedded into the C cathode to form a blocking layer to block Li + Insertion and extraction.
Disclosure of Invention
The invention designs a double-center cationic liquid for a lithium battery, and-CH is introduced into an ionic liquid structural formula 2 -O-CH 2 (OEG) contribution to Li + The migration is more efficient, so that the problem that the multiplying power charge and discharge performance of the battery is reduced when the existing ionic liquid is used for an electrolyte system is solved. The double-center cationic liquid can be used as lithium battery electrolyte and can also be added into organic electrolyte as an additive to prepare nonflammable electrolyteThe electrolyte system improves the thermal stability of the lithium battery, and when the electrolyte system is added into an organic electrolyte, compared with a common ionic liquid additive without functional groups, the electrolyte system can improve the cycle performance of the battery.
The pyrrole double-center cationic liquid provided by the invention has the following structural formula:
wherein n =1-4.
According to the double-center cation disclosed by the invention, more lithium salts can be dissolved by introducing an OEG group, so that the transport effect of cations is enhanced, and the conductivity is improved. Meanwhile, compared with the design of a single-side chain, the design of the double-center cation has higher chemical and thermal stability, and meanwhile, the ionic liquid based on the pyrrolidinium has better compatibility with the cathode of the lithium battery.
The invention also provides a preparation method of the pyrrole double-center cationic liquid [ DiMPy1O ] [ TFSI ], [ DiMPy2O ] [ TFSI ], [ DiMPy3O ] [ TFSI ], [ DiMPy4O ] [ TFSI ], and the specific steps of the synthesis of the pyrrole double-center cationic liquid are as follows:
(1) The chloride and 1-methylpyrrole were dissolved in 10 ml of distilled acetonitrile and stirred under reflux for more than 4 hours. The reaction mixture was then cooled to room temperature and stirred overnight. The solvent was evaporated off, the product was washed three times with 15 ml of ether, and the remaining solvent was removed by vacuum to give an intermediate product.
Wherein the chloride is bis (chloroethyl) ether, 1,2-bis (2-chloroethoxy) ethane, 1-chloro-2- (2- ((2-chloroethoxy) ethoxy) ethane or 1,2-bis (2- (2-chloroethoxy) ethoxy) ethane, and the molar ratio of the chloride to the 1-methylpyrrole is 1.
(2) Taking the intermediate product obtained in the step (1), dissolving the intermediate product in 8 ml of deionized water, adding slightly excessive lithium bis (trifluoromethylsulfonyl) imide (the molar ratio of the lithium bis (trifluoromethylsulfonyl) imide to the intermediate product is 2.1), stirring the mixed solution at room temperature overnight to fully exchange halogen anions, extracting with 30 ml of dichloromethane to obtain an organic layer, adding 10 ml of saturated saline, fully shaking and standing to obtain a lower organic layer, repeatedly washing with saturated saline for three times, then taking the organic layer to remove water and purify by using anhydrous magnesium sulfate and activated carbon, further purifying and concentrating the obtained organic layer by using an alumina column chromatography, and obtaining a final product under reduced pressure, namely pyrrole double-center cation liquid brown liquid.
The method for synthesizing the pyrrole double-center cationic ionic liquid has the advantages of economic and simple operation, no by-product and easy purification of the product. The obtained product has good thermal stability. The physicochemical property of the dicationic ionic liquid can be adjusted by adjusting the length of a hydrocarbon chain connecting two cation linking groups and changing the structures of anions and cations.
The pyrrole double-center cationic liquid prepared by the invention can be used as an additive to modify and dope the original electrolyte when being used for a lithium ion battery, and can effectively improve the flame retardant capability of the lithium battery and greatly improve the safety performance of the battery along with the improvement of the component proportion of the ionic liquid.
The ionic liquid is used as an additive to modify and dope a carbonate electrolyte, wherein the carbonate electrolyte comprises Propylene Carbonate (PC), ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC) or methyl ethyl carbonate (EMC) and the like, a common electrolyte solvent system is an electrolyte of an EC-DMC or EC-DEC system, and the dosage of the ionic liquid as the additive is 40-50%.
The pyrrole double-center cationic liquid can also be designed into a ternary electrolyte together with 1-ethyl-3-methylimidazolium dicyanamide ([ MImEt ] [ DCA ]) ionic liquid and lithium salt, and the conductivity and the safety of the lithium ion battery are improved through design and optimization.
Wherein, the ionic liquid: [ MImEt][DCA]Has the structural formula
Can be used as a cosolvent.
Lithium usedThe salt is: lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium perchlorate (LiClO) 4 ) Lithium hexafluorophosphate (LiPF) 6 )。
The amount of lithium salt used was: 0.5M LiTFSI in pyrrole double-centered cationic liquid/1-ethyl-3-methylimidazolium dicyanamide salt.
The specific application method comprises the following steps: lithium salt, the ionic liquid synthesized by the invention and [ MImEt ] [ DCA ] ionic liquid (wherein the weight ratio of the ionic liquid of the invention to the [ MImEt ] [ DCA ] ionic liquid is fixed to be 1:1) are continuously stirred until the ionic liquid is uniform (the LiTFSI is completely dissolved in the ionic liquid), and the ternary electrolyte consisting of the ionic liquid/[ MIEt ] [ DCA ]/0.5M LiTFSI is prepared.
The invention has the advantages that:
compared with the traditional organic solvent and electrolyte, the ionic liquid has the following outstanding advantages:
(1) The liquid state range is wide, the temperature is from lower than or close to room temperature to more than 300 ℃, the liquid is non-combustible, has high thermal stability and chemical stability, is easy to separate from other substances, and can be recycled;
(2) The ionic liquid is tasteless and non-inflammable, has very small vapor pressure, is non-volatile, can not evaporate and dissipate in use and storage, can be recycled, and eliminates the problem of environmental pollution caused by volatile organic compounds;
(3) The conductivity is high, the electrochemical window is large, and the electrolyte can be used as electrolyte for electrochemical research of a plurality of substances;
(4) The solubility of the compound to inorganic matters, organic matters and polymers can be adjusted through the design of anions and cations, and the acidity of the compound can be adjusted to be super-acid;
(5) Has great polarity controllability, low viscosity and large density, can form a two-phase or multi-phase system, and is suitable to be used as a separation solvent or form a new reaction-separation coupling system.
Drawings
Fig. 1 is a graph showing the effect of a flammability test on a ternary electrolyte system E3a made from the ionic liquid synthesized in example 1.
FIG. 2 is a graph showing the results of measuring the electrical conductivity of the ionic liquid [ DiMPy1O ] [ TFSI ] synthesized in example 1 at different temperatures at 25 ℃,30 ℃, 40 ℃, 50 ℃,60 ℃ and 70 ℃ in a drying chamber under a controlled environment.
FIG. 3 is a graph showing the results of conductivity measurements at different temperatures for E3a electrolyte at 25 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C in a controlled environment drying chamber.
Detailed Description
Example 1
(1) Bis (chloroethyl) ether (4.06 g, 28.4 mmol), and 1-methylpyrrole (5.13 g, 60.2 mmol) were dissolved in 10 ml of distilled acetonitrile and stirred under reflux for 4 hours. The resulting mixture was cooled to room temperature and stirred overnight. After the solvent was distilled off, the product was washed three times with 15 ml of diethyl ether, and the remaining solvent was removed by vacuum to give the desired compound 1,1' - (oxybis (ethyl-2-yl)) bis (1-methylpyrrolidinium) dichloride salt (yield: 8.05g, yield 90.5%) as a yellow liquid.
(2) The product 1,1' - (oxybis (ethyl-2-yl)) dichlorobis (1-methylpyrrolidinium-1-yl) salt (1.85 g, 5.9 mmol) from the previous step was taken, dissolved in 8 ml of deionized water, and a slight excess of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI, 3.55 g, 12.37 mmol) was added. The mixed solution was stirred at room temperature overnight to allow halogen anions to be sufficiently exchanged, and extracted with 30 ml of dichloromethane. Obtaining an organic layer, adding 10 ml of saturated saline, fully shaking, standing, taking the lower organic layer, repeatedly washing with saturated saline for three times, and then taking the organic layer, removing water by using anhydrous magnesium sulfate and activated carbon, and purifying. The resulting organic layer was further purified by alumina column chromatography and concentrated under reduced pressure to give the final product. 1,1' - (oxybis (ethyl-2,1-yl)) bis (1-methylpyrrolidin-1-yl) bistrifluoromethanesulfonylimide salt, [ DiMPy1O ] [ TFSI ] (yield: 3.32 g, 70.2%) as a brown liquid.
Product [ DiMPy1O][TFSI]3563cm of infrared spectrum -1 (w),2973cm -1 ,2901(C-H, s),2386.94cm -1 ,1931.99-1797.99cm -1 ,1633.0cm -1 1476.73cm -1 ,(s＝o,s), 1351.76cm -1 (C-N,w),1186.75cm -1 (C-O,s),1055.42cm -1 (C-F,s), 999.41-876.99cm -1 ,789.95-740.46cm -1 ,645.75-571.02cm -1 .
1 H NMR nuclear magnetic hydrogen spectrum: (300MHz, CDCl) 3 ):δ(ppm)3.96(m,4H),3.85–3.51 (m,12H),3.04(s,6H),2.19(m,8H). 13 C NMR nuclear magnetic carbon spectrum: (300MHz, CDCl) 3 ): δ(ppm)124.02,121.9,117.7,114.44,69.33,64.41,63.98,61.81,47.93, 20.84.
Firstly, mixing the ionic liquid synthesized in the embodiment with [ MImEt ] [ DCA ] according to the weight ratio of 1:1, then adding a proper amount of LiTFSI, and continuously stirring until the LiTFSI is completely dissolved in the ionic liquid to prepare the [ DiMPy1O ] [ TFSI ]/[ MImEt ] [ DCA ]/0.5M LiTFSI ternary electrolyte (E3 a for short).
Fig. 1 is a graph showing the effect of flammability tests on a ternary electrolyte system (E3 a) made with a synthesized ionic liquid. I.e. the flammability test is carried out by igniting the test specimen and recording its self-ignition time (SET). The ionic liquid is ignited by open fire, the ionic liquid is removed from a fire source after being ignited for more than 1s, and the ionic liquid is not ignited and does not volatilize, so that the ionic liquid is proved to be non-combustible and to have higher thermal stability.
The ionic conductivity of the electrolyte is characterized in a drying chamber with a controllable environment at 25-70 ℃ by adopting a double-electrode battery and a Gamry potentiostat. The conductivity values of the instrument were calibrated using 0.1mol/kg KCl in water as a standard solution. The conductivity of DiMPy1O TFSI was then measured by the apparatus itself, as was the conductivity of the E3a ternary electrolyte.
Wherein, FIG. 2 is a graph of the conductivity measurement results of the [ DiMPy1O ] [ TFSI ] ionic liquid at 25 ℃,30 ℃, 40 ℃, 50 ℃,60 ℃,70 ℃ and different temperatures in a drying chamber with a controllable environment. In FIG. 2 [ DiMPy1O ] [ TFSI ] conductivity was 1.23mS/cm at 25 ℃ and 7.39mS/cm at 70 ℃ by itself.
FIG. 3 shows the conductivity measurements of E3a electrolyte at different temperatures at 25 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C in a controlled environment drying chamber. The conductivity of the E3a ternary electrolyte rose to 8.1mS/cm at 25 ℃ and to 26.6mS/cm at 70 ℃.
Example 2
Preparation of [ DiMPy2O ] [ TFSI ] using a similar procedure as in example 1:
1,2-bis (2-chloroethoxy) ethane (2.99g, 169mol), 1-methylpyrrole (2.86g, 33.6 mmol) to give the intermediate (5.43 g, 95.1% yield);
taking the intermediate (4.08g, 11.4 mmol) and LiTFSI (6.49g, 22.6 mmol) to obtain the final product [ DiMPy2O ] [ TFSI ] (6.49 g, 67.1 percent yield);
product [ DiMPy2O][TFSI]3563cm of infrared spectrum -1 (w),2964cm -1 ,2902.84(C-H, s),2379.03cm -1 ,1931.76-1798.58cm -1 (w),1634.43cm -1 ,1463.43cm -1 ,(s＝o, s),1352.48cm -1 (C-N,w),1193.83cm -1 (C-O,s),1054.56cm -1 (C-F,s), 953.83-877.41cm -1 ,789.69-739.92cm -1 .
1 H NMR nuclear magnetic hydrogen spectrum (300MHz, CDCl) 3 ):δ(ppm)3.84(m,4H),3.73–3.50 (m,16H),3.03(s,6H),2.17(m,8H). 13 C NMR Nuclear magnetic carbon Spectroscopy (300MHz, CDCl) 3 ):δ (ppm)124.02,121.9,117.7,114.44,70.2,65.4,65.0,63.5,48.6,21.1.
The ionic liquid synthesized in example 2 and [ MImEt ] [ DCA ] were mixed according to the weight ratio of 1:1, and an appropriate amount of LiTFSI was added thereto, and continuously stirred until the LiTFSI was completely dissolved in the ionic liquid, to prepare a [ DiMPy2O ] [ TFSI ]/[ MImEt ] [ DCA ]/0.5M LiTFSI ternary electrolyte (E4 a for short).
The conductivity of the E4a ternary electrolyte rose to 9.74mS/cm at 25 ℃ and to 28.5mS/cm at 70 ℃.
Example 3
Preparation of [ DiMPy3O ] [ TFSI ] using a similar procedure as in example 1:
1-chloro-2- (2- ((2-chloroethoxy) ethoxy) ethane (4.01g, 17.3mmol), 1-methylpyrrole (3.14g, 36.9mmol) to give the intermediate (6.58 g, 94.5% yield);
taking the intermediate (2.01g, 5.0mmol) and LiTFSI (3.02g, 10.5mmol) to obtain a final product [ DiMPy3O ] [ TFSI ] (3.17 g, yield 71%);
product [ DiMPy3O][TFSI]3563cm of infrared spectrum -1 (w),2973cm -1 ,2877.73(C-H, s),2387.01cm -1 ,1931.61-1797.99cm -1 (w),1673.96cm -1 ,1462.84cm -1 ,(s＝o, s),1352.42cm -1 (C-N,w),1193.55cm -1 (C-O,s),1056.58cm -1 (C-F,s), 998.26-877.85cm -1 ,789.24-741.40cm -1 .
1 H NMR nuclear magnetic hydrogen spectrum ((300MHz, CDCl) 3 ):δ(ppm)3.87(m,4H),3.75–3.54 (m,20H),3.08(s,6H),2.21(m,8H). 13 C NMR Nuclear magnetic carbon Spectroscopy (300MHz, CDCl) 3 ):δ (ppm)124.02,121.9,117.7,114.44,70.63,70.16,65.50,64.90,48.69, 21.2.
The ionic liquid synthesized in example 3 and [ MImEt ] [ DCA ] were mixed in the weight ratio of 1:1, and an appropriate amount of LiTFSI was added thereto, followed by continuous stirring until the LiTFSI was completely dissolved in the ionic liquid, to prepare a [ DiMPy3O ] [ TFSI ]/[ MImEt ] [ DCA ]/0.5M LiTFSI ternary electrolyte (E5 a for short).
The conductivity of the E5a ternary electrolyte rose to 6.95mS/cm at 25 ℃ and 22.1mS/cm at 70 ℃.
Example 4
Preparation of [ DiMPy4O ] [ TFSI ] using a similar procedure as in example 1:
1,2-bis (2- (2-chloroethoxy) ethoxy) ethane (3.02g, 11mmol), 1-methylpyrrole (2.00g, 23.5mmol) to give the intermediate (4.02 g, 82.4% yield);
taking the intermediate (2.66g, 6.0 mmol) and LiTFSI (3.58g, 12.5 mmol) to obtain the final product [ DiMPy4O ] [ TFSI ] (3.97 g, yield 70.9%);
product [ DiMPy4O][TFSI]3542cm of infrared spectrum -1 (w),2880.44(C-H,s), 2387.01cm -1 ,1932.03-1723.60cm -1 (w),1673.96cm -1 ,1462.71cm -1 ,(s＝o, s),1352.47cm -1 (C-N,w),1193.89cm -1 (C-O,s),1056.94cm -1 (C-F,s), 998.59-839.90cm -1 ,789.16-740.05cm -1 .
1 H NMR nuclear magnetic hydrogen spectrum ((300MHz, CDCl) 3 ):δ(ppm)3.87(m,4H),3.73–3.52 (m,24H),3.11(s,6H),2.20(m,8H). 13 C NMR Nuclear magnetic carbon Spectroscopy ((300MHz, CDCl) 3 ): δ(ppm)124.02,121.9,117.7,114.44,70.3,70.0,65.50,64.90,48.7, 21.2.
The ionic liquid synthesized in example 4 and [ MImEt ] [ DCA ] were mixed in the weight ratio of 1:1, and an appropriate amount of LiTFSI was added thereto, followed by continuous stirring until the LiTFSI was completely dissolved in the ionic liquid, to prepare a [ DiMPy4O ] [ TFSI ]/[ MImEt ] [ DCA ]/0.5M LiTFSI ternary electrolyte (E6 a for short).
The conductivity of the E6a ternary electrolyte rose to 4.68mS/cm at 25 ℃ and 16.37mS/cm at 70 ℃.
The physical properties of the synthesized double-center cationic ionic liquids of examples 1-4 of the invention are shown in Table 1.
TABLE 1
The invention also examines the solubility of the synthesized double-center cationic ionic liquid in examples 1-4 in various polar and non-polar organic solvents, and the test results are shown in table 2.
TABLE 2
m: means miscible with the solvent
i: means immiscible with the solvent
Wherein the solvent is selected from dimethyl sulfoxide (DMSO), acetonitrile (MeCN), methanol (MeOH), and deionized water (H) 2 O), diethyl ether (Et) 2 O), dichloromethane (DCM), ethyl acetate (EtOAc), acetone (Acetone), tetrahydrofuran (THF) and Hexane (Hexane).
Example 5
The ionic liquid of example 1 of the invention is doped in an EC-DMC electrolyte solvent, the content of the ionic liquid is 40%, and the mixed electrolyte has incombustibility.
Example 6
The ionic liquid of the embodiment 1 of the invention is doped in an EC-DMC electrolyte solvent, the content of the ionic liquid is 50%, and the obtained electrolyte is applied to a graphite electrode to form a stable SEI film.
Example 7
(1) Bis (chloroethyl) ether (4.28 g, 30 mmol), and 1-methylpyrrole (5.13 g, 60.2 mmol) were dissolved in 10 ml of distilled acetonitrile and stirred under reflux for 4 hours. The resulting mixture was cooled to room temperature and stirred overnight. After the solvent was rotary distilled off, the product was washed three times with 15 ml of diethyl ether, and the remaining solvent was removed by vacuum to obtain the desired compound 1,1' - (oxybis (ethyl-2-yl)) dichlorobis (1-methylpyrrolidinium-1-yl) salt (yield: 7.51g, yield 84%) as a yellow liquid. The yield is significantly reduced.
(2) The product 1,1' - (oxybis (ethyl-2-yl)) dichlorobis (1-methylpyrrolidinium-1-yl) salt (1.85 g, 5.9 mmol) from the previous step was taken, dissolved in 8 ml of deionized water, and a slight excess of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI, 3.22 g, 11.21 mmol) was added. The mixed solution was stirred at room temperature overnight to allow halogen anions to be sufficiently exchanged, and extracted with 30 ml of dichloromethane. Obtaining an organic layer, adding 10 ml of saturated saline water, fully shaking and standing, taking the lower organic layer, repeatedly washing the lower organic layer with saturated saline water for three times, and then taking the organic layer to remove water and purify by using anhydrous magnesium sulfate and activated carbon. The resulting organic layer was further purified by alumina column chromatography and concentrated under reduced pressure to give the final product. 1,1' - (oxybis (ethyl-2,1-yl)) bis (1-methylpyrrolidin-1-yl) bistrifluoromethanesulfonylimide salt, [ DiMPy1O ] [ TFSI ] (yield: 3.02g, 63%) as a brown liquid. The yield is significantly reduced.
Claims (1)
1. A ternary electrolyte is characterized in that the ternary electrolyte is prepared by mixing pyrrole double-center cationic liquid and [ MImEt ] [ DCA ] according to the weight ratio of 1:1, adding LiTFSI into the mixture, and continuously stirring until the LiTFSI is completely dissolved in the ionic liquid, wherein the ternary electrolyte is 1,1' - (oxybis (ethyl-2,1-yl)) bis (1-methylpyrrolonium-1-yl) bistrifluoromethanesulfonylimide [ DiMPy2O ] [ TFSI ]/[ MImEt ] [ DCA ]/0.5M LiTFSI;
the [ MImEt ]][DCA]Structural formula (II)Comprises the following steps:
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| CN102738508A (en) * | 2011-04-11 | 2012-10-17 | 中国科学院过程工程研究所 | Lithium ion battery electrolyte with low lithium salt content |
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| CN109776423A (en) * | 2019-03-20 | 2019-05-21 | 厦门大学 | A kind of double imidazole ring functional ion liquids and preparation method thereof and electrolyte and lithium secondary battery |
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