CN113097565A - Ionic liquid-like electrolyte for aluminum secondary battery and preparation method thereof - Google Patents
Ionic liquid-like electrolyte for aluminum secondary battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ionic liquid-like electrolyte and a preparation method thereof, and the ionic liquid-like electrolyte is applied to an aluminum secondary battery. The ionic liquid electrolyte comprises solute aluminum salt, a solvent hydrogen bond donor and an organic salt additive for modification, wherein the organic salt additive is one or more than one selected from room-temperature molten salts. The ionic liquid-like electrolyte provided by the invention is very suitable for being used as an electrolyte of an aluminum secondary battery, and has extremely low cost and high air stability. Room temperature molten salt is added into the ionic liquid electrolyte for modification, so that on one hand, the physical property of the ionic liquid is improved, the conductivity of the ionic liquid is improved, the viscosity of the ionic liquid is reduced, and meanwhile, the eutectic point of an electrolyte system is reduced; on the other hand, the electrochemical window of the ionic liquid can be widened, so that higher energy density is obtained; the ionic liquid has the characteristics of non-volatility, high heat resistance and non-flammability, and can also improve the safety performance of the aluminum secondary battery.
Description
Technical Field
The invention relates to the field of battery materials, in particular to an ionic liquid-like electrolyte and a preparation method thereof, and the ionic liquid-like electrolyte is applied to an aluminum secondary battery.
Background
Under the rapid promotion of the economic globalization process and the continuous development of the human society, the human demand for energy is increased year by year, and 70 percent of the total energy consumed in the world every year comes from fossil fuels such as petroleum, coal, natural gas and the like. In view of the ever increasing demand for fossil fuels and the limited availability of non-renewable resources, stable energy supply is a crucial global issue. Meanwhile, a large amount of greenhouse gases generated when fossil fuels are burned are problematic in terms of climate change caused by an increase in atmospheric concentration. Increased awareness of the environment and concerns about energy safety have prompted society to seek ways to generate, utilize, and store energy in a more sustainable and efficient manner.
Nowadays, sustainable renewable energy sources such as wind energy, light energy, tidal energy, chemical power sources and the like are actively developed all over the world, and batteries can store and convert energy sources whether the renewable energy sources are renewable energy sources or non-renewable energy sources, so that the batteries play an increasingly important role. Since the first commercialization of lithium ion batteries by sony corporation in 1991, lithium ion batteries have been the leading position in the market of portable electronic products, and show great prospects in large-scale applications such as electric vehicles and smart grids. The lithium ion battery has the advantages of high specific energy, low self-discharge, no memory effect, environmental friendliness and the like, gradually becomes a novel chemical power supply which is developed fastest at present, and has very wide application in a plurality of fields such as new energy automobiles, aerospace, 3C digital codes and the like. However, due to the astronomical demand for lithium and other key elements (e.g., metallic cobalt, etc.) and the uneven distribution of lithium resources around the world, it remains an urgent task to develop a replacement system that is abundant and cost-advantageous. Because the aluminum ions can realize three-electron conversion in the electrochemical processThe aluminum has the characteristic of extremely low density, and can provide the highest volume specific capacity (8050 mAh/cm)3). Although aluminum has a higher electrochemical redox potential than other metals (-2.71V compared to a common hydrogen electrode (NHE)), its theoretical specific mass capacity (2980mAh/g) is second only to lithium, and is third in the earth's crust, with very low cost and a cation radius even smaller than that of lithium ions. In addition to the above advantages, the high stability of aluminum in air and moisture leads to a significant improvement in safety compared to lithium ion batteries. Aluminum secondary batteries with a wide application prospect are considered to be one of the most promising next-generation energy storage systems.
In recent years, aluminum secondary batteries have attracted much attention, and most of the existing aluminum secondary batteries are made of ionic liquid aluminum trichloride/1-ethyl-3-methylimidazolium chloride (AlCl)3EMImCl) as an electrolyte. Ionic liquids are salts consisting of organic cations and inorganic/organic anions that are liquid at room temperature. Due to its low flammability, high thermal stability, negligible vapor pressure, wide voltage window, ionic liquids have attracted extensive attention. However, the high viscosity of the extremely expensive ionic liquid at normal temperature and the compatibility of the electrode material of the battery have been problems, which have hindered the development of aluminum secondary batteries. The cheap and stable ionic liquid analogue (similar ionic liquid) is applied to the aluminum secondary battery and becomes a hotspot of battery research work in recent years, has the characteristics of the ionic liquid, has the advantages of easily available raw materials, low price, simple and convenient synthesis and the like, and is an aluminum secondary battery electrolyte system with high performance, high safety, long cycle life and low cost and great prospect.
Ionic liquid-like liquids, which may also be referred to as ionic liquid analogs, eutectic solvents, refer to two-or three-component eutectic mixtures of hydrogen bond acceptors (e.g., quaternary ammonium salts) and hydrogen bond donors (e.g., amides, carboxylic acids, and polyols) in stoichiometric proportions, with freezing points significantly below the melting points of the pure materials of the individual components. The physicochemical properties of the ionic liquid were very similar to those of the ionic liquid, as first reported by Abbott et al in 2003. The organic solvent is a new green solvent due to unique properties such as easy synthesis, low cost, environmental friendliness, low volatility, high dissolving capacity, high biodegradability and feasibility of structural design. Unlike ionic liquids in the conventional definition, ionic liquids refer to liquids composed entirely of ions, substances composed of ions that are liquid at or around room temperature. The ion-like liquid not only contains ions, but also contains neutral ligand groups in molecular form and cationic groups formed by heterolysis, and the eutectic temperature of the ion-like liquid is more widely defined and is not limited to the range of room temperature and the range near the room temperature. Compared with ionic liquid, the ionic liquid has the advantages of low cost, easy preparation, low toxicity, environmental friendliness and the like.
Disclosure of Invention
The present invention has been made to overcome the above problems occurring in the prior art, and an object of the present invention is to provide an electrolyte for an aluminum secondary battery, which can be prepared by a simple method and has low cost, high conductivity, and good stability. The aluminum secondary battery formed by the invention has higher specific discharge capacity and more stable cycle performance, reversible intercalation/deintercalation reaction is realized in the charging and discharging processes, and the electrolyte has good compatibility with active substances of the battery and can not react or dissolve with active materials of electrodes, binders, conductive agents and the like.
In order to achieve the above objects, the present invention provides a low-cost method for preparing an electrolyte solution, comprising an aluminum salt, a hydrogen bond donor, and at least one organic salt additive, by a simple one-step synthesis method to prepare an ionic liquid analog electrolyte solution, which is simple and economical, does not require any auxiliary technique, and has easily available and inexpensive raw materials.
According to a first aspect of the present invention, there is provided a method for preparing an ionic liquid-like electrolyte for an aluminum secondary battery, in which the specific embodiment of the present invention:
an ionic liquid-like electrolyte is prepared from solute Al salt, solvent hydrogen bond donor and organic salt additive through proportional mixing at room temp and inertial gas atmosphere, stirring at proper temp and constant speed in inertial gas atmosphere, and natural cooling.
Providing an aluminum salt as a solute, wherein the aluminum salt is selected from aluminum chloride (AlCl)3) Aluminum bromide (AlBr)3) Aluminum iodide (AlI)3) Aluminum sulfate (Al)2(SO4)3) Aluminum nitrate (Al (NO)3)3) Aluminum silicate (Al)2(SiO3)3) Aluminum sulfide (Al)2S3) Aluminum potassium sulfate dodecahydrate (KAl (SO)4)2·12H2O), aluminum trimethyl sulfate (C)3H3AlO6) And the like.
Providing a hydrogen bond donor as a solvent, wherein the hydrogen bond donor is selected from one of urea, methylurea, 1, 3-dimethylurea, allylurea, thiourea, salicylamide, acetamide, benzamide, acrylamide, hydroxylamine hydrochloride, 2,2, 2-trifluoroacetamide, triethanolamine, vanillin, ethylene glycol, glycerol, mannitol, D-fructose, 1, 4-butanediol, phenol, o-cresol, 2, 3-xylenol, glucose, acrylic acid, valeric acid, mandelic acid, 4-hydroxybenzoic acid, galloyl base, trans-cinnamic acid, p-coumaric acid, caffeic acid, itaconic acid, methacrylic acid, tartaric acid, glutamic acid, trifluoroacetic acid, tricarballylic acid, adipic acid, benzoic acid, citric acid, malonic acid, oxalic acid, phenylacetic acid, resorcinol, tricarballylic acid, and the like.
Providing an organic salt as an additive, wherein the cation of the organic salt is selected from one of quaternary ammonium salt ion, quaternary phosphonium salt ion, quaternary sulfonium salt ion, imidazolium salt ion, amide salt ion, pyrrole salt ion and the like, and the anion is selected from halogen ion (F)-、Cl-、Br-、I-) Tetrafluoroborate ion (BF)4 -) Tetrachloroaluminate (AlCl)4 -) Hexafluorophosphate ion (PF)6 -) Bis (trifluoromethanesulfonyl) imide (TFSI)-) Bis (fluorosulfonyl) imide (FSI)-) Triflic acid (CF)3SO3 -) Difluoro (oxalato) borate (DFOB)-) Tetrafluoroaluminate (AlF)4 -) Fluorosulfonyl- (trifluoromethanesulfonyl) imide (FTFSI)-) Perchlorate (ClO)4 -) And the like.
The molar ratio of the solute aluminum salt to the solvent hydrogen bond donor is 0.1: 1-5: 1, and the preferred molar ratio is 1.1: 1-1.5: 1. The content of the organic salt additive is 0.1-30% (mass ratio) based on the total amount of the formed ionic liquid-like electrolyte, preferably 3-10%.
The reaction temperature in the preparation process is 30-100 ℃, and the preferable reaction temperature is 45-80 ℃.
The rotation speed of stirring in the preparation process is 50-1000 r/min, and the preferred rotation speed is 200-600 r/min.
According to the ionic liquid-like electrolyte of the present invention, in a preferred embodiment, the aluminum salt is aluminum chloride (AlCl)3) The hydrogen bond donor is urea, the organic salt additive is 1-ethyl-3-methylimidazolium chloride, and the ionic liquid-like electrolyte according to the preferred embodiment shows more excellent electrochemical performance.
According to a second aspect of the present invention, there is provided an aluminum secondary battery comprising a battery case, an electrode group and a nonaqueous electrolyte, the electrode group and the nonaqueous electrolyte being sealed in the battery case, the electrode group comprising a positive electrode, a negative electrode and a separator provided between the positive electrode and the negative electrode, wherein the nonaqueous electrolyte is the ionic liquid-like electrolyte according to the first aspect of the present invention.
The aluminum secondary battery comprises a positive electrode consisting of a positive electrode current collector and positive electrode slurry coated on the positive electrode current collector, wherein the positive electrode slurry comprises graphite positive electrode active substances, a conductive agent and a binder, the positive electrode active substances account for 70-85% by mass, the conductive agent accounts for 10-20% by mass and the binder accounts for 5-10%, the positive electrode current collector is made of foamed nickel, foamed copper, foamed titanium, foamed iron, a stainless steel net, carbon paper, carbon fiber cloth, tantalum foil (Ta), niobium foil (Nb) or molybdenum foil (Mo), the conductive agent is selected from at least one of acetylene black, carbon fiber (VGCF), Carbon Nano Tubes (CNTs), Ketjenblack (Ketjenblak), graphene and conductive carbon black (Super-P), and the binder is selected from polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), sodium carboxymethylcellulose (CMC), styrene butadiene styrene rubber (SBR), styrene butadiene rubber (ABS), styrene butadiene styrene rubber (ABS), and/styrene butadiene styrene (ABS), At least one of polyacrylic acid (PAA), Polytetrafluoroethylene (PTFE), and polyvinyl alcohol (PVA).
According to the invention, the conductive agent is preferably conductive carbon black (Super-P).
According to the invention, polyvinylidene fluoride (PVDF) is preferably used as the binder.
According to the present invention, the positive electrode current collector is preferably made of molybdenum (Mo) foil.
The aluminum secondary battery according to the present invention further includes a negative electrode, a negative electrode current collector, and a separator. In the invention, the cathode material is an aluminum sheet, the purity range is more than or equal to 95%, the thickness range is 0.02-5 mm, and high-purity aluminum with the thickness of 0.02mm (the purity is more than or equal to 99.99%) is preferred in order to avoid the influence of excessive metal aluminum on the volume energy density, the weight energy density and other side reactions of the battery.
In the present invention, the separator material may be a PE film (polyethylene), a PP film (polypropylene), a glass cellulose separator (GF/C), a nonwoven fabric separator, or the like, and preferably the separator is a glass cellulose separator (GF/C).
In the present invention, the negative electrode current collector may be a current collector conventional in the art, and the current collector is selected from a stainless steel spring and gasket, a nickel foam, a copper foam, a titanium foam, an iron nickel foam, a stainless steel mesh, a carbon paper or a carbon fiber cloth, and preferably, the current collector is a nickel foam.
The method is economic and simple to operate, and the target ionic liquid electrolyte is synthesized by a one-step synthesis method without byproducts, is very suitable for being used as the electrolyte of the aluminum secondary battery, and has extremely low cost and high air stability. Firstly, aluminum salt and a hydrogen bond donor form an ionic liquid, and then room-temperature molten salt is added into the electrolyte for modification, so that on one hand, the physical property of the ionic liquid is improved, the conductivity of the ionic liquid is improved, the viscosity of the ionic liquid is reduced, and meanwhile, the eutectic point of an electrolyte system is reduced; on the other hand, the electrochemical window of the ionic liquid can be widened, so that higher energy density is obtained; the ionic liquid has the characteristics of non-volatility, high heat resistance and non-flammability, and can also improve the safety performance of the aluminum secondary battery. The additive has good affinity with the electrolyte and low consumption, and has good industrialization prospect.
Drawings
FIGS. 1 and 2 are schematic diagrams showing dissolution of three different amounts of organic salt at heating temperatures of 40 ℃ and 50 ℃ in preparation examples 1, 2 and 3, respectively.
Fig. 3 is a first cycle charge and discharge curve of the aluminum secondary battery in example 3 of the present invention.
Fig. 4 is a graph comparing the ac impedance curves of the aluminum secondary batteries of examples 1, 2 and 3 of the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass close proximity to such ranges or values. For ranges of values, one or more new ranges of values may be obtained from combinations of values between the endpoints of each range, the endpoints of each range and the individual values, and the individual values are to be considered as specifically disclosed herein.
The present invention will be described in further detail with reference to specific production examples, examples and comparative examples.
Preparation example 1
Under the condition of room temperature and in an inert gas atmosphere, respectively weighing 2.7g of aluminum chloride powder and 0.9g of urea according to the molar ratio of an aluminum salt solute to a hydrogen bond donor solvent of 1.3:1, and sequentially adding the aluminum chloride powder and the urea into a 10mL isotope bottle; this preparation is a blank control, modified without the addition of an organic salt additive. Continuously stirring for 24h at the stirring speed of 300r/min in the temperature environment of 60 ℃ and the inert gas atmosphere, and naturally cooling the mixed liquid to room temperature to obtain the ionic liquid-like electrolyte A-0%.
Preparation example 2
Under the condition of room temperature and in an inert gas atmosphere, respectively weighing 2.7g of aluminum chloride powder and 0.9g of urea according to the molar ratio of an aluminum salt solute to a hydrogen bond donor solvent of 1.3:1, and sequentially adding the aluminum chloride powder and the urea into a 10mL isotope bottle; subsequently, 1-ethyl-3-methylimidazolium chloride salt (EMImCl) was weighed out, and the organic salt accounted for 3% of the total electrolyte mass. Continuously stirring for 24h at the stirring speed of 300r/min in the temperature environment of 60 ℃ and the inert gas atmosphere, and naturally cooling the mixed liquid to room temperature to obtain the ionic liquid-like electrolyte A-3%.
Preparation example 3
Under the condition of room temperature and in an inert gas atmosphere, respectively weighing 2.7g of aluminum chloride powder and 0.9g of urea according to the molar ratio of an aluminum salt solute to a hydrogen bond donor solvent of 1.3:1, and sequentially adding the aluminum chloride powder and the urea into a 10mL isotope bottle; subsequently, 1-ethyl-3-methylimidazolium chloride salt (EMImCl) was weighed out, and the organic salt accounted for 5% of the total electrolyte mass. Continuously stirring for 24h at the stirring speed of 300r/min in the temperature environment of 60 ℃ and the inert gas atmosphere, and naturally cooling the mixed liquid to room temperature to obtain the ionic liquid-like electrolyte A-5%.
Preparation example 4
Under the condition of room temperature and in an inert gas atmosphere, respectively weighing 2.7g of aluminum chloride powder and 0.9g of urea according to the molar ratio of an aluminum salt solute to a hydrogen bond donor solvent of 1.3:1, and sequentially adding the aluminum chloride powder and the urea into a 10mL isotope bottle; subsequently, 1-ethyl-3-methylimidazolium chloride salt (EMImCl) was weighed out, and the organic salt accounted for 10% of the total mass of the electrolyte. Continuously stirring for 24 hours at the stirring speed of 300r/min in the temperature environment of 60 ℃ and the inert gas atmosphere, and naturally cooling the mixed liquid to room temperature to obtain the ionic liquid-like electrolyte A-10%.
Preparation example 5
Under the condition of room temperature and in an inert gas atmosphere, respectively weighing 2.2g of aluminum chloride powder and 0.9g of urea according to the molar ratio of an aluminum salt solute to a hydrogen bond donor solvent of 1.1:1, and sequentially adding the aluminum chloride powder and the urea into a 10mL isotope bottle; subsequently, 1-ethyl-3-methylimidazolium chloride salt (EMImCl) was weighed out, and the organic salt accounted for 3% of the total electrolyte mass. Continuously stirring for 24h at the stirring speed of 200r/min in the temperature environment of 80 ℃ and the inert gas atmosphere, and naturally cooling the mixed liquid to room temperature to obtain the ionic liquid-like electrolyte B-3%.
Preparation example 6
Under the condition of room temperature and in an inert gas atmosphere, respectively weighing 3.0g of aluminum chloride powder and 0.9g of urea according to the molar ratio of an aluminum salt solute to a hydrogen bond donor solvent of 1.5:1, and sequentially adding the aluminum chloride powder and the urea into a 10mL isotope bottle; subsequently, 1-ethyl-3-methylimidazolium chloride salt (EMImCl) was weighed out, and the organic salt accounted for 3% of the total electrolyte mass. Continuously stirring for 24h at the stirring speed of 200r/min in the temperature environment of 80 ℃ and the inert gas atmosphere, and naturally cooling the mixed liquid to room temperature to obtain the ionic liquid-like electrolyte C-3%.
Preparation example 7
Under the condition of room temperature and in an inert gas atmosphere, respectively weighing 2.2g of aluminum chloride powder and 0.6g of urea according to the molar ratio of an aluminum salt solute to a hydrogen bond donor solvent of 1.1:1, and sequentially adding the aluminum chloride powder and the urea into a 10mL isotope bottle; tetraethyl ammonium hexafluorophosphate salt is weighed, and the organic salt accounts for 3% of the total mass of the electrolyte. Continuously stirring for 36h at the stirring speed of 400r/min in the temperature environment of 80 ℃ and the inert gas atmosphere, and naturally cooling the mixed liquid to room temperature to obtain the ionic liquid-like electrolyte D-3%.
Preparation example 8
Under the condition of room temperature and in an inert gas atmosphere, respectively weighing 2.2g of aluminum chloride powder and 0.9g of urea according to the molar ratio of an aluminum salt solute to a hydrogen bond donor solvent of 1.1:1, and sequentially adding the aluminum chloride powder and the urea into a 10mL isotope bottle; then, the alkyl triphenyl phosphonium salt is weighed, and the organic salt accounts for 5% of the total mass of the electrolyte. Continuously stirring for 24 hours at the stirring speed of 800r/min in the temperature environment of 80 ℃ and the inert gas atmosphere, and naturally cooling the mixed liquid to room temperature to obtain the ionic liquid-like electrolyte E-5%.
Preparation example 9
Under the condition of room temperature and in an inert gas atmosphere, respectively weighing 3.0g of aluminum chloride powder and 0.9g of urea according to the molar ratio of an aluminum salt solute to a hydrogen bond donor solvent of 1.5:1, and sequentially adding the aluminum chloride powder and the urea into a 10mL isotope bottle; tetraethyl ammonium hexafluorophosphate salt is weighed, and the organic salt accounts for 5% of the total mass of the electrolyte. Continuously stirring for 40h at the stirring speed of 100r/min in the temperature environment of 80 ℃ and the inert gas atmosphere, and naturally cooling the mixed liquid to room temperature to obtain the ionic liquid-like electrolyte F-5%.
Example 1
(1) Preparation of the Positive electrode
Mixing the positive active material graphite, the conductive carbon black and the binder according to the weight ratio of 8:1:1, grinding the mixture by using an agate mortar for 30min to uniformly mix the materials, transferring the mixed dry material into an isotope bottle, adding an organic solvent, and stirring at a medium speed for 12h to form uniform battery slurry; coating the battery slurry on a positive current collector molybdenum foil with the diameter of 11mm, transferring the positive current collector molybdenum foil into a vacuum oven at 80 ℃ for baking for 12 hours, wherein the loading capacity of the positive active material on the current collector is 0.6mg/cm2And obtaining the cathode material.
(2) Assembled aluminum secondary battery
An aluminum sheet is selected as a negative electrode, a glass cellulose diaphragm is selected as a diaphragm, the ionic liquid-like electrolyte A-0% in preparation example 1 is selected as the electrolyte, the addition amount of the electrolyte is 60 mu L, and the electrolyte is assembled into a CR2025 experimental button cell in a glove box filled with argon atmosphere. And placing the assembled aluminum secondary battery into a 30 ℃ thermostat, standing for 12 hours, and then performing constant-current charging and discharging tests on a LAND CT2001A tester, wherein the charging and discharging current density is 20 mA/g. The battery is labeled S1.
Example 2
(1) The procedure is as in example 1 except that in (2) the electrolyte is selected from the ionic liquid-like electrolyte A-3% of preparation 2, the cell being designated S2.
Example 3
(1) The procedure was followed as in example 1 except that in (2), the electrolyte was selected from the ion-like liquid electrolyte A-3% in preparation example 2, and the amount of the electrolyte added was 30. mu.L, and the cell was designated as S3.
Example 4
(1) The procedure is as in example 1, (2) except that the electrolyte is selected from the ionic liquid-like electrolyte a-5% of preparation 3, the cell being designated S4.
Example 5
(1) The procedure is as in example 1, (2) except that the electrolyte is selected from the ionic liquid-like electrolytes a-10% of preparation 4, the cell being designated S5.
Example 6
(1) The procedure is as in example 1, (2) except that the electrolyte is selected from the ionic liquid-like electrolyte B-3% of preparation 5, and the cell is labeled S6.
Example 7
(1) The procedure is as in example 1, (2) except that the electrolyte is selected from the ionic liquid-like electrolyte C-3% of preparation 6, and the cell is labeled S7.
Example 8
The procedure is as in example 4, except that the charge-discharge current density is 100mA/g, and the cell is labeled S8.
Comparative example 1
(1) A positive electrode was produced in the same manner as in example 4, except that the coating amount was such that the loading amount of the positive electrode active material graphite on the current collector after baking was 10mg/cm2(per 1 cm)2Coated with 10mg of positive electrode active material).
(2) An aluminum secondary battery was assembled according to the method of example 4, and the performance of the aluminum secondary battery was tested.
Comparative example 2
An aluminum secondary battery was assembled according to the method of example 1, except that the electrolyte was selected to be aluminum chloride: ionic liquid electrolyte (AlCl) with 1.3:1 molar ratio of 1-ethyl-3-methylimidazolium chloride salt3: EMImCl 1.3:1), and performance tests were performed on the aluminum secondary battery.
Comparative example 3
An aluminum secondary battery was assembled according to the method of example 1, except that the electrolyte was selected to be aluminum chloride: ionic liquid electrolyte (AlCl) with 1.3:1 molar ratio of 1-butyl-3-methylimidazolium chloride salt3: BMImCl 1.3:1), and performance testing was performed on the aluminum secondary battery.
Two electrolytes in example 1 and comparative example 1 (example 1: AlCl)3Urea (urea) molar ratio composition 1.3: 1; comparative example 1: AlCl31-Ethyl-3-methyl-imidazolium chloride salt (EMImCl) molThe particle compositions in the specific composition 1.3:1) are shown in table 1 below.
TABLE 1 particle composition in Ionic liquids and Ionic-like liquids
The relevant performance tests of the assembled batteries of the above examples and comparative examples are shown in table 2 below.
TABLE 2 Battery-related Performance test data
As can be seen from the results in fig. 1 and 2, the optimization method by adding the organic salt additive according to the present invention can significantly reduce the eutectic point when synthesizing the ionic liquid, the preparation example with no organic salt added is partially soluble at 40 ℃, and the preparation example with 3% of the organic salt added is partially soluble, and exhibits a completely soluble state as the organic salt added increases, and thus has important practical significance for saving energy, reducing consumption, etc. in industrial production.
As can be seen from the results of fig. 3, the proposed ionic liquid-like electrolyte of the present invention has a significantly increased oxidative decomposition potential, thereby achieving a higher energy density, indicating that the ionic liquid-like electrolyte according to the present invention is suitable for use as an electrolyte of a high-voltage aluminum secondary battery.
As can be seen from the results of table 2, the aluminum secondary battery of the present invention has a higher specific discharge capacity and a better cycle stability. In the embodiment, the physical property of the ionic liquid is improved, the conductivity of the ionic liquid is improved, and the viscosity of the ionic liquid is reduced by adjusting the proportion of the organic salt additive. Compared with the technical scheme that the invention is not adopted in the comparative examples 2 and 3, the ionic liquid-like electrolyte provided by the invention has higher matching performance with the positive electrode graphite material. The ionic liquid has the characteristics of non-volatility, high heat resistance and non-flammability, and can also improve the safety performance of the aluminum secondary battery. The additive has good affinity with the electrolyte and low consumption, and has good industrialization prospect.
The preferred embodiments of the present invention have been described in detail, however, the present invention 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 invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention. It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The ionic liquid electrolyte is characterized by comprising solute aluminum salt, a solvent hydrogen bond donor and an organic salt additive for modification, wherein the organic salt additive is one or more selected from room-temperature molten salts.
2. The ionic liquid-like electrolyte of claim 1, wherein the solute aluminum salt is selected from aluminum chloride (AlCl)3) Aluminum bromide (AlBr)3) Aluminum iodide (AlI)3) Aluminum sulfate (Al)2(SO4)3) Aluminum nitrate (Al (NO)3)3) Aluminum silicate (Al)2(SiO3)3) Aluminum sulfide (Al)2S3) Aluminum potassium sulfate dodecahydrate (KAl (SO)4)2·12H2O), aluminum trimethyl sulfate (C)3H3AlO6) At least one of (1).
3. The ionic liquid-like electrolyte of claim 1, wherein the solvent hydrogen bond donor is selected from urea, methylurea, 1, 3-dimethylurea, allylurea, thiourea, salicylamide, acetamide, benzamide, acrylamide, hydroxylamine hydrochloride, 2,2, 2-trifluoroacetamide, triethanolamine, vanillin, ethylene glycol, glycerol, mannitol, D-fructose, 1, 4-butanediol, phenol, o-cresol, 2, 3-xylenol, glucose, acrylic acid, valeric acid, mandelic acid, 4-hydroxybenzoic acid, gallic base, trans-cinnamic acid, p-coumaric acid, caffeic acid, itaconic acid, methacrylic acid, tartaric acid, glutamic acid, trifluoroacetic acid, tricarballylic acid, adipic acid, benzoic acid, citric acid, malonic acid, oxalic acid, phenylacetic acid, resorcinol, and mixtures thereof, One of the tricarballylic acids.
4. The ionic liquid-like electrolyte according to claim 1, wherein the molar ratio of the solute aluminum salt to the solvent hydrogen bond donor is 0.1:1 to 5:1, and the mass content of the organic salt additive is 0.1 to 30% based on the total amount of the ionic liquid-like electrolyte.
5. The method according to claim 1, wherein the cation of the organic salt additive is selected from one of quaternary ammonium salt ion, quaternary phosphonium salt ion, quaternary sulfonium salt ion, imidazolium salt ion, amide salt ion and pyrrole salt ion, and the anion is selected from halogen ion, tetrafluoroborate ion (BF)4 -) Tetrachloroaluminate (AlCl)4 -) Hexafluorophosphate ion (PF)6 -) Bis (trifluoromethanesulfonyl) imide (TFSI)-) Bis (fluorosulfonyl) imide (FSI)-) Triflic acid (CF)3SO3 -) Difluoro (oxalato) borate (DFOB)-) Tetrafluoroaluminate (AlF)4 -) Fluorosulfonyl- (trifluoromethanesulfonyl) imide (FTFSI)-) Perchlorate (ClO)4 -) One kind of (1).
6. A method of preparing an ionic liquid electrolyte according to any of claims 1 to 5, comprising the steps of:
(1) weighing reactants according to a fixed molar ratio of solute aluminum salt to solvent hydrogen bond donor under room temperature and inert gas atmosphere, sequentially adding the reactants into a container, heating and stirring;
(2) and weighing the organic salt additive, adding the organic salt additive into the container, stirring the mixture together, and naturally cooling the mixed liquid to room temperature to obtain the ionic liquid-like electrolyte.
7. The method according to claim 6, wherein the reaction temperature in the step (1) and the reaction temperature in the step (2) are 30-100 ℃, and the stirring speed is 50-1000 r/min.
8. An aluminum secondary battery comprising a positive electrode, a negative electrode, a separator and the electrolyte according to any one of claims 1 to 5.
9. The aluminum secondary battery according to claim 8, comprising a positive electrode current collector and a positive electrode slurry applied on the positive electrode current collector, wherein the positive electrode slurry comprises 70 to 85 mass% of a positive electrode active material, 10 to 20 mass% of a conductive agent, and 5 to 10 mass% of a binder, and the positive electrode active material is selected from graphite (C) and tungsten sulfide (WS)2) Molybdenum sulfide (MoS)2) Cobaltosic sulfide (Co)3S4) Titanium sulfide (TiS)2) Nickel sulfide (NiS), antimony oxide (TeO)2) Bismuth trioxide (Bi)2O3) Vanadium pentoxide (V)2O5) Manganese dioxide (MnO)2) Cobaltosic oxide (Co)3O4) Copper oxide (CuO), titanium dioxide (TiO)2) Molybdenum selenide (MoSe)2) Copper phosphide (Cu)3P), one of Prussian blue; the positive current collector is made of nickel foam, copper foam, titanium foam, iron foam, stainless steel mesh, carbon paper, carbon fiber cloth, tantalum foil (Ta), niobium foil (Nb) or molybdenum foil (Mo), the conductive agent is selected from at least one of acetylene black, carbon fiber (VGCF), Carbon Nanotubes (CNTs), Ketjenblack (Ketjenblack), graphene and conductive carbon black (Super-P), and the binder is selected from polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR), polyacrylic acid(PAA), Polytetrafluoroethylene (PTFE), and polyvinyl alcohol (PVA).
10. The aluminum secondary battery according to claim 8, wherein the negative electrode is made of an aluminum sheet having a purity of 99.99% or more and a thickness of 0.02 to 5mm, and further comprises a negative electrode current collector made of a stainless steel spring, a foamed nickel, a foamed copper, a foamed titanium, a foamed iron nickel, a stainless steel mesh, a carbon paper or a carbon fiber cloth, and the separator is made of a Polyethylene (PE) film, a polypropylene (PP) film, a glass cellulose (GF/C) film or a non-woven cloth film.
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