CN109962289B - Electrolyte composition and metal ion battery comprising same - Google Patents
Electrolyte composition and metal ion battery comprising same Download PDFInfo
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- CN109962289B CN109962289B CN201711403721.7A CN201711403721A CN109962289B CN 109962289 B CN109962289 B CN 109962289B CN 201711403721 A CN201711403721 A CN 201711403721A CN 109962289 B CN109962289 B CN 109962289B
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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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
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Abstract
The present disclosure provides an electrolyte composition and a metal ion battery including the same. The electrolyte composition comprises a metal halide; a solvent, wherein the solvent is a halogen-containing ionic liquid or an organic solvent, and the molar ratio of the metal halide to the solvent is 1:1 to 2.2: 1; and an additive, wherein the additive is added in an amount of 0.1-25 wt%, based on the total weight of the metal halide and the solvent. The additive is monochloroethane, trichloroethylene, dichloroethane, trichloroethane, phosphorus trichloride, phosphorus pentachloride, picoline, methyl nicotinate, or combinations thereof. The electrolyte composition of the present invention can improve the conductivity of the electrolyte composition, increase the capacity of the metal ion battery, shorten the charging time, and prolong the cycle life of the metal ion battery.
Description
Technical Field
The present disclosure relates to an electrolyte composition and a metal ion battery including the same.
Background
Aluminum is abundant in the earth, and an electronic device using aluminum as a material has a low cost. Because aluminum has low flammability and electronic redox property, the safety of the metal ion battery in use is greatly improved.
However, electrolyte compositions used in conventional metal ion batteries have poor conductivity, resulting in insufficient capacity and short battery life of the metal ion batteries.
Therefore, there is a need for a new electrolyte composition to solve the above problems.
Disclosure of Invention
It is an object of the present invention to provide an electrolyte composition having better conductivity that substantially overcomes the disadvantages of the prior art.
According to an embodiment of the present disclosure, there is provided an electrolyte composition comprising: a metal halide; a solvent; and, an additive. The solvent is a halogen-containing ionic liquid or an organic solvent, and the molar ratio of the metal halide to the solvent is 1:1 to 2.2: 1. The additive is added in an amount of 0.1 to 25 wt% based on the total weight of the metal halide and the solvent. And the additive is monochloroethane, trichloroethylene, dichloroethane, trichloroethane, phosphorus trichloride, phosphorus pentachloride, picoline, methyl nicotinate, or a combination thereof.
According to an embodiment of the present disclosure, a metal-ion battery is also provided, including: a positive electrode; an isolation film; a negative electrode, wherein the negative electrode is separated from the positive electrode by an isolating film; and the electrolyte composition is arranged between the positive electrode and the negative electrode.
Compared with the prior art, the invention has the advantages that: the electrolyte composition of the present invention contains additives having a specific content in addition to the metal halide and the solvent, and thus can improve the conductivity of the electrolyte composition, increase the electric capacity of the metal ion battery, shorten the charging time, and extend the cycle life of the metal ion battery.
Drawings
Fig. 1 is a schematic diagram of a metal-ion battery according to an embodiment of the present disclosure;
FIG. 2 is a graph of 1,2-dichloroethane versus conductivity for electrolyte compositions described in examples 1-5 and comparative example 1 of the present disclosure; and
FIG. 3 is a graph of 1,2-dichloroethane versus conductivity for electrolyte compositions described in examples 6-11 and comparative example 2 of the present disclosure;
wherein the symbols illustrate
10 positive electrode 11 current collecting layer
12 negative electrode 13 active material
14 separator 20 electrolyte composition
100 metal-ion battery.
Detailed Description
The electrolyte compositions and metal ion batteries described in the present disclosure are described in detail below. It is to be understood that the following description provides many different embodiments, or examples, for implementing different aspects of the disclosure. The specific components and arrangements described below are merely illustrative of the present disclosure. These are, of course, merely examples and are not intended to be limiting. Moreover, repeated reference numerals or designations may be used in various embodiments. These iterations are merely for simplicity and clarity in describing the present disclosure, and are not intended to represent any correlation between the various embodiments and/or structures discussed. Also, the shape, number, or thickness of the embodiments may be exaggerated in the drawings for simplicity or convenience. Moreover, although the invention has been described in connection with specific embodiments thereof, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The present disclosure provides an electrolyte composition and a metal ion battery including the same. According to the embodiments of the present disclosure, the electrolyte composition further includes an additive having a specific content in addition to the metal halide and the solvent, which can improve the conductivity of the electrolyte composition, increase the change capacity of the metal ion battery, shorten the charging time, and prolong the cycle life of the metal ion battery.
According to embodiments of the present disclosure, the electrolyte composition may include a metal halide; a solvent; and, an additive. The solvent is a halogen-containing ionic liquid or an organic solvent, and the molar ratio of the metal halide to the solvent can be about 1:1 to 2.2: 1. For example, the molar ratio of the metal halide to the solvent can be about 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, or 2.2. And, the additive may be monochloroethane, trichloroethylene, dichloroethane, trichloroethane, phosphorus trichloride (phosphorus trichloride), phosphorus pentachloride (phosphorus pentachloride), picoline (methyl pyridine), methyl nicotinate (methyl nicotinate), or combinations thereof.
According to an embodiment of the present disclosure, the dichloroethane can be 1, 1-dichloroethane, or 1, 2-dichloroethane; the trichloroethane may be 1,1, 1-trichloroethane, or 1,1, 2-trichloroethane.
According to embodiments of the present disclosure, the additive is added in an amount of about 0.1-25 wt% (e.g., 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, or 24 wt%), based on the total weight of the metal halide and the solvent. If the amount of the additive is too low, the purpose of improving the conductivity of the electrolyte composition cannot be achieved. If the amount of the additive is too high, the content of the active material for intercalation is diluted and the total capacitance is decreased.
According to an embodiment of the present disclosure, the metal halide may be a metal chloride, such as aluminum chloride, ferric chloride, zinc chloride, copper chloride, manganese chloride, chromium chloride, or a combination thereof.
When the solvent is a halogen-containing ionic liquid, the molar ratio of the metal halide to the halogen-containing ionic liquid may be about 1:1 to 2.2:1, according to embodiments of the present disclosure. For example, the molar ratio of the metal halide to the halogen-containing ionic liquid can be about 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, or 2.2.
According to an embodiment of the present disclosure, the halogen-containing ionic liquid is a salt having a melting point below 100 ℃. According to an embodiment of the present disclosure, the halogen-containing ionic liquid may be a chloride-containing ionic liquid. In accordance with embodiments of the present disclosure, the halogen-containing ionic liquid may be ammonium chloride (ammonium chloride), azaannulenium chloride (azaanulium chloride), azathiazolium chloride (azathium chloride), benzimidazolium chloride (benzazimidium chloride), benzofuranylium chloride (benzofurazonium chloride), benzotriazolium chloride (benzotriazolium chloride), borazonium chloride (borolidium chloride), choline chloride (chloium chloride), cinnolinium chloride (cinnolinium chloride), diazabicyclocylindium chloride (diazenium chloride), diazabicyclononenium chloride (diazacyclonium chloride), diazabicyclononenium chloride (diazenium chloride), dicyclanilium chloride (dicyclanilium chloride), and indolium chloride (indolium chloride), a chloride (chlorinate), a chloride (dicyclanilium chloride), a chloride (indolium chloride), a chloride (chlorinate), a chloride (indolium chloride), a chloride (chlorinate), a chloride (indolium chloride), a chloride (indolium chloride), a chloride (chlorinate), a chloride (indolium chloride), a chloride (chloride), a chloride (chloride), a chloride (chloride), a chloride (chloride), a chloride (chloride), a chloride (chloride), a chloride (or (chloride), a chloride (or (chloride) or (or a chloride) salt, or (chloride) or a chloride) or (or a chloride (or a chloride) salt, or (or a chloride) may be-chloride) or a chloride (or a chloride) or a chloride, or a chloride (or a chloride, or a chloride (or a chloride, or a chloride (or a chloride, or a chloride (or a chloride, or, Morpholinium chloride (morpholinonium chloride), oxaborolidium chloride (oxozolium chloride), oxyphospholidium chloride (oxophospholidium chloride), oxazinium chloride (oxazinium chloride), oxazolium chloride (oxozolium chloride), isoxazolium chloride (iso-oxozolium chloride), oxathiazolium chloride (oxothiazolium chloride), pentazolium chloride (pentazolium chloride), phospholidium chloride (phosphoolium chloride), phosphonium chloride (phosphonium chloride), phthalazinium chloride (phthalazinium chloride), piperazinium chloride (piperazinium chloride), piperidinium chloride (piperidinium chloride), piperidinium chloride (pyridinium chloride), pyridinium chloride (chloride), pyridinium chloride (chloride), pyridinium chloride (chloride), chloride (chloride), chloride (chloride), chloride (chloride), chloride (chloride), chloride (chloride), chloride (chloride), chloride (chloride, chloride (chloride), chloride (chloride ), chloride (chloride), chloride (chloride ), chloride, Quinolinium chloride (quinoxalinium chloride), isoquinolinium chloride (iso-quinoxalinium chloride), quinoxalinium chloride (quinoxalinium chloride), selenazolium chloride (selenozolinium chloride), sulfonium chloride (sulfonitrium chloride), tetrazolium chloride (tetrazolium chloride), isothiadiazolium chloride (iso-thiadiazolium chloride), thiazinium chloride (thiazinium chloride), thiazolium chloride (thiazoylium chloride), thiophenium chloride (thiophanatium chloride), thiouronium chloride (thiauronium chloride), triazacyclonium chloride (triazadecenium chloride), triazinium chloride (triazidium chloride), triazolium chloride (triazolium chloride), and triazacyclonium chloride (triazacyrium-urea).
According to some embodiments of the present disclosure, the halogen-containing ionic liquid may be a methylimidazolium chloride salt (methylimidazolium chloride), 1-ethyl-3-methylimidazolium chloride salt (1-ethyl-3-methylimidazolium chloride), 1-butyl-3-methylimidazolium chloride salt (1-butyl-3-methylimidazolium chloride), choline chloride salt (cholinium chloride), or a combination thereof.
According to embodiments of the present disclosure, when 1,2-dichloroethane is used as the additive, the 1,2-dichloroethane is a high dielectric constant solvent, is compatible with halogen-containing ionic liquids, and makes the resulting electrolyte composition suitable for operation at high temperatures.
According to an embodiment of the present disclosure, when the solvent is an organic solvent, the molar ratio of the metal halide to the organic solvent may be about 1:1 to 2.2: 1. For example, the molar ratio of the metal halide to the organic solvent can be about 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, or 2.2.
According to the disclosed embodiments, the electrolyte composition disclosed in the present disclosure may be applied to a plating process or an electrolytic process. Furthermore, according to embodiments of the present disclosure, the electrolyte compositions of the present disclosure may also be applied in metal ion batteries.
According to an embodiment of the present disclosure, a metal-ion battery is also provided. Fig. 1 is a schematic diagram of a metal-ion battery 100 according to an embodiment of the disclosure. The metal ion battery 100 may include a positive electrode 10, a negative electrode 12, and a separator 14, wherein the separator 14 may be disposed between the positive electrode 10 and the negative electrode 12, such that the negative electrode is separated from the positive electrode by the separator 14, and the positive electrode 10 is prevented from directly contacting the negative electrode 12. The metal ion battery 100 comprises the electrolyte composition 20 disposed in the metal ion battery 100 and between the positive electrode and the negative electrode such that the electrolyte composition 20 is in contact with the positive electrode 10 and the negative electrode 12. The metal-ion battery 100 may be a rechargeable secondary battery, but the present disclosure also covers a primary battery.
According to the disclosed embodiment, the positive electrode 10 may include a current collecting layer 11 and an active material 13 disposed on the current collecting layer 11. According to the disclosed embodiment, the positive electrode 10 may also be composed of the current collecting layer 11 and an active material 13. According to the disclosed embodiment, the current collecting layer 11 may be a conductive carbon substrate, such as carbon cloth, carbon felt, or carbon paper. The current collecting layer 11 may also be made of metal such as aluminum, nickel, copper, etc. The current collecting layer 11 may be a composite layer of a carbon material and a metal. For example, the conductive carbon substrate can have a sheet resistance of between about 1m Ω -cm2To 6m omega·cm2And a carbon content greater than about 65 wt%. The active material 13 may be a carbon material having a layered structure, a vanadium-based oxide, a metal sulfide, or an agglomerate of the above materials. According to an embodiment of the present disclosure, the carbon material having a layered structure is graphite, carbon nanotubes, graphene, or a combination thereof.
According to an embodiment of the present disclosure, the carbon material with a layered structure may be an intercalated carbon material, such as: graphite (including natural graphite, artificial graphite, pyrolytic graphite, foamed graphite, flake graphite, or expanded graphite), graphene, carbon nanotubes, or a combination thereof. The active material 13 may have a porosity of between about 0.05 and 0.95, such as between about 0.3 and 0.9. Furthermore, according to the disclosed embodiment, the active material 13 can be grown directly on the collector layer 11 (i.e. without any medium therebetween), or the active material 13 can be fixed on the collector layer 11 by using an adhesive.
According to the embodiment of the present disclosure, the material of the isolation film 14 may be glass fiber, Polyethylene (PE), Polypropylene (PP), non-woven fabric, wood fiber, polyethersulfone (poly (ethylene) resins, PEs), ceramic fiber, or a combination thereof.
According to the disclosed embodiment, the negative electrode 12 is a metal or a metal-containing alloy. According to embodiments of the present disclosure, the metal may be aluminum, copper, iron, indium, nickel, tin, chromium, yttrium, titanium, manganese, or molybdenum. In addition, the cathode 12 may further include a current collector layer (not shown) on which the metal or metal-containing alloy is disposed. According to embodiments of the present disclosure, the metal or metal-containing alloy may be grown directly on the collector layer (i.e., without any medium therebetween), or the metal or metal-containing alloy may be fixed on the collector layer by an adhesive. According to the disclosed embodiment, the metal can be a metal with a reduction potential less than that of aluminum, so as to improve the problem of corrosion of the cathode of the metal-ion battery.
In order to make the aforementioned and other objects, features, and advantages of the present disclosure more comprehensible, several embodiments and comparative embodiments accompanied with figures are described in detail below:
preparation of electrolyte compositions
Comparative example 1
Aluminum chloride was mixed with 1-butyl-3-methylimidazolium chloride (1-butyl-3-methylimidazolium chloride). After stirring was continued for 12 hours, electrolyte composition (1) was obtained in which the molar ratio of aluminum chloride to 1-butyl-3-methylimidazolium chloride (1-butyl-3-methylimidazolium chloride) was 1.5 to 1. The conductivity of electrolyte composition (1) was measured, and the results are shown in fig. 2 and table 1.
Example 1
5 parts by weight of 1,2-dichloroethane (1,2-dichloroethane) was mixed with 100 parts by weight of the electrolyte composition (1). After stirring was continued for 12 hours, electrolyte composition (2) was obtained. The conductivity of electrolyte composition (2) was measured, and the results are shown in fig. 2 and table 1.
Example 2
Electrolyte composition (3) was obtained following the procedure for the preparation of electrolyte composition (2) described in example 1, except that 1,2-dichloroethane was increased from 5 parts by weight to 10 parts by weight. The conductivity of electrolyte composition (3) was measured, and the results are shown in fig. 2 and table 1.
Example 3
Electrolyte composition (4) was obtained following the procedure for the preparation of electrolyte composition (2) described in example 1, except that 1,2-dichloroethane was increased from 5 parts by weight to 15 parts by weight. The conductivity of electrolyte composition (4) was measured, and the results are shown in fig. 2 and table 1.
Example 4
Electrolyte composition (5) was obtained by following the procedure for the preparation of electrolyte composition (2) described in example 1, except that 1,2-dichloroethane was increased from 5 parts by weight to 20 parts by weight. The conductivity of electrolyte composition (5) was measured, and the results are shown in fig. 2 and table 1.
Example 5
Electrolyte composition (6) was obtained following the procedure for the preparation of electrolyte composition (2) described in example 1, except that 1,2-dichloroethane was increased from 5 parts by weight to 25 parts by weight. The conductivity of the electrolyte composition (6) was measured, and the results are shown in fig. 2 and table 1.
TABLE 1
As is apparent from Table 1, the conductivity was measured to be 9.53ms/cm without adding 1,2-dichloroethane, and the conductivity of the electrolyte composition gradually increased as the concentration of 1,2-dichloroethane added increased. When the concentration of 1,2-dichloroethane is 25 wt%, the conductivity of the electrolyte composition can reach 15.32 ms/cm.
Comparative example 2
Aluminum chloride is mixed with urea (urea). After stirring was continued for 12 hours, an electrolyte composition (7) was obtained in which the molar ratio of aluminum chloride to urea was 1.6 to 1. The conductivity of electrolyte composition (7) was measured, and the results are shown in fig. 3 and table 2.
Example 6
0.115 parts by weight of 1,2-dichloroethane (1,2-dichloroethane) was mixed with 100 parts by weight of the electrolyte composition (7). After stirring was continued for 12 hours, the electrolyte composition (8) was obtained. The conductivity of the electrolyte composition (8) was measured, and the results are shown in fig. 3 and table 2.
Example 7
Electrolyte composition (9) was prepared according to the procedure for the preparation of electrolyte composition (8) described in example 6, except that 1,2-dichloroethane was increased from 0.115 parts by weight to 0.383 parts by weight. The conductivity of the electrolyte composition (9) was measured, and the results are shown in fig. 3 and table 2.
Example 8
The procedure was followed for the preparation of electrolyte composition (8) as described in example 6, except that 1,2-dichloroethane was increased from 0.115 parts by weight to 1.141 parts by weight to obtain electrolyte composition (10). The conductivity of the electrolyte composition (10) was measured, and the results are shown in fig. 3 and table 2.
Example 9
Electrolyte composition (11) was prepared according to the procedure for the preparation of electrolyte composition (8) described in example 6, except that 1,2-dichloroethane was increased from 0.115 parts by weight to 2.072 parts by weight. The conductivity of the electrolyte composition (11) was measured, and the results are shown in fig. 3 and table 2.
Example 10
The procedure was followed for the preparation of electrolyte composition (8) as described in example 6, except that 1,2-dichloroethane was increased from 0.115 parts by weight to 3.704 parts by weight to obtain electrolyte composition (12). The conductivity of the electrolyte composition (12) was measured, and the results are shown in fig. 3 and table 2.
Example 11
The procedure was followed for the preparation of the electrolyte composition (8) described in example 6, except that 1,2-dichloroethane was increased from 0.115 parts by weight to 5.455 parts by weight to obtain an electrolyte composition (13). The conductivity of the electrolyte composition (13) was measured, and the results are shown in fig. 3 and table 2.
TABLE 2
As is clear from Table 2, the conductivity was measured to be 0.883ms/cm without adding 1,2-dichloroethane, and the conductivity of the electrolyte composition gradually increased as the concentration of 1,2-dichloroethane added increased. When the c concentration is 5.455 wt%, the conductivity of the electrolyte composition can reach 1.385 ms/cm. The addition of 1,2-dichloroethane can increase the conductivity of electrolyte compositions comprising aluminum chloride and urea. As can be seen from table 2, when 1,2-dichloroethane was added, the conductivity was improved by 57% (compared with electrolyte composition (7) (without 1, 2-dichloroethane).
Comparative example 3
Aluminum chloride was reacted with 1-butyl-3-methylimidazolium chloride (1-butyl-3-methylimidazolium chloride). After stirring was continued for 12 hours, an electrolyte composition (14) was obtained in which the molar ratio of aluminum chloride to 1-butyl-3-methylimidazolium chloride was 1.6 to 1.
Example 12
Methyl pyridine (3 parts by weight) was mixed with electrolyte composition (14) of 100 parts by weight. After stirring was continued for 12 hours, an electrolyte composition (15) was obtained.
Example 13
Methyl nicotinate (methyl nicotinate) was mixed with 100 parts by weight of an electrolyte composition (14). After stirring was continued for 12 hours, the electrolyte composition (16) was obtained.
Metal ion battery
Comparative example 3
An aluminum foil with the thickness of 0.05mm is provided and cut to obtain the aluminum electrode. Next, a separator (glass filter paper (2 layers), product number Whatman GFA) and a graphite electrode (comprising an active material disposed on a collector substrate, wherein the collector substrate is carbon fiber paper and the active material is natural graphite (302.82mg)) were provided. Then, an aluminum electrode (as a negative electrode), a separator, and a graphite electrode (as a positive electrode) were arranged in this order, and they were encapsulated with an aluminum plastic film and injected with an electrolyte composition (14) (aluminum chloride (AlCl)3) L-Ethyl-3-methylimidazolium chloride (1-ethyl-3-methylimidazolium chloride, [ EMIm ]]Cl), wherein AlCl3And [ EMIm]Cl in a molar ratio of about 1.6:1) to obtain a metal-ion battery (1). Then, the cell performance of the aluminum-ion cell (1) was measured using a NEWARE cell analyzer (under the conditions of a charging current of 500mA/g, a cut-off voltage of 2.45V, a discharging current of 500mA/g, and a cut-off voltage of 1V), and the gram-charge capacity and cycle life of the metal-ion cell (1) were obtained, and the results are shown in Table 3.
Example 14
An aluminum foil with the thickness of 0.05mm is provided and cut to obtain the aluminum electrode. Next, a separator (glass filter paper (2 layers), product number Whatman GFA) and a graphite electrode (comprising an active material disposed on a collector substrate, wherein the collector substrate is carbon fiber paper and the active material is natural graphite (346mg)) were provided. Next, an aluminum electrode (as a negative electrode), a separator, and a graphite electrode (as a positive electrode) were arranged in this order. Then, the electrolyte composition (15) was encapsulated and injected with an aluminum plastic film to obtain a metal ion battery (2). Then, the cell (2) performance of the aluminum ion cell obtained was measured using a NEWARE cell analyzer (measurement conditions were: 500mA/g of charging current, 2.45V of cutoff voltage, 500mA/g of discharging current, 1V of cutoff voltage), and the gram-charge capacity and cycle life of the metal ion cell (2) were obtained, and the results are shown in Table 3.
Example 15
An aluminum foil with the thickness of 0.05mm is provided and cut to obtain the aluminum electrode. Next, a separator (glass filter paper (2 layers), product number Whatman GFA) and a graphite electrode (including an active material disposed on a collector substrate, wherein the collector substrate is carbon fiber paper and the active material is natural graphite (349mg)) were provided. Next, an aluminum electrode (as a negative electrode), a separator, and a graphite electrode (as a positive electrode) were arranged in this order, and then, they were encapsulated with an aluminum-plastic film and injected with an electrolyte composition (16), to obtain a metal-ion battery (3). Then, the cell performance of the aluminum-ion cell (3) was measured using a NEWARE cell analyzer (under the conditions of a charging current of 500mA/g, a cut-off voltage of 2.45V, a discharging current of 500mA/g, and a cut-off voltage of 1V), and the gram-charge capacity and cycle life of the metal-ion cell (3) were obtained, and the results are shown in Table 3.
TABLE 3
As can be seen from Table 3, the gram-discharge capacity of the metal-ion battery (1) without the additive can only reach 39(mAh/g), and the cycle life of the metal-ion battery with the capacity capable of maintaining more than 80% of the original capacity is only 180 cycles. In the metal ion battery (2) using the electrolyte composition added with the picoline, the discharge gram capacitance is increased by 1.128 times, and the cycle life of the metal ion battery which can maintain the original charge above 80% is increased by 2.16 times. In addition, the metal ion battery (3) using the electrolyte composition added with methyl nicotinate has a lower gram-discharge capacity, but the cycle life of the battery capable of maintaining 80% or more of the original charge is increased by 5.55 times.
Although the present disclosure has been described with reference to several embodiments, it should be understood that the scope of the present disclosure is not limited to the embodiments described above, but is intended to be defined by the appended claims.
Claims (15)
1. An electrolyte composition comprising:
a metal halide;
a solvent, wherein the solvent is a halogen-containing ionic liquid or an organic solvent, and the molar ratio of the metal halide to the solvent is 1:1 to 2.2: 1; and
an additive, wherein the additive is added in an amount of 0.1-25 wt%, based on the total weight of the metal halide and the solvent, wherein the additive is phosphorus trichloride, phosphorus pentachloride, methyl nicotinate, or a combination thereof.
2. The electrolyte composition of claim 1, wherein the metal halide is aluminum chloride, ferric chloride, zinc chloride, copper chloride, manganese chloride, chromium chloride, or a combination thereof.
3. The electrolyte composition of claim 1, wherein the halogen-containing ionic liquid is an ammonium chloride salt, an azaannulenium chloride salt, an azathiazolium chloride salt, a benzimidazolium chloride salt, a benzofuranylium chloride salt, a benzotriazolium chloride salt, a boratabenium chloride salt, a choline chloride salt, a cinnolinium chloride salt, a diazabicyclo decenyl onium chloride salt, a diazabicyclononenium chloride salt, a diazabicycloundecenyl onium chloride salt, a dithiazolium chloride salt, a furanylium chloride salt, a guanidinium chloride salt, an imidazolium chloride salt, an indazolium chloride salt, a indolium chloride salt, an indolium chloride salt, a morpholinium chloride salt, a oxaborole chloride salt, an oxaphospholenium chloride salt, an oxazinium chloride salt, an oxazolium chloride salt, an isoxazolium chloride salt, an oxathiazolium chloride salt, a pentaazolium chloride salt, a phospholenium chloride salt, a phosphonium chloride salt, a phthalazinium chloride salt, a piperazinium chloride salt, a piperidinium chloride salt, a salt of a, Pyranium chloride salt, pyrazinium chloride salt, pyrazolium chloride salt, pyridazinium chloride salt, pyridinium chloride salt, pyrimidinium chloride salt, pyrrolidinium chloride salt, pyrrolium chloride salt, quinazolinium chloride salt, quinolinium chloride salt, isoquinolinium chloride salt, quinoxalinium chloride salt, selenazolium chloride salt, sulfonium chloride salt, tetrazolium chloride salt, isothiadiazolium chloride salt, thiazinium chloride salt, thiazolium chloride salt, thiophenium chloride salt, thiouronium chloride salt, triazadecanium chloride salt, triazinium chloride salt, triazolium chloride salt, isotriazolinium chloride salt, or uronium chloride salt.
4. The electrolyte composition of claim 1, wherein the organic solvent is urea, N-methylurea, dimethylsulfoxide, dimethylsulfone, or mixtures thereof.
5. The electrolyte composition of claim 1, wherein the halogen-containing ionic liquid is a methylimidazolium chloride salt, a 1-ethyl-3-methylimidazolium chloride salt, a 1-butyl-3-methylimidazolium chloride salt, a choline chloride salt, or a combination thereof.
6. A metal-ion battery comprising:
a positive electrode;
an isolation film;
a negative electrode, wherein the negative electrode is separated from the positive electrode by a separator; and
the electrolyte composition of claim 1 disposed between the positive electrode and the negative electrode.
7. The metal-ion battery of claim 6, wherein the positive electrode is comprised of a current collector layer and an active material.
8. The metal-ion battery of claim 7, wherein the current collector layer is a conductive carbon substrate.
9. The metal-ion battery of claim 8, wherein the conductive carbon substrate is a carbon cloth, carbon felt, or carbon paper.
10. The metal-ion battery of claim 7, wherein the active material is a carbon material, a vanadium-based oxide, or a metal sulfide having a layered structure.
11. The metal-ion battery of claim 10, wherein the carbon material with a layered structure is graphite, carbon nanotubes, graphene, or a combination thereof.
12. The metal-ion battery of claim 11, wherein the graphite is natural graphite, artificial graphite, pyrolytic graphite, expanded graphite, flake graphite, expanded graphite, or a combination of the foregoing materials.
13. The metal-ion battery of claim 6, wherein the negative electrode comprises a metal or alloy thereof, a current collector layer, or a combination thereof.
14. The metal-ion battery of claim 13, wherein the metal is aluminum, copper, iron, zinc, indium, nickel, tin, chromium, yttrium, titanium, manganese, or molybdenum.
15. The metal-ion battery of claim 6, wherein the separator is glass fiber, polyethylene, polypropylene, non-woven fabric, wood fiber, polyethersulfone resin, ceramic fiber, or a combination thereof.
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