TWI624990B - Electrolyte composition and metal-ion battery employing the same - Google Patents

Abstract

The present disclosure provides an electrolyte composition and a metal ion battery comprising the same. The electrolyte composition comprises: a metal chloride; a chlorine ion-containing liquid; and an additive, wherein the additive is a compound having the structure of the formula (I): [M] _i [(A(SO ₂ C _x F _{2x) +1} ) _y ) ^b- ] _j formula (I)

Wherein M may be ammonium cation, azaannulenium cation, azathiazolium cation, benzimidazolium cation, benzofuranium cation ), benzotriazolium cation, borolium cation, cholinium cation, cinnolinium cation, diazabicyclononene Diazabicyclodecenium cation, diazabicyclononenium cation, diazabicyclo-undecenium cation, dithiazolium cation, furan cation (furanium cation), guanidinium cation, imidazolium cation, indazolium cation, indolinium cation, indolium cation, Morpholinium cation, oxaborolium cation , oxaphospholium cation, oxazinium cation, oxazolium cation, iso-oxazolium cation, oxathiazolium cation Cation), pentazolium cation, phospholinium cation, phosphonium cation, phthalazinium cation, piperazinium cation, Piperidinium cation, pyranium cation, pyrazinium cation, pyrazolium cation, pyridazinium cation, pyridinium cation Cation), pyrimidinium cation, pyrrolidinium cation, pyrrolium cation, quinazolinium cation, quinolinium cation, isoquinoline Iso-quinolinium cation, quinoxalinium cation, selenazole Selenozolium cation, sulfonium cation, tetrazolium cation, iso-thiadiazolium cation, thiazinium cation, thiazolium cation Cation), thiophenium cation, thiuronium cation, triazadecenium cation, triazinium cation, triazolium cation, Iso-triazolium cation or uronium cation, wherein the valence of M can be a; a is 1, 2, or 3; A can be nitrogen, oxygen, hydrazine, or carbon; x may be 1, 2, 3, 4, 5, or 6; y may be 1, 2, or 3; b may be 1, 2, or 3; i may be 1, 2, or 3; j may be 1 2, or 3; a/b=j/i; and, when y is 2 or 3, the (SO ₂ C _x F _2x+1 ) groups may be the same or different.

Description

Electrolyte composition and metal ion battery containing same

The present disclosure relates to an electrolyte composition and a metal ion battery comprising the same.

Aluminum is abundant in the earth, and electronic devices using aluminum as a material have lower costs. In the application of energy storage components, the number of electron transfer in aluminum during electrochemical charging and discharging can reach three, thus providing a higher energy storage capacity. Furthermore, since aluminum has low flammability and electronic redox properties, the safety of the metal ion battery is greatly improved.

However, the electrolyte composition used in the conventional metal ion battery is easy to absorb moisture and deliquesce, so it is necessary to perform electrolyte filling and metal ion battery encapsulation under relatively strict conditions (low moisture and oxygen content atmosphere), resulting in mass production. Limited on.

Therefore, the industry needs a new electrolyte composition to solve the above problems.

According to an embodiment of the present disclosure, the present disclosure provides an electrolyte composition comprising: a metal chloride; a chlorine ion-containing liquid; and an additive, wherein the additive is a compound having the structure of the formula (I): [M] _i [(A(SO ₂ C _x F _2x+1 ) _y ) ^b- ] _j Formula (I)

Wherein M may be ammonium cation, azaannulenium cation, azathiazolium cation, benzimidazolium cation, benzofuranium cation ), benzotriazolium cation, borolium cation, cholinium cation, cinnolinium cation, diazabicyclononene Diazabicyclodecenium cation, diazabicyclononenium cation, diazabicyclo-undecenium cation, dithiazolium cation, furan cation (furanium cation), guanidinium cation, imidazolium cation, indazolium cation, indolinium cation, indolium cation, Morpholinium cation, oxaborolium cation , oxaphospholium cation, oxazinium cation, oxazolium cation, iso-oxazolium cation, oxathiazolium cation Cation), pentazolium cation, phospholinium cation, phosphonium cation, phthalazinium cation, piperazinium cation, Piperidinium cation, pyranium cation, pyrazinium cation, pyrazolium cation, pyridazinium cation, pyridinium cation Cation), pyrimidinium cation, pyrrolidinium cation, pyrrolium cation, quinazolinium cation, quinolinium cation, isoquinoline Iso-quinolinium cation, quinoxalinium cation, selenazole Selenozolium cation, sulfonium cation, tetrazolium cation, iso-thiadiazolium cation, thiazinium cation, thiazolium cation Cation), thiophenium cation, thiuronium cation, triazadecenium cation, triazinium cation, triazolium cation, Iso-triazolium cation or uronium cation, wherein the valence of M can be a; a is 1, 2, or 3; A is nitrogen, oxygen, hydrazine, or carbon; May be 1, 2, 3, 4, 5, or 6; y is 1, 2, or 3; b is 1, 2, or 3; i is 1, 2, or 3; j is 1, 2, or 3 ; a / b = j / i; and, when y is 2 or 3, the (SO ₂ C _x F _2x+1 ) groups may be the same or different.

According to an embodiment of the present disclosure, the present disclosure also provides a metal ion battery comprising: a positive electrode; a separator; a negative electrode, wherein the negative electrode is separated from the positive electrode by a separator; and the electrolyte composition is disposed on the positive electrode Between the negative electrode and the negative electrode.

10‧‧‧ positive

11‧‧‧ Collector layer

12‧‧‧negative

13‧‧‧Active materials

14‧‧‧Separator

20‧‧‧Electrolyte composition

100‧‧‧metal ion battery

1 is a schematic view of a metal ion battery according to an embodiment of the present invention; and FIG. 2 is a diagram showing a relationship between charge and discharge voltage and time of the metal ion battery (1) of Comparative Example 1; FIG. 3 is a disclosure of the present invention. A graph showing a relationship between a discharge specific capacity and a number of charge and discharge cycles of the metal ion battery (1) according to Comparative Example 1; 4 is a diagram showing the relationship between charge and discharge voltage and time of the metal ion battery (2) according to Embodiment 5; FIG. 5 is a discharge ratio capacity and charge of the metal ion battery (2) according to Embodiment 5 of the present disclosure. FIG. 6 is a diagram showing the relationship between charge and discharge voltage and time of the metal ion battery (3) according to the embodiment 6; and FIG. 7 is a metal ion battery according to the embodiment 6 of the present disclosure ( 3) a relationship between the discharge specific capacity and the number of charge and discharge cycles; FIG. 8 is a diagram showing the relationship between charge and discharge voltage and time of the metal ion battery (4) according to the embodiment 7; FIG. 9 is a disclosure of the disclosure FIG. 7 is a graph showing the relationship between the discharge specific capacity and the number of charge and discharge cycles of the metal ion battery (4); and FIG. 10 is a graph showing the relationship between the charge and discharge voltage and time of the metal ion battery (5) according to the embodiment 8. Fig. 11 is a graph showing the relationship between the discharge specific capacity and the number of charge and discharge cycles of the metal ion battery (5) according to the embodiment 8.

Hereinafter, the electrolyte composition and the metal ion battery described in the present disclosure will be described in detail. It will be appreciated that the following description provides many different embodiments or examples for implementing the various aspects of the disclosure. The specific elements and arrangements described below are merely illustrative of the disclosure. Of course, these are only used as examples and not as a limitation of the disclosure. Moreover, repeated numbers or labels may be used in different embodiments. These repetitions are merely for the purpose of simplicity and clarity of the disclosure, and are not intended to represent any of the various embodiments and/or structures discussed. And in the drawings, the shape, the number, or the thickness of the embodiment Can be expanded and simplified or conveniently labeled. Furthermore, the components of the drawings will be described separately, and it is noted that the components not shown or described in the drawings are known to those of ordinary skill in the art and, in addition, The embodiments are merely illustrative of specific ways of using the disclosure, and are not intended to limit the disclosure.

The present disclosure provides an electrolyte composition and a metal ion battery comprising the same. According to an embodiment of the present disclosure, the electrolyte composition further comprises a specific content of an additive in addition to the metal chloride and the chlorine ion-containing liquid, which can reduce the hygroscopicity of the electrolyte composition and increase the hydrolysis resistance of the electrolyte composition. Improve the tolerance of metal ion batteries to environmental water oxygen, and extend the cycle life of metal ion batteries.

According to an embodiment of the present disclosure, the electrolyte composition may comprise a metal chloride, a chlorine ion-containing liquid, and an additive. Wherein the additive may have a compound of the formula (I): [M] _i [(A(SO ₂ C _x F _2x+1 ) _y ) ^b- ] _j Formula (I)

Wherein M may be ammonium cation, azaannulenium cation, azathiazolium cation, benzimidazolium cation, benzofuranium cation ), benzotriazolium cation, borolium cation, cholinium cation, cinnolinium cation, diazabicyclononene Diazabicyclodecenium cation, diazabicyclononenium cation, diazabicyclo-undecenium cation, dithiazolium cation, furan cation (furanium cation), guanidinium cation, imidazolium cation, indazolium cation, indolinium cation, indolium cation, Morpholinium cation, oxaborolium cation , oxaphospholium cation, oxazinium cation, oxazolium cation, iso-oxazolium cation, oxathiazolium cation Cation), pentazolium cation, phospholinium cation, phosphonium cation, phthalazinium cation, piperazinium cation, Piperidinium cation, pyranium cation, pyrazinium cation, pyrazolium cation, pyridazinium cation, pyridinium cation Cation), pyrimidinium cation, pyrrolidinium cation, pyrrolium cation, quinazolinium cation, quinolinium cation, isoquinoline Iso-quinolinium cation, quinoxalinium cation, selenazole Selenozolium cation, sulfonium cation, tetrazolium cation, iso-thiadiazolium cation, thiazinium cation, thiazolium cation Cation), thiophenium cation, thiuronium cation, triazadecenium cation, triazinium cation, triazolium cation, Iso-triazolium cation or uronium cation, wherein the valence of M can be a; a can be 1, 2, or 3; A can be nitrogen, oxygen, hydrazine, or carbon ;x may be 1, 2, 3, 4, 5, or 6; y may be 1, 2, or 3; b may be 1, 2, or 3; i may be 1, 2, or 3; j may be 1, 2, or 3; a/b = j / i; and, when y is 2, or 3, the (SO ₂ C _x F _2x+1 ) groups may be the same or different.

According to an embodiment of the present disclosure, the additive may have a compound of the formula (II): [M] _i [(OSO ₂ C _x F _2x+1 ) ^- ] _j Formula (II)

Wherein M may be ammonium cation, azaannulenium cation, azathiazolium cation, benzimidazolium cation, benzofuranium cation ), benzotriazolium cation, borolium cation, cholinium cation, cinnolinium cation, diazabicyclononene Diazabicyclodecenium cation, diazabicyclononenium cation, diazabicyclo-undecenium cation, dithiazolium cation, furan cation (furanium cation), guanidinium cation, imidazolium cation, indazolium cation, indolinium cation, indolium cation, Morpholinium cation, oxaborolium cation , oxaphospholium cation, oxazinium cation, oxazolium cation, iso-oxazolium cation, oxathiazolium cation Cation), pentazolium Cation), phospholinium cation, phosphonium cation, phthalazinium cation, piperazinium cation, piperidinium cation, Pyranium cation, pyrazinium cation, pyrazolium cation, pyridazinium cation, pyridinium cation, pyrimidinium cation a pyrrolidine cation, a pyrrolium cation, a quinazolinium cation, a quinolinium cation, an iso-quinolinium cation, Quinoxalinium cation, selenozolium cation, sulfonium cation, tetrazolium cation, iso-thiadiazolium cation, thiophene Thiazinium cation, thiazolium cation, thiophene cation Thiophenium cation, thiuronium cation, triazadecenium cation, triazinium cation, triazolium cation, isotriazolium cation (iso-triazolium cation) or urea cation (uronium cation), wherein the valence of M can be a; a can be 1, 2, or 3; x can be 1, 2, 3, 4, 5, or 6; i may be 1, 2, or 3; j may be 1, 2, or 3; and, a = j/i.

According to an embodiment of the present disclosure, the additive may have a compound of the formula (III): [M] _i [(N(SO ₂ C _x F _2x+1 ) ₂ ) ^- ] _j Formula (III)

Wherein M can be an ammonium cation, aza olefin Azaannulenium cation, azathiazolium cation, benzimidazolium cation, benzofuranium cation, benzotriazolium cation, boron heterocycle Carbolium cation, cholinium cation, cinnolinium cation, diazabicyclodecenium cation, diazabicyclononene cation Diazabicyclononenium cation), diazabicyclo-undecenium cation, dithiazolium cation, furanium cation, guanidinium cation, imidazolium cation (imidazolium cation), indazolium cation, indolinium cation, indolium cation, morpholinium cation, oxocyclopentadiene Oxalborolium cation, oxaphospholium cation, Oxazinium cation, oxazolium cation, iso-oxazolium cation, oxathiazolium cation, pentazolium cation, phosphorus heterocycle Phosphonium cation, phosphonium cation, phthalazinium cation, piperazinium cation, piperidinium cation, pyranium cation Cation), pyrazinium cation, pyrazolium cation, pyridazinium cation, pyridinium cation, pyrimidinium cation, pyrrolidinium cation (pyrrolidinium cation), pyrrolium cation, quinazolinium cation (quinazolinium) Cation), quinolinium cation, iso-quinolinium cation, quinoxalinium cation, selenozolium cation, sulfonium cation , tetrazolium cation, iso-thiadiazolium cation, thiazinium cation, thiazolium cation, thiophenium cation, thiourea Thiuronium cation, triazadecenium cation, triazinium cation, triazolium cation, iso-triazolium cation or urea An uronium cation wherein the valence of M can be a; a can be 1, 2, or 3; x can be 1, 2, 3, 4, 5, or 6; i can be 1, 2, or 3; j can be 1, 2, or 3; and, a = j / i.

According to some embodiments of the present disclosure, the additive may be 1-ethyl-3-methylimidazolium triflate, [EMI ⁺ ][OTf ^- ], 1- Ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide, [EMI ⁺ ][TFSI ^- ], 1-butyl- 3-methylimidazolium triflate (1-butyl-3-methylimidazolium triflate, [BMI ⁺ ][OTf ^- ]), 1-butyl-3-methylimidazolium-bis(trifluoromethylsulfonate) Imino (1-butyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide, [BMI ⁺ ][TFSI ^- ]), or a combination thereof.

According to an embodiment of the present disclosure, the metal chloride may be aluminum chloride, iron chloride, zinc chloride, copper chloride, manganese chloride, chromium chloride, or a combination thereof.

According to an embodiment of the present disclosure, the chlorine-containing liquid comprises ammonium chloride salt (ammonium chloride), azaannulenium chloride, azathiazolium chloride, benzimidazolium chloride, benzofuranium chloride, Benzotriazolium chloride, borolium chloride, cholinium chloride, cinnolinium chloride, diazabicyclic quinone Diazabicyclodecenium chloride, diazabicyclononenium chloride, diazabicyclo-undecenium chloride, dithiazolium Chloride), furanium chloride, guanidinium chloride, imidazolium chloride, indazolium chloride, indolinium chloride ), indolium chloride, morpholinium chloride, oxaborolium chloride, oxaphospholi Um chloride), oxazinium chloride, oxazolium chloride, iso-oxazolium chloride, oxathiazolium chloride, pentabazolium Pentazolium chloride, phospholium chloride, phosphonium chloride, phthalazinium chloride, piperazinium chloride, piperazine Piperidinium chloride, pyranium chloride, pyrazinium chloride, pyrazolium chloride, pyridazinium chloride, pyridine Pyridinium chloride, pyrimidinium chloride, pyrrolidinium chloride Chloride), pyrrolium chloride, quinazolinium chloride, quinolinium chloride, iso-quinolinium chloride, quinoxaline Chlorine salt (quinoxalinium chloride), selenozolium chloride, sulfonium chloride, tetrazolium chloride, iso-thiadiazolium chloride, Thiazinium chloride, thiazolium chloride, thiophenium chloride, thiurium chloride, triazadecenium chloride , triazinium chloride, triazolium chloride, iso-triazolium chloride, or uronium chloride.

According to an embodiment of the present disclosure, the chlorine-containing ionic liquid comprises ammonium chloride (for example, alkylammonium chloride, azaarnulenium chloride (eg, alkyl aza) Alkthiazolium chloride, azathiazolium chloride (eg, alkylazathiazolium chloride), benzimidazolium chloride (eg, : alkylbenzimidazolium chloride, benzofuranium chloride (eg, alkylbenzofuranium chloride), benzotriazolium chloride ( Benzotriazolium chloride (for example: alkylbenzotriazolium chloride), borolium chloride (for example: alkylborolium chloride) ), cholinium chloride (eg, alkylcholinium chloride), porphyrin chlorochloride Cinnolinium chloride (eg, alkylcinnolinium chloride), diazabicyclodecenium chloride (eg, alkyldiazabicyclononene chloride) (alkyldiazabicyclodecenium chloride)), diazabicyclononenium chloride (eg alkyldiazabicyclononenium chloride), diazabicycloundecene Diazabicyclo-undecenium chloride (eg alkyldiazabicyclo-undecenium chloride), dithiazolium chloride (eg alkyl dithiazole) An alkyldithiazolium chloride, a furanium chloride (eg, alkylfuranium chloride), or a guanidinium chloride (eg, an alkyl phosphonium chloride) Alkylguanidium chloride)), imidazolium chloride (eg alkylimidazolium chloride), indazolium chloride (eg alkyl oxazolium) (alkylindazolium chloride), indolinium chloride (eg, alkylindolinium chloride), indolium chloride (eg, alkyl) Alkalinium chloride, morpholinium chloride (eg alkylmorpholinium chloride), oxaborolium chloride (oxaborolium chloride) For example: alkyloxaborolium chloride, oxaphospholium chloride (eg, alkyloxaphospholium chloride) ), oxazinium chloride (eg, alkyloxazinium chloride), oxazolium chloride (eg, alkyloxazolium chloride) (alkyloxazolium chloride)), iso-oxazolium chloride (eg, iso-alkyloxazolium chloride), oxathiazolium chloride (eg, alkane) An alkyloxathiazolium chloride, a pentazolium chloride (eg, an alkylpentazolium chloride), a phospholium chloride (phospholium chloride) For example: alkylphospholium chloride, phosphonium chloride (eg, alkylphosphonium chloride), phthalazinium chloride (Example: alkylphthalazinium chloride), piperazinium chloride (eg alkylpiperazinium chloride), piperidinium chloride (Example: alkylpiperidinium chloride), pyranium chloride (eg alkylpyranium chloride), pyrazinium chloride (E.g: Alkylpyrazinium chloride, pyrazolium chloride (eg, alkylpyrazolium chloride), pyridazinium chloride (eg: Alkylpyridazinium chloride, pyridinium chloride (eg, alkylpyridinium chloride), pyrimidinium chloride (eg, alkylpyrimidine) An alkylpyrimidinium chloride, pyrrolidinium chloride (eg, alkylpyrrolidinium chloride), pyrrolium chloride (eg, alkylpyrrolidinium chloride) (alkylpyrrolium chloride), quinazolinium chloride (eg alkyl quinazolinium chloride) (alkylquinazolinium chloride)), quinolinium chloride (eg, alkylquinolinium chloride), iso-quinolinium chloride (eg, alkylisoquine) Iso-alkylquinolinium chloride, quinoxalinium chloride (eg alkylquinoxalinium chloride), selenozolium chloride (eg : alkylselenozolium chloride, sulfonium chloride (for example: alkylsulfonium chloride), tetrazolium chloride (for example: alkane) Isotetradialium chloride, iso-thiadiazolium chloride (eg, iso-alkylthiadialium chloride), thiazinium chloride (thiazinium chloride) (for example: alkylthiazinium chloride), thiazolium chloride (for example: alkylthiazolium chloride), thiophenium chloride ) Such as: alkylthiophenium chloride, thiurium chloride (for example: alkylthiuronium chloride), triazadecenium chloride (for example: alkyltriazadecenium chloride), triazinium chloride (for example: alkyltriazinium chloride), triazolium chloride (triazolium chloride) (eg, alkyltriazolium chloride), iso-triazolium chloride (eg, iso-alkyltriazolium chloride) Or uronium chloride (for example: alkyluronium chloride). Or a combination of the above.

According to some embodiments of the present disclosure, the chloride ion-containing liquid system methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 1 1-butyl-3-methylimidazolium chloride, cholinium chloride, or a combination thereof.

According to an embodiment of the present disclosure, the metal chloride has a molar ratio to the chlorine-containing liquid of at least or greater than about 1.1, or at least or greater than about 1.2, such as between about 1.1 and 2.05. For example, the molar ratio of the metal chloride to the chloride-containing liquid can be about 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. According to an embodiment of the present disclosure, the additive may be included in an amount of from 1% by weight to 10% by weight based on the total weight of the metal chloride and the chlorine-containing ionic liquid. If the content of the additive is too low, the hygroscopicity of the electrolyte composition cannot be effectively lowered, and the hydrolysis resistance of the electrolyte composition cannot be effectively increased, resulting in a decrease in the resistance of the metal ion battery to environmental water and oxygen. If the content of the additive is too high, the viscosity of the electrolyte composition increases, and the electrolyte composition is less likely to enter the layered active material, thereby reducing the total power generation of the metal ion battery.

According to an embodiment of the present disclosure, the present disclosure also provides a metal ion battery. Please refer to FIG. 1 , which is a schematic diagram of a metal ion battery 100 according to an embodiment of the present disclosure. The metal ion battery 100 can include a positive electrode 10, a negative electrode 12, and a separator 14, wherein the separator 14 can be disposed between the positive electrode 10 and the negative electrode 12 such that the negative electrode is the separator 14 and the positive electrode. Separately, the positive electrode 10 is prevented from coming into direct contact with the negative electrode 12. The metal ion battery 100 includes the electrolyte composition 20 disposed in the metal ion battery 100 and located 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 can be a rechargeable secondary battery, but This disclosure also covers primary batteries.

According to the embodiment of the present disclosure, the positive electrode 10 may include a collector layer 11 and an active material 13 disposed on the collector layer 11. According to the disclosed embodiment, the positive electrode 10 can also be composed of the collector layer 11 and the active material 13. According to an embodiment of the present disclosure, the collector layer 11 may be a conductive carbon substrate such as carbon cloth, carbon felt, or carbon paper. The collector layer 11 may also be a metal material such as aluminum, nickel, copper or the like. Further, the collector layer 11 may be a composite layer of a carbon material and a metal. For example, the conductive carbon substrate may have a sheet resistance of about 1 mΩ. Cm ² to 6mΩ. Between cm ² and carbon content greater than 65 wt%. The active material 13 may be a carbon material having a layered structure, a vanadium-based oxide, a metal sulfide, or agglomerates of the above materials. According to an embodiment of the present disclosure, the carbon material having a layered structure is graphite, a carbon nanotube, graphene, or a combination thereof.

According to an embodiment of the present disclosure, the carbon material having 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 of the above materials. 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. In addition, according to the embodiment of the present disclosure, the active material 13 may be directly grown on the collector layer 11 (ie, without any medium between them), or the active material 13 may be fixed to the collector layer by an adhesive. 11 on.

According to the embodiment of the disclosure, the material of the separator 14 can be glass fiber, polyethylene (PE), polypropylene (polypropylene, PP), non-woven fabric, wood fiber, polyether epoxy resin (Poly (ether sulfones), PES ), ceramic fibers, etc. or a combination thereof.

According to an embodiment of the present disclosure, the negative electrode 12 is a metal or a metal-containing alloy. According to an embodiment of the disclosure, the metal may be copper, iron, indium, nickel, tin, chromium, Niobium, titanium, manganese, or molybdenum. In addition, the negative electrode 12 may further include a collector layer (not shown), and the metal or metal-containing alloy is disposed on the collector layer. According to an embodiment of the present disclosure, the metal or metal-containing alloy may be directly grown on the collector layer (ie, without any medium between them), or the metal or the alloy containing the metal may be fixed by an adhesive. On the collector layer. According to an embodiment of the present disclosure, the metal may be a metal having a reduction potential smaller than aluminum to improve the corrosion of the negative electrode of the metal ion battery.

The above and other objects, features and advantages of the present invention will become more apparent and understood.

Preparation of electrolyte composition

Example 1

Mix 1.4mole of aluminum chloride with 1.0mole of 1-ethyl-3-methylimidazolium chloride in the atmosphere. Since the sample has room temperature eutectic properties, it can be The solid phase is converted to a liquid phase. Next, 1 wt% of 1-ethyl-3-methylimidazolium triflate (1-ethyl-3-methylimidazolium triflate, [EMI ⁺ ][OTf ^- ]) was added (to the aluminum chloride and 1- The total weight of ethyl-3-methylimidazolium chloride is the basis). After continuously stirring for 12 hours, an electrolyte composition (1) was obtained.

Example 2

Mix 1.4mole of aluminum chloride with 1.0mole of 1-ethyl-3-methylimidazolium chloride in the atmosphere. Since the sample has room temperature eutectic properties, it can be The solid phase is converted to a liquid phase. Next, 10% by weight of 1-ethyl-3-methylimidazolium triflate (1-ethyl-3-methylimidazolium triflate, [EMI ⁺ ][OTf ^- ]) was added (to the aluminum chloride and 1- The total weight of ethyl-3-methylimidazolium chloride is the basis). After continuously stirring for 12 hours, an electrolyte composition (2) was obtained.

Example 3

Mix 1.4mole of aluminum chloride with 1.0mole of 1-ethyl-3-methylimidazolium chloride in the atmosphere. Since the sample has room temperature eutectic properties, it can be The solid phase is converted to a liquid phase. Next, 1% by weight of 1-ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide, [EMI ⁺ ][TFSI ^- ]) (based on the total weight of the aluminum chloride and 1-ethyl-3-methylimidazolium chloride). After continuously stirring for 12 hours, an electrolyte composition (3) was obtained.

Example 4

Mix 1.4mole of aluminum chloride with 1.0mole of 1-ethyl-3-methylimidazolium chloride in the atmosphere. Since the sample has room temperature eutectic properties, it can be The solid phase is converted to a liquid phase. Next, 10% by weight of 1-ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide, [EMI ⁺ ][TFSI ^- ]) (based on the total weight of the aluminum chloride and 1-ethyl-3-methylimidazolium chloride). After continuously stirring for 12 hours, an electrolyte composition (4) was obtained.

Comparative example 1

1.4 moles of aluminum chloride was mixed with 1.0 mole of 1-ethyl-3-methylimidazolium chloride in the atmosphere without the addition of the additives described in the disclosure. After stirring for 12 hours, an electrolyte composition (5) was obtained.

Water and oxygen resistance test

The electrolyte compositions (1) to (5) were placed in a constant temperature and humidity chamber at a relative humidity of 60% and an ambient temperature of 25 ° C, respectively, and at the 5th, 10th, 20th, and 30th minutes, Karl Fisher (Karl) The water content of the electrolyte compositions (1) to (5) was measured by a moisture meter, and the results are shown in Table 1.

As can be seen from Table 1, the electrolyte composition (1) of the present disclosure is compared with the electrolyte composition (5) consisting solely of aluminum chloride and 1-ethyl-3-methylimidazolium chloride. To (4), it can be lowered by further adding 1-ethyl-3-methylimidazolium triflate or 1-ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide The hygroscopicity of the electrolyte composition is such that a decrease in water content can be observed. In addition, as can be seen from Table 1, the addition of 1-ethyl-3-methylimidazolium triflate or 1-ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide The amount added can improve the hygroscopicity of the electrolyte composition.

Metal ion battery

Comparative example 2

The electrolyte composition (5) prepared in Comparative Example 1 was placed in a constant temperature and humidity chamber having a relative humidity of 60% and an ambient temperature of 25 ° C, and allowed to stand for 30 minutes. Next, an aluminum foil (manufactured by Alfa Aesar) having a thickness of 0.025 mm was provided, which was cut to obtain an aluminum electrode. Next, a separator (glass filter paper (6 layers 1/2 inch), product number: Whatman 934-AH) and a graphite electrode (including an active material disposed on a current collecting substrate, wherein the set is provided) The electric substrate is made of carbon fiber paper and the active material is graphite, and is arranged in the order of the aluminum electrode, the separator, and the graphite electrode. Connect And encapsulating and injecting the electrolyte composition (5) with an aluminum plastic film to obtain a metal ion battery (1).

Next, the metal ion battery (1) was activated for 30 cycles using a MTI battery analyzer (BST8-WA, Richmond) with a current of 500 mAg ^-1 , and the output of the discharge capacity was stabilized, and then a current of 1000 mAg ^{-1 was} used for the charge and discharge test. Fig. 2 shows the relationship between the charge and discharge voltage of the metal ion battery (1) at 1000 mAg ^-1 and time (the first five charge and discharge cycles). It can be seen from Fig. 2 that the metal ion battery (1) is affected by water due to the large water content in the electrolyte composition (5), and it takes up to 45 minutes to charge to the target in the first charge and discharge cycle. The voltage is 2.45V. Fig. 3 shows the charge and discharge capacity retention rate of the metal ion battery (1) at 1000 mAg ^-1 . It can be seen from Fig. 3 that the metal ion battery (1) has poor charge and discharge performance and extremely low discharge specific capacity (< ¹ mAhg ^-1 ) due to the large water content in the electrolyte composition (5), and it is impossible to achieve the use of water removal. Battery performance of an electrolyte (electrolyte composition (5) having a water content of less than 300 ppm).

Example 5

The electrolyte composition (1) prepared in Example 1 was placed in a constant temperature and humidity chamber having a relative humidity of 60% and an ambient temperature of 25 ° C, and allowed to stand for 30 minutes. Next, an aluminum foil (manufactured by Alfa Aesar) having a thickness of 0.025 mm was provided, which was cut to obtain an aluminum electrode. Next, a separator (glass filter paper (6 layers 1/2 inch), product number: Whatman 934-AH) and a graphite electrode (including an active material disposed on a current collecting substrate, wherein the set is provided) The electric substrate is made of carbon fiber paper and the active material is graphite, and is arranged in the order of the aluminum electrode, the separator, and the graphite electrode. Next, it was packaged with an aluminum plastic film and injected into the electrolyte composition (1) to obtain a metal ion battery (2).

Next, the metal ion battery (2) was activated for 30 cycles using a MTI battery analyzer (BST8-WA, Richmond) with a current of 500 mAg ^-1 , and the output of the discharge capacity was stabilized, and then a current of 1000 mAg ^{-1 was} used for the charge and discharge test. Fig. 4 shows the relationship between the charge and discharge voltage of the metal ion battery (2) at 1000 mAg ^-1 and time (the first five charge and discharge cycles). As can be seen from Fig. 4, the metal ion battery (2) was charged to the target voltage of 2.45 V in 15 minutes during the first charge and discharge cycle, and the charging time was shortened by 30 minutes as compared with Comparative Example 1. Fig. 5 shows the charge and discharge capacity retention rate of the metal ion battery (2) at 1000 mAg ^-1 . It can be seen from Fig. 5 that 1% by weight of 1-ethyl-3-methylimidazolium triflate (1-ethyl-3-methylimidazolium triflate, [EMI ⁺ ] is added to the electrolyte composition (1). [OTf ^- ]), which reduces the hygroscopicity of the electrolyte composition (1), so that the metal ion battery (2) operates normally. As can be seen from Fig. 5, the metal ion battery (2) has a discharge specific capacity of about 83 mAhg ^-1 and a cycle life of more than 400 cycles.

Example 6

The electrolyte composition (2) prepared in Example 2 was placed in a constant temperature and humidity chamber having a relative humidity of 60% and an ambient temperature of 25 ° C, and allowed to stand for 30 minutes. Next, an aluminum foil (manufactured by Alfa Aesar) having a thickness of 0.025 mm was provided, which was cut to obtain an aluminum electrode. Next, a separator (glass filter paper (6 layers 1/2 inch), product number: Whatman 934-AH) and a graphite electrode (including an active material disposed on a current collecting substrate, wherein the set is provided) The electric substrate is made of carbon fiber paper and the active material is graphite, and is arranged in the order of the aluminum electrode, the separator, and the graphite electrode. Next, it was packaged with an aluminum plastic film and injected into the electrolyte composition (2) to obtain a metal ion battery (3).

Next, the metal ion battery (3) was activated for 30 cycles using a MTI battery analyzer (BST8-WA, Richmond) with a current of 500 mAg ^-1 , and the output of the discharge capacity was stabilized, and then a current of 1000 mAg ^{-1 was} used for the charge and discharge test. Fig. 6 shows the relationship between the charge and discharge voltage of the metal ion battery (3) at 1000 mAg ^-1 and time (the first five charge and discharge cycles). As can be seen from Fig. 6, the metal ion battery (3) is hardly affected by the water charging behavior during the first charge and discharge cycle. Fig. 7 shows the charge and discharge capacity retention rate of the metal ion battery (3) at 1000 mAg ^-1 . As can be seen from Fig. 7, the metal ion battery (3) has a discharge specific capacity of about 45 mAhg ^-1 and a cycle life of more than 6000 turns.

Example 7

The electrolyte composition (3) prepared in Example 3 was placed in a constant temperature and humidity chamber having a relative humidity of 60% and an ambient temperature of 25 ° C, and allowed to stand for 30 minutes. Next, an aluminum foil (manufactured by Alfa Aesar) having a thickness of 0.025 mm was provided, which was cut to obtain an aluminum electrode. Next, a separator (glass filter paper (6 layers 1/2 inch), product number: Whatman 934-AH) and a graphite electrode (including an active material disposed on a current collecting substrate, wherein the set is provided) The electric substrate is made of carbon fiber paper and the active material is graphite, and is arranged in the order of the aluminum electrode, the separator, and the graphite electrode. Next, it was packaged with an aluminum plastic film and injected into the electrolyte composition (3) to obtain a metal ion battery (4).

Next, the metal ion battery (4) was activated for 30 cycles with a current of 500 mAg ^-1 using an MTI battery analyzer (BST8-WA, Richmond), and the output of the discharge capacity was stabilized, and then a current of 1000 mAg ^{-1 was} used for charge and discharge test. Fig. 8 shows the relationship between the charge and discharge voltage of the metal ion battery (4) at 1000 mAg ^-1 and time (the first five charge and discharge cycles). As can be seen from Fig. 8, the metal ion battery (4) was charged to the target voltage of 2.45 V in 9 minutes during the first charge and discharge cycle, and the charging time was shortened by 36 minutes as compared with Comparative Example 1. Fig. 9 shows the charge and discharge capacity retention ratio of the metal ion battery (4) at 1000 mAg ^-1 . As can be seen from Fig. 9, the metal ion battery (4) has a discharge specific capacity of about 80 mAhg ^-1 and a cycle life of more than 60 cycles.

Example 8

The electrolyte composition (4) prepared in Example 4 was placed in a constant temperature and humidity chamber having a relative humidity of 60% and an ambient temperature of 25 ° C, and allowed to stand for 30 minutes. Next, an aluminum foil (manufactured by Alfa Aesar) having a thickness of 0.025 mm was provided, which was cut to obtain an aluminum electrode. Next, a separator (glass filter paper (6 layers 1/2 inch), product number: Whatman 934-AH) and a graphite electrode (including an active material disposed on a current collecting substrate, wherein the set is provided) The electric substrate is made of carbon fiber paper and the active material is graphite, and is arranged in the order of the aluminum electrode, the separator, and the graphite electrode. Next, it was packaged with an aluminum plastic film and injected into the electrolyte composition (4) to obtain a metal ion battery (5).

Next, the metal ion battery (5) was activated for 30 cycles with a current of 500 mAg ^-1 using an MTI battery analyzer (BST8-WA, Richmond), and the output of the discharge capacity was stabilized, and then a current of 1000 mAg ^{-1 was} used for charge and discharge test. Fig. 10 shows the relationship between the charge and discharge voltage of the metal ion battery (5) at 1000 mAg ^-1 and time (the first five charge and discharge cycles). It can be seen from Fig. 10 that the metal ion battery (5) can be charged to the target voltage of 2.45 V in 9 minutes during the first charge and discharge cycle. Fig. 11 shows the charge and discharge capacity retention rate of the metal ion battery (5) at 1000 mAg ^-1 . As can be seen from Fig. 11, the metal ion battery (5) has a discharge specific capacity of about 45 mAhg ^-1 and a cycle life of more than 2,500 cycles.

In summary, the electrolyte composition of the present invention, in addition to the metal chloride and the chlorine-containing ionic liquid, further comprises a specific amount of an additive, which can reduce the hygroscopicity of the electrolyte composition and increase the hydrolysis resistance of the electrolyte composition. Improve the resistance of metal ion batteries to environmental water oxygen, improve the stability of metal ion batteries and extend the cycle life of metal ion batteries.

Although the disclosure has been disclosed above in several embodiments, it is not In order to limit the disclosure, any person skilled in the art can make any changes and refinements without departing from the spirit and scope of the disclosure. Therefore, the scope of protection of the present disclosure is to be attached to the patent application scope. The definition is final.

Claims (14)

An electrolyte composition comprising: a metal chloride; a chlorine ion-containing liquid; and an additive, wherein the additive is a compound having the structure of the formula (I): [M] _i [(A(SO ₂ C _x F _2x+1 ) _y ) ^b- ] _j Formula (I) wherein M is an ammonium cation, azaannulenium cation, azathiazolium cation, benzimidazolium cation (benzimidazolium cation), benzofuranium cation, benzotriazolium cation, borolium cation, cholinium cation, porphyrin cation (cinnolinium cation), diazabicyclodecenium cation, diazabicyclononenium cation, diazabicyclo-undecenium cation , dithiazolium cation, furanium cation, guanidinium cation, imidazolium cation, carbazole Indazolium cation, indolinium cation, indolium cation, morpholinium cation, oxaborolium cation, oxyphosphorus An oxaphospholium cation, an oxazinium cation, an oxazolium cation, an iso-oxazolium cation, an oxathiazolium cation, Pentazolium cation, phospholinium cation, phosphonium cation, phthalazinium cation, piperazinium cation, piperidinium a piperidinium cation, a pyranium cation, a pyrazinium cation, a pyrazolium cation, a pyridazinium cation, a pyridinium cation, Pyrimidinium cation, pyrrolidinium cation, pyrrole cation (pyrrolium cation), quinazolinium cation, quinolinium cation, iso-quinolinium cation, quinoxalinium cation, selenazolium cation (selenozolium cation), sulfonium cation, tetrazolium cation, iso-thiadiazolium cation, thiazinium cation, thiazolium cation ), thiophenium cation, thiuronium cation, triazadecenium cation, triazinium cation, triazolium cation, different Iso-triazolium cation or uronium cation, wherein the valence of M is a; a is 1, 2, or 3; A is nitrogen, oxygen, hydrazine, or carbon; x is 1 , 2, 3, 4, 5, or 6; y is 1, 2, or 3; b is 1, 2, or 3; i is 1, 2, or 3; j is 1, 2, or 3; a/ b = j / i; and, when y based 2, or _{3, (SO 2 C x F 2x} + 1) group based phase Or different; the metal chloride is aluminum chloride, ferric chloride, zinc chloride, copper chloride, manganese chloride, chromium chloride, or a combination thereof; the chloride ion-containing liquid comprises ammonium chloride , azaannulenium chloride, azathiazolium chloride, benzimidazolium chloride, benzofuranium chloride, benzotriazole Benzyltriazolium chloride, borolium chloride, cholinium chloride, cinnolinium chloride, diazabicyclononene chloride (diazabicyclodecenium chloride), diazabicyclononenium chloride, diazabicyclo-undecenium chloride, dithiazolium chloride, furan Furanium chloride, guanidinium chloride, imidazolium chloride, indazolium chloride, indolinium chloride, hydrazine Indolium chloride, morpholinium chloride, oxaborolium chloride, oxaphospholium chloride, oxazinium chloride Oxazinium chloride, oxazolium chloride, iso-oxazolium chloride, oxathiazolium chloride, pentazolium chloride, phosphorus Phosphoium chloride, phosphonium chloride, phthalazinium chloride, piperazinium chloride, piperidinium chloride , pyranium chloride, pyrazinium chloride, pyrazolium chloride, pyridazinium chloride, pyridinium chloride, pyridinium chloride Pyrimidinium chloride, pyrrolidinium chloride, pyrrolium chloride, quinazolinium chloride, quinolinium chloride, Iso-quinolinium chloride, quinoxalinium chloride, selenozolium chloride, sulfonium chloride, tetrazolium chloride ), iso-thiadiazolium chloride, thiazinium chloride, thiazolium chloride, thiophenium chloride, thiourea chloride Thiuronium chloride), triazadecenium chloride, triazinium chloride, triazolium chloride, iso-triazolium chloride, Or a uronium chloride; the molar ratio of the metal chloride to the chloride ion-containing liquid is 1.1 to 2.05; and the content of the additive is 1 to 10% by weight, the metal chloride and the chlorine The total weight of the ionic liquid is the basis. The electrolyte composition according to claim 1, wherein the chlorine ion-containing liquid comprises methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride (1-ethyl-) 3-methylimidazolium chloride), 1-butyl-3-methylimidazolium chloride, cholinium chloride, or a combination thereof. The electrolyte composition according to claim 1, wherein the additive is 1-ethyl-3-methylimidazolium triflate (1-ethyl-3-methylimidazolium triflate, [EMI ⁺ ][OTf ^- ]) or 1-butyl-3-methylimidazolium triflate ([BMI ⁺ ][OTf ^- ]). The electrolyte composition according to claim 1, wherein the additive is 1-ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide (1-ethyl-3-methylimidazolium-bis (trifluoromethylsulfonyl)imide, [EMI ⁺ ][TFSI ^- ]) or 1-butyl-3-methylimidazolium-bis(trifluoromethylsulfonyl) Imide, [BMI ⁺ ][TFSI ^- ]). A metal ion battery comprising: a positive electrode; a separator; a negative electrode, wherein the negative electrode is separated from the positive electrode by a separator; and the electrolyte composition according to any one of claims 1 to 4, The positive electrode is between the negative electrode and the negative electrode. The metal ion battery of claim 5, wherein the positive electrode is composed of a collector layer and an active material. The metal ion battery according to claim 6, wherein the collector layer is a conductive carbon substrate. The metal ion battery according to claim 7, wherein the conductive carbon substrate is carbon cloth, carbon felt, or carbon paper. The metal ion battery according to claim 6, wherein the active material is a carbon material having a layered structure, a vanadium oxide, or a metal sulfide. The metal ion battery according to claim 9, wherein the carbon material having a layered structure is graphite, a carbon nanotube, graphene, or a combination thereof. The metal ion battery according to claim 10, wherein the graphite is natural graphite, artificial graphite, pyrolytic graphite, expanded graphite, flake graphite, expanded graphite, or a combination thereof. The metal ion battery of claim 5, wherein the negative electrode comprises a metal or an alloy thereof, a collector layer, or a combination thereof. A metal ion battery according to claim 12, wherein the gold The genus or its alloy contains copper, iron, aluminum, zinc, indium, nickel, tin, chromium, bismuth, titanium, manganese, or molybdenum. The metal ion battery according to claim 5, wherein the separator is glass fiber, polyethylene, PE, polypropylene, PP, non-woven fabric, wood fiber, polyether resin (Poly(ether) Sulfones, PES), ceramic fibers, or combinations of the foregoing.