TW201742296A - Metal-ion battery - Google Patents

Abstract

A metal-ion battery is provided. The metal-ion battery includes a positive electrode, a separator, a negative electrode, and an electrolyte. The positive electrode is separated from the negative electrode via the separator, and the electrolyte is disposed between the positive electrode and the negative electrode, wherein the electrolyte includes aluminum halide and an ionic liquid. In particular, the negative electrode is a metal or an alloy thereof, wherein the metal is Cu, Fe, Co, Zn, In, Ni, Sn, Cr, La, Y, Ti, Mn, or Mo.

Description

Metal ion battery

The present disclosure relates to an energy storage component, and more particularly to a metal ion battery.

Aluminum is abundant in the earth, and electronic devices using aluminum as a material have lower costs. In the application of energy storage components, aluminum and its compounds are not biotoxic in nature compared to metals such as lithium and cadmium. They are environmentally friendly energy storage materials and the number of electron transfer in aluminum during electrochemical charging and discharging can reach three. Provides high energy storage capacity. Furthermore, aluminum has a low flammability and electronic redox properties, which greatly enhances the safety of the use of aluminum ion batteries. However, the conventional metal ion battery using aluminum as a negative electrode faces problems such as damage of the negative electrode material, low battery discharge voltage, discharge voltage plateaus, and insufficient cycle life with rapid battery capacity reduction.

Therefore, the industry needs a new metal ion battery to solve the above problems.

In accordance with an embodiment of the present disclosure, the present disclosure provides an energy storage component, such as a metal ion battery. The metal ion battery comprises: a positive electrode; an isolating layer; a negative electrode, wherein the negative electrode is separated from the positive electrode by a separating layer, wherein the negative electrode is a negative electrode a metal or an alloy thereof, wherein the metal is copper, iron, zinc, cobalt, indium, nickel, tin, chromium, lanthanum, cerium, titanium, manganese, or molybdenum; and an electrolyte disposed between the positive electrode and the negative electrode Wherein the electrolyte comprises an aluminum halide and an ionic liquid.

10‧‧‧ positive

11‧‧‧ Collector layer

12‧‧‧negative

13‧‧‧Active materials

14‧‧‧Separator

20‧‧‧ Electrolytes

100‧‧‧metal ion battery

1 is a schematic view of a metal ion battery according to an embodiment of the present invention; and FIGS. 2-4 are diagrams showing voltage versus time during charging and discharging of the metal ion battery according to the embodiment of the present disclosure.

The metal ion battery of the present disclosure will be described in detail below. 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 be a limitation of the various embodiments and/or structures discussed. In the drawings, the shape, number, or thickness of the embodiments may be expanded and simplified or conveniently indicated. 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 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, wherein the negative electrode is a metal or an alloy thereof, wherein the metal is copper, iron, Zinc, cobalt, indium, Nickel, tin, chromium, ruthenium, osmium, titanium, manganese, or molybdenum; and an electrolyte disposed between the positive electrode and the negative electrode, wherein the electrolyte comprises an aluminum halide and an ionic liquid. According to an embodiment of the present disclosure, the metal of the negative electrode of the metal ion battery is not aluminum. According to an embodiment of the present disclosure, the metal and the halogen anion in the electrolyte may form a metal halide, and the halide of the metal is a Lewis acid. Therefore, when the metal ion battery is charged and discharged, the metal eluted from the negative electrode can react with the electrolyte to form a metal halide, and the aluminum halide in the electrolyte can also react with the ionic liquid to form a halogenated aluminate to make the electrolyte system. Maintain reversibility. Further, according to some embodiments of the present disclosure, the metal halide formed by reacting the metal eluted from the negative electrode with the electrolyte may have a smaller ion size than the halogenated aluminate, and thus may be more easily associated with the active material (for example: Graphite) intercalation reaction, or further assist in the intercalation reaction between the aluminum chloride acid and the active material to increase the total power generation of the metal ion battery and prolong the service life of the 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 an isolation layer 14 , wherein the isolation layer 14 can be disposed. Between the positive electrode 10 and the negative electrode 12, the negative electrode is separated from the positive electrode by the isolation layer 14 to avoid direct contact between the positive electrode 10 and the negative electrode 12. The metal ion battery 100 includes an electrolyte 20 disposed in the metal ion battery 100 and located between the positive electrode and the negative electrode such that the electrolyte 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 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 a metal such as aluminum, nickel or copper, and 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 comprises a layered active material or agglomerates of the layered active material. According to the disclosed embodiment, the active material 13 may be an intercalated carbon material, such as graphite (including natural graphite, artificial graphite, pyrolytic graphite, foamed graphite, flake graphite, or expanded graphite), graphene, nano carbon. Tube or a combination of the above materials. According to an embodiment of the present disclosure, the active material 13 may be a layered double hydroxide, a layered oxide, a layered chalcogenide or a combination of the above. The active material 13 can 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 isolation layer 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 M or an alloy containing metal M. Wherein, the metal halide (MX _y , X is a halogen, y may be an integer between 1 and 4) is a Lewis acid, so that the metal eluted from the negative electrode can react with the electrolyte 20 to form a metal halide. To maintain the ionic liquid system reversible. According to an embodiment of the present disclosure, the metal M may be copper, iron, zinc, cobalt, indium, nickel, tin, chromium, niobium, tantalum, titanium, manganese, or molybdenum. Further, when the negative electrode 12 is an alloy containing metal M, the metal M-containing alloy does not contain aluminum. In addition, the negative electrode 12 may further include a collector layer (not shown), and the first metal or the alloy containing the first metal is disposed on the collector layer. According to an embodiment of the present disclosure, the first metal or the alloy containing the first metal may be directly grown on the collector layer (ie, without any medium between them), or may be made of the metal by an adhesive. An alloy of metal is fixed on the collector layer. According to an embodiment of the present disclosure, the metal M may be a metal having a reduction potential lower than aluminum to improve the corrosion of the negative electrode of the metal ion battery.

According to an embodiment of the present disclosure, the electrolyte 20 comprises an ionic liquid and an aluminum halide. In an embodiment, the electrolyte further comprises a halide of the metal. The ionic liquid has a melting point of less than 100 ° C and may be room temperature ion liquid (RTIL). For example, the ionic liquid may comprise an alkylimidazolium salt, an alkylpyridinium salt, an alkylfluoropyrazolium salt, an alkyltriazolium salt. , aralkylammonium aluminates, alkylalkoxyammonium aluminates, aralkylphosphonium salts, aralkylsulfonium salts, alkylguanidinium salts ), and mixtures thereof. The ionic liquid and the metal halide have a molar ratio of at least or greater than about 1.1, or at least or greater than about 1.2, such as between 1.1 and 2.1, such as about 1.3, 1.5, 1.6, or 1.8. According to an embodiment of the present disclosure, when the aluminum halide is aluminum chloride (AlCl ₃ ), the ionic liquid may be, for example, 1-ethyl-3-methylimidazolium chloride, and aluminum chloride and 1-ethyl chloride. The molar ratio of -3-methylimidazolium is at least or greater than about 1.2, such as between 1.2 and 1.8. The ionic liquid electrolyte may be doped (or added with additives) to increase conductivity and reduce viscosity, or the ionic liquid electrolyte may be altered in other ways to obtain a composition that facilitates reversible electrodeposition of the metal.

According to an embodiment of the present disclosure, the ionic liquid may be a salt having a halide ion. After the metal ion battery is charged and discharged, the aluminum halide may form a halogenated aluminate with the ionic liquid, such as aluminum chloride (AlCl ₄ ^- ). Further, after the metal ion battery is charged and discharged, the metal of the negative electrode reacts with the electrolyte to form a halogenated metal acidate.

According to some embodiments of the present disclosure, the metal M may be Cu, Fe, Cr, Co, Mn, Zn, or Ni, and the aluminum halide may be aluminum chloride. In this way, when the metal ion battery is subjected to a charge and discharge reaction, the formed metal chloride metalate (MCl _(x+1) ^- , x may be an integer ranging from 1 to 4), for example, CuCl ₂ ^- , CuCl ₃ ^- , FeCl ₃ ^- , FeCl ₄ ^- , MnCl ₃ ^- , MnCl ₄ ^- , ZnCl ₃ ^- , NiCl ₃ ^- , CoCl ₃ ^- , CoCl ₄ ^- CrCl ₃ ^- , or CrCl ₄ ^- . Therefore, the metal chloride acid chloride can be more easily intercalated with an active material (for example, graphite), or further assist the intercalation reaction between the aluminum chloride acid and the active material, thereby increasing the total power generation of the metal ion battery and prolonging the metal ion battery. Service life.

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

Example 1:

A copper foil (manufactured by Alfa Aesar) having a thickness of 0.025 mm was provided and cut to obtain a copper electrode. Next, a separator film (glass filter paper (2 layers), product number: Whatman GFA) and a graphite electrode (including an active material disposed on a current collecting substrate, wherein the current collecting substrate is carbon fiber paper, The active material is expanded graphite (60.5 mg)). Next, it is arranged in the order of a copper electrode (as a negative electrode), a separator, and a graphite electrode (as a positive electrode), and is encapsulated and injected into an electrolyte (aluminum chloride (AlCl ₃ ) / 1-ethyl chloride) in an aluminum plastic film. 3-ethyl-3-methylimidazolium chloride ([EMIm]Cl), wherein the ratio of AlCl ₃ to [EMIm]Cl is about 1.4:1), a metal ion battery (1) is obtained.

Next, the battery performance of the aluminum ion battery (1) obtained in Example 1 was measured using a NEWARE battery analyzer (measurement conditions were: charging current 100 mA/g, cutoff voltage 2.45 V, discharge current 100 mA/g, cutoff voltage 1 V) It can be known that its maximum specific capacity is 95.8 mAh/g. Figure 1 is a graph showing the relationship between voltage and time during charging of a metal ion battery (2). As can be seen from Fig. 2, the metal ion battery (1) exhibits a charging voltage platform at 2.0V to 2.1V and 1.8V to 1.9V, respectively, in addition to a significant charging voltage platform at 2.3V to 2.45V. In addition, when the metal ion battery (1) is subjected to charge and discharge tests at a current of 500 mA/g, the specific capacity can also reach 87.43 mAh/g. Since copper is used as the negative electrode, chloride chloride (CuCl ₃ ^- ) and cuprous chloride (CuCl ₂ ^- ) having a small ion size can be formed during charge and discharge, so that the ratio of the metal ion battery (1) can be made. Capacity increase.

Example 2:

A nickel foil (Vess sold) having a thickness of 0.03 mm was provided, which was cut to obtain a nickel electrode. Next, a separator film (glass filter paper (2 layers), product number: Whatman GFA) and a graphite electrode (including an active material disposed on a current collecting substrate, wherein the current collecting substrate is carbon fiber paper, The active material is expanded graphite (72 mg)). Next, it is arranged in the order of a nickel electrode (as a negative electrode), a separator, and a graphite electrode (as a positive electrode), and is encapsulated and injected into an electrolyte (aluminum chloride (AlCl ₃ ) / 1-ethyl chloride) in an aluminum plastic film. 3-ethyl-3-methylimidazolium chloride ([EMIm]Cl), wherein the ratio of AlCl ₃ to [EMIm]Cl is about 1.4:1), a metal ion battery (2) is obtained.

Next, the battery performance of the aluminum ion battery (2) obtained in Example 2 was measured using a NEWARE battery analyzer (measurement conditions were: charging current 100 mA/g, cutoff voltage 2.45 V, discharge current 100 mA/g, cutoff voltage 1 V) It can be known that its maximum specific capacity is 88 mAh/g. Figure 3 is a graph showing the relationship between voltage and time during charging and discharging of a metal ion battery (2). As can be seen from Fig. 3, the metal ion battery (2) exhibits a charging voltage platform at 2.0V to 2.1V and 1.8V to 1.9V, respectively, in addition to a significant charging voltage platform at 2.3V to 2.45V, and in 2.3. V to 2.0V and 1.8V to 1.5V also exhibit multiple discharge voltage platforms, respectively.

After the metal ion battery (2) was subjected to a plurality of charge and discharge cycles, the nickel ion electrode (as a negative electrode) of the metal ion battery (2) was observed, and no perforation or breakage was observed. Therefore, the use of a nickel electrode as a negative electrode with an aluminum chloride/1-ethyl-3-methylimidazolium chloride electrolyte can provide a relatively good improvement in the corrosion of the negative electrode.

Example 3:

A stainless steel foil (manufactured and sold by Nippon Steel, numbered YUS190, containing iron and chromium) was cut and cut to obtain a stainless steel electrode. Next, a separator film (glass filter paper (2 layers), product number: Whatman GFA) and a graphite electrode (including an active material disposed on a current collecting substrate, wherein the current collecting substrate is carbon fiber paper, The active material is expanded graphite (45 mg)). Next, it is arranged in the order of a stainless steel electrode (as a negative electrode), a separator, and a graphite electrode (as a positive electrode), and is encapsulated and injected into an electrolyte (aluminum chloride (AlCl ₃ ) / 1-ethyl chloride) in an aluminum plastic film. 3-ethyl-3-methylimidazolium chloride ([EMIm]Cl), wherein the ratio of AlCl3 to [EMIm]Cl is about 1.4:1), a metal ion battery (3) is obtained.

Next, the battery performance of the aluminum ion battery (3) obtained in Example 3 was measured using a NEWARE battery analyzer (measurement conditions were: charging current 100 mA/g, cutoff voltage 2.45 V, discharge current 100 mA/g, cutoff voltage 1 V) It can be known that its maximum specific capacity can reach 95.8mAh/g. Fig. 4 is a graph showing voltage vs. time during charge and discharge (current of 100 mA/g) of the metal ion battery (3). As can be seen from Fig. 4, the metal ion battery (3) exhibits a charging voltage platform at 2.0V to 2.2V in addition to a significant charging voltage platform at 2.3V to 2.45V, and also appears at 2.3V to 1.5V, respectively. Multiple discharge voltage platforms. Since stainless steel is used as the negative electrode, chlorite chromite (CrCl ₃ ^- ) and ferrous chloride (FeCl ₃ ^- ) having a small ion size can be formed during charging and discharging, thereby making the metal ion battery (3) Specific capacity increase.

Comparative Example 1:

An aluminum foil having a thickness of 0.025 mm was provided and cut to obtain an aluminum electrode. Next, a separator film (glass filter paper (2 layers), product number: Whatman GFA) and a graphite electrode (including an active material disposed on a current collecting substrate, wherein the current collecting substrate is carbon fiber paper, The active material is expanded graphite (57 mg)). Next, it is arranged in the order of an aluminum electrode (as a negative electrode), a separator, and a graphite electrode (as a positive electrode), and is encapsulated and injected into an electrolyte (aluminum chloride (AlCl 3 ) / 1-ethyl chloride -) 3-ethyl-3-methylimidazolium chloride ([EMIm]Cl), wherein the ratio of AlCl ₃ to [EMIm]Cl is about 1.4:1), a metal ion battery (4) is obtained.

Next, the battery performance of the aluminum ion battery (4) obtained in Comparative Example 1 was measured using a NEWARE battery analyzer (measurement conditions were: charging current 100 mA/g, cutoff voltage 2.45 V, discharge current 100 mA/g, cutoff voltage 1.5 V) ), it can be known that its maximum specific capacity can reach 80.7mAh / g.

Compared with Comparative Example 1, the non-aluminum electrodes were used as negative in Examples 1 and 3. A very large metal ion battery, since the negative electrode can react with the electrolyte to form a metal chloride having a smaller ion size than the aluminum chloride after charging and discharging, so it is easier to intercalate with graphite or further assist the aluminum chloride Intercalation reaction with graphite to increase the specific capacity of the metal ion battery. In addition, in the metal ion battery using nickel as the negative electrode as described in Embodiment 2, since the nickel electrode still has no corrosion after charging and discharging, the total power generation of the metal ion battery can be increased and the service life of the metal ion battery can be prolonged.

The present disclosure has been disclosed in the above several embodiments, but it is not intended to limit the disclosure, and any one 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 this disclosure is subject to the definition of the scope of the patent application.

10‧‧‧ positive

11‧‧‧ Collector layer

12‧‧‧negative

13‧‧‧Active materials

14‧‧‧Separator

20‧‧‧ Electrolytes

100‧‧‧metal ion battery

Claims (17)

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, wherein the negative electrode is a metal or an alloy thereof, wherein the metal is copper, iron, zinc, cobalt And indium, nickel, tin, chromium, lanthanum, cerium, titanium, manganese, or molybdenum; and an electrolyte disposed between the positive electrode and the negative electrode, wherein the electrolyte comprises an aluminum halide and an ionic liquid. The metal ion battery according to claim 1, wherein the positive electrode is composed of a collector layer and an active material. The metal ion battery according to claim 2, wherein the collector layer is a conductive carbon substrate. The metal ion battery according to claim 3, wherein the conductive carbon substrate is carbon cloth, carbon felt, or carbon paper. The metal ion battery of claim 2, wherein the active material is a layered active material. The metal ion battery of claim 2, wherein the active material is graphite, carbon nanotubes, graphene, or a combination thereof. The metal ion battery according to claim 6, wherein the graphite is natural graphite, artificial graphite, pyrolytic graphite, expanded graphite, expanded graphite, or a combination thereof. The metal ion battery according to claim 1, wherein the metal ion battery The electrolyte further includes a halide of the metal. The metal ion battery of claim 8, wherein the halide of the metal is a metal chloride. The metal ion battery of claim 8, wherein the metal halide is a Lewis acid. The metal ion battery of claim 1, wherein the aluminum halide comprises aluminum fluoride, aluminum chloride, aluminum bromide or a combination thereof. The metal ion battery according to claim 1, wherein the ionic liquid comprises an alkylimidazolium salt, an alkylpyridinium salt, or an alkylfluoropyrazolium salt. , alkyltriazolium salt, aralkylammonium aluminates, alkylalkoxyammonium aluminates, aralkylphosphonium salts, aralkylsulfonium salts , an alkylguanidinium salt, or a combination thereof. The metal ion battery of claim 12, wherein the ionic liquid comprises 1-ethyl-3-methylimidazolium chloride. The metal ion battery according to claim 1, wherein after the metal ion battery is charged and discharged, the aluminum halide reacts with the ionic liquid to form a halogenated aluminate. The metal ion battery according to claim 14, wherein after the metal ion battery is charged and discharged, the metal of the negative electrode reacts with the electrolyte to form a halogenated metalate. The metal ion battery of claim 15, wherein the metal halide ion has an ion size smaller than an ion size of the haloaluminate. The metal ion battery of claim 16, wherein the halogenated aluminate is aluminosilicate.