The technical field relates to an electrode, to a method for fabricating the same, and to a metal ion battery employing the same.
Aluminum is the most abundant metal on earth, and electronic devices made of aluminum have the advantage of costing little. An aluminum-based redox couple, which involves three electron transfers during the electrochemical charge/discharge reactions, provides storage capacity that in comparison with that of a single-electron lithium-ion battery. Additionally, because of its lower reactivity and flammability, such an aluminum-ion battery might offer significant safety improvements.
Given the foregoing enhanced theoretical capacity of an aluminum-ion battery, aluminum-ion battery constructions are desirable in that they may feasibly and reliably provide enhanced battery performance, such as enhanced capacity and discharge voltage.
According to embodiments of the disclosure, the disclosure provides an electrode, such as an electrode of a metal-ion battery. The electrode includes a carbon substrate; a metal layer disposed on the carbon substrate; and a crystalline carbon material disposed between the carbon substrate and the metal layer. In particular, the crystalline carbon material is in direct contact with the carbon substrate or the metal layer.
According to other embodiments of the disclosure, the disclosure provides a method for fabricating the aforementioned electrode. The method includes providing a carbon substrate, wherein the carbon substrate has a first region and a second region; forming a metal layer on the first region, wherein the first region is disposed between the metal layer and the second region; and subjecting the carbon substrate and the metal layer to a thermal treatment, thereby converting the first region of the carbon substrate into a crystalline carbon material.
According to other embodiments of the disclosure, the disclosure provides a metal-ion battery. The metal-ion battery includes a first electrode, a first separator and a second electrode, wherein the second electrode is the aforementioned electrode, wherein the first separator is disposed between the first electrode and the second electrode.
A detailed description is given in the following embodiments with reference to the accompanying drawings.
In the following detailed description, for the purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the disclosed embodiments. It will be apparent, however, that one or more embodiments may be practiced without these specific details. In other instances, well-known structures and devices are shown schematically in order to simplify the drawing.
The disclosure provides an electrode (such as a positive electrode of metal-ion battery) and a metal-ion battery employing the same. The electrode includes a carbon substrate, a metal layer disposed on the carbon substrate and a crystalline carbon material disposed between the carbon substrate and the metal layer. The carbon material of the carbon substrate (such as non-crystalline carbon material) in contact with the metal surface is converted into a crystalline carbon material by subjecting a metal layer disposed on a carbon substrate to a thermal treatment to form an orderly layered carbon material (crystalline carbon material, such as graphite or graphene) via solid-phase precipitation at high temperature, thereby obtaining an electrode with improved electrical characteristics and high conductivity. As a result, the capacity of the metal-ion battery employing the electrode of the disclosure is increased. In addition, according to embodiments of the disclosure, an active material layer can be formed on the metal layer via vapor deposition to increase the capacity of the whole electrode. The crystalline carbon material of the electrode of the disclosure can be affixed to the carbon substrate the metal layer in the absence of an adhesive. Therefore, the performance of the electrode would not be deteriorated by the adhesive. Moreover, since the metal layer can be conformally formed on the surface of the carbon substrate, the obtained crystalline carbon material has the same specific surface area as that of the carbon substrate, when subjecting the carbon substrate and the metal layer to a thermal treatment to convert the carbon substrate (directly in contact with the metal layer) into the crystalline carbon material. Therefore, the obtained crystalline carbon material also has a high specific surface area, when the carbon substrate having a high specific surface area (such as carbon cloth or carbon fiber) is employed in fabricating the electrode.
According to embodiments of the disclosure, suitable materials for the metal layer may include catalytic metal. When subjecting the catalytic metal to a thermal treatment, the carbon substrate (such as non-crystalline carbon material) contacting catalytic metal can be converted into an orderly layered carbon material (crystalline carbon material, such as graphite or graphene) via solid-phase precipitation. For example, suitable materials for the metal layer include Fe, Co, Ni, Cu, a combination thereof or an alloy thereof. According to other embodiments of the disclosure, the metal layer can consist of a plurality of metal particles. Suitable materials for the aforementioned metal particles include Fe, Co, Ni, Cu, a combination thereof or an alloy thereof. In addition, According to other embodiments of the disclosure, at least some of the metal particles can be covered by the crystalline carbon material.
According to embodiments of the disclosure, the disclosure also provides a method for fabricating the aforementioned electrode.
The initial step 61 of the method for fabricating the electrode of the disclosure provides a carbon substrate 10, wherein the carbon substrate 10 has a first region 11 and a second region 13, as shown in
According to embodiments of the disclosure, the disclosure also provides a metal-ion battery. As shown in
According to embodiments of the disclosure, the metal-ion battery 200 can be an aluminum-ion battery, although other types of metal ion batteries are encompassed by the disclosure. The first metal electrode 101 and the third electrode 107 can include aluminum, such as a non-alloyed form of aluminum or an aluminum alloy. More generally, suitable materials for the first metal electrode 101 and the third electrode 107 may include one or more of an alkali metal (e.g., lithium, potassium, sodium, and so forth), an alkaline earth metal (e.g., magnesium, calcium, and so forth), a transition metal (e.g., zinc, iron, nickel, cobalt, and so forth), a main group metal or metalloid (e.g., aluminum, silicon, tin, and so forth), and a metal alloy of two or more of the foregoing elements (e.g., an aluminum alloy). The first separator 102 and the second separator 109 can mitigate against electrical shorting of the first electrode 101 and the second electrode 103, and the electrolyte 105 can support reversible deposition and dissolution (or stripping) of the second electrode 103, and reversible intercalation and de-intercalation of anions at the electrode 100. The electrolyte 105 can include an ionic liquid, which can support reversible redox reaction of a metal or a metal alloy included in the first electrode 101. For example, the electrolyte 105 can correspond to, or can include, a mixture of a metal halide (which is not an alkali halide) (such as aluminum halide) and an ionic liquid, a molar ratio of the metal halide and the ionic liquid is at least or greater than about 1.1 or at least or greater than about 1.2, and is up to about 1.5, up to about 1.8, or more, such as where the aluminum halide is A1C13, the ionic liquid is 1-ethyl-3-methylimidazolium chloride, and the molar ratio of the aluminum chloride to 1-ethyl-3-methylimidazolium chloride is at least or greater than about 1.2, such as between 1.2 and 1.8. Examples of ionic liquids include choline chloride, alkali halide, alkylimidazolium salt, alkylpyridinium salt, alkylfluoropyrazolium salt, alkyltriazolium salt, aralkylammonium salt, alkylalkoxyammonium salt, aralkylphosphonium salt, aralkylsulfonium salt, or a combination thereof. According to embodiments of the disclosure, the electrolyte 105 can be a mixture of a metal halide (such as aluminum halide) and a solvent, wherein the solvent is urea, N-methylurea, dimethyl sulfoxide, methylsulfonylmethane, or a mixture thereof. The molar ratio of the aluminum chloride to the solvent is greater than or equal to about 1.2, such as between 1.2 and 1.8. An ionic liquid electrolyte can be doped (or have additives added) to increase electrical conductivity and lower the viscosity, or can be otherwise altered to yield compositions that favor the reversible electrodeposition of metals.
Below, exemplary embodiments will be described in detail with reference to the accompanying drawings so as to be easily realized by a person having ordinary knowledge in the art. The inventive concept may be embodied in various forms without being limited to the exemplary embodiments set forth herein. Descriptions of well-known parts are omitted for clarity, and like reference numerals refer to like elements throughout.
First, a carbon cloth (having a size of 70 mm×70 mm and a thickness of 0.4 mm ) was provided. Next, a nickel layer (having a thickness of 1.5 μm) was formed on the carbon cloth by an electroplating process, wherein the weight ratio between the nickel layer and the carbon cloth was 1:1. The electroplating process included the following steps. The carbon cloth (serving as an anode) was immersed in a nickel-metal-ion-containing electrolyte solution, wherein the nickel-metal-ion-containing electrolyte solution included nickel sulfate, nickel chloride, and boron acid. The electrolyte solution had a pH value of 4.6. Nickel served as a cathode. When the direct-current input voltage was applied, nickel metal was precipitated from the carbon cloth surface. The amount of nickel was directly proportional to the duration of the electroplating process. Finally, the obtained carbon cloth (having the nickel layer) was washed with hot water to remove the remaining electrolyte, and then was baked in an oven at 80° C. After, the carbon cloth having the nickel layer was subjected to a thermal treatment via a high-temperature vacuum furnace under an argon gas or hydrogen atmosphere. The temperature of the thermal treatment temperature was about 1000° C. and the duration of the thermal treatment was 30 minutes. After cooling, a graphite electrode was obtained.
Next, an aluminum foil (with a thickness of 0.025 mm, manufactured by Alfa Aesar) was cut to obtain the aluminum electrode (having a size of 70 mm×70 mm). Next, separators (of glass filter paper (two layers), with trade No. Whatman) were provided. Next, the aluminum electrode, the separator, the graphite electrode, the separator, and the aluminum electrode were placed in sequence and sealed within an aluminum plastic pouch. Next, an electrolyte (including aluminum chloride (AlCl3) and 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl, wherein the molar ratio between AlCl3 and [EMIm]Cl was about 1.3) was injected into the aluminum plastic pouch, obtaining the metal-ion battery (1).
Next, the aluminum-ion battery (1) was then charged (to about 2.4 V) and discharged (to about 1.1 V) at a current density of about 200 mA/g by a battery analyzer to analyze the performance of the aluminum-ion battery.
First, a carbon cloth (having a size of 70 mm×70 mm and a thickness of 0.4 mm) was provided. Next, a nickel layer (having a thickness of 1.5 μm) was formed on the carbon cloth by the process described in Example 1, wherein the weight ratio between the nickel layer and the carbon cloth was 1:1. Next, the carbon cloth having the nickel layer was subjected to a thermal treatment via a high-temperature vacuum furnace under an argon gas or hydrogen atmosphere. The temperature of the thermal treatment temperature was about 1000° C. and the time of the thermal treatment was 30 minutes. Next, the carbon cloth was disposed in the high-temperature vacuum furnace and then methane gas was introduced into the high-temperature vacuum furnace. Thus, a graphite layer was formed on the nickel layer by chemical vapor deposition (CVD) (with a process temperature of about 1000° C). After performing the chemical vapor deposition for 30 minutes, a graphite electrode was obtained.
Next, an aluminum foil (with a thickness of 0.025 mm, manufactured by Alfa Aesar) was cut to obtain the aluminum electrode (having a size of 70 mm×70 mm). Next, separators (of glass filter paper (two layers), with trade No. Whatman) were provided. Next, the aluminum electrode, the separator, the graphite electrode, the separator, and the aluminum electrode were placed in sequence and sealed within an aluminum plastic pouch. Next, an electrolyte (including aluminum chloride (AlCl3) and 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl, wherein the molar ratio between AlCl3 and [EMIm]Cl was about 1.3) was injected into the aluminum plastic pouch, obtaining the metal-ion battery (2).
Next, the aluminum-ion battery (2) was then charged (to about 2.4 V) and discharged (to about 1.1 V) at a current density of about 200 mA/g by a battery analyzer to analyze the performance of the aluminum-ion battery.
First, a carbon cloth (having a size of 70 mm×70 mm and a thickness of 0.4 mm) was provided. Next, a nickel layer (having a thickness of 1.5 μm) was formed on the carbon cloth by the process described in Example 1, wherein the weight ratio between the nickel layer and the carbon cloth was 1:1. Next, the carbon cloth having the nickel layer was heated at 1000° C. Next, a graphite layer was formed on the nickel layer by chemical vapor deposition (CVD) as described in Example 2. After performing the chemical vapor deposition for 60 minutes, a graphite electrode was obtained.
Next, an aluminum foil (with a thickness of 0.025 mm, manufactured by Alfa Aesar) was cut to obtain the aluminum electrode (having a size of 70 mm×70 mm). Next, separators (of glass filter paper (two layers), with trade No. Whatman) were provided. Next, the aluminum electrode, the separator, the graphite electrode, the separator, and the aluminum electrode were placed in sequence and sealed within an aluminum plastic pouch. Next, an electrolyte (including aluminum chloride (AlCl3) and 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl, wherein the molar ratio between AlCl3 and [EMIm]Cl was about 1.3) was injected into the aluminum plastic pouch, obtaining the metal-ion battery (3).
Next, the aluminum-ion battery (3) was then charged (to about 2.4 V) and discharged (to about 1.1 V) at a current density of about 200 mA/g by a battery analyzer to analyze the performance of the aluminum-ion battery.
First, a carbon cloth (having a size of 70 mm×70 mm and a thickness of 0.4 mm) was provided. Next, a nickel layer (having a thickness of 1.5 μm) was formed on the carbon cloth by the process described in Example 1, obtaining a carbon electrode.
Next, an aluminum foil (with a thickness of 0.025 mm, manufactured by Alfa Aesar) was cut to obtain the aluminum electrode (having a size of 70 mm×70 mm). Next, separators (of glass filter paper (two layers), with trade No. Whatman) were provided. Next, the aluminum electrode, the separator, the carbon electrode, the separator, and the aluminum electrode were placed in sequence and sealed within an aluminum plastic pouch. Next, an electrolyte (including aluminum chloride (AlCl3) and 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl, wherein the molar ratio between AlCl3 and [EMIm]Cl was about 1.3) was injected into the aluminum plastic pouch, obtaining the metal-ion battery (4).
Next, the aluminum-ion battery (4) was then charged (to about 2.7 V) and discharged (to about 0.4 V) at a current density of about 200 mA/g by a battery analyzer to analyze the performance of the aluminum-ion battery. The result showed that the metal-ion battery (4) of Comparative Example 1 had no capacity.
First, a carbon cloth (having a size of 70 mm×70 mm and a thickness of 0.4 mm) was provided. Next, a graphite layer was formed on the carbon cloth by chemical vapor deposition (CVD) as described in Example 2, obtaining a carbon electrode.
Next, an aluminum foil (with a thickness of 0.025 mm, manufactured by Alfa Aesar) was cut to obtain the aluminum electrode (having a size of 70 mm×70 mm). Next, separators (of glass filter paper (two layers), with trade No. Whatman) were provided. Next, the aluminum electrode, the separator, the carbon electrode, the separator, and the aluminum electrode were placed in sequence and sealed within an aluminum plastic pouch. Next, an electrolyte (including aluminum chloride (AlCl3) and 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl, wherein the molar ratio between AlCl3 and [EMIm]Cl was about 1.3) was injected into the aluminum plastic pouch, obtaining the metal-ion battery (5).
Next, the aluminum-ion battery (5) was then charged (to about 2.37 V) and discharged (to about 1.1 V) at a current density of about 50 mA/g by a battery analyzer to analyze the performance of the aluminum-ion battery. The result showed that the metal-ion battery (5) of Comparative Example 2 had no capacity.
Accordingly, due to the improved electrical characteristics and high conductivity of the electrode of the disclosure, the capacity of the metal-ion battery employing the electrode can be increased. In addition, in the electrode of the disclosure, a crystalline carbon material can be affixed to the carbon substrate and the metal layer in the absence of an adhesive. Therefore, the performance of the electrode would not be deteriorated by the adhesive.
It will be clear that various modifications and variations can be made to the disclosed methods and materials. It is intended that the specification and examples be considered as exemplary only, with the true scope of the disclosure being indicated by the following claims and their equivalents.
Number | Date | Country | Kind |
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105141734 | Dec 2016 | TW | national |
This application claims the benefit of U.S. Provisional Application No. 62/383,883, filed on Sep. 6, 2016, which is hereby incorporated herein by reference. The application is based on, and claims priority from, Taiwan Application Serial Number 105141734, filed on Dec. 16, 2016, the disclosure of which is hereby incorporated by reference herein in its entirety.
Number | Date | Country | |
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62383883 | Sep 2016 | US |