TW201813164A - Electrode, method for fabricating the same, and metal ion battery employing the same - Google Patents

Abstract

An electrode, a method for fabricating the same, and a metal ion battery employing the same are provided. 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 directly contacts the carbon substrate or the metal layer.

Description

 Electrode, method of manufacturing the same, and metal ion battery including the same  

The present disclosure relates to an electrode, a method of manufacturing the same, and a metal ion battery including the same.

Aluminum is abundant in the earth, and electronic devices using aluminum as a material have lower costs. In addition, compared with single-electron transfer lithium-ion batteries, aluminum can achieve three electron transfer numbers during electrochemical charge and discharge, thus providing higher 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.

Despite these theoretical advantages, in order to meet the needs of practical commercial applications, the performance of aluminum-ion batteries (such as low discharge voltage, and capacitance) still needs to be further improved.

In accordance with an embodiment of the present disclosure, the present disclosure provides an electrode, such as an electrode of a metal ion battery. The electrode comprises 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 and the carbon substrate or the metal layer direct contact.

According to other embodiments of the present disclosure, the present disclosure provides a method of fabricating the above electrode. The method includes providing a carbon substrate, wherein the carbon substrate has a first region and a second region; forming a metal layer over the first region, wherein the first region is located in the metal layer and the second region And heat-treating the carbon substrate and the metal layer to convert the first region of the carbon substrate into a crystalline carbon material.

According to other embodiments of the present disclosure, the present disclosure provides a metal ion battery. The metal ion battery includes: a first electrode; a first isolation film; and a second electrode, wherein the first isolation film is disposed between the first electrode and the second electrode, and the second electrode system The above electrodes are disclosed.

2‧‧‧ Area

10‧‧‧carbon substrate

11‧‧‧First area

12‧‧‧metal layer

13‧‧‧Second area

14‧‧‧Crystalline carbon

16‧‧‧Active materials

20‧‧‧ pores

51‧‧‧ Nickel layer 51

52‧‧‧ carbon cloth

53‧‧‧ graphite layer

60‧‧‧ method

61, 62, 63, 64 ‧ ‧ steps

100‧‧‧electrode

101‧‧‧First electrode

102‧‧‧First barrier film

103‧‧‧second electrode

105‧‧‧ Electrolytes

107‧‧‧ third electrode

109‧‧‧Second isolation film

200‧‧‧metal ion battery

1 is a schematic view of an electrode according to an embodiment of the present disclosure; FIG. 2 is an enlarged schematic view of a region 2 of the electrode shown in FIG. 1; FIG. 3 is an enlarged schematic view of a region 2 according to another embodiment of the present disclosure. 4-6 is a schematic view of an electrode according to another embodiment of the present disclosure; FIG. 7 is a flow chart of a method for manufacturing an electrode according to an embodiment of the present disclosure; and FIGS. 8A to 8C are a series of cross-sectional structural views. FIG. 9 is a schematic view showing a metal ion battery according to an embodiment of the present disclosure; FIG. 10 is a schematic view showing a metal ion battery according to another embodiment of the present disclosure; 11 is a transmission electron microscope (TEM) spectrum of the graphite electrode of the first embodiment; and FIG. 12 is a diagram showing the voltage of the metal ion battery (1) of the embodiment 1 during charge and discharge. Fig. 13 is a graph showing the results of the cycle stability test of the metal ion battery (1) described in Example 1 during charge and discharge. Figure 14 is a graph showing the relationship between voltage and time during charging and discharging of the metal ion battery (1) of the second embodiment; and Fig. 15 is a diagram showing charging and discharging of the metal ion battery (1) of the second embodiment. The cycle stability test results in the process. Figure 16 is a graph showing the relationship between voltage and time during charging and discharging of the metal ion battery (1) of the third embodiment; and Fig. 17 is a diagram showing charging and discharging of the metal ion battery (1) of the third embodiment. The cycle stability test results in the process; the 18th is a transmission electron microscope (TEM) spectrum of the carbon electrode described in Comparative Example 1; and the 19th is the graphite electrode described in Embodiments 1 and 3, and The X-ray Diffractometer (XRD) pattern of the carbon electrode described in Comparative Examples 1 and 2.

The electrode of the present invention and a metal ion battery including the same will be described in detail below. It will be appreciated that the following description provides many different embodiments or examples for implementing the invention. The specific elements and arrangements described below are merely illustrative of the invention. Of course, these are by way of example only and not as a limitation of the invention. Moreover, repeated numbers or labels may be used in different embodiments. These repetitions are merely for the purpose of simplicity and clarity of the invention and are not to be construed as 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 examples are merely illustrative of specific ways of using the invention and are not intended to limit the invention.

The present disclosure provides an electrode (for example, a positive electrode of a metal ion battery) and a metal ion battery including the same. By forming a metal layer on the carbon substrate and performing heat treatment, the ordered surface layer carbon material (crystalline carbon material, such as graphite) is solid-dissolved on the carbon substrate (for example, amorphous carbon material) by using the metal surface at a high temperature to make the original A carbon material, such as a non-crystalline carbon material, is converted into a crystalline carbon material to form a high-power and high-conductivity electrode, and further increases the capacitance of the metal ion battery including the electrode. In addition, the present disclosure may further utilize vapor deposition to form an active material layer over the metal layer, increasing the capacitance of the overall electrode. According to the disclosed electrode, the crystalline carbon material can be formed on the carbon substrate and the metal layer without using an adhesive, so that the use of the adhesive can be avoided to affect the electrode performance. Furthermore, since the metal layer is conformable on the surface of the carbon substrate, when the heat treatment is performed to convert the carbon substrate in contact with the metal layer into a crystalline carbon material, the formed crystalline carbon material has the carbon substrate Corresponding specific surface area. Therefore, if the carbon substrate used is a carbon material having a high specific surface area (for example, carbon cloth or carbon fiber), the formed crystalline carbon material also has a high specific surface area.

Please refer to FIG. 1 , which is a schematic cross-sectional view of an electrode 100 according to an embodiment of the present disclosure. The electrode 100 may have a carbon substrate 10 and a metal layer 12, wherein the metal layer 12 is disposed on the carbon substrate; and a crystalline carbon material 14, as shown in FIG. 1, the metal layer 12 is A continuous film layer. Fig. 2 is an enlarged schematic view showing a region 2 of the electrode 100 shown in Fig. 1. As can be seen from Fig. 2, the crystalline carbon material 14 is disposed between the carbon substrate 10 and the metal layer 12. According to an embodiment of the present disclosure, the crystalline carbon material 14 is in direct contact with the carbon substrate 10 or/and the metal layer 12. According to an embodiment of the present disclosure, the carbon substrate may be a non-crystalline carbon (ie, disordered carbon) substrate. For example, the carbon substrate can be carbon cloth, carbon paper, or carbon fiber. FIG. 3 is an enlarged schematic view showing a partial region of the electrode 100 according to another embodiment of the present disclosure. The carbon substrate of the present disclosure may also have a plurality of pores 20, and the metal layer 12 may be further filled into the pores 20, and the crystalline carbon material 14 is also filled in the pores 20 and located on the carbon substrate 10 and the Between the metal layers 12, as shown in Fig. 3. As a result, the formed crystalline carbon material 14 can have a high specific surface area. According to an embodiment of the present disclosure, the crystalline carbon material may be layered graphite, and may have a thickness of between about 1 nm and 50 μm, such as between about 10 nm and 50 μm, or between 1 nm and 5 μm.

According to an embodiment of the disclosure, the material of the metal layer may be a catalytic metal. The catalytic metal can solidify and deposit an ordered layered carbon material (crystalline carbon material such as graphite) by heat treatment of a carbon material (for example, a non-crystalline carbon material). For example, the material of the metal layer may be Fe, Co, Ni, Cu, or a combination or alloy thereof. According to other embodiments of the present disclosure, the metal layer may also be composed of a plurality of metal particles, and the material of the metal particles may be Fe, Co, Ni, Cu, or a combination or alloy thereof. Moreover, according to other embodiments of the present disclosure, at least a portion of the metal particles may be coated with the crystalline carbon material.

Please refer to FIG. 4 , which is a schematic cross-sectional view of the electrode 100 according to another embodiment of the present disclosure. As can be seen from FIG. 4, the metal layer 12 of the present disclosure may also be a discontinuous film layer, and the crystalline carbon material 14 is still disposed between the carbon substrate 10 and the metal layer 12, and the crystalline carbon The material 14 is in direct contact with the carbon substrate 10 or/and the metal layer 12. As a result, the formed crystalline carbon material 14 can also be a discontinuous film layer. According to other embodiments of the present disclosure, the electrode of the present disclosure can further infiltrate at least a portion of the discontinuous metal layer 12 via solid carburization by controlling the thickness of the metal layer, the temperature of the heat treatment, and/or the heat treatment time. The formed crystalline carbon material 14 is completely covered, please refer to Fig. 5.

Please refer to FIG. 6 , which is a schematic cross-sectional view of the electrode 100 according to another embodiment of the present disclosure. It can be seen from FIG. 6 that the electrode 100 of the present disclosure may further comprise an active material 16 formed on the metal layer 12, wherein the active material 16 is processed by a deposition process (for example, chemical vapor deposition) The deposition)) is formed on the metal layer 12. The active material 16 comprises a layered active material or agglomerates of the layered active material. According to an embodiment of the invention, the active material 16 may be an intercalated carbon material such as graphite, graphene, carbon nanotubes or a combination of the above.

According to an embodiment of the present disclosure, the present disclosure also provides a method of manufacturing the above electrode. Figure 7 is a manufacturing flow diagram for explaining a method 60 for fabricating an electrode according to an embodiment of the present disclosure. It will be appreciated that in addition to the steps described in the fabrication flow diagrams, other additional steps may be implemented before, after, or interspersed with the method 60.

In the initial step 61 of the method for manufacturing the electrode, a carbon substrate 10 having a first region 11 and a second region 13 is provided. Please refer to FIG. 8A. Next, a metal layer 12 is formed over the first region 11 (step 62). Referring to FIG. 8B , the first region 11 is located between the metal layer 12 and the second region 13 . The metal layer 12 can be formed, for example, by sputtering, electron beam evaporation, thermal evaporation, electroplating, or electroless plating. The metal layer 12 formed may completely or partially cover the carbon substrate 10. In other words, the metal layer 12 can be a continuous or discontinuous film layer. According to an embodiment of the present disclosure, the weight ratio of the formed metal layer 12 to the carbon substrate 10 may be between about 0.01 and 10, for example between about 0.04 and 10, or may be between about 0.01 and 5. between. Next, the metal layer 12 is heat-treated on the carbon substrate 10 (step 63), and the first region 11 in which the carbon substrate 10 is in contact with the metal layer 12 is converted into a crystalline carbon material 14, please refer to FIG. 8C. The heat treatment may be carried out in a high temperature furnace tube under an inert gas (for example, argon, nitrogen, etc.) or a hydrogen atmosphere, wherein the heat treatment temperature may be between about 800 ° C and 1150 ° C, and the heat treatment time may be from several minutes to several Hours (for example, about 30 minutes to 2 hours). It is worth noting that the weight of the formed crystalline carbon material 14 is proportional to the heat treatment time. Further, the weight of the formed crystalline carbon material 14 is also proportional to the contact area of the carbon substrate 10 and the metal layer 12. According to some embodiments of the present disclosure, the method for fabricating the electrode of the present disclosure may further include forming an active material layer 16 over the metal layer 12 by chemical vapor deposition (step 64). The electrode shown in Figure 6. It is to be noted that the substrate heating step may be substituted for the above heat treatment step in the chemical vapor deposition method, but the temperature of the heating step is required to be between about 900 ° C and 1150 ° C.

According to an embodiment of the present disclosure, the present disclosure also provides a metal ion battery. Referring to FIG. 9, the metal ion battery 200 includes a first electrode 101, a first isolation film 102, and a second electrode 103. The second electrode 103 is the exposed electrode, and the first The isolation film 102 is disposed between the first electrode 101 and the second electrode 103. The metal ion battery 200 also includes an electrolyte 105 disposed between the first electrode 101 and the second electrode 103. The metal ion battery 200 may be a rechargeable metal ion secondary battery, but the present disclosure also covers a primary battery.

According to another embodiment of the present invention, reference is made to FIG. 10, which is a schematic diagram of a battery according to an embodiment of the present invention. The metal ion battery 200 may further include a third electrode 107 and a second isolation film 109, wherein the first electrode is The first isolation film 102, the second electrode 103, and the second isolation film 109 are sequentially disposed between the 101 and the third electrode 107.

According to embodiments of the present disclosure, the metal ion battery 200 can be an aluminum ion battery, but other embodiments of the present disclosure also encompass other types of metal ion batteries. The first electrode 101 and the third electrode 107 comprise aluminum, such as aluminum or an aluminum alloy in an unalloyed form. Further, materials suitable as the first electrode 101 and the third electrode 107 may include one or more of the following: an alkali metal (for example, lithium, potassium, sodium, etc.), an alkaline earth metal (for example, magnesium, calcium, etc.), Transition metal (eg, zinc, iron, nickel, cobalt, etc.), main group metal or metalloid (eg, aluminum, antimony, tin, etc.) and two or more of the foregoing elements Metal alloy (for example, aluminum alloy). The first isolation film 102 and the second isolation film 109 can prevent the first electrode 101 from directly contacting the second electrode 103 to cause a short circuit, and the electrolyte 105 supports the reversible relocation and migration of the anion at the second electrode 103, and supports the aluminum. Reversible deposition and stripping at the first electrode 101. Examples of ionic liquids include urea (urea), choline chloride, ethylchlorine chloride, alkali halide, dimethyl sulfoxide, alkyl imidazolium Salt (alkylimidazolium salt), alkylpyridinium salt, alkylfluoropyrazolium salt, alkyltriazolium salt, aralkylammonium salt, alkyl An alkylalkoxyammonium salt, an aralkylphosphonium salt, an aralkylsulfonium salt, an alkylguanidinium salt, and mixtures thereof. For example, the electrolyte 105 can correspond to or can comprise a mixture of an aluminum halide and an ionic liquid, and the molar ratio of the aluminum halide to the ionic liquid is at least or greater than about 1.1, or at least or greater than about 1.2, and Up to about 1.5, up to about 1.8 or more, such as in the case where the aluminum halide is AlCl ₃ , the ionic liquid is 1-ethyl-3-methylimidazolium chloride, and aluminum chloride and chloride 1- The molar ratio of ethyl-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 an additive) to increase conductivity and reduce viscosity, or the ionic liquid electrolyte may be otherwise altered to provide a composition that facilitates reversible electrodeposition of the metal.

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

Example 1:

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 (thickness: 1.5 μm) is formed on the carbon cloth by electroplating, wherein the weight ratio of the nickel layer to the carbon cloth is 1:1, and the nickel plating method is to use the carbon cloth as a cathode and immerse in the In the electrolyte of nickel metal ions, the electrolyte composition is nickel sulfate, nickel chloride, boric acid, and the pH is 4.6. Nickel plate is used as the anode. When DC power is applied, nickel metal is deposited on the surface of the carbon cloth. The amount of nickel is matched with the plating time, and the longer the plating time, the greater the nickel weight. Finally, the electrolyte was removed by hot water and placed in an oven at 80 ° C for drying. After completion, the vacuum high temperature furnace tube is placed with a nickel-plated carbon cloth material, and heat treatment is performed under an argon or hydrogen atmosphere. The heat treatment temperature is between 1000 ° C and the heat treatment time is 30 minutes. After cooling, it is taken out to obtain a graphite electrode. Figure 11 is a transmission electron microscope (TEM) image of the above graphite electrode. As can be seen from Fig. 11, in the graphite electrode, a graphite layer 53 (crystalline carbon material) is surely formed between the nickel layer 51 and the carbon cloth 52 (non-crystalline carbon material).

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 (having a size of 70 mm × 70 mm). Next, a separator (glass filter paper (2 layers), product number: Whatman 934-AH) is provided, which is sequentially arranged in accordance with an aluminum electrode, a separator, a graphite electrode, a separator, and an aluminum electrode, and is formed of an aluminum film. It is encapsulated and injected into an electrolyte (aluminum chloride (AlCl ₃ ) / 1-ethyl-3-methylimidazolium chloride, [EMIm]Cl), among which AlCl ₃ and [ The EMIm]Cl ratio is about 1.3), and a metal ion battery (1) is obtained.

Next, the battery performance of the metal ion battery (1) obtained in Example 1 was measured using a battery analyzer (measurement conditions were: charge and discharge test in a constant current mode (200 mA, charge cutoff voltage was 2.4 V, discharge cutoff voltage was 1.1V). Fig. 12 is a diagram showing the relationship between voltage and time during charge and discharge of a metal ion battery (1), and Fig. 13 is a diagram showing the stability of a metal ion battery (1) during charge and discharge. The result of the test results. It can be seen from Fig. 13 that the metal ion battery (1) described in Example 1 has a capacitance of up to 28.5 mAh.

Example 2:

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 (thickness: 1.5 μm) was formed on the carbon cloth by the same electroplating nickel method as in Example 1, wherein the weight ratio of the nickel layer to the carbon cloth was 1:1. Next, a heat treatment was performed on the carbon cloth having a nickel layer in which the temperature of the heat treatment was 1000 ° C and the heat treatment time was 30 minutes. Next, methane was introduced by chemical vapor deposition (CVD) to form a graphite layer (a vacuum high temperature furnace tube was placed on the nickel-plated carbon cloth material, and the growth temperature was 1000 ° C). A chemical vapor deposition time of 30 minutes gave a graphite electrode.

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 (having a size of 70 mm × 70 mm). Next, a separator (glass filter paper (2 layers), product number: Whatman 934-AH) is provided, which is sequentially arranged in accordance with an aluminum electrode, a separator, a graphite electrode, a separator, and an aluminum electrode, and is formed of an aluminum film. It is encapsulated and injected into an electrolyte (aluminum chloride (AlCl ₃ ) / 1-ethyl-3-methylimidazolium chloride, [EMIm]Cl), among which AlCl ₃ and [ The EMIm]Cl ratio is about 1.3), and a metal ion battery (2) is obtained.

Next, the battery performance of the metal ion battery (2) obtained in Example 2 was measured using a battery analyzer (measurement conditions were: charge and discharge test (200 mA) in a constant current mode, charge cutoff voltage was 2.4 V, discharge cutoff voltage Is 1.1V). Figure 14 is a graph showing the relationship between voltage and time during charging and discharging of a metal ion battery (2), and Figure 15 is a graph showing the results of cyclic stability testing of a metal ion battery (2) during charge and discharge. As can be seen from Fig. 15, the metal ion battery (2) of the second embodiment has a capacitance of 33.1 mAh.

Example 3:

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 same electroplating method as in Example 1, wherein the weight ratio of the nickel layer to the carbon cloth was 1:1. Next, the nickel layer and the carbon cloth are heated (about 1000 ° C), and then a graphite layer is formed on the nickel layer by the same chemical vapor deposition (CVD) as in the embodiment 2 (chemical vapor phase). The deposition time was 60 minutes) to obtain a graphite electrode.

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 (having a size of 70 mm × 70 mm). Next, a separator (glass filter paper (2 layers), product number: Whatman 934-AH) is provided, which is sequentially arranged in accordance with an aluminum electrode, a separator, a graphite electrode, a separator, and an aluminum electrode, and is formed of an aluminum film. It is encapsulated and injected into an electrolyte (aluminum chloride (AlCl ₃ ) / 1-ethyl-3-methylimidazolium chloride, [EMIm]Cl), among which AlCl ₃ and [ The EMIm]Cl ratio is about 1.3), and a metal ion battery (3) is obtained.

Next, the battery performance of the metal ion battery (3) obtained in Example 3 was measured using a battery analyzer (measurement conditions were: charge and discharge test (200 mA) in a constant current mode, charge cutoff voltage was 2.4 V, discharge cutoff voltage Is 1.1V). Figure 16 is a graph showing the relationship between voltage and time during charge and discharge of a metal ion battery (3), and Fig. 17 is a graph showing the results of a cycle stability test of a metal ion battery (3) during charge and discharge. As can be seen from Fig. 17, the metal ion battery (3) of the third embodiment has a capacitance of 37.1 mAh.

Comparative Example 1:

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 (thickness: 1.5 μm) was formed on the carbon cloth by the same electroplating method as in Example 1, to obtain a carbon electrode. Figure 18 is a transmission electron microscope (TEM) spectrum of the carbon electrode. As can be seen from Fig. 18, in the carbon electrode, the carbon layer (carbon cloth 52) in the vicinity of the nickel layer 51 is an amorphous carbon material.

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 (having a size of 70 mm × 70 mm). Next, a separator (glass filter paper (2 layers), product number: Whatman 934-AH) is provided, which is arranged in the order of aluminum electrode, separator, carbon electrode, separator, and aluminum electrode, and is made of aluminum film. It is encapsulated and injected into an electrolyte (aluminum chloride (AlCl ₃ ) / 1-ethyl-3-methylimidazolium chloride, [EMIm]Cl), among which AlCl ₃ and [ The EMIm]Cl ratio is about 1.3), and a metal ion battery (4) is obtained.

Next, the battery performance of the metal ion battery (4) obtained in Comparative Example 1 was measured using a battery analyzer (measurement conditions were: charge and discharge test (200 mA) in a constant current mode, charge cutoff voltage was 2.7 V, discharge cutoff voltage It is 0.4V), and it is known from the results that the battery has no electricity.

Comparative Example 2:

First, a carbon cloth (having a size of 70 mm × 70 mm and a thickness of 0.4 mm) was provided. Next, graphite was directly grown on the carbon cloth by the same chemical vapor deposition (CVD) method as in Example 2 to obtain a carbon electrode.

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 (having a size of 70 mm × 70 mm). Next, a separator (glass filter paper (2 layers), product number: Whatman 934-AH) is provided, which is arranged in the order of aluminum electrode, separator, carbon electrode, separator, and aluminum electrode, and is made of aluminum film. It is encapsulated and injected into an electrolyte (aluminum chloride (AlCl ₃ ) / 1-ethyl-3-methylimidazolium chloride, [EMIm]Cl), among which AlCl ₃ and [ The ratio of EMIm]Cl is about 1.3), and an aluminum ion battery (5) is obtained.

Next, the battery performance of the metal ion battery (5) obtained in Comparative Example 2 was measured using a battery analyzer (measurement conditions were: charge and discharge test (50 mA) in a constant current mode, charge cutoff voltage was 2.37 V, discharge cutoff voltage It is 1.1V), and it is known from the results that the battery has no electricity.

Example 4

The graphite electrodes described in Examples 1 and 3 and the carbon electrodes described in Comparative Examples 1 and 2 were analyzed by an X-ray Diffractometer (XRD), and the results are shown in the figure. As can be seen from Fig. 19, the graphite electrodes of Examples 1 and 3 of the present disclosure exhibit a crystal characteristic peak at a diffraction angle (2θ) of 27 degrees, which indicates that Examples 1 and 3 are subjected to heat treatment or chemical vapor phase. The deposition method and the carbon material in the vicinity of the nickel layer (i.e., the carbon cloth in contact with the nickel layer) are converted into a graphite layer (crystalline carbon material) in the presence of a catalytic metal (nickel layer). In contrast, the carbon electrodes described in Comparative Examples 1 and 2 exhibited an amorphous characteristic peak at a diffraction angle (2θ) of 27 degrees, which indicates that no graphite layer was formed.

Based on the above, the electrode of the present invention has high electric quantity and high electrical conductivity, and can increase the capacitance of the metal ion battery including the electrode. In addition, the electrode of the present invention can form a crystalline carbon material on the carbon substrate and the metal layer without using an adhesive, thereby avoiding the use of an adhesive and affecting the electrode performance.

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.

Claims (18)

 An electrode comprising: a carbon substrate; a metal layer disposed on the carbon substrate; a crystalline carbon material disposed between the carbon substrate and the metal layer, and the carbon substrate or the metal layer direct contact.    The electrode of claim 1, wherein the metal layer is a continuous film layer.    The electrode of claim 2, wherein the metal layer is a discontinuous film layer.    The electrode of claim 3, wherein at least a portion of the metal layer is completely covered by the crystalline carbon material.    The electrode according to claim 1, wherein the carbon substrate is a non-crystalline carbon substrate.    The electrode according to claim 5, wherein the amorphous carbon substrate is carbon cloth, carbon paper, or carbon fiber.    The electrode of claim 5, wherein the amorphous carbon substrate has a plurality of pores.    The electrode of claim 1, wherein the metal layer is further filled in the pores.    The electrode of claim 1, wherein the crystalline carbon material is layered graphite.    The electrode of claim 1, wherein the metal layer is composed of a plurality of metal particles.    The electrode of claim 10, wherein the metal particles are made of Fe, Co, Ni, Cu, or a combination thereof.    The electrode of claim 10, wherein at least a portion of the metal particles are coated with the crystalline carbon material.    The electrode of claim 1, further comprising an active material formed on the metal layer.    The electrode of claim 13, wherein the active material is graphite, carbon nanotubes, graphene, or a combination thereof.    A method for manufacturing an electrode, comprising: providing a carbon substrate, wherein the carbon substrate has a first region and a second region; forming a metal layer over the first region, wherein the first region is located on the metal layer and And between the second regions; and heat treating the carbon substrate and the metal layer to convert the first region of the carbon substrate into a crystalline carbon material.    The method for manufacturing an electrode according to claim 15, wherein after the carbon substrate and the metal layer are heat-treated, the carbon substrate and the metal layer are chemically vapor-deposited to form an active material layer. Above the metal layer.    A metal ion battery comprising: a first electrode; a first isolation film; and a second electrode, wherein the second electrode is the electrode according to claim 1, wherein the first isolation film is disposed on the Between the first electrode and the second electrode.    The metal ion battery of claim 17, further comprising: a third electrode; and a second isolation film, wherein the second isolation film is disposed between the second electrode and the third electrode, and The second electrode is disposed between the first isolation film and the second isolation film.