KR102389563B1 - Ultra thin anode for aluminium secondary battery and aluminium secondary battery including the same - Google Patents

Abstract

Disclosed are a negative electrode for an aluminum secondary battery made of an ultra-thin film, a manufacturing method thereof, and an aluminum secondary battery including the negative electrode.
Since the anode for the aluminum secondary battery can deposit aluminum as the anode active material on the anode current collector in an ultra-thin thickness by sputtering, the aluminum secondary battery including the same can be reduced in weight.

Description

Anode for ultra-thin aluminum secondary battery and aluminum secondary battery including same

The present invention relates to a negative electrode for an aluminum secondary battery made of an ultra-thin film, a method for manufacturing the same, and an aluminum secondary battery including the negative electrode.

Recently, the demand for lithium is expected to increase sharply due to the rapid growth of the electric vehicle and energy storage system market. There are issues such as lifespan, low output, and safety, which require improvement.

Beyond the lithium-based energy storage materials that have such resource limitations, there is a continuous demand for the development of secondary batteries based on alternative energy storage materials with ultra-low cost, high safety, high output and long lifespan characteristics that can be used as alternatives to them. Aluminum secondary batteries are the latest technology to store energy using aluminum ions. Aluminum has many resources, is cheap, and is eco-friendly, so there is a possibility that it can universally replace conventional lithium-ion batteries in the long term. It's a very high skill. Aluminum is the third most abundant element on earth after oxygen and silicon (about 8.23%), and there is no problem of resource depletion such as lithium (0.006%). The cost of lithium carbonate is 1/300 of that of lithium carbonate and the price of aluminum finished products is 1/10 of that of lithium. In addition, due to the low flammability and three-electron redox reaction characteristics of aluminum, aluminum-based secondary batteries can provide low cost, high-speed charging and discharging, high capacity, and high safety, thereby drawing great attention as a next-generation energy storage device.

However, research on aluminum secondary batteries over the past several years has not been as successful as other types of secondary batteries due to problems such as low voltage, low capacity compared to lithium secondary batteries, rapid battery capacity reduction, and short lifespan. Recently, as the possibility of improvement of the cathode material, which was considered a difficult problem for aluminum secondary batteries, has been reported recently, it is receiving great attention in related fields. of energy density and high power density of up to about 3,000 W/Kg. This is an energy density value at a level comparable to that of a conventional lead-acid battery and a nickel-metal hydride battery, and is similar to a supercapacitor in terms of output density (Reference: Nature 520, 324-328 (2015), Republic of Korea Patent Publication No. 10-2016- 0145557).

Aluminum-based energy storage device with low price, safety, long lifespan, and high rate characteristics is a technology that has recently been confirmed for batteryization. Through the development and improvement of lithium-ion batteries, it is expected that it will be possible to develop next-generation energy storage devices with ultra-low cost, high capacity, high output, and high safety that go beyond the overall performance of lithium-ion batteries in the long term.

In addition, in recent years, as the mobile device market is rapidly growing, the weight reduction of energy storage devices is required, and it is necessary to develop ultra-light energy storage devices with high capacity and high output characteristics.

Therefore, while the present inventors were researching to achieve ultra-light weight of an aluminum secondary battery, when aluminum as an anode active material was deposited as an ultra-thin film using sputtering on the anode current collector of an aluminum secondary battery, the conventional thick aluminum anode and By comparison, it was found that the electrode capacitance value was almost the same as well as high cell stability, thereby completing the present invention.

In this regard, as related prior art, there are Republic of Korea Patent No. 10-1705856 (aluminum ion capacitor and its use) and Japanese Patent Application Laid-Open No. 2018-037382 (aluminum secondary battery), which include an aluminum secondary battery and aluminum Disclosed is an aluminum active material used as a negative electrode of a capacitor.

The present invention has been devised to solve the above-described problem, and an embodiment of the present invention provides an anode for an ultra-thin aluminum secondary battery.

In addition, another embodiment of the present invention provides a method of manufacturing an anode for an ultra-thin aluminum secondary battery.

In addition, another embodiment of the present invention provides an aluminum secondary battery including an ultra-thin anode.

However, the technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned are clearly understood by those of ordinary skill in the art to which the present invention belongs from the description below. it could be

As a technical means for achieving the above-described technical problem, one aspect of the present invention is,

As a negative electrode for an aluminum secondary battery, the negative electrode includes a negative electrode current collector and aluminum deposited on the negative electrode current collector, and the thickness of the deposited aluminum is 1 μm to 10 μm It provides a negative electrode for an ultra-thin aluminum secondary battery.

The deposition of the aluminum may be deposited using sputtering.

The deposited aluminum may have a thickness of 1 μm to 5 μm.

In addition, another aspect of the present invention,

It provides a method of manufacturing an anode for an ultra-thin aluminum secondary battery, including; depositing aluminum on the anode current collector by sputtering, wherein the deposited aluminum has a thickness of 1 μm to 10 μm.

The sputtering may be performed by a DC (Direct Current) sputtering method.

In addition, another aspect of the present invention,

a negative electrode unit including a negative electrode current collector and a negative electrode active material deposited on the negative electrode current collector; a positive electrode unit including a positive electrode current collector and a positive electrode active material deposited on the positive electrode current collector; a separator interposed between the anode part and the cathode part; and an electrolyte, wherein the anode active material includes aluminum, and the thickness of the anode active material deposited on the anode current collector is 1 μm to 10 μm.

The energy density per unit weight of the aluminum secondary battery may be 40 Wh/Kg to 110 Wh/Kg.

The aluminum secondary battery may maintain a coulombic efficiency of 90% or more in 300 cycles or more.

The aluminum secondary battery may maintain a specific capacity of 50 mAh/g or more in 300 cycles or more.

The positive active material is composed of an active material forming a layered structure, and the active material constituting the layered structure is a three-dimensional composite of graphene and carbon nanotubes or a three-dimensional composite of transition metal dichalcogenide and carbon nanotubes. there is.

According to an embodiment of the present invention, since the anode for the aluminum secondary battery can deposit aluminum as the anode active material on the anode current collector to a very thin thickness by sputtering, the aluminum secondary battery including the same can be lightened. .

In addition, although the aluminum secondary battery includes an ultra-thin negative electrode, it may exhibit an electrode capacity value almost similar to that of an aluminum secondary battery including a conventional thick negative electrode, and may have a remarkably high energy density per unit weight. In addition, excellent cell stability may be exhibited even after 500 cycles or more.

According to an embodiment of the present invention, since the anode for the aluminum secondary battery can deposit aluminum as the anode active material on the anode current collector to a very thin thickness by sputtering, the aluminum secondary battery including the same can be lightened. .
In addition, although the aluminum secondary battery includes an ultra-thin negative electrode, it can exhibit an electrode capacity value almost similar to that of an aluminum secondary battery including a conventional thick negative electrode, and can have a remarkably high energy density per unit weight. In addition, excellent cell stability may be exhibited even after 500 cycles or more.

Hereinafter, the present invention will be described in more detail. However, the present invention may be embodied in various different forms, and the present invention is not limited by the embodiments described herein, and the present invention is only defined by the claims to be described later.

In addition, the terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the entire specification of the present invention, 'including' any component means that other components may be further included, rather than excluding other components, unless otherwise stated.

The first aspect of the present application is

As a negative electrode for an aluminum secondary battery, the negative electrode includes a negative electrode current collector and aluminum deposited on the negative electrode current collector, and the thickness of the deposited aluminum is 1 μm to 10 μm It provides a negative electrode for an ultra-thin aluminum secondary battery.

The second aspect of the present application is

It provides a method of manufacturing an anode for an ultra-thin aluminum secondary battery, including; depositing aluminum on the anode current collector by sputtering, wherein the deposited aluminum has a thickness of 1 μm to 10 μm.

Hereinafter, the manufacturing method of the anode for an ultra-thin film aluminum secondary battery according to the first aspect of the present application and the anode for an ultra-thin film aluminum secondary battery according to the second aspect of the present application will be described in detail step by step of the manufacturing method.

First, in one embodiment of the present application, the method of manufacturing the anode for an ultra-thin aluminum secondary battery includes depositing aluminum on the anode current collector by sputtering; It may include; preparing the negative electrode current collector before.

In one embodiment of the present application, the negative electrode current collector may be a carbon material having high conductivity or various metal materials. The carbon material may include, for example, graphite, graphene, glassy carbon, activated carbon or carbon nanotubes, and the metal material is, for example, molybdenum, gold, nickel, aluminum, titanium, stainless steel. It may include steel, chromium, tantalum or copper. Meanwhile, the anode current collector may be one in which an aluminum anode is coated to a predetermined thickness on the anode current collector by removing an oxide film on the surface by plasma surface treatment to improve surface roughness.

In addition, by forming a three-dimensional aluminum negative electrode pattern on the negative electrode current collector, the reactivity or output characteristics of the aluminum secondary battery may be improved.

Next, in one embodiment of the present application, the method for manufacturing the anode for an ultra-thin aluminum secondary battery includes depositing aluminum on the anode current collector by sputtering.

In one embodiment of the present application, the aluminum is used as an anode active material, and in this case, the aluminum may be a material of aluminum alone or an alloy containing aluminum. Meanwhile, the aluminum alloy may include, for example, Al-Mo, Al-Au, Al-Ga, Al-In, Al-Mn, Al-Ni, Al-Pt, or Al-Si.

In one embodiment of the present application, the aluminum anode active material is a pretreatment process of immersing the aluminum halide and an ionic liquid in an electrolyte for 1 second to 48 hours to remove the oxide film on the surface of the aluminum anode active material and activate the anode. there is.

In one embodiment of the present application, the aluminum halide may include a material selected from the group consisting of AlCl ₃ , AlBr ₃ , AlI ₃ and combinations thereof. In addition, the ionic liquid is 1-ethyl-3-methylimidazolium chloride (1-Ethyl-3-methylimidazolium chloride, [EMIM]Cl), 1-ethyl-3-methylimidazolium bromide (1-Ethyl- 3-methylimidazolium bromide, [EMIM]Br), 1-ethyl-3-methylimidazolium iodide (1-Ethyl-3-methylimidazolium iodide, [EMIM]I), 1-butyl-3-methylimidazolium Chloride (1-butyl-3-methylimidazolium cholride, [BMIM]Cl]), 1-butyl-3-methylimidazolium bromide ([BMIM]Br]), 1-butyl- 3-methylimidazolium iodide (1-butyl-3-methylimidazolium iodide, [BMIM] I]), 1- (1-butyl) pyridium chloride (1- (1-butyl) pyridinium chloride), 1- It may include a material selected from the group consisting of (1-butyl)pyridinium chloride (1-(1-butyl)pyridinium chloride) and combinations thereof.

In one embodiment of the present application, the sputtering may be performed by a DC (Direct Current) sputtering method.

In one embodiment of the present application, the sputtering may be to form an aluminum layer on the anode current collector by evaporating aluminum from an aluminum target attached to a sputtering evaporation source under an inert gas atmosphere.

Preferably, the sputtering may be performed by irradiating DC (Direct Current) 2.5 kW using a multi-target sputter, and injecting 65 sccm of argon gas under a pressure of 5 mTorr, through which molyb It may be to deposit aluminum on the denium current collector.

In this case, the thickness of the aluminum deposited on the current collector may be 200 nm to 10 μm, preferably 1 μm to 5 μm, and more preferably 2 μm to 5 μm. That is, by depositing aluminum on the anode current collector through the sputtering, the thin aluminum deposition as described above may be possible, and through this, an ultra-light aluminum secondary battery may be manufactured.

In one embodiment of the present application, since the anode for an aluminum secondary battery includes aluminum deposited as an ultra-thin film on the anode current collector through sputtering, the aluminum anode may be evenly distributed on the anode current collector.

In one embodiment of the present application, the aluminum negative electrode has a larger capacity per unit volume or unit weight than an electrode of a bulk-type battery, but has a thin thickness, so that the discharge capacity of the battery that can be implemented is 100 to 200 μAh/cm ² Conventional Compared to the thin film battery, the electrode capacity value may be the same regardless of the thickness of the aluminum anode.

A third aspect of the present application, a negative electrode portion comprising a negative electrode current collector and a negative electrode active material deposited on the negative electrode current collector; a positive electrode unit including a positive electrode current collector and a positive electrode active material deposited on the positive electrode current collector; a separator interposed between the anode part and the cathode part; and an electrolyte, wherein the anode active material includes aluminum, and the thickness of the anode active material deposited on the anode current collector is 1 μm to 10 μm.

Although detailed descriptions of parts overlapping with the first and second aspects of the present application are omitted, the descriptions of the first and second aspects of the present application may be equally applied even if the description is omitted in the third aspect. .

In one embodiment of the present application, the negative electrode current collector and the negative electrode portion including the negative electrode active material deposited on the negative electrode collector are the same as those described in the first and second aspects of the present application, and in the third aspect of the present application The description will be omitted.

In one embodiment of the present application, the positive electrode may include porous carbon having a large surface area as an active material, and may also include an active material selected from materials such as oxides, sulfides and nitrides. Specifically, the cathode active material may include a carbon material such as carbon nanohorn, Ketjen black, hard carbon, or the like, a fluorinated carbon material, a metal oxide, a transition metal oxide, a transition metal fluoride, or a transition metal chalcogenide.

In one embodiment of the present application, the positive electrode is preferably composed of an active material forming a layered structure, and the active material constituting the layered structure is a graphite material and a one-dimensional carbon structure material or a composite of carbon nanoparticles. can

In one embodiment of the present application, the graphite material may include a material selected from the group consisting of a graphite film, graphite flakes, graphene, and combinations thereof.

In one embodiment of the present application, the material of the one-dimensional carbon structure may include carbon nanotubes, and the carbon nanotubes may include single-walled carbon nanotubes or multi-walled carbon nanotubes.

In one embodiment of the present application, the active material constituting the layered structure may include a composite of graphene and carbon nanotubes.

In one embodiment of the present application, the anode may be formed in a three-dimensional structure in which carbon nanotubes having a one-dimensional structure are inserted between two-dimensional graphene nanosheets.

In one embodiment of the present application, the active material constituting the layered structure may include a transition metal dichalcogenide.

In one embodiment of the present application, the active material constituting the layered structure may be composed of a complex of a transition metal dichalcogenide and a material having a one-dimensional carbon structure or carbon nanoparticles.

In one embodiment of the present application, the transition metal dichalcogenide is MX ₂ (where M means a transition metal such as Mo, W or Ti, and X means a chalcogen atom such as S, Se or Te) ) may be composed of

In one embodiment of the present application, the transition metal dichalcogenide is more specifically MoS ₂ , WS ₂ , TiS ₂ , MoSe ₂ , WSe ₂ , TiSe ₂ , MoTe ₂ , WTe ₂ , TiTe ₂ and combinations thereof. It may include a material selected from the group consisting of.

In one embodiment of the present application, the positive electrode may include a material capable of intercalation and removal of Al ³⁺ or aluminum-containing complex ions as an active material. For example, it may include a complex ion represented by AlX ₄ ^- or Al ₂ X ₇ ^- (X is Cl, Br or I, and each X may be the same or different.). In addition, as the positive electrode active material, a material capable of converting Al ³⁺ or aluminum-containing complex ions may be used. In the conversion reaction, the metal oxide may react with Al ³⁺ or aluminum-containing complex ions, and the oxide may be reduced to change the metal and aluminum oxide.

In one embodiment of the present application, the separation membrane is to include a material selected from the group consisting of glass fiber, nano cellulose, polyacrylonitrile (PAN) coated cellulose or glass fiber, and combinations thereof. can

In one embodiment of the present application, the aluminum secondary battery enables reversible dissolution and deposition of aluminum in a negative electrode containing aluminum, a positive electrode containing an active material forming a layered structure, and a negative electrode, The positive electrode may include an electrolyte for causing intercalation and deintercalation reactions of anions to occur.

In one embodiment of the present application, the electrolyte may include aluminum ions.

In one embodiment of the present application, an ionic liquid electrolyte, an organic electrolyte, or an aqueous electrolyte may be used as the electrolyte containing the aluminum ions. The ionic liquid electrolyte may include dissolving an aluminum salt such as AlCl ₃ in an ionic liquid, and an alkylimidazolium aluminates, alkylpyridinium containing the aluminum ions. aluminates, alkylfluoropyrazolium aluminates, alkyltriazolium aluminates, aralkylammonium aluminates, dialkylpipendinium aluminates, alkylalkoxy Ammonium aluminates (alkylalkoxyammonium aluminates), alalkylphosphonium aluminates (aralkylphosphonium aluminates), alalkylsulfonium aluminates (aralkylsulfonium aluminates), ethylmethylimidazolium tetrachloroaluminate (ethylmethylimidazolium tetrachloroaluminate), etc. may be included. . As the organic electrolyte, aluminum salts such as AlCl ₃ and Al(NO ₃ ) ₃ are mixed with propylene carbonate, acetonitrile, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and ethyl methyl carbonate (Ethyl). Methyl Carbonate), diethyl carbonate (Diethyl Carbonate), methyl tert-butyl ether (Methyl tert-butyl ether), propylene glycol (Propylene glycol), such as dissolved in an organic solvent may be included. The aqueous electrolyte may include an aqueous solution such as AlCl ₃ , Al(NO ₃ ) ₃ .

In one embodiment of the present application, the electrolyte may preferably be a mixture of aluminum halide and an ionic liquid.

In one embodiment of the present application, the aluminum halide and the ionic liquid may be mixed in a molar ratio of 1: 1.1 to 2.0.

In one embodiment of the present application, the aluminum halide may include at least one selected from the group consisting of AlCl ₃ , AlBr ₃ and AlI ₃ .

In one embodiment of the present application, the ionic liquid is 1-ethyl-3-methylimidazolium chloride (1-Ethyl-3-methylimidazolium chloride, [EMIM]Cl), 1-ethyl-3-methylimidazolium Bromide (1-Ethyl-3-methylimidazolium bromide, [EMIM]Br), 1-Ethyl-3-methylimidazolium iodide (1-Ethyl-3-methylimidazolium iodide, [EMIM]I), 1-Butyl- 3-methylimidazolium chloride (1-butyl-3-methylimidazolium cholride, [BMIM]Cl]), 1-butyl-3-methylimidazolium bromide ([BMIM]Br] ), 1-butyl-3-methylimidazolium iodide (1-butyl-3-methylimidazolium iodide, [BMIM] I]), 1- (1-butyl) pyridium chloride (1- (1-butyl) pyridinium chloride) and 1-(1-butyl)pyridium bromide (1-(1-butyl)pyridinium chloride).

In one embodiment of the present application, the method for manufacturing the aluminum secondary battery comprises sequentially stacking a negative electrode current collector, a negative electrode, a separator, a positive electrode and a positive electrode current collector, and then injecting an electrolyte. As a manufacturing method, the negative electrode is configured to include aluminum, and the positive electrode is prepared by mixing a graphite material or transition metal dichalcogenide, a one-dimensional carbon structure material or carbon nanoparticles, and a binder to collect a slurry. It may be formed by a method of coating on the whole,

In one embodiment of the present application, the binder is a group consisting of polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR) and carboxymethyl cellulose sodium salt (CMC). It may be configured to include one or more selected from, preferably, styrene-butadiene rubber (SBR) and carboxymethyl cellulose sodium salt (CMC) of 1:1 to 50 It may be used by mixing in a mass ratio (more preferably a mass ratio of 1:1).

In one embodiment of the present application, the operating mechanism of the aluminum secondary battery occurring during the charging process is as follows (Reference: Chem. Mater. 29, 4484 (2017)). Specifically, on the cathode side, metals Al, AlCl ₄ ⁻ and Al ₂ Cl ₇ ⁻ may act as active species during the charging and discharging reactions, respectively. On the anode side, mainly AlCl ₄ ⁻ can intercalate and deintercalate into the space between the graphite layer planes during the charging and discharging reactions, respectively.

(cathode): 4Al ₂ Cl ₇ ^- + 3e ^- ⇔ 7AlCl ₄ ^- + Al

(Anode): xC + AlCl ₄ ^- ⇔ Cx(AlCl ₄ ^- ) + e ^-

In one embodiment of the present application, the energy density per unit weight of the aluminum secondary battery may be 40 Wh/Kg to 110 Wh/Kg, preferably 60 Wh/Kg to 110 Wh/Kg, More preferably, it may be 80 Wh/Kg to 110 Wh/Kg. This exceeds the known energy density per unit weight of 40 Wh/Kg of an aluminum secondary battery, and may have an energy density improved by a maximum of about 2.5 times. In addition, the aluminum secondary battery may have a coulombic efficiency of 90% or more at 300 cycles, preferably 500 cycles or more, and a specific capacity of 50 mAh/g or more. there is. That is, the aluminum secondary battery according to the present invention may have excellent electrochemical properties despite using an ultra-thin aluminum negative electrode having a thickness of 1 μm to 10 μm, and an ultra-light aluminum secondary battery may be manufactured.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

Example 1-1. Manufacture of an aluminum secondary battery using ultra-thin aluminum (2 μm thick) as a negative electrode

1. Manufacture of anode for ultra-thin aluminum secondary battery

The aluminum secondary battery negative electrode was assembled in a glove box. Prior to electrode preparation, a pretreatment process was performed in which the aluminum anode active material was immersed in an electrolyte in which aluminum halide and an ionic liquid were mixed for 1 second to 48 hours. By removing the oxide film or impurities on the surface of the aluminum anode through this process, it was possible to drive the aluminum secondary battery to be manufactured later. The negative active material that has undergone the pretreatment process is irradiated with DC (Direct Current) 2.5 kW using SRN-110 of Sorona, a multi-target sputtering equipment, and 65 sccm of argon gas is injected under a pressure of 5 mTorr while molybdenum current collector (Fig. A negative electrode for an aluminum secondary battery was prepared by depositing on 1a). At this time, the thickness of the deposited aluminum anode active material was 2 μm ( FIGS. 1B to 1E ). An SEM photograph of the molybdenum current collector is shown in FIG. 1A, and the SEM images of the deposited aluminum negative active material are shown in FIGS. 1B to 1E at different magnifications, respectively.

2. Manufacturing of aluminum secondary battery

A pyrolytic graphite foil (PG foil) was used alone as the positive electrode of the aluminum secondary battery, and the pyrolytic graphite foil was made into a coin type electrode having a diameter of 18 mm.

In addition, as a separator, an 18 mm-sized Whatman's glass fiber separator (glass microfiber filters, Grade GF/B) was used.

Finally, AlCl3:[EMIM]Cl (1.5:1 molar ratio) ionic liquid electrolyte filled in the anode and cathode was used. As the negative electrode, ultra-thin aluminum deposited to a thickness of 2 μm on a molybdenum current collector was used, and the aluminum was made into a coin-type electrode having a diameter of 18 mm.

Example 1-2. Manufacture of an aluminum secondary battery using ultra-thin aluminum (2 μm thick) as a negative electrode

1. Manufacture of anode for ultra-thin aluminum secondary battery

It was prepared in the same manner as the negative electrode for an ultra-thin aluminum secondary battery of Example 1-1.

2. Manufacturing of aluminum secondary battery

An aluminum secondary battery was manufactured in the same manner as in Example 1-1, except that graphene and carbon nanotubes coated on a pyrolytic graphite foil (PG foil), which are a positive electrode current collector, were used as the positive electrode of the aluminum secondary battery. did

Examples 1-3. Manufacture of an aluminum secondary battery using ultra-thin aluminum (2 μm thick) as a negative electrode

1. Manufacture of anode for ultra-thin aluminum secondary battery

It was prepared in the same manner as the negative electrode for an ultra-thin aluminum secondary battery of Example 1-1.

2. Manufacturing of aluminum secondary battery

Molybdenum disulfide (MoS ₂ ), a transition metal dichalcogenide material coated on pyrolytic graphite foil (PG foil) or molybdenum foil (Mo foil), is used as the positive electrode of the aluminum secondary battery. Except for that, an aluminum secondary battery was prepared in the same manner as in Example 1-1.

Examples 1-4. Manufacture of an aluminum secondary battery using ultra-thin aluminum (2 μm thick) as a negative electrode

1. Manufacture of anode for ultra-thin aluminum secondary battery

It was prepared in the same manner as the negative electrode for an ultra-thin aluminum secondary battery of Example 1-1.

2. Manufacturing of aluminum secondary battery

Molybdenum disulfide (MoS ₂ ), a transition metal dichalcogenide material coated on pyrolytic graphite foil (PG foil) or molybdenum foil (Mo foil) as a positive electrode of an aluminum secondary battery, and carbon nano An aluminum secondary battery was prepared in the same manner as in Example 1-1, except that the composite material of the tube was used.

Example 2. Manufacture of an aluminum secondary battery using ultra-thin aluminum (thickness of 5 μm) as a negative electrode

An aluminum secondary battery was prepared in the same manner as in Examples 1-1 to 1-4, except that an aluminum anode active material was deposited on a molybdenum current collector to a thickness of 5 μm in the preparation of the anode for ultra-thin aluminum secondary battery 1. prepared.

Comparative Example 1. Preparation of an aluminum secondary battery having a thickness of 10 μm of aluminum as an anode

Although the manufacturing method and materials used as the negative electrode of the aluminum secondary battery of the above embodiment are the same, an aluminum secondary battery having a thickness of 10 μm of aluminum used as the negative electrode was prepared.

Comparative Example 2. Preparation of an aluminum secondary battery having a thickness of 25 μm of aluminum as an anode

Although the manufacturing method and materials used as the negative electrode of the aluminum secondary battery of the above embodiment are the same, an aluminum secondary battery having a thickness of 25 μm of aluminum used as the negative electrode was prepared.

Experimental Example 1. Measurement of Energy Density of Aluminum Secondary Battery

In order to measure the energy density per unit weight of the aluminum secondary batteries prepared in Example 1 and Comparative Examples 1 and 2, a constant current charging/discharging reaction was performed at a battery voltage of 0.01 V to 2.45 V, and having multiple channels. Using a constant potential (VSP potentiostat/galvanostat/EIS, BioLogic) equipment, constant current charge/discharge capacity was measured. The results are shown in FIGS. 2 to 4, respectively.

Referring to FIG. 2 , the aluminum secondary battery manufactured according to Example 1 had an energy density value of about 103 Wh/kg and a charge/discharge efficiency value of about 98.8% at a current density of about 66 mA/g. could see what was visible. On the other hand, referring to FIGS. 3 (Comparative Example 1) and 4 (Comparative Example 2), as the thickness of the aluminum anode increases to 10 μm and 25 μm, respectively, the energy density values are lowered to 72 Wh/kg and 40 Wh/kg, respectively. I could see losing.

Accordingly, it was confirmed that the energy density per unit weight of the aluminum secondary battery prepared in Example 1 was higher than those of Comparative Examples 1 and 2.

Experimental Example 2. Measurement of cycle characteristics of an aluminum secondary battery

In order to analyze the cycle characteristics of the aluminum secondary battery prepared in Example 1, the cycle characteristics were evaluated using a constant potential (VSP potentiostat/galvanostat/EIS, BioLogic) equipment having multiple channels, and the results are shown 5 is shown.

Referring to FIG. 5 , the aluminum secondary battery prepared in Example 1 exhibited a high coulombic efficiency of about 95% or more even after 500 cycles, and exhibited a charge/discharge capacity of about 60 mAh/g, resulting in excellent stability. was confirmed to have

Claims (6)

a negative electrode unit including a negative electrode current collector and a negative electrode active material deposited on the negative electrode current collector;
a positive electrode unit including a positive electrode current collector and a positive electrode active material deposited on the positive electrode current collector;
a separator interposed between the anode part and the cathode part; and
An aluminum secondary battery comprising an electrolyte, comprising:
The negative active material includes aluminum,
The anode active material is deposited using sputtering so that the anode active material is evenly distributed on the anode current collector,
The thickness of the negative electrode active material deposited on the negative electrode current collector is less than 1 to 5 μm,
The energy density per unit weight of the aluminum secondary battery is 80 Wh/Kg to 110 Wh/Kg,
In the aluminum secondary battery, a coulombic efficiency of 90% or more is maintained at 300 cycles or more.
The method of claim 1,
The aluminum secondary battery is an aluminum secondary battery that maintains a charge/discharge capacity (specific capacity) of 60 mAh/g or more in 300 cycles or more.
The method of claim 1,
The positive electrode active material is composed of an active material forming a layered structure,
The active material constituting the layered structure is an aluminum secondary battery comprising a three-dimensional composite of graphene and carbon nanotubes or a three-dimensional composite of transition metal dichalcogenide and carbon nanotubes.
As a method for manufacturing the aluminum secondary battery of claim 1,
preparing a negative electrode current collector, a negative electrode, a separator, a positive electrode, and a positive electrode current collector, respectively;
stacking the negative current collector, the negative electrode, the separator, the positive electrode and the positive electrode current collector; and
injecting an electrolyte;
A method of manufacturing an aluminum secondary battery comprising a.
5. The method of claim 4,
Preparing the negative electrode current collector, the negative electrode, the separator, the positive electrode and the positive electrode current collector, respectively;
Depositing aluminum on the negative electrode current collector by sputtering; comprising, a method of manufacturing an aluminum secondary battery.
6. The method of claim 5,
The sputtering is a method of manufacturing an aluminum secondary battery that is performed by a DC (Direct Current) sputtering method.

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