KR20180103453A - Negative Electrode for Non-aqueous Aluminum ion Battery and Method for Preparation of the Same - Google Patents

Abstract

The present invention relates to a negative electrode material for non-aqueous aluminum ion batteries, and a production method thereof. More specifically, the present invention relates to a method for producing a negative electrode material for non-aqueous aluminum ion batteries, and an aluminum negative electrode material for non-aqueous aluminum ion batteries produced thereby. To this end, the specific capacity of the non-aqueous aluminum ion battery can be remarkably increased, and the surface area can be increased without formation of oxide layers by treating a surface of the aluminum negative electrode material via an electrochemical method in order to greatly enhance charge/discharge stability.

Description

TECHNICAL FIELD [0001] The present invention relates to a negative electrode material for a non-aqueous aluminum ion battery and a method for manufacturing the negative electrode material.

The present invention relates to a negative electrode material for a nonaqueous aluminum ion battery and a method of manufacturing the same, and more particularly, to a negative electrode material for a nonaqueous aluminum ion battery which can dramatically increase the specific capacity of a nonaqueous aluminum ion battery, A negative electrode material for a battery, and a manufacturing method thereof.

Recently, due to environmental problems and fuel depletion problems caused by the use of fossil fuels, the development and research of new energy systems such as lithium ion batteries or green renewable energy are continuing.

However, as the cost of raw materials such as LiCoO ₂ and Li ₂ MnO ₄ used as an anode material for a lithium ion battery increases, it is necessary to use a redox flow battery, a sodium ion battery, a magnesium ion battery, Research has been conducted on metal ion batteries such as aluminum ion batteries.

Aluminum ion batteries, which are considered as a dual alternative energy system, can make low-cost batteries due to the third richness of aluminum in the Earth's crustal composition ratio, and it is a big economic impact if they replace commercial lithium-ion batteries It is expected.

Aluminum offers three electrons per aluminum atom in the electrochemical oxidation process, and the theoretical capacity is quite good. However, since the standard reduction potential of aluminum is -1.667V (vs. RHE) lower than the standard reduction potential of hydrogen (vsRHE), the hydrogen proton is reduced to generate hydrogen (HER) It prevails. Due to such a problem, aluminum has only been driven by a primary battery, such as an aluminum air battery, in a battery system.

However, when an organic electrolyte which does not use an electrolyte is used in a battery using an aluminum electrode, hydrogen generation is suppressed and a reduction reaction of aluminum becomes possible, so that it can be used as an electrode of a secondary battery using an aluminum material. Aluminum ion batteries using various cathode materials have been actively studied.

In Patent Document 1, an aluminum ion battery was fabricated using vanadium oxide as a cathode material, which has a short cycle life and a low Coulomb efficiency. In addition, attempts have been made to increase the specific capacity by applying various cathode materials such as Mo ₆ S ₈ , LiFePO ₄ , and graphite (Non-Patent Documents 1 to 3). Although research on the development of cathode material has been continuously carried out, there has not been reported in the academia about cathode material aluminum.

Korean Patent Publication No. 10-2014-0076589 (June 20, 2014)

 L. Geng, G. Lv, X. Xing and J. Guo, Reversible electrochemical intercalation of aluminum in Mo6S8, Chem. Mater. 27 (2015) 4926-4929.  X.G. Sun, Z. Bi, H. Liu, Y. Fang, C.A. Bridges, M.P. Paranthaman, S. Dai and G. M. Brown, A high performance hybrid battery based on aluminum anode and LiFePO4 cathode, Chem. Commun. 52 (2016) 1713-1716  M.C. Lin, M. Gong, B. Lu, Y. Wu, D.Y. Wang, M. Guan, M. Angell, C. Chen, J. Yang, B.J. Hwang and H. Dai, An ultrafast rechargeable aluminum-ion battery, Nature 520 (2015) 325-328

The main object of the present invention is to provide a non-aqueous aluminum-based battery having an improved surface area without forming an oxide film by electrochemically treating the surface of an aluminum anode material in order to drastically increase the specific capacity of the non- Ion battery, and an aluminum anode material of a non-aqueous aluminum ion battery manufactured from the method.

In order to achieve the above object, an embodiment of the present invention is a method for manufacturing an anode material for a non-aqueous aluminum ion battery, comprising the steps of: (a) pretreating an aluminum foil; (b) immersing the pretreated aluminum foil in an electrolytic solution, and applying an electric current to etch the aluminum foil; And (c) washing and drying the etched aluminum foil. The present invention also provides a method of manufacturing an anode material for a non-aqueous aluminum ion battery.

In a preferred embodiment of the present invention, the step (a) may be performed by immersing the aluminum foil in a pretreatment solution of 1 to 5 M for 30 seconds to 5 minutes.

In a preferred embodiment of the present invention, the pretreatment solution may be at least one selected from the group consisting of hydrochloric acid, hydrofluoric acid, sulfuric acid, silicic acid fluoride, and caustic soda.

In a preferred embodiment of the present invention, the etching in the step (b) is performed by immersing the pretreated aluminum foil as a working electrode in a container containing an electrolyte and applying an alternating current thereto have.

In a preferred embodiment of the present invention, the current density when the alternating current is applied is 40 to 400 mA / cm ² , and the frequency is 0.1 Hz to 20 Hz.

In one preferred embodiment of the present invention, the temperature of the electrolytic solution is 30 to 60 ° C and the etching time is 50 to 500 seconds.

In one preferred embodiment of the present invention, the electrolytic solution is at least one selected from the group consisting of chromic acid (H ₂ CrO ₄ ), nitric acid (HNO ₃ ), hydrochloric acid (HCl) and sulfuric acid (H ₂ SO ₄ ) can do.

In one preferred embodiment of the present invention, the electrolytic solution contains 0.5 M to 5 M hydrochloric acid and 0.005 M to 0.05 M sulfuric acid, and the ratio of hydrochloric acid and sulfuric acid is 1: 0.01 to 3.

In a preferred embodiment of the present invention, drying in the step (c) may be performed at room temperature in an inert atmosphere.

In one preferred embodiment of the present invention, the aluminum foil has a purity of 99.00 to 99.99% and a thickness of 0.01 to 0.1 mm.

Another embodiment of the present invention provides an anode material for a nonaqueous-based aluminum ion battery, which is produced in the method for manufacturing an anode material for a nonaqueous-based aluminum ion battery and has an etch pit formed on the surface thereof.

In another preferred embodiment of the present invention, the etch pit may be characterized in that the average diameter of the grooves is 0.1 탆 to 10 탆.

By applying an aluminum anode material having an increased surface area by an electrochemical method to a non-aqueous aluminum ion battery, the cost of the non-aqueous aluminum battery is drastically increased due to the formation of the pore structure on the surface and the increase of the electrochemical activation area, The charge / discharge stability is also greatly increased.

1 is a schematic diagram of a two-electrode system for etching an aluminum foil according to an embodiment of the present invention.
Fig. 2 is a graph showing the relationship between the aluminum anode material of Example 1 (a), Example 2 (c) and Example 3 (d), and the aluminum cathode material of Comparative Example 1 (b), Comparative Example 2 (e) It is a scanning electron microscope photograph of ashes.
Fig. 3 is a graph of the results of the purification voltage and current method (CV) measurement of the non-aqueous aluminum battery of Example 1. Fig.
4 is a graph showing a result of charging / discharging (non-capacity vs. voltage) measurement of the non-aqueous aluminum battery (a) of Example 1 and the non-aqueous aluminum battery (b) of Comparative Example 1. Fig.
5 is a graph showing a result of charging / discharging (charge / discharge cycle vs. non-capacity) measurement of the non-aqueous aluminum battery (a) of Example 1 and the non-aqueous aluminum battery (b) of Comparative Example 1;
6 is a graph showing a result of charge / discharge (time vs. voltage) measurement of the non-aqueous aluminum battery of Example 1. Fig.

Hereinafter, a method for manufacturing an anode material for a non-aqueous alkaline ion battery according to the present invention and a method for manufacturing the same will be described with reference to the accompanying drawings, in order to facilitate the present invention by those skilled in the art. A preferred embodiment of the negative electrode material will be described in detail.

In the drawings of the present invention, the sizes and dimensions of the structures are enlarged or reduced from the actual size in order to clarify the present invention, and the known structures are omitted so as to reveal the characteristic features, and the present invention is not limited to the drawings .

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description, well-known functions or constructions are not described in detail to avoid obscuring the subject matter of the present invention.

In addition, since the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention, It is to be understood that equivalents and modifications are possible.

In one aspect, the present invention provides a method of manufacturing an anode material for a non-aqueous aluminum ion battery, comprising the steps of: (a) pretreating an aluminum foil; (b) immersing the pretreated aluminum foil in an electrolytic solution, and applying an electric current to etch the aluminum foil; And (c) washing and drying the etched aluminum foil. The present invention also relates to a method of manufacturing an anode material for a non-aqueous aluminum ion battery.

More specifically, the method for manufacturing an anode material for a non-aqueous alkaline ion battery according to the present invention is characterized in that the surface of an aluminum foil to be used as an anode material for an aluminum ion battery is etched by using an electrochemical method without forming an oxide film, By increasing the surface area, it is possible to drastically increase the specific capacity of the non-aqueous aluminum ion battery and to greatly improve the charging / discharging stability.

In the method of manufacturing an anode material for a non-aqueous alkaline ion battery according to the present invention, pretreatment is performed using a pretreatment solution (step (a)) to make an optimum surface state in which an etch pit of an aluminum foil can be formed.

The pretreatment of the aluminum foil can be performed by immersing the aluminum foil in a pretreatment solution of an acid or an alkali component at a concentration of 1 to 5 M at room temperature for 30 seconds to 5 minutes. If the concentration or the pretreatment time of the pretreatment solution is less than the above range, the optimum surface condition for forming the etch pit can not be obtained. If the concentration or the pretreatment time of the pretreatment solution exceeds the above range, excessive chemical erosion There is a problem that the size of the pit becomes too large during etching and the surface area is rather reduced.

The aluminum foil used as the negative electrode material for the non-aqueous aluminum ion battery may be a high purity aluminum foil having a purity of 99.00 to 99.99% and a thickness of 0.01 to 0.1 mm. If the purity is low or the thickness is out of the above range, it may not be used as a negative electrode material for a non-aqueous aluminum ion battery, or the electrode may be short-circuited due to excessive corrosion.

The pretreatment solution used for the pretreatment may be hydrochloric acid, hydrofluoric acid, sulfuric acid, silicic acid fluoride, caustic soda, or the like.

The pretreated aluminum foil forms a weak site with the acid on the surface of the aluminum foil (Al ₂ O ₃ ) so that an optimal surface state can be obtained so that an etch pit can be formed during etching.

Thereafter, the pretreated aluminum foil is immersed in an electrolytic solution, and an electric current is applied to etch the aluminum foil by an electrochemical method (step (b)).

Etching of the pretreated aluminum foil can be performed by specifically immersing the pretreated aluminum foil as a working electrode in a container containing an electrolyte and applying an electric current. At this time, the current application can apply an alternating current in terms of etch pit formation, and the current density when an alternating current is applied is 40 to 400 mA / cm ² Preferably 100 to 350 mA / cm < ² >, and more preferably 200 to 300 mA / cm < ² >. Also, the frequency at the time of application of the alternating current may be 0.1 Hz to 20 Hz, preferably 5 Hz to 15 Hz, and more preferably 10 Hz.

If the current density is out of the range of 40 to 400 mA / cm ² upon application of the alternating current, the surface may be excessively eluted or the density of the pits may be reduced, which may make it difficult to enlarge the surface area of the aluminum foil. When the frequency is out of 20 Hz, the waveform becomes almost the same as the direct current, and the AC etching may not be performed, or the specific surface area may be increased due to the high frequency waveform, and then the phenomenon may be reduced.

Etch pits are not formed when the etching time is less than 50 seconds. When the etching time is more than 500 seconds, the aluminum foil is etched with the holes holes may be generated to reduce the mechanical strength.

The electrolytic solution used for etching the aluminum foil includes at least one selected from the group consisting of chromic acid (H ₂ CrO ₄ ), nitric acid (HNO ₃ ), hydrochloric acid (HCl) and sulfuric acid (H ₂ SO ₄ ) And may preferably include hydrochloric acid and sulfuric acid. At this time, the electrolyte concentration is 0.001 M to 10 M. If it is out of the above range, the etching pit may not be formed properly, or the size of the formed etching pit may be too large.

Particularly, the electrolytic solution containing 0.5 M to 5 M of hydrochloric acid can form an etch pit having a high density of aluminum foil by the action of chlorine ions during the etching process according to the application of the alternating current, and the electrolytic solution of 0.005 M to 0.05 M By adding a small amount of sulfuric acid in the electrolytic solution containing hydrochloric acid, it is possible to suppress the formation of holes in the aluminum foil due to the excessive chlorine ion activity in the electrolytic solution containing hydrochloric acid and to induce the formation of deep and uniform pits in the formation of etch pits.

If hydrochloric acid and sulfuric acid are used which are out of the above concentration range, it is difficult to obtain uniform etch pit formation. At this time, the volume ratio of hydrochloric acid and sulfuric acid used in the electrolytic solution may be 1: 0.01 to 3, preferably 1: 0.5 to 2, and when the content of sulfuric acid is less than 0.01 volume ratio with respect to hydrochloric acid, If the content of sulfuric acid is more than 3 vol% with respect to hydrochloric acid, the activity of chlorine ion is inhibited and the etching efficiency may be lowered.

The temperature of the electrolytic solution may be 30 to 60 ° C, preferably 35 to 50 ° C, so as to form an etched pit on the aluminum foil most actively on the activity of the electrolyte ion during the chemical etching process acting on the aluminum foil. Lt; 0 > C. If the temperature of the electrolytic solution is less than 30 ° C, the pit size may become larger and the density may be smaller. If the temperature of the electrolytic solution is higher than 60 ° C, the opposite phenomenon occurs. If the temperature of the electrolytic solution is not controlled, So that the size and shape of the substrate are uneven.

Hereinafter, the etching process of the present invention will be described with reference to the two-electrode system for etching the aluminum foil of FIG. 1 schematically illustrates a two-electrode system 100 according to an embodiment of the present invention. The aluminum foil is used to etch the working electrode 1 of the two-electrode system 100 and the counter electrode 2 Platinum < / RTI > In the two-electrode system, the cylindrical vessel 10 is filled with the electrolytic solution 12, and the working electrode and the counter electrode are sufficiently immersed in the electrolytic solution. In order to maintain the temperature of the electrolyte solution at a constant temperature, the container 10 containing the electrolyte solution is heated on a hot plate, and the temperature of the electrolyte solution is measured using a thermometer 3. The temperature of the electrolyte solution is controlled by a temperature controller 6, And the magnetic bar (4).

When the temperature of the electrolytic solution is maintained at an appropriate temperature, an aluminum foil surface used as the working electrode is etched by supplying an alternating current through a power supply (not shown).

Thereafter, the etched aluminum foil is washed to remove aluminum particles remaining on the surface and then dried (step (c)).

At this time, it is necessary to sufficiently clean the aluminum foil so that the aluminum particles remaining on the surface of the etched aluminum foil can be completely removed. In the washing process, the temperature of the distilled water should be the same as the electrolytic solution temperature of 30 to 60 ° C. .

The drying after the washing may be sufficiently dried at room temperature (20 to 27 ° C) in the presence of an inert gas.

In general, non-aqueous aluminum ion batteries are accompanied by electrochemical reactions at the electrolyte (or electrode surface) along with charge transfer. Charging and discharging occur due to such reactions. Therefore, the surface of the anode material used in non- Al ₂ O ₃ ) is formed, the electric conductivity is deteriorated and the charge and discharge of the battery are adversely affected. In particular, to dry the aluminum foil washed at a high temperature, the dense Al ₂ O ₃ on the aluminum surface The oxide film can be formed rapidly. Therefore, in the present invention, the aluminum foil is dried at room temperature in the presence of an inert gas so that an oxide film is not formed on the surface of the aluminum foil. The inert gas can be used without limitation as long as it is chemically inert. For example, the inert gas may be argon, nitrogen, helium, or the like.

By applying the aluminum anode material manufactured in this way to a non-aqueous aluminum ion battery, the cost of the non-aqueous aluminum battery is drastically increased due to the formation of the pore structure on the surface and the increase of the electrochemical activation area, and the charge- .

The present invention relates to an anode material for a nonaqueous-based aluminum ion battery, which is produced in the above-described method for producing an anode material for a nonaqueous-based aluminum ion battery and etch pits on its surface.

The negative electrode material for a nonaqueous-based aluminum ion battery according to the present invention can be obtained by treating the surface of an aluminum negative electrode material electrochemically to uniformly form etch pits having an average diameter of the grooves of 0.1 mu m to 10 mu m without forming an oxide film, Has a high specific capacity of 22% or more and a high charge / discharge stability than an aluminum ion battery.

Hereinafter, the present invention will be described more specifically by way of specific examples. The following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

< Example  1>

1-1: Aluminum Anode material  Produce

A high purity aluminum foil with a purity of 99% or more was pretreated in a 1M hydrochloric acid solution for 3 minutes, and then subjected to primary distillation and then sufficiently washed with distilled water filtered through an ion exchange resin. The washed high purity aluminum foil was attached to the working electrode of the two-electrode system shown in Fig. 1, and platinum (Pt) was used as a counter electrode. The electrolytic solution was prepared by mixing 250 ml and 250 ml of 2.2 M hydrochloric acid and 0.01 M sulfuric acid in a two-electrode system, placing it on a hot plate and keeping it constant at 40 ° C. Thereafter, the temperature was kept constant and then alternating (AC) etching was performed at a frequency of 10 Hz at a constant current density of 300 mA / cm &lt; ² &gt; through a power supply device (AUTOLAB (PGSTAT128N)) for 300 seconds. The etched aluminum foil was thoroughly washed at room temperature with distilled water, and dried at room temperature in a glove box filled with argon gas to prepare an aluminum anode material.

1-2: Anode  Produce

A high purity graphite (99%, Sigma Aldrich) as a positive electrode active material, a polyvinylidene fluoride (PVDF) and a carbon black for improving electric conductivity were mixed in a mass ratio of 8: 1: 1 with a binder, 50 ml of ethanol (C ₂ H ₅ OH (anhydrous, Sigma Aldrich)) was poured into the mixture, stirred well to mix, and subjected to sonication for 2 hours or more for a second time to uniformly disperse the materials in the NMP. The dispersion was dried in an oven at 90 캜 for a sufficiently long time to obtain a dark gray light dried graphite. 1-Methyl-2-pyrrolidone (NMP) was added to 5 g of the dried graphite in small portions to obtain a slurry-type paste. At this time, the NMP solvent was injected until a slight flow was felt.

After placing a GDL (Gas Diffusion Layer) on a flat glass substrate, 1 g of the prepared graphite slurry was spread evenly on the GDL. Then, using an applicator (Baker Type Applicator, Wellcos Corporation) to obtain a uniform thickness, 0.254 mm Lt; / RTI &gt; At this time, since the thickness is dominantly influenced by the viscosity of the slurry dough, the weight is preferably set to 3.248 mg / cm ² and 5 mg / 1.53938 cm ² based on the 14 pi cell area. The GDL with the graphite active material was dried in a vacuum oven at 120 DEG C for 8 hours. The completely dried graphite active material was circularly punched with a 14 pi punching tool to prepare a cathode material.

1-3: Non-aqueous system  Preparation of Liquid Electrolyte

The water-insoluble liquid electrolyte is a high-purity, translucent solid 1-ethyl-3-methylimidazolium chloride (EMIM] Cl (97%, TCI) Aluminum chloride in the form of white powder (AlCl ₃ (99.99%, Sigma Aldrich)) was prepared by mixing in a molar ratio of 1: 1.3. At this time, in order to prevent oxidation and deterioration of the sample due to contact with oxygen and moisture in the air, the O ₂ concentration was maintained at 1.0 ppm or less, and the reaction was carried out in a room temperature glove box filled with argon gas as an inert gas. By the eutectic reaction at the moment of contact of the two samples, a bright and transparent light-yellowish ionic liquid is obtained, which is used as a non-aqueous liquid electrolyte in the post-process.

1-4: Manufacture of non-aqueous electrolytic aluminum battery

In order to measure the performance of the aluminum anode material manufactured by the manufacturing method according to the present invention, a battery was constructed as follows.

The anode material prepared in Example 1-1 was used as the cathode material, and the graphite prepared in Example 1-2 was used as the cathode material. As the electrolyte, 1-ethyl-3-methyl Imidazolium chloride and aluminum chloride were mixed in a molar ratio of 1: 1.3, and GF / D was used as a separation membrane. In order to prevent the deterioration of the current collecting electrode by each electrolyte, a nickel current collector was used for the positive electrode and the negative electrode portion so that the electrolyte could prevent direct contact with the current collecting electrode (SUS316). The nickel current collectors were made smaller in size than the separator to prevent direct shots of the negative electrode and the positive electrode, and the nickel current collector was made larger than the current collecting electrode (SUS316) to be completely covered. When constructing a battery by using a self-fabricated Swagelok Cell, keep the O ₂ concentration below 1.0 ppm to prevent degradation of the electrolyte in the air due to moisture or oxygen contact, and proceed in a glove box filled with an inert gas such as argon gas Respectively.

< Example  2>

An aluminum anode material was prepared in the same manner as in Example 1-1 except that the etching time was changed to 100 seconds to prepare an anode material and then mounted on the nonaqueous aluminum ion battery of Example 1.

< Example  3>

An aluminum anode material was prepared in the same manner as in Example 1-1 except that the current density was changed to 200 mA / cm &lt; ² &gt; to prepare an anode material, which was then mounted on the nonaqueous aluminum ion battery of Example 1.

< Comparative Example  1>

A non-aqueous aluminum ion battery was produced in the same manner as in Example 1 except that a high purity aluminum foil (99.99%, Sigma Aldrich) was subjected to sonication for 30 minutes in acetone and ethanol respectively to remove impurities on the surface, Aluminum foil was attached to a non-aqueous aluminum ion battery.

< Comparative Example  2>

An aluminum anode material was prepared in the same manner as in Example 1-1 except that the etching time was changed to 20 seconds to prepare an anode material and then mounted on the nonaqueous aluminum ion battery of Example 1.

< Comparative Example  3>

An aluminum anode material was prepared in the same manner as in Example 1-1 except that the current density was changed to 700 mA / cm &lt; ² &gt; to prepare an anode material, which was then mounted on the nonaqueous aluminum ion battery of Example 1.

[ Experimental Example  One: Anode material  Surface condition measurement]

In order to observe the surface state of the negative electrode material according to Examples 1 to 3 and Comparative Examples 1 to 3, a scanning electron microscope (SEM-4300SE) was used at a magnification of 5,000 times, and the results are shown in FIG.

In the case of the negative electrode material prepared in Examples 1 to 3, grooves (etch pits) having an average diameter of 1 占 퐉 were uniformly formed as compared with the negative electrode material of Comparative Example 1, while the negative electrode material of Comparative Example 1 had a smooth surface .

It can be seen that the cathode materials of Examples 1 to 3 have a large surface area compared to the cathode material of Comparative Example 1 (Fig. 2B) due to the etch pits formed in the anode material of Examples 1 to 3 (Figs. 2A, there was.

In the case of the negative electrode material of Comparative Example 2 (FIG. 2E), the surface area enlargement due to the formation of etch pits was not large due to the etching time insufficient for the formation of etch pits. In the case of the negative electrode material of Comparative Example 3 Due to the high current density, the surface was excessively eluted and the density of the pits was small and appeared to be in a deep pit shape.

[ Experimental Example  2: Of aluminum ion battery  Cyclic Voltage Current Measurement]

In order to evaluate the electrochemical reversible stability of the aluminum ion battery according to Example 1, the cyclic voltammetry was measured at a voltage of 0.0 to 2.5 V at a scan rate of 1 mV / s, and the voltage was measured by galvanic corrosion Since there is a potential reduction, after the cell assembly, the open circuit voltage stabilization time is set to 6 hours, or preferably, the open circuit voltage is left unchanged for at least two decades before the decimal point. Is shown in Fig.

As shown in FIG. 3, oxidation peaks were observed at reduction potentials of 1.0 V, 1.2 V, and 2.0 V at the reduction reaction of 0.5 V, 1.7 V, and 2.2 V of the aluminum ion battery according to Example 1. The electrochemical reversible stability of the aluminum ion battery according to Example 1 showed an increase in the capacitor area as the cycle peaked the maximum height of the main peak (0.5 V, 1.0 V, 1.2 V). It was confirmed that the area of electrochemical activation increased as the cycle progressed. Also, as the cycle progressed, the positions of the main peaks were found to be the same. From this, it can be confirmed that the aluminum ion battery manufactured by the method of Example 1 performs the oxidation and reduction reaction reversibly and stably even when charging and discharging proceed.

[ Experimental Example  3: Of aluminum ion battery Charging and discharging  Measure]

In order to evaluate the charging and discharging characteristics of the aluminum ion battery according to Example 1, a constant current charging and discharging test was carried out at a battery voltage of 0.3 to 2.5 V at a current density of 5 mA / cm ² at a charging and discharging current, Since there is a potential reduction due to galvanic corrosion, after the cell is assembled, the open circuit voltage stabilization time is set to 6 hours, or preferably, the open circuit voltage is left unchanged for two or more periods to the second decimal place, The measurement was carried out, and the results are shown in Figs.

FIG. 4A is a graph of the non-capacity vs. voltage of the aluminum ion battery of Example 1, FIG. 4B is a graph of the capacity vs. voltage of the aluminum ion battery of Comparative Example 1, And the results of charging and discharging were shown.

As shown in FIG. 4, the maximum specific capacity of the aluminum ion battery of Example 1 was 104 mAh / g, and that of the aluminum ion battery of Comparative Example 1 was 85 mAh / g.

5 is a graph showing the results of comparative measurement of the discharge capacities of the aluminum ion batteries of Example 1 (a) and Comparative Example 1 (b). In the case of the aluminum ion battery of Comparative Example 1, And the charging voltage (2.5 V) does not rise during the charging process after 200 cycles. As a result, it can be confirmed that the performance as a battery can not be performed. On the other hand, the aluminum ion battery a ), Stable operation of 400 cycles or more was confirmed without reducing the large discharge capacity.

In the case of the negative electrode material for a nonaqueous-based aluminum ion battery manufactured by the manufacturing method according to the present invention, the electrochemical reaction occurs preferentially in the etch pit where relatively few Al ₂ O ₃ oxide films (oxide layers) exist, While deposition and dissolution occur stably and repeatedly in this region during discharge, in the case of common aluminum cathodes, Al ₂ O ₃ And relatively dense film is formed in the oxide, is deposited and dissolved, depending on the charging and discharging proceeds, regardless of the specific point as Al ₂ O ₃ As the oxide film is preferentially involved in the electrochemical reaction in the thin layer, the charge voltage does not rise and the maximum cost amount is considered to be small.

FIG. 6 is a graph showing the voltage change with time of the aluminum ion battery of Example 1. As a similar graph form is repeated even when charge and discharge are repeated four times, the charge / discharge of the aluminum ion battery of Example 1 is reversible And it can be confirmed that it is reproducibly constant.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

1: working electrode 2: counter electrode
3: Thermometer 4: Magnetic bar
6: Temperature controller 8: Oscilloscope
9: computer 10: container
11: container lid 12: electrolyte
100: two electrode system

Claims (12)

A method for manufacturing a negative electrode material for a non-aqueous aluminum ion battery,
(a) pretreating aluminum foil;
(b) immersing the pretreated aluminum foil in an electrolytic solution, and applying an electric current to etch the aluminum foil; And
(c) washing and drying the etched aluminum foil.
The method according to claim 1,
Wherein the step (a) is carried out by immersing the aluminum foil in a pretreatment solution of 1 to 5 M for 30 seconds to 5 minutes to pre-treat the aluminum foil.
3. The method of claim 2,
Wherein the pretreatment solution is at least one selected from the group consisting of hydrochloric acid, hydrofluoric acid, sulfuric acid, silicofluoric acid, and caustic soda.
The method according to claim 1,
Wherein the etching in the step (b) is performed by immersing the pretreated aluminum foil as a working electrode in a container containing an electrolyte, and applying an alternating current.
5. The method of claim 4,
The current density upon application of the alternating current is 40 to 400 mA / cm &lt; ² &gt; , And the frequency is 0.1 Hz to 20 Hz.
The method according to claim 1,
Wherein the temperature of the electrolytic solution is 30 to 60 ° C and the etching time is 50 to 500 seconds.
The method according to claim 1,
Wherein the electrolytic solution is at least one selected from the group consisting of chromic acid (H ₂ CrO ₄ ), nitric acid (HNO ₃ ), hydrochloric acid (HCl) and sulfuric acid (H ₂ SO ₄ ) Gt;
The method according to claim 1,
Wherein the electrolytic solution contains 0.5 M to 5 M of hydrochloric acid and 0.005 to 0.05 M of sulfuric acid, and the volume ratio of hydrochloric acid and sulfuric acid is 1: 0.01 to 3. The method for manufacturing an anode material for a non-
The method according to claim 1,
Wherein the drying in step (c) is performed at room temperature in an inert atmosphere.
The method according to claim 1,
Wherein the aluminum foil has a purity of 99.00 to 99.99% and a thickness of 0.01 to 0.1 mm.
A negative electrode material for a nonaqueous-based aluminum ion battery, which is produced by the method for producing an anode material for a non-aqueous alkaline ion battery according to any one of claims 1 to 9 and has an etch pit formed on its surface.
12. The method of claim 11,
Wherein the etch pits have an average diameter of the grooves of 0.1 占 퐉 to 10 占 퐉.

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