KR20220052549A - Nano carbon battery for ESS wall and ESS wall comprising thereof - Google Patents

Abstract

The present invention relates to a nano-carbon battery for an ESS wall, and more specifically, to a nano-carbon battery for an ESS wall which has increased fire safety by including a negative electrode active material capable of controlling the crystal size of lead sulfate generated in a negative electrode during discharge, and an ESS wall including the same.

Description

Nano carbon battery for ESS wall and ESS wall including the same {Nano carbon battery for ESS wall and ESS wall comprising thereof}

The present invention relates to a nano-carbon battery for an ESS (Energy Storage System, ESS) wall and an ESS wall including the same, and more particularly, includes a negative electrode active material capable of controlling the crystal size of lead sulfate generated in the negative electrode during discharge Accordingly, it relates to a nano-carbon battery for an ESS wall with increased fire safety and an ESS wall including the same.

Lead-acid battery systems are mainly applied to automobiles because of their low cost and excellent safety. A lead-acid battery, which is a typical secondary battery, uses lead as an anode and lead having lead oxide on its surface as an anode, and has a structure in which the electrode is immersed in dilute sulfuric acid. When the lead-acid battery is discharged, lead (Pb) on the surface of the negative electrode reacts with sulfate ions to become lead sulfate (PbSO ₄ ) and emits electrons. After receiving this electron, lead oxide (PbO ₂ ) on the surface of the anode reacts with sulfuric acid to become lead sulfate. Through this reaction, current flows in the lead-acid battery. When charging a lead-acid battery, the reverse reaction occurs during discharging. Accordingly, the secondary battery has an advantage in that it can be used for a long period of time by repeating charging and discharging. However, when discharging the conventional lead-acid battery, lead sulfate is precipitated as particles in the active material at the positive and negative electrodes, and its solubility is low, so it easily grows into a crystalline state, and it gradually loses its activity and cannot be used. As the cycle progresses, it becomes a factor to degrade the performance during partial charging. In particular, lead sulfate formed on the negative electrode has a great effect.

On the other hand, an electrical double layer capacitor (EDLC) with excellent charge/discharge cycle is being developed as an alternative to lead-acid batteries, but low energy density and high price are a problem.

The Pb/C battery is a secondary battery system using a negative electrode manufactured by coating a carbon active material with a binder (PTFE, CMC, etc.) on a grid composed of lead components to overcome the disadvantages of lead-acid batteries. Generally, sulfuric acid is used as the electrolyte in Pb/C batteries, the positive electrode is a lead dioxide electrode like the positive electrode of a lead-acid battery, and the negative electrode is a capacitor electrode using activated carbon, so the electrode reaction occurring at both electrodes is as follows.

Anode: 1/2PbO ₂ + 1/2H ₂ SO ₄ + H ⁺ + e ^- ↔ 1/2PbSO ₄ + H ₂ O

Cathode: (C _s ^- //H ⁺ ) ↔ C _s + H ⁺ + e ^-

Total reaction: 1/2PbO ₂ + 1/2H ₂ SO ₄ + (C _s ^- //H ⁺ ) ↔ 1/2PbSO ₄ + H ₂ O + C _s

Here, C _s is a carbon atom on the electrode surface, // means a double layer of charges accumulated in each layer, and an electrode composed of activated carbon having a very high surface area (1500 m2/g) is formed from acid on the electrode surface layer. Protons, the resulting hydrogen cations, accumulate. That is, in the case of a battery-type lead dioxide electrode during charging and discharging, the charge moves through the paradoxical process and proceeds with oxidation and reduction reactions, whereas in the carbon electrode operated as a capacitor, the charge accumulates or discharges through a non-paradic process in the double layer. because it becomes

However, in the case of Pb/C batteries known so far, as with conventional lead-acid batteries, as well as the problem of gaps between the electrodes due to hydrogen gas generated by the electrochemical reaction (oxidation/reduction reaction) that occurs when the cell is driven, the generated PbSO ₄ Due to this, there is still a problem due to the volume change of the electrode active material, such as a pulsation phenomenon. That is, the larger crystal formation of PbSO ₄ in the negative electrode limits the long-life performance of the lead-acid battery system.

Therefore, there is a need for a new electrode active material capable of controlling the crystal size growth during lead sulfate production.

On the other hand, an energy storage system (ESS) refers to a system that increases energy efficiency by storing generated electricity in a storage device (battery, etc.) and supplying power when needed. Various ESS research is being conducted for stable power supply, and recently, research on ESS wall that can be used as interior and exterior materials of a building is being actively conducted without ESS in a separate space.

However, conventionally, the ESS wall has a lithium-based battery built-in as an energy storage device, and it is difficult to use stably as the risk of fire due to self-explosion and use management is very high due to the lithium-based battery. There is a problem that it is difficult to become.

Patent Publication No. 10-2018-0049607

It is an object of the present invention to provide a battery for an ESS wall including an anode active material that effectively controls the crystal size of lead sulfate generated during discharge and provides an increased Faraday electrochemical process.

Another object of the present invention is to include the above-described novel active material, so that during long-term operation, high-rate partial state of charge (HRPSoC) and high-capacity performance can be implemented, and ESS wall that can further improve charge/discharge capacity performance and provide long-life performance to provide batteries for

The object of the present invention is not limited to the object mentioned above, and even if not explicitly mentioned, the object of the invention that can be recognized by those of ordinary skill in the art from the description of the detailed description of the invention to be described later may also be included. .

The battery for an ESS wall according to the present invention includes a porous carbon material having a plurality of pores; and a negative electrode active material containing; and lead nanoparticles formed in the pores.

In the battery for an ESS wall according to an embodiment of the present invention, the porous carbon material may be any one or two or more selected from the group consisting of activated carbon, carbon nanotubes, and carbon nanofibers.

In the battery for an ESS wall according to an embodiment of the present invention, the specific surface area (BET) total pore volume of the activated carbon may be 0.1 m ³ /g to 2.0 m ³ /g.

In the battery for an ESS wall according to an embodiment of the present invention, the porous carbon material and the lead nanoparticles may be included in a ratio of 90:10 to 50:50.

In the battery for an ESS wall according to an embodiment of the present invention, the lead nanoparticles have a size of 1 to 1000 nm and may be uniformly supported on the porous carbon material.

The ESS wall according to the present invention includes the above-described battery for the ESS wall.

The present invention can effectively control the crystal size of lead sulfate produced during discharge and provide increased Faraday electrochemical performance.

In addition, the present invention can realize high-rate partial charge state (HRPSoC) and high-capacity performance during long-term operation by including the novel active material, further improve charge/discharge capacity performance, and provide long-life performance and high safety.

These technical effects of the present invention are not limited only to the range mentioned above, and even if not explicitly mentioned, the effect of the invention that can be recognized by those of ordinary skill in the art from the description of the specific content for the implementation of the invention to be described later is also of course included

1 is a schematic diagram schematically illustrating the structure of an ESS wall including a nano-carbon battery for an ESS wall according to an embodiment of the present invention.
2 is a schematic diagram showing a method for manufacturing an anode active material included in a battery for an ESS wall according to an embodiment of the present invention.
3 and 4 are graphs showing measurement results of specific surface area and pore size distribution of a negative active material included in a battery for an ESS wall according to an embodiment of the present invention.
5 is a high-resolution scanning electron microscope (HR-SEM) and energy dispersive X-ray spectroscopy (EDAX) of the negative active material included in the battery for the ESS wall according to an embodiment of the present invention is a graph showing the.
6 is a TEM photograph (a to h), STEM image (j), and EDX mapping (k carbon, l lead) result photograph of a negative active material included in a battery for an ESS wall according to an embodiment of the present invention.
7 is a graph showing the discharge performance characteristics at 1C rate in a nano-carbon battery (lead acid battery) containing an anode active material included in the battery for ESS wall according to an embodiment of the present invention.
8 is a nano-carbon battery (lead-acid battery) as a negative active material included in a battery for an ESS wall when the negative active material for a lead-acid battery according to an embodiment of the present invention is introduced and when activated carbon is introduced, performance at 0.05 and 0.1C rates; This is a comparison graph.

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 present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the description of the invention exists, but is not limited to one or more other It should be understood that this does not preclude the possibility of addition or presence of features or numbers, steps, operations, components, parts, or combinations thereof.

Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present invention. does not

In interpreting the components, it is construed as including an error range even if there is no separate explicit description. In particular, when the terms "about", "substantially", etc. of degree are used, they may be construed as being used in a sense at or close to the numerical value when manufacturing and material tolerances inherent in the stated meaning are presented. .

In the case of a description of a temporal relationship, for example, 'immediately' or 'directly' when a temporal precedence is described as 'after', 'following', 'after', 'before', etc. This includes cases that are not continuous unless this is used.

Hereinafter, the technical configuration of the present invention will be described in detail with reference to the accompanying drawings and preferred embodiments.

However, the present invention is not limited to the embodiments described herein, and like reference numerals indicate like elements in different forms.

The technical feature of the present invention is to improve the oxidation/reduction reversibility of lead sulfate to effectively control the crystal size of lead sulfate generated during discharge of a lead acid battery and to provide an increased Faraday electrochemical performance. is in

That is, when the negative electrode active material in which lead nanoparticles are introduced into the micropores of the carbon material is prepared by reducing the lead (Pb) precursor by inserting it into the micropores of the porous carbon material carrier, lead sulfate salt (PbSO ₄ ), provides increased Faraday electrochemical performance due to enhanced electrochemical activity in the interfacial reaction between lead (Pb) nanoparticles and a carbon material carrier, and nano-sized lead (Pb) is introduced. This is because higher electrical conductivity and electrochemically active surface area can be obtained due to the carbon material support structure.

The anode active material of the present invention includes a porous carbon material having pores; and lead nanoparticles formed in the pores.

Here, the porous carbon material is not limited as long as it is a porous carbon material having an empty space therein, but as an embodiment may be any one or two or more selected from the group consisting of activated carbon, carbon nanotubes, and carbon nanofibers. As an embodiment, when the porous carbon material is activated carbon, a plurality of nano-sized and meso-sized pores are formed, and the BET surface area is 200 m ² /g or more and the total BET pore volume may be 0.1 to 2.0 cm ³ /g. When the total BET pore volume is less than 0.1cm ³ /g, there is a problem that it is difficult to manufacture a high-capacity electrode material due to the low amount of metal oxide supported ^. Since the particles are formed, lead nanoparticles aggregate and the size exceeds 1000 nm, so the problem that the lead active material is converted to lead sulfate (PbSO ₄ ) in a typical discharge process and causes volume expansion cannot be improved. . As such, the coexistence of mesopores and micropores in porous carbon materials is a result of large and rapid ion transport and good for conductivity.

Lead nanoparticles are derived from a lead precursor such as lead nitrate (Pb(NO ₃ ) ₂ ) and can be uniformly supported inside the pores of the porous carbon material or formed by attaching to the outer surface of the porous carbon material. The size of the lead nanoparticles supported inside the pores of the or formed on the surface is controlled through the pore size of the porous carbon material, the content of the lead precursor, and the treatment method, and is formed in a size of 1 to 1000 nm.

As such, when the negative electrode active material includes the porous carbon material and the lead nanoparticles formed inside the pores and the size of the lead nanoparticles is less than 1000 nm, in a typical discharge process that occurs in the negative electrode of known lead acid batteries and Pb/C batteries Unlike lead active material, which is converted to lead sulfate (PbSO ₄ ) and causes a decrease in lifespan by causing volume expansion, the size of lead sulfate produced in the negative electrode can be controlled by preventing the formation of oxides of lead during nucleation and growth. By improving the oxidation/reduction reversibility of lead, the performance and lifespan of the battery can be greatly improved.

Accordingly, the negative active material of the present invention includes a porous carbon material and lead nanoparticles, and the porous carbon material and lead nanoparticles may be included in a weight ratio of 100:0 to 50:50. On the other hand, if the weight ratio of the porous carbon material to the lead nanoparticles is less than 90:10, the lead nanoparticles are not uniformly formed on the porous carbon material, so the capacity is low. This is because lead nanoparticles are aggregated to not only increase in size exceeding 1000 nm, but also decrease in homogeneity.

Next, the method for preparing an anode active material of the present invention includes the steps of preparing a carbon material dispersion solution by dispersing a porous carbon material having a plurality of pores in a solvent; an impregnation step of impregnating the pores of the carbon material with a lead precursor by adding a lead precursor to the carbon material dispersion solution; obtaining an anode active material by reducing the impregnated lead precursor to form lead nanoparticles in pores of the carbon material; and washing and drying the negative active material.

In the step of preparing the carbon material dispersion solution, the step of ultrasonicating with a stirrer may be further performed to disperse the porous carbon material to a nano size. Here, the porous carbon material may be activated carbon or carbon nanotubes, and in the case of activated carbon, it is obtained by activating at a temperature of 100-3000°C with any one of KOH, NaOH, and a combination thereof and then carbonizing it at a temperature of 300-900°C. can

The impregnation step includes the steps of adding a predetermined amount of lead precursor dropwise to the dispersion solution while first treating the carbon material dispersion solution with a stirrer and ultrasonic waves; and secondarily treating the dispersion solution in which the dropwise addition of the lead precursor is completed with a stirrer and ultrasonic waves to obtain a precursor solution. Here, the lead precursor is lead nitrate (Pb(NO ₃ ) ₂ ), lead sulfate (PbSO ₄ ), lead hydrochloride (PbCl ₂ ), lead acetate (Pb(CH ₃ COO) ₂ ), lead chromate (Pb(CrO ₄ ) ), lead bromate (PbBr ₂ ), and lead iodate (PbI ₂ ) may be any one selected from the group consisting of, the lead precursor added dropwise to the dispersion solution is dispersed in nano size through a stirrer and ultrasonication to form a porous carbon material. It may be formed in a state in which the nano-lead particles are supported in the pores. In addition, when the lead precursor is dispersed to a nano size through a stirrer and ultrasonic treatment as described above, the formation of nano lead particles mainly in the pores of the porous carbon material and on the surface can be minimized by controlling the content of the lead precursor. Furthermore, even if lead particles are formed on the surface of the porous carbon material, it is possible to prevent the formation of lead oxide during nucleation and growth during discharge, unlike conventional negative electrode active materials, because they are formed into nano lead particles through a stirrer and ultrasonic treatment.

The step of obtaining the anode active material includes cooling the precursor solution obtained in the impregnation step to 0 to 10°C; adding a reducing agent to the cooled precursor solution; heating and then stirring the precursor solution to which the reducing agent is added; After cooling the heated precursor solution to room temperature, tertiary treatment with a stirrer and ultrasonic waves; and maintaining and fixing the precursor solution tertiarily treated with a stirrer and ultrasonic waves at room temperature for a certain period of time.

Here, the reducing agent may be any known reducing agent, but as an embodiment, any one selected from the group consisting of sodium borohydride, iron(ii) sulfate, lithium aluminum hydride, metal salts, and sulfur compounds, and in the precursor solution 0.01-5M may be included. Through such a reduction process, it is possible to obtain the effect of producing Pb nanoparticles having a uniform distribution, that is, producing Pb nanoparticles having a uniform particle size.

The fixing step is performed at room temperature, atmospheric pressure, or vacuum conditions. When performed under vacuum conditions, the Pb particles are easily adsorbed into the pores of the porous carbon material to increase electrochemical activity, and solvent removal is easy in the active material manufacturing process.

A negative electrode comprising a negative electrode active material having the above-described configuration and a secondary battery to which the negative electrode is applied provided a higher discharge capacity (1.938 Ah at 0.05 C rate) than the conventionally known activated carbon having lead (Pb) particles. As such, the anode active material of the novel hybrid structure of the present invention controls the generation size of lead sulfate of a larger size, gives pseudocapacitance, high electrical conductivity, reduces electrochemical reaction resistance, and provides synergistic effects such as efficient storage capacity performance. can do.

In addition, the negative active material having the above-described configuration may be applied to a nano-carbon battery for an ESS (Energy Storage System, ESS) wall. Conventionally, the battery for the ESS wall is a lithium-based battery, and the risk of fire due to self-explosion and use management is high. However, the nano-carbon battery for ESS wall containing the anode active material of the present invention has enhanced fire safety so that it is possible to provide an ESS wall that can substantially replace the interior and exterior walls of buildings. The nano-carbon battery for ESS wall of the present invention may be a secondary battery, and may be the lead-acid battery and Pb/C battery described above as non-limiting examples.

1 is a schematic diagram of the ESS wall in which the nano-carbon battery for the ESS wall of the present invention is embedded is shown. Referring to Figure 1, the ESS wall of the present invention is equipped with a turbine generator capable of generating power inside the wall, a condenser for converting the produced DC current into AC, and a nano-carbon battery for the ESS wall capable of storing the converted AC current. However, it is not limited thereto, and the structure of the ESS wall known in the art is applicable. However, it is preferable to have fire safety by applying the battery for the ESS wall of the present invention instead of the battery for the conventional ESS wall. The ESS wall of the present invention may be capable of freely designing capacity and output through series-parallel connection of the nano-carbon batteries for the ESS wall of the present invention using a modular method.

[Example 1]

An anode active material was prepared by performing the following steps. Each process was performed in an inert gas atmosphere to avoid contamination.

1. Step of preparing a carbon material dispersion solution

Add 0.8 g of activated carbon P-60 (Hanil Chemical, Korea) to a 3-neck round-bottom flask containing 100 ml of deionized water. Activated carbon uniformly dispersed in deionized water was treated with a stirrer and ultrasonic wave (40 kHz) for 10 minutes to prepare a carbon material dispersion solution.

2. Impregnation step

Lead nitrate (Pb(NO ₃ ) ₂ ) was added dropwise over 20 minutes while continuously primary stirring and ultrasonication at room temperature so that the supported amount was 10% by weight in the prepared carbon material dispersion solution. Thereafter, the carbon material dispersion solution obtained by second stirring and ultrasonication of the carbon material dispersion solution for 30 minutes was cooled to 5°C.

3. Step of obtaining an anode active material

0.3M NaBH ₄ in 25 mL of deionized water was added dropwise to the carbon material dispersion solution. After complete addition of the reducing agent, the solution was heated to 80° C. and stirring was continued for 2 hours. After cooling to room temperature, the solution was stirred and sonicated for 15 min. The solution was then held stationary at room temperature for 12 hours.

4. Washing and drying steps

The solution was filtered, and the contained solid material (negative active material) was washed several times with deionized water and ethanol, and then dried in a hot air oven to obtain a negative electrode active material 1.

Here, the obtained negative active material 1 (Activated Carbon-lead(Pb) from 10%(Pb(NO ₃ ) ₂ )) is formed by inserting lead (Pb) nanoparticles into the micropores of activated carbon as shown in the schematic diagram in FIG. 2 . do.

[Example 2]

Anode active material 2 (Activated Carbon-lead(Pb) from 30%(Pb(NO ₃ ) ₂ )) was obtained.

[Example 3]

Anode active material 3 (Activated Carbon-lead(Pb) from 50%(Pb(NO ₃ ) ₂ )) was obtained.

[Experimental Example 1]

Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halenda (BJH) analysis of specific surface area (SSA) and pore volume for negative active materials 1 to 3 obtained in Examples 1 to 3 through nitrogen sorption (adsorption/desorption) isotherms ) method (ASAP 2020). The N ₂ adsorption/desorption isotherm curves for the negative active materials 1 to 3 are shown in FIG. 3 .

As shown in FIG. 3 , a hysteresis loop appeared for all negative active materials. A decrease in specific surface area was observed for all negative active materials. When the content of lead (Pb) nanoparticles was 0 (activated carbon), 10, 30, and 50 wt % (negative active materials 1 to 3), respectively, the specific surface areas were 1787 and 1669, respectively. , 1445 and 1305 m ² g ^-1 . As such, the specific surface area of the active material continuously decreases as the lead content is increased by inserting lead (Pb) nanoparticles into the micropores of the activated carbon. This is because nano-sized lead (Pb) particles were successfully inserted into the carbon pores.

[Experimental Example 2]

In order to determine whether lead (Pb) nanoparticles were supported and formed in the negative active materials 1 to 3 obtained in Examples 1 to 3, the total pore volume was measured by BJH analysis, and the results are shown in FIG. it was

As shown in Figure 4, when the content of lead (Pb) nanoparticles is 0 (activated carbon), 10, 30, and 50 wt% (cathode active materials 1 to 3), respectively, the total pore volume of the active material is 0.805, 0.759, 0.657 and 0.592 cm ³ g ^-1 . In the process of synthesizing the anode active material of the present invention, it can be seen that the pore volume of the activated carbon is continuously decreased because lead (Pb) nanoparticles are included in the pores.

[Experimental Example 3]

A high-resolution scanning electron microscope (HR-SEM) (SU-70, HITACHI) to confirm whether lead (Pb) nanoparticles were supported and formed in the pores inside the activated carbon of the negative active materials 1 to 3 obtained in Examples 1 to 3 and energy dispersive X-ray spectroscopy (EDAX), and the results are shown in FIG. 5 .

In FIG. 5, (a) shows SEM photos and EDAX results of activated carbon, and (b)-(d) shows SEM photos and EDAX results of negative active materials 1 to 3 obtained in Examples 1-3.

As shown in FIG. 5 , lead peaks were observed in the EDAX results of negative active materials 1 to 3 on which lead (Pb) nanoparticles were supported. In addition, it can be confirmed that the intensity of the Pb peak increases as the Pb content increases. As a result of synthesizing the anode active material of the present invention, it can be seen that the lead loading was successful.

In addition, as shown in FIG. 5, as a result of EDAX Mapping analysis, it can be observed that Pb nanoparticles are uniformly distributed and supported.

[Experimental Example 4]

A high-resolution transmission electron microscope (HR-TEM), a scanning transmission electron microscope (STEM) (TECNAI F20, Philips) and energy dispersive X-ray spectroscopy (EDAX) were performed, and the results are shown in FIG. 6 .

6 (a) and (b) show TEM micrographs of activated carbon. The microstructure of activated carbon showed a sheet-like shape, and it can be seen that it was composed of carbon nanosheets with a hollow microstructure.

6 (c) to (h) are TEM images of the negative active materials 1 to 3, showing lead (Pb) nanoparticles uniformly distributed on the large surface of the activated carbon and its pores. The Pb nanoparticles formed by being supported in the internal pores of activated carbon are in the nanoscale range (<5 nm) and have almost uniform sizes.

In FIG. 6 (i) is a high-magnification TEM image of the negative active material 2, showing that the lead (Pb) nanoparticles are uniformly dispersed and the particle size is less than 5 nm.

6 (j) to (l) show the EDX mapping analysis results for further confirmation of the homogeneous dispersion of the lead active material of the negative electrode active material 2. Through this, it was confirmed that the lead (Pb) nanoparticles were uniformly introduced into the activated carbon.

[Examples 4 to 6]

Anodes 1 to 3 were respectively prepared in the same manner, except that negative active materials 1 to 3 were changed as follows.

30 wt% of the negative active materials 1 to 3 prepared in Examples 1 to 3, and 2 wt% of the binder were mixed with 68 wt% of deionized water. The mixed solution was coated on a Pb anode and dried at room temperature for 3 days to prepare anodes 1 to 3.

[Example 7]

Two positive PbO ₂ electrodes and one negative electrode 1 prepared in Example 4 were assembled as a negative electrode to prepare a lead-acid battery 1 (Activated Carbon-Pb (derived from 10%(Pb(NO ₃ ) ₂ )). At this time, the anode and the cathode were separated by an absorbent glass fiber sheet (AGM), and diluted sulfuric acid (H ₂ SO ₄ , Sigma Aldrich, USA) having a specific gravity of 1.28 was used as an electrolyte.

[Example 8]

A lead acid battery 2 (Activated Carbon-Pb (derived from 30%(Pb(NO ₃ ) ₂ )) was prepared in the same manner as in Example 7, except that the negative electrode 2 obtained in Example 5 was used as the negative electrode.

[Example 9]

A lead acid battery 3 (Activated Carbon-Pb (derived from 50%(Pb(NO ₃ ) ₂ )) was prepared in the same manner as in Example 7, except that the negative electrode 3 obtained in Example 6 was used as the negative electrode.

[Experimental Example 5]

For the purpose of electrochemical characterization in order to optimize the introduction of lead (Pb) nanoparticles introduced into the internal pores of the porous carbon material in the negative electrode active material of the present invention, the discharge curves for the lead-acid batteries 1 to 3 obtained in Examples 7 to 9 observed and the results are shown in FIG. 7 . At this time, the lead-acid batteries 1 to 3 were charged and discharged at a rate of 1C. The charging and discharging performance of the lead-acid battery was evaluated in a McScience battery tester Q101 by applying a constant electrical load.

As shown in FIG. 7 , the battery discharge time according to the active material is different depending on the content of lead (Pb) nanoparticles supported on the activated carbon. That is, compared to lead-acid battery 1 in which anode active material 1 in which 10 wt% of lead (Pb) nanoparticles were supported on activated carbon was used and lead-acid battery 3 in which anode active material 3 in which 50 wt% of lead (Pb) nanoparticles were supported, 30 wt% was supported A higher discharge performance was observed in the lead-acid battery 2 in which the negative electrode active material 2 was used. That is, the discharge capacities of the lead-acid batteries 1 to 3 are 0.8395, 0.9601, and 0.8625 Ah at 1C rate, respectively.

[Experimental Example 6]

For performance analysis of the anode active material of the present invention, a negative electrode coated with activated carbon without Pb nanoparticles was compared and tested as follows. The performance test of the lead-acid battery unit cell test compares and analyzes the discharge performance of the anode coated with activated carbon and the lead-acid battery 2 through the charging (2.33V) and discharging (various C rates-0.05, 0.1, 0.2, 0.5 and 1) processes, and The results are shown in FIG. 8 .

As shown in FIG. 8 , it can be seen that the negative electrode coated with the negative electrode active material of the present invention provides a higher discharge capacity than the negative electrode coated with activated carbon. The discharge capacity of the battery to which the electrode coated with activated carbon was introduced was 1.783 Ah, and the battery assembled with the electrode to which the negative active material of the present invention was introduced exhibited a C-rate performance of 1.938 Ah at a rate of 0.05 C. The higher the C-rate, the higher the discharge capacity was obtained in the negative electrode including the negative electrode active material of the present invention.

Lead-acid battery performance is directly related to the surface and porous properties of the electrode material. Therefore, as is evident from the above experimental results, the negative active material of the present invention is formed by inserting Pb nanoparticles into the micropores of activated carbon through wet impregnation technology through ultra sonication, and this hybrid structure is the lead-acid battery performance implementation period It is expected to be a promising anode material for next-generation lead-acid battery systems, as it can act as a huge active site for electrochemical reaction progress regarding initial performance and long-term stability during the period.

[Example 10]

2V, 100Ah completed batteries were assembled with the cell configurations obtained in Examples 7 to 9. Each of the completed batteries was configured in series and parallel and fixed to the ESS wall. Specifically, in the case of a 2V, 100Ah battery, 12 cells were configured in series, and then an additional 12 cells were configured in parallel to complete a 24V, 200Ah battery system.

[Example 11]

The cell configuration obtained in Examples 7 to 9 was the same as in Example 10 except that the completed battery was 2V and 200Ah. Each of the completed batteries was configured in series and parallel and fixed to the ESS wall. Specifically, in the case of a 2V, 200Ah battery, 12 cells were configured in series and then an additional 12 cells were configured in parallel to complete a 24V, 400Ah battery system.

[Example 12]

The cell configuration obtained in Examples 7 to 9 was the same as in Example 10, except that the completed battery was 2V and 400Ah. Each of the completed batteries was configured in series and parallel and fixed to the ESS wall. Specifically, in the case of a 2V 400Ah battery, 12 cells were configured in series, and then additional 12 cells were configured in parallel to complete a 24V, 800Ah battery system.

[Example 13]

The cell configuration obtained in Examples 7 to 9 was the same as in Example 10 except that the completed battery was 2V and 2000Ah. Each of the completed batteries was configured in series and parallel and fixed to the ESS wall. Specifically, in the case of a 2V, 2000Ah battery, 12 cells were configured in series, and then an additional 12 cells were configured in parallel to complete a 24V, 4000Ah battery system.

[Example 14]

The cell configuration obtained in Examples 7 to 9 was the same as in Example 10 except that the completed battery was 12V and 100Ah. Specifically, in the case of a 12V, 100Ah battery, two cells were configured in series, and two additional cells were configured in parallel to complete a 24V, 200Ah battery system.

[Example 15]

The cell configuration obtained in Examples 7 to 9 was the same as in Example 10 except that the completed battery was 12V and 70Ah. Specifically, in the case of a 12V, 70Ah battery, two cells were configured in series, and two additional cells were configured in parallel to complete a 24V, 140Ah battery system.

[Example 16]

The cell configuration obtained in Examples 7 to 9 was the same as in Example 10 except that the completed battery was 12V and 60Ah. Specifically, in the case of a 12V, 60Ah battery, two cells were configured in series, and then two additional cells were configured in parallel to complete a 24V, 120Ah battery system.

As described in Examples 10 to 16, the nano-carbon battery for ESS Wall of the present invention enables free capacity and output design through series-parallel connection using a modular method.

Although the present invention has been illustrated and described with reference to preferred embodiments as described above, it is not limited to the above-described embodiments and those of ordinary skill in the art to which the present invention pertains within the scope of the present invention do not depart from the spirit of the present invention. Various changes and modifications will be possible.

Claims (6)

a porous carbon material having a plurality of pores; and
A battery for an ESS wall comprising an anode active material containing; lead nanoparticles formed in the pores. The method of claim 1,
The porous carbon material is any one or two or more selected from the group consisting of activated carbon, carbon nanotubes and carbon nanofibers. 3. The method of claim 2,
The battery for ESS wall, characterized in that the specific surface area (BET) of the activated carbon and the total pore volume is 0.1m ³ /g to 2.0m ³ /g. The method of claim 1,
The porous carbon material and the lead nanoparticles are in a weight ratio of 90:10 to 50:50
Battery for ESS wall, characterized in that it is included. 5. The method according to any one of claims 1 to 4,
The lead nanoparticles have a size of 1 to 1000 nm and a battery for an ESS wall, characterized in that it is uniformly supported on the porous carbon material. ESS wall comprising a battery for the ESS wall of any one of claims 1 to 4

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