KR102580193B1 - Method for manufacturing anode active material for lead-acid battery using MXene - Google Patents

Abstract

The present invention relates to a method of manufacturing a negative active material for a lead acid battery using MXene powder. More specifically, the present invention relates to a method of manufacturing a negative active material for a lead acid battery using MXene powder, and more specifically, by adding MXene powder to the active material added to the negative electrode of a conventional lead acid battery, ion movement and surface chemical reaction between the electrolyte solution in the electrode plate and the interface of the active material. It relates to a method of manufacturing a negative active material for a lead acid battery using MXene powder, which can improve the basic performance and durability of a lead acid battery by increasing the internal electrical conductivity of the negative active material.
Through the present invention, the addition of Ti ₃ C ₂ MXene provides the effect of increasing the basic performance and charging efficiency of the lead acid battery by increasing the activation of ion movement and increasing the internal electrical conductivity of the negative electrode active material.

Description

Method for manufacturing anode active material for lead-acid battery using MXene}

The present invention relates to a method of manufacturing a negative active material for a lead acid battery using MXene powder. More specifically, the present invention relates to a method of manufacturing a negative active material for a lead acid battery using MXene powder, and more specifically, by adding MXene powder to the active material added to the negative electrode of a conventional lead acid battery, ion movement and surface chemical reaction between the electrolyte solution in the electrode plate and the interface of the active material. It relates to a method of manufacturing a negative active material for a lead acid battery using MXene powder, which can improve the basic performance and durability of a lead acid battery by increasing the internal electrical conductivity of the negative active material.

Currently, the lead acid battery active material mechanism adds polyester-based fiber to the active material to secure physical strength and a surface area for reaction with sulfuric acid.

Typically, polyester-based fibers with a fineness of 0.8 to 5 denier and a length of 1 to 10 mm are added to the lead acid battery active material, and these fibers have excellent acid resistance and oxidation resistance.

At this time, the organic synthetic short fibers added typically have a circular cross-section and are about 2 to 10 mm in length.

The ingredients of organic synthetic short fibers are mainly polypropylene, polyester, and modacrylic, which have excellent acid and oxidation resistance.

The prior art, Korean Patent Registration No. 10-0603908, “electrode plate for storage battery and method for manufacturing the same,” is to manufacture an electrode plate by attaching fiber-reinforced paper by applying pressure so that fiber filaments are embedded on the surface of the active material and filling the uneven portions of the surface with the active material. Disclose the method.

The above-mentioned conventional Korean registered patent relates to "electrode plates for storage batteries and their manufacturing method," in which an active material with electrochemical activity is applied to a substrate that serves as a passage for electricity to flow, and fiber-reinforced paper is applied to the surface of the active material. In the attaching or pressing step, pressure is applied so that the fiber filaments of the fiber-reinforced paper are embedded to a certain depth, and the surface irregularities of the fiber-reinforced paper are filled with the active material to increase the bonding surface area, thereby preventing the active material from being detached from the substrate. Technology that improves the initial high-rate discharge characteristics of the electrode plate due to the porosity of the fiber-reinforced paper and extends the life of the storage battery by retaining and supporting the active material due to the stable support and acid resistance of the fiber filament structure of the fiber-reinforced paper. It's about.

Until now, lead (Pb)-calcium (Ca)-tin (Sn) alloy has been used as the grid alloy for lead acid batteries, but this alloy composition alone cannot sufficiently respond to the harsh operating environment (high temperature and overcharge phenomenon), leading to corrosion or corrosion of the grid. It has been pointed out as a problem that the lifespan of lead acid batteries is shortening due to deformation due to growth.

Accordingly, there is a need to improve grid corrosion resistance, mechanical strength, and suppress growth deformation.

Meanwhile, the active materials of conventional lead acid batteries are generally based on lead powder and aqueous sulfuric acid solution, and other additives are mixed according to the characteristics of the anode and cathode and then mixed to make the active material.

The active material made in this way goes through a coating process, which is a process of applying it to a substrate, and then goes through a maturation process and drying process depending on the positive/cathode characteristics, and then multiple sheets of prepared positive and negative electrode plates are alternately overlapped to prevent electrical short-circuiting between the electrode plates. For this purpose, a non-conductive separator is installed so that the positive electrode plate, negative electrode plate, and separator plate form a group of electrode plates.

Several groups of electrode plates are connected in series according to the capacity of the storage battery and accommodated in the cell.

The received group of electrode plates undergoes a supercharged chemical process to obtain electrical properties. At this time, the active material of the positive plate is lead dioxide (PbO2), and due to its characteristics, countless fine particles of oxidized lead are combined, and the particles are rich in porosity. Electrolytes are allowed to freely diffuse and penetrate the liver.

In addition, the active material of the negative electrode plate is spongy lead (Pb), which is also rich in porosity and reactivity, allowing the electrolyte to freely diffuse and penetrate.

Only then can products made in this way become available on the market.

In addition, to facilitate the initial charging process and improve the durability of the product, separate aging and drying processes are performed for each polarity.

The aging process of the positive plate is an important process that increases the durability of the product. The hot temperature of steam (approximately 70 ~ 100℃) and moisture (humidity of 99% or more) convert lead (Pb), a component of the active material, into lead oxide (lead oxide). Not only does it change it to PbO), but it also changes the crystal structure of the active material.

If the negative electrode plate is left in natural conditions without any additional processing, it can be aged and dried at the same time.

However, if sufficient aging and drying are not achieved, the electrode plates stick together during the assembly process to form the electrode group, and the durability of the active material decreases due to the presence of moisture, so the active material embedded between the substrates easily falls off even with a small impact.

As the number of charging and discharging of a lead-acid battery made through this process increases, the active material falls off the substrate more easily due to the reaction between lead and sulfuric acid, and the fallen active materials can no longer participate in the reaction, ultimately leading to the breakdown of the lead-acid battery. By degrading performance, the lifespan of lead acid batteries is usually only 1 to 2 years.

Therefore, there is a need for a manufacturing process that can improve the durability and performance of lead acid batteries in line with the current demand for high-performance lead acid batteries.

As a conventional technology, 'Negative active material and its manufacturing method and lead acid battery' has disclosed a technology related to a negative electrode active material characterized in that lignin is added to lead powder.

However, it was difficult to expect the above technology to improve the lifespan of the active material.

Meanwhile, recent research literature on adding nanomaterials for the purpose of improving the performance of automobile starting and driving batteries can be found.

Targeted elements include carbon, nitrogen, TiO2, Graphene Oxide, PbO, and PbO2.

Among these, one of the purposes of adding carbon-based materials and carbon compounds (Activated Carbon, Carbon Black, CNT, Graphene, etc.) to lead-acid batteries such as AGM is to improve the lifespan of lead-acid batteries by suppressing the generation of PbSO4.

By applying this, N-doped carbon materials are added to lead-acid batteries and the lifespan of lead-acid batteries is improved by suppressing the generation of PbSO4 in lead-acid batteries. In addition, N-doped Graphene Oxide/PbO, etc. are added to lead-acid batteries and the remaining capacity of lead-acid batteries ( You can also check out separate research and development cases aimed at improving PSoC (Partial State of Charge) performance.

However, although the above-described technologies include technologies related to secondary battery anode materials containing carbon black, the development of composite anode materials with higher electrical conductivity and excellent mechanical strength and stability is still required.

Republic of Korea Patent Registration No. 10-0483246

Therefore, the present invention was devised to solve the above conventional problems,

The purpose of the present invention is to improve the ion movement and surface chemical reaction between the electrolyte and the active material interface in the electrode plate by adding Ti ₃ C ₂ MXene powder to the active material added to the negative electrode of a conventional lead acid battery, thereby improving the internal electrical conductivity of the negative electrode active material. The purpose of this study is to provide a method for manufacturing a negative active material for lead acid batteries using MXene powder, which can improve the basic performance and durability of lead acid batteries by increasing .

In order to achieve the problem to be solved by the present invention, a method for manufacturing a negative active material for a lead acid battery using MXene powder according to an embodiment of the present invention,

In the mixing process of negative active materials for lead acid batteries,

When mixing lead powder, sulfuric acid, and additives according to the negative electrode, Ti ₃ C ₂ MXene powder is added and mixed to distribute it in the negative electrode active material (S100);

The problem of the present invention is solved by including a natural aging and drying step (S200) for applying a negative electrode active material containing Ti ₃ C ₂ MXene powder to a substrate made of lead and then naturally maturing and drying it in the air. do.

Through the present invention's method of manufacturing a negative electrode active material for lead acid batteries using MXene powder, Ti ₃ C ₂ MXene powder is added to the active material added to the conventional lead acid battery negative electrode to improve ion movement and surface chemical reaction between the electrolyte solution in the electrode plate and the interface of the active material. By being able to do so, the internal electrical conductivity of the negative electrode active material is increased, thereby improving the basic performance and durability of the lead acid battery.

Specifically, the addition of Ti ₃ C ₂ MXene increases the activation of ion movement and increases the internal electrical conductivity of the negative electrode active material, providing the effect of increasing the basic performance and charging efficiency of the lead acid battery.

Figure 1 is a process diagram of a method for manufacturing a negative active material for a lead acid battery using MXene powder according to an embodiment of the present invention.
Figure 2 is a photograph showing Ti ₃ C ₂ MXene included in the present invention.
Figure 3 is a graph showing the durability evaluation between a lead acid battery manufactured by a method of manufacturing an anode active material for a lead acid battery using MXene powder according to an embodiment of the present invention and a conventional lead acid battery.

A method for producing a negative active material for a lead acid battery using MXene powder according to an embodiment of the present invention,

In the mixing process of negative active materials for lead acid batteries,

When mixing lead powder, sulfuric acid, and additives according to the negative electrode, Ti ₃ C ₂ MXene powder is added and mixed to distribute it in the negative electrode active material (S100);

After applying the negative electrode active material containing Ti ₃ C ₂ MXene powder to a substrate made of lead, a natural aging and drying step (S200) for natural aging and drying in the air.

At this time, the MXene powder mixing step (S100),

A basic anode active material mixing step of mixing 80 to 83 parts by weight of lead dust, 5 to 10 parts by weight of sulfuric acid, 10 to 15 parts by weight of water, and 1 to 3 parts by weight of anode additive based on the total weight of the anode active material;

To the mixture mixed in the basic anode active material mixing step, add 30 to 40 parts by weight of Ti ₃ C ₂ MXene powder based on the total weight of the mixture and stir at a temperature of 55 to 75 degrees to obtain a cathode active material with a density of 75 to 80 g/in ³ . It is characterized by including a MXene-added negative electrode active material acquisition step for.

At this time, the content of Ti ₃ C ₂ MXene powder in the negative electrode active material is,

It is characterized by adding 30 to 40 parts by weight based on 100 parts by weight of the negative electrode active material excluding Ti ₃ C ₂ MXene powder.

At this time, in the MXene powder mixing step (S100),

The addition of Ti ₃ C ₂ MXene powder increases the basic performance and durability of the lead acid battery by activating pores, increasing the reaction area with sulfuric acid, and increasing the internal electrical conductivity of the negative electrode active material.

At this time, by the method of manufacturing a negative active material for lead acid batteries using the MXene powder,

It can provide a 10% improvement from C20 70.1Ah without the addition of Ti ₃ C ₂ MXene powder to C20 77.8 Ah with the addition of Ti ₃ C ₂ MXene powder.

It is characterized in that _{it can provide a 3% improvement from EN CCA 7.31V without the addition of Ti 3 C 2} MXene powder to EN CCA 7.53V with the addition of Ti 3 C ₂ MXene powder.

At this time, it is possible to provide a lead-acid battery containing an electrode plate for a lead-acid battery to which a negative electrode active material for a lead-acid battery using Ti ₃ C ₂ MXene powder manufactured by the manufacturing method of the present invention is applied.

Hereinafter, the method for manufacturing a negative active material for a lead acid battery using MXene powder according to the present invention will be described in detail through examples.

Figure 1 is a process diagram of a method for manufacturing a negative active material for a lead acid battery using MXene powder according to an embodiment of the present invention.

As shown in Figure 1, the method for producing a negative active material for a lead acid battery using MXene powder of the present invention is,

In the mixing process of negative active materials for lead acid batteries,

When mixing lead powder, sulfuric acid, and additives according to the negative electrode, Ti ₃ C ₂ MXene powder is added and mixed to distribute it in the negative electrode active material (S100);

After applying the negative electrode active material containing Ti ₃ C ₂ MXene powder to a substrate made of lead, a natural aging and drying step (S200) for natural aging and drying in the air.

The present invention is a method of manufacturing a negative electrode active material for a lead acid battery using MXene powder. Ti ₃ C ₂ MXene powder is added to the active material added to the conventional negative electrode of a lead acid battery to improve ion movement and surface chemical reaction between the electrolyte solution in the electrode plate and the interface of the active material. This is a technology that improves the basic performance and durability of lead acid batteries by increasing the internal electrical conductivity of the negative electrode active material.

This is to improve the basic performance and charging efficiency of lead acid batteries by increasing the internal electrical conductivity of the negative electrode active material by using Ti3C ₂ MXene instead of the polyester-based fiber used conventionally.

As shown in FIG. 2, Ti ₃ C ₂ MXene described in the present invention is a two-dimensional plate-shaped nanomaterial with excellent electrical conductivity. When applied as an additive to the negative electrode active material of a lead acid battery, ion movement between the interface of the active material and the electrolyte solution or the surface occurs. Due to chemical reaction, faster charge and discharge performance can be expected compared to existing fibers.

Additionally, as the number of wearable electronic devices, mobile robots, and electric vehicles using energy storage devices increases, the demand for high-capacity energy storage devices is also increasing.

In particular, AGM lead acid batteries are attracting attention due to their high energy density and lifespan.

In the components of AGM lead acid batteries, electrodes are one of the key components to achieve high energy density, power density, and long-term use.

In general, graphite, which has a porous structure, is used in commercial lead-acid batteries due to its large surface area, high electrical conductivity, and excellent mechanical and chemical stability.

However, the theoretical electrical storage capacity of graphite is limited to 372 mAh/g.

For this reason, a transition metal carbide called MXene, which has high electric capacity, high hydrophilicity, and high electrical conductivity, is attracting attention as a promising anode active material.

MXene is synthesized by etching the A component layer from the MAX phase.

Here, MAX phase, M _n+1 AX _n (n = 1, 2, or 3), where M is a transition metal, A is a layer of IIIV or IVA component, and X means carbon or nitrogen.

When component A is etched, MXene _becomes M _{n +1}

Here, T _x refers to the functional group (-F, -O, -OH) generated during the synthesis process.

Among MXenes, titanium carbide (Ti ₃ C ₂ T _x ) was first synthesized in the laboratory of Yury Gogotsi by etching the Ti ₃ AlC ₂ MAX phase using hydrogen fluoride (HF).

MXene showed high electrical conductivity due to the presence of two layers of carbon atoms between three layers of titanium atoms, and its electrochemical properties can be controlled by adjusting the surface functional groups and the interlayer distance.

Additionally, surface functional groups affect the adsorption and insertion/desorption mechanisms of metal ions such as lithium, sodium, potassium, and magnesium.

This not only increases the active site where ions can react at the electrode of the lead acid battery, but also helps achieve high electric storage capacity.

There is also a synthetic method in which lithium fluoride and hydrochloric acid are used together instead of hydrogen fluoride for etching.

This method is mildetching and can synthesize MXene with larger flakes than when using HF.

Therefore, the electrical conductivity was recorded at 6,500 S/cm, which is about 6.5 times better than the electrical conductivity (1,000 S/cm) of the flake synthesized with HF, and the interlayer distance was larger.

As a result, MXene synthesized by mild etching is suitable for systems that require high electrical conductivity.

It is known that MXene's lithium ion storage mechanism involves etching the Al atomic layer and inserting/desorbing ions into the empty space.

MXene not only has an excellent structure, but also its functional groups affect electrochemical performance.

However, since the functional groups of synthesized MXene are not evenly distributed, it is important to completely remove the layer of component A from the MAX phase and synthesize the functional groups evenly dispersed.

By synthesizing functional groups evenly dispersed on the surface of titanium carbide through mild etching using lithium fluoride and hydrochloric acid, it is possible to provide electrochemical properties as a negative active material for lead acid batteries.

That is, when MXene is added, the fluorine group (-F) has high electronegativity when used as an electrode active material due to the functional groups (-O, -F, -OH) generated during the synthesis of MXene. It increases cycle stability by lowering the activation barrier for lithium ion hopping, and oxygen (-O) helps ions to be absorbed into the active material, increasing electric capacity.

Through this, Ti ₃ C _{2 T}

Therefore, it was confirmed through the following experiment that titanium-based MXene, Ti ₃ C _{2 T}

As a result, it was confirmed through experiments that the efficiency of the active material could be improved and the charging performance could be improved.

In order to provide the above functions, in the MXene powder mixing step (S100) of the present invention, when mixing lead powder, sulfuric acid, and additives according to the negative electrode, Ti ₃ C ₂ MXene powder is added and mixed to distribute within the negative electrode active material. This is the step.

In order to provide the effect of the present invention, the content of Ti ₃ C ₂ MXene powder in the negative electrode active material is,

It is characterized by adding 30 to 40 parts by weight based on 100 parts by weight of the negative electrode active material excluding Ti ₃ C ₂ MXene powder.

Specifically, the MXene powder mixing step (S100),

A basic anode active material mixing step of mixing 80 to 83 parts by weight of lead dust, 5 to 10 parts by weight of sulfuric acid, 10 to 15 parts by weight of water, and 1 to 3 parts by weight of anode additive based on the total weight of the anode active material;

To the mixture mixed in the basic anode active material mixing step, add 30 to 40 parts by weight of Ti ₃ C ₂ MXene powder based on the total weight of the mixture and stir at a temperature of 55 to 75 degrees to obtain a cathode active material with a density of 75 to 80 g/in ³ . It includes a step of obtaining a MXene-added negative electrode active material.

If the weight part of the added MXene powder is less than 30 parts by weight, the electrical conductivity of the electrode plate is similar to the conventional one, so it is a small amount where it is difficult to expect performance improvement, and if it exceeds 40 parts by weight, the lifespan is reduced, as proven in accelerated life tests. It is difficult to expect more than 40 parts by weight of the cycle, and it only serves to increase the price.

Therefore, it would be desirable to add MXene powder within the above range.

In addition, the natural aging and drying step (S200) is a process of applying a negative electrode active material containing Ti ₃ C ₂ MXene powder to a substrate made of lead and then naturally maturing and drying it in the air.

That is, a certain amount of a negative electrode active material containing highly conductive MXene is evenly spread on a lead substrate, and then it is naturally aged and dried in the air for 2 to 3 days.

As described above, in order to determine the effect of the present invention, the organic synthetic short fibers previously used when mixing active materials were replaced with highly conductive MXene and added at the same weight ratio to manufacture electrode plates, and then aged through an aging process, and then the basic performance was measured. and life tests were conducted.

The conventional product described below refers to a product manufactured using a negative electrode plate applied after including organic synthetic short fibers in the active material used in the lead acid battery (BX80) manufactured by the applicant, and the improved product is manufactured through the manufacturing method of the present invention. This refers to a product containing electrode plates for lead acid batteries using highly conductive MXene.

In addition, through subsequent processes such as assembly and chemical conversion to impart electrical conductivity to the substrate, a conventional product (containing organic synthetic short fibers) and an improved product (containing high conductivity MXene) with a final capacity of 70 Ah (20 hour rate capacity) are produced. ) was produced, and charge acceptability and 50% DoD durability tests were conducted to prove the effectiveness of the highly conductive MXene.

1) Charge Acceptance test (CA: Charge Acceptance test)

A fully charged sample is discharged for 2.5 hours at room temperature (25±2℃) at a 5-hour rate current (17.5A based on 70Ah), and then left at 0±2℃ for more than 12 hours.

Afterwards, charge it at a constant voltage of 14.4V±0.1V and measure the current at 10 minutes of charging.

As a result of the test, it was found that the battery conductivity and charging efficiency were high, and the current of the improved product increased by 17% in about 10 minutes compared to the conventional product.

division hour Conventional products improvement




Charge income 1 min 27.25 28.67 2 minutes 24.21 26.28 3 minutes 22.14 24.83 4 minutes 21.25 23.72 5 minutes 20.11 21.89 6 minutes 19.35 20.81 7 minutes 18.74 19.36 8 minutes 17.68 19.89 9 minutes 17.04 19.67 10 minutes 16.43 19.29

Organic synthetic short fibers are added to the active material for the purpose of increasing the mechanical strength of the battery active material.

Considering acid resistance to sulfuric acid aqueous solution, which is an electrolyte, polypropylene, polyester, and modacrylic series are used as materials.

The organic synthetic short fibers used have a circular cross-section, which is the specification of a typical synthetic short fiber produced by direct spinning, a fineness of 2 to 5 denier (diameter is about 12 to 20 micrometers), and a length of 2 to 20 micrometers. It's 10 millimeters.

The amount added during mixing is 0.1 to 0.5 wt%, which improves the mechanical strength of the final electrode active material and suppresses the phenomenon of destruction of the active material structure due to contraction and expansion of the active material due to vibration and charging and discharging.

However, in the case of the organic synthetic short fibers, problems have arisen in providing performance in the current 4th industrial environment of automobiles and other industries that require increasingly higher basic performance.

Therefore, in order to improve this problem, in the present invention, highly conductive MXene with excellent electrical conductivity was used.

This highly conductive MXene is a two-dimensional plate-shaped nanomaterial with excellent electrical conductivity, as shown in Figure 2. By increasing the ion movement activation and reaction area with sulfuric acid compared to existing fibers, it can bring about high output and improved life expectancy, ultimately It improves the basic performance and lifespan of the battery.

Therefore, highly conductive MXene having the above-mentioned characteristics was introduced in the present invention, and by using highly conductive MXene as an additive to the negative electrode active material, ion movement between the interface between the active material and the electrolyte solution, maximization of the surface chemical reaction area, and electrical conductivity were achieved. It provides an increasing effect.

Experimental data for this will be described later.

2) 20 hour rate capacity (AH)

This is to determine the low-rate discharge characteristics, by continuously discharging at 3.75A, which is a relatively small current for the storage battery capacity, and measuring the discharge capacity (AH) until the voltage reaches 10.5V.

division Req Conventional products improvement C20 70Ah 70.1Ah 77.8Ah

As a result of the test, it showed an 11% performance improvement compared to the existing product at 77.5 Ah, showing that the active material for lead acid batteries using MXene had a positive effect on the 20 hour rate capacity (AH).

3) Cold Cranking Ampere (CCA: Cold Cranking Ampere)

In general, the rapid discharge characteristics of storage batteries rapidly deteriorate below -10℃. Cold starting current (CCA) is a high-rate discharge test to evaluate automobile starting ability at low temperatures. After full charge, the battery's rapid discharge characteristics decrease rapidly at -10℃ and below. Measure the voltage during super discharge.

In this test, the voltage for 30 seconds is required to be 7.5V or higher, and the higher the voltage, the better the performance.

division Req Conventional products improvement EN CCA 7.5V 7.31V 7.53V

As shown in Table 3, the 30-second voltage was 7.53V, showing a 3% performance improvement compared to existing products, showing that the active material for lead-acid batteries using MXene had a positive effect on low-temperature starting current. I could see that it had been given.

4) Accelerated life test (SAE J2801)

The lead acid battery is subjected to 34 charge/discharge cycles in a water bath at 75°C for approximately one week, similar to typical vehicle conditions.

After performing 34 cycles, the life test is conducted by discharging at 200A for 10 seconds, and if the voltage is maintained above 7.2V, the cycle is repeated 34 times.

Additionally, the test is stopped if the charging current rises above 15A or the discharge voltage falls below 12.0V during the cycle.

Table 4 below shows the results of the SAE J2801 test, showing the voltage when discharged at 200A for 10 seconds for every 34 charge/discharge cycles.

cycle Maxine 0
weight part maxine 20
weight part maxine 30
weight part maxine 40
weight part maxine 50
weight part 34 11.82 11.83 11.85 11.87 11.89 68 11.76 11.77 11.80 11.83 11.87 102 11.72 11.73 11.78 11.80 11.84 136 11.69 11.70 11.76 11.79 11.82 170 11.65 11.69 11.74 11.77 11.80 204 11.55 11.65 11.69 11.70 11.76 238 11.43 11.47 11.60 11.63 11.70 272 7.2 and below 7.2 and below 11.49 11.55 11.65 306 7.2 and below 11.50 11.55 340 7.2 and below 7.2 and below

As shown in Table 4 above, the test results show that when high conductivity MXene is not added and when 20 parts by weight is added, the lifespan is 238 cycles, but when 30 parts by weight is added, the lifespan is 272 cycles, and when 40 parts by weight is added, the lifespan is 238 cycles. It was possible to provide a 28.5% lifespan improvement with 306 cycles.

However, it can be seen that even with the addition of highly conductive MXene in excess of 40 parts by weight, the lifespan does not increase further at 306 cycles. Accordingly, the most optimal condition among 30 parts by weight and 40 parts by weight is 40 parts by weight, so the above range It is preferable to add it within.

This appears to be the result of improved electrical conductivity between active materials, lowering electrical resistance, and increased ion movement activation, which increases charging efficiency and reduces the sulphation content accumulated in the active material.

In other words, it showed a 28.5% improvement in lifespan compared to conventional products, showing that the addition of highly conductive MXene had a positive effect on increasing the lifespan.

5) Durability evaluation (50% DoD)

As a result of conducting a durability evaluation on the conventional product and the improved product, it was found that the improved product showed a durability of 118% based on 100% of the conventional product, so it could provide an 18% durability improvement.

That is, as shown in Figure 3, durability was improved by 18% compared to the conventional product, indicating that the addition of highly conductive MXene had a positive effect on increasing durability.

Through the above manufacturing method, it is possible to improve ion movement and surface chemical reaction between the electrolyte solution in the electrode plate and the active material interface by adding Ti ₃ C ₂ MXene powder to the active material added to the negative electrode of a conventional lead acid battery, thereby improving the negative electrode active material. By increasing internal electrical conductivity, the basic performance and durability of the lead acid battery are improved.

Those skilled in the art to which the present invention pertains as described above will understand that the present invention can be implemented in other specific forms without changing its technical idea or essential features. Therefore, the embodiments described above should be understood in all respects as illustrative and not limiting.

S100: Maxine powder mixing step
S200: Natural ripening and drying stage

Claims (5)

In the method of manufacturing a negative active material for a lead acid battery using MXene powder,
In the mixing process of negative active materials for lead acid batteries,
When mixing lead powder, sulfuric acid, and additives according to the negative electrode, Ti ₃ C ₂ MXene powder is added and mixed to distribute it in the negative electrode active material (S100);
After applying the negative electrode active material containing Ti ₃ C ₂ MXene powder to a substrate made of lead, a natural aging and drying step (S200) for natural aging and drying in the air,
The MXene powder mixing step (S100),
A basic anode active material mixing step of mixing 80 to 83 parts by weight of lead dust, 5 to 10 parts by weight of sulfuric acid, 10 to 15 parts by weight of water, and 1 to 3 parts by weight of anode additive based on the total weight of the anode active material;
40 parts by weight of Ti ₃ C ₂ MXene powder was added to the mixture mixed in the basic anode active material mixing step, based on 100 parts by weight of the mixture, and stirred at a temperature of 55 to 75 degrees to obtain a negative electrode active material with a density of 75 to 80 g/in ³ . Characterized by comprising a step of obtaining an added negative electrode active material,
In the MXene powder mixing step (S100),
The addition of Ti ₃ C ₂ MXene powder increases the basic performance and durability of the lead acid battery by activating pores, increasing the reaction area with sulfuric acid, and increasing the internal electrical conductivity of the negative electrode active material.
By the method for producing a negative active material for lead acid batteries using the MXene powder,
It is characterized in that it can provide a 10% improvement from C20 70.1 Ah when Ti ₃ C ₂ MXene powder is not added to C 20 77.8 Ah when Ti ₃ C ₂ MXene powder is added.
It is characterized in that it can provide a 3% improvement from EN CCA 7.31V when Ti ₃ C ₂ MXene powder is not added to EN CCA 7.53V when Ti ₃ C ₂ MXene powder is added.
When Ti ₃ C ₂ MXene powder is not added, the chargeability is characterized as being able to provide a 17% improvement from 16.43 to 19.29 when Ti ₃ C ₂ MXene powder is added.
Lead using MXene powder, which provides a 28.5% lifespan improvement from 238 cycles when Ti ₃ C ₂ MXene powder is not added to 306 cycles when 40 parts by weight of Ti ₃ C ₂ MXene powder is added. Method for manufacturing anode active material for storage battery.
delete delete delete By the manufacturing method of claim 1,
A lead-acid battery containing an electrode plate for a lead-acid battery using a negative electrode active material for a lead-acid battery using Ti ₃ C ₂ MXene powder.