The microscopic mechanism of vulcanization failure of lead-acid batteries was analyzed from the phenomenon of electrochemical oscillation

Analysis of lead-acid battery vulcanization failure from electrochemical oscillation phenomenon

Time：2025-03-15 10:19:47

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In recent years, starting from the electrochemical oscillation phenomenon, researchers have opened up a new path for in-depth analysis of the microscopic mechanism of lead-acid battery vulcanization failure.

In the field of energy storage, lead-acid batteries, with their advantages of low cost and mature technology, are widely used in automotive startup, backup power supply and other scenarios. However, the problem of vulcanization failure is always the key factor restricting its service life and performance. In recent years, starting from the electrochemical oscillation phenomenon, researchers have opened up a new path for in-depth analysis of the microscopic mechanism of lead-acid battery vulcanization failure, which is expected to provide theoretical support for extending the life of lead-acid batteries and improving their stability.

## Overview of lead-acid battery basics and vulcanization problems

The working principle of the lead-acid battery is based on the positive and negative active substance lead dioxide and the complex electrochemical reaction between lead and sulfuric acid electrolyte. In the process of charge and discharge, the positive and negative electrodes undergo REDOX reaction respectively to realize the mutual conversion of electric energy and chemical energy. Under normal circumstances, the negative lead loses electrons to lead sulfate when discharging, and lead sulfate is reduced to lead when charging. However, when the battery is in poor use conditions, such as long-term undercharge, overdischarge or working in a high temperature environment, the negative surface will gradually form a layer of dense and difficult to reduce lead sulfate crystals, which is the so-called "vulcanization" phenomenon. Once the vulcanization occurs, the internal resistance of the battery increases, the capacity decreases sharply, and eventually the battery fails, which greatly limits the practical application and economy of the lead-acid battery.

## Electrochemical oscillations: A window into the microscopic world

Electrochemical oscillation refers to the phenomenon that electrochemical parameters such as electrode potential and current change periodically and regularly with time in some electrochemical systems. In the lead-acid battery system, this oscillation is not a simple interference signal, but reflects the dynamic balance changes of material transport, charge transfer and interface reaction during the complex chemical reaction inside the battery. When the battery is in normal working state, its internal electrochemical reaction is relatively stable, and the fluctuation of each parameter is small. However, with the development of vulcanization trend, the characteristics of electrochemical oscillation began to change significantly. Through high-precision electrochemical testing instruments, these subtle changes can be captured and used as clues to delve into the microscopic world inside the battery.

## The microscopic mechanism of vulcanization is analyzed from the oscillation characteristics

### Mass transport and concentration oscillations

In lead-acid batteries, the transport of sulfate ions between electrolyte and electrode interface is very important for electrochemical reaction. When the battery begins to appear vulcanization tendency, the gradual accumulation of lead sulfate crystals on the negative electrode surface changes the microscopic environment near the electrode. In the process of diffusion to the negative surface, sulfate ions are hindered by the crystal layer of lead sulfate, causing the concentration distribution to oscillate in space and time dimensions. This concentration oscillation further affects the electrochemical reaction rate because the electrochemical reaction rate is closely related to the reactant concentration. For example, when the concentration of sulfate ions is locally reduced, the forward reaction rate of the negative reaction is slowed down, and the reduction reaction during reverse charging is also inhibited, making it difficult for lead sulfate to be completely converted back to lead, accelerating the process of vulcanization.

### Charge transfer and potential oscillation

With the development of vulcanization, the charge transfer process inside the battery is also seriously disturbed, which is directly reflected in the oscillation of the electrode potential. In normal lead-acid batteries, the electrode potential is in a relatively stable range, reflecting a stable electrochemical balance between the positive and negative electrodes. However, the vulcanization results in the change of the surface state of the negative electrode, the decrease of its electron conduction ability, and the transfer of charge between the electrode and the electrolyte interface becomes not smooth. This makes the electrode potential fluctuate, and this fluctuation shows a specific periodicity. The results show that the frequency and amplitude of potential oscillation are closely related to the degree of vulcanization. When the vulcanization is more serious, the amplitude of potential oscillation increases and the frequency decreases, which means that the obstruction of the charge transfer process inside the battery is intensified, and the internal resistance of the battery is significantly increased, thus affecting the overall performance of the battery.

### Interface reaction kinetics and oscillation coupling

The electrochemical reaction of lead-acid battery mainly occurs at the interface between electrode and electrolyte, and vulcanization has a profound effect on the kinetics of this interface reaction, and forms a complex coupling relationship with electrochemical oscillation. Under normal conditions, the active site on the electrode surface can effectively adsorb and catalyze electrochemical reactions. However, with the covering of lead sulfate crystals on the negative electrode surface, the active site gradually decreases and the reaction kinetics changes. The newly formed Pb sulfate crystals change the physicochemical properties of the interface, which increases the activation energy and decreases the reaction rate constant. This change leads to the electrochemical reaction is no longer stable, but interacts with the material transport and charge transfer process, and jointly causes electrochemical oscillations. For example, at a certain moment, due to local changes in material transport, the reaction rate of a region on the electrode surface is accelerated, more lead sulfate is produced, and the charge distribution and potential of the region are further changed, which in turn affects the subsequent material transport and reaction rate, and so on, forming a continuous electrochemical oscillation. This process is a microscopic portrayal of the continuous development of vulcanization and the gradual deterioration of battery performance.

Research progress and future prospects

At present, researchers have used a variety of advanced in-situ testing technologies, such as in-situ electrochemical scanning tunneling microscopy and in-situ Raman spectroscopy, to combine the electrochemical oscillation phenomenon with the internal microstructure changes of lead-acid batteries to deeply explore the microscopic mechanism of vulcanization failure. These studies have achieved initial results, providing a more intuitive and accurate microscopic image for understanding the vulcanization process of lead-acid batteries. In the future, based on the in-depth understanding of the electrochemical oscillation phenomenon and the microscopic mechanism of vulcanization, it is expected to develop new battery management strategies and repair technologies. For example, the use of specific frequency of electrochemical excitation signals to interfere with or regulate the electrochemical oscillation inside the battery, inhibit the development of vulcanization; Or real-time monitoring of the degree of battery vulcanization according to the oscillation characteristics, maintenance measures are taken in advance to extend the service life of lead-acid batteries, and further tap the potential of lead-acid batteries in the field of energy storage, so that they continue to play an important role in the future energy landscape.

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