What Roles does Zirconia Play in Batteries?

- Sep 30, 2022 -

What is zirconia?

Zirconium dioxide is the main oxide of zirconium, usually white odorless and tasteless crystal, insoluble in water, hydrochloric acid and dilute sulfuric acid.


It is chemically inactive, and has the properties of high melting point, high hardness, high refractive index and low thermal expansion coefficient, which makes it a very important high temperature resistant material and ceramic material.


In recent years, with the rapid development of lithium battery and the in-depth study of solid oxide fuel cell, the application potential of zirconia in battery has been continuously developed. it plays an important role in the electrolyte, electrode material and diaphragm material of the battery.


Electrolyte

Solid oxide fuel cell (SOFC) is an efficient and clean energy conversion system, which can directly convert the chemical energy of fuel gas and oxidation gas into electrical energy, and has the advantages of high power generation efficiency, short start-up time, fast response speed, small size, low pollution, easy assembly and maintenance, etc., and is regarded as an efficient, energy-saving and environment-friendly power generation technology after hydropower, thermal power generation and nuclear power generation.


The development and application of SOFC has become a research hotspot in the field of new materials and new energy.


In SOFC, the selection and preparation of electrolytes is one of the most important links.

SOFC requires electrolytes to have high ionic conductivity (0.1S/cm), low electron transfer number (< 10-3), chemical stability with electrode materials, oxygen and gas, thermodynamic stability in a wide range of temperature and oxygen partial pressure, matching with other battery modules in thermal expansion coefficient, good air tightness and suitable mechanical properties.


These performance requirements limit the selection of electrolyte materials, which are currently limited to oxide-based ceramic materials.


Cubic zirconia has good oxygen ion transport properties at high temperature and can be used as solid electrolyte in SOFC.


Zirconia-based electrolyte is a kind of high temperature electrolyte, and high operating temperature can easily cause some problems, such as electrode sintering, mutual diffusion of battery module materials at the interface, thermal expansion mismatch, rapid aging of performance and so on.


Reducing the thickness of the electrolyte can reduce the ohmic loss of the battery, so the use of zirconia-based electrolyte film is an effective way to reduce the battery operating temperature and maintain high performance.


Cathode material additive.

In recent years, nano-zirconia has been used as an additive in ternary materials such as nickel-cobalt lithium manganate Li (NiCoMn) O2, lithium cobalt oxide (LiCoO2), lithium manganate (LiMn2O4) and other lithium battery cathode materials, which can significantly improve the cycle performance and rate performance of lithium batteries.


It is found that the discharge specific capacity of ZrO2-doped electrode materials increases obviously, which may be related to the smaller particle size of ZrO2-doped materials. When the particle size becomes smaller, it is easier to deintercalate the material in the process of charge and discharge, so the discharge specific capacity of the doped materials increases.


With the progress of charge and discharge, a certain amount of doped ion Zr4+ may migrate to the surface of the electrode and form a solid solution, which prevents the structure collapse caused by the change of anisotropic structure during charge and discharge. At the same time, the solid solution acts as a protective coating to prevent cobalt from dissolving into the electrolyte, so the material structure becomes very stable during the phase transition and the cycle stability is enhanced.


In addition, the addition of ZrO2 to the positive electrode of Ni-MH battery can restrain the decrease of positive capacity at high temperature, and with the increase of ZrO2 content, the high-temperature performance of the electrode is also improved, thus improving the charging efficiency of the battery at high temperature.


Diaphragm material

As an important component of lithium-ion battery, diaphragm accounts for about 30% of the cost of lithium-ion battery.

The main function of the diaphragm is to separate the positive and negative electrodes of the battery and to insulate the electrons, so as to prevent the battery from short circuit caused by direct contact between the positive and negative electrodes or the occurrence of electron conduction.


Secondly, the diaphragm allows lithium ions to pass through freely to complete the charge and discharge of the battery.


Therefore, the diaphragm not only affects the discharge performance and capacity of the battery, but also has a close relationship with the safety performance of lithium-ion battery.


In addition, the diaphragm also has a self-closing effect, which can protect the battery to a certain extent from fire or explosion when the temperature rises and the current is too large.


Zirconia fiber can effectively improve the thermal stability of the diaphragm and the wettability of the electrolyte, and enhance the safety and discharge performance of the battery. 


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