Recharging the Future: Batteries Built for Extreme Cold Using Negative Thermal Expansion

Most solids expand as temperatures increase and shrink as they cool. Some materials do the opposite, expanding in the cold. Lithium titanium phosphate is one such substance and could provide a solution to the problem of steeply declining performance of lithium-ion batteries in cold environments. In the journal Angewandte Chemie, a Chinese team has demonstrated its suitability for use in electrodes for rechargeable batteries.

Temperatures Pose a Challenge for Lithium-Ion Batteries in Cold Environments

Lithium-ion batteries and other rechargeable batteries based on metal ions provide our portable devices with electricity, power vehicles, and store solar and wind energy. They work well—as long as it is warm. As temperatures drop, the performance of these batteries can decrease sharply—a problem for electric cars, aerospace, and military applications. Countermeasures such as integrated heaters, improved electrolytes, or electrode coatings increase the cost and complexity of battery production or reduce performance.

Teams Collaborate to formulate a Sustainable Approach Towards Temperature Sensitivity

One of the causes of the cold problem is the slowed diffusion of lithium ions within the electrode material. A team from Donghua University and Fudan University in Shanghai, as well as Inner Mongolia University in Hohhot has proposed a new approach to tackling this issue: electrodes made of electrochemical energy-storage materials with negative thermal expansion (NTE), such as lithium titanium phosphate LiTi₂(PO₄)₃ (LTP). Led by Liming Wu, Chunfu Lin, and Renchao Che, the team used LTP as a model substance to demonstrate that electrode materials with NTE properties can provide good performance at low temperatures.

Analysis of the crystal structure revealed a three-dimensional lattice of TiO₆ octahedra and PO₄ tetrahedra with an open, flexible structure that contains both “cavities” and “channels”, where lithium ions can lodge. When cooled, the structure stretches along one of its crystal axes. By using spectrometric and electron microscopic analyses in conjunction with computer modeling, the team determined that the vibrational modes of the atoms change at low temperature. This increases the occurrence of special transverse vibrations of certain oxygen atoms, increasing their distances from each other and widening the cavities in the lattice. This facilitates storage and transport of the lithium ions. At −10 °C, their diffusion rate is still at 84% of the value obtained at 25 °C. Electrochemical tests on carbon-coated LTP at −10 °C also showed good electrochemical performance with high capacity and a high rate capability, as well as a high retention of capacity over 1000 charge/discharge cycles.

An Apt Solution for Cold Environments

Materials with negative thermal expansion are thus highly promising for use as an electrode material in lithium-ion batteries in cold environments.

About the Author
Dr Chunfu Lin is an Associate Professor of Physics at Donghua University, and has been working in the area of energy storage and conversion for over 20 years.

Original Publication
Dr. Qiao Li, Dr. Liting Yang, Dr. Guisheng Liang, Dr. Jiahui Yu, Dr. Shaowu Huang, Prof. Liming Wu, Prof. Chunfu Lin, Prof. Renchao Che
Journal: Angewandte Chemie
Article Title: Negative Thermal Expansion Behavior Enabling Good Electrochemical-Energy-Storage Performance at Low Temperatures
Article Publication Date: 09 December 2024
DOI: https://doi.org/10.1002/anie.202419300

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