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With the rapid development of portable electronic devices and electric vehicles, people are not only pursuing larger capacity and faster charging and discharging speed of lithium batteries, but also more concerned about how to ensure the safety of lithium battery use. Due to occasional incidents such as lithium battery explosions, one's nerves are inevitably tense. The prerequisite for solving the safety issues of lithium batteries is for scientists to have a thorough and comprehensive understanding of the causes of lithium battery explosions.

The current scientific explanation is that lithium deposition on the electrode surface will form dendrites, which will continue to grow, causing internal short circuits in the battery, leading to battery failure or potential fire hazards. But in the past, there was a lack of effective technical means to understand and study from the perspective of atomic structure, and then find solutions to problems.

The cryo EM technology, which won the 2017 Nobel Prize in Chemistry this month, provides strong technical support for this. The research team led by Professor Cui Yi from Stanford University and the SLAC National Accelerator Laboratory directly under the US Department of Energy, as well as Nobel laureate Steven Chu in 1997, captured the first image of atomic level lithium metal dendrites using cryo electron microscopy (cryo EM). The research findings were published in the international academic journal Science on October 27th local time.

Each lithium metal dendrite is a long, perfectly formed hexagonal crystal. Previously, only irregularly shaped crystals were observed through electron microscopy. Cui Yi said, "The research results are very exciting and have opened up a new era for related research!"

Cryoelectron microscope, as the name suggests, is a microscopic technique that uses cryofixation to observe samples at low temperatures using a Transmission Electron Microscope (TEM). Cryoelectron microscopy is an important structural biology research method and a crucial means of obtaining the structure of biomolecules.

Because images are the key to understanding mechanisms, scientific breakthroughs often rely on using the naked eye to successfully obtain the visual image of the target. For a long time, it has been believed that TEM is not suitable for observing biomolecules because powerful electron beams can damage biological materials. However, the emergence of cryo electron microscopy has enabled researchers to "freeze" biomolecules and observe and analyze their motion processes unprecedentedly. These characterizations have a decisive impact on the understanding of biochemistry and the development of pharmacology. Therefore, cryo electron microscopy will also be included in this year's Nobel Prize in Chemistry.

Left image: In the TEM image at room temperature, lithium dendrites are corroded due to exposure to air, and electron beams melt a large number of pores on them; Right image: Image under cryo EM, with its original state preserved in a frozen environment, indicating the presence of crystal nanowires with clear interfaces.

For materials such as lithium, it is also not possible to use a projection electron microscope to view results at the atomic level of dendrites. Similar to biomaterials, when using TEM at room temperature, the edges of dendrites will curl or even melt due to electron beam impact. Yanbin Li, a doctoral student from Stanford University who participated in this work, said, "The preparation of transmission electron microscopy samples is done in air, but lithium metal will quickly corrode in the air." "Whenever we try to observe lithium metal under a high-power electron microscope, electrons will 'drill holes' in the dendrites and even completely melt it."

Yanbin Li, a PhD student from Stanford University who participated in this study, said, "It's like shining a magnifying glass on a leaf in sunlight. However, if you can cool the leaf, this problem will be solved easily: if you focus light on the leaf, the heat will also be lost, and the leaf will not be damaged. This is what we can achieve with a cryoelectron microscope, and the difference in imaging when using battery materials is very obvious."

So, cryo electron microscopy not only ushered in a new era in biochemistry, but also allowed scientists to see the complete structure of lithium dendrites at the atomic level for the first time. Researchers also found that dendrites in carbonate based electrolytes grow in a specific direction into single crystal nanowires. Some of them may experience knotting during the growth process, but their crystal structure remains intact.

Yuzhangli, another Stanford University doctoral student who participated in this research, said that the solid electrolyte interface facial mask (SEI) could also be seen, and also revealed different SEI nanostructures formed in different electrolytes. Because the same coating also forms on the metal electrode when the battery is charged and discharged, controlling its generation and stability is crucial for the efficient utilization of the battery.

Using cryo EM, scientists can observe how electrons eject from atoms in dendrites, revealing the position of individual atoms (left figure). Scientists can even measure the distance between atoms (top right), and the atomic spacing precisely indicates that they are lithium atoms (bottom right).

The press release released by SLAC shows that under the microscope, researchers use different techniques to observe the way electrons are ejected from the atoms of the dendrite, revealing the position of a single atom in the facial mask coating of the crystal and its solid electrolyte interface. When they add chemicals commonly used to improve battery performance, the atomic structure of the solid electrolyte interface facial mask coating becomes more orderly, which will help explain why additives play a role.

"We are very excited. This is the first time that we can obtain such a detailed image of dendrites, and it is also the first time that we can see the nanostructure of the solid electrolyte interface facial mask layer." YanbinLi said, "This tool can help us understand the role of different electrolytes, and why some electrolytes have better effects than others."

The relevant data observed from these experiments can provide a further understanding of battery failure mechanisms. Although this work is using lithium metal as an example to demonstrate the practicality of cryo EM, this method may also be extended to other studies involving beam sensitive materials such as lithium silicon or sulfur. The research team also said that they planned to focus on more understanding of the chemical properties and structure of the solid electrolyte facial mask layer.

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