Giving batteries a longer life with the Advanced Photon Source
New research uncovers a hydrogen-centered mechanism that triggers degradation in the lithium-ion batteries that power electric vehicles
DOE/Argonne National Laboratory
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From left: Physicist and Group Leader Shelly Kelly describes the unique monochromator in the recently upgraded 25-ID beamline at the APS to Senior Chemist Zonghai Chen, Postdoc Jiyu Cai and Physicist Zhan Zhang.
view moreCredit: (Image by Argonne National Laboratory/Mark Lopez.)
While the lithium-ion battery could help save the planet, it is in some ways like any other battery: it degrades with time and operation, taking a toll on its lifespan.
Along with enabling much of our digital and mobile lifestyle, lithium-ion batteries power most electric vehicles (EVs). For that reason, extending the battery’s lifetime is critical to widespread adoption of EVs in the transition away from fossil fuel-burning cars. Scientists are working to find the causes of battery degradation with the goal of extending battery lifespan.
Specifically, scientists at the U.S. Department of Energy’s (DOE) Argonne National Laboratory are collaborating with other U.S. laboratories and academic institutions to study a phenomenon called self-discharge. This is a series of chemical reactions in the battery that causes performance loss over time, shortening the battery’s lifespan.
“By mitigating self-discharge, we can design a smaller, lighter and cheaper battery without sacrificing end-of-life battery performance.” — Argonne Senior Chemist Zonghai Chen
During self-discharge, the charged lithium-ion battery loses stored energy even when not in use. For example, an EV that sits for a month or more may not run due to low battery voltage and charge.
“Self-discharge is a phenomenon experienced by all rechargeable electrochemical devices,” said Zonghai Chen, an Argonne senior chemist. “The process slowly consumes precious functional battery materials and deposits undesired side products on the surface of the battery components. This leads to continuous degradation of battery performance.”
To find the cause of self-discharge, scientists need to identify the complex chemical mechanisms that trigger the degradation process in the battery. Lithium-ion batteries are rechargeable and use lithium ions to store energy. The cathode and the electrolyte are two key components in lithium-ion batteries. The battery’s longevity can be influenced by the degradation of cathodes.
While scientists are making significant progress in understanding lithium-ion batteries, there is an ongoing debate on what causes the self-discharge phenomenon.
The prevailing wisdom on cathode degradation centers on two areas: a loss of lithium or oxygen release from cathodes. Meanwhile, theoretical studies have predicted that electrolytes tend to decompose on cathode surfaces. This has created a critical knowledge gap between the decomposition of the electrolyte and the degradation of the cathode within lithium-ion batteries.
Recently, a research team across several academic universities and national laboratories including Argonne, DOE’s SLAC National Accelerator Laboratory and the DEVCOM U.S. Army Research Laboratory (ARL) published a new paper in Science bridging this knowledge gap. This research validates a cathode hydrogenation mechanism as a pathway to the self-discharge that leads to battery degradation. The research was funded by DOE’s Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office.
Scientists say they could not have validated their findings without access to the Advanced Photon Source (APS) at Argonne, one of the world’s premier storage-ring-based high-energy X-ray light source facilities. The APS is a DOE Office of Science user facility. The light sources use electrons circling in a storage ring at near the speed of light to produce X-ray beams that allow scientists to unveil the battery’s inner workings at an atomic level.
“We are deeply grateful to the state-of-art X-ray facilities and support available at the Advanced Photon Source. It is the ideal pairing of the X-ray studies and electrochemistry that enables our discoveries on how cathode hydrogenation occurs in lithium-ion batteries and impacts self-discharge,” said study lead Gang Wan, a physical science research scientist at Stanford University.
A new pathway to self-discharge leading to battery degradation
While the inner workings are more complicated, batteries basically convert electrochemical energy directly to electrical energy. Batteries consist of an anode, electrolyte, separator and cathode.
The electrolyte transfers ions, or charge-carrying particles, between the cathode and anode that store the lithium. Self-discharge occurs in both the cathode and anode. The cathode material is critical, since it determines how much energy the battery can store. In their new research, the team used layered lithium transition metal oxides, a prototype cathode material.
“Finding the right chemistry for these cathode materials is necessary to improve the battery’s chemical stability and reduce the rate of self-discharge,” said co-author Michael F. Toney, professor of chemical engineering and materials science and a fellow in the Renewable and Sustainable Energy Institute at the University of Colorado Boulder. “Degradation of the cathode reduces the battery’s lifetime.”
In their research, this team discovered experimental and computational proof of a mechanism that triggers self-discharge: cathode hydrogenation, or the process of dynamically transferring the protons and electrons from the electrolyte solvent into highly charged layered oxides in the cathode. The mechanism explains the chemical nature of the contamination products on the cathode that lead to battery degradation.
Along with Chen’s early seminal paper investigating the decomposition mechanism of cathode materials using high-energy X-ray diffraction, this new study sheds light on the cathode hydrogenation-based degradation mechanism.
Based on their results, scientists can further develop bottom-up approaches to reduce self-discharge and cathode degradation, with the goal of lengthening battery life.
“By mitigating self-discharge, we can design a smaller, lighter and cheaper battery without sacrificing end-of-life battery performance,” Chen said.
Advanced Photon Source helps validate research findings
Argonne beamline scientists Cheng-Jun Sun, Shelly Kelly and Zhan Zhang used the APS to work with Wan to design the X-ray spectroscopy and scattering experiments that validated the landmark findings.
“X-ray spectroscopy measurements allow an atomic view of the nickel, manganese and cobalt metal atoms within the cathode,” Kelly said. “Using the APS, we could see the effect of the accumulation of protons at the surface of the cathode, which ultimately results in self-discharge.”
The APS, which welcomes more than 5,500 scientists from around the world in a typical year, is currently undergoing a massive upgrade that will replace the current electron storage ring with a new, more powerful model. When completed later in 2024, the upgrade will increase the brightness of the APS X-ray beams by up to 500 times.
“The research team, which includes a number of longtime APS users, is excited to embrace the new and exciting opportunities brought by the APS upgrade to target the grand challenges in energy sciences, including building better batteries,” Wan said.
Other senior co-authors include Oleg Borodin, a scientist at ARL, and Kang Xu, a fellow of the Materials Research Society and the Electrochemical Society and an ARL fellow emeritus who was a former team leader at ARL and is now chief scientist at SES AI.
The research team dedicated their paper to the late George Crabtree and the late Peter Faguy. Crabtree, an Argonne Senior Scientist and Distinguished Fellow, served as director of the DOE’s Joint Center for Energy Storage Research from 2012 to 2023. Faguy, an electrochemist at the DOE, served as the DOE project manager on this research.
About the Advanced Photon Source
The U. S. Department of Energy Office of Science’s Advanced Photon Source (APS) at Argonne National Laboratory is one of the world’s most productive X-ray light source facilities. The APS provides high-brightness X-ray beams to a diverse community of researchers in materials science, chemistry, condensed matter physics, the life and environmental sciences, and applied research. These X-rays are ideally suited for explorations of materials and biological structures; elemental distribution; chemical, magnetic, electronic states; and a wide range of technologically important engineering systems from batteries to fuel injector sprays, all of which are the foundations of our nation’s economic, technological, and physical well-being. Each year, more than 5,000 researchers use the APS to produce over 2,000 publications detailing impactful discoveries, and solve more vital biological protein structures than users of any other X-ray light source research facility. APS scientists and engineers innovate technology that is at the heart of advancing accelerator and light-source operations. This includes the insertion devices that produce extreme-brightness X-rays prized by researchers, lenses that focus the X-rays down to a few nanometers, instrumentation that maximizes the way the X-rays interact with samples being studied, and software that gathers and manages the massive quantity of data resulting from discovery research at the APS.
This research used resources of the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.
Argonne National Laboratory seeks solutions to pressing national problems in science and technology by conducting leading-edge basic and applied research in virtually every scientific discipline. Argonne is managed by UChicago Argonne, LLC for the U.S. Department of Energy’s Office of Science.
The U.S. Department of Energy’s Office of Science is the single largest supporter of basic research in the physical sciences in the United States and is working to address some of the most pressing challenges of our time. For more information, visit https://energy.gov/science.
Experimental Table at APS
From left: Physicist Zhan Zhang, Postdoc Jiyu Cai, Senior Chemist Zonghai Chen and Physicist and Group Leader Shelly Kelly working on the experimental table for X-ray measurements at the recently upgraded 25-ID beamline at the APS.
Credit
(Image by Argonne National Laboratory/Mark Lopez.)
Journal
Science
Article Title
Solvent-mediated oxide hydrogenation in layered cathodes
Harnessing the power of porosity: A new era for aqueous zinc-ion batteries and large-scale energy storage
Tsinghua University Press
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This diagram illustrates the primary benefits of porous zinc anodes, including enhanced electric field distribution, improved Zn²⁺ ion flux, effective volume change accommodation, and internal stress relaxation, all of which contribute to the suppression of dendrite growth and increased battery performance in aqueous zinc-ion batteries.
view moreCredit: Yao Wang, Tsinghua University
As the global demand for energy storage solutions grows, the limitations of current lithium-ion batteries, such as safety concerns and high costs, have driven the exploration of alternative technologies. Aqueous zinc-ion batteries (AZIBs) have emerged as a promising candidate due to their inherent safety, cost-effectiveness, and environmental sustainability. However, challenges like zinc dendrite growth continue to hinder their widespread adoption. Due to these challenges, there is a pressing need to delve deeper into innovative solutions to improve AZIB performance.
The study (DOI: 10.26599/EMD.2024.9370040), conducted by researchers from Tsinghua University and the University of Technology Sydney, was published in Energy Materials and Devices on August 16, 2024. It provides a comprehensive review of recent advancements in the engineering of porous zinc metal anodes for AZIBs. The focus of the research is on the structural orderliness of these porous anodes and their critical role in enhancing battery performance. The review underscores the potential of porous zinc anodes in overcoming the limitations of traditional planar zinc anodes.
The research highlights the significant advantages of porous zinc anodes over traditional planar zinc anodes. The porous structures provide numerous nucleation sites, which reduce the nuclear energy barriers and mitigate localized charge accumulation. This, in turn, suppresses dendrite growth, ensuring a longer battery lifespan. The study also emphasizes the role of three-dimensional porous structures in facilitating uniform electric field distribution and homogeneous ion flux, which are crucial for stable zinc deposition and stripping. Additionally, the substantial internal volume in these anodes accommodates volume changes and deposition stress, further enhancing battery performance. The review presents various fabrication techniques for porous zinc anodes, including etching, self-assembly, laser lithography, electrochemical methods, and 3D printing. The researchers also provide strategic insights into the design of porous zinc anodes to facilitate the practical implementation of AZIBs for grid-scale energy storage applications.
Prof. Dong Zhou, one of the lead researchers, remarked, "The development of porous zinc anodes represents a significant step forward in the advancement of zinc-ion batteries. By addressing the dendrite growth issue, we are moving closer to making AZIBs a commercially viable alternative to lithium-ion batteries. Our work not only provides a comprehensive understanding of the current advancements but also offers strategic insights into future research directions."
The innovative design of porous zinc anodes has the potential to revolutionize the field of energy storage. By improving the performance and safety of AZIBs, these anodes could enable the development of large-scale, sustainable energy storage systems, crucial for integrating renewable energy sources into the grid. Moreover, the advancements in porous zinc anodes could also lead to the development of safer and more cost-effective batteries for a wide range of applications, from electric vehicles to portable electronics, thus contributing to the global transition towards cleaner energy solutions.
This work is granted by National Natural Science Foundation of China (Grant No. 22309102), China Postdoctoral Science Foundation (Grant No. 2222M711788), National Key Research and Development Program of China (Grant No.2022YFB2404500), Fundamental Research Project of Shenzhen (Grant No. JCYJ20230807111702005), the Australian Research Council through the ARC Discovery Project (Grant No. DP230101579) and ACR Linkage Project (Grant No. LP200200926).
About Energy Materials and Devices
Energy Materials and Devices is launched by Tsinghua University, published quarterly by Tsinghua University Press, exclusively available via SciOpen, aiming at being an international, single-blind peer-reviewed, open-access and interdisciplinary journal in the cutting-edge field of energy materials and devices. It focuses on the innovation research of the whole chain of basic research, technological innovation, achievement transformation and industrialization in the field of energy materials and devices, and publishes original, leading and forward-looking research results, including but not limited to the materials design, synthesis, integration, assembly and characterization of devices for energy storage and conversion etc.
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Journal
Energy Materials and Devices
Article Title
Porous zinc metal anodes for aqueous zinc-ion batteries: Advances and prospectives
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