Scientists at Argonne National Laboratory discovered a fluoride electrolyte that improves the performance of next-generation batteries beyond lithium-ion. This new electrolyte enhances energy density and prolongs battery lifespan, potentially revolutionizing the electric vehicle industry.
A new fluoride-containing electrolyte paves the way for high-performance, long-lasting batteries.
Many toothpastes contain sodium fluoride, a compound of fluorine, to defend teeth from decay. However, compounds containing fluorine have additional unexpected applications. Researchers from the U.S. Department of Energy’s Argonne National Laboratory identified a fluoride electrolyte that could safeguard future batteries from performance decline.
“An exciting new generation of battery types for electric vehicles beyond lithium-ion is on the horizon,” said Zhengcheng (John) Zhang, a group leader in Argonne’s Chemical Sciences and Engineering division.
The chemistries of non-lithium-ion batteries offer twice or more energy stored in a given volume or weight compared to lithium-ion. They could power cars for much longer distances and could even power long-haul trucks and aircraft one day. The expectation is that the widespread use of such batteries will help address the problem of climate change. The main problem is that their high energy density declines rapidly with repeated charge and discharge.
One of the main contenders has an anode (negative electrode) made of lithium metal in place of the graphite normally used in lithium-ion batteries. It is thus called a “lithium metal” battery. The cathode (positive electrode) is a metal oxide that contains nickel, manganese, and cobalt (NMC). While it can deliver more than double the energy density possible with a lithium-ion battery, that outstanding performance rapidly vanishes within less than a hundred charge-discharge cycles.
The team’s solution involved changing the electrolyte, a liquid through which lithium ions move between cathode and anode to implement charge and discharge. In lithium metal batteries, the electrolyte is a liquid consisting of a lithium-containing salt dissolved in a solvent. The source of the short cycle-life problem is that the electrolyte does not form an adequate protective layer on the anode surface during the first few cycles. This layer, also called solid-electrolyte-interphase (SEI), acts like a guardian, allowing lithium ions to freely pass in and out of the anode to charge and discharge the battery, respectively.
Design of lithium metal battery with an electrolyte containing a fluorinated cation (atomic structure at center). The “interface” area represents the layer with fluorine that forms on the anode surface, as well as the cathode surface. Credit: Argonne National Laboratory
The team discovered a new fluoride solvent that maintains a robust protective layer for hundreds of cycles. It couples a fluorinated component that is positively charged (cation) with a different fluorinated component that is negatively charged (anion). This combination is what scientists call an ionic liquid — a liquid consisting of positive and negative ions.
“The key difference in our new electrolyte is the substitution of fluorine for hydrogen atoms in the ring-like structure of the cation part of the ionic liquid,” Zhang said. “This made all the difference in maintaining high performance for hundreds of cycles in a test lithium metal cell.”
To better understand the mechanism behind this difference at the atomic scale, the team drew upon the high-performance computing resources of the Argonne Leadership Computing Facility (ALCF), a DOE Office of Science user facility.
As Zhang explained, simulations on the ALCF’s Theta supercomputer revealed that the fluorine cations stick to and accumulate on the anode and cathode surfaces before any charge-discharge cycling. Then, during the early stages of cycling, a resilient SEI layer forms that is superior to what is possible with previous electrolytes.
High-resolution electron microscopy at Argonne and Pacific Northwest National Laboratory revealed that the highly protective SEI layer on the anode and cathode led to the stable cycling.
The team was able to tune the proportion of fluoride solvent to lithium salt to create a layer with optimal properties, including an SEI thickness that is not too thick or thin. Because of this layer, lithium ions could efficiently flow in and out of the electrodes during charge and discharge for hundreds of cycles.
The team’s new electrolyte offers many other advantages as well. It is low cost because it can be made with extremely high purity and yield in one simple step rather than multiple steps. It is environmentally friendly because it uses much less solvent, which is volatile and can release contaminants into the environment. And it is safer because it is not flammable.
“Lithium metal batteries with our fluorinated cation electrolyte could considerably boost the electric vehicle industry,” Zhang said. “And the usefulness of this electrolyte undoubtedly extends to other types of advanced battery systems beyond lithium-ion.”
Reference: “A fluorinated cation introduces new interphasial chemistries to enable high-voltage lithium metal batteries” by Qian Liu, Wei Jiang, Jiayi Xu, Yaobin Xu, Zhenzhen Yang, Dong-Joo Yoo, Krzysztof Z. Pupek, Chongmin Wang, Cong Liu, Kang Xu and Zhengcheng Zhang, 21 June 2023, Nature Communications.
DOI: 10.1038/s41467-023-38229-7
A paper on this research appeared in Nature Communications. In addition to Zhang, Argonne authors include Qian Liu, Wei Jiang, Jiayi Xu, Zhenzhen Yang, Doo-Joo Yoo, Krzysztof Z. Pupek, and Cong Liu. Other contributors include Chongmin Wang and Yaobin Xu from Pacific Northwest National Laboratory and Kang Xu from the U.S. Army Research Laboratory.
This work was supported by the DOE Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Computing time on the ALCF was awarded through DOE’s ASCR Leadership Computing Challenge.
I learned 40 years ago that the positively charged terminal was the anode, not the cathode. When did this long-term usage of the terms for “+” and “-” get reversed?
My years-ago trick for remembering the “+” terminal’s name was “anode” was because the “+” had more ions than the negative “cathode”, and the word anode is close to “add” or “and” which indicates a “surplus” or a “positivity”.