Penn State researchers have proposed cold sintering as an improved method of solid-state battery production that enables multi-material integration for better batteries. A paper on their work is published in ACS Applied Materials & Interfaces.
Solid-state batteries have a lot of advantages from a safety perspective in that they don’t catch on fire, because they’re a lot more stable owing to their stronger bonding. Because of that stronger bonding, they’re also more mechanically robust. This prevents fire-causing short circuits, but also in theory it enables solid-state batteries to have higher energy density. They have an order of magnitude increase in performance relative to the batteries that we have now, which are reaching their limit. But there’s also a lot of problems in making solid-state batteries.—Zane Grady, lead author
One of the larger issues for solid-state batteries making the transition from laboratory to the market is the challenges inherent in their production. Current battery electrodes are a mixture of active material, carbon, and the liquid electrolyte. Without a liquid electrolyte, there is no longer any direct path for the ions to move around in the electrode. The best way to give ions a path is by introducing a solid electrolyte, which requires sintering, and conventional sintering is too hot for carbon and active material, causing them to degrade. Cold sintering enables introducing the sintered solid electrolyte at very low temperatures.
In liquid batteries, you can take your two electrodes, and then add the electrolyte and as long as there’s something separating the two, usually a polymer, you have a battery. But making a solid-state battery involves producing a material such as a very thin layer of dense, conductive ceramic glass for a solid electrolyte, which is very difficult to do at scale.—Zane Grady
According to the researchers, cold sintering may offer a solution. Cold sintering is a process that enables sintering of ceramics at a much lower temperature than traditional methods, therefore using much less energy and enabling potential new material combinations. It was developed at Penn State by the research team led by Clive Randall, director of the Materials Research Institute, distinguished professor of materials science and engineering, and co-author of the study.
Sintered triphasic cathode. Cold sintering allows for the fabrication of composites with three components; the active material, the solid electrolyte, and the carbon fiber. This unique microstructure provides both the ionic and electronic pathways necessary to drive the redox reaction in the electrode in a solid-state battery. Credit: Zane Grady/The Randall Group.
What we do in cold sintering is we reduce the sintering temperature of the ceramic solid electrolytes from the usual 1,200 degrees Celsius down to under 400 degrees Celsius. When you do that, now you can integrate your solid electrolytes with everything else in the battery, like your active material and the electrodes, and cold sinter the interfaces together. It addresses all the different manufacturing challenges that are vexing everyone else who wants to make solid-state batteries by lowering the temperature. It opens up a whole window of co-processability between the solid-state battery materials that you can’t get out for any other ceramic processing method. So, what cold sintering does is really serve as an indication that it’s possible to make solid-state batteries out of ceramics.—Zane Grady
In a prior study, the research team demonstrated how cold sintering can be employed at temperatures below 300 degrees Fahrenheit (150 degrees Celsius) to fabricate multilayered, solid-state lithium-ion batteries. They relied on conductive salts to obtain suitable electrochemical properties, which undercut some of the conductive and safety advantages of solid-state batteries.
Then, the team demonstrated that a solid electrolyte with sodium zirconium silicate phosphate (the NASICON solid electrolyte), could be cold-sintered at a slightly higher temperature, 707 degrees Fahrenheit (375 degrees Celsius), by replacing the liquid transient solvent with a more reactive, solid sodium hydroxide transient solvent. This resulted in a highly conductive ceramic solid electrolyte without the use of any additional conductive salts.
For this current study, the team demonstrated a novel route toward the fabrication of mixed conducting electrodes for solid-state batteries. The team took a NASICON cathode ceramic powder that is densified into a ceramic composite pellet with a transient solvent to help it densify, and used a carver press to apply necessary pressure to the powder. The pressure is applied and heated for three hours at 707 degrees Farenheit (375 degrees Celsius).
Next steps for the research team include fine-tuning the cold sintering process of the solid-state batteries. The researchers will then explore some additional issues and work to solve them.
We will then ask questions such as how do you slap the cathode and the electrolyte on top of each other in a way that you don't get a bottleneck of ions at that interface? How thin can you make the electrolyte? These are important steps in moving towards an actual, practical solid-state battery.—Zane Grady
The US Department of Energy and the US Department of Defense supported this research.
Zane Grady, Zhongming Fan, Arnaud Ndayishimiye, and Clive A. Randall (2021) “Design and Sintering of All-Solid-State Composite Cathodes with Tunable Mixed Conduction Properties via the Cold Sintering Process” ACS Applied Materials & Interfaces 13 (40), 48071-48087 doi: 10.1021/acsami.1c13913