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Autumn 2015

Nanowires' Growth Reveals Insights into Electrical Resistance

Experiments with tiny wires provide insight into reducing internal energy loss in batteries

Timothy Plett

Using a glass slide as a base, she employs high-energy light to pattern a photoresistive chemical layer (red) in regular intervals on top of a thin gold layer. Next, gold is etched (step 1) to create a small trench. Next, MnO2 is deposited in the trench, creating the nano-electrodes. These nano-electrodes are isolated by dissolving the gold and photoresist (step 2). A layer of photoresistive material is applied over the section that will become the final electrodes (step 3). Gold is applied to the entire surface (step 4). The gold-topped photoresistive layer is removed (step 5), leaving the electrodes with gold-capped ends, which forms the electrical contacts for the experiment.

Transmission electron microscopy images of nano-electrode growth

All batteries lose energy because of internal resistance, which is why batteries get hot after long use. To make more efficient batteries, scientists are researching methods to lower internal resistance. Mya Le and her colleagues from the Energy Frontier Research Center Nanostructures for Electrical Energy Storage (NEES) approached the challenge of internal resistance for the case of tiny electrodes, a key component for new, novel battery design. Understanding internal resistance could lead to "nano-batteries" that take advantage of nanoscale structures to improve electrical energy storage, lasting longer and delivering more energy than conventional technologies.

Le and the team discovered that the conductivity of manganese dioxide (MnO2), a commonly used material in lithium-ion batteries, scales inversely with its size when charged, which could directly impact the efficiency of these nano-batteries.

Using a glass slide as a base, she employs high-energy light to pattern a photoresistive chemical layer (red) in regular intervals on top of a thin gold layer. Next, gold is etched (step 1) to create a small trench. Next, MnO2 is deposited in the trench, creating the nano-electrodes. These nano-electrodes are isolated by dissolving the gold and photoresist (step 2). A layer of photoresistive material is applied over the section that will become the final electrodes (step 3). Gold is applied to the entire surface (step 4). The gold-topped photoresistive layer is removed (step 5), leaving the electrodes with gold-capped ends, which forms the electrical contacts for the experiment.
Transmission electron microscopy images of nano-electrode growth

MnO2 as an electrode for lithium-ion batteries is a bit like a sponge in water. As a sponge absorbs water and releases it when squeezed, so MnO2 takes in lithium ions when charging and releases them when the battery is put to use in a cellphone or laptop computer. But, just as a sponge needs a hand to squeeze it dry, a MnO2 electrode requires electrons to move to release lithium. Optimizing electron motion is crucial for maximizing the performance of batteries that rely on these tiny or nano-sized electrodes.

To make the nano-electrodes, Le employs a technique called lithographically patterned nanowire electrodeposition. Using a glass slide as a base, she employs high-energy light to pattern a photoresistive chemical layer in regular intervals on top of a thin gold layer. Next, gold is etched to create a small trench between the photoresist and the gold layers. MnO2 is deposited in the trench using an electrical pulse. She then isolates these nano-electrodes by dissolving the gold and photoresist. Finally, the electrodes are capped on two ends with a new gold layer, which forms the electrical contacts for her experiment.

Le specifically examined the MnO2 nano-electrodes while charged with lithium to determine how conductivity changed in electrodes of varying widths. When she did this, she discovered that charged wires with smaller cross-sections exhibited higher electrical conductivities. In other words, a thinner wire allowed electrons to move more easily than a thicker wire. Normally, a thicker wire allows for easier electron movement, so, confronted with this strange result, Le decided to examine the structure more closely to understand why.

Under a transmission electron microscope, the team discovered the porous structure had tendril-like characteristics. Dense "roots" dominated the structure near the gold contact, and branched out, tapering with distance. This led the team to suggest a growth mechanism for MnO2: the initial deposition was consistent in rate, but as time went on, the thickness along these tendrils became disparate, as diffusion properties of the depositing MnO2 changed. The team concluded that the dense roots in wider nano-electrodes prevent lithium ions from being taken in. This would lead to the roots having a lower electrical conductivity because lithium ions increase the conductivity of the material. Computer models later revealed that lithium creates conduction channels in MnO2, where electrons may more freely move. These two effects explain the strange finding of how the smaller width could lead to higher material conductivity and provide insight into overcoming the challenge of internal resistance at the nanoscale.

While nanobatteries face other challenges before being ready for commercial use, these small structures have the potential to make big changes in energy storage.

Acknowledgments

This work was primarily supported as a part of the NEES, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under award number DESC0001160. Work done to supply collaborative X-ray photoelectron spectroscopy data was funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under award DE-FG02-96ER45576. Collaborative computational efforts were supported by the National Science Foundation Center for Chemical Innovation on Chemistry at the Space-Time Limit under grant CHE-0802913, and by Extreme Science and Engineering Discovery Environment for computing time.

More Information

Le M, Y Liu, H Wang, RK Dutta, W Yan, JC Hemminger, RQ Wu, and RM Penner. 2015. “In Situ Electrical Conductivity of LixMnO2 Nanowires as a Function of x and Size.” Chemistry of Materials 27:3494-3504. DOI: 10.1021/acs.chemmater.5b00912

About the author(s):

  • Timothy Plett is a Ph.D. candidate in the Physics and Astronomy Department at the University of Irvine, California. He is a member of the Nanostructures for Electrical Energy Storage Energy Frontier Research Center and serves as student coordinator for Thrust 1, which focuses on nano-interface research. His emphasis is biophysics, but specific research has been directed at understanding solution behavior in nano-confinement: nanopore rectification and cation dependence, ionic conductivity in manganese dioxide rods, solid electrolytes, and non-aqueous salt solutions.

Ending Electrons' Road Rage

Fewer roadblocks in thin electrodes let electrons flow freely, reduce overheating in batteries

To make more efficient batteries, scientists are researching methods to overcome the molecular roadblocks associated with internal resistance.

Molecular roadblocks inside batteries can cause a host of problems, including shorting and overheating. The challenge is to eliminate these roadblocks by creating electrodes that let ions and electrons move freely. Scientists found that manganese dioxide can be formed into tiny electrodes that provide little resistance. Surprisingly, the thinner the electrode, the better it worked. Thicker electrodes have dense "roots" that interfere with the battery and create resistance. Thinner electrodes don't have these roots. This work is part of the broader energy storage effort to store sporadic wind and solar energy for later use. Scientists at the Nanostructures for Electrical Energy Storage Center, led by the University of Maryland, performed the study.

More Information

Le M, Y Liu, H Wang, RK Dutta, W Yan, JC Hemminger, RQ Wu, and RM Penner. 2015. “In Situ Electrical Conductivity of LixMnO2 Nanowires as a Function of x and Size.” Chemistry of Materials 27:3494-3504. DOI: 10.1021/acs.chemmater.5b00912

Disclaimer: The opinions in this newsletter are those of the individual authors and do not represent the views or position of the Department of Energy.