Georgia Tech team develops simple, low-cost process for oxide nanowires; superior separators for Li-ion batteries
20 January 2017
Researchers at Georgia Tech have developed a simple technique for producing oxide nanowires directly from bulk materials under ambient conditions without the use of catalysts or any external stimuli. The process could significantly lower the cost of producing the one-dimensional (1D) nanostructures, enabling a broad range of uses in lightweight structural composites, advanced sensors, electronic devices—and thermally-stable and strong battery membranes able to withstand temperatures of more than 1,000 ˚C.
In a paper in the journal Science, the team reported the transformation of multimicrometer-sized particles of aluminum or magnesium alloys into alkoxide nanowires of tunable dimensions, which were converted into oxide nanowires upon heating in air. Fabricated separators based on aluminum oxide nanowires enhanced the safety and rate capabilities of lithium-ion batteries.
Advanced energy-storage and energy-harvesting devices, catalyst supports, sensors, flexible electronic devices, lightweight structural composites, building materials, insulation, cutting tools, and membranes are examples of the important and rapidly growing applications of one dimensional (1D) dielectric and semiconductor (ceramic) nanomaterials. Nanowires, nanowhiskers, nanofibers, nanotubes, and other 1D nanostructures have demonstrated remarkable abilities for enhancing the electrical, optical, thermal, and mechanical properties of a broad range of functional materials and composites. Such performance enhancements substantially exceed those offered by the additions of micrometer- or nano-sized particles.
Most synthesis routes for producing 1D nanomaterials, such as catalyst-assisted vapor deposition, physical vapor deposition, hydrothermal synthesis, the use of sacrificial templates, and others, are relatively expensive and difficult to scale. In contrast to synthesis of 2D materials from bulk, examples of the formation of 1D materials from bulk are rare. … We report a direct transformation of bulk materials into nanowires at room temperature and ambient pressure via a synthesis mechanism based on the strain energy minimization at the boundary of the chemical transformation reaction front.—Lei et al.
The research was supported by the National Science Foundation and California-based Sila Nanotechnologies. The process is believed to be the first to convert bulk powders to nanowires at ambient conditions.
Fabrication of the nanowires begins with formation of bimetallic alloys composed of one reactive and one non-reactive metal, such as lithium and aluminum (or magnesium and lithium). The alloy is then placed in a suitable solvent, which could include a range of alcohols, such as ethanol. The reactive metal (lithium) dissolves from the surface into the solvent, initially producing nuclei (nanoparticles) comprising aluminum.
Though bulk aluminum is not reactive with alcohol due to the formation of the passivation layer, the continuous dissolution of lithium prevents the passivation and allows gradual formation of aluminum alkoxide nanowires, which grow perpendicular to the surface of the particles starting from the nuclei until the particles are completely converted. The alkoxide nanowires can then be heated in open air to form aluminum oxide nanowires and may be formed into paper-like sheets.
The dissolved lithium can be recovered and reused. The dissolution process generates hydrogen gas, which could be captured and used to help fuel the heating step.
This technique could open the door for a range of synthesis opportunities to produce low-cost 1D nanomaterials in large quantities. You can essentially put the bulk materials into a bucket, fill it with a suitable solvent and collect nanowires after a few hours, which is way simpler than how many of these structures are produced today.—Gleb Yushin, corresponding author
Yushin’s research team, which included former graduate students Danni Lei and James Benson, has produced oxide nanowires from lithium-magnesium and lithium-aluminum alloys using a variety of solvents, including simple alcohols. Production of nanowires from other materials is part of ongoing research that was not reported in the paper.
The dimensions of the nanowire structures can be controlled by varying the solvent and the processing conditions. The structures can be produced in diameters ranging from tens of nanometers up to microns.
Minimization of the interfacial energy at the boundary of the chemical reaction front allows us to form small nuclei and then retain their diameter as the reaction proceeds, thus forming nanowires. By controlling the volume changes, surface energy, reactivity and solubility of the reaction products, along with the temperature and pressure, we can tune conditions to produce nanowires of the dimensions we want.—Gleb Yushin
One of the attractive applications may be separator membranes for lithium-ion batteries. The polymer separation membranes conventionally used in these batteries cannot withstand the high temperatures generated by certain failure scenarios. As result, commercial batteries may induce fires and explosions, if not designed very carefully; further, it’s extremely hard to avoid defects and errors consistently in tens of millions of devices.
Using low-cost paper-like membranes made of ceramic nanowires could help address those concerns because the structures are strong and thermally stable, while also being flexible—unlike many bulk ceramics. The material is also polar, meaning it would more thoroughly wetted by various battery electrolyte solutions.
Overall, this is a better technology for batteries, but until now, ceramic nanowires have been too expensive to consider seriously,” Yushin said. “In the future, we can improve mechanical properties further and scale up synthesis, making the low-cost ceramic separator technology very attractive to battery designers.—Gleb Yushin
Though the process was studied first to make magnesium and aluminum oxide nanowires, Yushin believes it has a broad potential for making other materials. Future work will explore synthesis of new materials and their applications, and develop improved fundamental understanding of the process and predictive models to streamline experimental work.
The researchers have so far produced laboratory amounts of the nanowires, but Yushin believes that the process could be scaled up to produce industrial quantities. Though the ultimate cost will depend on many variables, he expects to see fabrication costs cut by several orders of magnitude over existing techniques.
With this technique, you could potentially produce nanowires for a cost not much more than that of the raw materials.—Gleb Yushin
Beyond battery membranes, the nanowires could be useful in energy harvesting, catalyst supports, sensors, flexible electronic devices, lightweight structural composites, building materials, electrical and thermal insulation and cutting tools.
The new technique was discovered accidentally while Yushin’s students were attempting to create a new porous membrane material. Instead of the membrane they had hoped to fabricate, the process generated powders composed of elongated particles.
In addition to those already named, the research included Alexandre Magaskinski of Georgia Tech and Gene Berdichevsky of Sila Nanotechnologies. Gleb Yushin and Gene Berdichevsky are shareholders of Sila Nanotechnologies.
Danni Lei, Jim Benson, Alexandre Magasinski, Gene Berdichevsky, Gleb Yushin (2017) “Transformation of bulk alloys to oxide nanowires,” Science Vol. 355, Issue 6322, pp. 267-271 DOI: 10.1126/science.aal2239