Super-wrinkled Graphene Improves Battery Electrode Performance

A new method for making ultrathin metal-oxide sheets containing intricate wrinkle and crumple patterns has been found by researchers at Brown University. The textured metal-oxide films have better performance when used as photocatalysts and as battery electrodes, the researchers show in the journal ACS Nano.

The findings extend previous work done by the same research group in which they developed a method for introducing finely tuned wrinkle and crumple textures into sheets of the nanomaterial graphene oxide.

The study showed that the process enhanced some of graphene’s properties. The textures made the graphene better able to repel water, which would be useful in making water-resistant coatings, and enhanced graphene’s ability to conduct electricity.

The researchers thought that similar structures might enhance the properties of other materials, specifically metal oxides, but there’s a problem. To introduce wrinkle and crumple structures in graphene, the team compressed the sheets multiple times in multiple orientations.

That process won’t work for metal oxides.

says Po-Yen Chen, a postdoctoral researcher in Brown University’s School of Engineering who led the work.

Metal-oxide Films

So Chen, working with the labs of Brown engineering professors Robert Hurt and Ian Y. Wong, developed a method of using the crumpled graphene sheets as templates for making crumpled metal-oxide films.

The team started by making stacks of crumpled graphene sheets using the method they had developed previously. They deposited the graphene on a polymer substrate that shrinks when heated.

As the substrate shrinks, it compresses the graphene sitting on top, creating wrinkle or crumple structures. The substrate is then removed, leaving free-standing sheets of crumpled graphene behind.

[caption id="attachment_3985” align="aligncenter” width="600”]graphene Different modes of shrinking in different orders creates different types of structures.
Hurt and Wong Labs / Brown University[/caption]

The compression process can be done multiple times, creating ever more complex structures. The process also allows control of what types of textures are formed.

Clamping shrink film on opposite sides and shrinking it in only one direction creates periodic wrinkles. Shrinking in all directions creates crumples.

These shrinks can be performed multiple times in multiple configurations to create a wide variety of textures.

Pattern Transfer

To transfer those patterns onto metal oxides, Chen placed the stacks of wrinkled graphene sheets in a water-based solution containing positively charged metal ions. The negatively charged graphene pulled those ions into the spaces between the sheets.

The particles bonded together within the interlayer space, creating thin sheets of metal that followed the wrinkle patterns of the graphene.

The graphene was then oxidized away, leaving the wrinkled metal-oxide sheets. Chen showed that the process works with a variety of metal oxides—zinc, aluminum, manganese, and copper oxides.

[caption id="attachment_3986” align="aligncenter” width="680”]graphene Hurt/Wong Labs/Brown University[/caption]

Once they had made the materials, the researchers then tested them to see if, as was the case with graphene, the textured surfaces enhanced the metal oxides’ properties.

They showed that wrinkled manganese oxide, when used as a battery electrode, had charge-carrying capacity that was four times higher than a planar sheet. That’s probably because the wrinkle ridges give electrons a defined path to follow, enabling the material to carry more of them at a time, the researchers say.

Photocatalytic Reactions

The team also tested the ability of crumpled zinc oxide to perform a photocatalytic reaction — reducing a dye dissolved in water under ultraviolet light.

The experiment showed the crumpled zinc oxide film to be four times more reactive than a planar film. That’s probably because the crumpled films have higher surface area, which give the material more reactive sites, Chen says.

In addition to improving the properties of the metals, Chen points out that the process also represents a way of making thin films out of materials that don’t normally lend themselves to ultrathin configurations.

Original Study

Top Image: Hurt and Wong Labs / Brown University

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