A revolutionary conducting polymer enables the use of low-cost, high-energy silicon for the next generation of lithium-ion battery anodes
Lithium-ion batteries are everywhere, in smart phones, laptops, an array of other consumer electronics, and the newest electric cars. Good as they are, they could be much better, especially when it comes to lowering the cost and extending the range of electric cars. To do that, batteries need to store a lot more energy.
The anode is a critical component for storing energy in lithium-ion batteries. A team of scientists at the U.S. Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) has designed a new kind of anode that can absorb eight times the lithium of current designs, and has maintained its greatly increased energy capacity after over a year of testing and many hundreds of charge-discharge cycles.
The secret is a tailored polymer that conducts electricity and binds closely to lithium-storing silicon particles, even as they expand to more than three times their volume during charging and then shrink again during discharge. The new anodes are made from low-cost materials, compatible with standard lithium-battery manufacturing technologies. The research team reports its findings inAdvanced Materials, now available online.
“High-capacity lithium-ion anode materials have always confronted the challenge of volume change – swelling – when electrodes absorb lithium,” says Gao Liu of Berkeley Lab’s Environmental Energy Technologies Division (EETD), a member of the BATT program (Batteries for Advanced Transportation Technologies) managed by the Lab and supported by DOE’s Office of Vehicle Technologies.
Says Liu, “Most of today’s lithium-ion batteries have anodes made of graphite, which is electrically conducting and expands only modestly when housing the ions between its graphene layers. Silicon can store 10 times more – it has by far the highest capacity among lithium-ion storage materials – but it swells to more than three times its volume when fully charged.”
This kind of swelling quickly breaks the electrical contacts in the anode, so researchers have concentrated on finding other ways to use silicon while maintaining anode conductivity. Many approaches have been proposed; some are prohibitively costly.
One less-expensive approach has been to mix silicon particles in a flexible polymer binder, with carbon black added to the mix to conduct electricity. Unfortunately, the repeated swelling and shrinking of the silicon particles as they acquire and release lithium ions eventually push away the added carbon particles. What’s needed is a flexible binder that can conduct electricity by itself, without the added carbon.
“Conducting polymers aren’t a new idea,” says Liu, “but previous efforts haven’t worked well, because they haven’t taken into account the severe reducing environment on the anode side of a lithium-ion battery, which renders most conducting polymers insulators.”
One such experimental polymer, called PAN (polyaniline), has positive charges; it starts out as a conductor but quickly loses conductivity. An ideal conducting polymer should readily acquire electrons, rendering it conducting in the anode’s reducing environment.
The signature of a promising polymer would be one with a low value of the state called the “lowest unoccupied molecular orbital,” where electrons can easily reside and move freely. Ideally, electrons would be acquired from the lithium atoms during the initial charging process. Liu and his postdoctoral fellow Shidi Xun in EETD designed a series of such polyfluorene-based conducting polymers – PFs for short.
Compared with the electronic structure of PAN, the absorption spectra Yang obtained for the PFs stood out immediately. The differences were greatest in PFs incorporating a carbon-oxygen functional group (carbonyl).
The icing on the anode cake is that the new PF-based anode is not only superior but economical. “Using commercial silicon particles and without any conductive additive, our composite anode exhibits the best performance so far,” says Gao Liu. “The whole manufacturing process is low cost and compatible with established manufacturing technologies. The commercial value of the polymer has already been recognized by major companies, and its possible applications extend beyond silicon anodes.”
This story is reprinted from material from Berkeley Lab, with editorial changes made by Materials Today. The views expressed in this article do not necessarily represent those of Elsevier. Link to original source.
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