The challenges for further development of Li rechargeable batteries for electric vehicles are reviewed. Most important is safety, which requires development of a nonflammable electrolyte with either a larger window between its lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) or a constituent (or additive) that can develop rapidly a solid/ electrolyte-interface (SEI) layer to prevent plating of Li on a carbon anode during a fast charge of the battery. A high Li-ion conductivity (σ Li > 10 ―4 S/cm) in the electrolyte and across the electrode/ electrolyte interface is needed for a power battery. Important also is an increase in the density of the stored energy, which is the product of the voltage and capacity of reversible Li insertion/extraction into/from the electrodes. It will be difficult to design a better anode than carbon, but carbon requires formation of an SEI layer, which involves an irreversible capacity loss. The design of a cathode composed of environmentally benign, low-cost materials that has its electrochemical potential μ C well-matched to the HOMO of the electrolyte and allows access to two Li atoms per transition-metal cation would increase the energy density, but it is a daunting challenge. Two redox couples can be accessed where the cation redox couples are "pinned" at the top of the O 2p bands, but to take advantage of this possibility, it must be realized in a framework structure that can accept more than one Li atom per transition-metal cation. Moreover, such a situation represents an intrinsic voltage limit of the cathode, and matching this limit to the HOMO of the electrolyte requires the ability to tune the intrinsic voltage limit. Finally, the chemical compatibility in the battery must allow a long service life.

Challenges for Rechargeable Li Batteries

Energy storage is more important today than at any time in human history. Future generations of rechargeable lithium batteries are required to power portable electronic devices (cellphones, laptop computers etc.), store electricity from renewable sources, and as a vital component in new hybrid electric vehicles. To achieve the increase in energy and power density essential to meet the future challenges of energy storage, new materials chemistry, and especially new nanomaterials chemistry, is essential. We must find ways of synthesizing new nanomaterials with new properties or combinations of properties, for use as electrodes and electrolytes in lithium batteries. Herein we review some of the recent scientific advances in nanomaterials, and especially in nanostructured materials, for rechargeable lithium-ion batteries.

Nanomaterials for rechargeable lithium batteries

Li-ion battery materials: present and future

Lithium-ion batteries have had a profound impact on our daily life, but inherent limitations make it difficult for Li-ion chemistries to meet the growing demands for portable electronics, electric vehicles and grid-scale energy storage. Therefore, chemistries beyond Li-ion are currently being investigated and need to be made viable for commercial applications. The use of metallic Li is one of the most favoured choices for next-generation Li batteries, especially Li-S and Li-air systems. After falling into oblivion for several decades because of safety concerns, metallic Li is now ready for a revival, thanks to the development of investigative tools and nanotechnology-based solutions. In this Review, we first summarize the current understanding on Li anodes, then highlight the recent key progress in materials design and advanced characterization techniques, and finally discuss the opportunities and possible directions for future development of Li anodes in applications.

Reviving the lithium metal anode for high-energy batteries

[Liu, Chang; Li, Feng; Ma, Lai-Peng; Cheng, Hui-Ming] Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, Shenyang 110016, Peoples R China.;Cheng, HM (reprint author), Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, 72 Wenhua Rd, Shenyang 110016, Peoples R China;cheng@imr.ac.cn

Advanced Materials for Energy Storage

There is great interest in developing rechargeable lithium batteries with higher energy capacity and longer cycle life for applications in portable electronic devices, electric vehicles and implantable medical devices. Silicon is an attractive anode material for lithium batteries because it has a low discharge potential and the highest known theoretical charge capacity (4,200 mAh g(-1); ref. 2). Although this is more than ten times higher than existing graphite anodes and much larger than various nitride and oxide materials, silicon anodes have limited applications because silicon's volume changes by 400% upon insertion and extraction of lithium which results in pulverization and capacity fading. Here, we show that silicon nanowire battery electrodes circumvent these issues as they can accommodate large strain without pulverization, provide good electronic contact and conduction, and display short lithium insertion distances. We achieved the theoretical charge capacity for silicon anodes and maintained a discharge capacity close to 75% of this maximum, with little fading during cycling.

/pdf/high-performance-lithium-battery-anodes-using-silicon-58e1j6kr4f.pdf

High-performance lithium battery anodes using silicon nanowires

Ge nanowire electrodes fabricated by using vapor−liquid−solid growth on metallic current collector substrates were found to have good performance during cycling with Li. An initial discharge capacity of 1141 mA·h/g was found to be stable over 20 cycles at the C/20 rate. High power rates were also observed up to 2C with Coulombic efficiency > 99%. Structural characterization revealed that the Ge nanowires remain intact and connected to the current collector after cycling. Nanowires connected directly to the current collector have facile strain relaxation and material durability, short Li diffusion distances, and good electronic conduction. Thus, Ge nanowire anodes are promising candidates for the development of high-energy-density lithium batteries.

/pdf/high-capacity-li-ion-battery-anodes-using-ge-nanowires-2leehy44ni.pdf

High Capacity Li Ion Battery Anodes Using Ge Nanowires

Layered-structure nanoribbons with efficient electron transport and short lithium ion insertion lengths are promising candidates for Li battery applications. Here we studied at the single nanostructure level the chemical, structural, and electrical transformations of V 2O5 nanoribbons. We found that transformation of V 2O5 into the ˆ-Li3V2O5 phase depends not only on the width but also the thickness of the nanoribbons. Transformation can take place within 10 s in thin nanoribbons, suggesting a Li diffusion constant 3 orders of magnitude faster than in bulk materials, resulting in a significant increase in battery power density (360 C power rate). For the first time, complete delithiation of ˆ-Li3V2O5 back to the single-crystalline, pristine V2O5 nanoribbon was observed, indicating a 30% higher energy density. These new observations are attributed to the ability of facile strain relaxation and phase transformation at the nanoscale. In addition, efficient electronic transport can be maintained to charge a Li 3V2O5 nanoribbon within less than 5 s. These exciting nanosize effects can be exploited to fabricate high-performance Li batteries for applications in electric and hybrid electric vehicles.

https://web.stanford.edu/group/cui_group/papers/Fast,%20Completely%20Reversible%20Li%20Insertion%20in%20Vanadium%20Pentoxide%20Nanoribbons.pdf

Fast, completely reversible li insertion in vanadium pentoxide nanoribbons.

III−VI and I−III−VI semiconductors with anomalous grain boundaries have been actively studied for high efficiency photovoltaic applications. Nanowire morphology can provide a well-defined nanodomain for studying grain boundary and p−n junction physics for improving solar cell efficiency. We report the synthesis of In2Se3 and CuInSe2 single crystalline nanowires via a Au-catalyzed vapor−liquid−solid growth. Superlattice forms in In2Se3 nanowires at room temperature and a reversible superlattice transformation takes place at 200 °C. Cu concentration in CuInSe2 nanowires can be controlled, and nanowires show a dependence of crystal structure on Cu concentration.

Synthesis and Phase Transformation of In2Se3 and CuInSe2 Nanowires

Phase-change memory materials have stimulated a great deal of interest although the size-dependent behaviors have not been well studied due to the lack of method for producing their nanoscale structures. We report the synthesis and characterization of GeTe and Sb2Te3 phase-change nanowires via a vapor−liquid−solid growth mechanism. The as-grown GeTe nanowires have three different types of morphologies:  single-crystalline straight and helical rhombohedral GeTe nanowires and amorphous curly GeO2 nanowires. All the Sb2Te3 nanowires are single-crystalline.

Xiao Feng Zhang

Papers

High-performance lithium battery anodes using silicon nanowires

High Capacity Li Ion Battery Anodes Using Ge Nanowires

Fast, completely reversible li insertion in vanadium pentoxide nanoribbons.

Synthesis and Phase Transformation of In2Se3 and CuInSe2 Nanowires

Synthesis and characterization of phase-change nanowires.