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

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Ageing mechanisms in lithium-ion batteries

Solid-state electrolytes are attracting increasing interest for electrochemical energy storage technologies. In this Review, we provide a background overview and discuss the state of the art, ion-transport mechanisms and fundamental properties of solid-state electrolyte materials of interest for energy storage applications. We focus on recent advances in various classes of battery chemistries and systems that are enabled by solid electrolytes, including all-solid-state lithium-ion batteries and emerging solid-electrolyte lithium batteries that feature cathodes with liquid or gaseous active materials (for example, lithium–air, lithium–sulfur and lithium–bromine systems). A low-cost, safe, aqueous electrochemical energy storage concept with a ‘mediator-ion’ solid electrolyte is also discussed. Advanced battery systems based on solid electrolytes would revitalize the rechargeable battery field because of their safety, excellent stability, long cycle lives and low cost. However, great effort will be needed to implement solid-electrolyte batteries as viable energy storage systems. In this context, we discuss the main issues that must be addressed, such as achieving acceptable ionic conductivity, electrochemical stability and mechanical properties of the solid electrolytes, as well as a compatible electrolyte/electrode interface. This Review details recent advances in battery chemistries and systems enabled by solid electrolytes, including all-solid-state lithium-ion, lithium–air, lithium–sulfur and lithium–bromine batteries, as well as an aqueous battery concept with a mediator-ion solid electrolyte.

Lithium battery chemistries enabled by solid-state electrolytes

Ionically conducting polymer membranes (polymer electrolytes) might enhance lithium-battery technology by replacing the liquid electrolyte currently in use and thereby enabling the fabrication of flexible, compact, laminated solid-state structures free from leaks and available in varied geometries1. Polymer electrolytes explored for these purposes are commonly complexes of a lithium salt (LiX) with a high-molecular-weight polymer such as polyethylene oxide (PEO). But PEO tends to crystallize below 60 °C, whereas fast ion transport is a characteristic of the amorphous phase. So the conductivity of PEO–LiX electrolytes reaches practically useful values (of about 10−4 S cm−1) only at temperatures of 60–80 °C. The most common approach for lowering the operational temperature has been to add liquid plasticizers, but this promotes deterioration of the electrolyte's mechanical properties and increases its reactivity towards the lithium metal anode. Here we show that nanometre-sized ceramic powders can perform as solid plasticizers for PEO, kinetically inhibiting crystallization on annealing from the amorphous state above 60 °C. We demonstrate conductivities of around 10−4 S cm−1 at 50 °C and 10−5 S cm−1 at 30 °C in a PEO–LiClO4 mixture containing powders of TiO2 and Al2O3 with particle sizes of 5.8–13 nm. Further optimization might lead to practical solid-state polymer electrolytes for lithium batteries.

Nanocomposite polymer electrolytes for lithium batteries

Electroactive phases of poly(vinylidene fluoride) : determination, processing and applications

An investigation of the conducting species in polymer electrolytes

The effects of radiation-induced crosslinking on the conductance of LiClO4·PEO electrolytes

It is known that stoichiometric spinel, , when used as a lithium‐ion battery cathode, exhibits significant capacity fade on cycling at room temperature, whereas by making the spinel slightly nonstoichiometric the capacity retention on cycling is improved to a great extent. To help understand this difference in performance, X‐ray diffraction (XRD) was used to investigate the spinel structure during lithium extraction and reinsertion. The stoichiometric spinel shows degradation during the first lithium extraction which becomes more severe at high rates. The XRD pattern measured at the end of 50 cycles showed significant loss of structural integrity, with several prominent peaks that were not present prior to cycling. In contrast, the nonstoichiometric spinel showed no evidence of degradation up to at least 300 cycles, even at high rates. It is suggested that in the case of stoichiometric spinel, , which forms upon extraction of lithium, accumulates during cycling and, because it becomes disconnected from the active electrode, capacity fade is significant. © 1999 The Electrochemical Society. All rights reserved.

Correlating Capacity Loss of Stoichiometric and Nonstoichiometric Lithium Manganese Oxide Spinel Electrodes with Their Structural Integrity

The determination of transference numbers in solid polymer electrolytes using the Hittorf method

Electrolyte a base d'un copolymere styrene-butadiene-styrene avec une courte chaine laterale polyoxyde d'ethylene et interaction avec le trifluoromethanesulfonate de lithium. Relation entre la concentration et la conductivite

Colin A. Vincent

Papers

An investigation of the conducting species in polymer electrolytes

The effects of radiation-induced crosslinking on the conductance of LiClO4·PEO electrolytes

Correlating Capacity Loss of Stoichiometric and Nonstoichiometric Lithium Manganese Oxide Spinel Electrodes with Their Structural Integrity

The determination of transference numbers in solid polymer electrolytes using the Hittorf method

Novel polymer electrolytes based on ABA block copolymers