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

The advantages in using nanostructured materials for electrochemical energy storage have largely focused on the benefits associated with short path lengths. In this paper, we consider another contribution, that of the capacitive effects, which become increasingly important at nanoscale dimensions. Nanocrystalline TiO2 (anatase) was studied over a dimensional regime where both capacitive and lithium intercalation processes contribute to the total stored charge. An analysis of the voltammetric sweep data was used to distinguish between the amount of charge stored by these two processes. At particle sizes below 10 nm, capacitive contributions became increasingly important, leading to greater amounts of total stored charge (gravimetrically normalized) with decreasing TiO2 particle size. The area normalized capacitance was determined to be well above 100 μF/cm2, confirming that the capacitive contribution was pseudocapacitive in nature. Moreover, reducing the particle size to the nanoscale regime led to faster...

Pseudocapacitive Contributions to Electrochemical Energy Storage in TiO2 (Anatase) Nanoparticles

Electrolytes and interphases in Li-ion batteries and beyond.

Energy production and storage have become key issues concerning our welfare in daily life. Present challenges for batteries are twofold. In the first place, the increasing demand for powering systems of portable electronic devices and zero-emission vehicles stimulates research towards high energy and high voltage systems. In the second place, low cost batteries are required in order to advance towards smart electric grids that integrate discontinuous energy flow from renewable sources, optimizing the performance of clean energy sources. Na-ion batteries can be the key for the second point, because of the huge availability of sodium, its low price and the similarity of both Li and Na insertion chemistries. In spite of the lower energy density and voltage of Na-ion based technologies, they can be focused on applications where the weight and footprint requirement is less drastic, such as electrical grid storage. Much work has to be done in the field of Na-ion in order to catch up with Li-ion technology. Cathodic and anodic materials must be optimized, and new electrolytes will be the key point for Na-ion success. This review will gather the up-to-date knowledge about Na-ion battery materials, with the aim of providing a wide view of the systems that have already been explored and a starting point for the new research on this battery technology.

Na-ion batteries, recent advances and present challenges to become low cost energy storage systems

Graphene and related two-dimensional crystals and hybrid systems showcase several key properties that can address emerging energy needs, in particular for the ever growing market of portable and wearable energy conversion and storage devices. Graphene's flexibility, large surface area, and chemical stability, combined with its excellent electrical and thermal conductivity, make it promising as a catalyst in fuel and dye-sensitized solar cells. Chemically functionalized graphene can also improve storage and diffusion of ionic species and electric charge in batteries and supercapacitors. Two-dimensional crystals provide optoelectronic and photocatalytic properties complementing those of graphene, enabling the realization of ultrathin-film photovoltaic devices or systems for hydrogen production. Here, we review the use of graphene and related materials for energy conversion and storage, outlining the roadmap for future applications.

Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage

Solid polymer electrolytes with high ionic conductivities are prepared by using poly(ethylene oxide) (PEO) and poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) as polymer matrixes, succinonitrile (SN) as an additive, and lithium bis-trifluoromethanesulfonimide (LiTFSI) and lithium bisperfluoroethylsulfonylimide (LiBETI) as salts. In these systems, the introduction of succinonitrile into the polymer electrolytes increases the material's ionic conductivity and conveys excellent mechanical properties. The described composites, with their beneficial combination of mechanical and electric properties, are expected to have significant potential for lithium batteries.

Succinonitrile as a Versatile Additive for Polymer Electrolytes

Employing synergistic interactions between few-layer WS2 and reduced graphene oxide to improve lithium storage, cyclability and rate capability of Li-ion batteries

Second Phase Effects on the Conductivity of Non‐Aqueous Salt Solutions: “Soggy Sand Electrolytes”

Nano-ionics in the context of lithium batteries

Neuroglobin (Ngb) is a recently discovered protein in vertebrate brain tissue that belongs to the globin family of proteins. It has been implicated in the neuronal response to hypoxia or ischemia, although its physiological role has been hitherto unknown. Ngb is hexacoordinate in the ferrous deoxy form under physiological conditions. To bind exogenous ligands like O(2) and CO, the His E7 endogenous ligand is displaced from the sixth coordination. By using infrared spectroscopy and nanosecond time-resolved visible spectroscopy, we have investigated the ligand-binding reaction over a wide temperature range (3-353 K). Multiple, intrinsically heterogeneous distal heme pocket conformations exist in NgbCO. Photolysis at cryogenic temperatures creates a five-coordinate deoxy species with very low geminate-rebinding barriers. The photodissociated CO is observed to migrate within the distal heme pocket even at 20 K. Flash photolysis near physiological temperature (275-353 K) exhibits four sequential kinetic features: (i) geminate rebinding (t < 1 micros); (ii) extremely fast bimolecular exogenous ligand binding (10 micros < t < 1 ms) with a nontrivial temperature dependence; (iii) endogenous ligand binding (100 micros < t < 10 ms), which can be studied by using flash photolysis on deoxy Ngb; and (iv) displacement of the endogenous by the exogenous ligand (10 ms < t < 10 ks). All four processes are markedly nonexponential, suggesting that Ngb fluctuates among different conformations on surprisingly long time scales.

https://www.pnas.org/content/pnas/99/12/7992.full.pdf

Aninda J. Bhattacharyya

Papers

Succinonitrile as a Versatile Additive for Polymer Electrolytes

Employing synergistic interactions between few-layer WS2 and reduced graphene oxide to improve lithium storage, cyclability and rate capability of Li-ion batteries

Second Phase Effects on the Conductivity of Non‐Aqueous Salt Solutions: “Soggy Sand Electrolytes”

Nano-ionics in the context of lithium batteries

Ligand binding and protein dynamics in neuroglobin