Technological improvements in rechargeable solid-state batteries are being driven by an ever-increasing demand for portable electronic devices. Lithium-ion batteries are the systems of choice, offering high energy density, flexible and lightweight design, and longer lifespan than comparable battery technologies. We present a brief historical review of the development of lithium-based rechargeable batteries, highlight ongoing research strategies, and discuss the challenges that remain regarding the synthesis, characterization, electrochemical performance and safety of these systems.

Issues and challenges facing rechargeable lithium batteries

In the previous paper Ralph Brodd and Martin Winter described the different kinds of batteries and fuel cells. In this paper I will describe lithium batteries in more detail, building an overall foundation for the papers that follow which describe specific components in some depth and usually with an emphasis on the materials behavior. The lithium battery industry is undergoing rapid expansion, now representing the largest segment of the portable battery industry and dominating the computer, cell phone, and camera power source industry. However, the present secondary batteries use expensive components, which are not in sufficient supply to allow the industry to grow at the same rate in the next decade. Moreover, the safety of the system is questionable for the large-scale batteries needed for hybrid electric vehicles (HEV). Another battery need is for a high-power system that can be used for power tools, where only the environmentally hazardous Ni/ Cd battery presently meets the requirements. A battery is a transducer that converts chemical energy into electrical energy and vice versa. It contains an anode, a cathode, and an electrolyte. The anode, in the case of a lithium battery, is the source of lithium ions. The cathode is the sink for the lithium ions and is chosen to optimize a number of parameters, discussed below. The electrolyte provides for the separation of ionic transport and electronic transport, and in a perfect battery the lithium ion transport number will be unity in the electrolyte. The cell potential is determined by the difference between the chemical potential of the lithium in the anode and cathode, ∆G ) -EF. As noted above, the lithium ions flow through the electrolyte whereas the electrons generated from the reaction, Li ) Li+ + e-, go through the external circuit to do work. Thus, the electrode system must allow for the flow of both lithium ions and electrons. That is, it must be both a good ionic conductor and an electronic conductor. As discussed below, many electrochemically active materials are not good electronic conductors, so it is necessary to add an electronically conductive material such as carbon * To whom correspondence should be addressed. Phone and fax: (607) 777-4623. E-mail: stanwhit@binghamton.edu. 4271 Chem. Rev. 2004, 104, 4271−4301

http://www.chemie.uni-regensburg.de/Anorganische_Chemie/Vortrag/StudentenWS06-07/Vortrag_Amereller.pdf

Lithium Batteries and Cathode Materials

Research Development on Sodium-Ion Batteries

The status of ambient temperature sodium ion batteries is reviewed in light of recent developments in anode, electrolyte and cathode materials. These devices, although early in their stage of development, are promising for large-scale grid storage applications due to the abundance and very low cost of sodium-containing precursors used to make the components. The engineering knowledge developed recently for highly successful Li ion batteries can be leveraged to ensure rapid progress in this area, although different electrode materials and electrolytes will be required for dual intercalation systems based on sodium. In particular, new anode materials need to be identified, since the graphite anode, commonly used in lithium systems, does not intercalate sodium to any appreciable extent. A wider array of choices is available for cathodes, including high performance layered transition metal oxides and polyanionic compounds. Recent developments in electrodes are encouraging, but a great deal of research is necessary, particularly in new electrolytes, and the understanding of the SEI films. The engineering modeling calculations of Na-ion battery energy density indicate that 210 Wh kg−1 in gravimetric energy is possible for Na-ion batteries compared to existing Li-ion technology if a cathode capacity of 200 mAh g−1 and a 500 mAh g−1 anode can be discovered with an average cell potential of 3.3 V.

Sodium‐Ion Batteries

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

Pumped-Storage of Water: It is the most efficient; it is developed in very large scale capacity storage facilities which require specific sites; nevertheless, in the future due to its long lifetime it will play a significant role for intermediate time storage of a few hours to several days, and even for intermediate scale capacity energy storage. Electrochemical Energy Storage in Batteries: It is now used locally in some places that are not connected to the electricity network and on the smart grids for frequency regulation or small peak production shifts. Examples include sodium sulfur batteries (NaS) which are used in Japan; redox flow batteries under development, and some large scale lithium–ion batteries (LIBs) that are used in specific places. Storage via Hydrogen: The development of hydrogen as a way of using fuel cells is considered and seems very interesting from the pollution point of view at the local scale. From the technical point of view, most of the problems are almost solved. Nevertheless, hydrogen has to be produced and stored; and in this case, the yield is quite low, similar to that of the internal combustion engine. Electricity storage via hydrogen requires water electrolysis, H2 gas storage, and electricity production in fuel cells, all of which leads to a low efficiency and therefore, significant energy loss during electricity storage.

Sodium and Sodium‐Ion Batteries: 50 Years of Research

Electrochemical intercalation and deintercalation of NaxMnO2 bronzes

Operando X-ray absorption spectroscopy investigations have been carried out to follow changes in the atomic and electronic local structures of all three transition metals for the Li1.20Mn0.54Co0.13Ni0.13O2 layered oxide during the first and second charges and discharges of lithium batteries. The experiments were performed using a Quick-XAS monochromator on the SAMBA beamline at Synchrotron SOLEIL to record the three K-edges by edge-jumping between two energy ranges ([Mn, Co] and [Co, Ni]) every 3 min during the cycling of the battery. The results obtained especially at the Mn K-edge fully support the participation of oxygen in the reversible charge–discharge reaction of this Li- and Mn-rich layered material as a redox center and not only with oxygen loss, as was proposed previously.

Operando X-ray Absorption Study of the Redox Processes Involved upon Cycling of the Li-Rich Layered Oxide Li1.20Mn0.54Co0.13Ni0.13O2 in Li Ion Batteries

ω-LixV2O5 — a new electrode material for rechargeable lithium batteries☆

The NaMnFe2(PO4)3 alluaudite phase was prepared either by classical solid-state chemistry or by the sol−gel method. Its structure was investigated by Rietveld refinement of XRD and neutron diffraction data in order to precisely determine the cationic distribution. This 3D skeleton structure exhibits two types of 1D tunnels where the Na+ ions are localized. The material obtained by the sol−gel method exhibits a composition very close to the ideal one, contrary to previous works reported in literature. This study leads us to propose the following formulation for our sample: (Na0.81)A(1)(Na0.19)A(2)′(MnII0.87FeII0.13)M(1)(FeIII1.87MnIII0.13)M(2)(PO4)3. The iron/manganese exchange was revealed from neutron data and was supported by Mossbauer spectroscopy (presence of small amount of Fe2+ ions in the M(1) type site). The stability of the various Na+ ions sites within the tunnels were studied by DFT calculations. The intercalation/deintercalation properties of NaMnFe2(PO4)3 as positive electrode were tested in ...

Claude Delmas

Papers

Sodium and Sodium‐Ion Batteries: 50 Years of Research

Electrochemical intercalation and deintercalation of NaxMnO2 bronzes

Operando X-ray Absorption Study of the Redox Processes Involved upon Cycling of the Li-Rich Layered Oxide Li1.20Mn0.54Co0.13Ni0.13O2 in Li Ion Batteries

ω-LixV2O5 — a new electrode material for rechargeable lithium batteries☆

NaMnFe2(PO4)3 Alluaudite Phase: Synthesis, Structure, and Electrochemical Properties As Positive Electrode in Lithium and Sodium Batteries