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

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

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

BACKGROUND Materials by design is an appealing idea that is very hard to realize in practice. Combining the best of different ingredients in one ultimate material is a task for which we currently have no general solution. However, we do have some successful examples to draw upon: Composite materials and III-V heterostructures have revolutionized many aspects of our lives. Still, we need a general strategy to solve the problem of mixing and matching crystals with different properties, creating combinations with predetermined attributes and functionalities. ADVANCES Two-dimensional (2D) materials offer a platform that allows creation of heterostructures with a variety of properties. One-atom-thick crystals now comprise a large family of these materials, collectively covering a very broad range of properties. The first material to be included was graphene, a zero-overlap semimetal. The family of 2D crystals has grown to includes metals (e.g., NbSe 2 ), semiconductors (e.g., MoS 2 ), and insulators [e.g., hexagonal boron nitride (hBN)]. Many of these materials are stable at ambient conditions, and we have come up with strategies for handling those that are not. Surprisingly, the properties of such 2D materials are often very different from those of their 3D counterparts. Furthermore, even the study of familiar phenomena (like superconductivity or ferromagnetism) in the 2D case, where there is no long-range order, raises many thought-provoking questions. A plethora of opportunities appear when we start to combine several 2D crystals in one vertical stack. Held together by van der Waals forces (the same forces that hold layered materials together), such heterostructures allow a far greater number of combinations than any traditional growth method. As the family of 2D crystals is expanding day by day, so too is the complexity of the heterostructures that could be created with atomic precision. When stacking different crystals together, the synergetic effects become very important. In the first-order approximation, charge redistribution might occur between the neighboring (and even more distant) crystals in the stack. Neighboring crystals can also induce structural changes in each other. Furthermore, such changes can be controlled by adjusting the relative orientation between the individual elements. Such heterostructures have already led to the observation of numerous exciting physical phenomena. Thus, spectrum reconstruction in graphene interacting with hBN allowed several groups to study the Hofstadter butterfly effect and topological currents in such a system. The possibility of positioning crystals in very close (but controlled) proximity to one another allows for the study of tunneling and drag effects. The use of semiconducting monolayers leads to the creation of optically active heterostructures. The extended range of functionalities of such heterostructures yields a range of possible applications. Now the highest-mobility graphene transistors are achieved by encapsulating graphene with hBN. Photovoltaic and light-emitting devices have been demonstrated by combining optically active semiconducting layers and graphene as transparent electrodes. OUTLOOK Currently, most 2D heterostructures are composed by direct stacking of individual monolayer flakes of different materials. Although this method allows ultimate flexibility, it is slow and cumbersome. Thus, techniques involving transfer of large-area crystals grown by chemical vapor deposition (CVD), direct growth of heterostructures by CVD or physical epitaxy, or one-step growth in solution are being developed. Currently, we are at the same level as we were with graphene 10 years ago: plenty of interesting science and unclear prospects for mass production. Given the fast progress of graphene technology over the past few years, we can expect similar advances in the production of the heterostructures, making the science and applications more achievable.

2D materials and van der Waals heterostructures

The lithium metal battery is strongly considered to be one of the most promising candidates for high-energy-density energy storage devices in our modern and technology-based society. However, uncontrollable lithium dendrite growth induces poor cycling efficiency and severe safety concerns, dragging lithium metal batteries out of practical applications. This review presents a comprehensive overview of the lithium metal anode and its dendritic lithium growth. First, the working principles and technical challenges of a lithium metal anode are underscored. Specific attention is paid to the mechanistic understandings and quantitative models for solid electrolyte interphase (SEI) formation, lithium dendrite nucleation, and growth. On the basis of previous theoretical understanding and analysis, recently proposed strategies to suppress dendrite growth of lithium metal anode and some other metal anodes are reviewed. A section dedicated to the potential of full-cell lithium metal batteries for practical applicatio...

Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review.

A new dissipation behavior is reported in superconducting Bi2.2Sr2Ca0.8Cu2Oa+δfor all temperatures belowTc and all magnetic fields exceeding Hc1. The current-independent electrical resistivity is thermally activated and can be described by an Arrhenius law with a single prefactor and a magnetic-field-and orientation-dependent activation energyU 0 (H,o).This behavior is markedly different from past observations and will be discussed in terms of flux creep and flux flow. This thermally activated behavior implies a finite resistance at all temperatures and all fields exceeding H c1 determined by the activation energy as the only parameter.

/pdf/thermally-activated-dissipation-in-bi2-2sr2ca0-8cu2o8-d-3gc0z58l7n.pdf

Thermally activated dissipation in Bi2.2Sr2Ca0.8Cu2O8+δ

The dissipation below ${\mathit{T}}_{\mathit{c}}$ has been studied for representatives of all classes of cuprate high-temperature superconductors, including ${\mathrm{Ba}}_{2}$${\mathrm{YCu}}_{3}$${\mathrm{O}}_{7\mathrm{\ensuremath{-}}\mathrm{\ensuremath{\delta}}}$, and Bi and Tl compounds. The results are parametrized in the framework of flux creep, with the largest activation energies found in ${\mathrm{Ba}}_{2}$${\mathrm{YCu}}_{3}$${\mathrm{O}}_{7}$. It is argued that the magnitude of dissipative flux motion is more related to the electronic anisotropy of the material than the actual defect structure. The thermally activated flux creep model, whose parameters are extracted from dc measurements, consistently describes also dynamic measurements, including the irreversibility line and the melting transition. Finally, the similarities in dissipative behavior are emphasized between high-${\mathit{T}}_{\mathit{c}}$ materials, very thin films, and layered low-${\mathit{T}}_{\mathit{c}}$ superconductors.

/pdf/dissipative-flux-motion-in-high-temperature-superconductors-1k71lm9xlm.pdf

Dissipative flux motion in high-temperature superconductors

The Abrikosov flux lattice is imaged in NbSe2 by tunneling into the superconducting gap edge with a low-temperature scanning-tunneling microscope. The tunneling conductance into a single vortex core is strongly peaked at the Fermi energy, suggesting the existence of core states or core excitations. As one moves away from the core, this feature evolves into a density of states which is consistent with a BCS superconducting gap.

Scanning-tunneling-microscope observation of the Abrikosov flux lattice and the density of states near and inside a fluxoid

Single crystal sof the 84-K superconductor ${\mathrm{Bi}}_{2.2}{\mathrm{Sr}}_{2}{\mathrm{Ca}}_{0.8}{\mathrm{Cu}}_{2}{\mathrm{O}}_{8+\ensuremath{\delta}}$ were characterized by x-ray diffraction, dc magnetic susceptibility, electrical resistivity, and microwave absorption. The structure has ${[\mathrm{Cu}{\mathrm{O}}_{2}]}_{\ensuremath{\infty}}$ planes separated by calcium atoms, edge-shared bismuth oxide double layers, and an incommensurate superlattice along $b$ with a period of 4.76. The in-plane resistivity above ${T}_{c}$ is linear in $T$, with ${\ensuremath{\rho}}_{\mathrm{RT}}=130$ \ensuremath{\mu}\ensuremath{\Omega} cm. Initial results on Pb substitution yielding ${T}_{c}'\mathrm{s}$ of 107 K are reported.

Structure and physical properties of single crystals of the 84-K superconductor Bi 2.2 Sr 2 Ca 0.8 Cu 2 O 8+δ

Neutron-diffraction studies of ${\mathrm{TiSe}}_{2}$ show that a second-order structural phase transition occurs at ${T}_{0}=202$ K involving transverse atomic displacements with wave vector $\stackrel{\ensuremath{\rightarrow}}{\mathrm{q}}=(\frac{1}{2},0,\frac{1}{2})$. The electronic transport properties of the most nearly stoichiometric crystals show that ${\mathrm{TiSe}}_{2}$ is a semimetal with ${n}_{e}={n}_{h}={10}^{20}$/${\mathrm{cm}}^{3}$. Small impurity concentrations or deviations from stoichiometry reduce ${n}_{h}$, increase ${n}_{e}$, and suppress the phase transition. This reduction together with the observed displacement pattern lead us to speculate that the transition is driven by an electron-hole coupling.

Joseph V. Waszczak

Papers

Thermally activated dissipation in Bi2.2Sr2Ca0.8Cu2O8+δ

Dissipative flux motion in high-temperature superconductors

Scanning-tunneling-microscope observation of the Abrikosov flux lattice and the density of states near and inside a fluxoid

Structure and physical properties of single crystals of the 84-K superconductor Bi 2.2 Sr 2 Ca 0.8 Cu 2 O 8+δ

Electronic properties and superlattice formation in the semimetal TiSe 2