Challenges for Rechargeable Li Batteries
TL;DR: In this paper, the authors reviewed the challenges for further development of Li rechargeable batteries for electric vehicles and proposed a nonflammable electrolyte with either a larger window between its lowest unoccupied molecular orbital and highest occupied molecular orbital (HOMO) or a constituent 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.
Abstract: 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.
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TL;DR: The battery systems reviewed here include sodium-sulfur batteries that are commercially available for grid applications, redox-flow batteries that offer low cost, and lithium-ion batteries whose development for commercial electronics and electric vehicles is being applied to grid storage.
Abstract: The increasing interest in energy storage for the grid can be attributed to multiple factors, including the capital costs of managing peak demands, the investments needed for grid reliability, and the integration of renewable energy sources. Although existing energy storage is dominated by pumped hydroelectric, there is the recognition that battery systems can offer a number of high-value opportunities, provided that lower costs can be obtained. The battery systems reviewed here include sodium-sulfur batteries that are commercially available for grid applications, redox-flow batteries that offer low cost, and lithium-ion batteries whose development for commercial electronics and electric vehicles is being applied to grid storage.
11,144 citations
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Abstract: The is a comprehensive review on the needs and potential storage technologies for electrical grid that is expected to integrate significant levels of renewables. This review offers details of the technologies, in terms of needs, status, challenges and future R&d directions.
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TL;DR: This review presents a comprehensive overview of the lithium metal anode and its dendritic lithium growth, summarizing the theoretical and experimental achievements and endeavors to realize the practical applications of lithium metal batteries.
Abstract: 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...
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TL;DR: This review describes some recent developments in the discovery of nanoelectrolytes and nanoeLECTrodes for lithium batteries, fuel cells and supercapacitors and the advantages and disadvantages of the nanoscale in materials design for such devices.
Abstract: New materials hold the key to fundamental advances in energy conversion and storage, both of which are vital in order to meet the challenge of global warming and the finite nature of fossil fuels. Nanomaterials in particular offer unique properties or combinations of properties as electrodes and electrolytes in a range of energy devices. This review describes some recent developments in the discovery of nanoelectrolytes and nanoelectrodes for lithium batteries, fuel cells and supercapacitors. The advantages and disadvantages of the nanoscale in materials design for such devices are highlighted.
8,157 citations
TL;DR: In this article, the authors showed that a reversible loss in capacity with increasing current density appears to be associated with a diffusion-limited transfer of lithium across the two-phase interface.
Abstract: Reversible extraction of lithium from LiFePO 4 (triphylite) and insertion of lithium into FePO 4 at 3.5 V vs. lithium at 0.05 mA/cm 2 shows this material to be an excellent candidate for the cathode of a low-power, rechargeable lithium battery that is inexpensive, nontoxic, and environmentally benign. Electrochemical extraction was limited to ∼0.6 Li/formula unit; but even with this restriction the specific capacity is 100 to 110 mAh/g. Complete extraction of lithium was performed chemically; it gave a new phase, FePO 4 , isostructural with heterosite, Fe 0.65 Mn 0.35 PO 4 . The FePO 4 framework of the ordered olivine LiFePO 4 is retained with minor displacive adjustments. Nevertheless the insertion/extraction reaction proceeds via a two-phase process, and a reversible loss in capacity with increasing current density appears to be associated with a diffusion-limited transfer of lithium across the two-phase interface. Electrochemical extraction of lithium from isostructural LiMPO 4 (M = Mn, Co, or Ni) with an LiClO 4 electrolyte was not possible; but successful extraction of lithium from LiFe 1-x Mn x PO 4 was accomplished with maximum oxidation of the Mn 3+ /Mn 2+ occurring at x = 0.5. The Fe 3+ /Fe 2+ couple was oxidized first at 3.5 V followed by oxidation of the Mn 3+ /Mn 2+ couple at 4.1 V vs. lithium. The Fe 3+ -O-Mn 2+ interactions appear to destabilize the Mn 2+ level and stabilize the Fe 2+ level so as to make the Mn 3+ /Mn 2+ energy accessible.
6,945 citations
TL;DR: The theoretical charge capacity for silicon nanowire battery electrodes is achieved and maintained a discharge capacity close to 75% of this maximum, with little fading during cycling.
Abstract: 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.
6,104 citations
TL;DR: The phytochemical properties of Lithium Hexafluoroarsenate and its Derivatives are as follows: 2.2.1.
Abstract: 2.1. Solvents 4307 2.1.1. Propylene Carbonate (PC) 4308 2.1.2. Ethers 4308 2.1.3. Ethylene Carbonate (EC) 4309 2.1.4. Linear Dialkyl Carbonates 4310 2.2. Lithium Salts 4310 2.2.1. Lithium Perchlorate (LiClO4) 4311 2.2.2. Lithium Hexafluoroarsenate (LiAsF6) 4312 2.2.3. Lithium Tetrafluoroborate (LiBF4) 4312 2.2.4. Lithium Trifluoromethanesulfonate (LiTf) 4312 2.2.5. Lithium Bis(trifluoromethanesulfonyl)imide (LiIm) and Its Derivatives 4313
5,710 citations
TL;DR: Some of the recent scientific advances in nanomaterials, and especially in nanostructured materials, for rechargeable lithium-ion batteries are reviewed.
Abstract: 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.
5,441 citations