Recent advances in the electrolytes for interfacial stability of high-voltage cathodes in lithium-ion batteries
TL;DR: In this article, the authors describe several challenges for the cathode (spinel lithium manganese oxide (LMO), lithium cobalt oxide (LCO), lithium nickel cobalt manganes oxide (NCM), spinel lithium ion ion oxide (SILO), and lithium-rich layered oxide (Li-rich cathode))-electrolyte interfaces and highlight the recent progress in the use of oxidative additives and highvoltage solvents in high-performance cells.
Abstract: Advanced electrolytes with unique functions such as in situ formation of a stable artificial solid electrolyte interphase (SEI) layer on the anode and the cathode, and the improvement in oxidation stability of the electrolyte have recently gained recognition as a promising means for highly reliable lithium-ion batteries with high energy density. In this review, we describe several challenges for the cathode (spinel lithium manganese oxide (LMO), lithium cobalt oxide (LCO), lithium nickel cobalt manganese oxide (NCM), spinel lithium manganese nickel oxide (LNMO), and lithium-rich layered oxide (Li-rich cathode))-electrolyte interfaces and highlight the recent progress in the use of oxidative additives and high-voltage solvents in high-performance cells.
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TL;DR: Li et al. as discussed by the authors employed a non-nucleophilic organic base, ethoxy(pentafluoro) cyclotriphosphazene (PFN), as a multifunctional additive to simultaneously enhance the chemical stability and safety of the FEC-LiPF6 carbonate-based electrolytes.
21 citations
TL;DR: LiPO3, one of the compounds from the Li2O-P2O5 binary phase diagram, is successfully coated on LiNi0.5Mn1.5O4 particles as a bifunctional layer with respect to its good ionic conductivity and chemical passivation properties.
Abstract: LiPO3, one of the compounds from the Li2O–P2O5 binary phase diagram, is successfully coated on LiNi0.5Mn1.5O4 particles as a bifunctional layer with respect to its good ionic conductivity and chemical passivation properties. The coating layer with a thickness of 1 nm is identified by X-ray diffraction (XRD) and high resolution transition electron microscopy (TEM). Fourier transform-infrared spectrometer (FT-IR) and Raman spectra reveal that LiPO3 coated LiNi0.5Mn1.5O4 (LiPO3/LiNi0.5Mn1.5O4) possesses a cubic spinel structure with a space group of Fdm. The electrochemical properties of synthesized materials are evaluated in both Li ion half cells and full cells. LiPO3/LiNi0.5Mn1.5O4 exhibits significantly enhanced rate performance and superior cyclability compared with non-coated LiNi0.5Mn1.5O4. Impedance analysis indicates that the LiPO3 coating dramatically reduces the LiPO3/LiNi0.5Mn1.5O4 cell impedance, especially the resistances of the lithium ion migration compared with non-coated LiNi0.5Mn1.5O4. In addition, the LiPO3 coating can effectively act as a passivation layer to minimize electrolyte–electrode interface side reactions and thus improve the long-term cyclability.
21 citations
TL;DR: In this paper, the authors report on the fabrication and characterization of functional 3D LiMn2O4 thin-film electrodes giving a footprint capacity of 0.5 mA h cm−2.
Abstract: In this paper, we report on the fabrication and characterization of functional 3D LiMn2O4 thin-film electrodes giving a footprint capacity of 0.5 mA h cm−2, i.e. surpassing any thin-film electrode reported thus far. Using a novel process based on a solid state reaction between electrolytic manganese dioxide (EMD) and Li2CO3 stacked-layers, crack-free, uniform and continuous lithium manganese oxide (LMO) thin films were fabricated on planar and high aspect ratio microstructured substrates. The fabricated LMO films are shown to have a stoichiometry close to that of spinel LiMn2O4 with a homogeneous elemental distribution throughout the layer. The prepared thin films are electrochemically active reaching a volumetric capacity of 1200 A h L−1, which is close to the theoretical capacity of spinel LiMn2O4. The few hundred nanometer thin-film morphology allows for use of both the 3 V and 4 V regions. The 3D LMO thin-film electrodes had 21 times the capacity of the planar LMO thin film with similar thickness due to the area enhancement and the excellent conformal coating of the high aspect ratio micropillar substrates. An excellent rate performance was demonstrated for both the planar and the high aspect ratio substrates where 48% and 30% of the theoretical LiMn2O4 capacity are maintained at very high C-rates of 20C and 100C, respectively.
21 citations
TL;DR: In this article, the authors reported the synthesis of a LLO and its performance enhancement by using boron-containing electrolyte additives, achieving a stable specific capacity of 202 mA h g−1 at 0.5C and a remarkable capacity retention of 96.4% after 100 cycles.
Abstract: Lithium-rich layered oxides (LLO), as the most attractive cathode materials for high-energy lithium-ion batteries (LIBs), are plagued by poor cyclability due to structural and electrode/electrolyte interface instability. Herein, we report the synthesis of a LLO and its performance enhancement by using boron-containing electrolyte additives. In a formulated 1.0 M LiPF6 ethylene carbonate/ethyl methyl carbonate electrolyte with 0.1 M lithium bis(oxalato)borate (LiBOB), the battery assembled with Li1.2Mn0.54Co0.13Ni0.13O2 microspheres presents a stable specific capacity of 202 mA h g−1 at 0.5C and a remarkable capacity retention of 96.4% after 100 cycles, significantly outperforming the cathode in the baseline electrolyte without LiBOB. The combination of voltammetry, impedance, microscopy, and spectroscopic analysis and density functional theory (DFT) calculations corroborates the beneficial effect of LiBOB in stabilizing the LLO/electrolyte interface. Reactions between LiBOB and activated oxygen radicals result in the formation of a dense cathode electrolyte interface (CEI) film (∼15 nm) containing oxalate, lithium fluoride and alkyl borate species, which contributes to suppression of the capacity/voltage decay of the LLO. These results would provide insight in understanding the effect of boron-containing electrolyte additives in upgrading high-capacity Li-rich cathode materials.
20 citations
TL;DR: In this paper, the highvoltage stability of propylene carbonate solutions in intermediate concentration range is studied by means of cyclic voltammetry, galvanostatic cycling and X-ray photoelectron spectroscopy using LiCoPO4 and LiNi0.5Mn1.5O4 cathode materials.
19 citations
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TL;DR: A brief historical review of the development of lithium-based rechargeable batteries is presented, ongoing research strategies are highlighted, and the challenges that remain regarding the synthesis, characterization, electrochemical performance and safety of these systems are discussed.
Abstract: 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.
17,496 citations
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
TL;DR: The energy that can be stored in Li-air and Li-S cells is compared with Li-ion; the operation of the cells is discussed, as are the significant hurdles that will have to be overcome if such batteries are to succeed.
Abstract: Li-ion batteries have transformed portable electronics and will play a key role in the electrification of transport. However, the highest energy storage possible for Li-ion batteries is insufficient for the long-term needs of society, for example, extended-range electric vehicles. To go beyond the horizon of Li-ion batteries is a formidable challenge; there are few options. Here we consider two: Li-air (O(2)) and Li-S. The energy that can be stored in Li-air (based on aqueous or non-aqueous electrolytes) and Li-S cells is compared with Li-ion; the operation of the cells is discussed, as are the significant hurdles that will have to be overcome if such batteries are to succeed. Fundamental scientific advances in understanding the reactions occurring in the cells as well as new materials are key to overcoming these obstacles. The potential benefits of Li-air and Li-S justify the continued research effort that will be needed.
7,895 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: The Review will consider some of the current scientific issues underpinning lithium batteries and electric double-layer capacitors.
Abstract: Energy-storage technologies, including electrical double-layer capacitors and rechargeable batteries, have attracted significant attention for applications in portable electronic devices, electric vehicles, bulk electricity storage at power stations, and “load leveling” of renewable sources, such as solar energy and wind power. Transforming lithium batteries and electric double-layer capacitors requires a step change in the science underpinning these devices, including the discovery of new materials, new electrochemistry, and an increased understanding of the processes on which the devices depend. The Review will consider some of the current scientific issues underpinning lithium batteries and electric double-layer capacitors.
2,412 citations