The rampant generation of lithium hydroxide and carbonate impurities, commonly known as residual lithium, is a practical obstacle to the mass‐scale synthesis and handling of high‐nickel (>90 %) ...layered oxides and their use as high‐energy‐density cathodes for lithium‐ion batteries. Herein, we suggest a simple in situ method to control the residual lithium chemistry of a high‐nickel lithium layered oxide, Li(Ni0.91Co0.06Mn0.03)O2 (NCM9163), with minimal side effects. Based on thermodynamic considerations of the preferred reactions, we systematically designed a synthesis process that preemptively converts residual Li2O (the origin of LiOH and Li2CO3) into a more stable compound by injecting reactive SO2 gas. The preformed lithium sulfate thin film significantly suppresses the generation of LiOH and Li2CO3 during both synthesis and storage, thereby mitigating slurry gelation and gas evolution and improving the cycle stability.
A simple in situ method to control the residual lithium in high‐nickel lithium layered oxide is designed. Residual Li2O (the origin of LiOH and Li2CO3) is preemptively converted into the Li2SO4 thin film by injecting SO2 gas during calcination. This method suppresses the generation of LiOH and Li2CO3 during both synthesis and storage, thereby mitigating slurry gelation and gas evolution and improving cycle stability.
Since their market introduction in 1991, lithium ion batteries (LIBs) have developed evolutionary in terms of their specific energies (Wh/kg) and energy densities (Wh/L). Currently, they do not only ...dominate the small format battery market for portable electronic devices, but have also been successfully implemented as the technology of choice for electromobility as well as for stationary energy storage. Besides LIBs, a variety of different technologically promising battery concepts exists that, depending on the respective technology, might also be suitable for various application purposes. These systems of the “next generation,” the so-called post-lithium ion batteries (PLIBs), such as metal/sulfur, metal/air or metal/oxygen, or “post-lithium technologies” (systems without Li), which are based on alternative single (Na
+
, K
+
) or multivalent ions (Mg
2+
, Ca
2+
), are currently being studied intensively. From today’s point of view, it seems quite clear that there will not only be a single technology for all applications (technology monopoly), but different battery systems, which can be especially suitable or combined for a particular application (technology diversity). In this review, we place the lithium ion technology in a historical context and give insights into the battery technology diversity that evolved during the past decades and which will, in turn, influence future research and development.
All‐solid‐state lithium batteries (ASSLBs) are considered as the next generation electrochemical energy storage devices because of their high safety and energy density, simple packaging, and wide ...operable temperature range. The critical component in ASSLBs is the solid‐state electrolyte. Among all solid‐state electrolytes, the sulfide electrolytes have the highest ionic conductivity and favorable interface compatibility with sulfur‐based cathodes. The ionic conductivity of sulfide electrolytes is comparable with or even higher than that of the commercial organic liquid electrolytes. However, several critical challenges for sulfide electrolytes still remain to be solved, including their narrow electrochemical stability window, the unstable interface between the electrolyte and the electrodes, as well as lithium dendrite formation in the electrolytes. Herein, the emerging sulfide electrolytes and preparation methods are reviewed. In particular, the required properties of the sulfide electrolytes, such as the electrochemical stabilities of the electrolytes and the compatible electrode/electrolyte interfaces are highlighted. The opportunities for sulfide‐based ASSLBs are also discussed.
All‐solid‐state lithium batteries are considered to be next‐generation devices for electrochemical energy storages due to their superiority in high safety and energy density. Sulfide electrolytes have become one of the most promising ion conductors due to their high ionic conductivities. At the same time, the favorable interface compatibility of sulfide electrolytes with sulfide‐based cathodes delivers bright prospect of all‐solid‐state lithium batteries.
To achieve high ionic conductivity for solid electrolyte, an artificial Li‐rich interface layer of about 60 nm thick has been constructed in polymer‐based poly(ethylene oxide)‐lithium ...bis(trifluoromethanesulfonyl)imide composite solid electrolyte (briefly noted as PEOm) by adding Li‐based alloys. As revealed by high‐resolution transmission electron microscopy and electron energy loss spectroscopy, an artificial interface layer of amorphous feature is created around the Li‐based alloy particles with the gradient distribution of Li across it. Electrochemical analysis and theoretical modeling demonstrate that the interface layer provides fast ion transport path and plays a key role in achieving high and stable ionic conductivity for PEOm‐Li21Si5 composite solid electrolyte. The PEOm‐5%Li21Si5 composite electrolyte exhibits an ionic conductivity of 3.9 × 10–5 S cm−1 at 30 °C and 5.6 × 10−4 S cm−1 at 45 °C. The LiFePO4 | PEOm‐5%Li21Si5 | Li all‐solid‐state batteries could maintain a stable capacity of 129.2 mA h g−1 at 0.2 C and 30 °C after 100 cycles, and 111.3 mA h g−1 after 200 cycles at 0.5 C and 45 °C, demonstrating excellent cycling stability and high‐rate capability.
A Li‐rich artificial solid electrolyte interface (SEI) layer about 60 nm thick is successfully designed and constructed in a Li alloy filled poly(ethylene oxide) polymer electrolyte to achieve high ionic conductivity for lithium metal batteries. The LiFePO4|Li all‐solid‐state batteries exhibit high cycling performance of 111.3 mA h g–1 after 200 cycles at 0.5 C in 45 °C.
Batteries are a promising technology in the field of electrical energy storage and have made tremendous strides in recent few decades. In particular, lithium‐ion batteries are leading the smart ...device era as an essential component of portable electronic devices. From the materials aspect, new and creative solutions are required to resolve the current technical issues on advanced lithium (Li) batteries and improve their safety. Metal‐organic frameworks (MOFs) are considered as tempting candidates to satisfy the requirements of advanced energy storage technologies. In this review, we discuss the characteristics of MOFs for application in different types of Li batteries. A review of these emerging studies in which MOFs have been applied in lithium storage devices can provide an informative blueprint for future MOF research on next‐generation advanced energy storage devices.
In this review, we discuss the characteristics of metal‐organic frameworks (MOFs) applied to lithium storage devices containing Li‐ion, Li‐sulfur, Li‐metal, and Li‐O2. We summarize the origin, nomenclature, and synthesis method of MOFs, and report on recent studies in which MOFs and MOF‐derived materials are applied to lithium rechargeable batteries. This provides an informative roadmap for next‐generation advanced energy storage devices.
A molten lithium infusion strategy has been proposed to prepare stable Li‐metal anodes to overcome the serious issues associated with dendrite formation and infinite volume change during cycling of ...lithium‐metal batteries. Stable host materials with superior wettability of molten Li are the prerequisite. Here, it is demonstrated that a series of strong oxidizing metal oxides, including MnO2, Co3O4, and SnO2, show superior lithiophilicity due to their high chemical reactivity with Li. Composite lithium‐metal anodes fabricated via melt infusion of lithium into graphene foams decorated by these metal oxide nanoflake arrays successfully control the formation and growth of Li dendrites and alleviate volume change during cycling. A resulting Li‐Mn/graphene composite anode demonstrates a super‐long and stable lifetime for repeated Li plating/stripping of 800 cycles at 1 mA cm−2 without voltage fluctuation, which is eight times longer than the normal lifespan of a bare Li foil under the same conditions. Furthermore, excellent rate capability and cyclability are realized in full‐cell batteries with Li‐Mn/graphene composite anodes and LiCoO2 cathodes. These results show a major advancement in developing a stable Li anode for lithium‐metal batteries.
A series of metal oxide nanoflakes are explored as new lithiophilic materials for ultra‐stable anodes of lithium‐metal batteries. By minimizing the volume change of Li metal and dendrite formation, the composite Li anode exhibits a super‐long and stable lifetime for over 800 cycles.
The lithium–sulfur (Li–S) battery is a promising high‐energy‐density storage system. The strong anchoring of intermediates is widely accepted to retard the shuttle of polysulfides in a working ...battery. However, the understanding of the intrinsic chemistry is still deficient. Inspired by the concept of hydrogen bond, herein we focus on the Li bond chemistry in Li–S batteries through sophisticated quantum chemical calculations, in combination with 7Li nuclear magnetic resonance (NMR) spectroscopy. Identified as Li bond, the strong dipole–dipole interaction between Li polysulfides and Li–S cathode materials originates from the electron‐rich donors (e.g., pyridinic nitrogen (pN)), and is enhanced by the inductive and conjugative effect of scaffold materials with π‐electrons (e.g., graphene). The chemical shift of Li polysulfides in 7Li NMR spectroscopy, being both theoretically predicted and experimentally verified, is suggested to serve as a quantitative descriptor of Li bond strength. These theoretical insights were further proved by actual electrochemical tests. This work highlights the importance of Li bond chemistry in Li–S cell and provides a deep comprehension, which is helpful to the cathode materials rational design and practical applications of Li–S batteries.
Lithium bond chemistry in Li–S batteries is probed by sophisticated quantum chemical calculations in combination with 7Li NMR spectroscopy. The chemical shift in 7Li NMR spectroscopy is suggested to be a quantitative descriptor of Li bond strength, propelling the advances in Li–S chemistry through materials genome design and high throughput screening.
Ti3C2Tx, a typical representative among the emerging family of 2D layered transition metal carbides and/or nitrides referred to as MXenes, has exhibited multiple advantages including metallic ...conductivity, a plastic layer structure, small band gaps, and the hydrophilic nature of its functionalized surface. As a result, this 2D material is intensively investigated for application in the energy storage field. The composition, morphology and texture, surface chemistry, and structural configuration of Ti3C2Tx directly influence its electrochemical performance, e.g., the use of a well‐designed 2D Ti3C2Tx as a rechargeable battery anode has significantly enhanced battery performance by providing more chemically active interfaces, shortened ion‐diffusion lengths, and improved in‐plane carrier/charge‐transport kinetics. Some recent progresses of Ti3C2Tx MXene are achieved in energy storage. This Review summarizes recent advances in the synthesis and electrochemical energy storage applications of Ti3C2Tx MXene including supercapacitors, lithium‐ion batteries, sodium‐ion batteries, and lithium–sulfur batteries. The current opportunities and future challenges of Ti3C2Tx MXene are addressed for energy‐storage devices. This Review seeks to provide a rational and in‐depth understanding of the relation between the electrochemical performance and the nanostructural/chemical composition of Ti3C2Tx, which will promote the further development of 2D MXenes in energy‐storage applications.
2D MXenes have gained attention as one promising kind of materials for electrochemical energy storage due to their high conductivity, layered structure, and tunable electrical/mechanical properties. Herein, for Ti3C2Tx MXene, recent advances in synthesis strategies, tailored properties, and material design are reviewed, along with detailed examples of energy‐storage applications, including lithium‐ion batteries, sodium‐ion batteries, lithium–sulfur batteries, and supercapacitors.
This book features an in-depth description of different lithium-ion applications, including important features such as safety and reliability. This title acquaints readers with the numerous and often ...consumer-oriented applications of this widespread battery type. This book also explores the concepts of nanostructured materials, as well as the importance of battery management systems. This handbook is an invaluable resource for electrochemical engineers and battery and fuel cell experts everywhere, from research institutions and universities to a worldwide array of professional industries.
Although metallic lithium is an extremely promising anode for lithium‐based batteries due to its high theoretical capacity, the uncontrollable growth of lithium dendrites, in particular under deep ...stripping and plating, have stagnated its application. It is demonstrated that parallelly aligned MXene (Ti3C2Tx
) layers enable the efficient guiding of lithium nucleation and growth on the surface of 2D MXene nanosheets, giving rise to horizontal‐growth lithium anodes. Moreover, the inherent fluorine terminations in MXene afford a uniform and durable solid electrolyte interface with lithium fluoride at the anode/electrolyte interface, efficiently regulating electromigration of lithium ions. Thus, a dendrite‐free lithium anode with a long cycle life up to 900 h and excellent deep stripping–plating capabilities up to 35 mAh cm−2 is achieved, which can further serve as an anode for a lithium metal battery, exhibiting high cycle stability up to 1000 cycles.
A dendrite‐free lithium anode with good deep striping–plating up to 35 mAh cm−2 is achieved via parallelly aligned MXene (Ti3C2Tx) layers. This not only allows the efficient guiding of lithium nucleation on the surface of the MXene nanosheets, but also facilitates the horizontal growth of lithium on the MXene layers.
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