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Over the past decades, Li-ion battery (LIB) has turned into one of the most important advances in the history of technology due to its extensive and in-depth impact on our life. Its omnipresence in all electric vehicles, consumer electronics and electric grids relies on the precisely tuned electrochemical dynamics and interactions among the electrolytes and the diversified anode and cathode chemistries therein. With consumers' demand for battery performance ever increasing, more and more stringent requirements are being imposed upon the established equilibria among these LIB components, and it became clear that the state-of-the-art electrolyte systems could no longer sustain the desired technological trajectory. Driven by such gap, researchers started to explore more unconventional electrolyte systems. From superconcentrated solvent-in-salt electrolytes to solid-state electrolytes, the current research realm of novel electrolyte systems has grown to unprecedented levels. In this review, we will avoid discussions on current state-of-the-art electrolytes but instead focus exclusively on unconventional electrolyte systems that represent new concepts. [ABSTRACT FROM AUTHOR]

Abstract: Well dispersed chestnut-like Cd2Ge2O6 (CGO) and Cd2Ge2O6/reduced graphene oxide (CGO/RGO) nanocomposites are successfully prepared via a facile one-pot hydrothermal method and characterized as novel lithium storage materials for the first time. Electrochemical characterization of lithiation/delithiation of the CGO/RGO nanocomposites reveals a large capacity of 943mAhg−1 for the first cycle and a capacity retention of 721mAhg−1 even after 100 cycles. The superior electrochemical performance of the CGO/RGO nanocomposites electrode compared to the pure CGO electrode can be attributed to the well dispersed RGO which enhances the electronic conductivity and accommodate the volume change during the lithium storage process. [Copyright &y& Elsevier]

Abstract: Equilibrium potential hysteresis of electrode materials refers to the phenomenon that discharge equilibrium potential is lower than charge equilibrium potential. It is induced by the strain accommodation energy of phase transformation. Taking LiFePO4 as an example, the equilibrium potential hysteresis and accommodation energy of two LiFePO4 with different particle sizes were characterized using galvanostatic intermittent titration technique (GITT), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) methods. The LiFePO4 sample with 40nm particle size has lower accommodation energy than that of 100nm LiFePO4, which is due to a narrower miscibility gap and smaller potential hysteresis of 40nm LiFePO4 comparing to 100nm LiFePO4. The phase transformation of LiFePO4 occurs only at potential levels above delithiation (charge) equilibrium potential and below lithiation (discharge) equilibrium potential. No phase transformation occurs when charge/discharge is limited in the potential hysteresis range, i.e. LiFePO4 behaves like a solid solution in the potential hysteresis range. A reliable EIS can only be obtained when it is performed at the center of potential hysteresis and the potential amplitude does not exceed the range of equilibrium potential hysteresis. The analysis on strain accommodation and potential hysteresis of LiFePO4 cathodes during Li ion insertion/extraction is also suitable for other phase transformation electrodes. [ABSTRACT FROM AUTHOR]

Abstract: The rate performances of four mixed conductive electrodes (Li4/3Ti5/3O4, LiFePO4, LiCoO2 and LiCo1/3Ni1/3Mn1/3O2) were investigated using galvanostatic charge/discharge, electrochemical impedance Spectroscopy (EIS) and galvanostatic intermittent titration (GITT). These four electrode materials can be roughly divided into two groups according to the structure change during Li intercalation/extraction, i.e. the phase transition materials (Li4/3Ti5/3O4 and LiFePO4) and mixed phase transformation and solid solution materials (LiNi1/3Mn1/3Co1/3O2 and LiCoO2). Both the ionic conductivity and phase transition kinetics have a strong impact on the rate capability of the electrode material in addition to the generally accepted factors such as particle size and electronic conductivity. The rate capabilities of Li4/3Ti5/3O4 and LiFePO4, which have an extended flat region in the charge/discharge curves, mainly depended on their phase transition kinetics. The rate performance of the solid solution materials were controlled by the ionic conductivity, with some influence from the electronic conductivity. [Copyright &y& Elsevier]

Abstract: The increase in energy density and power density requirements for lithium-ion secondary cells for commercial applications has led to a search for higher capacity electrode materials than those available today. Silicon would seem to be a possible alternative for the graphite or carbon anode because its intercalation capacity is the highest known. However, the large capacity fade observed during initial cycling has prevented the silicon anode from being commercialized. Here we present a review of methodologies adopted for reducing the capacity fade observed in silicon-based anodes, discuss the challenges that remain in using silicon and silicon-based anodes, and propose possible approaches for overcoming them. [Copyright &y& Elsevier]

Abstract: LiFe0.9Mg0.1PO4 material was prepared by mechanical milling method, followed by heat treatment. The equilibrium potential-composition isotherm of LiFe0.9Mg0.1PO4 and charge–discharge kinetics of LiFe0.9Mg0.1PO4 were measured using galvanostatic intermittent titration technique (GITT), potential-step chronoamperometry (PSCA), and electrochemical impedance spectroscopy (EIS). The rate performance of the cathode is controlled by the charge-transfer kinetics, electronic conductivity, Li-ion diffusion capability, and phase transformation rate. Since LiFe0.9Mg0.1PO4 has a fast charge-transfer reaction and high electronic and ionic diffusivity, the phase transformation between LiFe0.9Mg0.1PO4 and Li0.1Fe0.9Mg0.1PO4 begins to play a more important role in the charge–discharge process, as is evident by an inductive loop induced by the phase transformation in the low frequency region of EIS. The phase purity and morphology of LiFe0.9Mg0.1PO4 were also observed using X-ray diffraction (XRD) and scanning electron microscopy (SEM). [Copyright &y& Elsevier]

The accurate estimation of the state of charge (SOC) of lithium-ion batteries is critical in battery energy storage systems. This paper introduces a novel approach, the AdaBoost–BPNN model, to overcome the limitations of traditional data-driven estimation methods, such as a low estimation accuracy and poor generalization ability. The proposed model employs a back propagation neural network (BPNN) for the preliminary estimation. Subsequently, an AdaBoost–BPNN model is developed as a strong learner using the AdaBoost integration algorithm. Each BPNN sub-model serves as a weak learner within the AdaBoost framework. The final output of the strong learner is obtained by combining the individual outputs from the weak learners using weighting factors. This adaptive adjustment of weighting factors enhances the accuracy of SOC estimation. The proposed SOC estimation algorithm is evaluated and validated through experimental analysis. Throughout the paper, theoretical analysis is conducted, and the proposed AdaBoost–BPNN model is validated and verified using experimental results. The results demonstrate that the AdaBoost–BPNN model outperforms traditional methods in accurately estimating SOC under various conditions, including constant current-constant voltage (CCCV) charging, dynamical stress testing (DST), US06, a federal urban driving schedule (FUDS), and pulse discharge conditions. [ABSTRACT FROM AUTHOR]

Synthesis of silicon/carbon (Si/C) composites from biomass resources could enable the effective utilization of agricultural products in the battery industry with economical as well as environmental benefits. Herein, a simplified process was developed to synthesize Si/C from biomass, by using a low‐cost agricultural byproduct "rice husk (RH)" as a model. This process includes the calcination of RH for SiO2/C and the reduction of SiO2/C by Al in molten salts at a moderate temperature. This process does not need the removal of carbon before thermal reduction of SiO2, which is thought to be necessary to avoid the formation of SiC at elevated temperatures. Thus, carbon derived from biomass can be directly used for Si/C composites for anode materials. The resultant Si/C shows a high reversible capacity of 1309 mAh g−1 and long cycle life (300 cycles). This research advocates a new and simplified strategy for the synthesis of RH‐based biomass‐derived Si/C, which is beneficial for low‐cost, environmentally friendly, and green energy storage applications. [ABSTRACT FROM AUTHOR]

• Li 3 VO 4 nanoparticles in porous N-doped carbon are synthesized. • Porous N-doped carbon is derived from melamine and citric acid. • Porous N-doped carbon and Li 3 VO 4 nanoparticles together give superior performances. • This composite exhibits a capacity of 236.6 mAh g−1 after 1000 cycles at 4.0 A g−1. • This composite coupled with LiCoO 2 as full cells are examined. Li 3 VO 4 nanoparticles in N-doped carbon with porous structure are synthesized using supermolecular aggregates formed by melamine and citric acid as the nitrogen source, via a dry-freezing process, followed with a calcination. Nitrogen doping enhances the interaction between Li 3 VO 4 and carbon, reduces the charge-transfer resistance over the interface, and restrains the pulverization and aggregation upon cycling. The design of porous structure accelerates the permeation of electrolyte and increases the contact between active materials and electrolyte. The synergistic effects between N-doped carbon and porous structure significantly improve the electrochemical performances. Thus, this composite delivers a capacity of 405.1 mAh g−1 at 0.1 A g−1 or 199.9 mAh g−1 at 10.0 A g−1 within 0.2–3.0 V. After 1000 cycles at 4.0 A g−1, the specific capacity is still kept as 236.6 mAh g−1. By pairing with commercial LiCoO 2 , this composite delivers a high energy density of 195.05 Wh kg−1 total at 70.52 W kg−1 total , and 94.06 Wh kg−1 total at 3.9 kW kg−1 total. [ABSTRACT FROM AUTHOR]

Solid polymer electrolytes (SPEs) have the potential to meet evolving Li‐ion battery demands, but for these electrolytes to satisfy growing power and energy density requirements, both transport properties and electrochemical stability must be improved. Unfortunately, improvement in one of these properties often comes at the expense of the other. To this end, a "hybrid aqueous/ionic liquid" SPE (HAILSPE) which incorporates triethylsulfonium‐TFSI (S2,2,2) or N‐methyl‐N‐propylpyrrolidinium‐TFSI (Pyr1,3) ionic liquid (IL) alongside H2O and LiTFSI salt to simultaneously improve transport and electrochemical stability is studied. This work focuses on the impact of HAILSPE composition on electrochemical performance. Analysis shows that an increase in LiTFSI content results in decreased ionic mobility, while increasing IL and water content can offset its impact. pfg‐NMR results reveal that preferential lithium‐ion transport is present in HAILSPE systems. Higher IL concentrations are correlated with an increased degree of passivation against H2O reduction. Compared to the Pyr1,3 systems, the S2,2,2 systems exhibit a stronger degree of passivation due to the formation of a multicomponent interphase layer, including LiF, Li2CO3, Li2S, and Li3N. The results herein demonstrate the superior electrochemical stability of the S2,2,2 systems compared to Pyr1,3 and provide a path toward further enhancement of HAILSPE performance via composition optimization. [ABSTRACT FROM AUTHOR]

An in-situ enabled lithium battery (or called a "Li-free" battery) is proposed by using Li-rich Li 2 CuO 2 additive to pre-plate Li metal onto Cu current collector. Conventional Cu foil is unsuitable for efficient Li cycling particularly due to poor adhesion of Li deposits to the Cu substrate and the dendritic deposition nature of Li metal. As a solution to this problem, a very thin Li metal layer is in-situ pre-plated onto the Cu surface and served as the primer layer for next Li cycling in the battery. Results show that the addition of Li 2 CuO 2 not only provides extra Li + ions for forming a very thin Li primer layer on the Cu current collector but also enhances rate capability of LiNi 0.80 Mn 0.10 Co 0.10 O 2 cathode, which is probably because the presence of CuO particles (one of Li 2 CuO 2 decomposition products) increases liquid electrolyte uphold in the cathode. [ABSTRACT FROM AUTHOR]

Silicon (Si) nanomaterials attract tremendous attentions when applied as anodes for lithium ion batteries (LIBs) owing to their high capacity, however, they usually suffer from low electronic conductivity and large volume expansion during the charge/discharge processes, resulting in the poor cycling stabilities. In this study, horsetails (HTs) are explored as low cost and renewable resources for deriving Si materials for Li-ion half/full cells for the first time. Moreover, Si@N-doped carbon nanocomposites are fabricated by polypyrrole (PPy) coating and pyrolysis carbonization of PPy at 400 °C for 2 h in Ar atmosphere, and they show enhanced long cycle stabilities for Li-ion half cells (1047.1 mAh g −1 at 0.5 A g −1 after 450 cycles, and 750 mAh g −1 at 1 A g −1 after 760 cycles). Furthermore, the Si@N-doped carbon//LiCoO 2 Li-ion full cells are assembled successfully, which display high discharge capacity (705 mAh g −1 at 0.5 A g −1 after 100 cycles). The high performance of Si@N-doped carbon nanocomposite could be attributed to the synergistic effect of high capacity of nanoscale sized Si and long cycle stability of N-doped carbon. It is believed the HTs-derived Si@N-doped carbon nanocomposite has great prospects for practical applications due to low cost and sufficient source of HTs. [ABSTRACT FROM AUTHOR]

A single-crystalline Ni-rich (SCNR) cathode with a large particle size can achieve higher energy density, and is safer, than polycrystalline counterparts. However, synthesizing large SCNR cathodes (>5 μm) without compromising electrochemical performance is very challenging due to the incompatibility between Ni-rich cathodes and high temperature calcination. Herein, we introduce Vegard's Slope as a guide for rationally selecting sintering aids, and we successfully synthesize size-controlled SCNR cathodes, the largest of which can be up to 10 μm. Comprehensive theoretical calculation and experimental characterization show that sintering aids continuously migrate to the particle surface, suppress sublattice oxygen release and reduce the surface energy of the typically exposed facets, which promotes grain boundary migration and elevates calcination critical temperature. The dense SCNR cathodes, fabricated by packing of different-sized SCNR cathode particles, achieve a highest electrode press density of 3.9 g cm−3 and a highest volumetric energy density of 3000 Wh L−1. The pouch cell demonstrates a high energy density of 303 Wh kg−1, 730 Wh L−1 and 76% capacity retention after 1200 cycles. SCNR cathodes with an optimized particle size distribution can meet the requirements for both electric vehicles and portable devices. Furthermore, the principle for controlling the growth of SCNR particles can be widely applied when synthesizing other materials for Li-ion, Na-ion and K-ion batteries. [ABSTRACT FROM AUTHOR]

Solid electrolyte interphase (SEI) formation and H2O activity reduction in Water‐in‐Salt electrolytes (WiSE) with an enlarged stability window of 3.0 V have provided the feasibility of the high‐energy‐density aqueous Li‐ion batteries. Here, we extend the cathodic potential of WiSE by rationally controlling intermolecular interaction and interphase chemistry with the introduction of trimethyl phosphate (TMP) into WiSE. The TMP not merely limits the H2O activity via the strong interaction between TMP and H2O but also contributes to the formation of reinforced SEI involving phosphate and LiF by manipulating the Li+ solvation structure. Thus, water‐tolerance LiMn2O4 (LMO)||Li4Ti5O12 (LTO) full cell with a P/N ratio of 1.14 can be assembled and achieve a long cycling life of 1000 times with high coulombic efficiency of >99.9 %. This work provides a promising insight into the cost‐effective practical manufacture of LMO||LTO cells without rigorous moisture‐free requirements. [ABSTRACT FROM AUTHOR]

Solid electrolyte interphase (SEI) formation and H2O activity reduction in Water‐in‐Salt electrolytes (WiSE) with an enlarged stability window of 3.0 V have provided the feasibility of the high‐energy‐density aqueous Li‐ion batteries. Here, we extend the cathodic potential of WiSE by rationally controlling intermolecular interaction and interphase chemistry with the introduction of trimethyl phosphate (TMP) into WiSE. The TMP not merely limits the H2O activity via the strong interaction between TMP and H2O but also contributes to the formation of reinforced SEI involving phosphate and LiF by manipulating the Li+ solvation structure. Thus, water‐tolerance LiMn2O4 (LMO)||Li4Ti5O12 (LTO) full cell with a P/N ratio of 1.14 can be assembled and achieve a long cycling life of 1000 times with high coulombic efficiency of >99.9 %. This work provides a promising insight into the cost‐effective practical manufacture of LMO||LTO cells without rigorous moisture‐free requirements. [ABSTRACT FROM AUTHOR]

[Display omitted] Pre-lithiation is critical for improving the energy density of lithium-ion batteries (LIBs) in practical applications. The pre-lithiation of the high-capacity anode with a large surface area enhances the initial coulombic efficiency (ICE) by compensating the lithium loss from the formation of solid electrolyte interphase (SEI). However, pre-lithiation also affects cycle life, which has been paid little attention to. Here, we first discuss the impact of pre-lithiation on the cycling stability of the full cells, which is closely related to anode material, the degree of pre-lithiation, and the stability of SEI. Then we provide suggestions on how to achieve both high energy density and long cycle life by pre-lithiation. The understanding of the correlation between pre-lithiation and cycling stability sheds light on achieving the optimal performance of lithium-ion batteries from pre-lithiation technology. [ABSTRACT FROM AUTHOR]

The capacity of transition metal oxide cathode for Li‐ion batteries can be further enhanced by increasing the charging potential. However, these high voltage cathodes suffer from fast capacity decay because the large volume change of cathode breaks the active materials and cathode‐electrolyte interphase (CEI), resulting in electrolyte penetration into broken active materials and continuous side reactions between cathode and electrolytes. Herein, a robust LiF‐rich CEI was formed by potentiostatic reduction of fluorinated electrolyte at a low potential of 1.7 V. By taking LiCoO2 as a model cathode, we demonstrate that the LiF‐rich CEI maintains the structural integrity and suppresses electrolyte penetration at a high cut‐off potential of 4.6 V. The LiCoO2 with LiF‐rich CEI exhibited a capacity of 198 mAh g−1 at 0.5C and an enhanced capacity retention of 63.5 % over 400 cycles as compared to the LiF‐free LiCoO2 with only 17.4 % of capacity retention. [ABSTRACT FROM AUTHOR]

The capacity of transition metal oxide cathode for Li‐ion batteries can be further enhanced by increasing the charging potential. However, these high voltage cathodes suffer from fast capacity decay because the large volume change of cathode breaks the active materials and cathode‐electrolyte interphase (CEI), resulting in electrolyte penetration into broken active materials and continuous side reactions between cathode and electrolytes. Herein, a robust LiF‐rich CEI was formed by potentiostatic reduction of fluorinated electrolyte at a low potential of 1.7 V. By taking LiCoO2 as a model cathode, we demonstrate that the LiF‐rich CEI maintains the structural integrity and suppresses electrolyte penetration at a high cut‐off potential of 4.6 V. The LiCoO2 with LiF‐rich CEI exhibited a capacity of 198 mAh g−1 at 0.5C and an enhanced capacity retention of 63.5 % over 400 cycles as compared to the LiF‐free LiCoO2 with only 17.4 % of capacity retention. [ABSTRACT FROM AUTHOR]

Abstract: A porous silicon–carbon anode on a lightweight carbon fiber current collector is reported here for lithium-ion batteries. This Si–C anode was synthesized through a one-step carbonization of a Si-poly(acrylonitrile-co-methyl acrylate) precursor, which was directly deposited on a carbon fiber mat. The carbon fiber curent collector allows higher loading of active materials, resulting in high energy to mass and area ratios. The obtained Si–C electrode demonstrated superior overall capacity, cyclability, and rate capacity. [Copyright &y& Elsevier]

Rechargeable magnesium and calcium metal batteries (RMBs and RCBs) are promising alternatives to lithium-ion batteries because of the high crustal abundance and capacity of magnesium and calcium. Yet, they are plagued by sluggish kinetics and parasitic reactions. We found a family of methoxyethyl-amine chelants that greatly promote interfacial charge transfer kinetics and suppress side reactions on both the cathode and metal anode through solvation sheath reorganization, thus enabling stable and highly reversible cycling of the RMB and RCB full cells with energy densities of 412 and 471 watt-hours per kilogram, respectively. This work provides a versatile electrolyte design strategy for divalent metal batteries. [ABSTRACT FROM AUTHOR]

Water‐in‐salt (WIS) electrolytes using super‐concentrated organic lithium (Li) salts are of interest for aqueous Li‐ion batteries. However, the high salt cost, high viscosity, poor wettability, and environmental hazards remain a great challenge. Herein, we present a localized water‐in‐salt (LWIS) electrolyte based on low‐cost lithium nitrate (LiNO3) salt and 1,5‐pentanediol (PD) as inert diluent. The addition of PD maintains the solvation structure of the WIS electrolyte, improves the electrolyte stability via hydrogen‐bonding interactions with water and NO3− molecules, and reduces the total salt concentration. By in situ gelling the LWIS electrolyte with tetraethylene glycol diacrylate (TEGDA) monomer, the electrolyte stability window can be further expanded to 3.0 V. The as‐developed Mo6S8|LWIS gel electrolyte|LiMn2O4 (LMO) batteries delivered outstanding cycling performance with an average Coulombic efficiency of 98.53 % after 250 cycles at 1 C. [ABSTRACT FROM AUTHOR]

Water‐in‐salt (WIS) electrolytes using super‐concentrated organic lithium (Li) salts are of interest for aqueous Li‐ion batteries. However, the high salt cost, high viscosity, poor wettability, and environmental hazards remain a great challenge. Herein, we present a localized water‐in‐salt (LWIS) electrolyte based on low‐cost lithium nitrate (LiNO3) salt and 1,5‐pentanediol (PD) as inert diluent. The addition of PD maintains the solvation structure of the WIS electrolyte, improves the electrolyte stability via hydrogen‐bonding interactions with water and NO3− molecules, and reduces the total salt concentration. By in situ gelling the LWIS electrolyte with tetraethylene glycol diacrylate (TEGDA) monomer, the electrolyte stability window can be further expanded to 3.0 V. The as‐developed Mo6S8|LWIS gel electrolyte|LiMn2O4 (LMO) batteries delivered outstanding cycling performance with an average Coulombic efficiency of 98.53 % after 250 cycles at 1 C. [ABSTRACT FROM AUTHOR]

Following the fundamental research conducted by J. B. Goodenough, the important role of electron localization induced by elemental substitution is studied. The size and electron negativity of host and substituting ions are two important factors in tuning material properties such as local structure and transition metal (TM) oxygen covalency. However, another factor, electron localization, which is widely studied in catalyst research but largely overlooked for battery materials, deserves systematic studies. A combined investigation using synchrotronbased X‐ray spectroscopy and theoretical calculations is carried out on the Li‐Co‐Mn‐O model system in which the substituting cation Mn4+, with its 3d3 electronic structure, is used as a promoter for electron localization. Results indicate that electron localization greatly influences the CoO bond by making it less covalent, which increases the delithiation voltage. It is also found that during charge/discharge, electron localization tends to make TM K‐edge X‐ray absorption near edge spectroscopy (XANES) spectra show a more "rigid shift" behavior while electron delocalization makes the XANES exhibit a "shape change." It clearly explains why the K‐edge XANES data of some TM oxides show no "rigid shift" while the nominal valence states changed. This work highlights the importance of electron localization with guidance for XANES interpretation. [ABSTRACT FROM AUTHOR]

Benefiting from a higher volumetric capacity (3833 mA h cm−3 for Mg vs. 2046 mA h cm−3 for Li) and dendrite-free Mg metal anode, reversible Mg batteries (RMBs) are a promising chemistry for applications beyond Li ion batteries. However, RMBs are still severely restricted by the absence of high performance cathodes for any practical application. In this review, we provide a critical and rigorous review of Mg battery cathode materials, mainly reported since 2013, focusing on the impact of structure and composition on magnesiation kinetics. We discuss cathode materials, including intercalation compounds, conversion materials (O2, S, organic compounds), water co-intercalation cathodes (V2O5, MnO2etc.), as well as hybrid systems using Mg metal anode. Among them, intercalation cathodes are further categorized by 3D (Chevrel phase, spinel structure etc.), 2D (layered structure), and 1D materials (polyanion: phosphate and silicate), according to the diffusion pathway of Mg2+ in the framework. Instead of discussing every published work in detail, this review selects the most representative works and highlights the merits and challenges of each class of cathodes. Advances in theoretical analysis are also reviewed and compared with experimental results. This critical review will provide comprehensive knowledge of Mg cathodes and guidelines for exploring new cathodes for rechargeable magnesium batteries. [ABSTRACT FROM AUTHOR]

Abstract: Organic electrode materials are promising for green and sustainable lithium‐ion batteries. However, the high solubility of organic materials in the liquid electrolyte results in the shuttle reaction and fast capacity decay. Herein, azo compounds are firstly applied in all‐solid‐state lithium batteries (ASSLB) to suppress the dissolution challenge. Due to the high compatibility of azobenzene (AB) based compounds to Li3PS4 (LPS) solid electrolyte, the LPS solid electrolyte is used to prevent the dissolution and shuttle reaction of AB. To maintain the low interface resistance during the large volume change upon cycling, a carboxylate group is added into AB to provide 4‐(phenylazo) benzoic acid lithium salt (PBALS), which could bond with LPS solid electrolyte via the ionic bonding between oxygen in PBALS and lithium ion in LPS. The ionic bonding between the active material and solid electrolyte stabilizes the contact interface and enables the stable cycle life of PBALS in ASSLB. [ABSTRACT FROM AUTHOR]

Abstract: Solid electrolytes have been considered as a promising approach for Li dendrite prevention because of their high mechanical strength and high Li transference number. However, recent reports indicate that Li dendrites also form in Li2S‐P2S5 based sulfide electrolytes at current densities much lower than that in the conventional liquid electrolytes. The methods of suppressing dendrite formation in sulfide electrolytes have rarely been reported because the mechanism for the “unexpected” dendrite formation is unclear, limiting the successful utilization of high‐energy Li anode with these electrolytes. Herein, the authors demonstrate that the Li dendrite formation in Li2S‐P2S5 glass can be effectively suppressed by tuning the composition of the solid electrolyte interphase (SEI) at the Li/electrolyte interface through incorporating LiI into the electrolyte. This approach introduces high ionic conductivity but electronic insulation of LiI in the SEI, and more importantly, improves the mobility of Li atoms, promoting the Li depositon at the interface and thus suppresses dendrite growth. It is shown that the critical current density is improved significantly after incorporating LiI into Li2S‐P2S5 glass, reaching 3.90 mA cm−2 at 100 °C after adding 30 mol% LiI. Stable cycling of the Li‐Li cells for 200 h is also achieved at 1.50 mA cm−2 at 100 °C. [ABSTRACT FROM AUTHOR]

Abstract: Sodium (Na) is one of the more abundant elements on earth and exhibits similar chemical properties as lithium (Li), indicating that Na could be applied to a similar battery system. Like aqueous Li‐ion batteries, aqueous sodium‐ion batteries (ASIBs) are also demonstrated to be one of the most promising stationary power sources for sustainable energies such as wind and solar power. Compared to traditional nonaqueous batteries, ASIBs may solve the safety problems associated with the highly toxic and flammable organic electrolyte in the traditional lithium‐ion and sodium‐ion batteries. During the past decades, many efforts are made to improve the performance of the ASIBs. The present review focuses on the latest advances in the exploration and development of ASIB systems and related components, including cathodes, anodes, and electrolytes. Previously reported studies are briefly summarized, together with the presentation of new findings based on the electrochemical performance, cycling stability, and morphology approaches. In addition, the main opportunities, achievements, and challenges in this field are briefly commented and discussed. [ABSTRACT FROM AUTHOR]

Lithium-ion capacitors, as a hybrid electrochemical energy storage device, realize high specific energy and power density within one device, thus attracting extensive attention. Here, hierarchically porous Li 3 VO 4 /C nanocomposite is prepared by a solvo-thermal reaction, followed with a post-annealing process. This composite has macropores at the center and mesopores in the wall, thus effectively promoting electrolyte penetration and structure stability upon cycling simultaneously. Compared to mesoporous Li 3 VO 4 , the enhanced rate capability and specific capacity of hierarchically porous Li 3 VO 4 /C indicate the synergistic effect of mesopores and macropores. Inspired by these results, this composite is coupled with mesoporous carbon (CMK-3) for lithium-ion capacitors, generating a specific energy density of 105 Wh kg −1 at a power density of 188 W kg −1 . Even if the power density increases to 9.3 kW kg −1 , the energy density still remains 62 Wh kg −1 . All these results demonstrate the promising potential of hierarchically porous Li 3 VO 4 in lithium ion capacitors. [ABSTRACT FROM AUTHOR]

Abstract: Sustainable sodium‐ion batteries (SSIBs) using renewable organic electrodes are promising alternatives to lithium‐ion batteries for the large‐scale renewable energy storage. However, the lack of high‐performance anode material impedes the development of SSIBs. Herein, we report a new type of organic anode material based on azo group for SSIBs. Azobenzene‐4,4′‐dicarboxylic acid sodium salt is used as a model to investigate the electrochemical behaviors and reaction mechanism of azo compound. It exhibits a reversible capacity of 170 mAh g−1 at 0.2C. When current density is increased to 20C, the reversible capacities of 98 mAh g−1 can be retained for 2000 cycles, demonstrating excellent cycling stability and high rate capability. The detailed characterizations reveal that azo group acts as an electrochemical active site to reversibly bond with Na+. The reversible redox chemistry between azo compound and Na ions offer opportunities for developing long‐cycle‐life and high‐rate SSIBs. [ABSTRACT FROM AUTHOR]

High electrochemical reversibility of the TiS 2 anode in “Water-in-Salt” electrolyte (21 m LiTFSI in H 2 O) is demonstrated for the first time. The wide electrochemical window and low chemical activity of H 2 O in the “Water-in-Salt” electrolyte not only significantly enhanced the electrochemical reversibility of TiS 2 but also effectively suppressed the hydrolysis side reaction in the aqueous electrolyte. Paired with a LiMn 2 O 4 cathode, the LiMn 2 O 4 /TiS 2 full cell delivers a relatively high discharge voltage of 1.7 V and an energy density of 78 Wh kg − 1 as well as a satisfactory rate performance. [ABSTRACT FROM AUTHOR]

A 2.9 V intrinsic safe aqueous LiNi0.5Mn1.5O4/Mo6S8 full cell delivers 80 W h kg−1 energy density with capacity decay of 0.075% per cycle (5 C). After the electrolyte pH value adjustment, almost full capacity of LiNi0.5Mn1.5O4 (125 mA h kg−1) is achieved, and 126 W h kg−1 energy density is provided for LiNi0.5Mn1.5O4/Mo6S8 cell, representing one of the highest voltage and energy density among all the aqueous batteries. [ABSTRACT FROM AUTHOR]

Advanced electrode materials have been intensively explored for next-generation lithium-ion batteries (LIBs), and great progresses have been achieved for many potential candidates at the lab-scale. To realize the commercialization of these materials, industrially-viable synthetic approaches are urgently needed. Spray pyrolysis (SP), which is highly scalable and compatible with on-line continuous production processes, offers great fidelity in synthesis of electrode materials with complex architectures and chemistries. In this review, motivated by the rapid advancement of the given technology in the battery area, we have summarized the recent progress on SP for preparing a great variety of anode and cathode materials of LIBs with emphasis on their unique structures generated by SP and how the structures enhanced the electrochemical performance of various electrode materials. Considering the emerging popularity of sodium-ion batteries (SIBs), recent electrode materials for SIBs produced by SP will also be discussed. Finally, the powerfulness and limitation along with future research efforts of SP on preparing electrode materials are concisely provided. Given current worldwide interests on LIBs and SIBs, we hope this review will greatly stimulate the collaborative efforts among different communities to optimize existing approaches and to develop innovative processes for preparing electrode materials. [ABSTRACT FROM AUTHOR]

Exceptional cycling performance of graphite anode in K-ion batteries is demonstrated with a reversible capacity of 246 mAh g-1 and 89% retention of the initial capacity after 200 cycles. Although the graphite anode experiences huge volume change and worse kinetics during K intercalation/deintercalation, the cycling stability delivered in K-ion batteries is comparable to that of Li-ion batteries using the same graphite anode. The combination of excellent electrochemical performance, the abundance and wide availability of K in earth's crust, and the well-developed technology of the graphite anode make the K-ion battery very attractive for offering a low cost battery chemistry for large-scale energy storage applications. [ABSTRACT FROM AUTHOR]

A new super-concentrated aqueous electrolyte is proposed by introducing a second lithium salt. The resultant ultra-high concentration of 28 m led to more effective formation of a protective interphase on the anode along with further suppression of water activities at both anode and cathode surfaces. The improved electrochemical stability allows the use of TiO2 as the anode material, and a 2.5 V aqueous Li-ion cell based on LiMn2O4 and carbon-coated TiO2 delivered the unprecedented energy density of 100 Wh kg−1 for rechargeable aqueous Li-ion cells, along with excellent cycling stability and high coulombic efficiency. It has been demonstrated that the introduction of a second salts into the 'water-in-salt' electrolyte further pushed the energy densities of aqueous Li-ion cells closer to those of the state-of-the-art Li-ion batteries. [ABSTRACT FROM AUTHOR]

The electrochemical stability window of solid electrolyte is overestimated by the conventional experimental method using a Li/electrolyte/inert metal semiblocking electrode because of the limited contact area between solid electrolyte and inert metal. Since the battery is cycled in the overestimated stability window, the decomposition of the solid electrolyte at the interfaces occurs but has been ignored as a cause for high interfacial resistances in previous studies, limiting the performance improvement of the bulk-type solid-state battery despite the decades of research efforts. Thus, there is an urgent need to identify the intrinsic stability window of the solid electrolyte. The thermodynamic electrochemical stability window of solid electrolytes is calculated using first principles computation methods, and an experimental method is developed to measure the intrinsic electrochemical stability window of solid electrolytes using a Li/electrolyte/electrolyte-carbon cell. The most promising solid electrolytes, Li10GeP2S12 and cubic Li-garnet Li7La3Zr2O12, are chosen as the model materials for sulfide and oxide solid electrolytes, respectively. The results provide valuable insights to address the most challenging problems of the interfacial stability and resistance in high-performance solid-state batteries. [ABSTRACT FROM AUTHOR]

Transition metal fluorides (such as FeF 3 and FeF 2 ) based on conversion chemistry have been considered as a promising alternative to the intercalation cathode materials due to the high capacity and high energy density. However, the critical challenges for these materials come from the absence of Li source in them, and low power density and poor cycling stability. Herein, pre-lithiated FeF 3 with extremely small size of Fe and LiF nanoparticles (both ∼6 nm) homogeneously embedded in the carbon matrix were synthesized using a facile and scalable in situ strategy. Benefited from the ultra-small Fe and LiF nanoparticles, uniform distribution, and intimate contact between the active species and the carbon matrix, the particle-to-particle interfacial resistance and diffusion length for Li and F are dramatically reduced. As a result, a high specific capacity of over 400 mA h g −1 with a discharge energy density of ∼700 W h kg −1 and favorable cycling performance are achieved, making such composite a promising high-capacity cathode for LIBs. Furthermore, the built-in Li source in this composite renders it a drop-in replacement for cathode materials used in the current LIB configurations, thus paving the way for the practical applications in the next generation of high energy density LIBs. [ABSTRACT FROM AUTHOR]

Sulfur intercalated expanded graphite for Li‐S battery cathodes is synthesized by in situ one‐step sulfur reduction and intercalation of graphite oxide (GO). The unique structural reduced graphene oxide (RGO)/S nanocomposite cathodes exhibit high capacity, super rate capability, and long cycle stability. The exceptional electrochemical properties of the RGO/S composites plus their simple fabrication make this class of materials attrac­tive for further investigation in Li‐S batteries applications. [ABSTRACT FROM AUTHOR]

A copper-stabilized sulfur-microporous carbon (MC-Cu-S) composite is synthesized by uniformly dispersing 10% highly electronically conductive Cu nanoparticles into microporous carbon (MC), followed by wet-impregnating S. In the MC-Cu-S composite, the MC host that physically confines S/polysulfides provides free space to accommodate volumetric expansion of S during lithiation, while the Cu nanoparticles that are anchored in the MC further chemically interact with S/polysulfides through bonding between Cu and S/polysulfides. The Cu loading allows the S content to increase from 30 to 50% in the carbon-S cathode material without scarifying the electrochemical performance in a low-cost carbonate electrolyte. At a current density of 100 mA g-1, the MC-Cu-S cathode shows that Coulumbic efficiency is close to 100% and capacity maintains more than 600 mAh g-1 with progressive cycling up to more than 500 cycles. In addition, the Cu nano-inclusins also enhance the electronic conductivity of the MC-Cu-S composite, remarkably increasing the rate capabilities. Even the current density increases 10.0 A g-1, the MC-Cu-S cathode can still deliver a capacity of 200 mAh g-1. This strategy of stabilization of S with small amount of metal nanoparticles anchored in MC provides an effective approach to improve the cycling stability, Coulumbic efficiency, and S loading for Li-S batteries. [ABSTRACT FROM AUTHOR]

The electroactive organic materialsare promising alternativesto inorganic electrode materials for the new generation of green Li-ionbatteries due to their sustainability, environmental benignity, andlow cost. Croconic acid disodium salt (CADS) was used as Li-ion batteryelectrode, and CADS organic wires with different diameters were fabricatedthrough a facile synthetic route using antisolvent crystallizationmethod to overcome the challenges of low electronic conductivity ofCADS and lithiation induced strain. The CADS nanowire exhibits muchbetter electrochemical performance than its crystal bulk materialand microwire counterpart. CADS nanowire with a diameter of 150 nmdelivers a reversible capability of 177 mAh g–1ata current density of 0.2 C and retains capacity of 170 mAh g–1after 110 charge/discharge cycles. The nanowire structure also remarkablyenhances the kinetics of croconic acid disodium salt. The CADS nanowireretains 50% of the 0.1 C capacity even when the current density increasesto 6 C. In contrast, the crystal bulk and microwire material completelylose their capacities when the current density merely increases to2 C. Such a high rate performance of CADS nanowire is attributed toits short ion diffusion pathway and large surface area, which enablefast ion and electron transport in the electrode. The theoreticalcalculation suggests that lithiation of CADS experiences an ion exchangeprocess. The sodium ions in CADS will be gradually replaced by lithiumions during the lithiation and delithiation of CADS electrode, whichis confirmed by inductively coupled plasma test. [ABSTRACT FROM AUTHOR]

Nano-Sn/C composites are ideal anode materials for highenergyand power density Li-ion batteries. However, because of the low meltingpoint of Sn and the tendency of grain growth, especially during hightemperature carbonization, it has been a significant challenge tocreate well-dispersed ultrasmall Sn nanoparticles within a carbonmatrix. In this paper, we demonstrate an aerosol spray pyrolysis technique,as a facile and scalable method, to synthesize a nano-Sn/C compositewith uniformly dispersed 10 nm nano-Sn within a spherical carbon matrix.The discharge capacity of nano-Sn/C composite sphere anodes maintainsthe initial capacity of 710 mAh/g after 130 cycles at 0.25 C. Thenano-Sn/C composite sphere anodes can provide ∼600 mAh/g evenat a high rate of 20 C. To the best of our knowledge, such high rateperformance for Sn anodes has not been reported previously. The exceptionalperformance of the nano-Sn/C composite is attributed to the uniquenano-Sn/C structure: (1) carbon matrix offers mechanical support toaccommodate the stress associated with the large volume change ofnano-Sn, thus alleviating pulverization; (2) the carbon matrix preventsSn nanoparticle agglomeration upon prolonged cycling; and (3) carbonnetwork provides continuous path for Li ions and electrons insidethe nano-Sn/C composite spheres. [ABSTRACT FROM AUTHOR]

Abstract: A patterned 3D Si anode is fabricated by physical vapor deposition of n-type Si on a self-assembled TMV1cys-structured nickel current collector. The combination of the large surface area conferred by the virus-enabled 3D Ni/TMV1cys current collector with the high electric conductivity of n-type Si rods results in excellent cyclic stability and rate capability for the core-shell n-type Si/Ni/TMV1cys anodes. Electrochemical impedance spectroscopy reveals that the high electronic conductivity of n-type Si significantly reduces charge transfer resistance, thus even at high current densities the capacity of the n-type Si is increased to almost 630mAh/g compared to undoped Si. [Copyright &y& Elsevier]

Abstract: The effects of carbonization process and carbon nanofiber/nanotube additives on the cycling stability of silicon–carbon composite anodes were investigated by monitoring the impedance evolution during charge/discharge cycles with electrochemical impedance spectroscopy (EIS). Three types of Si–C anodes were investigated: the first type consisted of Si nanoparticles incorporated into a network of carbon nanofibers (CNFs) and multi-walled carbon nanotubes (MWNTs), with annealed polymer binder. The second type of Si–C anodes was prepared by further heat treatment of the first Si–C anodes to carbonize the polymer binder. The third Si–C anode was as same as the second one except no CNFs and MWNTs being added. Impedance analysis revealed that the carbonization process stabilized the Si–C anode structure and decreased the charge transfer resistance, thus improving the cycling stability. On the other hand, although the MWNTs/CNFs additives could enhance the electronic conductivity of the Si–C anodes, the induced inhomogeneous structure decreased the integrity of the electrode, resulting in a poor long term cycling stability. [Copyright &y& Elsevier]

A system of electrolytes using water as a solvent was successfully used to support a typical lithium-ion battery chemistry that operates at 3.7V–4.2 V using standard ultraviolet-cured acrylic-based polymers as hydrophobic barriers. The aqueous electrolyte is contained in a system of poly(ethylene glycol) acrylate polymers crosslinked to produce an electrolyte gel that has electrochemical properties similar to that of the liquid phase component. The electrolyte gels have elastic moduli in the kPa range, making them soft enough to tolerant flexing, cutting, and blunt force impacts while keeping the electrodes covered and safe from shorting. While batteries based on water-in-salt electrolyte provides intrinsic safety that is otherwise unavailable from typical non-aqueous electrolytes, acrylate-based aqueous gel electrolytes offer the potential of large-scale manufacturing owing to the relatively low volatility of the electrolyte components and the low complexity of the proposed manufacturing process. • UV-cured gel electrolytes were used to construct a 4 V lithium ion battery. • The main gel electrolyte was water-based, making the battery safe. • Gel electrolytes had conductivity ≥0.3 mS/cm. • Gel electrolytes exhibited favorable impedance characteristics. • Battery cells used graphite anodes and LiCoO 2 cathodes. [ABSTRACT FROM AUTHOR]

A novel bismuth-carbon composite, in which bismuth nanoparticles were anchored in a nitrogen-doped carbon matrix (Bi@NC), is proposed as anode for high volumetric energy density lithium ion batteries (LIBs). Bi@NC composite was synthesized via carbonization of Zn-containing zeolitic imidazolate (ZIF-8) and replacement of Zn with Bi, resulting in the N-doped carbon that was hierarchically porous and anchored with Bi nanoparticles. The matrix provides a highly electronic conductive network that facilitates the lithiation/delithiation of Bi. Additionally, it restrains aggregation of Bi nanoparticles and serves as a buffer layer to alleviate the mechanical strain of Bi nanoparticles upon Li insertion/extraction. With these contributions, Bi@NC exhibits excellent cycling stability and rate capacity compared to bare Bi nanoparticles or their simple composites with carbon. This study provides a new approach for fabricating high volumetric energy density LIBs. [ABSTRACT FROM AUTHOR]

A novel bismuth-carbon composite, in which bismuth nanoparticles were anchored in a nitrogen-doped carbon matrix (Bi@NC), is proposed as anode for high volumetric energy density lithium ion batteries (LIBs). Bi@NC composite was synthesized via carbonization of Zn-containing zeolitic imidazolate (ZIF-8) and replacement of Zn with Bi, resulting in the N-doped carbon that was hierarchically porous and anchored with Bi nanoparticles. The matrix provides a highly electronic conductive network that facilitates the lithiation/delithiation of Bi. Additionally, it restrains aggregation of Bi nanoparticles and serves as a buffer layer to alleviate the mechanical strain of Bi nanoparticles upon Li insertion/extraction. With these contributions, Bi@NC exhibits excellent cycling stability and rate capacity compared to bare Bi nanoparticles or their simple composites with carbon. This study provides a new approach for fabricating high volumetric energy density LIBs. [ABSTRACT FROM AUTHOR]

A new high energy single-material all-solid-state lithium ion battery is reported wherein the cathode, electrolyte, and anode consists of Li10GeP2S12 mixed with electronically conductive carbon. [ABSTRACT FROM AUTHOR]