One-Step Molten-Salt-Assisted Approach for Direct Preparation and Regeneration of LiNi0.6Co0.2Mn0.2O2 Cathode.

Single-crystal lithium-nickel-manganese-cobalt-oxide (SC-NMC) is attracting increasing attention due to its excellent structural stability. However, its practical production faces challenges associated with complex precursor preparation processes and severe lithium-nickel cation mixing at high temperatures, which restricts its widespread application. Here, a molten-salt-assisted method is proposed using low-melting-point carbonates. This method obviates the necessity for precursor processes and simplified the synthetic procedure for SC-NMC down to a single isothermal sintering step. Multiple characterizations indicate that the acquired SC-LiNi0.6Mn0.2Co0.2O2 (SC-622) exhibits favorable structural capability against intra-granular fracture and suppressive Li+/Ni2+ cation mixing. Consequently, the SC-622 exhibits superior electrochemical performance with a high initial specific capacity (174 mAh g-1 at 0.1 C, 3.0-4.3 V) and excellent capacity retention (87.5% after 300 cycles at 1C). Moreover, this molten-salt-assisted method exhibits its effectiveness in directly regenerating SC-622 from spent NMC materials. The recovered material delivered a capacity of 125.4 mAh g-1 and retained 99.4% of the initial capacity after 250 cycles at 1 C. This work highlights the importance of understanding the process-structure-property relationships and can broadly guide the synthesis of other SC Ni-rich cathode materials.

Interphasial Pre-lithiation and Reinforcement of Micro-Si Anode through Fluorine-free Electrolytes.

Micro-sized silicon (mSi) anodes offer advantages in cost and tap density over nanosized counterparts. However, its practical application still suffers from poor cyclability and low initial and later-cycle coulombic efficiency (CE), caused by the unstable solid electrolyte interphase (SEI) and irreversible lithiation of the surface oxide layer. Herein, a bifunctional fluorine (F)-free electrolyte was designed for the mSi anode to stabilize the interphase and improve the CE. A combined analysis revealed that this electrolyte can chemically pre-lithiate the native oxide layer by the reductive LiBH4 , and relieve SEI formation and accumulation to preserve the internal conductive network. The significance of this F-free electrolyte brings unprecedented F-free interphase that also enables the high-performance mSi electrode (80 wt % mSi), including high specific capacity of 2900 mAh/g, high initial CE of 94.7 % and excellent cyclability capacity retention of 94.3 % after 100 cycles at 0.2 C. This work confirms the feasibility of F-free interphase, thus opening up a new avenue toward cost-advantaged and environmentally friendly electrolytes for more emerging battery systems.

Flower-Like Interlayer-Expanded MoS2- x Nanosheets Confined in Hollow Carbon Spheres with High-Efficiency Electrocatalysis Sites for Advanced Sodium-Sulfur Battery.

The room-temperature sodium-sulfur (RT-Na/S) battery is one of the most promising technologies for low-cost energy storage. However, application of RT-Na/S batteries is currently impeded by severe shuttle effects and volume expansion that limits both energy density and cycling stability. Herein, first, the first-principal calculation is used to find that the introduction of sulfur vacancies in MoS2 can effectively enhance polysulfide adsorption and catalytic ability as well as both the ion and electron conductivities. Then, unique MoS2- x /C composite spheres are further designed and synthesized with flower-like few-layer and interlayer-enlarged MoS2- x nanosheets space-confined in hollow carbon nanospheres by a "ship-in-a-bottle" strategy. With this novel design, the mass loading of S in the MoS2- x /C composite can be reached to as high as 75 wt%. Owing to the synergetic effect of interlayer-expanded and few-layer MoS2- x nanosheets and hollow carbon spheres matrix with high electronic/Na+ conductivity, the RT-Na/S batteries deliver highly stable cycle durability (capacity retention of 85.2% after 100 cycles at 0.1 A g-1 ) and remarkable rate capability (415.7 mAh g-1 at 2 A g-1 ) along with high energy density. This design strategy of defect- and interlayer-engineering may find wide applications in synthesizing electrode materials for high-performance RT-Na/S batteries.

Enhancing Conversion Kinetics through Electron Density Dual-Regulation of Catalysts and Sulfur toward Room-/Subzero-Temperature Na-S Batteries.

Room-temperature sodium-sulfur (RT Na/S) batteries have received increasing attention for the next generation of large-scale energy storage, yet they are hindered by the severe dissolution of polysulfides, sluggish redox kinetic, and incomplete conversion of sodium polysulfides (NaPSs). Herein, the study proposes a dual-modulating strategy of the electronic structure of electrocatalyst and sulfur to accelerate the conversion of NaPSs. The selenium-modulated ZnS nanocrystals with electron rearrangement in hierarchical structured spherical carbon (Se-ZnS/HSC) facilitate Na+ transport and catalyze the conversion between short-chain sulfur and Na2S. And the in situ introduced Se within S can enhance conductivity and form an S─Se bond, suppressing the "polysulfides shuttle". Accordingly, the S@Se-ZnS/HSC cathode exhibits a specific capacity of as high as 1302.5 mAh g-1 at 0.1 A g-1 and ultrahigh-rate capability (676.9 mAh g-1 at 5.0 A g-1). Even at -10 °C, this cathode still delivers a high reversible capacity of 401.2 mAh g-1 at 0.05 A g-1 and 94% of the original capacitance after 50 cycles. This work provides a novel design idea for high-performance Na/S batteries.

Respective Roles of Inner and Outer Carbon in Boosting the K+ Storage Performance of Dual-Carbon-Confined ZnSe.

Potassium-ion batteries (PIBs) have been considered as potential alternatives for lithium-ion batteries since there is a demand for better anode with superior energy, excellent rate capability, and long cyclability. The high-capacity zinc selenide (ZnSe) anode, which combines the merits of conversion and alloying reactions, is promising for PIBs but suffers from poor cyclability and low electronic conductivity. To effectively boost electrochemical performance of ZnSe, a "dual-carbon-confined" structure is constructed, in which an inner N-doped microporous carbon (NMC)-coated ZnSe wrapped by outer-rGO (ZnSe@i-NMC@o-rGO) is synthesized. Combining finite element simulation, dynamic analysis, and density functional theory calculations, the respective roles of inner- and outer-carbon in boosting performance are revealed. The inner-NMC increased the reactivity of ZnSe with K+ and alleviated the volume expansion of ZnSe, while outer-rGO further stabilized the structure and promoted the reaction kinetics. Benefiting from the synergistic effect of dual-carbon, ZnSe@i-NMC@o-rGO exhibited a high specific capacity 233.4 mAh g-1 after 1500 cycles at 2.0 A g-1 . Coupled with activated carbon, a potassium-ion hybrid capacitor displayed a high energy density of 176.6 Wh kg-1 at 1800 W kg-1 and a superior capacity retention of 82.51% at 2.0 A g-1 after 11000 cycles.

Enabling a Stable Room-Temperature Sodium-Sulfur Battery Cathode by Building Heterostructures in Multichannel Carbon Fibers.

Room-temperature sodium-sulfur (RT Na-S) batteries are widely considered as one of the alternative energy-storage systems with low cost and high energy density. However, the both poor cycle stability and capacity are two critical issues arising from low conversion kinetics and sodium polysulfides (NaPSs) dissolution for sulfur cathodes during the charge/discharge process. Herein, we report a highly stable RT Na-S battery cathode via building heterostructures in multichannel carbon fibers. The TiN-TiO2@MCCFs, fabricated by electrospinning and nitriding techniques, are loaded with the active material S, forming S/TiN-TiO2@MCCFs as the cathode in a RT Na-S battery. At 0.1 A g-1, the cathode produces the capacity of more than 640 mAh g-1 within 100 cycles with a high Coulombic efficiency of nearly 100%. Even at 5 A g-1, the battery still exhibites a capacity of 257.1 mAh g-1 after 1000 cycles. Combining structural and electrochemical analyses with the first-principles calculations reveals that the incorporation of the highly electrocatalytic activity of TiN with the powerful chemisorption of TiO2 well stabilizes S and also alleviates the shuttle effects of polysulfides. This work with simple processes and low cost is expected to promote the further development and application of metal-S batteries.

Tailor-Made Gives the Best Fits: Superior Na/K-Ion Storage Performance in Exclusively Confined Red Phosphorus System.

As the most promising anodic candidate for alkali ion batteries, red phosphorus (P) still faces big challenges, such as the poor rate and cycling performance, which are caused by the insulative nature and the large volume change throughout the alloy/dealloy process. To ameliorate above issues, the traditional way is confining P into the carbon host. However, investigations on maximizing P utilization are inadequate; in other words, how to achieve entire confinement with a high loading amount is still a problem. Additionally, the application of P in potassium-ion batteries (PIBs) is in its infant stage, and the corresponding potassiation product is controversial. Herein, a nitrogen-doped stripped-graphene CNT (N-SGCNT) as carbon framework is prepared to exclusively confine ultrafine P to construct P@N-SGCNT composites. Benefitting from the in situ cross-linked structure, N-SGCNT loaded with 41.2 wt % P (P2@N-SGCNT) shows outstanding Na+/K+ storage performance. For instance, P2@N-SGCNT exhibits high reversible capacities of 2480 mAh g-1 for sodium-ion batteries (SIBs) and 762 mAh g-1 for PIBs, excellent rate capabilities of 1770 mAh g-1 for SIBs and 354 mAh g-1 for PIBs at 2.0 A g-1, and long cycling stability (a capacity of 1936 mAh g-1 after 2000 cycles for SIBs and 319 mAh g-1 after 1000 cycles for PIBs). Furthermore, due to this exclusively confined P structure, the K+ storage mechanism with the end product of K4P3 has been identified by experimental and theoretical results.

Fast and Stable Batteries with High Capacity Enabled by Germanium-Phosphorus Binary Nanoparticles Embedded in a Porous Carbon Matrix via Metallothermic Reduction.

Lithium-alloyable materials such as Ge and P have attracted considerable attention as promising anode materials for lithium-ion batteries (LIBs) owing to their high theoretical capacity. However, these materials inevitably undergo capacity attenuation caused by large volume expansion in repeated electrochemical processes. Herein, we propose a facile strategy to synthesize germanium-phosphorus binary nanoparticles embedded in porous carbon (GPBN/C) via metallothermic reduction. As an LIB anode, the GPBN/C electrode exhibits outstanding rate performance (368 mAh g-1 at 40 A g-1) and remarkable long-term cycling ability (541 mAh g-1 at 1.0 A g-1 after 1000 cycles). Besides, the GPBN/C composite electrode presents an outstanding cycling performance at wide temperature ranges, showing reversible capacities of 1030 and 696 mAh g-1 at 60 and 0 °C, respectively. Attributed to the formation of highly dispersed Ge-P nanoparticles in a porous carbon matrix, the GPBN/C electrode shows exceptional electrochemical performance. Importantly, our strategy provides an effective way to explore alloy-type electrodes to develop fast and stable high-capacity batteries.

Boosting lithium ion storage of lithium nickel manganese oxide via conformally interfacial nanocoating.

In this work, a conformally interfacial nanocoating strategy is introduced to enhance the lithium ion storage performance of LiNi0.5Mn1.5O4 (LNMO). Stable cycling of LNMO is achieved through La2O3 coating at both room and elevated temperatures. A series of La2O3-coated LNMO composites with various coating contents ranging from 0 to 3 wt% is prepared, and their electrochemical behaviors are systematically investigated. Among them, the 2 wt% La2O3-coated LNMO cathode presents the best comprehensive lithium ion storage performance; for instance, it retains more than 75% capacity retention after 500 cycles at room temperature and 93% capacity retention after 50 cycles at an elevated temperature of 55 °C with 1C rate. Moreover, the modified samples show more stable plateau potential than the pristine one during the cycling process. It is believed that the introduction of the La2O3 nanocoating layer can effectively suppress side reactions between electrode and electrolyte, thus maintaining stable structure of electrode material and reducing polarization during cycling. Our work provides an effective approach to improve the electrochemical stability of LNMO high-potential cathode for future large-scale applications of enhanced lithium ion batteries with high energy density and long cycle life.

Homologous Strategy to Construct High-Performance Coupling Electrodes for Advanced Potassium-Ion Hybrid Capacitors.

Potassium-ion hybrid capacitors (PIHCs) have been considered as promising potentials in mid- to large-scale storage system applications owing to their high energy and power density. However, the process involving the intercalation of K+ into the carbonaceous anode is a sluggish reaction, while the adsorption of anions onto the cathode surface is relatively faster, resulting in an inability to exploit the advantage of high energy. To achieve a high-performance PIHC, it is critical to promote the K+ insertion/desertion in anodic materials and design suitable cathodic materials matching the anodes. In this study, we propose a facile "homologous strategy" to construct suitable anode and cathode for high-performance PIHCs, that is, unique multichannel carbon fiber (MCCF)-based anode and cathode materials are firstly prepared by electrospinning, and then followed by sulfur doping and KOH activation treatment, respectively. Owing to a multichannel structure with a large interlayer spacing for introducing S in the sulfur-doped multichannel carbon fiber (S-MCCF) composite, it presents high capacity, super rate capability, and long cycle stability as an anode in potassium-ion cells. The cathode composite of activated multichannel carbon fiber (aMCCF) has a considerably high specific surface area of 1445 m2 g-1 and exhibits outstanding capacitive performance. In particular, benefiting from advantages of the fabricated S-MCCF anode and aMCCF cathode by homologous strategy, PIHCs assembled with the unique MCCF-based anode and cathode show outstanding electrochemical performance, which can deliver high energy and power densities (100 Wh kg-1 at 200 W kg-1, and 58.3 Wh kg-1 at 10,000 W kg-1) and simultaneously exhibit superior cycling stability (90% capacity retention over 7000 cycles at 1.0 A g-1). The excellent electrochemical performance of the MCCF-based composites for PIHC electrodes combined with their simple construction renders such materials attractive for further in-depth investigations of alkali-ion battery and capacitor applications.

Revealing the Role of Liquid Metals at the Anode-Electrolyte Interface for All Solid-State Lithium-Ion Batteries.

All-solid-state lithium-ion batteries (ASSLIBs) are receiving tremendous attention for safety concerns over liquid system. However, current ASSLIBs still suffer from poor cycling and rate performance because of unfavorable interfacial contact between solid electrolyte and electrodes, especially in the alloy-based anode. To wet the solid electrode/electrolyte interface, accommodate volume change, and further boost kinetics, liquid metal Ga is introduced into the representative Sb anode, and its corresponding role is comprehensively revealed by experimental results and theoretical calculations for the first time. In addition to interface contact and strain accommodation, with the aid of in situ generation of liquid metal Ga, the lithiation/de-lithiation activity of Sb is stimulated, showing outstanding rate and cycling performance in half cells. Furthermore, benefited from the in situ chemical reaction, TiS2 powder can be directly used to construct a novel "Li-free" TiS2|LiBH4|GaSb full cell, which exhibits an outstanding capacity retention of 226 mA h g-1 after 1000 cycles at a current density of 0.5 A g-1. This work provides guidance for implementing future rational design of alloy anodes within ASSLIBs.

Rational Construction of a Binder-Free and Universal Electrode for Stable and Fast Alkali-Ion Storage.

Na-ion batteries (SIBs) and K-ion batteries (PIBs) are considered as promising alternatives to Li-ion batteries (LIBs) for large-scale electrical-energy-storage applications. Thus, developing an advanced anodic material with appropriate structure for both SIBs and PIBs is urgently desirable but remains an eager challenge because of the relatively large ionic radius of Na+ or K+. Herein, we rationally design a sulfur-mediated three-dimensional graphene aerogel (SMGA) with plant cell wall structure as a binder-free anodic material for SIBs and PIBs as well as LIBs, exhibiting high capacity and excellent rate capability along with long cycling stability. For instance, at 0.1 A g-1, the SMGA anodes can deliver a high capacity of 320 mAh g-1 in PIBs after 500 cycles and 304 mAh g-1 in SIBs and 690 mAh g-1 in LIBs after 200 cycles. Furthermore, a detailed electrochemical kinetic calculation manifests that the Li/Na/K-ion storage capability is mainly ascribed to the introduction of sulfur in graphene aerogel (GA) to enlarge the interlayer distance, the three-dimensional interconnected network with porous structure providing sufficient space to accommodate volumetric expansion, and a short transport pathway for electrons/alkali-ions. Our results demonstrate the advanced performance of alkali-ion batteries, thus making it possible to develop a universal electrode for applications of cost-effective next-generation rechargeable batteries.

Sulfur encapsulated in thermally reduced graphite oxide as a cathode for Li-S batteries.

Rechargeable Li-S batteries are receiving ever-increasing attention due to their high theoretical energy density and inexpensive raw sulfur materials. However, their practical applications have been hindered by short cycle life and limited power density owing to the poor electronic conductivity of sulfur species, diffusion of soluble polysulfide intermediates (Li2S n , n = 4-8) and the large volume change of the S cathode during charge/discharge. Optimizing the carbon framework is considered as an effective approach for constructing high performance S/carbon cathodes because the microstructure of the carbon host plays an important role in stabilizing S and restricting the "shuttle reaction" of polysulfides in Li-S batteries. In this work, reduced graphite oxide (rGO) materials with different oxidation degree were investigated as the matrix to load the active material by an in situ thermally reducing graphite oxide (GO) and intercalation strategy under vacuum at 600 °C. It has been found that the loaded amount of S embedded in the rGO layer for the S/carbon cathode and its electrochemical performance strongly depended on the oxidation degree of GO. In particular, on undergoing CS2 treatment, the rGO-S cathode exhibits extraordinary performances in Li-S batteries. For instance, at a current density of 0.2 A g-1, the optimized rGO-S cathode shows a columbic efficiency close to 100% and retains a capacity of around 750 mA h g-1 with progressive cycling up to over 250 cycles.

Red Phosphorus-Embedded Cross-Link-Structural Carbon Films as Flexible Anodes for Highly Reversible Li-Ion Storage.

Red phosphorus (P) is considered to be one of the most attractive anodic materials for lithium-ion batteries (LIBs) due to its high theoretical capacity of 2596 mAh g-1. However, intrinsic characteristics such as the poor electronic conductivity and large volume expansion at lithiation impede the development of red P. Here, we design a new strategy to embed red P particles into a cross-link-structural carbon film (P-C film), in order to improve the electronic conductivity and accommodate the volume expansion. The red P/carbon film is synthesized via vapor phase polymerization (VPP) followed by the pyrolysis process, working as a flexible binder-free anode for LIBs. High cycle stability and good rate capability are achieved by the P-C film anode. With 21% P content in the film, it displays a capacity of 903 mAh g-1 after 640 cycles at a current density of 100 mA g-1 and a capacity of 460 mAh g-1 after 1000 cycles at 2.0 A g-1. Additionally, the Coulombic efficiency reaches almost 100% for each cycle. The superior properties of the P-C films together with their facile fabrication make this material attractive for further flexible and high energy density LIB applications.

Flexible Overoxidized Polypyrrole Films with Orderly Structure as High-Performance Anodes for Li- and Na-Ion Batteries.

Flexible polypyrrole (PPy) films with highly ordered structures were fabricated by a novel vapor phase polymerization (VPP) process and used as the anode material in lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). The PPy films demonstrate excellent rate performance and cycling stability. At a charge/discharge rate of 1 C, the reversible capacities of the PPy film anode reach 284.9 and 177.4 mAh g-1 in LIBs and SIBs, respectively. Even at a charge/discharge rate of 20 C, the reversible capacity of the PPy film anode retains 54.0% and 52.9% of the capacity of 1 C in LIBs and SIBs, respectively. After 1000 electrochemical cycles at a rate of 10 C, there is no obvious capacity fading. The molecular structure and electrochemical behaviors of Li- and Na-ion doping and dedoping in the PPy films are investigated by XPS and ex situ XRD. It is believed that the PPy film electrodes in the overoxidized state can be reversibly charged and discharged through the doping and dedoping of lithium or sodium ions. Because of the self-adaptation of the doped ions, the ordered pyrrolic chain structure can realize a fast charge/discharge process. This result may substantially contribute to the progress of research into flexible polymer electrodes in various types of batteries.