Tight Binding and Dual Encapsulation Enabled Stable Thick Silicon/Carbon Anode with Ultrahigh Volumetric Capacity for Lithium Storage.

Silicon (Si) is regarded as one of the most promising anode materials for high-performance lithium-ion batteries (LIBs). However, how to mitigate its poor intrinsic conductivity and the lithiation/delithiation-induced large volume change and thus structural degradation of Si electrodes without compromising their energy density is critical for the practical application of Si in LIBs. Herein, an integration strategy is proposed for preparing a compact micron-sized Si@G/CNF@NC composite with a tight binding and dual-encapsulated architecture that can endow it with superior electrical conductivity and deformation resistance, contributing to excellent cycling stability and good rate performance in thick electrode. At an ultrahigh mass loading of 10.8 mg cm-2 , the Si@G/CNF@NC electrode also presents a large initial areal capacity of 16.7 mA h cm-2 (volumetric capacity of 2197.7 mA h cm-3 ). When paired with LiNi0.95 Co0.02 Mn0.03 O2 , the pouch-type full battery displays a highly competitive gravimetric (volumetric) energy density of ≈459.1 Wh kg-1 (≈1235.4 Wh L-1 ).

Realizing High Utilization of High-Mass-Loading Sulfur Cathode via Electrode Nanopore Regulation.

One main challenge of realizing high-energy-density lithium-sulfur batteries is low active materials utilization, excessive use of inert components, high electrolyte intake, and mechanical instability of high-mass-loading sulfur cathodes. Herein, chunky sulfur/graphene particle electrodes were designed, where active sulfur was confined in vertically aligned nanochannels (width ∼12 nm) of chunky graphene-based particles (∼70 µm) with N, O-containing groups. The short charge transport distance and low tortuosity enabled high utilization of active materials for high-mass-loading chunky sulfur/graphene particle electrodes. The intermediate polysulfide trapping effect by capillary effect and heteroatoms-containing groups, and a mechanically robust graphene framework, helped to realize stable electrode cycling. The as-designed electrode showed high areal capacity (10.9 mAh cm-2) and high sulfur utilization (72.4%) under the rigorous conditions of low electrolyte/active material ratio (∼2.5 µL mg-1) and high sulfur loading (9.0 mg cm-2), realizing high energy densities (520 Wh kg-1, 1635 Wh L-1).

Manipulating Redox Kinetics of Sulfur Species Using Mott-Schottky Electrocatalysts for Advanced Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries suffer from sluggish sulfur redox reactions under high-sulfur-loading and lean-electrolyte conditions. Herein, a typical Co@NC heterostructure composed of Co nanoparticles and a semiconductive N-doped carbon matrix is designed as a model Mott-Schottky catalyst to exert the electrocatalytic effect on sulfur electrochemistry. Theoretical and experimental results reveal the redistribution of charge and a built-in electric field at the Co@NC heterointerface, which are critical to lowering the energy barrier of polysulfide reduction and Li2S oxidation in the discharge and charge process, respectively. With Co@NC Mott-Schottky catalysts, the Li-S batteries display an ultrahigh capacity retention of 92.1% and a system-level gravimetric energy density of 307.8 Wh kg-1 under high S loading (10.73 mg cm-2) and lean electrolyte (E/S = 5.9 µL mgsulfur-1) conditions. The proposed Mott-Schottky heterostructure not only deepens the understanding of the electrocatalytic effect in Li-S chemistry but also inspires a rational catalyst design for advanced high-energy-density batteries.

Red Phosphorus Nanoparticle@3D Interconnected Carbon Nanosheet Framework Composite for Potassium-Ion Battery Anodes.

Red phosphorus (P) has been recognized as a promising storage material for Li and Na. However, it has not been reported for K storage and the reaction mechanism remains unknown. Herein, a novel nanocomposite anode material is designed and synthesized by anchoring red P nanoparticles on a 3D carbon nanosheet framework for K-ion batteries (KIBs). The red P@CN composite demonstrates a superior electrochemical performance with a high reversible capacity of 655 mA h g-1 at 100 mA g-1 and a good rate capability remaining 323.7 mA h g-1 at 2000 mA g-1 , which outperform reported anode materials for KIBs. The transmission electron microscopy and theoretical calculation results suggest a one-electron reaction mechanism ofP + K+ + e- → KP, corresponding to a theoretical capacity of 843 mA h g-1 ,which is the highest value for anode materials investigated for KIBs. The study not only sheds light on the rational design of high performance red P anodes for KIBs but also offers a fundamental understanding of the potassium storage mechanism of red P.

Engineering a Low-Strain Si@TiSi2@NC Composite for High-Performance Lithium-Ion Batteries.

The huge volume expansion/contraction of silicon (Si) during the lithium (Li) insertion/extraction process, which can lead to cracking and pulverization, poses a substantial impediment to its practical implementation in lithium-ion batteries (LIBs). The development of low-strain Si-based composite materials is imperative to address the challenges associated with Si anodes. In this study, we have engineered a TiSi2 interface on the surface of Si particles via a high-temperature calcination process, followed by the introduction of an outermost carbon (C) shell, leading to the construction of a low-strain and highly stable Si@TiSi2@NC composite. The robust TiSi2 interface not only enhances electrical and ionic transport but also, more critically, significantly mitigates particle cracking by restraining the stress/strain induced by volumetric variations, thus alleviating pulverization during the lithiation/delithiation process. As a result, the as-fabricated Si@TiSi2@NC electrode exhibits a high initial reversible capacity (2172.7 mAh g-1 at 0.2 A g-1), superior rate performance (1198.4 mAh g-1 at 2.0 A g-1), and excellent long-term cycling stability (847.0 mAh g-1 after 1000 cycles at 2.0 A g-1). Upon pairing with LiNi0.6Co0.2Mn0.2O2 (NCM622), the assembled Si@TiSi2@NC||NCM622 pouch-type full cell exhibits exceptional cycling stability, retaining 90.1% of its capacity after 160 cycles at 0.5 C.

Micrometer-scale single crystalline particles of niobium titanium oxide enabling an Ah-level pouch cell with superior fast-charging capability.

Wadsley-Roth phase niobium titanium oxide (TiNb2O7) is widely regarded as a promising anode candidate for fast-charging lithium-ion batteries due to its safe working potential and doubled capacity in comparison to the commercial fast-charging anode material (lithium titanium oxide, Li4Ti5O12). Although good fast charge/discharge performance was shown for nanostructured TiNb2O7, the small size would cause the low electrode compensation density and energy density of batteries, as well as parasitic reactions. Fundamental understanding of the electrochemical lithium insertion/extraction process and the structural evolution for the micrometer-scale single crystalline TiNb2O7 (MSC-TiNb2O7) could provide insights to understand its inherent properties and possibility for fast-charging application. Here, we revealed the highly reversible structural evolution of the MSC-TiNb2O7 during the lithiation/delithiation processes. Interestingly, an ion-conductive lithium niobate interphase was in situ formed on the MSC-TiNb2O7 surface during the formation cycle, which could facilitate fast ion diffusion on the material surface and support fast electrochemical reaction kinetics. Experimentally, the MSC-TiNb2O7 delivered a high reversible capacity of 291.9 mA h g-1 at 0.5C with a high initial Coulombic efficiency (>95%), and showed superb rate capability with a reasonable capacity of 55.6 mA h g-1 under a high current density of 40C. An Ah-level pouch cell with a lithium cobalt oxide (LiCoO2) cathode exhibited 91.5% capacity retention at 3C charging rate, which revealed the significant role of high crystallinity and in situ formation of an ion conductive nano-interphase in realizing fast charging capability of practical TiNb2O7-based lithium-ion batteries.

Reaction-passivation mechanism driven materials separation for recycling of spent lithium-ion batteries.

Development of effective recycling strategies for cathode materials in spent lithium-ion batteries are highly desirable but remain significant challenges, among which facile separation of Al foil and active material layer of cathode makes up the first important step. Here, we propose a reaction-passivation driven mechanism for facile separation of Al foil and active material layer. Experimentally, >99.9% separation efficiency for Al foil and LiNi0.55Co0.15Mn0.3O2 layer is realized for a 102 Ah spent cell within 5 mins, and ultrathin, dense aluminum-phytic acid complex layer is in-situ formed on Al foil immediately after its contact with phytic acid, which suppresses continuous Al corrosion. Besides, the dissolution of transitional metal from LiNi0.55Co0.15Mn0.3O2 is negligible and good structural integrity of LiNi0.55Co0.15Mn0.3O2 is well-maintained during the processing. This work demonstrates a feasible approach for Al foil-active material layer separation of cathode and can promote the green and energy-saving battery recycling towards practical applications.

Nanocomposite of Conducting Polymer and Li Metal for Rechargeable High Energy Density Batteries.

The structure and electrochemical performance of lithium (Li) metal degrade quickly owing to its hostless nature and high reactivity, hindering its practical application in rechargeable high energy density batteries. In order to enhance the electrochemical reversibility of metallic Li, we designed a Li/Li2S-poly(acrylonitrile) (LSPAN) composite foil via a facile mechanical kneading approach using metallic Li and sulfurized poly(acrylonitrile) as the raw materials. The uniformly dispersed Li2S-poly(acrylonitrile) (Li2S-PAN) in a metallic Li matrix buffered the volume change on cycling, and its high Li ion conductivity enabled fast Li ion diffusion behavior of the composite electrode. As expected, the LSPAN electrode showed reduced voltage polarization, enhanced rate capability, and prolonged cycle life compared with the pure Li electrode. It exhibited stable cycling for 600 h with a symmetric cell configuration at 1 mA cm-2 and 1 mA h cm-2, far outperforming the pure metallic Li counterpart (400 h). Also, the LiCoO2||LSPAN full cells with a cathode mass loading of ∼16 mg cm-2 worked stably for 100 cycles at 0.5 C with a high capacity retention of 96.5%, while the LiCoO2||Li full cells quickly failed within only 50 cycles.

Functionally Gradient Silicon/Graphite Composite Electrodes Enabling Stable Cycling and High Capacity for Lithium-Ion Batteries.

Silicon (Si) is regarded as one of the most promising anode materials for high-energy-density lithium (Li)-ion batteries (LIBs). However, Li insertion/extraction induced large volume change, which can lead to the fracture of the Si material itself and the delamination/pulverization of electrodes, is the major challenge for the practical application of Si-based anodes. Herein, a facile and scalable multilayer coating approach was proposed for the large-scale fabrication of functionally gradient Si/graphite (Si/Gr) composite electrodes to simultaneously mitigate the volume change-caused structural degradation and realize high capacity by regulating the spatial distributions of Si and Gr particles in the electrodes. Both our experimental characterizations and chemomechanical simulations indicated that, with a parabolic gradient (PG) distribution of Si through the thickness direction that the two Si-poor surface layers guarantee the major mechanical support and the middle Si-rich layer ensures the high capacity, the as-prepared PG-Si/Gr electrode can not only effectively improve the stability of the electrode structure but also efficiently enable high capacity and stable electrochemical reactions. Consequently, the PG-Si/Gr electrode with a mass loading of 3.15 mg cm-2 exhibited a reversible capacity of 579.2 mAh g-1 (1.82 mAh cm-2) after 200 cycles at 0.2C. Even with a mass loading of 8.45 mg cm-2, the PG-Si/Gr anodes still delivered a high reversible capacity of 4.04 mAh cm-2 after 100 cycles and maintained excellent cycling stability. Moreover, when paired with a commercial LiNi0.5Mn0.3Co0.2O2 (NCM532) cathode (9.56 mg cm-2), the PG-Si/Gr||NCM532 full cell revealed an initial reversible areal capacity of 1.64 mAh cm-2 and sustained a stable areal capacity of 0.94 mAh cm-2 at 0.2C after 100 cycles.

Single-Layer-Particle Electrode Design for Practical Fast-Charging Lithium-Ion Batteries.

Efforts to enable fast charging and high energy density lithium-ion batteries (LIBs) are hampered by the trade-off nature of the traditional electrode design: increasing the areal capacity usually comes with sacrificing the fast charge transfer. Here a single-layer chunky particle electrode design is reported, where red-phosphorus active material is embedded in nanochannels of vertically aligned graphene (red-P/VAG) assemblies. Such an electrode design addresses the sluggish charge transfer stemming from the high tortuosity and inner particle/electrode resistance of traditional electrode architectures consisting of randomly stacked active particles. The vertical ion-transport nanochannels and electron-transfer conductive nanowalls of graphene confine the direction of charge transfer to minimize the transfer distance, and the incomplete filling of nanochannels in the red-P/VAG composite buffers volume change locally, thus avoiding the variation of electrodes thickness during cycling. The single-layer chunky particle electrode displays a high areal capacity (5.6 mAh cm-2 ), which is the highest among the reported fast-charging battery chemistries. Paired with a high-loading LiNi0.6 Co0.2 Mn0.2 O2 (NCM622) cathode, a pouch cell shows stable cycling with high energy and power densities. Such a single-layer chunky particle electrode design can be extended to other advanced battery systems and boost the development of LIBs with fast-charging capability and high energy density.

Uniform Mesoporous MnO2 Nanospheres as a Surface Chemical Adsorption and Physical Confinement Polysulfide Mediator for Lithium-Sulfur Batteries.

The actual implementation of lithium-sulfur batteries is hindered by inferior cyclic stability and poor coulombic efficiency stemming from the notorious shuttling of soluble polysulfide intermediates. Herein, uniform mesoporous MnO2 nanospheres were prepared using a facile self-assembly and room-temperature reaction method. As a sulfur carrier of sulfur cathodes, the versatile architecture of MnO2 not only provides powerful chemical adsorption to anchor polysulfide intermediates on the large polar surface area but also restrains them within the nanopores by physical confinement. The mesoporous MnO2-stabilized sulfur cathode demonstrates a high initial reversible capacity of 1349.3 mA h g-1 and a capacity fading rate of 0.073% at 1.0 C over 500 cycles. Furthermore, a reversible areal capacity of 2.5 mA h cm-2 was achieved with stable cycling performance at a sulfur content of 80.7%. Our work offers a facile method to build efficient sulfur cathodes for high performance lithium-sulfur batteries.

A Polysulfide-Immobilizing Polymer Retards the Shuttling of Polysulfide Intermediates in Lithium-Sulfur Batteries.

Lithium-sulfur batteries are regarded as one of the most promising candidates for next-generation rechargeable batteries. However, the practical application of lithium-sulfur (Li-S) batteries is seriously impeded by the notorious shuttling of soluble polysulfide intermediates, inducing a low utilization of active materials, severe self-discharge, and thus a poor cycling life, which is particularly severe in high-sulfur-loading cathodes. Herein, a polysulfide-immobilizing polymer is reported to address the shuttling issues. A natural polymer of Gum Arabic (GA) with precise oxygen-containing functional groups that can induce a strong binding interaction toward lithium polysulfides is deposited onto a conductive support of a carbon nanofiber (CNF) film as a polysulfide shielding interlayer. The as-obtained CNF-GA composite interlayer can achieve an outstanding performance of a high specific capacity of 880 mA h g-1 and a maintained specific capacity of 827 mA h g-1 after 250 cycles under a sulfur loading of 1.1 mg cm-2 . More importantly, high reversible areal capacities of 4.77 and 10.8 mA h cm-2 can be obtained at high sulfur loadings of 6 and even 12 mg cm-2 , respectively. The results offer a facile and promising approach to develop viable lithium-sulfur batteries with high sulfur loading and high reversible capacities.