Biomaterials for High‐Energy Lithium‐Based Batteries: Strategies,Challenges, and Perspectives

Developing high‐performance batteries through applying renewable resources is of great significance for meeting ever‐growing energy demands and sustainability requirements. Biomaterials have overwhelming advantages in material abundance, environmental benignity, low cost, and more importantly, multifunctionalities from structural and compositional diversity. Therefore, significant and fruitful research on exploiting various natural biomaterials (e.g., soy protein, chitosan, cellulose, fungus, etc.) for boosting high‐energy lithium‐based batteries by means of making or modifying critical battery components (e.g., electrode, electrolyte, and separator) are reported. In this review, the recent advances and main strategies for adopting biomaterials in electrode, electrolyte, and separator engineering for high‐energy lithium‐based batteries are comprehensively summarized. The contributions of biomaterials to stabilizing electrodes, capturing electrochemical intermediates, and protecting lithium metal anodes/enhancing battery safety are specifically emphasized. Furthermore, advantages and challenges of various strategies for fabricating battery materials via biomaterials are described. Finally, future perspectives and possible solutions for further development of biomaterials for high‐energy lithium‐based batteries are proposed.     

3D Hyperbranched Hollow Carbon Nanorod Architectures for High‐Performance Lithium‐Sulfur Batteries

Lithium‐sulfur batteries have been plagued for a long time by low Coulombic efficiency, fast capacity loss, and poor high rate performance. Here, the synthesis of 3D hyperbranched hollow carbon nanorod encapsulated sulfur nanocomposites as cathode materials for lithium‐sulfur batteries is reported. The sulfur nanocomposite cathodes deliver a high specific capacity of 1378 mAh g^‐1 at a 0.1C current rate and exhibit stable cycling performance. The as‐prepared sulfur nanocomposites also achieve excellent high rate capacities and cyclability, such as 990 mAh g^‐1 at 1C, 861 mAh g^‐1 at 5C, and 663 mAh g^‐1 at 10C, extending to more than 500 cycles. The superior electrochemical performance are ascribed to the unique 3D hyperbranched hollow carbon nanorod architectures and high length/radius aspect ratio of the carbon nanorods, which can effectively prevent the dissolution of polysulfides, decrease self‐discharge, and confine the volume expansion on cycling. High capacity, excellent high‐rate performance, and long cycle life render the as‐developed sulfur/carbon nanorod nanocomposites a promising cathode material for lithium‐sulfur batteries.     

3D,Mutually Embedded MOF@Carbon Nanotube Hybrid Networks for High‐Performance Lithium‐Sulfur Batteries

Metal‐organic frameworks (MOFs) hybridized with a conductive matrix could potentially serve as a sulfur host for lithium‐sulfur (Li‐S) battery electrodes; so far most of the previously studied hybrid structures are in the powder form or thin compact films. This study reports 3D porous MOF@carbon nanotube (CNT) networks by grafting MOFs with tailored particle size uniformly throughout a CNT sponge skeleton. Growing larger‐size MOF particles to entrap the conductive CNT network yields a mutually embedded structure with high stability, and after sulfur encapsulation, it shows an initial discharge capacity of ≈1380 mA h g^?1 (at 0.1 C) and excellent cycling stability with a very low fading rate. Furthermore, owing to the 3D porous network that is suitable for enhanced sulfur loading, a remarkable areal capacity of ≈11 mA h cm^?2 (at 0.1 C) is obtained, which is much higher than other MOF‐based hybrid electrodes. The mutually embedded MOF@CNTs with simultaneously high specific capacity, areal capacity, and cycling stability represent an advanced candidate for developing high‐performance Li‐S batteries and other energy storage systems.     

Silica Restricting the Sulfur Volatilization of Nickel Sulfide for High‐Performance Lithium‐Ion Batteries

Nickel sulfides are regarded as promising anode materials for advanced rechargeable lithium‐ion batteries due to their high theoretical capacity. However, capacity fade arising from significant volume changes during operation greatly limits their practical applications. Herein, confined NiS_x@C yolk–shell microboxes are constructed to address volume changes and confine the active material in the internal void space. Having benefited from the yolk–shell structure design, the prepared NiS_x@C yolk–shell microboxes display excellent electrochemical performance in lithium‐ion batteries. Particularly, it delivers impressive cycle stability (460 mAh g^?1 after 2000 cycles at 1 A g^?1) and superior rate performance (225 mAh g^?1 at 20 A g^?1). Furthermore, the lithium storage mechanism is ascertained with in situ synchrotron high‐energy X‐ray diffractions and in situ electrochemical impedance spectra. This unique confined yolk–shell structure may open up new strategies to create other advanced electrode materials for high performance electrochemical storage systems.     

High‐Energy,High‐Rate,Lithium–Sulfur Batteries: Synergetic Effect of Hollow TiO2‐Webbed Carbon Nanotubes and a Dual Functional Carbon‐Paper Interlayer

A novel nanocomposite cathode consisting of sulfur and hollow‐mesoporous titania (HMT) embedded within carbon nanotubes (CNT), which is designated as S‐HMT@CNT, has been obtained by encapsulating elemental sulfur into the pores of hollow‐mesoporous, spherical TiO₂ particles that are connected via CNT. A carbon‐paper interlayer, referred to as dual functional porous carbon wall (DF‐PCW), has been obtained by filling the voids in TiO₂ spheres with carbon and then etching the TiO₂ template with a chemical process. The DF‐PCW interlayer provides a medium for scavenging the lithium polysulfides and suppressing them from diffusing to the anode side when it is inserted between the sulfur cathode and the separator. Lithium–sulfur cells fabricated with the thus prepared S‐HMT@CNT cathode and the DF‐PCW interlayer exhibit superior performance due to the containment of sulfur in TiO₂ and improved lithium–ion and electron transports. The Li–S cells display high capacity with excellent capacity retention at rates as high as 1C, 2C, and 5C rates.     

High‐Performance and Low‐Temperature Lithium–Sulfur Batteries: Synergism of Thermodynamic and Kinetic Regulation

The intrinsic polysulfides shuttle, resulting from not only concentration‐gradient diffusion but also slow conversion kinetics of polysulfides, bears the primary responsibility for the poor capacity and cycle stability of lithium–sulfur batteries (LSBs). Here, it is first presented that enriched edge sites derived from vertical standing and ultrathin 2D layered metal selenides (2DLMS) can simultaneously achieve the thermodynamic and kinetic regulation for polysulfides diffusion, which is systematically elucidated through theoretical calculation, electrochemical characterization, and spectroscopic/microscopic analysis. When employed to fabricate compact coating layer of separator, an ultrahigh capacity of 1338.7 mA h g^?1 is delivered after 100 cycles at 0.2 C, which is the best among the reports. Over 1000 cycles, the cell still maintains the capacity of 546.8 mA h g^?1 at 0.5 C. Moreover, the cell exhibits outstanding capacities of 1106.2 and 865.7 mA h g^?1 after 100 cycles at stern temperature of 0 and ?25 °C. The superior low‐temperature performance is appealing for extended practical application of LSBs. Especially, in view of the economy, the 2DLMS is recycled as an anode of lithium‐ion and sodium‐ion batteries after finishing the test of LSBs. The low‐cost and scalable 2DLMS with enriched egde sites open a new avenue for the perfect regulation of the sulfur electrode.     

Synthesis and Characterization of High‐Energy,High‐Power Spinel‐Layered Composite Cathode Materials for Lithium‐Ion Batteries

Spinel‐layered composites, where a high‐voltage spinel is incorporated in a layered lithium‐rich (Li‐rich) cathode material with a nominal composition x{0.6Li₂MnO₃ · 0.4[LiCo_0.333Mn_0.333Ni_0.333]O₂} · (1 – x) Li[Ni_0.5Mn_1.5]O₄ (x = 0, 0.3, 0.5, 0.7, 1) are synthesized via a hydroxide assisted coprecipitation route to generate high‐energy, high‐power cathode materials for Li‐ion batteries. X‐ray diffraction patterns and the cyclic voltammetry investigations confirm the presence of both the parent components in the composites. The electrochemical investigations performed within a wide potential window show an increased structural stability of the spinel component when incorporated into the composite environment. All the composite materials exhibit initial discharge capacities >200 mAh g^–1. The compositions with x = 0.5 and 0.7 show excellent cycling stability among the investigated materials. Moreover, the first cycle Coulombic efficiency achieve a dramatic improvement with the incorporation of the spinel component. More notably, the composite materials with increased spinel component exhibit superior rate capability compared with the parent Li‐rich material especially together with the highest capacity retention for x = 0.5 composition, making this as the optimal high‐energy high‐power material. The mechanisms involved in the symbiotic relationship of the spinel and layered Li‐rich components in the above composites are discussed.     

Lithium‐ and Manganese‐Rich Oxide Cathode Materials for High‐Energy Lithium Ion Batteries

Layered lithium‐ and manganese‐rich oxides (LMROs), described as xLi₂MnO₃·(1–x)LiMO₂ or Li_1+yM_1–yO₂ (M = Mn, Ni, Co, etc., 0 < x <1, 0 < y ≤ 0.33), have attracted much attention as cathode materials for lithium ion batteries in recent years. They exhibit very promising capacities, up to above 300 mA h g^?1, due to transition metal redox reactions and unconventional oxygen anion redox reaction. However, they suffer from structural degradation and severe voltage fade (i.e., decreasing energy storage) upon cycling, which are plaguing their practical application. Thus, this review will aim to describe the pristine structure, high‐capacity mechanisms and structure evolutions of LMROs. Also, recent progress associated with understanding and mitigating the voltage decay of LMROs will be discussed. Several approaches to solve this problem, such as adjusting cycling voltage window and chemical composition, optimizing synthesis strategy, controlling morphology, doping, surface modification, constructing core‐shell and layered‐spinel hetero structures, are described in detail.