Localized Electrons Enhanced Ion Transport for Ultrafast Electrochemical Energy Storage

The rate-determining process for electrochemical energy storage is largely determined by ion transport occurring in the electrode materials. Apart from decreasing the distance of ion diffusion, the enhancement of ionic mobility is crucial for ion transport. Here, a localized electron enhanced ion transport mechanism to promote ion mobility for ultrafast energy storage is proposed. Theoretical calculations and analysis reveal that highly localized electrons can be induced by intrinsic defects, and the migration barrier of ions can be obviously reduced. Consistently, experiment results reveal that this mechanism leads to an enhancement of Li/Na ion diffusivity by two orders of magnitude. At high mass loading of 10 mg cm⁻² and high rate of 10C, a reversible energy storage capacity up to 190 mAh g⁻¹ is achieved, which is ten times greater than achievable by commercial crystals with comparable dimensions.     

A High‐Performance Lithium‐Ion Capacitor Based on 2D Nanosheet Materials

Lithium‐ion capacitors (LICs) are promising electrical energy storage systems for mid‐to‐large‐scale applications due to the high energy and large power output without sacrificing long cycle stability. However, due to the different energy storage mechanisms between anode and cathode, the energy densities of LICs often degrade noticeably at high power density, because of the sluggish kinetics limitation at the battery‐type anode side. Herein, a high‐performance LIC by well‐defined ZnMn₂O₄‐graphene hybrid nanosheets anode and N‐doped carbon nanosheets cathode is presented. The 2D nanomaterials offer high specific surface areas in favor of a fast ion transport and storage with shortened ion diffusion length, enabling fast charge and discharge. The fabricated LIC delivers a high specific energy of 202.8 Wh kg^?1 at specific power of 180 W kg^?1, and the specific energy remains 98 Wh kg^?1 even when the specific power achieves as high as 21 kW kg^?1.     

Chemically Integrated Inorganic‐Graphene Two‐Dimensional Hybrid Materials for Flexible Energy Storage Devices

State‐of‐the‐art energy storage devices are capable of delivering reasonably high energy density (lithium ion batteries) or high power density (supercapacitors). There is an increasing need for these power sources with not only superior electrochemical performance, but also exceptional flexibility. Graphene has come on to the scene and advancements are being made in integration of various electrochemically active compounds onto graphene or its derivatives so as to utilize their flexibility. Many innovative synthesis techniques have led to novel graphene‐based hybrid two‐dimensional nanostructures. Here, the chemically integrated inorganic‐graphene hybrid two‐dimensional materials and their applications for energy storage devices are examined. First, the synthesis and characterization of different kinds of inorganic‐graphene hybrid nanostructures are summarized, and then the most relevant applications of inorganic‐graphene hybrid materials in flexible energy storage devices are reviewed. The general design rules of using graphene‐based hybrid 2D materials for energy storage devices and their current limitations and future potential to advance energy storage technologies are also discussed.     

Strong Coupling of MoS2 Nanosheets and Nitrogen‐Doped Graphene for High‐Performance Pseudocapacitance Lithium Storage

Layered material MoS₂ is widely applied as a promising anode for lithium‐ion batteries (LIBs). Herein, a scalable and facile dopamine‐assisted hydrothermal technique for the preparation of strongly coupled MoS₂ nanosheets and nitrogen‐doped graphene (MoS₂/N‐G) composite is developed. In this composite, the interconnected MoS₂ nanosheets are well wrapped onto the surface of graphene, forming a unique veil‐like architecture. Experimental results indicate that dopamine plays multiple roles in the synthesis: a binding agent to anchor and uniformly disperse MoS₂ nanosheets, a morphology promoter, and the precursor for in situ nitrogen doping during the self‐polymerization process. Density functional theory calculations further reveal that a strong interaction exists at the interface of MoS₂ nanosheets and nitrogen‐doped graphene, which facilitates the charge transfer in the hybrid system. When used as the anode for LIBs, the resulting MoS₂/N‐G composite electrode exhibits much higher and more stable Li‐ion storage capacity (e.g., 1102 mAh g^?1 at 100 mA g^?1) than that of MoS₂/G electrode without employing the dopamine linker. Significantly, it is also identified that the thin MoS₂ nanosheets display outstanding high‐rate capability due to surface‐dominated pseudocapacitance contribution.     

Advanced Materials for Energy Storage

Popularization of portable electronics and electric vehicles worldwide stimulates the development of energy storage devices, such as batteries and supercapacitors, toward higher power density and energy density, which significantly depends upon the advancement of new materials used in these devices. Moreover, energy storage materials play a key role in efficient, clean, and versatile use of energy, and are crucial for the exploitation of renewable energy. Therefore, energy storage materials cover a wide range of materials and have been receiving intensive attention from research and development to industrialization. In this Review, firstly a general introduction is given to several typical energy storage systems, including thermal, mechanical, electromagnetic, hydrogen, and electrochemical energy storage. Then the current status of high‐performance hydrogen storage materials for on‐board applications and electrochemical energy storage materials for lithium‐ion batteries and supercapacitors is introduced in detail. The strategies for developing these advanced energy storage materials, including nanostructuring, nano‐/microcombination, hybridization, pore‐structure control, configuration design, surface modification, and composition optimization, are discussed. Finally, the future trends and prospects in the development of advanced energy storage materials are highlighted.     

Scalable 2D Mesoporous Silicon Nanosheets for High‐Performance Lithium‐Ion Battery Anode

Constructing unique mesoporous 2D Si nanostructures to shorten the lithium‐ion diffusion pathway, facilitate interfacial charge transfer, and enlarge the electrode–electrolyte interface offers exciting opportunities in future high‐performance lithium‐ion batteries. However, simultaneous realization of 2D and mesoporous structures for Si material is quite difficult due to its non‐van der Waals structure. Here, the coexistence of both mesoporous and 2D ultrathin nanosheets in the Si anodes and considerably high surface area (381.6 m² g^?1) are successfully achieved by a scalable and cost‐efficient method. After being encapsulated with the homogeneous carbon layer, the Si/C nanocomposite anodes achieve outstanding reversible capacity, high cycle stability, and excellent rate capability. In particular, the reversible capacity reaches 1072.2 mA h g^?1 at 4 A g^?1 even after 500 cycles. The obvious enhancements can be attributed to the synergistic effect between the unique 2D mesoporous nanostructure and carbon capsulation. Furthermore, full‐cell evaluations indicate that the unique Si/C nanostructures have a great potential in the next‐generation lithium‐ion battery. These findings not only greatly improve the electrochemical performances of Si anode, but also shine some light on designing the unique nanomaterials for various energy devices.     

二维材料MXene的储能性能与应用

能量存储和转化器件是现代社会的重要基础。随着清洁能源、便携式电子设备及电动汽车的快速发展,人们对储能器件性能的要求越来越高。储能材料是决定储能器件性能的重要因素。通常,储能材料需满足具有可逆的氧化还原反应、易于电解液离子脱嵌、尽可能多地提供氧化还原位点、良好的导电能力等要求。近年来,二维材料因比表面积大、离子传输路径短等特点而得到广泛关注,在储能领域也具有巨大的发展潜力。只有原子量级厚度的二维材料,表面活性位点多,力学性能优良,正契合储能器件对电极材料的要求。MXene是一类新型二维材料,通式为Mn+1XnTx,其中M代表过渡族金属元素,X为碳和/或氮,T代表MXene在制备过程中产生的官能团(-F、-OH、-O等),n一般为1～4。自2011年首次报道以来,MXene在储能领域就被寄予厚望。MXene含有碳原子层,所以具有类似石墨烯的良好导电性;而过渡金属层使其表现出类似过渡金属氧化物的性能;同时,表面多样的官能团赋予MXene良好的亲水性。这种独特的性能组合,使得MXene电荷响应速度快,具有赝电容特征且循环性能稳定,成为储能领域的研究焦点。另外,便携式储能器件要求更高的体积容量与体积能量密度,而MXene与碳基电极材料相比堆积密度高,可有效降低器件体积,拓展应用范围。目前,MXene及其复合材料已经在超级电容器、锂/钠/镁离子二次电池、锂硫电池、锌-空气电池、储氢等诸多储能领域展现出实用价值。但是,MXene容易发生塌陷和堆垛,影响其作为电极材料的性能。因此,需将MXene进行插层、改性、掺杂或与其他材料复合,以阻止MXene堆叠,减小离子扩散阻力,并增加离子吸附位点,从而提高其电化学性能。而且,不同的能量存储和转化装置对MXene的合成方法和结构特征有不同的要求,鉴于MXene能源应用相关研究的大量呈现,有必要对其进行全面总结与分析,以期推动MXene在该领域的发展。本文旨在综述MXene在制备、结构、性能及其在储能方面的最新研究动态与发展方向,并讨论面临的挑战。     

Hierarchical TiO2/SnO2 Hollow Spheres Coated with Graphitized Carbon for High‐Performance Electrochemical Li‐Ion Storage

A self‐templated strategy is developed to fabricate hierarchical TiO₂/SnO₂ hollow spheres coated with graphitized carbon (HTSO/GC‐HSs) by combined sol–gel processes with hydrothermal treatment and calcination. The as‐prepared mesoporous HTSO/GC‐HSs present an approximate yolk‐double–shell structure, with high specific area and small nanocrystals of TiO₂ and SnO₂, and thus exhibit superior electrochemical reactivity and stability when used as anode materials for Li‐ion batteries. A high reversible specific capacity of about 310 mAh g^?1 at a high current density of 5 A g^?1 can be achieved over 500 cycles indicating very good cycle stability and rate performance.     

MOF‐Derived Hollow Co9S8 Nanoparticles Embedded in Graphitic Carbon Nanocages with Superior Li‐Ion Storage

Novel electrode materials consisting of hollow cobalt sulfide nanoparticles embedded in graphitic carbon nanocages (HCSP?GCC) are facilely synthesized by a top‐down route applying room‐temperature synthesized Co‐based zeolitic imidazolate framework (ZIF‐67) as the template. Owing to the good mechanical flexibility and pronounced structure stability of carbon nanocages‐encapsulated Co₉S₈, the as‐obtained HCSP?GCC exhibit superior Li‐ion storage. Working in the voltage of 1.0?3.0 V, they display a very high energy density (707 Wh kg^?1), superior rate capability (reversible capabilities of 536, 489, 438, 393, 345, and 278 mA h g^?1 at 0.2, 0.5, 1, 2, 5, and 10C, respectively), and stable cycling performance (≈26% capacity loss after long 150 cycles at 1C with a capacity retention of 365 mA h g^?1). When the work voltage is extended into 0.01–3.0 V, a higher stable capacity of 1600 mA h g^?1 at a current density of 100 mA g^?1 is still achieved.     

Few‐Layer Silicene Nanosheets with Superior Lithium‐Storage Properties

Silicene, a 2D silicon allotrope with unique low‐buckled structure, has attracted increasing attention in recent years due to its many superior properties. So far, epitaxial growth is one of the very limited ways to obtain high‐quality silicene, which severely impedes the research and application of silicene. Therefore, large‐scale synthesis of silicene is a great challenge, yet urgently desired. Herein, the first scalable preparation of free‐standing high‐quality silicene nanosheets via liquid oxidation and exfoliation of CaSi₂ is reported. This new synthesis strategy successfully induces mild oxidation of the (Si²ⁿ)^2n? layers in CaSi₂ into neutral Si²ⁿ layers without damage of pristine silicene structure and promotes the exfoliation of stacked silicene layers. The obtained silicene sheets are dispersible and ultrathin ones with monolayer or few‐layer thickness and exhibit excellent crystallinity. As a unique 2D layered silicon allotrope, the silicene nanosheets are further explored as new anodes for lithium‐ion batteries and exhibit a nearly theoretical capacity of 721 mAh g^?1 at 0.1 A g^?1 and an extraordinary cycling stability with no capacity decay after 1800 cycles in contrast to previous most silicon anodes showing rapid capacity decay, thus holding great promise for energy storage and beyond.     

Ti‐Based Oxide Anode Materials for Advanced Electrochemical Energy Storage: Lithium/Sodium Ion Batteries and Hybrid Pseudocapacitors

Titanium‐based oxides including TiO₂ and M‐Ti‐O compounds (M = Li, Nb, Na, etc.) family, exhibit advantageous structural dynamics (2D ion diffusion path, open and stable structure for ion accommodations) for practical applications in energy storage systems, such as lithium‐ion batteries, sodium‐ion batteries, and hybrid pseudocapacitors. Further, Ti‐based oxides show high operating voltage relative to the deposition of alkali metal, ensuring full safety by avoiding the formation of lithium and sodium dendrites. On the other hand, high working potential prevents the decomposition of electrolyte, delivering excellent rate capability through the unique pseudocapacitive kinetics. Nevertheless, the intrinsic poor electrical conductivity and reaction dynamics limit further applications in energy storage devices. Recently, various work and in‐depth understanding on the morphologies control, surface engineering, bulk‐phase doping of Ti‐based oxides, have been promoted to overcome these issues. Inspired by that, in this review, the authors summarize the fundamental issues, challenges and advances of Ti‐based oxides in the applications of advanced electrochemical energy storage. Particularly, the authors focus on the progresses on the working mechanism and device applications from lithium‐ion batteries to sodium‐ion batteries, and then the hybrid pseudocapacitors. In addition, future perspectives for fundamental research and practical applications are discussed.     

Atomic Interface Engineering and Electric‐Field Effect in Ultrathin Bi2MoO6 Nanosheets for Superior Lithium Ion Storage

Ultrathin 2D materials can offer promising opportunities for exploring advanced energy storage systems, with satisfactory electrochemical performance. Engineering atomic interfaces by stacking 2D crystals holds huge potential for tuning material properties at the atomic level, owing to the strong layer–layer interactions, enabling unprecedented physical properties. In this work, atomically thin Bi₂MoO₆ sheets are acquired that exhibit remarkable high‐rate cycling performance in Li‐ion batteries, which can be ascribed to the interlayer coupling effect, as well as the 2D configuration and intrinsic structural stability. The unbalanced charge distribution occurs within the crystal and induces built‐in electric fields, significantly boosting lithium ion transfer dynamics, while the extra charge transport channels generated on the open surfaces further promote charge transport. The in situ synchrotron X‐ray powder diffraction results confirm the material's excellent structural stability. This work provides some insights for designing high‐performance electrode materials for energy storage by manipulating the interface interaction and electronic structure.