In Situ TEM Observations of Discharging/Charging of Solid‐State Lithium‐Sulfur Batteries at High Temperatures

Understanding the structural evolution of Li₂S upon operation of lithium‐sulfur (Li‐S) batteries is inadequate and a complete decomposition of Li₂S during charge is difficult. Whether it is the low electronic conductivity or the low ionic conductivity of Li₂S that inhibits its decomposition is under debate. Furthermore, the decomposition pathway of Li₂S is also unclear. Herein, an in situ transmission electron microscopy (TEM) technique implemented with a microelectromechanical systems (MEMS) heating device is used to study the precipitation and decomposition of Li₂S at high temperatures. It is revealed that Li₂S transformed from an amorphous/nanocrystalline to polycrystalline state with proceeding of the electrochemical lithiation at room temperature (RT), and the precipitation of Li₂S is more complete at elevated temperatures than at RT. Moreover, the decomposition of Li₂S that is difficult to achieve at RT becomes facile with increased Li⁺ ion conduction at high temperatures. These results indicate that Li⁺ ion diffusion in Li₂S dominates its reversibility in the solid‐state Li‐S batteries. This work not only demonstrates the powerful capabilities of combining in situ TEM with a MEMS heating device to explore the basic science in energy storage materials at high temperatures but also introduces the factor of temperature to boost battery performance.     

3D‐Printing Electrolytes for Solid‐State Batteries

Solid‐state batteries have many enticing advantages in terms of safety and stability, but the solid electrolytes upon which these batteries are based typically lead to high cell resistance. Both components of the resistance (interfacial, due to poor contact with electrolytes, and bulk, due to a thick electrolyte) are a result of the rudimentary manufacturing capabilities that exist for solid‐state electrolytes. In general, solid electrolytes are studied as flat pellets with planar interfaces, which minimizes interfacial contact area. Here, multiple ink formulations are developed that enable 3D printing of unique solid electrolyte microstructures with varying properties. These inks are used to 3D‐print a variety of patterns, which are then sintered to reveal thin, nonplanar, intricate architectures composed only of Li₇La₃Zr₂O₁₂ solid electrolyte. Using these 3D‐printing ink formulations to further study and optimize electrolyte structure could lead to solid‐state batteries with dramatically lower full cell resistance and higher energy and power density. In addition, the reported ink compositions could be used as a model recipe for other solid electrolyte or ceramic inks, perhaps enabling 3D printing in related fields.     

Elevated‐Temperature 3D Printing of Hybrid Solid‐State Electrolyte for Li‐Ion Batteries

While 3D printing of rechargeable batteries has received immense interest in advancing the next generation of 3D energy storage devices, challenges with the 3D printing of electrolytes still remain. Additional processing steps such as solvent evaporation were required for earlier studies of electrolyte fabrication, which hindered the simultaneous production of electrode and electrolyte in an all‐3D‐printed battery. Here, a novel method is demonstrated to fabricate hybrid solid‐state electrolytes using an elevated‐temperature direct ink writing technique without any additional processing steps. The hybrid solid‐state electrolyte consists of solid poly(vinylidene fluoride‐hexafluoropropylene) matrices and a Li⁺‐conducting ionic‐liquid electrolyte. The ink is modified by adding nanosized ceramic fillers to achieve the desired rheological properties. The ionic conductivity of the inks is 0.78 × 10 ^?3 S cm^?1. Interestingly, a continuous, thin, and dense layer is discovered to form between the porous electrolyte layer and the electrode, which effectively reduces the interfacial resistance of the solid‐state battery. Compared to the traditional methods of solid‐state battery assembly, the directly printed electrolyte helps to achieve higher capacities and a better rate performance. The direct fabrication of electrolyte from printable inks at an elevated temperature will shed new light on the design of all‐3D‐printed batteries for next‐generation electronic devices.     

30 Years of Lithium‐Ion Batteries

Over the past 30 years, significant commercial and academic progress has been made on Li‐based battery technologies. From the early Li‐metal anode iterations to the current commercial Li‐ion batteries (LIBs), the story of the Li‐based battery is full of breakthroughs and back tracing steps. This review will discuss the main roles of material science in the development of LIBs. As LIB research progresses and the materials of interest change, different emphases on the different subdisciplines of material science are placed. Early works on LIBs focus more on solid state physics whereas near the end of the 20th century, researchers began to focus more on the morphological aspects (surface coating, porosity, size, and shape) of electrode materials. While it is easy to point out which specific cathode and anode materials are currently good candidates for the next‐generation of batteries, it is difficult to explain exactly why those are chosen. In this review, for the reader a complete developmental story of LIB should be clearly drawn, along with an explanation of the reasons responsible for the various technological shifts. The review will end with a statement of caution for the current modern battery research along with a brief discussion on beyond lithium‐ion battery chemistries.     

Lithium–Graphite Paste: An Interface Compatible Anode for Solid‐State Batteries

All‐solid‐state batteries (ASSBs) with ceramic‐based solid‐state electrolytes (SSEs) enable high safety that is inaccessible with conventional lithium‐ion batteries. Lithium metal, the ultimate anode with the highest specific capacity, also becomes available with nonflammable SSEs in ASSBs, which offers promising energy density. The rapid development of ASSBs, however, is significantly hampered by the large interfacial resistance as a matched lithium/ceramic interface that is not easy to pursue. Here, a lithium–graphite (Li–C) composite anode is fabricated, which shows a dramatic modification in wettability with garnet SSE. An intimate Li–C/garnet interface is obtained by casting Li–C composite onto garnet‐type SSE, delivering an interfacial resistance as low as 11 Ω cm². As a comparison, pure Li/garnet interface gives a large resistance of 381 Ω cm². Such improvement can be ascribed to the experiment‐measured increased viscosity of Li–C composite and simulation‐verified limited interfacial reaction. The Li–C/garnet/Li–C symmetric cell exhibits stable plating/striping performance with small voltage hysteresis and endures a critical current density up to 1.0 mA cm^?2. The full cell paired with LiFePO₄ shows stable cycle performance, comparable to the cell with liquid electrolyte. The present work demonstrates a promising strategy to develop ceramic‐compatible lithium metal‐based anodes and hence low‐impedance ASSBs.     

Additive‐Assisted Novel Dual‐Salt Electrolyte Addresses Wide Temperature Operation of Lithium–Metal Batteries

In this study, self‐synthesized lithium trifluoro(perfluoro‐tert‐butyloxyl)borate (LiTFPFB) is combined with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to formulate a novel 1 m dual‐salt electrolyte, which contains lithium difluorophosphate (LiPO₂F₂) additive and dominant carbonate solvents with low melting point and high boiling point. The addition of LiPO₂F₂ into this novel dual‐salt electrolyte dramatically improves cycleability and rate capability of a LiNi_0.5Mn_0.3Co_0.2O₂/Li (NMC/Li) battery, ranging from ?40 to 90 °C. The NMC/Li batteries adopt a Li–metal anode with low thickness of 100 µm (even 50 µm) and a moderately high cathode mass loading level of 10 mg cm^?2. For the first time, this paper provides valuable perspectives for developing practical lithium–metal batteries over a wide temperature range.     

Silicon‐Based Anodes for Lithium‐Ion Batteries: From Fundamentals to Practical Applications

Silicon has been intensively studied as an anode material for lithium‐ion batteries (LIB) because of its exceptionally high specific capacity. However, silicon‐based anode materials usually suffer from large volume change during the charge and discharge process, leading to subsequent pulverization of silicon, loss of electric contact, and continuous side reactions. These transformations cause poor cycle life and hinder the wide commercialization of silicon for LIBs. The lithiation and delithiation behaviors, and the interphase reaction mechanisms, are progressively studied and understood. Various nanostructured silicon anodes are reported to exhibit both superior specific capacity and cycle life compared to commercial carbon‐based anodes. However, some practical issues with nanostructured silicon cannot be ignored, and must be addressed if it is to be widely used in commercial LIBs. This Review outlines major impactful work on silicon‐based anodes, and the most recent research directions in this field, specifically, the engineering of silicon architectures, the construction of silicon‐based composites, and other performance‐enhancement studies including electrolytes and binders. The burgeoning research efforts in the development of practical silicon electrodes, and full‐cell silicon‐based LIBs are specially stressed, which are key to the successful commercialization of silicon anodes, and large‐scale deployment of next‐generation high energy density LIBs.     

Graphitic Hollow Nanocarbon as a Promising Conducting Agent for Solid‐State Lithium Batteries

All‐solid‐state batteries (ASSBs) have lately received enormous attention for electric vehicle applications because of their exceptional stability by engaging all‐solidified cell components. However, there are many formidable hurdles such as low ionic conductivity, interface instability, and difficulty in the manufacturing process, for its practical use. Recently, carbon, one of the representative conducting agents, turns out to largely participate in side reactions with the solid electrolyte, which finally leads to the formation of insulating side products at the interface. Although the battery community mentioned that parasitic reactions are presumably attributed to carbon itself or the generation of electronic conducting paths lowering the kinetic barrier for reactions, the underlying origin for such reactions as well as appropriate solutions have not been provided yet. In this study, for the first time, it is verified that the functional group on carbon is an origin for causing negative effects on interfacial stability and a graphitized hollow nanocarbon as a promising solution for improving‐electrochemical performance is introduced. This work offers an invaluable lesson that a relatively minor part, such as a conducting agent, in ASSBs sometimes gives more positive impact on improving electrochemical performance than huge efforts for resolving other parts.     

Aliphatic Polycarbonate‐Based Solid‐State Polymer Electrolytes for Advanced Lithium Batteries: Advances and Perspective

Conventional liquid electrolytes based lithium‐ion batteries (LIBs) might suffer from serious safety hazards. Solid‐state polymer electrolytes (SPEs) are very promising candidate with high security for advanced LIBs. However, the quintessential frailties of pristine polyethylene oxide/lithium salts SPEs are poor ionic conductivity (≈10⁻⁸ S cm⁻¹) at 25 °C and narrow electrochemical window (<4 V). Many innovative researches are carried out to enhance their lithium‐ion conductivity (10⁻⁴ S cm⁻¹ at 25 °C), which is still far from meeting the needs of high‐performance power LIBs at ambient temperature. Therefore, it is a pressing urgency of exploring novel polymer host materials for advanced SPEs aimed to develop high‐performance solid lithium batteries. Aliphatic polycarbonate, an emerging and promising solid polymer electrolyte, has attracted much attention of academia and industry. The amorphous structure, flexible chain segments, and high dielectric constant endow this class of polymer electrolyte excellent comprehensive performance especially in ionic conductivity, electrochemical stability, and thermally dimensional stability. To date, many types of aliphatic polycarbonate solid polymer electrolyte are discovered. Herein, the latest developments on aliphatic polycarbonate SPEs for solid‐state lithium batteries are summarized. Finally, main challenges and perspective of aliphatic polycarbonate solid polymer electrolytes are illustrated at the end of this review.     

An Electron/Ion Dual‐Conductive Alloy Framework for High‐Rate and High‐Capacity Solid‐State Lithium‐Metal Batteries

The solid‐state Li battery is a promising energy‐storage system that is both safe and features a high energy density. A main obstacle to its application is the poor interface contact between the solid electrodes and the ceramic electrolyte. Surface treatment methods have been proposed to improve the interface of the ceramic electrolytes, but they are generally limited to low‐capacity or short‐term cycling. Herein, an electron/ion dual‐conductive solid framework is proposed by partially dealloying the Li–Mg alloy anode on a garnet‐type solid‐state electrolyte. The Li–Mg alloy framework serves as a solid electron/ion dual‐conductive Li host during cell cycling, in which the Li metal can cycle as a Li‐rich or Li‐deficient alloy anode, free from interface deterioration or volume collapse. Thus, the capacity, current density, and cycle life of the solid Li anode are improved. The cycle capability of this solid anode is demonstrated by cycling for 500 h at 1 mA cm^?2, followed by another 500 h at 2 mA cm^?2 without short‐circuiting, realizing a record high cumulative capacity of 750 mA h cm^?2 for garnet‐type all‐solid‐state Li batteries. This alloy framework with electron/ion dual‐conductive pathways creates the possibility to realize high‐energy solid‐state Li batteries with extended lifespans.     

Nanostructured Metal–Organic Framework (MOF)‐Derived Solid Electrolytes Realizing Fast Lithium Ion Transportation Kinetics in Solid‐State Batteries

Solid‐state batteries are hindered from practical applications, largely due to the retardant ionic transportation kinetics in solid electrolytes (SEs) and across electrode/electrolyte interfaces. Taking advantage of nanostructured UIO/Li‐IL SEs, fast lithium ion transportation is achieved in the bulk and across the electrode/electrolyte interfaces; in UIO/Li‐IL SEs, Li‐containing ionic liquid (Li‐IL) is absorbed in Uio‐66 metal–organic frameworks (MOFs). The ionic conductivity of the UIO/Li‐IL (15/16) SE reaches 3.2 × 10^?4 S cm^?1 at 25 °C. Owing to the high surface tension of nanostructured UIO/Li‐IL SEs, the contact between electrodes and the SE is excellent; consequently, the interfacial resistances of Li/SE and LiFePO₄/SE at 60 °C are about 44 and 206 Ω cm², respectively. Moreover, a stable solid conductive layer is formed at the Li/SE interface, making the Li plating/stripping stable. Solid‐state batteries from the UIO/Li‐IL SEs show high discharge capacities and excellent retentions (≈130 mA h g^?1 with a retention of 100% after 100 cycles at 0.2 C; 119 mA h g^?1 with a retention of 94% after 380 cycles at 1 C). This new type of nanostructured UIO/Li‐IL SEs is very promising for solid‐state batteries, and will open up an avenue toward safe and long lifespan energy storage systems.     

Sulfide‐Based Solid‐State Electrolytes: Synthesis,Stability, and Potential for All‐Solid‐State Batteries

Due to their high ionic conductivity and adeciduate mechanical features for lamination, sulfide composites have received increasing attention as solid electrolyte in all‐solid‐state batteries. Their smaller electronegativity and binding energy to Li ions and bigger atomic radius provide high ionic conductivity and make them attractive for practical applications. In recent years, noticeable efforts have been made to develop high‐performance sulfide solid‐state electrolytes. However, sulfide solid‐state electrolytes still face numerous challenges including: 1) the need for a higher stability voltage window, 2) a better electrode–electrolyte interface and air stability, and 3) a cost‐effective approach for large‐scale manufacturing. Herein, a comprehensive update on the properties (structural and chemical), synthesis of sulfide solid‐state electrolytes, and the development of sulfide‐based all‐solid‐state batteries is provided, including electrochemical and chemical stability, interface stabilization, and their applications in high performance and safe energy storage.