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.

30 Years of Lithium-Ion Batteries.

Solid-state electrolytes are attracting increasing interest for electrochemical energy storage technologies. In this Review, we provide a background overview and discuss the state of the art, ion-transport mechanisms and fundamental properties of solid-state electrolyte materials of interest for energy storage applications. We focus on recent advances in various classes of battery chemistries and systems that are enabled by solid electrolytes, including all-solid-state lithium-ion batteries and emerging solid-electrolyte lithium batteries that feature cathodes with liquid or gaseous active materials (for example, lithium–air, lithium–sulfur and lithium–bromine systems). A low-cost, safe, aqueous electrochemical energy storage concept with a ‘mediator-ion’ solid electrolyte is also discussed. Advanced battery systems based on solid electrolytes would revitalize the rechargeable battery field because of their safety, excellent stability, long cycle lives and low cost. However, great effort will be needed to implement solid-electrolyte batteries as viable energy storage systems. In this context, we discuss the main issues that must be addressed, such as achieving acceptable ionic conductivity, electrochemical stability and mechanical properties of the solid electrolytes, as well as a compatible electrolyte/electrode interface. This Review details recent advances in battery chemistries and systems enabled by solid electrolytes, including all-solid-state lithium-ion, lithium–air, lithium–sulfur and lithium–bromine batteries, as well as an aqueous battery concept with a mediator-ion solid electrolyte.

Lithium battery chemistries enabled by solid-state electrolytes

Electrochemical capacitors (i.e. supercapacitors) include electrochemical double-layer capacitors that depend on the charge storage of ion adsorption and pseudo-capacitors that are based on charge storage involving fast surface redox reactions. The energy storage capacities of supercapacitors are several orders of magnitude higher than those of conventional dielectric capacitors, but are much lower than those of secondary batteries. They typically have high power density, long cyclic stability and high safety, and thus can be considered as an alternative or complement to rechargeable batteries in applications that require high power delivery or fast energy harvesting. This article reviews the latest progress in supercapacitors in charge storage mechanisms, electrode materials, electrolyte materials, systems, characterization methods, and applications. In particular, the newly developed charge storage mechanism for intercalative pseudocapacitive behaviour, which bridges the gap between battery behaviour and conventional pseudocapacitive behaviour, is also clarified for comparison. Finally, the prospects and challenges associated with supercapacitors in practical applications are also discussed.

Electrochemical capacitors: mechanism, materials, systems, characterization and applications

Metal Oxides and Oxysalts as Anode Materials for Li Ion Batteries

Electrolytes have been identified as some of the most influential components in the performance of electrochemical supercapacitors (ESs), which include: electrical double-layer capacitors, pseudocapacitors and hybrid supercapacitors. This paper reviews recent progress in the research and development of ES electrolytes. The electrolytes are classified into several categories, including: aqueous, organic, ionic liquids, solid-state or quasi-solid-state, as well as redox-active electrolytes. Effects of electrolyte properties on ES performance are discussed in detail. The principles and methods of designing and optimizing electrolytes for ES performance and application are highlighted through a comprehensive analysis of the literature. Interaction among the electrolytes, electro-active materials and inactive components (current collectors, binders, and separators) is discussed. The challenges in producing high-performing electrolytes are analyzed. Several possible research directions to overcome these challenges are proposed for future efforts, with the main aim of improving ESs' energy density without sacrificing existing advantages (e.g., a high power density and a long cycle-life) (507 references).

A review of electrolyte materials and compositions for electrochemical supercapacitors

Rechargeable zinc-manganese dioxide batteries that use mild aqueous electrolytes are attracting extensive attention due to high energy density and environmental friendliness. Unfortunately, manganese dioxide suffers from substantial phase changes (e.g., from initial α-, β-, or γ-phase to a layered structure and subsequent structural collapse) during cycling, leading to very poor stability at high charge/discharge depth. Herein, cyclability is improved by the design of a polyaniline-intercalated layered manganese dioxide, in which the polymer-strengthened layered structure and nanoscale size of manganese dioxide serves to eliminate phase changes and facilitate charge storage. Accordingly, an unprecedented stability of 200 cycles with at a high capacity of 280 mA h g-1 (i.e., 90% utilization of the theoretical capacity of manganese dioxide) is achieved, as well as a long-term stability of 5000 cycles at a  utilization of 40%. The encouraging performance sheds light on the design of advanced cathodes for aqueous zinc-ion batteries.

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Polyaniline-intercalated manganese dioxide nanolayers as a high-performance cathode material for an aqueous zinc-ion battery.

A Metal-Organic Framework Host for Highly Reversible Dendrite-free Zinc Metal Anodes

Rechargeable batteries have been used to power various electric devices and store energy from renewables, but their toxic components (namely, electrode materials, electrolyte, and separator) generally cause serious environment issues when disused. Such toxicity characteristic makes them difficult to power future wearable electronic devices. Now an environmentally friendly and highly safe rechargeable battery, based on a pyrene-4,5,9,10-tetraone (PTO) cathode and zinc anode in mild aqueous electrolyte is presented. The PTO-cathode shows a high specific capacity (336 mAh g-1 ) for Zn2+ storage with fast kinetics and high reversibility. Thus, the PTO//Zn full cell exhibits a high energy density (186.7 Wh kg-1 ), supercapacitor-like power behavior and long-term lifespan (over 1000 cycles). Moreover, a belt-shaped PTO//Zn battery with robust mechanical durability and remarkable flexibility is first fabricated to clarify its potential application in wearable electronic devices.

An Environmentally Friendly and Flexible Aqueous Zinc Battery Using an Organic Cathode

Low-cost alkaline water electrolysis has been considered a sustainable approach to producing hydrogen using renewable energy inputs, but preventing hydrogen/oxygen mixing and efficiently using the instable renewable energy are challenging. Here, using nickel hydroxide as a redox mediator, we decouple the hydrogen and oxygen production in alkaline water electrolysis, which overcomes the gas-mixing issue and may increase the use of renewable energy. In this architecture, the hydrogen production occurs at the cathode by water reduction, and the anodic Ni(OH)2 is simultaneously oxidized into NiOOH. The subsequent oxygen production involves a cathodic NiOOH reduction (NiOOH→Ni(OH)2) and an anodic OH(-) oxidization. Alternatively, the NiOOH formed during hydrogen production can be coupled with a zinc anode to form a NiOOH-Zn battery, and its discharge product (that is, Ni(OH)2) can be used to produce hydrogen again. This architecture brings a potential solution to facilitate renewables-to-hydrogen conversion.

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Separating hydrogen and oxygen evolution in alkaline water electrolysis using nickel hydroxide

Portable and multifunctional electronic devices are developing in the trend of being small, flexible, roll-up, and even wearable, which asks us to develop flexible and micro-sized energy conversion/storage devices. Here, the high performance of a flexible, wire-shaped, and solid-state micro-supercapacitor, which is prepared by twisting a Ni(OH)2-nanowire fiber-electrode and an ordered mesoporous carbon fiber-electrode together with a polymer electrolyte, is demonstrated. This micro-supercapacitor displays a high specific capacitance of 6.67 mF cm-1 (or 35.67 mF cm-2) and a high specific energy density of 0.01 mWh cm-2 (or 2.16 mWh cm-3), which are about 10-100 times higher than previous reports. Furthermore, its capacitance retention is 70% over 10 000 cycles, indicating perfect cyclic ability. Two wire-shaped micro-supercapacitors (0.6 mm in diameter, approximate to 3 cm in length) in series can successfully operate a red light-emitting-diode, indicating promising practical application. Furthermore, synchrotron radiation X-ray computed microtomography technology is employed to investigate inner structure of the micro-device, confirming its solid-state characteristic. This micro-supercapacitor may bring new design opportunities of device configuration for energy-storage devices in the future wearable electronic area.

Xiaoli Dong

Papers

Polyaniline-intercalated manganese dioxide nanolayers as a high-performance cathode material for an aqueous zinc-ion battery.

A Metal-Organic Framework Host for Highly Reversible Dendrite-free Zinc Metal Anodes

An Environmentally Friendly and Flexible Aqueous Zinc Battery Using an Organic Cathode

Separating hydrogen and oxygen evolution in alkaline water electrolysis using nickel hydroxide

Flexible and Wire-Shaped Micro-Supercapacitor Based on Ni(OH)2-Nanowire and Ordered Mesoporous Carbon Electrodes