Based upon advances in theoretical algorithms, modeling and simulations, and computer technologies, the rational design of materials, cells, devices, and packs in the field of lithium-ion batteries is being realized incrementally and will at some point trigger a paradigm revolution by combining calculations and experiments linked by a big shared database, enabling accelerated development of the whole industrial chain. Theory and multi-scale modeling and simulation, as supplements to experimental efforts, can help greatly to close some of the current experimental and technological gaps, as well as predict path-independent properties and help to fundamentally understand path-independent performance in multiple spatial and temporal scales.

Interfacial charge transfer is the key kinetic process dictating the operation of lithium-ion battery. Redox-mediated charge propagations of the electronic (e^- and h⁺) and ionic species (Li⁺) at the electrode-electrolyte interface have recently gained increasing attention for better exploitation of battery materials. This article briefly summarises the energetic and kinetic aspects of lithium-ion batteries, and reviews the recent progress on various redox-assisted Li⁺ storage approaches. From molecular wiring to polymer wiring and from redox targeting to redox flow lithium battery, the role of redox mediators and the way of the redox species functioning in lithium-ion batteries are discussed.

The methods and techniques commonly used in investigating the change of entropy and heat generation in Li cells/batteries are introduced, as are the measurements, calculations and purposes. The changes of entropy and heat generation are concomitant with the use of Li cells/batteries. In order to improve the management and the application of Li cells/batteries, especially for large scale power batteries, the quantitative investigations of the change of entropy and heat generating are necessary.

The formidable challenge of developing high-performance battery system stems from the complication of battery operations, both mechanically and electronically. In the electrodes and at the electrode-electrolyte interfaces, chemical reactions take place with evolving electron states. In addition to the extensive studies of material synthesis, electrochemical, structural, and mechanical properties, soft x-ray spectroscopy provides unique opportunities for revealing the critical electron states in batteries. This review discusses some of the recent soft x-ray spectroscopic results on battery binder, transition-metal based positive electrodes, and the solid-electrolyte-interphase. By virtue of soft x-ray's sensitivity to electron states, the electronic property, the redox during electrochemical operations, and the chemical species of the interphases could be fingerprinted by soft x-ray spectroscopy. Understanding and innovating battery technologies need a multimodal approach, and soft x-ray spectroscopy is one of the incisive tools to probe the chemical and physical evolutions in batteries.

Progress in electrochromic lithium ion batteries (LIBs) is reviewed, highlighting advances and possible research directions. Methods for using the LIB electrode materials' magnetic properties are also described, using several examples. Li₄Ti₅O₁₂ (LTO) film is discussed as an electrochromic material and insertion compound. The opto-electrical properties of the LTO film have been characterized by electrical measurements and UV-Vis spectra. A prototype bi-functional electrochromic LIB, incorporating LTO as both electrochromic layer and anode, has also been characterized by charge-discharge measurements and UV-Vis transmittance. The results show that the bi-functional electrochromic LIB prototype works well. Magnetic measurement has proven to be a powerful tool to evaluate the quality of electrode materials. We introduce briefly the magnetism of solids in general, and then discuss the magnetic characteristics of layered oxides, spinel oxides, olivine phosphate LiFePO₄, and Nasicon-type Li₃Fe₂(PO₄)₃. We also discuss what kind of impurities can be detected, which will guide us to fabricate high quality films and high performance devices.

Although significant progress has been made in many aspects of the emerging aprotic Li-O₂ battery system, an in-depth understanding of the oxygen reactions is still underway. The oxygen reactions occurring in the positive electrode distinguish Li-O₂ batteries from the conventional Li-ion cells and play a crucial role in the Li-O₂ cell's performance (capacity, rate capability, and cycle life). Recent advances in fundamental studies of oxygen reactions in aprotic Li-O₂ batteries are reviewed, including the reaction route, kinetics, morphological evolution of Li₂O₂, and charge transport within Li₂O₂. Prospects are also provided for future fundamental investigations of Li-O₂ chemistry.

The application of wavy structures in stretchable electrochemical energy storage devices is reviewed. First, the mechanical analysis of wavy structures, specific to flexible electronics, is introduced. Second, stretchable electrochemical energy storage devices with wavy structures are discussed. Finally, the present problems and challenges are reviewed, and possible directions for future research are outlined.

Lithium ion batteries are important electrochemical energy storage devices for consumer electronics and the most promising candidates for electrical/hybrid vehicles. The surface chemistry influences the performance of the batteries significantly. In this short review, the evolution of the surface structure of the cathode materials at different states of the pristine, storage and electrochemical reactions are summarized. The main methods for the surface modification are also introduced.

Rechargeable batteries, such as lithium-ion batteries, play an important role in the emerging sustainable energy landscape. Mechanical degradation and resulting capacity fade in high-capacity electrode materials critically hinder their use in high-performance lithium-ion batteries. This paper presents an overview of recent advances in understanding the electrochemically-induced mechanical behavior of the electrode materials in lithium-ion batteries. Particular emphasis is placed on stress generation and facture in high-capacity anode materials such as silicon. Finally, we identify several important unresolved issues for future research.

Progress in the research on phase transitions during Li⁺ extraction/insertion processes in typical battery materials is summarized as examples to illustrate the significance of understanding phase transition phenomena in Li-ion batteries. Physical phenomena such as phase transitions (and resultant phase diagrams) are often observed in Li-ion battery research and already play an important role in promoting Li-ion battery technology. For example, the phase transitions during Li⁺ insertion/extraction are highly relevant to the thermodynamics and kinetics of Li-ion batteries, and even physical characteristics such as specific energy, power density, volume variation, and safety-related properties.

Physical models of ion diffusion at different interfaces are reviewed. The use of impedance spectroscopy (IS), nuclear magnetic resonance (NMR), and secondary ion mass spectrometry (SIMS) techniques are also discussed. The diffusion of ions is fundamental to the operation of lithium-ion batteries, taking place not only within the grains but also across different interfaces. Interfacial ion transport usually contributes to the majority of the resistance in lithium-ion batteries. A greater understanding of the interfacial diffusion of ions is crucial to improving battery performance.

Size-related properties of novel lithium battery materials, arising from kinetics, thermodynamics, and newly discovered lithium storage mechanisms, are reviewed. Complementary experimental and computational investigations of the use of the size effects to modify electrodes and electrolytes for lithium ion batteries are enumerated and discussed together. Size differences in the materials in lithium ion batteries lead to a variety of exciting phenomena. Smaller-particle materials with highly connective interfaces and reduced diffusion paths exhibit higher rate performance than the corresponding bulk materials. The thermodynamics is also changed by the higher surface energy of smaller particles, affecting, for example, secondary surface reactions, lattice parameter, voltage, and the phase transformation mechanism. Newly discovered lithium storage mechanisms that result in superior storage capacity are also briefly highlighted.

Structural transformation behaviors of several typical oxide cathode materials during a heating process are reviewed in detail to provide in-depth understanding of the key factors governing the thermal stability of these materials. We also discuss applying the information about heat induced structural evolution in the study of electrochemically induced structural changes. All these discussions are expected to provide valuable insights for designing oxide cathode materials with significantly improved structural stability for safe, long-life lithium ion batteries, as the safety of lithium-ion batteries is a critical issue; it is widely accepted that the thermal instability of the cathodes is one of the most critical factors in thermal runaway and related safety problems.

The physics of ionic and electrical conduction at electrode materials of lithium-ion batteries (LIBs) are briefly summarized here, besides, we review the current research on ionic and electrical conduction in electrode material incorporating experimental and simulation studies. Commercial LIBs have been widely used in portable electronic devices and are now developed for large-scale applications in hybrid electric vehicles (HEV) and stationary distributed power stations. However, due to the physical limits of the materials, the overall performance of today's LIBs does not meet all the requirements for future applications, and the transport problem has been one of the main barriers to further improvement. The electron and Li-ion transport behaviors are important in determining the rate capacity of LIBs.

The rapid evolution of high-throughput theoretical design schemes to discover new lithium battery materials is reviewed, including high-capacity cathodes, low-strain cathodes, anodes, solid state electrolytes, and electrolyte additives. With the development of efficient theoretical methods and inexpensive computers, high-throughput theoretical calculations have played an increasingly important role in the discovery of new materials. With the help of automatic simulation flow, many types of materials can be screened, optimized and designed from a structural database according to specific search criteria. In advanced cell technology, new materials for next generation lithium batteries are of great significance to achieve performance, and some representative criteria are: higher energy density, better safety, and faster charge/discharge speed.

The physical fundamentals and influences upon electrode materials' open-circuit voltage (OCV) and the spatial distribution of electrochemical potential in the full cell are briefly reviewed. We hope to illustrate that a better understanding of these scientific problems can help to develop and design high voltage cathodes and interfaces with low Ohmic drop. OCV is one of the main indices to evaluate the performance of lithium ion batteries (LIBs), and the enhancement of OCV shows promise as a way to increase the energy density. Besides, the severe potential drop at the interfaces indicates high resistance there, which is one of the key factors limiting power density.

An overview of ion transport in lithium-ion inorganic solid state electrolytes is presented, aimed at exploring and designing better electrolyte materials. Ionic conductivity is one of the most important indices of the performance of inorganic solid state electrolytes. The general definition of solid state electrolytes is presented in terms of their role in a working cell (to convey ions while isolate electrons), and the history of solid electrolyte development is briefly summarized. Ways of using the available theoretical models and experimental methods to characterize lithium-ion transport in solid state electrolytes are systematically introduced. Then the various factors that affect ionic conductivity are itemized, including mainly structural disorder, composite materials and interface effects between a solid electrolyte and an electrode. Finally, strategies for future material systems, for synthesis and characterization methods, and for theory and calculation are proposed, aiming to help accelerate the design and development of new solid electrolytes.

Recent progress in improving Li-S batteries' cathodes, anodes, and electrolytes via different approaches is summarized. The poor conductivity of sulfur cathodes, the dissolution of polysulfide intermediates, and the high reactivity of metal Li anodes currently motivate a great deal of research. Urgent challenges concerning Li anodes are also emphasized.

The scientific basis of all-solid-state lithium batteries with inorganic solid electrolytes is reviewed briefly, touching upon solid electrolytes, electrode materials, electrolyte/electrode interface phenomena, fabrication, and evaluation. The challenges and prospects are outlined as well.