Li-ion battery materials: present and future

Room-temperature stationary sodium-ion batteries have attracted great attention particularly in large-scale electric energy storage applications for renewable energy and smart grid because of the huge abundant sodium resources and low cost. In this article, a variety of electrode materials including cathodes and anodes as well as electrolytes for room-temperature stationary sodium-ion batteries are briefly reviewed. We compare the difference in storage behavior between Na and Li in their analogous electrodes and summarize the sodium storage mechanisms in the available electrode materials. This review also includes some new results from our group and our thoughts on developing new materials. Some perspectives and directions on designing better materials for practical applications are pointed out based on knowledge from the literature and our experience. Through this extensive literature review, the search for suitable electrode and electrolyte materials for stationary sodium-ion batteries is still challenging. However, after intensive research efforts, we believe that low-cost, long-life and room-temperature sodium-ion batteries would be promising for applications in large-scale energy storage system in the near future.

Room-temperature stationary sodium-ion batteries for large-scale electric energy storage

Alloy negative electrodes for Li-ion batteries.

Mobile and stationary energy storage by rechargeable batteries is a topic of broad societal and economical relevance. Lithium-ion battery (LIB) technology is at the forefront of the development, but a massively growing market will likely put severe pressure on resources and supply chains. Recently, sodium-ion batteries (SIBs) have been reconsidered with the aim of providing a lower-cost alternative that is less susceptible to resource and supply risks. On paper, the replacement of lithium by sodium in a battery seems straightforward at first, but unpredictable surprises are often found in practice. What happens when replacing lithium by sodium in electrode reactions? This review provides a state-of-the art overview on the redox behavior of materials when used as electrodes in lithium-ion and sodium-ion batteries, respectively. Advantages and challenges related to the use of sodium instead of lithium are discussed.

From Lithium-Ion to Sodium-Ion Batteries: Advantages, Challenges, and Surprises.

Tremendous progress has been made in the development of lithium-based rechargeable batteries in recent decades. Discoveries of new electrode materials as well as new storage mechanisms have substantially improved battery performance. In particular, nanomaterials design has emerged as a promising solution to tackle many fundamental problems in conventional battery materials. Here we discuss in detail several key issues in batteries, such as electrode volume change, solid–electrolyte interphase formation, electron and ion transport, and electrode atom/molecule movement, and then analyse the advantages presented by nanomaterials design. In addition, we discuss the challenges caused by using nanomaterials in batteries, including undesired parasitic reactions with electrolytes, low volumetric and areal energy density, and high costs from complex multi-step processing, and their possible solutions. Nanomaterials design may offer a solution to tackle many fundamental problems in conventional batteries. Cui et al. review both the promises and challenges of using nanomaterials in lithium-based rechargeable batteries.

Promises and challenges of nanomaterials for lithium-based rechargeable batteries

Nano-Sn/C composites are ideal anode materials for high energy and power density Li-ion batteries. However, because of the low melting point of Sn and the tendency of grain growth, especially during high temperature carbonization, it has been a significant challenge to create well-dispersed ultrasmall Sn nanoparticles within a carbon matrix. In this paper, we demonstrate an aerosol spray pyrolysis technique, as a facile and scalable method, to synthesize a nano-Sn/C composite with uniformly dispersed 10 nm nano-Sn within a spherical carbon matrix. The discharge capacity of nano-Sn/C composite sphere anodes maintains the initial capacity of 710 mAh/g after 130 cycles at 0.25 C. The nano-Sn/C composite sphere anodes can provide ~600 mAh/g even at a high rate of 20 C. To the best of our knowledge, such high rate performance for Sn anodes has not been reported previously. The exceptional performance of the nano-Sn/C composite is attributed to the unique nano-Sn/C structure: (1) carbon matrix offers mechanical support to accommodate the stress associated with the large volume change of nano-Sn, thus alleviating pulverization; (2) the carbon matrix prevents Sn nanoparticle agglomeration upon prolonged cycling; and (3) carbon network provides continuous path for Li ions and electrons inside the nano-Sn/C composite spheres.

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Uniform nano-Sn/C composite anodes for lithium ion batteries.

Molybdenum disulfide (MoS2 ) is a promising anode for high performance sodium-ion batteries due to high specific capacity, abundance, and low cost. However, poor cycling stability, low rate capability and unclear electrochemical reaction mechanism are the main challenges for MoS2 anode in Na-ion batteries. In this study, molybdenum disulfide/carbon (MoS2 /C) nanospheres are fabricated and used for Na-ion battery anodes. MoS2 /C nanospheres deliver a reversible capacity of 520 mAh g(-1) at 0.1 C and maintain at 400 mAh g(-1) for 300 cycles at a high current density of 1 C, demonstrating the best cycling performance of MoS2 for Na-ion batteries to date. The high capacity is attributed to the short ion and electron diffusion pathway, which enables fast charge transfer and low concentration polarization. The stable cycling performance and high coulombic efficiency (∼100%) of MoS2 /C nanospheres are ascribed to (1) highly reversible conversion reaction of MoS2 during sodiation/desodiation as evidenced by ex-situ X-ray diffraction (XRD) and (2) the formation of a stable solid electrolyte interface (SEI) layer in fluoroethylene carbonate (FEC) based electrolyte as demonstrated by fourier transform infrared spectroscopy (FTIR) measurements.

An advanced MoS2 /carbon anode for high-performance sodium-ion batteries.

Selenium-impregnated carbon composites were synthesized by infusing Se into mesoporous carbon at a temperature of 600 °C under vacuum. Ring-structured Se8 was produced and confined in the mesoporous carbon, which acts as an electronic conductive matrix. During the electrochemical process in low-cost LiPF6/EC/DEC electrolyte, low-order polyselenide intermediates formed and were stabilized by mesoporous carbon, which avoided the shuttle reaction of polyselenides. Exceptional electrochemical performance of Se/mesoporous carbon composites was demonstrated in both Li-ion and Na-ion batteries. In lithium-ion batteries, Se8/mesoporous carbon composite cathodes delivered a reversible capacity of 480 mAh g–1 for 1000 charge/discharge cycles without any capacity loss, while in Na-ion batteries, it provided initial capacity of 485 mAh g–1 and retained 340 mAh g–1 after 380 cycles. The Se8/mesoporous carbon composites also showed excellent rate capability. As the current density increased from 0.1 to 5 C, the capacit...

Selenium@mesoporous carbon composite with superior lithium and sodium storage capacity.

Silicon (Si) has been considered a very promising anode material for lithium ion batteries due to its high theoretical capacity. However, high-capacity Si nanoparticles usually suffer from low electronic conductivity, large volume change, and severe aggregation problems during lithiation and delithiation. In this paper, a unique nanostructured anode with Si nanoparticles bonded and wrapped by graphene is synthesized by a one-step aerosol spraying of surface-modified Si nanoparticles and graphene oxide suspension. The functional groups on the surface of Si nanoparticles (50–100 nm) not only react with graphene oxide and bind Si nanoparticles to the graphene oxide shell, but also prevent Si nanoparticles from aggregation, thus contributing to a uniform Si suspension. A homogeneous graphene-encapsulated Si nanoparticle morphology forms during the aerosol spraying process. The open-ended graphene shell with defects allows fast electrochemical lithiation/delithiation, and the void space inside the graphene shell accompanied by its strong mechanical strength can effectively accommodate the volume expansion of Si upon lithiation. The graphene shell provides good electronic conductivity for Si nanoparticles and prevents them from aggregating during charge/discharge cycles. The functionalized Si encapsulated by graphene sample exhibits a capacity of 2250 mAh g−1 (based on the total mass of graphene and Si) at 0.1C and 1000 mAh g−1 at 10C, and retains 85% of its initial capacity even after 120 charge/discharge cycles. The exceptional performance of graphene-encapsulated Si anodes combined with the scalable and one-step aerosol synthesis technique makes this material very promising for lithium ion batteries.

Alex Langrock

Papers

Uniform nano-Sn/C composite anodes for lithium ion batteries.

An advanced MoS2 /carbon anode for high-performance sodium-ion batteries.

Selenium@mesoporous carbon composite with superior lithium and sodium storage capacity.

Graphene‐Bonded and ‐Encapsulated Si Nanoparticles for Lithium Ion Battery Anodes

Carbon coated hollow Na2FePO4F spheres for Na-ion battery cathodes