Laifa Shen

Challenges and Perspectives for NASICON‐Type Electrode Materials for Advanced Sodium‐Ion Batteries

Sodium-ion batteries (SIBs) have attracted increasing attention in the past decades, because of high overall abundance of precursors, their even geographical distribution, and low cost. Apart from inherent thermodynamic disadvantages, SIBs have to overcome multiple kinetic problems, such as fast capacity decay, low rate capacities and low Coulombic efficiencies. A special case is sodium super ion conductor (NASICON)-based electrode materials as they exhibit - besides pronounced structural stability - exceptionally high ion conductivity, rendering them most promising for sodium storage. Owing to the limiting, comparatively low electronic conductivity, nano-structuring is a prerequisite for achieving satisfactory rate-capability. In this review, we analyze advantages and disadvantages of NASICON-type electrode materials and highlight electrode structure design principles for obtaining the desired electrochemical performance. Moreover, we give an overview of recent approaches to enhance electrical conductivity and structural stability of cathode and anode materials based on NASICON structure. We believe that this review provides a pertinent insight into relevant design principles and inspires further research in this respect.

Peapod‐like Li3VO4/N‐Doped Carbon Nanowires with Pseudocapacitive Properties as Advanced Materials for High‐Energy Lithium‐Ion Capacitors

Lithium ion capacitors are new energy storage devices combining the complementary features of both electric double-layer capacitors and lithium ion batteries. A key limitation to this technology is the kinetic imbalance between the Faradaic insertion electrode and capacitive electrode. Here, we demonstrate that the Li3 VO4 with low Li-ion insertion voltage and fast kinetics can be favorably used for lithium ion capacitors. N-doped carbon-encapsulated Li3 VO4 nanowires are synthesized through a morphology-inheritance route, displaying a low insertion voltage between 0.2 and 1.0 V, a high reversible capacity of ≈400 mAh g-1 at 0.1 A g-1 , excellent rate capability, and long-term cycling stability. Benefiting from the small nanoparticles, low energy diffusion barrier and highly localized charge-transfer, the Li3 VO4 /N-doped carbon nanowires exhibit a high-rate pseudocapacitive behavior. A lithium ion capacitor device based on these Li3 VO4 /N-doped carbon nanowires delivers a high energy density of 136.4 Wh kg-1 at a power density of 532 W kg-1 , revealing the potential for application in high-performance and long life energy storage devices.

Carbon‐Coated Li3VO4 Spheres as Constituents of an Advanced Anode Material for High‐Rate Long‐Life Lithium‐Ion Batteries

Lithium-ion batteries are receiving considerable attention for large-scale energy-storage systems. However, to date the current cathode/anode system cannot satisfy safety, cost, and performance requirements for such applications. Here, a lithium-ion full battery based on the combination of a Li3 VO4 anode with a LiNi0.5 Mn1.5 O4 cathode is reported, which displays a better performance than existing systems. Carbon-coated Li3 VO4 spheres comprising nanoscale carbon-coating primary particles are synthesized by a morphology-inheritance route. The observed high capacity combined with excellent sample stability and high rate capability of carbon-coated Li3 VO4 spheres is superior to other insertion anode materials. A high-performance full lithium-ion battery is fabricated by using the carbon-coated Li3 VO4 spheres as the anode and LiNi0.5 Mn1.5 O4 spheres as the cathode; such a cell shows an estimated practical energy density of 205 W h kg-1 with greatly improved properties such as pronounced long-term cyclability, and rapid charge and discharge.

Ultrathin Ti2Nb2O9 Nanosheets with Pseudocapacitive Properties as Superior Anode for Sodium-Ion Batteries

Sodium-ion batteries are emerging as promising candidates for grid energy storage because of the abundant sodium resources and low cost. However, the identification and development of suitable anode materials is far from being satisfactory. Here, it is demonstrated that the Ti2 Nb2 O9 nanosheets with tunnel structure can be used as suitable anode materials for sodium-ion batteries. Ti2 Nb2 O9 nanosheets are synthesized by liquid exfoliation combined with topotactic dehydration, delivering a high reversible capacity of 250 mAh g-1 at 50 mA g-1 at a suitable average voltage of ≈0.7 V. It is found that a low energy diffusion barrier, enlarged interlayer spacing, and exceptional nanoporosity together give rise to high rate performance characterized by pseudocapacitive behavior. The observed high reversible capacity, excellent rate capability, and good cyclability of Ti2 Nb2 O9 nanosheets make this material competitive when compared to other sodium insertion anode materials.