Yonggao Xia

Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries

Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas–solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g−1 with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g−1 still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.

Morphology controlled synthesis and modification of high-performance LiMnPO4 cathode materials for Li-ion batteries

Morphology-controlled monodispersed LiMnPO4 nanocrystals as high-performance cathode materials for Li-ion batteries have been successfully synthesized by a solvothermal method in a mixed solvent of water and polyethylene glycol (PEG). Morphology evolution of LiMnPO4 nanoparticles from a nanorod to a thick nanoplate (∼50 nm in thickness) and to a smaller thin nanoplate (20–30 nm in thickness) is observed by increasing the pH value of the reaction suspension. Electrochemical measurements confirm that the LiMnPO4 thin nanoplates display the best charge–discharge performance, thick nanoplates the intermediate, nanorods the worst, which can be mainly ascribed to the difference in their morphologies and particle sizes in three dimensions. Further modification of LiMnPO4 thin nanoplates with graphene gives rise to an improved electrochemical performance compared with conventional pyrolytic carbon coated ones. The LiMnPO4 thin nanoplate/graphene composites deliver a high capacity of 149 mA h g−1 at 0.1 C, 90 mA h g−1 at 1 C, and even 64 mA h g−1 at 5 C charge–discharge rate, with an excellent cycling stability.

New-concept Batteries Based on Aqueous Li+/Na+ Mixed-ion Electrolytes

Rechargeable batteries made from low-cost and abundant materials operating in safe aqueous electrolytes are attractive for large-scale energy storage. Sodium-ion battery is considered as a potential alternative of current lithium-ion battery. As sodium-intercalation compounds suitable for aqueous batteries are limited, we adopt a novel concept of Li+/Na+ mixed-ion electrolytes to create two batteries (LiMn2O4/Na0.22MnO2 and Na0.44MnO2/TiP2O7), which relies on two electrochemical processes. One involves Li+ insertion/extraction reaction, and the other mainly relates to Na+ extraction/insertion reaction. Two batteries exhibit specific energy of 17 Wh kg−1 and 25 Wh kg−1 based on the total weight of active electrode materials, respectively. As well, aqueous LiMn2O4/Na0.22MnO2 battery is capable of separating Li+ and Na+ due to its specific mechanism unlike the traditional “rocking-chair” lithium-ion batteries. Hence, the Li+/Na+ mixed-ion batteries offer promising applications in energy storage and Li+/Na+ separation.

Enhanced Electrochemical Performance with Surface Coating by Reactive Magnetron Sputtering on Lithium-Rich Layered Oxide Electrodes

Electrode films fabricated with lithium-rich layered 0.3Li2MnO3-0.7LiNi5/21Co5/21Mn11/21O2 cathode materials have been successfully modified with ZnO coatings via a reactive magnetron sputtering (RMS) process for the first time. The morphology and chemical composition of coating films on the electrodes have been in deep investigated by transmission electron microscopy (TEM), energy dispersive spectrometry (EDS), and X-ray photoelectron spectroscopy (XPS) characterizations. The results clearly demonstrate that ZnO film coatings are ultrathin, dense, uniform, and fully covered on the electrodes. The RMS-2 min (deposition time) coated electrode exhibits much higher initial discharge capacity and coulombic efficiency with 316.0 mAh g(-1) and 89.1% than that of the pristine electrode with 283.4 mAh g(-1) and 81.7%. In addition, the discharge capacity also reaches 256.7 and 187.5 mAh g(-1) at 0.1 and 1.0 C-rate, as compared to that of 238.4 and 157.8 mAh g(-1) after 50 cycles. The improved electrochemical performances of RMS-coated electrodes are ascribed to the high-quality ZnO film coatings that reduce charge transfer resistance and effectively protect active material from electrolyte oxidation.

Polyimide matrix-enhanced cross-linked gel separator with three-dimensional heat-resistance skeleton for high-safety and high-power lithium ion batteries

To develop a kind of gel polymer electrolyte with high ion conductivity and good mechanical strength and thermal stability, a polyimide (PI) matrix-enhanced cross-linked gel separator is designed and fabricated by a simple dip-coating and heat treatment method. The PI nonwoven substrate provides high-temperature thermal stability for the gel separator and the crosslinked gel part yields enhanced affinity with the liquid electrolyte. Besides, the cross-linked polymer network could solve the issue of long-term durability of the composite separator in batteries. The gel separator shows better cyclability and rate capability than the traditional PP separator, implying a promising potential application in high-power, high-safety lithium ion batteries. The preparation process is compatible with the traditional manufacturing process of nonwoven membranes, and can be easily converted into continuous production on the industrial scale.

Porous membrane with high curvature, three-dimensional heat-resistance skeleton: a new and practical separator candidate for high safety lithium ion battery

Separators with high reliability and security are in urgent demand for the advancement of high performance lithium ion batteries. Here, we present a new and practical porous membrane with three-dimension (3D) heat-resistant skeleton and high curvature pore structure as a promising separator candidate to facilitate advances in battery safety and performances beyond those obtained from the conventional separators. The unique material properties combining with the well-developed structural characteristics enable the 3D porous skeleton to own several favorable properties, including superior thermal stability, good wettability with liquid electrolyte, high ion conductivity and internal short-circuit protection function, etc. which give rise to acceptable battery performances. Considering the simply and cost-effective preparation process, the porous membrane is deemed to be an interesting direction for the future lithium ion battery separator.

Self-Templating Construction of 3D Hierarchical Macro-/Mesoporous Silicon from 0D Silica Nanoparticles

Porous silicon has found wide applications in many different fields including catalysis and lithium-ion batteries. Three-dimensional hierarchical macro-/mesoporous silicon is synthesized from zero-dimensional Stöber silica particles through a facile and scalable magnesiothermic reduction process. By systematic structure characterization of the macro-/mesoporous silicon, a self-templating mechanism governing the formation of the porous silicon is proposed. Applications as lithium-ion battery anode and photocatalytic hydrogen evolution catalyst are demonstrated. It is found that the macro-/mesoporous silicon shows significantly improved cyclic and rate performance over the commercial nanosized and micrometer-sized silicon particles. After 300 cycles at 0.2 A g-1, the reversible specific capacity is still retained as much as 959 mAh g-1 with a high mass loading density of 1.4 mg cm-2. With the large current density of 2 A g-1, a reversible capacity of 632 mAh g-1 is exhibited. The coexistence of both macro- and mesoporous structures is responsible for the enhanced performance. The macro-/mesoporous silicon also shows superior catalytic performance for photocatalytic hydrogen evolution compared to the silicon nanoparticles.

A comparative study on the oxidation state of lattice oxygen among Li1.14Ni0.136Co0.136Mn0.544O2, Li2MnO3, LiNi0.5Co0.2Mn0.3O2 and LiCoO2 for the initial charge–discharge

The Li-rich layered oxides are attractive electrode materials due to their high reversible specific capacity (>250 mA h g−1); however, the origin of their abnormal capacity is still ambiguous. In order to elucidate this curious anomaly, we compare the lattice oxygen oxidation states among the Li-rich layered oxide Li1.14Ni0.136Co0.136Mn0.544O2, Li2MnO3 and LiNi0.5Co0.2Mn0.3O2, the two components in Li-rich layered oxides, and the most common layered oxide LiCoO2 before and after initial charge–discharge. For simplicity, we employ chemical treatments of NO2BF4 and LiI acetonitrile solutions to simulate the electrochemical delithiation and lithiation processes. X-ray photoelectron spectroscopy (XPS) studies reveal that part of lattice oxygen in Li1.14Ni0.136Co0.136Mn0.544O2 and Li2MnO3 undergoes a reversible redox process (possibly O2− ↔ O22−), while this does not occur in LiNi0.5Co0.2Mn0.3O2 and LiCoO2. This indicates that the extra capacity of Li-rich layered oxides can be attributed to the reversible redox processes of oxygen in the Li2MnO3 component. Thermogravimetric analysis (TGA) further suggests that the formed O22− species in the delithiated Li1.14Ni0.136Co0.136Mn0.544O2 can decompose into O2 at about 210 °C. This phenomenon demonstrates a competitive relationship between extra capacity and thermal stability, which presents a big challenge for the practical applications of these materials.

Eliminating Voltage Decay of Lithium‐Rich Li1.14Mn0.54Ni0.14Co0.14O2 Cathodes by Controlling the Electrochemical Process

A lithium-rich cathode material Li1.14 Mn0.54 Ni0.14 Co0.14 O2 (LNMCO) is prepared by a co-precipitation method. The issue of voltage decay in long-term cycling is largely eliminated by control of the charge-discharge voltage range. The LNMCO material exhibits 9.8 % decay in discharge voltage over 200 cycles between 2.0-4.6 V, during which the working voltage decays significantly, from 3.57 V to 3.22 V. The decay was decelerated by a factor of six by using a voltage window of 2.0-4.4 V, from 3.53 V to 3.47 V. IR and Raman spectra reveal that the transformation of layered structure to spinel is significantly retarded under 2.0-4.4 V cycling conditions. Transmission electron microscopy (TEM) was also applied for examining phase change in an individual particle during cycling, showing that the spinel phase occurs both at 2.0-4.6 V and at 2.0-4.4 V, but is not dominant in the latter. Normalization of Li can remove the additional impact on the voltage decay which is brought by different amounts of Li intercalation. The mechanism of no voltage decay at 2.0-4.4 V cycling is raised and electrochemical impedance spectrum data also support the hypothesis.

Green facile scalable synthesis of titania/carbon nanocomposites: new use of old dental resins.

A green facile scalable method inspired by polymeric dental restorative composite is developed to synthesize TiO2/carbon nanocomposites for manipulation of the intercalation potential of TiO2 as lithium-ion battery anode. Poorly crystallized TiO2 nanoparticles with average sizes of 4-6 nm are homogeneously embedded in carbon matrix with the TiO2 mass content varied between 28 and 65%. Characteristic discharge/charge plateaus of TiO2 are significantly diminished and voltage continues to change along with proceeding discharge/charge process. The tap density, gravimetric and volumetric capacities, and cyclic and rate performance of the TiO2/C composites are effectively improved.