Minghao Zhang

Performance and design considerations for lithium excess layered oxide positive electrode materials for lithium ion batteries

The Li-excess oxide compound is one of the most promising positive electrode materials for next generation batteries exhibiting high capacities of >300 mA h g−1 due to the unconventional participation of the oxygen anion redox in the charge compensation mechanism. However, its synthesis has been proven to be highly sensitive to varying conditions and parameters where nanoscale phase separation may occur that affects the overall battery performance and life. In addition, several thermodynamic and kinetic drawbacks including large first cycle irreversible capacity, poor rate capability, voltage fading, and surface structural transformation need to be addressed in order to reach commercialization. This review will focus on the recent progress and performance trends over the years and provide several guidelines and design considerations based on the library of work done on this particular class of materials.

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.

Understanding the Role of NH4F and Al2O3 Surface Co-modification on Lithium-Excess Layered Oxide Li1.2Ni0.2Mn0.6O2

In this work we prepared Li1.2Ni0.2Mn0.6O2 (LNMO) using a hydroxide co-precipitation method and investigated the effect of co-modification with NH4F and Al2O3. After surface co-modification, the first cycle Coulombic efficiency of Li1.2Ni0.2Mn0.6O2 improved from 82.7% to 87.5%, and the reversible discharge capacity improved from 253 to 287 mAh g(-1) at C/20. Moreover, the rate capability also increased significantly. A combination of neutron diffraction (ND), high-resolution transmission electron microscopy (HRTEM), aberration-corrected scanning transmission electron microscopy (a-STEM)/electron energy loss spectroscopy (EELS), and X-ray photoelectron spectroscopy (XPS) revealed the changes of surface structure and chemistry after NH4F and Al2O3 surface co-modification while the bulk properties showed relatively no changes. These complex changes on the materials surface include the formation of an amorphous Al2O3 coating, the transformation of layered material to a spinel-like phase on the surface, the formation of nanoislands of active material, and the partial chemical reduction of surface Mn(4+). Such enhanced discharge capacity of the modified material can be primarily assigned to three aspects: decreased irreversible oxygen loss, the activation of cathode material facilitated with preactivated Mn(3+) on the surface, and stabilization of the Ni-redox pair. These insights will provide guidance for the surface modification in high-voltage-cathode battery materials of the future.

In situ TEM observation of the electrochemical lithiation of N-doped anatase TiO2 nanotubes as anodes for lithium-ion batteries

Due to their high specific capacity and negligible volume expansion during cycling, anatase titanium dioxide (a-TiO2) nanotubes have been considered as a prime candidate for anodes in lithium-ion batteries. However, their rate capability for electrochemical cycling is limited by the low electronic conductivity of a-TiO2 nanotubes. Here, we show that a desirable amount of nitrogen doping can significantly enhance the electronic conductivity in a-TiO2 nanotubes, resulting in improvements in both the capacity stability and the rate capability at fast charge–discharge rates. Electron energy loss spectroscopy revealed a high doping concentration of nitrogen (∼5%) by substituting for oxygen ions in a-TiO2 nanotubes. The lithiation mechanism of N-doped a-TiO2 nanotubes was further investigated using in situ transmission electron microscopy, where a three-step lithiation mechanism was revealed. Lithium ions initially intercalate into the a-TiO2 lattice structure. Further insertion of lithium ions triggers a phase transformation from a-TiO2 to orthorhombic Li0.5TiO2 and finally to polycrystalline tetragonal LiTiO2. Our results reveal that nitrogen doping significantly facilitates lithiation in TiO2 through enhanced electronic conductivity, while the structural and chemical evolutions during the lithiation process remain similar to those of undoped TiO2.

Mitigating thermal runaway of lithium-ion battery through electrolyte displacement

Alkanes are investigated as thermal-runaway retardants (TRR) for lithium-ion battery (LIB). TRR is a chemical that can rapidly terminate exothermic reactions in LIB. Under normal working conditions, TRR is sealed in separate packages in the LIB cell, and upon mechanical abuse, it is released to suppress heat generation. The alkanes under investigation include octane, pentadecane, and icosane, among which pentadecane has the highest thermal-runaway mitigation (TRM) efficiency. In nail penetration test on coin cells, ∼4 wt. % pentadecane reduced the maximum temperature by ∼60%; in impact test on pouch cells, ∼5 wt. % pentadecane reduced the maximum temperature by ∼90%. The high TRM efficiency of pentadecane is attributed to its high wettability to separator and its immiscibility with electrolyte. By forming a physical barrier between the cathode and anode, pentadecane interrupts lithium ion (Li+) transport and increases the charge transfer resistance by nearly two orders of magnitude. The diffusion rate of ...

Effects of electrode pattern on thermal runaway of lithium-ion battery

In the current study, through a set of nail penetration and impact tests on modified lithium-ion battery coin half-cells, we examine the effects of electrode pattern on the heat generation behaviors associated with internal shorting. The results show that the temperature profile is quite insensitive to the openings in cathode layer, which may be attributed to the high specific energy as well as the secondary conductive paths. This finding will considerably influence the study in the area of thermal runaway mitigation of energy storage systems.

Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging

Lithium-rich layered oxides (LRLO) are among the leading candidates for the next-generation cathode material for energy storage, delivering 50% excess capacity over commercially used compounds. Despite excellent prospects, voltage fade has prevented effective use of the excess capacity, and a major challenge has been a lack of understanding of the mechanisms underpinning the voltage fade. Here, using operando three-dimensional Bragg coherent diffractive imaging, we directly observe the nucleation of a mobile dislocation network in LRLO nanoparticles. The dislocations form more readily in LRLO as compared with a classical layered oxide, suggesting a link between the defects and voltage fade. We show microscopically how the formation of partial dislocations contributes to the voltage fade. The insights allow us to design and demonstrate an effective method to recover the original high-voltage functionality. Our findings reveal that the voltage fade in LRLO is reversible and call for new paradigms for improved design of oxygen-redox active materials.Voltage fade is a major obstacle for the efficient use of lithium-rich layered oxide materials in batteries. Here, the authors reveal the link between voltage fade and nucleation of a mobile dislocation network in the oxide nanoparticles, offering design ideas to restore the voltage.

Identifying the chemical and structural irreversibility in LiNi0.8Co0.15Al0.05O2 – a model compound for classical layered intercalation

In this work, we extracted 95% of the electrochemically available Li from LiNi0.8Co0.15Al0.05O2 (NCA) by galvanostatically charging the NCA/MCMB full cell to 4.7 V. Joint powder X-ray and neutron diffraction (XRD & ND) studies were undertaken for NCA at highly charged states at the first cycle, and discharged states at different cycles. The results indicate that the bulk structure of NCA maintains the O3 structure up to the extraction of 0.90 Li per formula unit. In addition, we found that the transition metal layer becomes more disordered along the c-axis than along the a- and b-axes upon charging. This anisotropic disorder starts to develop no later than 4.3 V on charge and continues to grow until the end of charge. As Li is re-inserted during discharge, the structure that resembles the pristine NCA is recovered. The irreversible loss of Li and the migration of Ni to the Li layer have been quantified by the joint XRD and ND refinement and the results were further verified by solid state 7Li NMR and magnetic measurements. Our work clearly demonstrates that the NCA bulk retains a robust, single phase O3 structure throughout the wide delithiation range (up to 0.9 Li per formula unit of NCA) and is suitable for higher energy density usage with proper modifications.

Internal short circuit mitigation of high-voltage lithium-ion batteries with functional current collectors

The safety of lithium-ion battery (LIB) becomes increasingly critical as the specific energy and cell capacity rapidly increase. Based on the modified current collector technique recently developed for nickel–cobalt–manganese active materials, here we investigate high-energy LIBs based on functional current collectors (FCC). Two high-voltage active materials were tested in our experiments: lithium-rich layered oxide (LRLO) and lithium nickel manganese oxide (LNMO). At the same time as a fully charged LIB cell is damaged, FCC isolates the internal short circuit (ISC) from the undamaged area; hence, the ISC-induced heat generation is drastically reduced to a negligible level. The electrochemical performance of FCC-based cells is nearly identical to that of reference cells.