Using ab initio calculations combined with experiments, we clarified how the kinetics of Li-ion diffusion can be tuned in LiNixMnyCozO2 (NMC, x + y + z = 1) materials. It is found that Li-ions tend to choose oxygen dumbbell hopping (ODH) at the early stage of charging (delithiation), and tetrahedral site hopping (TSH) begins to dominate when more than 1/3 Li-ions are extracted. In both ODH and TSH, the Li-ions surrounded by nickel (especially with low valence state) are more likely to diffuse with low activation energy and form an advantageous path. The Li slab space, which also contributes to the effective diffusion barriers, is found to be closely associated with the delithiation process (Ni oxidation) and the contents of Ni, Co, and Mn.

Layered transition-metal oxides (Li[NiMnCo]O, NMC, or NMCxyz) due to their poor stability when cycled at a high operating voltage (>4.5 V) have limited their practical applications in industry. Earlier researches have identified Mn(II)-dissolution and some parasitic reactions between NMC surface and electrolyte, especially when NMC is charged to a high potential, as primarily factors responsible for the fading. In our previous work, we have achieved a capacity of NMC active material close to theoretical value and optimized its cycling performance by a depolarized carbon nanotubes (CNTs) network and an unique "pre-lithiation process" that generates an in situ organic coating (∼40 nm) to prevent Mn(II) dissolution and minimize the parasitic reactions. Unfortunately, this organic coating is not durable enough during a long-term cycling when the cathode operates at a high potential (>4.5 V). This work attempts to improve the surface protection of the NMC532 particles by applying an active inorganic coating consisting of nanosized- and crystal-orientated LiFePO (LFP) (about 50 nm, exposed (010) face) to generate a core-shell nanostructure of Li(NiMnCo)O@LiFePO. Transmission electron microscopy (TEM) and etching X-ray photoelectron spectroscopy have confirmed an intimate contact coating (about 50 nm) between the original structure of NMC and LFP single-particle with atomic interdiffusion at the core-shell interface, and an array of interconnected aligned Li tunnels are observed at the interface by cross-sectional high-resolution TEM, which were formed by ball-milling and then strictly controlling the temperature below 100 °C. Batteries based on this modified NMC cathode material show a high reversible capacity when cycled between 3.0 and 4.6 V during a long-term cycling.

Transition metal oxide materials Li(NixMnyCoz)O2 (NMC) based on layered structures are expected to replace LiFePO4 in automotive Li-ion batteries because of their higher specific capacity and operating potential. However, the actual usable capacity is much lower than the promised theoretical value [Uchaker, E.; Cao, G. Nano Today 2014, 9, 499-524; Tarascon, J.-M.; Armand, M. Nature 2001, 414, 359-367], in addition to the often poor cycling performance and the first-cycle Coulombic efficiency, for which Mn(II)-dissolution, its immobilization in solid electrolyte interface (SEI), oxidation of electrolytes by Ni, and other parasitic process thereat have been held responsible [Zhan, C., et al. Nat. Commun. 2013, 4, 2437; Wang, L., et al. J. Solid State Electrochem. 2009, 13, 1157-1164; Lin, F., et al. Nat. Commun. 2014, 5, 4529]. Previously, we reported a composite Li(Ni0.5Mn0.3Co0.2)O2 (NMC532) depolarized by the embedded carbon nanotube (CNT) and achieved capacity close to the theoretical limit [Wu, Z., et al. Nano. Lett. 2014, 14, 4700-4706]; unfortunately, this high capacity failed to be maintained in long-term cycling due to the degrading contacts between the active ingredient and CNT network. On the basis of that NMC532/CNT composite, the present work proposes a unique "prelithiation process", which brought the cathode to low potentials before regular cycling and led to an interphase that is normally formed only on anode surfaces. The complete coverage of cathode surface by this ∼40 nm thick interphase effectively prevented Mn(II) dissolution and minimized the side reactions of Ni, Co, and Mn at the NMC interface during the subsequent cycling process. More importantly, such a "prelithiation" process activated a structure containing two Li layers near the surface of NMC532 particles, as verified by XRD and first principle calculation. Hence, a new cathode material of both high capacity with depolarized structure and excellent cycling performance was generated. This new structure can be incorporated in essentially all the NMC-based layered cathode materials, providing us with an effective tool to tailor-design future new cathode materials for lithium batteries.

Improving battery capacity and power is a daunting challenge, and in Li-ion batteries positive electrodes often set the limitation on both properties. Layered transition-metal oxides have served as the mainstream cathode materials for high-energy batteries due to their large theoretical capacity (∼ 280 mAh/g). Here we report a significant enhancement of cathode capacity utilization through a novel concept of material design. By embedding Li(Ni0.5Co0.2Mn0.3)O2 in the single wall carbon nanotube (CNT) network, we created a composite in which all components are electrochemically active. Long-term charge/discharge stability was obtained between 3.0 and 4.8 V, and both Li(Ni0.5Co0.2Mn0.3)O2 and CNT contribute to the overall reversible capacity by 250 and 50 mAh/g, respectively. The observed improvement causes significant depolarization within the electrodes through the CNT network system. Additionally, the depolarization provides the ideal template to understand the solid reaction mechanism of Li(Ni0.5Co0.2Mn0.3)O2 by demonstrating well-defined two-stage delithiation kinetics consistent with first-principle calculations, which would be otherwise impossible. These results deliver new insights on both practical designs and fundamental understandings of battery cathodes.

Transition metal oxide materials Li(NixMnyCoz)O2 (NMCxyz) based on layered structure are potential cathode candidates for automotive Li-ion batteries because of their high specific capacities and operating potentials. However, the actual usable capacity, cycling stability, and first-cycle Coulombic efficiency remain far from practical. Previously, we reported a combined strategy consisting of depolarization with embedded carbon nanotube (CNT) and activation through pre-lithiation of the NMC host, which significantly improved the reversible capacity and cycling stability of NMC532-based material. In the present work we attempt to understand how pre-lithiation leads to these improvements on an atomic level with experimental investigation and ab initio calculations. By lithiating a series of NMC materials with varying chemical compositions prepared via a conventional approach, we identified the Ni in the NMC lattice as the component responsible for accommodating a double-layered Li structure. Specifically, much better improvements in the cycling stability and capacity can be achieved with the NMC lattices populated with Ni(3+) than those populated with only Ni(2+). Using the XRD we also found that the emergence of a double-layer Li structure is not only reversible during the pre-lithiation and the following delithiation, but also stable against elevated temperatures up to 320 °C. These new findings regarding the mechanism of pre-lithiation as well as how it affects the reversibility and stability of NMC-based cathode materials prepared by the conventional slurry approach will promote the possibility of their application in the future battery industry.