Thermochemical Cyclization Constructs Bridged Dual-Coating of Ni-Rich Layered Oxide Cathodes for High-Energy Li-Ion Batteries.

Enhancing microstructural and electrochemical stabilities of Ni-rich layered oxides is critical for improving the safety and cycle-life of high-energy Li-ion batteries. Here we propose a thermochemical cyclization strategy where heating polyacrylonitrile with LiNi0.8Co0.1Mn0.1O2 can simultaneously construct a cyclized polyacrylonitrile outer layer and a rock-salt bridge-like inner layer, forming a compact dual-coating of LiNi0.8Co0.1Mn0.1O2. Systematic studies demonstrate that the mild cyclization reaction between polyacrylonitrile and LiNi0.8Co0.1Mn0.1O2 induces a desirable "layered to rock-salt" structural transformation to create a nano-intermedium that acts as the bridge for binding cyclized polyacrylonitrile to layered LiNi0.8Co0.1Mn0.1O2. Because of the improvement of the structural and electrochemical stability and electrical properties, this cathode design remarkably enhances the cycling performance and rate capability of LiNi0.8Co0.1Mn0.1O2, showing a high reversible capacity of 183 mAh g-1 and a high capacity retention of 83% after 300 cycles at 1 C rate. Notably, this facile and scalable surface engineering makes Ni-rich cathodes potentially viable for commercialization in high-energy Li-ion batteries.

A Plastic-Crystal Electrolyte Layer Promotes Interfacial Stability of Ni-Rich Oxide Cathode in Li6PS5Cl-Based All-Solid-State Rechargeable Li Batteries.

Unfavorable parasitic reactions between the Ni-rich layered oxide cathode and the sulfide solid electrolyte have plagued the realization of all-solid-state rechargeable Li batteries. The accumulation of inactive by-products (P2Sx, S, POxn-and SOxn-) at the cathode-sulfide interface impedes fast Li-ion transfer, which accounts for sluggish reaction kinetics and significant loss of cathode capacity. Herein, we proposed an easily scalable approach to stabilize the cathode electrochemistry via coating the cathode particles by a uniform, Li+-conductive plastic-crystal electrolyte nanolayer on their surface. The electrolyte, which simply consists of succinonitrile and Li bis(trifluoromethanesulphonyl)imide, serves as an interfacial buffer to effectively suppress the adverse phase transition in highly delithiated cathode materials, and the loss of lattice oxygen and generation of inactive oxygenated by-products at the cathode-sulfide interface. Consequently, an all-solid-state rechargeable Li battery with the modified cathode delivers high specific capacities of 168 mAh g-1 at 0.1 C and a high capacity retention >80% after 100 cycles. Our work sheds new light on rational design of electrode-electrolyte interface for the next-generation high-energy batteries.

Surface Gradient Ni-Rich Cathode for Li-Ion Batteries.

Nickel-rich layered oxide cathode material LiNixCoyMnzO2 (NCM) has emerged as a promising candidate for next-generation lithium-ion batteries (LIBs). These cathode materials possess high theoretical specific capacity, fast electron/ion transfer rate, and high output voltage. However, their potential is impeded by interface instability, irreversible phase transition, and the resultant significant capacity loss, limiting their practical application in LIBs. In this work, a simple and scalable approach is proposed to prepare gradient cathode material (M-NCM) with excellent structural stability and rate performance. Taking advantage of the strong coordination of Ni2+ with ammonia and the reduction reaction of KMnO4, the elemental compositions of the Ni-rich cathode are reasonably adjusted. The resulted gradient compositional design plays a crucial role in stabilizing the crystal structure, which effectively mitigates Li/Ni mixing and suppresses unwanted surficial parasitic reactions. As a result, the M-NCM cathode maintains 98.6% capacity after 200 cycles, and a rapid charging ability of 107.5 mAh g-1 at 15 C. Furthermore, a 1.2 Ah pouch cell configurated with graphite anode demonstrates a lifespan of over 500 cycles with only 8% capacity loss. This work provides a simple and scalable approach for the in situ construction of gradient cathode materials via cooperative coordination and deposition reactions.

Three-Dimensional Octahedral Nanocrystals of Cu2O/CuF2 Grown on Porous Cu Foam Act as a Lithophilic Skeleton for Dendrite-Free Lithium Metal Anode.

Metallic-lithium (Li) anodes are highly sought-after for next-generation energy storage systems due to their high theoretical capacity and low electrochemical potential. However, the commercialization of Li anodes faces challenges, including uncontrolled dendrite growth and volume changes during cycling. To address these issues, we developed a novel three-dimensional (3D) copper current collector. Here, we propose a two-step method to fabricate Cu2O/CuF2 octahedral nanocrystals (ONCs) onto 3D Cu current collectors. The resulting Cu foam with distributed ONCs provides active electrochemical sites, promoting uniform Li nucleation and dendrite-free Li deposition. The stable Cu2O/CuF2 ONCs@CF metallic current collector serves as a reliable host for dendrite-free lithium metal anodes. Additionally, the highly porous copper foam with a preconstructed conductive framework of Cu2O/CuF2 ONCs@CF effectively reduces local current density, suppressing volume changes during Li stripping and plating. The symmetric cell using Cu2O/CuF2 ONCs@CF metallic current collector exhibits excellent stability, maintaining over 1600 h at 1 mA cm-2 and a highly stable Coulombic efficiency of 98% over 100 cycles at the same current density, outperforming Li@CuF metallic current collectors. Furthermore, in a full-cell configuration paired with nickel-rich layered oxide cathode materials (Li@Cu2O/CuF2 ONCs@CF//NMC-811), the proposed setup demonstrates exceptional rate performance and an extended cycle life. In conclusion, our work presents a promising strategy to address Li anode challenges and highlights the exceptional performance of the Cu2O/CuF2 ONCs@CF metallic current collector, offering potential for high-capacity and long-lasting lithium-based energy storage systems.

Investigation of Fluorine and Nitrogen as Anionic Dopants in Nickel-Rich Cathode Materials for Lithium-Ion Batteries.

Advanced lithium-ion batteries are of great interest for consumer electronics and electric vehicle applications; however, they still suffer from drawbacks stemming from cathode active material limitations (e.g., insufficient capacities and capacity fading). One approach for alleviating such limitations and stabilizing the active material structure may be anion doping. In this work, fluorine and nitrogen are investigated as potential dopants in Li1.02(Ni0.8Co0.1Mn0.1)0.98O2 (NCM) as a prototypical nickel-rich cathode active material. Nitrogen doping is achieved by ammonia treatment of NCM in the presence of oxygen, which serves as an unconventional and new approach. The crystal structure was investigated by means of Rietveld and pair distribution function analysis of X-ray diffraction data, which provide very precise information regarding both the average and local structure, respectively. Meanwhile, time-of-flight secondary-ion mass spectroscopy was used to assess the efficacy of dopant incorporation within the NCM structure. Moreover, scanning electron microscopy and scanning transmission electron microscopy were conducted to thoroughly investigate the dopant influences on the NCM morphology. Finally, the electrochemical performance was tested via galvanostatic cycling of half- and full-cells between 0.1 and 2 C. Ultimately, a dopant-dependent modulation of the NCM structure was found to enable the enhancement of the electrochemical performance, thereby opening a route to cathode active material optimization.

Improved Electrochemical Performance of Surface Coated LiNi0.80Co0.15Al0.05O2 With Polypyrrole.

Nickel-rich ternary layered oxide (LiNi0.80Co0.15Al0.05O2, LNCA) cathodes are favored in many fields such as electric vehicles due to its high specific capacity, low cost, and stable structure. However, LNCA cathode material still has the disadvantages of low initial coulombic efficiency, rate capability and poor cycle performance, which greatly restricts its commercial application. To overcome this barrier, a polypyrrole (PPy) layer with high electrical conductivity is designed to coat on the surface of LNCA cathode material. PPy coating layer on the surface of LNCA successfully is realized by means of liquid-phase chemical oxidation polymerization method, and which has been verified by the scanning electron microscopy (SEM), transmission electron microscope (TEM) and fourier transform infrared spectroscopy (FTIR). PPy-coated LNCA (PL-2) exhibits satisfactory electrochemical performances including high reversible capacity and excellent rate capability. Furthermore, the capability is superior to pristine LNCA. So, it provides a new structure of conductive polymer modified cathode materials with good property through a mild modification method.

Enhancing the Structural Stability of Ni-Rich Layered Oxide Cathodes with a Preformed Zr-Concentrated Defective Nanolayer.

Nickel-rich layered oxides (NLOs) exhibit great potential to meet the ever-growing demand for further increases in the energy density of Li-ion batteries because of their high specific capacities. However, NLOs usually suffer from severe structural degradation and undesired side reactions when cycled above 4.3 V. These effects are strongly correlated with the surface structure and chemistry of the active NLO materials. Herein, we demonstrate a preformed cation-mixed ( Fm3̅ m) surface nanolayer (∼5 nm) that shares a consistent oxygen framework with the layered lattice through Zr modification, in which Ni cations reside in Li slabs and play the role of a "pillar". This preformed nanolayer alleviates the detrimental phase transformations upon electrochemical cycling, effectively enhancing the structural stability. As a result, the Zr-modified Li(Ni0.8Co0.1Mn0.1)0.985Zr0.015O2 material exhibits a high reversible discharge capacity of ∼210 mA h/g at 0.1 C (1 C = 200 mA/g) and outstanding cycling stability with a capacity retention of 93.2% after 100 cycles between 2.8 and 4.5 V. This strategy may be further extended to design and prepare other high-performance layered oxide cathode materials.

High-Performance Heterostructured Cathodes for Lithium-Ion Batteries with a Ni-Rich Layered Oxide Core and a Li-Rich Layered Oxide Shell.

The Ni-rich layered oxides with a Ni content of >0.5 are drawing much attention recently to increase the energy density of lithium-ion batteries. However, the Ni-rich layered oxides suffer from aggressive reaction of the cathode surface with the organic electrolyte at the higher operating voltages, resulting in consequent impedance rise and capacity fade. To overcome this difficulty, we present here a heterostructure composed of a Ni-rich LiNi0.7Co0.15Mn0.15O2 core and a Li-rich Li1.2-x Ni0.2Mn0.6O2 shell, incorporating the advantageous features of the structural stability of the core and chemical stability of the shell. With a unique chemical treatment for the activation of the Li2MnO3 phase of the shell, a high capacity is realized with the Li-rich shell material. Aberration-corrected scanning transmission electron microscopy (STEM) provides direct evidence for the formation of surface Li-rich shell layer. As a result, the heterostructure exhibits a high capacity retention of 98% and a discharge-voltage retention of 97% during 100 cycles with a discharge capacity of 190 mA h g-1 (at 2.0-4.5 V under C/3 rate, 1C = 200 mA g-1).