Addressing cation mixing in layered structured cathodes for lithium-ion batteries:A critical review

High-performance lithium-ion batteries(LIB)are important in powering emerging technologies.Cathodes are regarded as the bottleneck of increasing battery energy density,among which layered oxides are the most promising candidates for LIB.However,a limitation with layered oxides cathodes is the transition metal and Li site mixing,which significantly impacts battery capacity and cycling stability.Despite recent research on Li/Ni mixing,there is a lack of comprehensive understanding of the origin of cation mixing between the transition metal and Li;therefore,practical means to address it.Here,a critical review of cation mixing in layered cathodes has been provided,emphasising the understanding of cation mixing mechanisms and their impact on cathode material design.We list and compare advanced characterisation techniques to detect cation mixing in the material structure;examine methods to regulate the degree of cation mixing in layered oxides to boost battery capacity and cycling performance,and critically assess how these can be applied practically.An appraisal of future research directions,including superexchange interaction to stabilise structures and boost capacity retention has also been concluded.Findings will be of immediate benefit in the design of layered cathodes for high-performance rechargeable LIB and,therefore,of interest to researchers and manufacturers.

Cation mixing (Li_(0.5)Fe_(0.5))_2SO_4F cathode material for lithium-ion batteries

We study the crystal structure of a triplite-structured （Li0.5Fe0.5）SO4F with full Li＋/Fe2＋ mixing. This promising polyanion cathode material for lithium-ion batteries operates at 3.9 V versus Li＋/Li with a theoretical capacity of 151 mAh/g. Its unique cation mixing structure does not block the Li＋ diffusion and results in a small lattice volume change during the charge/discharge process. The calculations show that it has a three-dimensional network for Li-ion migration with an activation energy ranging from 0.53 eV to 0.68 eV, which is comparable with that in LiFePO4 with only one-dimensional channels. This work suggests that further exploring cathode materials with full cation mixing for Li-ion batteries will be valuable.

A-site phase segregation in mixed cation perovskite

Mixed cation strategy greatly benefits the enhancement of device performance and chemical stability.However,adverse impact also accompanies the mixed cation system simultaneously.It brings the compositional instability,wherein the homogeneous film is likely to segregate into multi-phases during the fabrication and ageing process,thus resulting in the efficiency reduction of perovskite solar cells(PSCs)devices.This review focuses on the cation induced phase segregation,and elucidates the segregation mechanisms from the perspectives of film formation and ageing process,respectively.Furthermore,the influence of cation segregation on device performance and operational stability are discussed.And based on these understandings,viable strategies are proposed for the design of phase-stable mixed composition halide perovskites and for suppressing segregation to benefit its development towards commercial applications.

Understanding the precursor chemistry for one-step deposition of mixed cation perovskite solar cells by methylamine route

Upscaling perovskite solar cell fabrication is one of the key challenges in the pathway for commercialization.The slow evaporation of frequently used solvents(DMF or DMSO) limits the fast perovskite layer crystallization,hindering their implementation in large scale deposition methods.Alternatively,methylamine-based precursors have demonstrated rapid crystallization,leading to uniform and specular films.Nonetheless,their application has been limited to MAPbI3 perovskites with limited efficiency and stability.In this work,we report the requirements for stabilizing α-phase of mixed cation perovskites with high amount of formamidinium by using a methylamine-based precursor.We found that even though,there are many methods for incorporating the methylamine(MA) in precursors or films;the MA content determines stabilization of the α-phase and therefore the viscous-solution route is the only method to incorporate high amounts of MA.At low amounts of MA,perovskite tend to crystallize in 1D dimensional FA_(3)(MA)PbI5 phases due to the incomplete solvation of the PbI6-clusters.In contrast,high MA ratio induces a full solvation of the clusters,leading to a rapid crystallization and a full stabilization of the active 3D α-phase.These results open a window in the development and understanding of new precursors for the fabrication of high efficient,stable and scalable perovskite devices.

A mixed-cation lead iodide MA_(1-x)EA_xPbI_3 absorber for perovskite solar cells

The mixed-cation lead halide perovskites have emerged as a new class of promising light harvesting materials for solar cells. The formamidinium（FA）, methylammonium（MA） and Cs cations are widely studied in the field of mixed-cation perovskites. Here, we have investigated ethylammonium（EA） as an alternative cation to fabricate a mixed-cation perovskite of MA_（1-x）EA_xPbI_3. We have characterized the materials using the X-ray diffraction（XRD）, scanning electron microscope（SEM）, and UV–vis spectrum. Our results have confirmed the successful incorporation of EA cations into MAPbI_3. Interestingly, the optimal amount of EA to achieve the best performance is quite low. This is different from the FA–MA mixed-cation perovskites although EA and FA have similar radii. In short, the EA–MA mixed-cation perovskite has some material and device properties highly distinguishable from the FA–MA one.

Coupling effect of the conductivities of Li ions and electrons by introducing LLTO@C fibers in the LiNi0.8Co0.15Al0.05O2 cathode

To probe the coupling effect of the electron and Li ion conductivities in Ni-rich layered materials(LiNi0.8Co0.15Al0.05O2,NCA),lithium lanthanum titanate(LLTO)nanofiber and carbon-coated LLTO fiber(LLTO@C)materials were introduced to polyvinylidene difluoride in a cathode.The enhancement of the conductivity was indicated by the suppressed impedance and polarization.At 1 and 5 C,the cathodes with coupling conductive paths had a more stable cycling performance.The coupling mechanism was analyzed based on the chemical state and structure evolution of NCA after cycling for 200 cycles at 5 C.In the pristine cathode,the propagation of lattice damaged regions,which consist of high-density edge-dislocation walls,destroyed the bulk integrity of NCA.In addition,the formation of a rock-salt phase on the surface of NCA caused a capacity loss.In contrast,in the LLTO@C modified cathode,although the formation of dislocation-driven atomic lattice broken regions and cation mixing occurred,they were limited to a scale of several atoms,which retarded the generation of the rock-salt phase and resulted in a pre-eminent capacity retention.Only NiO phase“pitting”occurred.A mechanism based on the synergistic transport of Li ions and electrons was proposed.

Advanced partial nucleation for single-phase FA0.92MA0.08PbI3-based high-efficiency perovskite solar cells

To date, extensive research has been carried out,with considerable success, on the development of highperformance perovskite solar cells(PSCs). Owing to its wide absorption range and remarkable thermal stability, the mixedcation perovskite FAxMA1-xPbI3(formamidinium/methylammonium lead iodide) promises high performance. However, the ratio of the mixed cations in the perovskite film has proved difficult to control with precursor solution. In addition, the FAxMA1-xPbI3 films contain a high percentage of MA+and suffer from serious phase separation and high trap states, resulting in inferior photovoltaic performance. In this study, to suppress phase separation, a post-processing method was developed to partially nucleate before annealing, by treating the as-prepared intermediate phase FAI-Pb I2-DMSO(DMSO: dimethylsulfoxide) with mixed FAI/MAI solution. It was found that in the final perovskite, FA0.92MA0.08 PbI3, defects were substantially reduced because the analogous molecular structure initiated ion exchange in the post-processed thin perovskite films, which advanced partial nucleation. As a result, the increased light harvesting and reduced trap states contributed to the enhancement of open-circuit voltage and short-circuit current. The PSCs produced by the post-processing method presented reliable reproducibility, with a maximum power conversion efficiency of 20.80% and a degradation of ~30% for 80 days in standard atmospheric conditions.

Highly compact and uniform CH3NH3Sn0.5Pb0.5I3 films for efficient panchromatic planar perovskite solar cells

An efficient panchromatic planar perovskite solar cell is developed based on highly uniform,lead-reduced CH3NH3Sn0.5Pb0.5I3 perovskite films with full film-coverage on the substrates.We demonstrate here that full-coverage of the CH3NH3Sn0.5Pb0.5I3 films can be developed by a facile chlorobenzene-assisted spin-coating method.A power conversion efficiency of 7 % is achieved using low-temperature processes,which is among the best-reported performance for panchromatic planar perovskite solar cells with a light-absorption over 1,000 nm.