Thermodynamically Revealing the Essence of Order and Disorder Structures in Layered Cathode Materials

Layered transition metal(TM) oxides are one of the most widely used cathode materials in lithium-ion batteries. The atomic configuration in TM layer of these materials is often known to be random when multiple TM elements co-exist in the layer(e.g. Ni, Co and Mn). By contrast, the configuration tends to be ordered if the elements are Li and Mn. Here, by using special quasi-random structures(SQS) algorithm, the essential reasons of the ordering in a promising Li-rich Mn-based cathode material Li2MnO3 are investigated. The difference of internal energy and entropy between ordered and disordered materials is calculated. As a result, based on the Gibbs free energy, it is found that Li2MnO3 should have an ordered structure in TM layer. In comparison, structures with Ni-Mn ratio of 2:1 are predicted to have a disordered TM layer, because the entropy terms have larger impact on the structural ordering than internal energy terms.

Mitigated lattice distortion and oxygen loss of Li-rich layered cathode materials through anion/cation regulation by Ti^(4+)-substitution

Lithium-rich layered cathode material(LLM)can meet the requirement of power lithium-ion energy storage devices due to the great energy density.However,the de/intercalation of Li+will cause the irreversible loss of lattice oxygen and trigger transition metal(TM)ions migrate to Li+vacancies,resulting in capacity decay.Here we brought Ti4+in substitution of TM ions in Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_(2),which could stabilize structure and expand the layer spacing of LLM.Moreover,optimized Ti-substitution can regulate the anions and cations of LLM,enhance the interaction with lattice oxygen,increase Ni^(3+) and Co^(3+),and improve Mn^(4+) coordination,improving reversibility of oxygen redox activation,maintaining the stable framework and facilitating the Li^(+) diffusion.Furthermore,we found 5%Ti-substitution sample delivered a high discharge capacity of 244.2 mAh/g at 50 mA/g,an improved cycling stability to 87.3%after 100 cycles and enhanced rate performance.Thereby Ti-substitution gives a new pathway to achieve high reversible cycle retention for LLMs.

Degradation analysis and doping modification optimization for high-voltage P-type layered cathode in sodium-ion batteries

Advancing high-voltage stability of layered sodium-ion oxides represents a pivotal avenue for their progress in energy storage applications.Despite this,a comprehensive understanding of the mechanisms underpinning their structural deterioration at elevated voltages remains insufficiently explored.In this study,we unveil a layer delamination phenomenon of Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2)(NNM)within the 2.0-4.3 V voltage,attributed to considerable volumetric fluctuations along the c-axis and lattice oxygen reactions induced by the simultaneous Ni^(3+)/Ni^(4+)and anion redox reactions.By introducing Mg doping to diminished Ni-O antibonding,the anion oxidation-reduction reactions are effectively mitigated,and the structural integrity of the P2 phase remains firmly intact,safeguarding active sites and precluding the formation of novel interfaces.The Na_(0.67)Mg_(0.05)Ni_(0.25)Mn_(0.7)O_(2)(NMNM-5)exhibits a specific capacity of100.7 mA h g^(-1),signifying an 83%improvement compared to the NNM material within the voltage of2.0-4.3 V.This investigation underscores the intricate interplay between high-voltage stability and structural degradation mechanisms in layered sodium-ion oxides.

Unlocking high-rate O3 layered oxide cathode for Na-ion batteries via ion migration path modulation

O3-NaNi1/3Fe1/3Mn1/3O2is a promising layered cathode material with high specific capacity,low cost,and simple synthesis.However,sluggish kinetic hindrance is attributed to the size discrepancy between the large Na-ion and narrow tetrahedral interstitial positions,leading to inferior rate capacity and low reversible capacity.Herein,F with light-weight and strong electronegativity is introduced to substitute O atoms in the bulk structure,which intensifies the bond strength of transition metal and oxygen and enlarges the Na+diffusion channel.In addition,density-functional theory(DFT) calculations demonstrate that the electrostatic interaction is weakened between Na+in the tetrahedral site and the transitionmetal cation directly below it,dramatically reducing the migration barriers of Na+diffusion.Consequently,the as-obtained NaNi1/3Fe1/3Mn1/3O1.95F0.05sample displays outstanding rate performance of 86.7 mA h g^(-1)at 10 C and excellent capacity retention of 84.1% after 100 cycles at 2 C.Moreover,a full cell configuration using a hard carbon anode reaches the energy density of 307.7 Wh kg^(-1).This strategy paves the way for novel means of modulating the Na-ion migration path for high-rate O3-type layered cathode materials.

Synthesis of layered cathode materials Li[Co_x Ni_y Mn_(1-x-y)]O_2 from layered double hydroxide precursors

Cathode materials Li[CoxNiyMn1-x-y]O2 for lithium secondary batteries have been prepared by a new route using layered double hydroxides （LDHs） as a precursor. The resulting layered phase with the α- NaFe02 structure crystallizes in the rhombohedral system, with space group R-3m having an interlayer spacing close to 0.47 nm. X-ray photoelectron spectroscopy （XPS） was used to measure the oxidation states of Co, Ni and Mn. The effects of varying the Co[Ni[Mn ratio on both the structure and electrochemical properties of Li[CoxNiyMn1-x-y]O2 have been investigated by X-ray diffraction and electrochemical tests. The products demonstrated a rather stable cycling behavior, with a reversible capacity of 118 mAh/g for the layered material with Co/Ni/Mn = 1/1/1.

Direct Synthesis of Al_2O_3-modified Li(Ni_(0.5)Co_(0.2)Mn_(0.3))O_2 Cathode Materials for Lithium Ion Batteries

To improve the cyclic stability at high temperature and thermal stability, the spherical Al2O3-modified Li（Ni0.5Co0.2Mn0.3）O2 was synthesized by a modified co-precipitation method, and the physical and electrochemical properties were studied. The TEM images showed that Li（Ni0.5Co0.2Mn0.3）O2 was modified successfully with nano-Al2O3. The discharge capacity retention of Al2O3-modified Li（Ni0.5Co0.2Mn0.3）O2 maintained about 99% after 200 cycles at high temperature（55 ℃）, while that of the bare one was only 86%. Also, unlike bare Li（Ni0.5Co0.2Mn0.3）O2, the Al2O3-modified material cathode exhibited good thermal stability.

Application of high energy X-ray diffraction and Rietveld refinement in layered lithium transition metal oxide cathode materials

Layered lithium transition metal oxide(LTMO)cathode materials have attracted much attention for lithium-ion batteries and are shining in the current market.Establishing a clear structure-performance relationship is necessary for the performance improvement of LTMO cathode materials.The combination of synchrotron X-ray diffraction(XRD)with high intensity and XRD Rietveld refinement is powerful for revealing the structural characteristics of LTMO cathode materials.This review summarizes the application of high energy XRD and Rietveld refinement in LTMO cathode materials,including the brief introduction of synchrotron XRD and Rietveld refinement and their applications in understanding the structural evolution related to the synthetic,thermal runaway,cycling,and high-rate charge/discharge process of LTMO cathode materials.Synchrotron XRD can provide insights into the intermediates and reaction paths in the synthesis process,the origin of thermal runaway,the mechanism of structural decay during cycles,and the structural evolution during high-rate charging/discharging.Future works should focus on the development of higher intensity X-rays to gain more in-depth insights into the intrinsic relationship between their structural characteristics and properties.

Synthesis of Cu-Doped Layered Transition Metal Oxide Cathode Materials Directly from Metal-Organic Frameworks for Sodium-Ion Batteries

Mn-based layered transition metal oxides are promising cathode materials for sodium-ion batteries(SIBs)because of their high theoretical capacities,abundant raw materials,and environment-friendly advantages.However,they often show insufficient performance due to intrinsic issues including poor structural stability and dissolution of Mn^(3+).Atomic doping is an effective way to address these structural degradation issues.Herein,we reported a new synthesis strategy of a Cu-doped layered cathode by directly calcinating a pure metal-organic framework.Benefiting from the unique structure of MOF with atomic-level Cu doping,a homogeneous Cu-doped layered compound P2-Na_(0.674)Cu_(0.01)Mn_(0.99)O_(2) was obtained.The Cu substitution promotes the crystal structural stability and suppresses the dissolution of Mn,thus preventing the structure degradation of the layered cathode materials.A remarkably enhanced cyclability is realized for the Cu-doped cathode compared with that without Cu doping,with 83.8%capacity retention after 300 cycles at 100 mA·g^(-1).Our findings provide new insights into the design of atomic-level doping layered cathode materials constructed by MOFs for high-performance SIBs.

On the role of surface carbonate species in determining the cycling performance of all-solid-state batteries

This short perspective summarizes recent findings on the role of residual lithium present on the surface of layered Ni-rich oxide cathode materials in liquid-and solid-electrolyte based batteries,with emphasis placed on the carbonate species.Challenges and future research opportunities in the development of carbonate-containing protective nanocoatings for inorganic solid-state battery applications are also discussed.