Probing Particle-Carbon/Binder Degradation Behavior in Fatigued Layered Cathode Materials through Machine Learning Aided Diffraction Tomography.

Understanding how reaction heterogeneity impacts cathode materials during Li-ion battery (LIB) electrochemical cycling is pivotal for unraveling their electrochemical performance. Yet, experimentally verifying these reactions has proven to be a challenge. To address this, we employed scanning µ-XRD computed tomography to scrutinize Ni-rich layered LiNi0.6Co0.2Mn0.2O2 (NCM622) and Li-rich layered Li[Li0.2Ni0.2Mn0.6]O2 (LLNMO). By harnessing machine learning (ML) techniques, we scrutinized an extensive dataset of µ-XRD patterns, about 100,000 patterns per slice, to unveil the spatial distribution of crystalline structure and microstrain. Our experimental findings unequivocally reveal the distinct behavior of these materials. NCM622 exhibits structural degradation and lattice strain intricately linked to the size of secondary particles. Smaller particles and the surface of larger particles in contact with the carbon/binder matrix experience intensified structural fatigue after long-term cycling. Conversely, both the surface and bulk of LLNMO particles endure severe strain-induced structural degradation during high-voltage cycling, resulting in significant voltage decay and capacity fade. This work holds the potential to fine-tune the microstructure of advanced layered materials and manipulate composite electrode construction in order to enhance the performance of LIBs and beyond.

Long-Range Cationic Disordering Induces two Distinct Degradation Pathways in Co-Free Ni-Rich Layered Cathodes.

Ni-rich layered oxides are one of the most attractive cathode materials in high-energy-density lithium-ion batteries, their degradation mechanisms are still not completely elucidated. Herein, we report a strong dependence of degradation pathways on the long-range cationic disordering of Co-free Ni-rich Li1-m (Ni0.94 Al0.06 )1+m O2 (NA). Interestingly, a disordered layered phase with lattice mismatch can be easily formed in the near-surface region of NA particles with very low cation disorder (NA-LCD, m≤0.06) over electrochemical cycling, while the layered structure is basically maintained in the core of particles forming a "core-shell" structure. Such surface reconstruction triggers a rapid capacity decay during the first 100 cycles between 2.7 and 4.3 V at 1 C or 3 C. On the contrary, the local lattice distortions are gradually accumulated throughout the whole NA particles with higher degrees of cation disorder (NA-HCD, 0.06≤m≤0.15) that lead to a slow capacity decay upon cycling.

Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li2MnO3·0.5LiNi0.3Co0.3Mn0.4O2 Cathode by in Situ Electrochemical Quartz Crystal Microbalance.

The first-cycle behavior of layered Li-rich oxides, including Li2MnO3 activation and cathode electrolyte interphase (CEI) formation, significantly influences their electrochemical performance. However, the Li2MnO3 activation pathway and the CEI formation process are still controversial. Here, the first-cycle properties of xLi2MnO3·(1- x) LiNi0.3Co0.3Mn0.4O2 ( x = 0, 0.5, 1) cathode materials were studied with an in situ electrochemical quartz crystal microbalance (EQCM). The results demonstrate that a synergistic effect between the layered Li2MnO3 and LiNi0.3Co0.3Mn0.4O2 structures can significantly affect the activation pathway of Li1.2Ni0.12Co0.12Mn0.56O2, leading to an extra-high capacity. It is demonstrated that Li2MnO3 activation in Li-rich materials is dominated by electrochemical decomposition (oxygen redox), which is different from the activation process of pure Li2MnO3 governed by chemical decomposition (Li2O evolution). CEI evolution is closely related to Li+ extraction/insertion. The valence state variation of the metal ions (Ni, Co, Mn) in Li-rich materials can promote CEI formation. This study is of significance for understanding and designing Li-rich cathode-based batteries.

Novel MnO-Graphite Dual-Ion Battery and New Insights into Its Reaction Mechanism during Initial Cycle by Operando Techniques.

Dual-ion battery complements lithium-ion batteries in terms of the use of inexpensive materials and ease to construct cells. To improve the safety and energy density of dual-ion battery, in this paper, a novel MnO-graphite dual-ion battery is reported for the first time. Microporous MnO materials are used as anode, which exhibits a low conversion potential and a low voltage hysteresis. The MnO-graphite dual-ion battery can deliver a capacity of 104 mAh g-1 at 0.5C and exhibits good rate performances and cycling stability (capacity retention >93% after 300 cycles). A mechanism is proposed to explain the irreversibility in capacity during the initial cycle by using operando X-ray diffraction in combination with online electrochemical mass spectrometry and electrochemical impedance spectroscopy.

Origin of Structural Evolution in Capacity Degradation for Overcharged NMC622 via Operando Coupled Investigation.

The nickel-rich layered oxide materials have been selected as promising cathode materials for the next generation lithium ion batteries because of their large capacity and comparably high operating voltage. However, at high voltage (beyond 4.30 V vs Li/Li+), the members of this family are all suffering from a rapid capacity decay, which was commonly concerned with crystal lattice distortion and related cation disordering. In this work, the quasi-spherical Ni-rich layered LiNi0.6Co0.2Mn0.2O2 (QS-NMC622) material was successfully synthesized through the carbonate co-precipitation method. A coupled measurement, which is a combination of potentiostatic intermittent titration technique (PITT) and in situ X-ray diffraction (XRD), was deployed to simultaneously capture the structural changes and lithium ion diffusion coefficient of QS-NMC622 material during the first cycle. With help of in situ XRD patterns and high-resolution transmission electron microscope (HR-TEM) images, a defective spinel framework of Fd3̅m space group was detected along with a rapid decreasing lattice-parameter c and lattice distortion at deep delithiated state, which causes poor kinetics related to lithium ion mobility. The new-born framework seems to transform and remain as full spinel structure in the parent phase to the end of charge/discharge with high voltage, which could deteriorate both the surface and body structure stability during the subsequent cycles. This established coupled in situ measurement could be applied to simultaneously investigate the structure transformation and kinetics of cathode materials during charge/discharge.

In Situ Multitechnical Investigation into Capacity Fading of High-Voltage LiNi0.5Co0.2Mn0.3O2.

LiNi0.5Co0.2Mn0.3O2 positive electrode materials of lithium ion battery can release a discharge capacity larger than 200 mAh/g at high potential (>4.30 V). However, its inevitable capacity fading, which is greatly related to the structural evolution, reduces the cycling performance. The origin of this capacity fading is investigated by coupled in situ XRD-PITT-EIS. A new phase of NiMn2O4 is discovered on the surface of the LiNi0.5Co0.2Mn0.3O2 upon charging to high voltage, which blocks Li+ diffusion pathways. Theoretical calculations predict the formation of cubic NiMn2O4. Moreover, corrosion, cracks, and microstress appear to increase the difficulty of Li+ transportation, which are attributed to the protection degradation of the interfacial film on the positive electrode material at high voltage. After 50 electrochemical cycles, the increase in degree of crystal defects by low-angle grain boundary, evidenced through HR-TEM, leads to poor Li+ kinetics, which in turn causes capacity loss. The in situ XRD-PITT-EIS technique can bring multiperspective insights into fading mechanism of the high-voltage positive electrode materials and provide a solution to control or suppress the problem on the basis of structural, kinetic, and electrochemical interfacial understandings.

New Insights into the Structure Changes and Interface Properties of Li3VO4 Anode for Lithium-Ion Batteries during the Initial Cycle by in-Situ Techniques.

Li3VO4 has been regarded as a new-type anode of lithium-ion batteries in recent years, which has a high theoretical specific capacity of 394 mAh g(-1), a proper potential for Li(+) insertion/deinsertion (∼1 V), and a good rate capacity. However, its low initial Coulombic efficiency, poor conductivity, and poor cycle performance restricts its development. In order to figure out the cause of the low initial Coulombic efficiency of Li3VO4 material, the nanosized Li3VO4 material was synthesized by citric acid-assisted sol-gel method. The lithium storage behaviors of the prepared Li3VO4 material were studied by in-situ XRD and in-situ EIS techniques. In-situ XRD results indicated that there was irreversible phase transformation of Li3VO4 during the initial charging/discharging process. In-situ EIS experiment was performed during the potentiostatic intermittent titration technique (PITT) process to discuss the formation of the solid electrolyte interface (SEI) on the Li3VO4 and the kinetics of lithium-ion diffusion. It is worth pointing out that this is the first time to prove the existence of SEI on Li3VO4 during the initial charging/discharging process by in-situ EIS experiment. It turned out that the irreversible phase transformation and the formation of SEI on Li3VO4 were the two important reasons causing the low initial Coulombic efficiency of Li3VO4 material.

Hierarchical Mn2O 3Hollow Microspheres as Anode Material of Lithium Ion Battery and Its Conversion Reaction Mechanism Investigated by XANES.

Hierarchical Mn2O3 hollow microspheres of diameter about 6-10 µm were synthesized by solvent-thermal method. When serving as anode materials of LIBs, the hierarchical Mn2O3 hollow microspheres could deliver a reversible capacity of 580 mAh g(-1) at 500 mA g(-1) after 140 cycles, and a specific capacity of 422 mAh g(-1) at a current density as high as 1600 mA g(-1), demonstrating a good rate capability. Ex situ X-ray absorption near edge structure (XANES) spectrum reveals that, for the first time, the pristine Mn2O3 was reduced to metallic Mn when it discharged to 0.01 V, and oxidized to MnO as it charged to 3 V in the first cycle. Furthermore, the XANES data demonstrated also that the average valence of Mn in the sample at charged state has decreased slowly with cycling number, which signifies an incomplete lithiation process and interprets the capacity loss of the Mn2O3 during cycling.

Kinetics and structural changes of Li-rich layered oxide 0.5Li2MnO3·0.5LiNi(0.292)Co(0.375)Mn(0.333)O2 material investigated by a novel technique combining in situ XRD and a multipotential step.

Li-rich layered oxide 0.5Li2MnO3·0.5LiNi0.292Co0.375Mn0.333O2 was prepared by an aqueous solution-evaporation route. X-ray powder diffraction (XRD) showed that the as-synthesized material was a solid solution consisting of layered α-NaFeO2-type LiMO2 (M = Ni, Co, Mn) and monoclinic Li2MnO3. The superlattice spots in the selected area electron diffraction pattern indicated the ordering of lithium ions with transition metal (TM) ions in TM layers in this Li-rich layered oxide. Electrochemical performance testing showed that the as-synthesized material could deliver an initial discharge capacity of 267.7 mAh/g, with a capacity retention of 88.5% after 33 cycles. A new combination technique, multipotential step in situ XRD (MPS in situ XRD) measurement, was applied for the first time to investigate the Li-rich layered oxide. Using this approach, the relationships between kinetics and structural variations can be obtained simutaneously. In situ XRD results showed that the c parameter decreased from 3.70 to 4.30 V and increased from 4.30 to 4.70 V, whereas the a parameter underwent a decrease above 4.30 V during the first charge process. Below 3.90 V during the first discharge process, a slight decrease in the c parameter was found along with an increase in the a parameter. During the first charge process, the value of the coefficient of diffusion for lithium ions (DLi+) decreased to its mininum at 4.55 V, which might be associated with Ni(2+) migration, as indicated by both Ni occupancy in 3b sites (Ni3b%) in the Li(+) layers and complicated chemical reactions. Remarkably, a lattice distortion might occur within the local domain in the host stucture during the first discharge process, indicated by a slight splitting of the (003) diffraction peak at 3.20 V.

Facile synthesis of the Li-rich layered oxide Li1.23Ni0.09Co0.12Mn0.56O2 with superior lithium storage performance and new insights into structural transformation of the layered oxide material during charge-discharge cycle: in situ XRD characterization.

In this work, the Li-rich oxide Li1.23Ni0.09Co0.12Mn0.56O2 was synthesized through a facile route called aqueous solution-evaporation route that is simple and without waste water. The as-prepared Li1.23Ni0.09Co0.12Mn0.56O2 oxide was confirmed to be a layered LiMO2-Li2MnO3 solid solution through ex situ X-ray diffraction (ex situ XRD) and transmission electron microscopy (TEM). Electrochemical results showed that the Li-rich oxide Li1.23Ni0.09Co0.12Mn0.56O2 material can deliver a discharge capacity of 250.8 mAhg(-1) in the 1st cycle at 0.1 C and capacity retention of 86.0% in 81 cycles. In situ X-ray diffraction technique (in situ XRD) and ex situ TEM were applied to study structural changes of the Li-rich oxide Li1.23Ni0.09Co0.12Mn0.56O2 material during charge-discharge cycles. The study allowed observing experimentally, for the first time, the existence of ß-MnO2 phase that is appeared near 4.54 V in the first charge process, and a phase transformation of the ß-MnO2 to layered Li0.9MnO2 is occurred in the initial discharge process by evidence of in situ XRD pattrens and selected area electron diffraction (SAED) patterns at different states of the initial charge and discharge process. The results illustrated also that the variation of the in situ X-ray reflections during charge-discharge cycling are clearly related to the changes of lattice parameters of the as-prepared Li-rich oxide during the charge-discharge cycles.