Operando chemo-mechanical evolution in LiNi0.8Co0.1Mn0.1O2 cathodes
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PROVIDER: S-EPMC11344168 | biostudies-literature | 2024 Aug
REPOSITORIES: biostudies-literature
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Project description:Ni-rich layered oxide cathode materials such as LiNi0.8Mn0.1Co0.1O2 (NMC811) are widely tipped as the next-generation cathodes for lithium-ion batteries. The NMC class offers high capacities but suffers an irreversible first cycle capacity loss, a result of slow Li+ diffusion kinetics at a low state of charge. Understanding the origin of these kinetic hindrances to Li+ mobility inside the cathode is vital to negate the first cycle capacity loss in future materials design. Here, we report on the development of operando muon spectroscopy (μSR) to probe the Å-length scale Li+ ion diffusion in NMC811 during its first cycle and how this can be compared to electrochemical impedance spectroscopy (EIS) and the galvanostatic intermittent titration technique (GITT). Volume-averaged muon implantation enables measurements that are largely unaffected by interface/surface effects, thus providing a specific characterization of the fundamental bulk properties to complement surface-dominated electrochemical methods. First cycle measurements show that the bulk Li+ mobility is less affected than the surface Li+ mobility at full depth of discharge, indicating that sluggish surface diffusion is the likely cause of first cycle irreversible capacity loss. Additionally, we demonstrate that trends in the nuclear field distribution width of the implanted muons during cycling correlate with those observed in differential capacity, suggesting the sensitivity of this μSR parameter to structural changes during cycling.
| S-EPMC10268956 | biostudies-literature
Project description:Surface coating has become an effective approach to improve the electrochemical performance of Ni-rich cathode materials. In this study, we investigated the nature of an Ag coating layer and its effect on electrochemical properties of the LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode material, which was synthesized using 3 mol.% of silver nanoparticles by a facile, cost-effective, scalable and convenient method. We conducted structural analyses using X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy, which revealed that the Ag nanoparticle coating did not affect the layered structure of NCM811. The Ag-coated sample had less cation mixing compared to the pristine NMC811, which could be attributed to the surface protection of Ag coating from air contamination. The Ag-coated NCM811 exhibited better kinetics than the pristine one, which is attributed to the higher electronic conductivity and better layered structure provided by the Ag nanoparticle coating. The Ag-coated NCM811 delivered a discharge capacity of 185 mAh·g-1 at the first cycle and 120 mAh·g-1 at the 100th cycle, respectively, which is better than the pristine NMC811.
| S-EPMC10221140 | biostudies-literature
Project description:Ni-rich LiNi0.8Co0.1Mn0.1O2 layered oxide cathodes have been highlighted for large-scale energy applications due to their high energy density. Although its specific capacity is enhanced at higher voltages as Ni ratio increases, its structural degradation due to phase transformations and lattice distortions during cycling becomes severe. For these reasons, we focused on the origins of crack generation from phase transformations and structural distortions in Ni-rich LiNi0.8Co0.1Mn0.1O2 using multiscale approaches, from first-principles to meso-scale phase-field model. Atomic-scale structure analysis demonstrated that opposite changes in the lattice parameters are observed until the inverse Li content x = 0.75; then, structure collapses due to complete extraction of Li from between transition metal layers. Combined-phase investigations represent the highest phase barrier and steepest chemical potential after x = 0.75, leading to phase transformations to highly Li-deficient phases with an inactive character. Abrupt phase transformations with heterogeneous structural collapse after x = 0.81 (~220 mAh g-1) were identified in the nanodomain. Further, meso-scale strain distributions show around 5% of anisotropic contraction with lower critical energy release rates, which cause not only micro-crack generations of secondary particles on the interfaces between the contracted primary particles, but also mechanical instability of primary particles from heterogeneous strain changes.
| S-EPMC5206713 | biostudies-literature
Project description:Ni-rich lithium nickel manganese cobalt (NMC) oxide cathode materials promise Li-ion batteries with increased energy density and lower cost. However, higher Ni content is accompanied by accelerated degradation and thus poor cycle lifetime, with the underlying mechanisms and their relative contributions still poorly understood. Here, we combine electrochemical analysis with surface-sensitive X-ray photoelectron and absorption spectroscopies to observe the interfacial degradation occurring in LiNi0.8Mn0.1Co0.1O2-graphite full cells over hundreds of cycles between fixed cell voltages (2.5-4.2 V). Capacity losses during the first ∼200 cycles are primarily attributable to a loss of active lithium through electrolyte reduction on the graphite anode, seen as thickening of the solid-electrolyte interphase (SEI). As a result, the cathode reaches ever-higher potentials at the end of charge, and with further cycling, a regime is entered where losses in accessible NMC capacity begin to limit cycle life. This is accompanied by accelerated transition-metal reduction at the NMC surface, thickening of the cathode electrolyte interphase, decomposition of residual lithium carbonate, and increased cell impedance. Transition-metal dissolution is also detected through increased incorporation into and thickening of the SEI, with Mn found to be initially most prevalent, while the proportion of Ni increases with cycling. The observed evolution of anode and cathode surface layers improves our understanding of the interconnected nature of the degradation occurring at each electrode and the impact on capacity retention, informing efforts to achieve a longer cycle lifetime in Ni-rich NMCs.
| S-EPMC9082506 | biostudies-literature
Project description:Ni-rich cathode materials suffer from rapid capacity fading caused by interface side reactions and bulk structure degradation. Previous studies show that Co is conducive to bulk structure stability and sulfate can react with the residual lithium (LiOH and Li2CO3) on the surface of Ni-rich cathode materials and form a uniform coating to suppress the side reactions between the cathode and electrolyte. Here, CoSO4 is utilized as a modifier for LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode materials. It reacts with the residual lithium on the surface of the NCM811 cathode to form Li-ion conductive Li2SO4 protective layers and Co doping simultaneously during the high-temperature sintering process, which can suppress the side reactions between the Ni-rich cathode and electrolyte and effectively prevent the structural transformation. As a result, the co-modified NCM811 cathode with 3 wt% CoSO4 exhibits an improved cycling performance of 81.1% capacity retention after 200 cycles at 1C and delivers an excellent rate performance at 5C of 187.4 mA h g-1, which is 10.2% higher than that of the pristine NCM811 cathode.
| S-EPMC10664004 | biostudies-literature
Project description:With continuous improvement of batteries in energy density, enhancing their safety is becoming increasingly urgent. Herein, practical high energy density LiNi0.8 Mn0.1 Co0.1 O2 |graphite-SiO pouch cell with nonflammable localized high concentration electrolyte (LHCE) is proposed that presents unique self-discharge characteristic before thermal runaway (TR), thus effectively reducing safety hazards. Compared with the reference electrolyte, pouch cell with nonflammable LHCE can increase self-generated heat temperature by 4.4 °C, increase TR triggering temperature by 47.3 °C, decrease the TR highest temperature by 71.8 °C, and extend the time from self-generated heat to triggering TR by ≈8 h. In addition, the cell with nonflammable LHCE presents superior high voltage cycle stability, attributed to the formation of robust inorganic-rich electrode-electrolyte interphase. The strategy represents a pivotal step forward for practical high energy and high safety batteries.
| S-EPMC9661853 | biostudies-literature
Project description:Femtosecond ultrafast-laser micro-patterning was employed to prepare a three-dimensional (3D) structure for the tape-casting Ni-rich LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode. The influences of laser structuring on the electrochemical performance of NMC811 were investigated. The 3D-NMC811 cathode retained capacities of 77.8% at 2 C of initial capacity at 0.1 C, which was thrice that of 2D-NMC811 with an initial capacity of 27.8%. Cyclic voltammetry (CV) and impedance spectroscopy demonstrated that the 3D electrode improved the Li+ ion transportation at the electrode-electrolyte interface, resulting in a higher rate capability. The diffusivity coefficient DLi+, calculated by both CV and electrochemical impedance spectroscopy, revealed that 3D-NMC811 delivered faster Li+ ion transportation with higher DLi+ than that of 2D-NMC811. The laser ablation of the active material also led to a lower charge-transfer resistance, which represented lower polarization and improved Li+ ion diffusivity.
| S-EPMC9654857 | biostudies-literature
Project description:Ni-rich layered transition metal oxides show great energy density but suffer poor thermal stability and inferior cycling performance, which limit their practical application. In this work, a minor content of Co and B were co-doped into the crystal of a Ni-rich cathode (LiNi0.8Co0.1Mn0.1O2) using cobalt acetate and boric acid as dopants. The results analyzed by XRD, TEM, XPS and SEM reveal that the modified sample shows a reduced energy barrier for Li+ insertion/extraction and alleviated Li+/Ni2+ cation mixing. With the doping of B and Co, corresponding enhanced cycle stability was achieved with a high capacity retention of 86.1% at 1.0C after 300 cycles in the range of 2.7 and 4.3 V at 25 °C, which obviously outperformed the pristine cathode (52.9%). When cycled after 300 cycles at 5C, the material exhibits significantly enhanced cycle stability with a capacity retention of 81.9%. This strategy for the enhancement of the electrochemical performance may provide some guiding significance for the practical application of high nickel content cathodes.
| S-EPMC9075131 | biostudies-literature
Project description:LiNi0.8Co0.1Mn0.1O2 cathodes suffer from severe bulk structural and interfacial degradation during battery operation. To address these issues, a three in one strategy using ZrB2 as the dopant is proposed for constructing a stable Ni-rich cathode. In this strategy, Zr and B are doped into the bulk of LiNi0.8Co0.1Mn0.1O2, respectively, which is beneficial to stabilize the crystal structure and mitigate the microcracks. Meanwhile, during the high-temperature calcination, some of the remaining Zr at the surface combined with the surface lithium source to form lithium zirconium coatings, which physically protect the surface and suppress the interfacial phase transition upon cycling. Thus, the 0.2 mol% ZrB2-LiNi0.8Co0.1Mn0.1O2 cathode delivers a discharge capacity of 183.1 mAh g-1 after 100 cycles at 50 °C (1C, 3.0-4.3 V), with an outstanding capacity retention of 88.1%. The cycling stability improvement is more obvious when the cut-off voltage increased to 4.4 V. Density functional theory confirms that the superior structural stability and excellent thermal stability are attributed to the higher exchange energy of Li/Ni exchange and the higher formation energy of oxygen vacancies by ZrB2 doping. The present work offers a three in one strategy to simultaneously stabilize the crystal structure and surface for the Ni-rich cathode via a facile preparation process.
| S-EPMC7816706 | biostudies-literature
Project description:The application of nickel-rich cathodes in lithium-ion batteries has been hampered by its rapid capacity/voltage fading and limited performance of rate. In this work, a passivation technique is used to create a stable composite interface on single-crystal LiNi0.8Co0.1Mn0.1O2 (NCM811) surface, which greatly improves the cycle life-span and high-voltage constancy of cathode with 4.5 and 4.6 V cut-off voltage. The improved Li+ conductivity of the interface enables a firm cathode-electrolyte interphase (CEI), which reduces interfacial side reactions, lowers the risk of safety hazards, and improves irreversible phase transitions. As a result, the electrochemical performance of single-crystal Ni-rich cathode are remarkably enhanced. The specific capacity of 152 mAh g-1 can be delivered at a charging/discharging rate of 5 C under 4.5 V cut-off voltage, much higher than 115 mAh g-1 of the pristine NCM811. After 200 cycles at 1 C, the composite interface modified NCM811 demonstrates outstanding capacity retention of 85.4% and 83.8% at 4.5 V and 4.6 V cut-off voltage, respectively.
| S-EPMC10224527 | biostudies-literature