The Effect of Doping Process Route on LiNiO2_2 Cathode Material Properties

The pursuit of higher energy density in lithium-ion batteries has driven the increase of the nickel content in lithium nickel cobalt manganese oxide cathode active materials (CAMs), ultimately approaching LiNiO$_2$ (LNO). The downside of the high specific capacity of LNO is more severe degradation of the CAM during battery operation. A common approach to increase structural stability is the introduction of dopants. Various dopants are discussed and compared with each other when integrated into the CAM and tested against undoped materials in the literature, but little attention is given to the role of the process route of their introduction. In this work, we demonstrate with a series of nominally equally Zr-doped LNO samples that effects on various physico- and electrochemical properties are due not to the dopant itself, as one would assume in comparison to an undoped sample, but to the process route and the resulting particle morphology. Dopant, concentration and process routes (co-precipitation, impregnation and co-calcination) were chosen based on their significance for industrial application

The LiNiO2_2 Cathode Active Material: A Comprehensive Study of Calcination Conditions and their Correlation with Physicochemical Properties. Part I. Structural Chemistry

Following the demand for increased energy density of lithium-ion batteries, the Ni content of the Nickel-Cobalt-Manganese oxide (NCM) cathode materials has been increased into the direction of LiNiO$_2$ (LNO), which regained the attention of both industry and academia. To understand the correlations between physicochemical parameters and electrochemical performance of LNO, a calcination study was performed with variation of precursor secondary particle size, maximum calcination temperature and Li stoichiometry. The structural properties of the materials were analyzed by means of powder X-ray diffraction, magnetization measurements and half-cell voltage profiles. All three techniques yield good agreement concerning the quantification of Ni excess in the Li layer (1.6%–3.7%). This study reveals that the number of Li equivalents per Ni is the determining factor concerning the final stoichiometry rather than the calcination temperature within the used calcination parameter space. Contrary to widespread belief, the Ni excess shows no correlation to the 1$^{st}$ cycle capacity loss, which indicates that a formerly overlooked physical property of LNO, namely primary particle morphology, has to be considered

The LiNiO2_{2} Cathode Active Material: A Comprehensive Study of Calcination Conditions and their Correlation with Physicochemical Properties Part II. Morphology

A better understanding of the cathode active material (CAM) plays a crucial role in the improvement of lithium-ion batteries. We have previously reported the structural properties of the model cathode material LiNiO$_{2}$ (LNO) in dependence of its calcination conditions and found that the deviation from the ideal stoichiometry in LiNiO2 (Ni excess) shows no correlation to the 1st cycle capacity loss. Rather, the morphology of LNO appears to be decisive. As CAM secondary agglomerates fracture during battery operation, the surface area in contact with the electrolyte changes during cycle life. Thus, particle morphology and especially the primary particle size become critical and are analyzed in detail in this report for LNO, using an automated SEM image segmentation method. It is shown that the accessible surface area of the pristine CAM powder measured by physisorption is close to the secondary particle geometric surface area. The interface area between CAM and electrolyte is measured by an in situ capacitance method and approaches a value proportional to the estimated primary particle surface area determined by SEM image analysis after just a few cycles. This interface area is identified to be the governing factor determining the 1st cycle capacity loss and long-term cycling behavior

Electron-momentum dependence of electron-phonon coupling underlies dramatic phonon renormalization in YNi2_{2}B2_{2}C

Electron-phonon coupling, i.e., the scattering of lattice vibrations by electrons and vice versa, is ubiquitous in solids and can lead to emergent ground states such as superconductivity and charge-density wave order. A broad spectral phonon line shape is often interpreted as a marker of strong electron-phonon coupling associated with Fermi surface nesting, i.e., parallel sections of the Fermi surface connected by the phonon momentum. Alternatively broad phonons are known to arise from strong atomic lattice anharmonicity. Here, we show that strong phonon broadening can occur in the absence of both Fermi surface nesting and lattice anharmonicity, if electron-phonon coupling is strongly enhanced for specific values of electron- momentum, k. We use inelastic neutron scattering, soft x-ray angle-resolved photoemission spectroscopy measurements and ab-initio lattice dynamical and electronic band structure calculations to demonstrate this scenario in the highly anisotropic tetragonal electron-phonon superconductor YNi2B2C. This new scenario likely applies to a wide range of compounds

Electron-momentum dependence of electron-phonon coupling underlies dramatic phonon renormalization in YNi2B2C

International audienceElectron-phonon coupling, i.e., the scattering of lattice vibrations by electrons and vice versa, is ubiquitous in solids and can lead to emergent ground states such as superconductivity and charge-density wave order. A broad spectral phonon line shape is often interpreted as a marker of strong electron-phonon coupling associated with Fermi surface nesting, i.e., parallel sections of the Fermi surface connected by the phonon momentum. Alternatively broad phonons are known to arise from strong atomic lattice anharmonicity. Here, we show that strong phonon broadening can occur in the absence of both Fermi surface nesting and lattice anharmonicity, if electron-phonon coupling is strongly enhanced for specific values of electron-momentum, k. We use inelastic neutron scattering, soft x-ray angle-resolved photoemission spectroscopy measurements and ab-initio lattice dynamical and electronic band structure calculations to demonstrate this scenario in the highly anisotropic tetragonal electron-phonon superconductor YNiBC. This new scenario likely applies to a wide range of compounds

Role of the polycomb protein EED in the propagation of repressive histone marks

Polycomb Group (PcG) proteins play an essential role in the epigenetic maintenance of repressive chromatin states. The gene silencing activity of the Polycomb Repressive Complex 2 (PRC2) depends on its ability to tri-methylate lysine 27 of histone H3 (H3K27) via the catalytic SET domain of the EZH2 subunit, and at least two other subunits of the complex: Suz12 and Eed. We show that the C-terminal domain of Eed specifically binds to histone tails carrying tri-methyl lysine residues associated with repressive chromatin marks and that this leads to the allosteric activation of the methyltransferase activity of PRC2. Mutations in Eed that prevent it from recognising repressive trimethyl-lysine marks abolish activation of PRC2 in vitro and, in Drosophila, reduces global methylation and disrupts development. These findings suggest a model for the propagation of the H3K27me3 mark that accounts for the maintenance of repressive chromatin domains and for the transmission of a histone modification from mother to daughter cells