In situ fracture behavior of single crystal LiNi0.8Mn0.1Co0.1O2 (NMC811)

Single crystal particle morphologies have become highly desirable for next generation cathode materials, removing grain boundary fracture and thereby reducing the surface area exposed to electrolyte. The intrinsic mechanical behavior of single crystal layered oxides, however, is poorly understood. Here, faceted single crystal LiNi0.8Mn0.1Co0.1O2 (NMC811) particles are compressed in situ in a scanning electron microscope (SEM), to determine mechanical deformation mechanisms as a function of crystallographic orientation. In situ, the dynamical deformation sequence observed is initial cracking at the compression zone, followed by accelerated transparticle crack propagation and concurrent (0001) slip band formation. The greatest loads and contact pressure at fracture, non-basal cracking, and activation of multiple basal slip systems in larger (>3 μm) particles, occur for compression normal to the (0001) layered structure. Loading on {012} preferentially activates basal fracture and slip at lower loads. Regardless of particle orientation, non-basal slip systems are not observed, and non-basal cracking and particle rotation occur during compression to compensate for this inability to activate dislocations in 3-dimensions. Crystallographic dependent mechanical behaviour of single crystal NMC811 means that particle texture in cathodes should be monitored, and sources of localised surface stress in cathodes, e. g. particle-to-particle asperity contacts during electrode manufacture, should be minimised

Insights into the electrochemical reduction products and processes in silica anodes for next-generation lithium-ion batteries

The use of silica as a lithium‐ion battery anode material requires a pretreatment step to induce electrochemical activity. The partially reversible electrochemical reduction reaction between silica and lithium has been postulated to produce silicon, which can subsequently reversibly react with lithium, providing stable capacities higher than graphite materials. Up to now, the electrochemical reduction pathway and the nature of the products were unknown, thereby hampering the design, optimization, and wider uptake of silica‐based anodes. Here, the electrochemical reduction pathway is uncovered and, for the first time, elemental silicon is identified as a reduction product. These insights, gleaned from analysis of the current response and capacity increase during reduction, conclusively demonstrated that silica must be reduced to introduce reversible capacity and the highest capacities of 600 mAh g−1 are achieved by using a constant load discharge at elevated temperature. Characterization via total scattering X‐ray pair distribution function analysis reveal the reduction products are amorphous in nature, highlighting the need for local structural methods to uncover vital information often inaccessible by traditional diffraction. These insights contribute toward understanding the electrochemical reduction of silica and can inform the development of pretreatment processes to enable their incorporation into next‐generation lithium‐ion batteries

Direct observation of dynamic lithium diffusion behavior in nickel-rich, LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes using operando muon spectroscopy

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

In situ diffusion measurements of a NASICON-structured all-solid-state battery using muon spin relaxation

In situ muon spin relaxation is demonstrated as an emerging technique that can provide a volume-averaged local probe of the ionic diffusion processes occurring within electrochemical energy storage devices as a function of state of charge. Herein, we present work on the conceptually interesting NASICON-type all-solid-state battery LiM2(PO4)3, using M = Ti in the cathode, M = Zr in the electrolyte, and a Li metal anode. The pristine materials are studied individually and found to possess low ionic hopping activation energies of ∼50−60 meV and competitive Li+ self-diffusion coefficients of ∼10^–10–10^–9 cm2 s^–1 at 336 K. Lattice matching of the cathode and electrolyte crystal structures is employed for the all-solid-state battery to enhance Li+ diffusion between the components in an attempt to minimize interfacial resistance. The cell is examined by in situ muon spin relaxation, providing the first example of such ionic diffusion measurements. This technique presents an opportunity to the materials community to observe intrinsic ionic dynamics and electrochemical behavior simultaneously in a nondestructive manner

The role of the reducible dopant in solid electrolyte–lithium metal interfaces

Garnet solid electrolytes, of the form Li7La3Zr2O12 (LLZO), remain an enticing prospect for solid-state batteries owing to their chemical and electrochemical stability in contact with metallic lithium. Dopants, often employed to stabilize the fast ion conducting cubic garnet phase, typically have no effect on the chemical stability of LLZO in contact with Li metal but have been found recently to impact the properties of the Li/garnet interface. For dopants more "reducible"than Zr (e.g., Nb and Ti), contradictory reports of either raised or reduced Li/garnet interfacial resistances have been attributed to the dopant. Here, we investigate the Li/LLZO interface in W-doped Li7La3Zr2O12 (LLZWO) to determine the influence of a "reducible"dopant on the electrochemical properties of the Li/garnet interface. Single-phase LLZWO is synthesized by a new sol-gel approach and densified by spark plasma sintering. Interrogating the resulting Li/LLZWO interface/interphase by impedance, muon spin relaxation and X-ray absorption spectroscopies uncover the significant impact of surface lithiation on electrochemical performance. Upon initial contact, an interfacial reaction occurs between LLZWO and Li metal, leading to the reduction of surface W6+ centers and an initial reduction of the Li/garnet interfacial resistance. Propagation of this surface reaction, driven by the high mobility of Li+ ions through the grain surfaces, thickens the resistive interphases throughout the material and impedes Li+ ion transport between the grains. The resulting high resistance accumulating in the system impedes cycling at high current densities. These insights shed light on the nature of lithiated interfaces in garnet solid electrolytes containing a reducible dopant where high Li+ ion mobility and the reducible nature of the dopant can significantly affect electrochemical performance

On the effects of the magnetic field and the isotopic substitution upon the infrared absorption of manganites

Employing a variational approach that takes into account electron-phonon and magnetic interactions in $La_{1-x}A_xMnO_3$ perovskites with $0<x<0.5$, the effects of the magnetic field and the oxygen isotope substitution on the phase diagram, the electron-phonon correlation function and the infrared absorption at $x=0.3$ are studied. The lattice displacements show a strong correlation with the conductivity and the magnetic properties of the system. Then the conductivity spectra are characterized by a marked sensitivity to the external parameters near the phase boundary.Comment: 10 figure

Influence of Cation Substitution on Cycling Stability and Fe-Cation Migration in Li3Fe3–xMxTe2O12 (M = Al, In) Cathode Materials

Li3Fe3Te2O12 adopts a crystal structure, described in space group Pnnm, related to that of LiSbO3, in which Te6+, Fe3+, and Li+ cations reside in a partially ordered configuration within an hcp array of oxide ions. Chemical or electrochemical insertion of lithium is accompanied by a fully reversible migration of some of the Fe cations with an initial capacity of 120 mA h g-1 (2.85 Li per formula unit). Long-term cycling stability is limited by the facile reduction of Te6+ to elemental Te, which leads to cathode decomposition. Partial substitution of Fe by In suppresses Te6+ reduction, such that Li3Fe2InTe2O12 shows no sign of this cathode decomposition pathway, even after 100 cycles. In contrast, Al-for-Fe substitution is chemically limited to Li3Fe2.6Al0.4Te2O12 and appears to have almost no influence on cathode longevity. These features of the Li3Fe3-xMxTe2O12 system are discussed on the basis of a detailed structural analysis performed using neutron and synchrotron X-ray diffraction

Fracture testing of lithium‐ion battery cathode secondary particles in‐situ inside the scanning electron microscope

Fracture of cathode secondary particles is a critical degradation mechanism in lithium-ion batteries. The microindentation strength of LiNi0.8Mn0.1Co0.1O2 secondary particles is measured in situ in the scanning electron microscope (SEM), enabling dynamical imaging of fracture. Crack propagation is intergranular between primary particles when induced by compressing between flat platens (analogous to calendaring), and with a cono-spherical indenter (representing particle-particle contact). Fracture occurs directly beneath the cono-spherical tip and at the centre of secondary particles when compressed between flat platens. Finite element modelling of stress states provides insight into the dependence of fracture load upon cohesive strength and particle toughness. Secondary particle indentation strength decreases with increasing secondary particle size, with cycling, and with increasing state of charge. The indentation strength decrease is greatest in earlier stages of delithiation. The novel microindentation technique allows assessment of strength and toughness of different cathode morphologies, aiding prediction of optimal particle structure and processing conditions

Measurement of the vector and tensor analyzing powers for dp- elastic scattering at 880 MeV

The vector Ay and tensor analyzing powers Ayy and Axx for dp- elastic scattering were measured at Td = 880 MeV over the c.m. angular range from 60 to 140 degrees at the JINR Nuclotron. The data are compared with predictions of different theoretical models based on the use of nucleon-nucleon forces only. The observed discrepancies of the measured analyzing powers from the calculations require the consideration of additional mechanisms.Comment: 5 pages,3 figure

Melting of Charge/Orbital Ordered States in Nd1/2_{1/2}Sr1/2_{1/2}MnO3_3: Temperature and Magnetic Field Dependent Optical Studies

We investigated the temperature ($T=$ 15 $\sim$ 290 K) and the magnetic field ($H=$ 0 $\sim$ 17 T) dependent optical conductivity spectra of a charge/orbital ordered manganite, Nd$_{1/2}$Sr$_{1/2}$MnO$_3$. With variation of $T$ and $H$, large spectral weight changes were observed up to 4.0 eV. These spectral weight changes could be explained using the polaron picture. Interestingly, our results suggested that some local ordered state might remain above the charge ordering temperature, and that the charge/orbital melted state at a high magnetic field (i.e. at $H=$ 17 T and $$ 4.2 K) should be a three dimensional ferromagnetic metal. We also investigated the first order phase transition from the charge/orbital ordered state to ferromagnetic metallic state using the $T$- and $H$% -dependent dielectric constants $\epsilon_1$. In the charge/orbital ordered insulating state, $\epsilon_1$ was positive and $d\epsilon_1/d\omega \approx 0$. With increasing $T$ and $H$, $\epsilon_1$ was increased up to the insulator-metal phase boundaries. And then, $\epsilon_1$ abruptly changed into negative and $d\epsilon_1/d\omega >0$, which was consistent with typical responses of a metal. Through the analysis of $\epsilon_1$ using an effective medium approximation, we found that the melting of charge/orbital ordered states should occur through the percolation of ferromagnetic metal domains.Comment: submitted to Phys. Rev.