Cobalt-free, lithium-rich composites are interesting cathodes for generation 3b Li-ion batteries due to their high discharge capacity and improved sustainability with respect to state-of-the-art NMC oxides, which are commonly doped with magnesium to stabilize their layered structure. In this article, the role of the magnesium dopant, including its solubility, chemical distribution, and phase evolution, has been characterized and optimized in the context of nanoscale composites. By combining XRD, XPS, TEM–EDX, and coin cell testing, a physically and chemically segregated model for Li1.21-2xMgxNi0.16Mn0.62O2 (x = 0, 0.01, 0.03, 0.05, and 0.1) as a function of Mg dopant level is presented, assuming an ionic doping compensation mechanism. The best-performing cathode, i.e., Li1.20Mg0.01Ni0.16Mn0.62O2, displays a homogeneous distribution of magnesium at the bulk particle level with an incipient phase-segregated Ni-rich structure at the particle edge, resulting in a discharge capacity of 187 mAhg−1 at 0.2C and an enhanced performance compared to undoped and x≥ 0.03 samples. The structural and chemical results presented herein highlight the complex engineering required to achieve a specific phase structure and chemical (dopant) distribution of Li-rich nanoscale composites.

Lithium-rich, cobalt-free oxides are promising potential positive electrode materials for lithium-ion batteries because of their high energy density, lower cost, and reduced environmental and ethical concerns. However, their commercial breakthrough is hindered because of their subpar electrochemical stability. This work studies the effect of aluminum doping on Li_1.26Ni_0.15Mn_0.61O₂ as a lithium-rich, cobalt-free layered oxide. Al doping suppresses voltage fade and improves the capacity retention from 46% for Li_1.26Ni_0.15Mn_0.61O₂ to 67% for Li_1.26Ni_0.15Mn_0.56Al_0.05O₂ after 250 cycles at 0.2 C. The undoped material has a monoclinic Li₂MnO₃-type structure with spinel on the particle edges. In contrast, Al-doped materials (Li_1.26Ni_0.15Mn_0.61-xAl_xO₂) consist of a more stable rhombohedral phase at the particle edges, with a monoclinic phase core. For this core-shell structure, the formation of Mn³⁺ is suppressed along with the material's decomposition to a disordered spinel, and the amount of the rhombohedral phase content increases during galvanostatic cycling. Whereas previous studies generally provided qualitative insight into the degradation mechanisms during electrochemical cycling, this work provides quantitative information on the stabilizing effect of the rhombohedral shell in the doped sample. As such, this study provides fundamental insight into the mechanisms through which Al doping increases the electrochemical stability of lithium-rich cobalt-free layered oxides.

The phase evolution of Li-rich Li-Mn-Ni-(Al)-O cathode materials upon heat treatments in the air at 900 °C was studied by X-ray and neutron powder diffraction. In addition, the structures of Li_1.26Mn_0.61−xAl_x Ni_0.15O₂, x = 0.0, 0.05, and 0.10, were refined from neutron powder diffraction data. For two-phase mixtures containing a monoclinic Li₂MnO₃ type phase M and a rhombohedral LiMn_0.5Ni_0.5O₂ type phase R, the structures, compositions, and phase fractions change with heat treatment time. This is realized by the substitution mechanism 3Ni²⁺ ↔ 2Li⁺ + 1Mn⁴⁺, which enables cation transport between the phases. A whole-powder pattern fitting analysis of size and strain broadening shows that strain broadening dominates. The X-ray domain size increases with heat treatment time and is larger than the sizes of the domains of M and R observed by electron microscopy. For heat-treated samples, the domain size is smaller for R than for M and decreases with increasing Al doping.

Despite significant potential as energy storage materials for electric vehicles due to their combination of high energy density per unit cost and reduced environmental and ethical concerns, Co-free lithium ion batteries based on layered Mn oxides presently lack the longevity and stability of their Co-containing counterparts. Here, a reduction in this performance gap is demonstrated via chemical doping, with Li_1.1Ni_0.35Mn_0.54Al_0.01O₂ achieving an initial discharge capacity of 159 mAhg⁻¹ at C/3 rate and a corresponding capacity retention of 94.3% after 150 cycles. The nanoscale origins of this improvement are subsequently explored through a combination of advanced diffraction, spectroscopy, and electron microscopy techniques, finding that optimized doping profiles lead to an improved structural and chemical compatibility between the two constituent sub-phases that characterize the layered Mn oxide system, resulting in the formation of unobstructed lithium ion pathways between them. A structural stabilization effect of the host compound is also directly observed near the surface using aberration corrected scanning transmission electron microscopy and integrated differential phase contrast imaging. 

Silicon powder kerf loss from diamond wire sawing in the photovoltaic wafering industry is a highly appealing source material for use in lithium-ion battery negative electrodes. Here, it is demonstrated for the first time that the kerf particles from three independent sources contain similar to 50% amorphous silicon. The crystalline phase is in the shape of nano-scale crystalline inclusions in an amorphous matrix. From literature on wafering technology looking at wafer quality, the origin and mechanisms responsible for the amorphous content in the kerf loss powder are explained. In order to better understand for which applications the material could be a valuable raw material, the amorphicity and other relevant features are thoroughly investigated by a large amount of experimental methods. Furthermore, the kerf powder was crystallized and compared to the partly amorphous sample by operando X-ray powder diffraction experiments during battery cycling, demonstrating that the powders are relevant for further investigation and development for battery applications.

Co-free Li-rich layered oxides are gaining interest as feasible positive electrode materials in lithium-ion batteries (LIBs) in terms of energy density, cost reduction, and alleviating safety concerns. Unfortunately, their commercialization is hindered by severe structural degradation that occurs during electrochemical operation. The study at hand demonstrates advanced structural engineering of a Li-rich Co-free oxide with composition Li_1.1Ni_0.35Mn_0.55O₂ by spray pyrolysis and subsequent calcination of an aqueous precursor, creating a segregated structure of two distinct layered phases with space groups R3̅m (rhombohedral) and C2/m (monoclinic). This particular structure was investigated with powder neutron diffraction, high-resolution analytical transmission electron microscopy imaging, and electron energy loss spectroscopic characterization. This complex structure contributes to the high electrochemical stability and good rate capability observed for this compound (160 mAh/g at C/3 and 100 mAh/g at 1C). These results provide new insights into the feasibility of developing and commercializing cobalt-free positive electrode materials for LIBs. 

Self-aggregated colloids can be used for the preparation of materials, and we studied long rod-like aggregates formed on the evaporation of water from dispersed particles of colloidal hydrochar. The monodispersed hydrochar particles (100–200 nm) were synthesized by the hydrothermal carbonization ofglucose and purified through dialysis. During the synthesis they formed colloidal dispersions which wereelectrostatically stable at intermediate to high pH and at low ion strengths. On the evaporation of water,macroscopically large rods formed from the dispersions at intermediate pH conditions. The rods formedat the solid-water interface orthogonally oriented with respect to the drying direction. Pyrolysis renderedthe rods highly porous without qualitatively affecting their shape. A Cu-Si alloy was reactively infiltratedinto the in-situ pyrolyzed hydrochars and composites of tricopper silicide (Cu3Si)-silicon carbide(SiC)/carbon formed. During this process, the Si atoms reacted with the C atoms, which in turned causedthe alloy to wet and further react with the carbon. The shape of the underlying carbon template wasmaintained during the reactions, and the formed composite preparation was subsequently calcined intoa Cu3Si-SiC-based replica of the rod-like assemblies of carbon-based colloidal particles. Transmission andscanning electron microscopy, and X-ray diffraction were used to study the shape, composition, andstructure of the formed solids. Further studies of materials prepared with reactive infiltration of alloysinto self-aggregated and carbon-based solids can be justified from a perspective of colloidal science, aswell as the explorative use of hydrochar prepared from real biomass, exploration of the compositionalspace in relation to the reactive infiltration, and applications of the materials in catalysis. 

K2Mn[Mn(CN)(6)] is synthesized, characterized, and evaluated as possible positive electrode material in nonaqueous Li-, Na-, and K-ion batteries. This compound belongs to the rich and versatile family of hexacyanometallates displaying distinctive structural properties, which makes it interesting for ion insertion purposes. It can be viewed as a perovskite-like compound in which CN-bridged Mn(CN)(6) octahedra form an open framework structure with sufficiently large diffusion channels able to accommodate a variety of insertion cations. By means of galvanostatic cycling and cyclic voltammetry tests in nonaqueous alkali metal half-cells, it is demonstrated that this material is able to reversibly host Li+, Na+, and K+ ions via electrochemical insertion/deinsertion within a wide voltage range. The general electrochemical features are similar for all of these three ion insertion chemistries. An in operando X-ray diffraction investigation indicates that the original monoclinic structure is transformed into a cubic one during charging (i.e., removal of cations from the host framework) and that such a process is reversible upon subsequent cell discharge and cation reuptake.

Microporous activated carbon was prepared by depositing and pyrolyzing propylene within the microporous voids of SAPO-37 and subsequently removing the template by a treatment with HCl and NaOH. The carbon had a high surface area and large micropore and ultramicropore volumes. The yield, crystallinity, morphology, and adsorption properties compared well with those of a structurally related zeolite-Y-templated carbon. No HF was needed to remove the SAPO-37 template in contrast to the zeolite Y template, which could be of industrial importance.

Vibrational spectroscopic study of crystalline copper hexacyanoferrate complexes of composition K4Cu6II [Fe-II(CN)(6)](4)nH(2)O (1) and Cu-6(II)[Fe-III(CN)(6)](4)nH(2)O (2) with -Cu-N equivalent to C-Fe- bridging structures have been performed. The cubic Fmm (O-h(5)) unit-cells contain ideally 4 Fe and 4 Cu ions which were calculated by periodic density functional theory (DFT) (using the Gaussian09 C.01 software package) for ideal lattice compositions of K8Cu4II[Fe-II(CN)(6)](4) (1a), K4Cu4II[Fe-III(CN)(6)](4) (2a) and with lattice water molecules KCu4II[Fe-III(CN)(6)](3)6H(2)O (3a). Systematically, non-linear Cu-N equivalent to C structure was fitted with Cu-N equivalent to C bond angles about 155 degrees for complexes 1a, 2a, and 3a. Practically, all optically active internal modes of Fe(CN6)(n-) moieties resulted from factor group analysis as 4A(1g) + 6E(g) + 4F(1g) + 10F(1u) were experimentally observed and assigned. Some low-frequency translatory and librational modes were also interpreted. Vibrational bands were assigned to cis- and trans-Cu(NC)(4)(OH2) complexes which are formed in the lattice holes of both complexes. Vibrational spectra and force constants of a great number of transition metal hexacyano complexes of compositions K-4[M-II(CN)(6)], K-3[M-III(CN)(6)], CsLi2[M-III(CN)(6)] and Prussian blue analogues have been reexamined and recalculated. Internal and external modes of 6 different lattice water species (coordinated, hydrogen bonded, or zeolitic type) have been interpreted for complex 2 using results of periodic DFT calculation of model complex 3a.