Dynamic Structure Evolution of Extensively Delithiated High Voltage Spinel Li1+xNi0.5Mn1.5O4 x < 1.5.

High voltage spinel is one of the most promising next-generation cobalt-free cathode materials for lithium ion battery applications. Besides the typically utilized compositional range of LixNi0.5Mn1.5O4 0 < x < 1 in the voltage window of 4.90-3.00 V, additional 1.5 mol of Li per formula unit can be introduced into the structure, in an extended voltage range to 1.50 V. Theoretically, this leads to significant increase of the specific energy from 690 to 1190 Wh/kg. However, utilization of the extended potential window leads to rapid capacity fading and voltage polarization that lack a comprehensive explanation. In this work, we conducted potentiostatic entropymetry, operando XRD and neutron diffraction on the ordered stoichiometric spinel LixNi0.5Mn1.5O4 within 0 < x < 2.5 in order to understand the dynamic structure evolution and correlate it with the voltage profile. During the two-phase reaction from cubic (x < 1) to tetragonal (x > 1) phase at ∼2.8 V, we identified the evolution of a second tetragonal phase with x > 2. The structural evaluation during the delithiation indicates the formation of an intermediate phase with cubic symmetry at a lithium content of x = 1.5. Evaluation of neutron diffraction data, with maximum entropy method, of the highly lithiated phase LixNi0.5Mn1.5O4 with 2 < x < 2.5 strongly suggests that lithium ions are located on octahedral 8a and tetrahedral 4a positions of the distorted tetragonal phase I41amd. Consequently, we were able to provide a conclusive explanation for the additional voltage step at 2.10 V, the sloping voltage profile below 1.80 V, and the additional voltage step at ∼3.80 V.

Enhanced Electrochemical Capacity of Spherical Co-Free Li1.2 Mn0.6 Ni0.2 O2 Particles after a Water and Acid Treatment and its Influence on the Initial Gas Evolution Behavior.

Li-rich layered oxides (LRLO) with specific energies beyond 900 Wh kg-1 are one promising class of high-energy cathode materials. Their high Mn-content allows reducing both costs and the environmental footprint. In this work, Co-free Li1.2 Mn0.6 Ni0.2 O2 was investigated. A simple water and acid treatment step followed by a thermal treatment was applied to the LRLO to reduce surface impurities and to establish an artificial cathode electrolyte interface. Samples treated at 300 °C show an improved cycling behavior with specific first cycle capacities of up to 272 mAh g-1 , whereas powders treated at 900 °C were electrochemically deactivated due to major structural changes of the active compounds. Surface sensitive analytical methods were used to characterize the structural and chemical changes compared to the bulk material. Online DEMS measurements were conducted to get a deeper understanding of the effect of the treatment strategy on O2 and CO2 evolution during electrochemical cycling.

Co-Crosslinked Water-Soluble Biopolymers as a Binder for High-Voltage LiNi0.5 Mn1.5 O4 |Graphite Lithium-Ion Full Cells.

The use of water-soluble, abundant biopolymers as binders for lithium-ion positive electrodes is explored because it represents a great step forward towards environmentally benign battery processing. However, to date, most studies that employ, for instance, carboxymethyl cellulose (CMC) as a binder have focused on rather low electrode areal loadings with limited relevance for industrial needs. This study concerns the use of natural guar gum (GG) as a binding agent for cobalt-free, high-voltage LiNi0.5 Mn1.5 O4 (LNMO), which realizes electrodes with substantially increased areal loadings, low binder content, and greatly enhanced cycling stability. Co-crosslinking GG through citric acid with CMC allows for an enhanced rate capability and essentially maintains the beneficial impact of using GG as a binder rather than CMC only. Lithium-ion full cells based on water-processed LNMO and graphite electrodes provide a remarkably high cycling stability with 80 % capacity retention after 1000 cycles at 1 C.

Influence of the Molecular Weight of Poly-Acrylic Acid Binder on Performance of Si-Alloy/Graphite Composite Anodes for Lithium-Ion Batteries.

In this study Si-alloy/graphite composite electrodes are manufactured using water-soluble poly-acrylic acid (PAA) binder of different molecular weights (250, 450 and 1250 kg mol-1). The study aims to assess the behavior of the different binders across all the steps needed for electrodes preparation and on their influence on the electrodes electrochemical behavior. At first, rheological properties of the water-based slurries containing Si-alloy, graphite, conductive carbon and PAA are studied. After coating, the adhesion strength and electronic conductivity of the manufactured electrodes are evaluated and compared. Finally, the electrochemical behavior of the composite anodes is evaluated. The electrodes show high gravimetric as well as high areal capacity (∼750 mAh/g; ∼3 mAh/cm2). The influence of the binder on the first cycle irreversible loss is considered as well as its effectiveness in minimizing the electrode volume variation upon lithiation/de-lithiation. It is finally demonstrated that the use of 8 wt.% of PAA-250k in the electrode formulation leads to the best performance in terms of high rate performance and long term stability.

Combining Optimized Particle Morphology with a Niobium-Based Coating for Long Cycling-Life, High-Voltage Lithium-Ion Batteries.

Morphologically optimized LiNi0.5 Mn1.5 O4 (LMNO-0) particles were treated with LiNbO3 to prepare a homogeneously coated material (LMNO-Nb) as cathode in batteries. Graphite/LMNO-Nb full cells present a twofold higher cycling life than cells assembled using uncoated LMNO-0 (graphite/LMNO-0 cell): Graphite/LMNO-0 cells achieve 80 % of the initial capacity after more than 300 cycles whereas for graphite/LMNO-Nb cells this is the case for more than 600 cycles. Impedance spectroscopy measurements reveal significantly lower film and charge-transfer resistances for graphite/LMNO-Nb cells than for graphite/LMNO-0 cells during cycling. Reduced resistances suggest slower aging related to film thickening and increase of charge-transfer resistances when using LMNO-Nb cathodes. Tests at 45 °C confirm the good electrochemical performance of the investigated graphite/LMNO cells while the cycling stability of full cells is considerably lowered under these conditions.

A High-Voltage and High-Capacity Li1+x Ni0.5 Mn1.5 O4 Cathode Material: From Synthesis to Full Lithium-Ion Cells.

We report Co-free, Li-rich Li1+x Ni0.5 Mn1.5 O4 (0