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.

Quantitative FIB/SEM tomogram analysis of closed and open porosity of spheroidized graphite anode materials for LiBs applications.

The electrochemical behaviour of rounded graphite particles as anode material in a lithium-ion battery strongly depends on the particle properties. The spheroidization process directly affects these properties, including the open porosity that determines the extent of direct contact between liquid electrolyte and carbon surface. Therefore, the quantification of the proportion between open and closed pores is of great interest. Here, we quantify the open and closed porosity of spheroidized porous graphite particles from FIB-SEM tomograms. Quantification is achieved based on two developments: (1) a new sample preparation strategy and (2) a newly developed image evaluation scheme based on neural networks. The sample preparation strategy involves embedding of many graphite powder particles in indium enabling the investigation of several graphite particles in one FIB/SEM tomogram with high stability and with high contrast between the conductive embedding material and porous graphite. A quantitative evaluation of closed and open porosity is achieved by machine learning in form of convolutional neural networks. The convolutional neural network is used to detect the bulk graphite and by further morphological operations, closed and open pores are identified. An error is determined by comparing automatically created quantifications with manual reference values. Our porosity data for two differently spheroidized graphite samples agree qualitatively well with corresponding results from nitrogen physisorption measurements. This approach may allow quantitative data evaluation from porous powders and support understanding of the correlation to the electrochemical behaviour in the lithium-ion battery.

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.

Detection of Copper Deposition on Anodes of Over-Discharged Lithium Ion Cells by GD-OES Depth Profiling.

A method based on glow discharge optical emission spectroscopy (GD-OES) depth profiling is developed to detect copper deposition on graphite electrodes for the first time. Commercial 18650 cells with graphite anodes were subject to Cu dissolution by over-discharge to 0 V. On a first approach, the depth profiles for Cu show significant differences for over-discharged cells compared to a baseline graphite electrode from cells discharged to the end-of-discharge voltage. An accumulation of Cu is found on the anode surface by GD-OES, which is consistent with SEM and EDX. The trend of the total Cu amount is compared with ICP-OES measurements.

Ternary Cathode Blend Electrodes for Environmentally Friendly Lithium-Ion Batteries.

The combination of two active materials into one positive electrode of a lithium-ion battery is an uncomplicated and cost-effective way to combine the advantages of different active materials while reducing the disadvantages of each material. In this work, the concept of binary blends is extended to ternary compositions. The combination of three different active materials provides high versatility in designing the properties of an electrode. Therefore, the unique properties of a layered oxide, phospho-olivine, and spinel type material are mixed to design a high-energy cathode with improved environmental friendliness. Four different compositions of blend electrodes are investigated, each with individual benefits. Synergistic effects improved the rate capability, power density, thermal and chemical stability simultaneously. The blend electrode consisting of 75 % NMC, 12.5 % LMFP and LMO provides similar energy and power density as a pure NMC electrode while economizing 25 % cobalt and nickel.

Stripping and Plating a Magnesium Metal Anode in Bromide-Based Non-Nucleophilic Electrolytes.

A non-nucleophilic Hauser base hexamethyldisilazide (HMDS) magnesium electrolyte possesses inherent properties required for a magnesium-sulfur battery. However, the development of full cell batteries using HMDSCl-based electrolytes is still hampered by a low coulombic efficiency. A new electrolyte formulation of non-nucleophilic HMDS magnesium containing bromide as a halide instead of chloride was obtained through a simple and straightforward synthesis route. The electrochemistry of magnesium was investigated through plating and stripping in three different HMDSBr-based electrolytes: Mg(HMDS)Br, Mg(HMDS)Br-BEt3 , and Mg(HMDS)Br-AlEt3 dissolved in tetrahydrofuran. The different magnesium species present in the electrolytes were determined using NMR. Weak electron-withdrawing Lewis acids, BEt3 and AlEt3 were used intentionally and their impact was investigated. Contrary to expectation, the substitution of chloride by bromide does not drastically narrow the electrochemical stability window. HMDSBr-based electrolytes demonstrated long-term (1000 cycles) stable reversibility and highly efficient (≈99 %) magnesium plating/tripping without a high ratio of bromide compared with the MgHMDSCl-based electrolytes. The aprotic electrolyte shows comparatively high anodic stability (≈2.4 V vs. Mg/Mg2+ ) and high ionic conductivity of 1.16 mS cm-1 at room temperature. Plating of magnesium with low overpotential (<188 mV) revealed a morphology dependence on the electrolyte type with a shiny metallic homogenous layer, suggesting a rational balance between the nucleation and growth process in HMDSBr-based electrolytes.

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.

Low-Temperature Charging and Aging Mechanisms of Si/C Composite Anodes in Li-Ion Batteries: An Operando Neutron Scattering Study.

The addition of Si compounds to graphite anodes has become an attractive way of increasing the practical specific energies in Li-ion cells. Previous studies involving Si/C anodes lacked direct insight into the processes occurring in full cells during low-temperature operation. In this study, a powerful combination of operando neutron diffraction, electrochemical tests, and post-mortem analysis is used for the investigation of Li-ion cells. 18650-type cylindrical cells in two different aging states are investigated by operando neutron diffraction. The experiments reveal deep insights and important trends in low-temperature charging mechanisms involving intercalation, alloying, Li metal deposition, and relaxation processes as a function of charging C-rates and temperatures. Additionally, the main aging mechanism caused by long-term cycling and interesting synergistic effects of Si and graphite are elucidated.

Biphenyl-Bridged Organosilica as a Precursor for Mesoporous Silicon Oxycarbide and Its Application in Lithium and Sodium Ion Batteries.

Silicon oxycarbides (SiOC) are an interesting alternative to state-of-the-art lithium battery anode materials, such as graphite, due to potentially higher capacities and rate capabilities. Recently, it was also shown that this class of materials shows great prospects towards sodium ion batteries. Yet, bulk SiOCs are still severely restricted with regard to their electrochemical performance. In the course of this work, a novel and facile strategy towards the synthesis of mesoporous and carbon-rich SiOC will be presented. To achieve this goal, 4,4'-bis(triethoxysilyl)-1,1'-biphenyl was sol-gel processed in the presence of the triblock copolymer Pluronic P123. After the removal of the surfactant using Soxhlet extraction the organosilica material was subsequently carbonized under an inert gas atmosphere at 1000 °C. The resulting black powder was able to maintain all structural features and the porosity of the initial organosilica precursor making it an interesting candidate as an anode material for both sodium and lithium ion batteries. To get a detailed insight into the electrochemical properties of the novel material in the respective battery systems, electrodes from the nanostructured SiOC were studied in half-cells with galvanostatic charge/discharge measurements. It will be shown that nanostructuring of SiOC is a viable strategy in order to outperform commercially applied competitors.

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

Study of Water-Based Lithium Titanate Electrode Processing: The Role of pH and Binder Molecular Structure.

This work elucidates the manufacturing of lithium titanate (Li4Ti5O12, LTO) electrodes via the aqueous process using sodium carboxymethylcellulose (CMC), guar gum (GG) or pectin as binders. To avoid aluminum current collector dissolution due to the rising slurries' pH, phosphoric acid (PA) is used as a pH-modifier. The electrodes are characterized in terms of morphology, adhesion strength and electrochemical performance. In the absence of phosphoric acid, hydrogen evolution occurs upon coating the slurry onto the aluminum substrate, resulting in the formation of cavities in the coated electrode, as well as poor cohesion on the current collector itself. Consequently, the electrochemical performance of the coated electrodes is also improved by the addition of PA in the slurries. At a 5C rate, CMC/PA-based electrodes delivered 144 mAh·g-1, while PA-free electrodes reached only 124 mAh·g-1. When GG and pectin are used as binders, the adhesion of the coated layers to the current collector is reduced; however, the electrodes show comparable, if not slightly better, electrochemical performance than those based on CMC. Full lithium-ion cells, utilizing CMC/PA-made Li[Ni0.33Mn0.33Co0.33]O2 (NMC) cathodes and LTO anodes offer a stable discharge capacity of ~120 mAh·g-1(NMC) with high coulombic efficiencies.

An in situ SEM-FIB-based method for contrast enhancement and tomographic reconstruction for structural quantification of porous carbon electrodes.

A new in situ Scanning Electron Microscope-Focused Ion Beam-based method to study porous carbon electrodes involving Pt filling of pores from gaseous precursors has been demonstrated to show drastically improved image contrast between the carbon and porous phases when compared with the Si-resin vacuum-impregnation method. Whereas, the latter method offered up to 20% contrast, the new method offers remarkably higher contrast (42%), which enabled fast semi-automated demarcation of carbon boundaries and subsequent binarization of the images with very high fidelity. Tomographic reconstruction of the porous carbon electrode was then obtained from which several morphological parameters were quantified. The porosity was found to be 72±2%. The axial and radial tortuosites were 1.45±0.04 and 1.43±0.04, respectively. Pore size, which is defined to be the distance from the medial axis of the pore to the nearest solid boundary, was quantified. Average pore size determined from the pore size distribution was 90 nm and the corresponding 1 sigma ranges from 45 to 134 nm. Surface-to-volume ratio of the carbon phase was 46.5 µm(-1). The ratio of total surface area to the total volume of electrode including pores (i.e., specific surface area) was 13 µm(-1).

Electrochemical and electron microscopic characterization of Super-P based cathodes for Li-O2 batteries.

Aprotic rechargeable Li-O2 batteries are currently receiving considerable interest because they can possibly offer significantly higher energy densities than conventional Li-ion batteries. The electrochemical behavior of Li-O2 batteries containing bis(trifluoromethane)sulfonimide lithium salt (LiTFSI)/tetraglyme electrolyte were investigated by galvanostatic cycling and electrochemical impedance spectroscopy measurements. Ex-situ X-ray diffraction and scanning electron microscopy were used to evaluate the formation/dissolution of Li2O2 particles at the cathode side during the operation of Li-O2 cells.

TiO2 anatase nanoparticle networks: synthesis, structure, and electrochemical performance.

Nanocrystalline anatase TiO(2) materials with different specific surface areas and pore size distributions are prepared via sol-gel and miniemulsion routes in the presence of surfactants. The samples are characterized by X-ray diffraction, nitrogen sorption, transmission electron microscopy, and electrochemical measurements. The materials show a pure anatase phase with average crystallite size of about 10 nm. The nitrogen sorption analysis reveals specific surface areas ranging from 25 to 150 m(2) g(-1) . It is demonstrated that the electrochemical performance of this material strongly depends on morphology. The mesoporous TiO(2) samples exhibit excellent high rate capabilities and good cycling stability.

Tris(oxalato)phosphorus acid and its lithium salt.

The conversion of three equivalents of anhydrous oxalic acid with phosphorus pentachloride yields tris(oxalato)phosphorus acid 1, which crystallizes from diethyl ether solutions as protonated diethyl ether complex [(Et2O)2H](+)[P(C2O3)3)]-. The superacidic compound can be used as catalyst for Friedel-Crafts-type reactions. Upon neutralization with lithium hydride, the lithium salt Li[P(C2O3)3] 2 is obtained, which is highly soluble in aprotic solvents and which exhibits a wide voltage window. Thus, the lithium compound is a promising candidate as electrolyte for high performance non-aqueous batteries.