Lithium ion battery performance at high charge/discharge rates is largely determined by the ionic resistivity of an electrode and separator which are filled with electrolyte. Key to understand and to model ohmic losses in porous battery components is porosity as well as tortuosity. In the first part, we use impedance spectroscopy measurements in a new experimental setup to obtain the tortuosities and MacMullin numbers of some commonly used separators, demonstrating experimental errors of <8%. In the second part, we present impedance measurements of electrodes in symmetric cells using a blocking electrode configuration, which is obtained by using a non-intercalating electrolyte. The effective ionic resistivity of the electrode can be fit with a transmission-line model, allowing us to quantify the porosity dependent MacMullin numbers and tortuosities of electrodes with different active materials and different conductive carbon content. Best agreement between the transmission-line model and the impedance data is found when constant-phase elements rather than simple capacitors are used. Motivation.-Advanced battery models are a valuable tool for evaluating the performance, safety, and life-time of lithium ion batteries, since they can provide insight into the kinetics and the transport characteristics of batteries, which are not or only partially accessible by experiments. To obtain quantitative and meaningful numerical results, the choice of appropriate physical models and boundary conditions with the corresponding, accurately determined, kinetic and transport parameters are key issues. For numerical simulations of battery systems, the ion-transport model for concentrated electrolyte solutions introduced by Newman et al.1 is frequently used. Since the microscopic geometry of actually used porous electrodes and separators are largely unknown, a homogenization approach is applied for the macroscopic description of porous media. In this case, the influence of the microstructure on the macroscopic behavior is modeled by additional geometric parameters such as the porosity ε and the tortuosity τ. The porosity ε is a well-defined property of a porous medium, which can be determined easily. In contrast, the effective tortuosity of separators and particularly of electrodes are more difficult to quantify, and, to further complicate the matter, many different definitions for the tortuosity τ are used in the literature. Thus, the different tortuosity definitions will be presented prior to reviewing the literature concerned with determining the tortuosity or the effective ionic conductivity of porous battery separators and electrodes.

The performance degradation of graphite/LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC) lithium ion cells, charged and discharged up to 300 cycles at different operating conditions of temperature and upper cutoff potential (4.2V/25 • C, 4.2V/60 • C, 4.6V/25 • C) was investigated. A combination of electrochemical methods with X-ray diffraction (XRD) both in situ and ex situ as well as neutron induced PromptGamma-Activation-Analysis (PGAA) allowed us to elucidate the main failure mechanisms of the investigated lithium ion cells. In situ XRD investigations of the NMC material revealed that the first cycle irreversible capacity is the cause of slow lithium diffusion kinetics. In full-cells, however, this "lost" lithium ions can be used to build up the SEI of the graphite electrode during the initial formation cycle. A new systematic approach to correlate the lithium content in NMC with its lattice parameters (c, a) allows a convenient quantification of the loss of active lithium in aged cells by determining the c/a ratio of harvested NMC cathodes in the discharged state using ex situ XRD. Besides loss of active lithium, transition metal dissolution/deposition on graphite and growth of cell impedance strongly effect cell aging, especially at elevated temperatures and high upper cutoff potentials. Besides their current use in portable power electronics, lithium ion batteries have recently been used for battery electric vehicles (BEV) and are envisioned for large-scale energy storage. For the latter applications, life times of >10 years are required so that it is essential to understand and quantify the mechanisms that contribute to battery failure. Among the commercially available lithium-ion battery chemistries, 1,2 the graphite/LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC) system is one of the materials currently envisioned for automotive applications. 3 This cathode material demonstrates high capacity, good structural stability due to its small volume changes (<2%) during Li insertion and extraction, and high thermal stability in the charged state. [4][5][6] In addition, this material could theoretically be operated with high charge cutoff potentials up to 5.0 V, as its bulk structure is claimed to be stabilized by the presence of Mn 4+ , 7 even though other authors suggest that irreversible structural changes occur at these very high potentials and at high temperature.8 Due to its sloped potential profile, the capacity and also the average cell voltage increase with increasing charging potential. 7,9 Despite the improved safety and cycling performance of NMC material, operating NMC based cells (full-cells or half-cells) at elevated temperatures or at high charge potential leads to poor cycle life. [10][11][12][13] During cycling of graphite/NMC full-cells, transition metal dissolution from the NMC material is found to be a crucial factor controlling capacity fade. 11,12 In one of these studies, Zheng et al. demonstrated that upper cutoff potentials of >4.3 V lead to transition metal dissolution from NMC and thus compromise cycling performa...

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Small-angle neutron scattering is a tool providing information on nanostructures of objects in the order of 1-300 nm. In this experiment a pouch bag lithium ion battery cell was investigated with SANS ex situ, in situ and in operando during charging and discharging. LiNi 0.33 Mn 0.33 Co 0.33 O 2 was used as cathode and graphite as anode material. The small-angle neutron scattering measurements were performed on the SANS-1 instrument at the FRM II neutron source of the Heinz Maier-Leibnitz Zentrum (MLZ) in Garching, Germany. Ex situ measurements of components of the cell as well as static in situ and dynamic in operando SANS experiments were performed with a complete Li-ion pouch bag cell. The cell was charged and discharged twice with C/3 and small-angle neutron scattering data were collected during the measurements. The observed intensity data were then evaluated and changes of the total scattering in the measured Q-range are correlated to the lithiation processes occurring inside the cell. Thus we can show that SANS can be used as a tool to monitor kinetic processes in Li-ion batteries in operando and non-destructively. Li-ion batteries have been used widely as power sources in transportable electronic devices and new markets such as hybrid and all battery electric vehicles are developing.1 This has also raised an enhanced interest in the development of analytical methods to study batteries during operation ("in operando"). Besides the improvement in energy and power density, researchers are trying to prolong the lifetime of lithium ion batteries. Cycle and storage life of Li-ion batteries are critical for electric vehicle or stationary power storage applications. A major degradation effect is the continuous decomposition of electrolyte -leading also to a growing solid electrolyte interface (SEI), a passivating layer on typically the anode active material (graphite), thus resulting in loss of conductivity and higher cell resistance. For the cathode phase transitions, structural disorder and metal dissolution are major aging effects. Corrosion of various materials in the battery and mechanical contact loss of active particles or current collectors are also an issue.2-4 One major goal is to understand the general reaction mechanism of the Li-intercalation process in the anode respectively cathode materials. The fundamental understanding of battery processes is a key for improving battery performance (e.g., in terms of energy density and power density) and lifetime.The small-angle scattering method is commonly used to gain information about the nanostructure of the investigated materials (i.e., size, volume and shape of particles). In combination with the special properties of neutrons, like the high penetration depth in materials, small-angle neutron scattering (SANS) can be used as a powerful tool for in situ investigations of Li-ion batteries. SANS can help to understand changes on the nanoscale of particles in cycled cells and during cell cycling. Our study's primary goal is to adapt, develop and extend this ...

Small-angle neutron scattering (SANS) was recently applied to the in situ and operando study of the charge/discharge process in Li-ion battery full-cells based on a pouch cell design. Here, this work is continued in a half-cell with a graphite electrode cycled versus a metallic lithium counter electrode, in a study conducted on the SANS-1 instrument of the neutron source FRM II at the Heinz Maier-Leibnitz Zentrum in Garching, Germany. It is confirmed that the SANS integrated intensity signal varies as a function of graphite lithiation, and this variation can be explained by changes in the squared difference in scattering length density between graphite and the electrolyte. The scattering contrast change upon graphite lithiation/delithiation calculated from a multi-phase neutron scattering model is in good agreement with the experimentally measured values. Due to the finite coherence length, the observed SANS contrast, which mostly stems from scattering between the (lithiated) graphite and the electrolyte phase, contains local information on the mesoscopic scale, which allows the development of lithiated phases in the graphite to be followed. The shape of the SANS signal curve can be explained by a core-shell model with step-wise (de)lithiation from the surface. Here, for the first time, X-ray diffraction, SANS and theory are combined to give a full picture of graphite lithiation in a half-cell. The goal of this contribution is to confirm the correlation between the integrated SANS data obtained during operando measurements of an Li-ion half-cell and the electrochemical processes of lithiation/delithiation in micro-scaled graphite particles. For a deeper understanding of this correlation, modelling and experimental data for SANS and results from X-ray diffraction were taken into account. research papers J. Appl. Cryst. (2020). 53, 210-221 Johannes Hattendorff et al. SANS operando study of Li-ion half-cells 211 research papers 212 Johannes Hattendorff et al. SANS operando study of Li-ion half-cells J. Appl. Cryst. (2020). 53, 210-221 Figure 2An operando X-ray diffractogram recorded from the Li/graphite half-cell cycled at C/5, showing the presence of well defined lithiation stages, which indicates good homogeneity across the electrode. J. Appl. Cryst. (2020). 53, 210-221 Johannes Hattendorff et al. SANS operando study of Li-ion half-cells 219 Figure 9An illustration of the calculation mesh and the coherence volumes centred at each mesh element k, (a) for small particles and (b) for a large particle with two phases, e.g. active material and electrolyte or solvent. One square is of the order of 30 nm.