High-Voltage Instability of Vinylene Carbonate (VC): Impact of Formed Poly-VC on Interphases and Toxicity.

Full exhaustion in specific energy/energy density of state-of-the-art LiNix Coy Mnz O2 (NCM)-based Li-ion batteries (LIB) is currently limited for reasons of NCM stability by upper cut-off voltages (UCV) below 4.3 V. At higher UCV, structural decomposition triggers electrode crosstalk in the course of enhanced transition metal dissolution and leads to severe specific capacity/energy fade; in the worst case to a sudden death phenomenon (roll-over failure). The additive lithium difluorophosphate (LiDFP) is known to suppress this by scavenging dissolved metals, but at the cost of enhanced toxicity due to the formation of organofluorophosphates (OFPs). Addition of film-forming electrolyte additives like vinylene carbonate (VC) can intrinsically decrease OFP formation in thermally aged LiDFP-containing electrolytes, though the benefit of this dual-additive approach can be questioned at higher UCVs. In this work, VC is shown to decrease the formation of potentially toxic OFPs within the electrolyte during cycling at conventional UCVs but triggers OFP formation at higher UCVs. The electrolyte contains soluble VC-polymerization products. These products are formed at the cathode during VC oxidation (and are found within the cathode electrolyte interphase (CEI), suggesting an OFP electrode crosstalk of VC decomposition species, as the OFP-precursor molecules are shown to be formed at the anode.

State-of-charge of individual active material particles in lithium ion batteries: a perspective of analytical techniques and their capabilities.

The state-of-charge (SOC) is an essential parameter for battery management systems to reflect and monitor the remaining capacity of individual battery cells. In addition to its application at the cell level, the SOC also plays an important role in the investigation of redox processes of cathode active materials (CAMs) in lithium ion batteries (LIBs) during electrochemical cycling. These processes can be influenced by a large variety of factors such as active material properties, inhomogeneities of the electrode, degradation phenomena and the charge/discharge protocol during cycling. Consequently, non-uniform redox reactions can occur, resulting in charge heterogeneities of the active material. This heterogeneity can translate into accelerated aging of the CAM and a reduction in reversible capacity of the battery cell, since the active material is not fully utilized. To understand and monitor the SOC heterogeneity at the mesoscale, a wide range of techniques have been implemented in the past. In this perspective an overview of current state-of-the-art techniques to evaluate charge heterogeneities of CAMs in LIBs is presented. Therefore, techniques which utilize synchrotron radiation like X-ray absorption near-edge structure (XANES) and transmission X-ray spectroscopy (TXM) are presented as well as Raman spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Next to these established techniques, classification single particle inductively coupled plasma optical emission spectroscopy (CL-SP-ICP-OES) as a new approach is also discussed in this perspective. For these techniques, the areas of application, advantages as well as drawbacks are highlighted and discussed.

Accessing the Primary Solid-Electrolyte Interphase on Lithium Metal: A Method for Low-Concentration Compound Analysis.

Invited for this month's cover is the group of Martin Winter at the University of Münster. The image shows idea of the developed sample treatment method enabling the accumulation of solid electrolyte interphase originating compounds. The Research Article itself is available at 10.1002/cssc.202201912.

Accessing the Primary Solid-Electrolyte Interphase on Lithium Metal: A Method for Low-Concentration Compound Analysis.

Despite large research efforts in the fields of lithium ion and lithium metal batteries, there are still unanswered questions. One of them is the formation of the solid-electrolyte interphase (SEI) in lithium-metal-anode-based battery systems. Until now, a compound profile analysis of the SEI on lithium metal was challenging as the amounts of many compounds after simple contact of lithium metal and the electrolyte were too low for detection with analytical methods. This study presents a novel approach on unravelling the SEI compound profile through accumulation in the gas, liquid electrolyte, and solid phase. The method uses the intrinsic behavior of lithium metal to spontaneously react with the liquid electrolyte. In combination with complementary, state-of-the-art analytical instrumentation and methods, this approach provides qualitative and quantitative results on all three phases revealing the vast variety of compounds formed in carbonate-based electrolytes.

State-of-Charge Distribution of Single-Crystalline NMC532 Cathodes in Lithium-Ion Batteries: A Critical Look at the Mesoscale.

The electrochemical response of layered lithium transition metal oxides LiMO2 [M=Ni, Mn, Co; e. g., Li(Ni0.5 Mn0.3 Co0.2 )O2 (NMC532)] with single-crystalline architecture to slow and fast charging protocols and the implication of incomplete and heterogeneous redox reactions on the active material utilization during cycling were the subject of this work. The role of the active material size and the influence of the local microstructural and chemical ramifications in the composite electrode on the evolution of heterogeneous state of charge (SOC) distribution were deciphered. For this, classification-single-particle inductively coupled plasma optical emission spectroscopy (CL-SP-ICP-OES) was comprehensively supplemented by various post mortem analytical techniques. The presented results question the impact of surface-dependent failure mechanisms of single crystals for the evolution of SOC heterogeneity and identify the deficient structural flexibility of the composite electrode framework as the main driver for the observed non-uniform active material utilization.

Direct Multielement Analysis of Polydisperse Microparticles by Classification-Single-Particle ICP-OES in the Field of Lithium-Ion Battery Electrode Materials.

The chemical and structural complexity of lithium-ion battery electrodes and their constituting materials requires comprehensive characterization techniques to reveal degradation phenomena at the mesoscale. For the first time, application of single-particle inductively coupled plasma-optical emission spectroscopy enables the investigation of the chemomechanical interplay on the particle level of lithium transition-metal oxide [e.g., Li(Ni1/3Co1/3Mn1/3)O2] cathode materials. The sample-inherent polydisperse size distribution of particles ranging up to 10 µm was effectively restricted with the use of a custom-made gravitational-counter-flow classifier to facilitate complete particle vaporization and excitation. After classification, the particles were transported directly to the plasma by means of an argon flow to prevent chemical alterations in aqueous media due to potentially occurring Li+-H+ exchange reactions. The size-separated particles were monitored online by flow cell particle analysis (FPA). The influence of different gas flow settings and plasma parameters on the peak emission intensity of Li and Mn was evaluated. A particle size detection limit of ∼0.5 µm was estimated based on the 3σ criterion of the baselines and the measured peak intensities for Li and Mn considering the particle size distribution as obtained by FPA. The corresponding analyte masses at the detection limits were ∼30 and ∼180 fg for Li and Mn, respectively. Furthermore, an approach for a matrix-matched external calibration with electrochemically delithiated lithium transition-metal oxides is presented.

A method for quantitative analysis of gases evolving during formation applied on LiNi0.6Mn0.2Co0.2O2 ∣∣ natural graphite lithium ion battery cells using gas chromatography - barrier discharge ionization detector.

To understand the overall processes behind the decomposition of state-of-the-art organic liquid electrolytes in lithium ion batteries (LIBs), it is necessary to investigate and quantify the permanent gases and light hydrocarbons evolving during electrolyte decomposition. In this work a convenient way of sampling gas from pouch cells without any previous preparation of the cell as well as a comprehensive gas chromatographic (GC) investigation of the gas phase is shown. A barrier discharge ionization detector (BID) was utilized for gas quantification and a multi component gas standard in combination with a gas mixing device was implemented to prepare calibration standards for validation. Therefore, sensitivity, linearity and reproducibility as well as the limits of detection (LOD) and limits of quantification (LOQ) were determined. Gas samples from pouch cells using LiNi0.6Mn0.2Co0.2O2 as cathode material and natural graphite (NMC622 ∣∣ NG) as anode material were analysed after formation. Gas volume and gas composition are key factors for a sufficient formation of LIBs and of interest for research with respect to the development of new materials and additives.

Preparative hydrophilic interaction liquid chromatography of acidic organofluorophosphates formed in lithium ion battery electrolytes.

The expansion of lithium ion battery (LIB) application is accompanied by the growth of battery pack sizes. This progression emphasizes the consideration of electrolyte safety as well as environmental aspects in case of abuse, accident, or recycling. Hexafluorophosphate is one of the most commonly used conducting salt anions in electrolytes. It has great potential to degrade to various acidic and non-acidic organo(fluoro)phosphates with presence of water and during battery cell operation. Consequently, toxicological investigation on these organo(fluoro)phosphates has emerged because they either have structural similarities as chemical warfare agents or play a widespread physiological role as phosphates in the human body. This circumstance underlines the need of isolated examination of these compounds for safety assessment. In this work, we used hydrophilic interaction liquid chromatography for the extraction of acidic organofluorophosphates from thermally aged LIB electrolytes. The developed two-step fractionation method provided high separation selectivity towards acidic head groups, which allowed the separation of undesired matrix and target compounds. These findings facilitate isolated toxicological investigations on organofluorophosphates that are beneficial for environmental and safety research, the battery cell industry, and human safety surveillance in regard to aged LIB electrolytes.

Analysis of acidic organo(fluoro)phosphates as decomposition product of lithium ion battery electrolytes via derivatization gas chromatography-mass spectrometry.

Nowadays, lithium ion batteries (LIBs) are the preferred energy supply for consumer electronics and electric vehicles. But, intrinsic reactions in the LIB system lead to a reduced battery life and impaired safety properties. Organo(fluoro)phosphates (O(F)Ps) as decomposition product of the conducting salt and the organic carbonate solvent molecules of the LIB electrolyte are of high interest due to structural similarities to chemical warfare agents and therefore a supposedly high toxicity. The reaction cascade shows a large variety of O(F)Ps including a wide spread of polarity. In this study, an approach for the investigation of acidic O(F)Ps with gas chromatography-mass spectrometry after derivatization is conducted. Analysis of a model substance, spike experiments in the electrolyte matrix and investigation of thermally treated electrolyte were performed. As a result, derivatization could be achieved in less than three minutes and screening could successfully be shown without impairing the originality of the sample (matrix). This derivatization approach shows the possibility of analysis for both acidic and non-acidic O(F)Ps using only one method.

A battery cell for in situ NMR measurements of liquid electrolytes.

This work describes the development of an in situ battery cell to monitor liquid electrolytes by means of NMR spectroscopy. The suitability of this approach is confirmed by NMR measurements and electrochemical analysis. The cell allows for undistorted high resolution NMR spectroscopy. Furthermore, constant current cycling data, C-rate sequences and impedance measurements indicates a long cycle life as well as reasonable specific capacities and Ohmic resistances.

Two-dimensional ion chromatography for the separation of ionic organophosphates generated in thermally decomposed lithium hexafluorophosphate-based lithium ion battery electrolytes.

A two-dimensional ion chromatography (IC/IC) technique with heart-cutting mode for the separation of ionic organophosphates was developed. These analytes are generated during thermal degradation of three different commercially available Selectilyte™ lithium ion battery electrolytes. The composition of the investigated electrolytes is based on 1M lithium hexafluorophosphate (LiPF6) dissolved in ethylene carbonate/dimethyl carbonate (50:50wt%, LP30), ethylene carbonate/diethyl carbonate (50:50wt%, LP40) and ethylene carbonate/ethyl methyl carbonate (50:50wt%, LP50). The organophosphates were pre-separated from PF6(-) anion on the low capacity A Supp 4 column, which was eluted with a gradient step containing acetonitrile. The fraction containing analytes was retarded on a pre-concentration column and after that transferred to the high capacity columns, where the separation was performed isocratically. Different stationary phases and eluents were applied on the 2nd dimension for the investigation of retention times, whereas the highly promising results were obtained with a high capacitive A Supp 10 column. The organophosphates generated in LP30 and LP40 electrolytes could be separated by application of an aqueous NaOH eluent providing fast analysis time within 35min. For the separation of the organophosphates of LP50 electrolyte due to its complexity a NaOH eluent containing a mixture of methanol/H2O was necessary. In addition, the developed two dimensional IC method was hyphenated to an inductively coupled plasma mass spectrometer (ICP-MS) using aqueous NaOH without organic modifiers. This proof of principle measurement was carried out for future quantitative investigation regarding the concentration of the ionic organophosphates. Furthermore, the chemical stability of several ionic organophosphates in water and acetonitrile at room temperature over a period of 10h was investigated. In both solvents no decomposition of the investigated analytes was observed and therefore water as solvent for dilution of samples was proved as suitable.