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Electrolyte additives are indispensable to enhance the performance of Li-ion batteries. Lithium bis(oxalato)borate (LiBOB) has been explored for many years, as it improves both cathode and anode performance. No consensus regarding its reaction mechanisms has, however, been established. A model operando study combining attenuated total reflection infrared spectroscopy (ATR-FTIR), electrochemical quartz crystal microbalance (EQCM), and online electrochemical mass spectrometry (OEMS) is herein presented to elucidate LiBOB reduction and electrode/electrolyte interphases thus formed. Reduction of the BOB– ion sets in at ∼1.8 V with solid lithium oxalate and soluble oxalatoborates as the main products. The reduced BOB– ion also reacts with itself and its environment to evolve CO2, which in turn impacts the interphase formed on the negative electrode. This study provides further insights into the reduction pathways of LiBOB and how they contribute to the interphase formation.

The reliance on Li-ion batteries is increasing as we transition from fossil fuels to renewable energy sources. Despite their widespread use, a gap remains in understanding certain processes within these batteries, especially regarding the solid electrolyte interphase (SEI) and the impact of side reactions on Li-ion batteries. A custom-made Online Electrochemical Mass Spectrometry (OEMS) instrument was designed to explore these aspects. The OEMS instrument was validated through the study of gas-evolving reactions in the classic LiCoO2 | Graphite system. In-depth studies focusing on the reaction pathways of ethylene carbonate, the archetype Li-ion battery electrolyte solvent, identified the specific reaction pathways contributing to SEI formation. Moreover, ethylene carbonate’s interaction with residual contaminants like OH– from H2O reduction was explored. It was revealed that the integrity of the SEI can be compromised by minor amounts of contaminants, establishing a competitive dynamic at the negative electrode surface between ethylene carbonate and residual contaminants such as H2O and HF. Additionally, the roles of additives like vinylene carbonate and lithium bis(oxolato) borate in SEI formation were explored. Vinylene carbonate was shown to form a layer on the negative electrode, but also scavenge protons and H2O, revealing that it is a multi-functional additive. Lithium bis(oxolato) borate on the other hand formed an SEI layer before H2O reduction, blocking the residual contaminant and ethylene carbonate from reaching the electrode surface. By providing insights into the negative electrode’s interphase and SEI formation through a custom-made OEMS instrument, this research underscores the complexity of reaction pathways and the necessity of considering both major and minor, as well as, primary and secondary reactions for a holistic understanding of Li-ion batteries.

Ethylene carbonate (EC) and vinylene carbonate (VC) are the archetypical electrolyte solvent and additive in Li-ion batteries (LIBs), respectively. However, our understanding of their reaction pathways remains incomplete. Herein, the reaction pathways of EC and VC are explored by using online electrochemical mass spectrometry complemented by nuclear magnetic resonance analysis. For EC, reduction occurs through two distinct pathways <0.8 V vs Li+/Li, one yielding C2H4 and the other yielding CO, depending on the electrode potential and the EC concentration. The CO-releasing pathway does not contribute to the solid electrolyte interphase formation. For VC, reduction commences at <1.9 V, but CO2 gas evolution proceeds through a chemical step via a nucleophilic attack and VC ring opening. Additionally, VC scavenges H2O and reduced protons via hydrolysis and via proton abstraction from the carbon electrode to form EC. Our study uncovers further reaction pathways and underscores the unique properties of EC and VC, both individually and in combination, and elucidates their roles in influencing the formation process in Li-ion batteries.

Vinylene carbonate (VC) is the most commonly applied performance-enhancing electrolyte additives in Li-ion batteries to date. Despite numerous studies, there is a lack of consensus regarding the various reaction pathways of VC and their implications. VC has primarily been observed to either polymerize forming poly(vinylene carbonate) (poly(VC)) or decompose releasing major amounts of CO2, two seemingly contradictory processes. Herein, we present evidence of additional reaction pathways of VC highlighting its role as a H2O scavenging agent. In contrast to the typical electrolyte solvent ethylene carbonate, VC reacts much more rapidly with water impurities, especially when in contact with hydroxides, forming products less likely to influence cell performance. Efficient removal of water and hydroxides is essential to preserve the stability of Li-ion electrolyte solvent and salt, hence guaranteeing a long lifetime of the battery. Model studies pinpointing reaction pathways of electrolytes and additives, as presented herein, are critical not only to improve modern Li-ion cells but also to establish design principles for future battery chemistries.

Triethyl phosphate (TEP) is a cheap, environmentally benign, and non‐flammable electrolyte solvent, whose implementation in lithium‐ion batteries is held back by its co‐intercalation into graphite anodes, resulting in exfoliation of the graphite structure. In this work, the electrode‐electrolyte interface behaviour of electrolytes containing up to 100% TEP was investigated and correlated to electrochemical performance. High capacity and stable cycling are maintained with up to 30% TEP in carbonate ester‐based electrolytes, but above this threshold the reversibility of Li+ intercalation into graphite drops sharply to almost zero. This represents a potential route to improved battery safety, while TEP can also improve safety indirectly by enabling the use of lithium bis(oxalato borate), a fluorine‐free salt with limited solubility in traditional electrolytes. To understand the poor performance at TEP concentrations of >30%, its solvation behaviour and interfacial reaction chemistry were studied. Nuclear magnetic resonance spectroscopy data confirms changes in the Li+ solvation shell above 30% TEP, while operando gas analysis indicates extensive gas evolution from TEP decomposition at the electrode above the threshold concentration, which is almost entirely absent below it. X‐ray photoelectron spectroscopy depth profiling of electrodes demonstrates poor passivation by the solid electrolyte interphase above 30% TEP and significant graphite exfoliation.

Ethylene carbonate (EC) is the archetype solvent in Li-ion batteries. Still, questions remain regarding the numerous possible reaction pathways of EC. Although the reaction pathway involving direct EC reduction and SEI formation is most commonly discussed, EC ring-opening is often observed, but seldomly addressed, especially with respect to SEI formation. By applying Online Electrochemical Mass Spectrometry, the EC ring-opening reaction on carbon is found to start already at similar to 2.5 V vs Li+/Li as initiated by oxygenic carbon surface groups. Later, OH- generated from H2O reduction reaction at similar to 1.6 V further propagates EC to ring-open. The EC reduction reaction occurs <0.9 V but is suppressed depending on the extent of EC ring-opening at higher potentials. Electrode/electrolyte impurities and handling conditions are found to have a significant influence on both processes. In conclusion, SEI formation is shown to be governed by several kinetically competing reaction pathways whereby EC ring-opening can play a significant role.

Advances in methodologies for real-time analysis of batteries have come a long way, especially with the development of Operando Electrochemical Mass Spectrometry (OEMS). These approaches allow for the deter-mination of side reactions during battery cycling with unprecedented selectivity and sensitivity, providing vital information necessary for determination of lifetime-limiting processes. However, the work thus far has primarily been carried out on model battery systems, where cell atmospheres are largely altered (through open flow, closed cell, and intermittent sampling approaches) and operation conditions are therefore not comparable with real-life situations. Herein, the development and validation of an intermittently closed OEMS system adapted for readily available commercial batteries is showcased. We provide a detailed description of a unique analysis design for large-format PHEV2 cells, with subsequent pressure and gassing data. A qualitative analysis of the results shows that side reactions brought on by structural transitions within both electrodes can be clearly observed. Transi-tions causing large volume changes in graphite induce H2 and C2H4 as SEI reformation products while the c lattice collapse in NMC induces CO2 evolution (through O2 release). OEMS can therefore be used for the quick and effective study of commercially available rechargeable batteries without influencing the internal battery chemistry.

Silyl groups are included in a wide range of electrolyte additives to enhance the performance of state-of-the-art Li-ion batteries. A recognized representative thereof is tris-(trimethylsilyl)phosphate (TMSPa) which, along with the similarly structured phosphite, has been at the center of numerous electrolyte studies. Even though the silyl group has already been widely reported to be specifically reactive towards fluorides, herein, a reactivity towards several Lewis bases typically found in Li-ion cells is postulated and investigated with the aim to establish a more simplified and generally applicable reaction mechanism thereof. Both gaseous and electrolyte soluble reactants and products are monitored by combining nuclear magnetic resonance and injection cell-coupled mass spectrometry. Experimental observations are supported by computational models. The results clearly demonstrate that the silyl groups react with water, hydroxide, and methoxide and thereby detach in a stepwise fashion from the central phosphate in TMSPa. Intermolecular interaction between TMSPa and the reactants likely facilitates dissolution and lowers the free energy of reaction. Lewis bases are well known to trigger side reactions involving both the Li-ion electrode and electrolyte. By effectively scavenging these, the silyl group can be explained to lower cell impedance and prolong the lifetime of modern Li-ion batteries.

The “ethylene carbonate (EC)–propylene carbonate (PC) mystery” has puzzled electrochemists for decades. Surprisingly, the minor structural difference between PC and EC, a methyl vis-à-vis a proton, prevents PC unlike EC to form a stable solid electrolyte interphase (SEI) on carbon (C), which along with the popularity of PC has impeded the development of Li-ion batteries with many years. Despite several hypotheses, the fundamental reason remains debated largely due to the lack of sufficient experimental evidence. Herein, SEI formed as a result of EC and PC reductions are analyzed by two state-of-the-art operando techniques, online electrochemical mass spectrometry and electrochemical quartz crystal microbalance with dissipation monitoring. Although both EC- and PC-based electrolytes appear to have virtually identical reaction pathways, PC is reduced much more extensively than EC and forms a much thicker SEI. However, while the SEI derived from EC remains on the electrode, PC reduction products redissolve in the electrolyte leaving the bare C electrode behind. The presented study illustrates the complex scheme of competing electro-/chemical reactions behind SEI formation and provides further scientific details needed to eventually form a consensus of the processes governing electrode/electrolyte interphases in Li-ion batteries.

Online Electrochemical Mass Spectrometry (OEMS) provides unparalleled access to the details of electrode/electrolyte interfacial reactions in electrochemical systems. Herein, the development and validation of an OEMS system along with detailed calibration protocols and limits of detection sensitivity are showcased. Combined partial and total pressure monitoring provides a clear advantage when detailing major and minor gas reactions as well as when determining unaccounted gases. A classical Li-ion LiCoO2/Graphite full cell is studied during overcharge to 4.9 V vs. Li+/Li at 50 degrees C at an unprecedented level of detail and the results are compared to LiCoO2/LiFePO4 and Graphite/LiFePO4 cells in order to differentiate between gases forming at the anode and cathode. The release of O-2 from LixCoO2 (x < 0.4) during both charge and discharge demonstrates that its degradation is dependent on state of charge 1-x rather than potential. The presented methodology establishes an improved experimental basis for deeper understanding of interfacial reactions in batteries and electrochemical systems alike.

The solid electrolyte interphase (SEI) is the most critical yet least understood component to guarantee stable and safe operation of a Li-ion cell. Herein, the early stages of SEI formation in a typical LiPF6 and organic carbonate-based Li-ion electrolyte are explored by operando surface-enhanced Raman spectroscopy, on-line electrochemical mass spectrometry, and electrochemical quartz crystal microbalance. The electric double layer is directly observed to charge as Li+ solvated by ethylene carbonate (EC) progressively accumulates at the negatively charged electrode surface. Further negative polarization triggers SEI formation, as evidenced by H-2 evolution and electrode mass deposition. Electrolyte impurities, HF and H2O, are reduced early and contribute in a multistep (electro)chemical process to an inorganic SEI layer rich in LiF and Li2CO3. This study is a model example of how a combination of highly surface-sensitive operando characterization techniques offers a step forward to understand interfacial phenomena in Li-ion batteries.

In industrial environments, operators are exposed to polluted air which after constant exposure can cause irreversible lethal diseases such as lung cancer. The current air monitoring techniques are carried out sparely in either a single day annually or at few measurement positions for a few days.In this thesis a theory-guided data science (TGDS) model is presented. This hybrid model combines a steady state Computational Fluid Dynamics (CFD) model with a machine learning model. Both the CFD model and the machine learning algorithm was developed in Matlab. The CFD model serves as a basis for the airflow whereas the machine learning model addresses dynamical features in the foundry. Measurements have previously been made at a foundry where five stationary sensors and one mobile robot were used for data acquisition. An Echo State Network was used as a supervised learning technique for airflow predictions at each robot measurement position and Gaussian Processes (GP) were used as a regression technique to form an Echo State Map (ESM). The stationary sensor data were used as input for the echo state network and the difference between the CFD and robot measurements were used as teacher signal which formed a dynamic correction map that was added to the steady state CFD. The proposed model utilizes the high spatio-temporal resolution of the echo state map whilst making use of the physical consistency of the CFD. The initial applications of the novel hybrid model proves that the best qualities of these two models could come together in symbiosis to give enhanced characterizations.The proposed model could have an important role for future characterization of airflow and more research on this and similar topics are encouraged to make sure we properly understand the potential of this novel model., Industriarbetare utsätts för skadliga luftburna ämnen vilket över tid leder till högre prevalens för lungsjukdomar så som kronisk obstruktiv lungsjukdom, stendammslunga och lungcancer. De nuvarande luftmätningsmetoderna genomförs årligen under korta sessioner och ofta vid få selekterade platser i industrilokalen. I denna masteruppsats presenteras en teorivägledd datavetenskapsmodell (TGDS) som kombinerar en stationär beräkningsströmningsdynamik (CFD) modell med en dynamisk maskininlärningsmodell. Både CFD-modellen och maskininlärningsalgoritmen utvecklades i Matlab. Echo State Network (ESN) användes för att träna maskininlärningsmodellen och Gaussiska Processer (GP) används som regressionsteknik för att kartlägga luftflödet över hela industrilokalen. Att kombinera ESN med GP för att uppskatta luftflöden i stålverk genomfördes första gången 2016 och denna modell benämns Echo State Map (ESM). Nätverket använder data från fem stationära sensorer och tränades på differensen mellan CFD-modellen och mätningar genomfördes med en mobil robot på olika platser i industriområdet. Maskininlärningsmodellen modellerar således de dynamiska effekterna i industrilokalen som den stationära CFD-modellen inte tar hänsyn till. Den presenterade modellen uppvisar lika hög temporal och rumslig upplösning som echo state map medan den också återger fysikalisk konsistens som CFD-modellen. De initiala applikationerna för denna model påvisar att de främsta egenskaperna hos echo state map och CFD används i symbios för att ge förbättrad karakteriseringsförmåga. Den presenterade modellen kan spela en viktig roll för framtida karakterisering av luftflöden i industrilokaler och fler studier är nödvändiga innan full förståelse av denna model uppnås.