Inhomogeneous temperature distribution in a large-format lithium-ion cell or between cells in a module/pack may cause a non-uniform current distribution, causing a local difference in aging, and potentially faster global aging (capacity fade and impedance rise) of the module. To study this effect, LiNi1/3Mn1/3Co1/3O2/graphite lithium-ion pouch cells were cycled at 32, 36, and 40 °C as single cells and in parallel connection, representing uniform and non-uniform temperature distributions. The results show that the current distribution becomes less uniform after cycling at a higher rate and in a narrower state-of-charge range. Cycling with non-uniform temperature at 3C rate results in aging similar to that at the maximum uniform temperature, while at 1C rate the non-uniform aging follows the trend at the average temperature. The performance decay of the cells cycled at 3C is mainly driven by the cell at 40 °C which shows 30 % more capacity loss than the corresponding cell cycled singularly. This leads to additional considerations when designing for cycle life and reliability in fast charging applications and high-power applications such as in electric vehicles or frequency regulation in stationary storage.

The Tesla Model 3 is currently one of the most popular electric vehicle (EV) and was the best selling EV in 2020. In this article, performance and degradation of 21700 cylindrical cells, taken from a new vehicle, were studied by cycling within 10% State of charge (SOC) windows. Cells tested in either very high and very low SOC windows show faster degradation than at moderate SOC. In particular, the shortest service life was for cells cycled below 25% SOC. The ageing mechanisms of the cells cycled in these most extreme windows have been monitored by non-destructive electrochemical methods including analyses of differential voltage, incremental capacity, and voltage hysteresis. The combination of loss of lithium inventory (LLI) accelerated in early cycling by SiOx utilization, paired with loss of active material (LAM) of SiOx are responsible for the most rapid ageing, which is observed in the cells cycled in the 5%–15% SOC window. Calendar ageing, however, is not accelerated by storage at low SOC. The results from this study offer an understanding of the distinct, SOC-dependent ageing patterns observed in the cells. This understanding of the ageing mechanisms in different cycling and storage conditions can be used to recommend improved customer usage patterns and substantially extend the lifetime of lithium-ion batteries in operation.

In this study, Synchrotron X-ray diffraction (XRD) radiography was utilized to investigate the ageing heterogeneity in 48 Ah prismatic lithium-ion cells with Ni-rich LiNi0.8Mn0.1Co0.1O2 (NMC811) as the positive electrode active material and graphite as the negative electrode active material after ∼2800 cycles. The study revealed that the area closest to the positive electrode tab is most vulnerable to degradation, particularly impacting the NMC material. Application of principal component analysis allowed to differentiate and visualize part of positive electrode material that has a different degradation due to the lithium plating. A comparison of non-destructive X-ray diffraction-based methods and electrochemical characterization method which was performed on the opened cell has shown an importance of a complementary approach. Our results highlight the feasibility of employing non-destructive techniques to study large prismatic cells, thereby presenting extensive opportunities for advancements in battery research and industry.

Lithium ion batteries (LIB) have become a cornerstone of the shift to electric transportation. In an attempt to decrease the production load and prolong battery life, understanding different degradation mechanisms in state-of-the-art LIBs is essential. Here, we analyze how operational temperature and state-of-charge (SoC) range in cycling influence the ageing of automotive grade 21700 batteries, extracted from a Tesla 3 long Range 2018 battery pack with positive electrode containing LiNixCoyAlzO2 (NCA) and negative electrode containing SiOx-C. In the given study we use a combination of electrochemical and material analysis to understand degradation sources in the cell. Herein we show that loss of lithium inventory is the main degradation mode in the cells, with loss of material on the negative electrode as there is a significant contributor when cycled in the low SoC range. Degradation of NCA dominates at elevated temperatures with combination of cycling to high SoC (beyond 50%).

Conditions such as the temperature and pressure experienced by lithium-ion battery components are dependent oncell geometry and can vary widely within a large cell. The resulting uneven degradation is challenging to study at thefull cell level but can be revealed upon disassembly and post mortem analysis. In this work, we report localizedlithium plating in automotive-grade, prismatic lithium-ion cells, also under cycling conditions generally consideredto be mild (e.g., 5–65 %SOC, 23 ◦C, 0.5C cycle rate). Dead lithium content is quantified using 7Li nuclear magneticresonance spectroscopy in both electrode and separator samples, corresponding to substantial capacity fade(26–46%) of the full cells. Severe lithium plating is typically initiated in regions near the positive tab, in which boththe separators and negative electrodes are ultimately deactivated. High pressure arises during cycling, and wepropose a deactivation mechanism based on high local stress due to electrode expansion and external constraint.Further, we develop a model to demonstrate that component deactivation can result in lithium plating even undermild cycling conditions. Notably, components harvested from regions with no detected lithium plating maintainedadequate electrochemical performance.

Lithium-ion batteries have enabled vast societal changes, ranging in scale from the adoption of personal electronics to electromobility and grid-scale, renewable energy storage. However, all applications face performance fade over time, observed as losses of battery capacity and power. This gradual degradation is most often due to electrochemical aging processes inside the cell, including phenomena causing a loss of cyclable lithium (e.g., lithium plating, growth of the solid­‑electrolyte interphase or SEI), a loss of active material (e.g., particle cracking), and/or a loss of ionic or electronic conductivity. In the compiled works, many individual batteries have been aged and analyzed to better understand the conditions contributing to aging in different cell designs. The cells studied include lab-built pouch cells, commercial cylindrical cells (with electrodes LiNi_xMn_yCo_1‑x‑yO₂‑LiMn₂O₄/C₆ and LiNi_xCo_yAl_1‑x‑yO₂/C₆‑SiO_x), and larger automotive-grade prismatic cells (LiNi_xMn_yCo_1‑x‑yO₂/C₆).

Complementary in situ and post mortem methods are developed, with relevance for both battery research and battery control systems. Excellent characterization can often be achieved by a combination of differential voltage and incremental capacity analyses. Obtained from a simple, slow cycle, the derivatives of the voltage profile reveal many features that can be tracked over aging. This thesis particularly develops these techniques for blended electrodes, deconvoluting the aging of individual components. Dynamic performance is resolved with a novel polarization factor, impedance spectroscopy, and tools based on current pulses/interruptions. Finally, a protocol based on nuclear magnetic resonance spectroscopy is developed, enabling fast and direct quantification of lithium plating and SEI on harvested battery components. With such tools, we can improve how batteries are used and monitored, paving the way for efficient research and safer, more reliable batteries.

Litiumjonbatterier har haft en stor betydelse för samhällsutvecklingen då de möjliggjort allt från bärbar elektronik till elektromobilitet och balansering av elnätet. Tyvärr tappar batterier prestanda över tid, både genom försämrad kapacitet och effekt. Den gradvisa försämringen beror främst på interna elektrokemiska processer, varav förluster av cyklingsbart litium genom plätering av litiummetall eller tillväxt av deponerade skikt av nedbrytningsmaterial, så kallat SEI-skikt, är typiska. Andra mekanismer är degradering av de elektrokemiskt aktiva materialen och/eller förluster i ledningsförmåga. Avhandlingen behandlar ett stort antal battericeller som åldrats och därefter analyserats elektrokemiskt både under och efter cyklingen. Syftet har varit att förbättra förståelsen av degradering av olika batterityper som funktion av hur de har använts. I arbetet ingår labbceller såväl som kommersiellt tillgängliga cylindriska och prismatiska celler med nickelrik cellkemi ämnade för fordons-tillämpningar.

Kompletterande in situ och post mortem metoder har utvecklas med relevans såväl för forskning som för kontrollsystem för batterier. Utförlig identifiering av åldringsprocesser är möjlig med en kombination av differentiella spännings- och kapacitetsanalyser. Derivatan av en långsam upp- eller urladdningscykel ger nyttig information om åldrings-processerna som pågår. Arbetet i den här avhandlingen syftar till att förbättra metoderna särskilt gällande elektroder med fler än en aktiv komponent. Dynamiska driftegenskaper påvisades med mätningar av polarisering och impedans, samt strömpulsmetoder. Slutligen har en metodik utvecklats för att kvantitativt bestämma förekomsten av litiumplätering och SEI i post mortem analys med kärnmagnetisk resonansspektroskopi. Med dessa metoder kan vi förbättra kontrollen av batterier för att förlänga deras livslängd, vilket gynnar såväl fortsatt forskning som en säkrare och mer tillförlitlig användning av batterier i framtiden.

During the last decade, the market interest for electrified vehicles has increased considerably alongside global climate initiatives. This has coincided with vast improvements in automotive-grade, lithium-ion battery performance. This has increased the range of battery electric vehicles and plug-in hybrids, but lifetime remains a challenge. Aging during fast charging is especially difficult to understand due to its nonlinear dependence on charge rate, state-of-charge, and temperature. We present results from fast charging of several energy-optimized, prismatic lithium-ion battery cell generations with a nickel manganese cobalt (NMC)/graphite chemistry through comparison of capacity retention, resistance, and dQ/dV analysis. Changes in cell design have increased energy density by almost 50% over six years of cell development and acceptable cycle life can be expected, even under fast charging, when restricting the usage of the available capacity. Even though this approach reduces the useable energy density of a battery system, this tradeoff could still be acceptable for vehicle applications where conventional overnight charging is not possible. The tested cell format has been used for a decade in electrified vehicles. The ongoing development and improvement of this cell format by several cell manufacturers suggests that it will continue to be a good choice for future vehicles.

A key degradation mechanism in lithium-ion batteries (LIBs) is the irreversible loss of cyclable lithium during cycling. At the graphite negative electrode, this loss occurs through the deposition of lithium-containing compounds in the solid-electrolyte interphase (SEI) and through plating of metallic lithium, resulting in so-called dead lithium. The separate quantification of SEI and dead lithium has so far been a challenge in post mortem analysis of commercial LIBs. Here we report a simple and fast 7Li nuclear magnetic resonance spectroscopy (NMR) protocol applied to solid-state samples derived from lab-built batteries to independently quantify these and other lithium species in graphite electrodes without the need for specialized cell design nor knowledge of prior charging history. The metallic lithium content is corroborated by electrochemical calculations; the total amount of lithium is also determined from 7Li liquid-state NMR and inductively coupled plasma optical emission spectroscopy (ICP-OES) in suitably digested samples. Factors influencing accuracy like the sample handling process, the radiofrequency skin effect, and re-intercalation losses are investigated. Measurements on samples from commercial cells aged under realistic conditions demonstrate quantification of dead lithium and remaining ionic species (SEI), and further reveal lithium dendrites entrained in the separator following cell disassembly. The method uses conventional and widely available NMR instrumentation and is applicable to samples from lab-scale test cells or commercial batteries, thereby presenting a vast improvement over prior post mortem methods. 

An important step toward safer and more reliable lithium-ion battery systems is the improvement of methods for detection and characterization of battery degradation. In this work, we develop and track aging indicators over the life of 18650-format lithium-ion batteries with a blended NMC532-LMO positive electrode and graphite negative electrode. Cells are cycled until reaching 80% of their original capacity under combinations of four cycling conditions: ambient and sub-ambient temperatures (29 degrees C and 10 degrees C) and fast and mild rates (2.7 and 1.0C). Loss of lithium inventory dominates aging for all cases, with additional loss of NMC capacity under the combination of sub-ambient temperature and mild rate. A novel, easily acquired polarization factor complements capacity fade analysis; it correlates well with impedance and galvanostatic cycle life and indicates changes in active aging processes. These processes are further revealed by differential voltage analysis (DVA) and incremental capacity analysis (ICA). New indicators and aging scenarios are evaluated for these techniques and supported by post mortem analysis. From in operando cycling data and a single, slow discharge curve, these four methods (capacity fade, polarization factor, DVA, and ICA) comprise a simple, explanatory, and non-invasive toolbox for evaluating aging in lithium-ion battery systems.

Lithium ion batteries (LIB) have become a cornerstone of the shift to electric transportation. In an attempt to decrease the production load and prolong battery life, understanding different degradation mechanisms in state-of-the-art LIBs is essential. Here, we analyze how operational temperature and state-of-charge (SoC) range in cycling influence the ageing of automotive grade 21700 batteries, extracted from a Tesla 3 Long Range 2018 battery pack with positive electrode containing LiNixCoyAlzO2 (NCA) and negative electrode containing SiOx-C. In the given study we use a combination of electrochemical and material analysis to understand degradation sources in the cell. Herein we show that loss of lithium inventory is the main degradation mode in the cells, with loss of material on the negative electrode as there is a significant contributor when cycled in the low SoC range. Degradation of NCA dominates at elevated temperatures with combination of cycling to high SoC (beyond 50%).