| 1. |
- Chen, Heyin, et al.
(författare)
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Investigating Surface Reactivity of a Ni-Rich Cathode Material toward CO2, H2O, and O2 Using Ambient Pressure X-ray Photoelectron Spectroscopy
- 2023
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Ingår i: ACS Applied Energy Materials. - : American Chemical Society (ACS). - 2574-0962. ; 6:22, s. 11458-11467
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Tidskriftsartikel (refereegranskat)abstract
- Layered Ni-rich transition metal oxide materials are considered the most promising cathodes for use in commercial Li-ion batteries. Due to their instability in air, an impurity layer forms during storage under ambient conditions, and this layer increases electrochemical polarization during charging and discharging, which ultimately leads to a lower cycling capacity. In this work, we found that storage of the LiNi0.8Mn0.1Co0.1O2 (NMC 811) material in ultrahigh vacuum (UHV) can restore the surface by reducing the amount of native carbonate species in the impurity layer. In this work, in situ soft X-ray ambient pressure photoelectron spectroscopy is used to directly follow the interaction between common gases found in air and the NMC 811 surface. During gas exposure of the NMC 811 surface to pure CO2, O2, and a mixture of both pure gases, surface-adsorbed CO2 or/and O2 were detected; however, permanent changes could not be identified under UHV after the gas exposure. In contrast, a permanent increase in metal hydroxide species was observed on the sample surface following H2O vapor exposure, and an increased intensity in the carboxylate peak was observed after exposure to a mixture of CO2/O2/H2O. Thus, the irreversible degradation reaction with CO2 is triggered in the presence of H2O (on relevant time scales defined by the experiment). Additional measurements revealed that X-ray irradiation induces the formation of metal carbonate species on the NMC 811 surface under CO2 and H2O vapor pressure.
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| 2. |
- Hirsbrunner, Moritz, et al.
(författare)
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Vibrationally-resolved RIXS reveals OH-group formation in oxygen redox active Li-ion battery cathodes
- 2024
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 26:28, s. 19460-19468
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Tidskriftsartikel (refereegranskat)abstract
- Vibrationally-resolved resonant inelastic X-ray scattering (VR-RIXS) at the O K-edge is emerging as a powerful tool for identifying embedded molecules in lithium-ion battery cathodes. Here, we investigate two known oxygen redox-active cathode materials: the commercial LixNi0.90Co0.05Al0.05O2 (NCA) used in electric vehicles and the high-capacity cathode material Li1.2Ni0.13Co0.13Mn0.54O2 (LRNMC) for next-generation Li-ion batteries. We report the detection of a novel vibrational RIXS signature for Li-ion battery cathodes appearing in the O K pre-peak above 533 eV that we attribute to OH-groups. We discuss likely locations and pathways for OH-group formation and accumulation throughout the active cathode material. Initial-cycle behaviour for LRNMC shows that OH-signal strength correlates with the cathodes state of charge, though reversibility is incomplete. The OH-group RIXS signal strength in long-term cycled NCA is retained. Thus, VR-RIXS offers a path for gaining new insights to oxygen reactions in battery materials.
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| 3. |
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| 4. |
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| 5. |
- Mikheenkova, Anastasiia, et al.
(författare)
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Ageing of High Energy Density Automotive Li-Ion Batteries : The Effect of Temperature and State-of-Charge
- 2023
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Ingår i: Journal of the Electrochemical Society. - : The Electrochemical Society. - 0013-4651 .- 1945-7111. ; 170:8
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Tidskriftsartikel (refereegranskat)abstract
- 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%).
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| 6. |
- Mikheenkova, Anastasiia, et al.
(författare)
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Ageing of High Energy Density Automotive Li-ion Batteries: The Effect of Temperature and State-of-Charge
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- 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%).
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| 7. |
- Mikheenkova, Anastasiia, 1995-
(författare)
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Investigating ageing mechanisms in electric vehicle batteries : A multiscale approach to material analysis
- 2023
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Electrifying passenger transport is a key strategy in combating global warming, with Li-ion batteries (LIBs) being the current go-to technology. Despite LIB’s satisfactory performance and carbon-neutral operation, lifetime and safety are still public concerns. A thorough understanding of battery ageing is crucial for improving LIBs and advancing the overall sustainability of LIB technology. This thesis bridges a gap between academic and industrial research by combining commercial battery investigation with a multiscale approach using a combination of in-house and synchrotron characterization methods used with the implementation of method development to study commercial batteries.The multiple degradation mechanisms were identified at various scales in the aged commercial cells. Specifically, the results show that the studied cells exhibit significant and distinct ageing heterogeneity in prismatic and cylindrical cell formats, where the area with the highest degradation is found on the side of the positive tab, where the current and temperature gradients are expected to be the strongest. After decoupling the performance on the electrode level, the Ni-rich layered oxide positive electrodes show a significant increase in Li+ diffusion resistance in the aged materials as a function of the State of Charge (SoC) range and temperature. Furthermore, heterogeneity is an issue relevant also on a secondary particle scale, where identified SoC gradients ranging from the centre to the surface of the particle might induce kinetic limitations and cause an increase in Li+ diffusion resistance. On a single particle level, the formation of a large number of voids within the grains was found. Such degradation can additionally contribute to the resistance increase in the material by changing tortuosity for Li-ions. Finally, at the atomic level, Ni was found to be the dominant charge compensator, which can decrease up to 25% of the redox activity after ageing. Compared to Ni, Co was found to be less redox-active, but more involved in charge compensation through changes in hybridization with the oxygen atom. The oxygen, in turn, was revealed to participate in anionic redox reactions at low SoC by both hybridization to TM and also through the formation of molecular oxygen at lower potentials than previously reported. The observed decrease in oxygen anion redox activity follows with material losing performance.The results presented in the thesis demonstrate the importance of the multiscale approach in order to form a more complete understanding of the degradation processes which have effects within different scales.
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| 8. |
- Mikheenkova, Anastasiia, et al.
(författare)
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Resolving high potential structural deterioration in Ni-rich layered cathode materials for lithium-ion batteries operando
- 2023
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Ingår i: Journal of Energy Storage. - : Elsevier. - 2352-152X .- 2352-1538. ; 57
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Tidskriftsartikel (refereegranskat)abstract
- LixNi0.90Co0.05Al0.05O2 (NCA) extracted from an automotive battery cell is studied using a combination of in-house operando techniques to understand the correlation between gas evolution and structural collapse when NCA is cycled to high potentials in a lithium-ion battery configuration. The operando techniques comprise X-ray diffraction (XRD) and online electrochemical mass spectrometry (OEMS), and cycled using intermittent current interruption (ICI). The ICI cycling protocol is used to assess the dynamic change in resistance as well as to provide a validation of the operando setups. Both gas evolution and structural collapse have previously been observed as degradation mechanisms of Ni-rich electrodes including NCA, however, their causal link is still under debate. Here our presented results show a correlation between the decrease of the interlayer distance in NCA with both an increase in CO2 evolution and diffusion resistance above 4.1 V. Additionally, particle cracking, which is a mechanism often correlated with gas evolution, was found to be reversible and visible before gas evolution and Li diffusion resistance increase. The ICI technique is shown to be useful for the correlation of operando experiments on parallel setups and evaluation of mass transport dependent processes.
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| 9. |
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| 10. |
- Mikheenkova, Anastasiia, et al.
(författare)
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The Role of Oxygen in Automotive Grade Lithium-Ion Battery Cathodes : An Atomistic Survey of Ageing
- 2024
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Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488 .- 2050-7496. ; 12:4, s. 2465-2478
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Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- The rising demand for high-performance lithium-ion batteries, pivotal to electric transportation, hinges on key materials like the Ni-rich layered oxide LiNixCoyAlzO2 (NCA) used in cathodes. The present study investigates the redox mechanisms, with particular focus on the role of oxygen in commercial NCA electrodes, both fresh and aged under various conditions (aged cells have performed >900 cycles until a cathode capacity retention of ∼80%). Our findings reveal that oxygen participates in charge compensation during NCA delithiation, both through changes in transition metal (TM)–O bond hybridization and formation of partially reversible O2, the latter occurs already below 3.8 V vs. Li/Li+. Aged NCA material undergoes more significant changes in TM–O bond hybridization when cycling above 50% SoC, while reversible O2 formation is maintained. Nickel is found to be redox active throughout the entire delithiation and shows a more classical oxidation state change during cycling with smaller changes in the Ni–O hybridization. By contrast, Co redox activity relies on a stronger change in Co–O hybridization, with only smaller Co oxidation state changes. The Ni–O bond displays an almost twice as large change in its bond length on cycling as the Co–O bond. The Ni–O6 octahedra are similar in size to the Co–O6 octahedra in the delithiated state, but are larger in the lithiated state, a size difference that increases with battery ageing. These contrasting redox activities are reflected directly in structural changes. The NCA material exhibits the formation of nanopores upon ageing, and a possible connection to oxygen redox activity is discussed. The difference in interaction of Ni and Co with oxygen provides a key understanding of the mechanism and the electrochemical instability of Ni-rich layered transition metal oxide electrodes. Our research specifically highlights the significance of the role of oxygen in the electrochemical performance of electric-vehicle-grade NCA electrodes, offering important insights for the creation of next-generation long-lived lithium-ion batteries.
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| 11. |
- Mikheenkova, Anastasiia, et al.
(författare)
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The role of oxygen in automotive grade lithium-ion battery cathodes : an atomistic survey of ageing
- 2024
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Ingår i: Journal of Materials Chemistry A. - 2050-7488 .- 2050-7496. ; 12:4, s. 2465-2478
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Tidskriftsartikel (refereegranskat)abstract
- The rising demand for high-performance lithium-ion batteries, pivotal to electric transportation, hinges on key materials like the Ni-rich layered oxide LiNixCoyAlzO2 (NCA) used in cathodes. The present study investigates the redox mechanisms, with particular focus on the role of oxygen in commercial NCA electrodes, both fresh and aged under various conditions (aged cells have performed >900 cycles until a cathode capacity retention of ∼80%). Our findings reveal that oxygen participates in charge compensation during NCA delithiation, both through changes in transition metal (TM)–O bond hybridization and formation of partially reversible O2, the latter occurs already below 3.8 V vs. Li/Li+. Aged NCA material undergoes more significant changes in TM–O bond hybridization when cycling above 50% SoC, while reversible O2 formation is maintained. Nickel is found to be redox active throughout the entire delithiation and shows a more classical oxidation state change during cycling with smaller changes in the Ni–O hybridization. By contrast, Co redox activity relies on a stronger change in Co–O hybridization, with only smaller Co oxidation state changes. The Ni–O bond displays an almost twice as large change in its bond length on cycling as the Co–O bond. The Ni–O6 octahedra are similar in size to the Co–O6 octahedra in the delithiated state, but are larger in the lithiated state, a size difference that increases with battery ageing. These contrasting redox activities are reflected directly in structural changes. The NCA material exhibits the formation of nanopores upon ageing, and a possible connection to oxygen redox activity is discussed. The difference in interaction of Ni and Co with oxygen provides a key understanding of the mechanism and the electrochemical instability of Ni-rich layered transition metal oxide electrodes. Our research specifically highlights the significance of the role of oxygen in the electrochemical performance of electric-vehicle-grade NCA electrodes, offering important insights for the creation of next-generation long-lived lithium-ion batteries.
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| 12. |
- Mikheenkova, Anastasiia, et al.
(författare)
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Visualizing ageing-induced heterogeneity within large prismatic lithium-ion batteries for electric cars using diffraction radiography
- 2024
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Ingår i: Journal of Power Sources. - : Elsevier BV. - 0378-7753 .- 1873-2755. ; 599
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 13. |
- Roy Chowdhury, Niladri, 1989, et al.
(författare)
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Influence of state of charge window on the degradation of Tesla lithium-ion battery cells
- 2024
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Ingår i: Journal of Energy Storage. - : Elsevier BV. - 2352-152X .- 2352-1538. ; 76
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 14. |
- Roy Chowdhury, Niladri, et al.
(författare)
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The state of charge dependence of degradation in lithium-ion cells from a Tesla Model 3
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- The Tesla Model 3 is currently one of the most popular electric vehicles (EV)and was the best selling EV in 2020. In this article, performance and degradation are studied for 21700 cylindrical cells from a Tesla Model 3 cycledwithin nine, sequential state of charge (SOC) windows, each using 10% ofthe cell capacity is studied. Cells tested in either very high and very low SOCwindows show faster degradation than at moderate SOC. In particular, theshortest service life was for cells cycled below 25% SOC. The ageing mechanisms of the cells cycled in these most extreme windows have been monitoredby non-destructive electrochemical methods including analyses of differentialvoltage, incremental capacity, and voltage hysteresis. The combination ofloss of active material (LAM) and loss of lithium inventory (LLI) are responsible for the most rapid ageing observed in the cells cycled in the 5-15%SOC window. Calendar ageing, however, is not accelerated by storage atlow SOC. The results from this study offer an understanding of the distinct,SOC-dependent ageing patterns observed in the cells. This understanding ofthe ageing mechanisms in different cycling and storage conditions can be usedto recommend improved customer usage patterns and substantially extendthe lifetime of lithium-ion batteries in operation.
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| 15. |
- Smith, Alexander J., et al.
(författare)
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Localized lithium plating under mild cycling conditions in high-energy lithium-ion batteries
- 2023
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Ingår i: Journal of Power Sources. - : Elsevier. - 0378-7753 .- 1873-2755. ; 573
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Tidskriftsartikel (refereegranskat)abstract
- Conditions such as the temperature and pressure experienced by lithium-ion battery components are dependent on cell geometry and can vary widely within a large cell. The resulting uneven degradation is challenging to study at the full cell level but can be revealed upon disassembly and post mortem analysis. In this work, we report localized lithium plating in automotive-grade, prismatic lithium-ion cells, also under cycling conditions generally considered to be mild (e.g., 5–65 %SOC, 23 °C, 0.5C cycle rate). Dead lithium content is quantified using 7Li nuclear magnetic resonance 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 both the separators and negative electrodes are ultimately deactivated. High pressure arises during cycling, and we propose 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 under mild cycling conditions. Notably, components harvested from regions with no detected lithium plating maintained adequate electrochemical performance.
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