| 1. |
- Tapia-Ruiz, Nuria, et al.
(author)
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2021 roadmap for sodium-ion batteries
- 2021
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In: Journal of Physics. - : Institute of Physics Publishing (IOPP). - 2515-7655. ; 3:3
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Journal article (peer-reviewed)abstract
- Increasing concerns regarding the sustainability of lithium sources, due to their limited availability and consequent expected price increase, have raised awareness of the importance of developing alternative energy-storage candidates that can sustain the ever-growing energy demand. Furthermore, limitations on the availability of the transition metals used in the manufacturing of cathode materials, together with questionable mining practices, are driving development towards more sustainable elements. Given the uniformly high abundance and cost-effectiveness of sodium, as well as its very suitable redox potential (close to that of lithium), sodium-ion battery technology offers tremendous potential to be a counterpart to lithium-ion batteries (LIBs) in different application scenarios, such as stationary energy storage and low-cost vehicles. This potential is reflected by the major investments that are being made by industry in a wide variety of markets and in diverse material combinations. Despite the associated advantages of being a drop-in replacement for LIBs, there are remarkable differences in the physicochemical properties between sodium and lithium that give rise to different behaviours, for example, different coordination preferences in compounds, desolvation energies, or solubility of the solid-electrolyte interphase inorganic salt components. This demands a more detailed study of the underlying physical and chemical processes occurring in sodium-ion batteries and allows great scope for groundbreaking advances in the field, from lab-scale to scale-up. This roadmap provides an extensive review by experts in academia and industry of the current state of the art in 2021 and the different research directions and strategies currently underway to improve the performance of sodium-ion batteries. The aim is to provide an opinion with respect to the current challenges and opportunities, from the fundamental properties to the practical applications of this technology.
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| 2. |
- Boras, Dominik, et al.
(author)
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Determining internal porosity in Prussian blue analogue cathode materials using positron annihilation lifetime spectroscopy
- 2023
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In: Journal of Materials Science. - : Springer Nature. - 0022-2461 .- 1573-4803. ; 58:42, s. 16344-16356
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Journal article (peer-reviewed)abstract
- Prussian blue analogues (PBAs), AxM[M’(CN)6]1–y·zH2O, are a highly functional class of materials with use in a broad range of applications, such as energy storage, due to their porous structure and tunable composition. The porosity is particularly important for the properties and is deeply coupled to the cation, water, and [M’(CN)6]n– vacancy content. Determining internal porosity is especially challenging because the three compositional parameters are dependent on each other. In this work, we apply a new method, positron annihilation lifetime spectroscopy (PALS), which can be employed for the characterization of defects and structural changes in crystalline materials. Four samples were prepared to evaluate the method’s ability to detect changes in internal porosity as a function of the cation, water, and [M’(CN)6]n– vacancy content. Three of the samples have identical [M’(CN)6]n– vacancy content and gradually decreasing sodium and water content, while one sample has no sodium and 25% [M’(CN)6]n– vacancies. The samples were thoroughly characterized using inductively coupled plasma-optical emission spectroscopy (ICP-OES), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and Mössbauer spectroscopy as well as applying the PALS method. Mössbauer spectroscopy, XRD, and TGA analysis revealed the sample compositions Na1.8(2)Fe2+0.64(6)Fe2.6+0.36(10)[Fe2+(CN)6]·2.09(2)H2O, Na1.1(2)Fe2+0.24(6)Fe2.8+0.76(6)[Fe2.3+(CN)6]·1.57(1)H2O, Fe[Fe(CN)6]·0.807(9)H2O, and Fe[Fe(CN)6]0.75·1.5H2O, confirming the absence of vacancies in the three main samples. It was shown that the final composition of PBAs could only be unambiguously confirmed through the combination of ICP, XRD, TGA, and Mössbauer spectroscopy. Two positron lifetimes of 205 and 405 ps were observed with the 205 ps lifetime being independent of the sodium, water, and/or [Fe(CN)6]n– vacancy content, while the lifetime around 405 ps changes with varying sodium and water content. However, the origin and nature of the 405 ps lifetime yet remains unclear. The method shows promise for characterizing changes in the internal porosity in PBAs as a function of the composition and further development work needs to be carried out to ensure the applicability to PBAs generally.
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| 3. |
- Brant, William R., et al.
(author)
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Local structure transformations promoting high lithium diffusion in defect perovskite type structures
- 2023
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In: Electrochimica Acta. - : Elsevier. - 0013-4686 .- 1873-3859. ; 441
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Journal article (peer-reviewed)abstract
- Defect perovskites, AxBO3 such as (Li3xLa2/3-x)TiO3, are attracting attention as high capacity electrodes in lithium-ion batteries. However, the mechanism enabling high lithium storage capacities has not been fully investigated. In this work, the reversible insertion and removal of lithium up to an average A-site cavity occupancy of 1.71 in the defect perovskite (Li0.18Sr0.66)(Ti0.5Nb0.5)O3 is investigated. It was shown that subtle lithium reorganization during lithiation has a significant impact on enabling high capacity. Contrary to previous studies, lithium was coordinated to triangular faces of Ti/Nb oxygen octahedra and offset from O4 windows between A-site cavities in the as-synthesised material. Upon electrochemical lithiation Li-Li repulsion redistributes of all the lithium towards the O4 window position resulting in a loss of lithium mobility. Surprisingly, the mobility is regained during over-lithiation and following multiple electrochemical cycles. It is suggested that lithium reorganisation into the center of the O4 window alleviates the Li-Li repulsion and modifies the diffusion behavior from site percolation to bond percolation. The results obtained provide valuable insight into the chemical drivers enabling higher capacities and enhanced diffusion in defect perovskites. More broadly the study delivers fundamental understanding on the non-equilibrium structural transformations occurring within electrode materials during repeated electrochemical cycles.
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| 4. |
- Chen, Heyin, et al.
(author)
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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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In: ACS Applied Energy Materials. - : American Chemical Society (ACS). - 2574-0962. ; 6:22, s. 11458-11467
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Journal article (peer-reviewed)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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| 5. |
- Chien, Yu-Chuan, 1990-, et al.
(author)
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Impact of Compression on the Electrochemical Performance of the Sulfur/Carbon Composite Electrode in Lithium-Sulfur Batteries
- 2022
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In: Batteries & Supercaps. - : Wiley-VCH Verlagsgesellschaft. - 2566-6223. ; 5:7
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Journal article (peer-reviewed)abstract
- While lithium-sulfur batteries theoretically have both high gravimetric specific energy and volumetric energy density, only its specific energy has been experimentally demonstrated to surpass that of the state-of-the-art lithium-ion systems at cell level. One major reason for the unrealized energy density is the low capacity density of the highly porous sulfur/carbon composite as the positive electrode. In this work, mechanical compression at elevated temperature is demonstrated to be an effective method to increase the capacity density of the electrode by at least 90 % and moreover extends its cycle life. Distinct impacts of compression on the resistance profiles of electrodes with different thickness are investigated by tortuosity factors derived from both electrochemical impedance spectroscopy, X-ray computed tomography and kinetic analysis based on operando X-ray diffraction. The results highlights the importance of a homogeneous electrode structure highlight lithium-sulfur system.
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| 6. |
- Chien, Yu-Chuan, 1990-, et al.
(author)
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Rapid determination of solid-state diffusion coefficients in Li-based batteries via intermittent current interruption method
- 2023
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In: Nature Communications. - : Springer Nature. - 2041-1723. ; 14:1
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Journal article (peer-reviewed)abstract
- The galvanostatic intermittent titration technique (GITT) is considered the go-to method for determining the Li+ diffusion coefficients in insertion electrode materials. However, GITT-based methods are either time-consuming, prone to analysis pitfalls or require sophisticated interpretation models. Here, we propose the intermittent current interruption (ICI) method as a reliable, accurate and faster alternative to GITT-based methods. Using Fick’s laws, we prove that the ICI method renders the same information as the GITT within a certain duration of time since the current interruption. Via experimental measurements, we also demonstrate that the results from ICI and GITT methods match where the assumption of semi-infinite diffusion applies. Moreover, the benefit of the non-disruptive ICI method to operando materials characterization is exhibited by correlating the continuously monitored diffusion coefficient of Li+ in a LiNi0.8Mn0.1Co0.1O2-based electrode to its structural changes captured by operando X-ray diffraction measurements.
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| 7. |
- Gustafsson, Olof, et al.
(author)
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Design and Operation of an Operando Synchrotron Diffraction Cell Enabling Fast Cycling of Battery Materials
- 2021
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In: Batteries & Supercaps. - : John Wiley & Sons. - 2566-6223. ; 4:10, s. 1599-1604
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Journal article (peer-reviewed)abstract
- Operation of a battery typically involves dynamic and non-equilibrium processes, making real time operando techniques crucial for understanding their nature. Operando X-ray diffraction is an important technique for investigating metastable intermediates and non-equilibrium phase transitions in crystalline electrode materials. Currently employed experimental setups often apply a disruptive approach to cell design, whereby the integrity of standard electrochemical cells is compromised to facilitate collection of high-quality diffraction data. Here, we present a non-disruptive approach to adapting the use of a standard pouch cell that enables fast and long-term cell cycling. Suitability of the setup is demonstrated on the well-studied cathode material LiNi0.5Mn1.5O4. While exhibiting comparable electrochemical behavior to a standard pouch cell up to a current rate of 8 C (∼6.6 mA cm−2), phase transitions could be monitored accurately. Thus, the cell provides a new alternative to investigating non-equilibrium transitions and long-term aging effects in battery materials.
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| 8. |
- Heintz, Mads C., et al.
(author)
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Photovoltaic Wafering Silicon Kerf Loss as Raw Material : Example of Negative Electrode for Lithium‐Ion Battery
- 2023
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In: ChemElectroChem. - : Wiley-VCH Verlagsgesellschaft. - 2196-0216. ; 10:19
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Journal article (peer-reviewed)abstract
- Silicon powder kerf loss from diamond wire sawing in the photovoltaic wafering industry is a highly appealing source material for use in lithium-ion battery negative electrodes. Here, it is demonstrated for the first time that the kerf particles from three independent sources contain ~50 % amorphous silicon. The crystalline phase is in the shape of nano-scale crystalline inclusions in an amorphous matrix. From literature on wafering technology looking at wafer quality, the origin and mechanisms responsible for the amorphous content in the kerf loss powder are explained. In order to better understand for which applications the material could be a valuable raw material, the amorphicity and other relevant features are thoroughly investigated by a large amount of experimental methods. Furthermore, the kerf powder was crystallized and compared to the partly amorphous sample by operando X-ray powder diffraction experiments during battery cycling, demonstrating that the powders are relevant for further investigation and development for battery applications.
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| 9. |
- Mikheenkova, Anastasiia, et al.
(author)
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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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In: Journal of Energy Storage. - : Elsevier. - 2352-152X .- 2352-1538. ; 57
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Journal article (peer-reviewed)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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| 10. |
- Mikheenkova, Anastasiia, et al.
(author)
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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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In: Journal of Power Sources. - : Elsevier BV. - 0378-7753 .- 1873-2755. ; 599
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Journal article (peer-reviewed)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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