| 1. |
- Brant, William, et al.
(författare)
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Selective Control of Composition in Prussian White for Enhanced Material Properties
- 2019
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Ingår i: Chemistry of Materials. - : AMER CHEMICAL SOC. - 0897-4756 .- 1520-5002. ; 31:18, s. 7203-7211
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Tidskriftsartikel (refereegranskat)abstract
- Sodium-ion batteries based on Prussian blue analogues (PBAs) are ideal for large-scale energy storage applications due to the ability to meet the huge volumes and low costs required. For Na2-xFe[Fe(CN)(6)](1-y)center dot zH(2)O, realizing its commercial potential means fine control of the concentration of sodium, Fe(CN)(6) vacancies, and water content. To date, there is a huge variation in the literature of composition leading to variable electrochemical performance. In this work, we break down the synthesis of PBAs into three steps for controlling the sodium, vacancy, and water content via an inexpensive, scalable synthesis method. We produce rhombohedral Prussian white Na1.88(5)Fe[Fe-(CN)(6)]center dot 0.18(9)H2O with an initial capacity of 158 mAh/g retaining 90% capacity after 50 cycles. Subsequent characterization revealed that the increased polarization on the 3 V plateau is coincident with a phase transition and reduced utilization of the high-spin Fe(III)/Fe(II) redox couple. This reveals a clear target for subsequent improvements of the material to boost long-term cycling stability. These results will be of great interest for the myriad of applications of PBAs, such as catalysis, magnetism, electrochromics, and gas sorption.
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| 2. |
- Chamoun, Mylad, et al.
(författare)
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Rechargeability of aqueous sulfate Zn/MnO2 batteries enhanced by accessible Mn2+ ions
- 2018
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Ingår i: Energy Storage Materials. - : Elsevier BV. - 2405-8289 .- 2405-8297. ; 15, s. 351-360
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Tidskriftsartikel (refereegranskat)abstract
- The Zn/MnO2 battery is safe, low cost and comes with a high energy density comparable to Li-ion batteries. However, irreversible spinel phases formed at the MnO2 electrode limits its cyclability. A viable solution to overcome this inactive phase is to use an aqueous ZnSO4-based electrolyte, where pH is mildly acidic leading to a different reaction mechanism. Most importantly, the addition of MnSO4 achieves excellent cyclability. How accessible Mn2+ ions in the electrolyte enhances the reversibility is presented. With added Mn2+, the capacity retention is significantly improved over 100 cycles. Zn2+ insertion plays an important role on the reversibility and a hydrated layered Zn-buserite structure formed during charge is reported. Furthermore, Zn4SO4(OH)(6) center dot 5H(2)O precipitates during discharge but is not involved in the electrochemical reaction. This precipitate both buffers the pH and partly insulates the surface. Described in operando study show how the phase transformations and the failure mechanisms depend on the presence of Mn2+-ions in the electrolyte. These results give insight necessary to improve this battery further to make it a worthy contender to the Li-ion battery in large scale energy storage solutions.
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| 3. |
- Boström, Hanna, et al.
(författare)
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Octahedral tilting in Prussian blue analogues
- 2022
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Ingår i: Journal of Materials Chemistry C. - : Royal Society of Chemistry (RSC). - 2050-7526 .- 2050-7534. ; 10:37, s. 13690-13699
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Tidskriftsartikel (refereegranskat)abstract
- Octahedral tilting is key to the structure and functionality of perovskites. We present a metastudy of published literature showing how these distortions manifest in the related Prussian blue analogues (PBAs): cyanide versions of double perovskites with formula AM[M '(CN)(6)](1-y)(y)center dot nH(2)O (A = alkali metal, M and M ' = transition metals, = vacancy/defect). Tilts are favoured by high values of x if A = Na or K, whereas the transition metals play a less important role. External hydrostatic pressure induces tilt transitions nearly irrespective of the stoichiometry, whereas thermal transitions are only reported for x > 1. Interstitial water can alter the transitions induced by a different stimulus, but (de)hydration per se does not lead to tilts. Finally, the implications for rational design of critical functionality-including improper ferroelectricity and electrochemical performance-are discussed. The results are integral for a fundamental understanding of phase transitions and for the development of functional materials based on PBAs.
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| 4. |
- Brant, William R., et al.
(författare)
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In Operando X-ray and Neutron Diffraction for Lithium Ion Batteries
- 2017
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- To find new materials for lithium-ion batteries (LIBs) or to improve existing materials is a huge field of research. The positive electrode material in these devices is a bottleneck for increasing the energy density for the LIB and numerous oxides, phosphates, and silicates based on transition metals have been suggested. The crystallinity, chemical composition and structure of the bulk and the surface of a potential material are some important parameters influencing battery performance. In this presentation, we will show some examples of iron and Mn/Ni based cathode materials, and how in operando X-ray and neutron diffraction results have contributed to the understanding of how these materials function in batteries. In operando X-ray and neutron diffraction are extremely powerful techniques for investigating reaction mechanisms in battery materials in general. To date, the vast majority of these experiments have been performed using synchrotron X-ray diffraction, predominantly due to the fast data collection times possible. Is it so that synchrotron based X-ray diffraction always is the best choice? We will discuss this and show why in house in operando diffraction still is powerful. In operando neutron diffraction experiments are becoming increasingly popular due to a range of new cell designs increasing the accessibility of the technique [1], [2]. This presentation will discuss two different approaches to in operando neutron diffraction: a larger format wound cell and a cheaper modified a coin type cell. The wound cell design contains a large quantity of active material (up to 4 g) enabling high quality diffraction patterns to be collected down to small d-spacings. When used to investigate the positive electrode material LiMn1.5Ni0.5O4, reflections arising from Mn/Ni ordering could be observed to change during battery cycling. The modified coin cell design utilizes a completely different approach to in operando neutron diffraction experiments. The modified coin cells contain a large quantity of active material (~300-400 mg) to a much smaller amount of electrolyte (~10‑50 μL), separator and lithium metal. The smaller volume of electrolyte is particularly vital as it substantially reduces the cost of the experiment, as deuteration may no longer be necessary. The modified coin cell exhibited favourable electrochemistry when cycled at C/12 and enabled unit cell and phase fraction information to be extracted from in operando data collection conditions (5-15 min data sets). [1] M. Bianchini, E. Suard, L. Croguennec, C. Masquelier, J. Phys. Chem. C, 2014, 118, 25947. [2] R. Petibon, J. Li, N. Sharma, W.K. Pang, V.K. Peterson, J.R. Dahn, Electrochim. Acta, 2015, 174, 417.
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| 5. |
- Chien, Yu-Chuan, 1990-, et al.
(författare)
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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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Ingår i: Nature Communications. - : Springer Nature. - 2041-1723. ; 14:1
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Tidskriftsartikel (refereegranskat)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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| 6. |
- Ojwang, Dickson O., 1985-, et al.
(författare)
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Guest water hinders sodium-ion diffusion in low-defect Berlin green cathode material
- 2022
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Ingår i: Dalton Transactions. - : Royal Society of Chemistry (RSC). - 1477-9226 .- 1477-9234. ; 51:38, s. 14712-14720
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Tidskriftsartikel (refereegranskat)abstract
- Among Prussian blue analogues (PBAs), NaxFe[Fe(CN)(6)](1-y)center dot nH(2)O is a highly attractive cathode material for sodium-ion batteries due to its high theoretical capacity of similar to 170 mA h g(-1) and inexpensive raw materials. However, concerns remain over its long-term electrochemical performance and structural factors which impact sources of resistance in the material and subsequently rate performance. Refined control of the [Fe(CN)(6)] vacancies and water content could help in realizing its market potential. In this context, we have studied a low-defect Berlin green (BG) Na0.30(5)Fe[Fe(CN)(6)](0.94(2))center dot nH(2)O with varied water content corresponding to 10, 8, 6, and 2 wt%. The impact of water on the electrochemical properties of BG was systematically investigated. The electrodes were cycled within a narrow voltage window of 3.15-3.8 V vs. Na/Na+ to avoid undesired phase transitions and side reactions while preserving the cubic structure. We demonstrate that thermal dehydration leads to a significantly improved cycling stability of over 300 cycles at 15 mA g(-1) with coulombic efficiency of >99.9%. In particular, the electrode with the lowest water content exhibited the fastest Na+-ion insertion/extraction as evidenced by the larger CV peak currents during successive scans compared to hydrated samples. The results provide fundamental insight for designing PBAs as electrode materials with enhanced electrochemical performance in energy storage applications.
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| 7. |
- Ojwang, Dickson O., et al.
(författare)
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Influence of sodium content on the thermal behavior of low vacancy Prussian white cathode material
- 2020
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Ingår i: Dalton Transactions. - : ROYAL SOC CHEMISTRY. - 1477-9226 .- 1477-9234. ; 49:11, s. 3570-3579
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Tidskriftsartikel (refereegranskat)abstract
- Rechargeable sodium-ion batteries are the most attractive substitutes for lithium-ion batteries in large-scale energy storage devices due to wide spread reserves and low-cost of sodium resources and the similarities between sodium and lithium chemistry. However, finding a suitable cathode material is still a hurdle to be overcome. To date, Prussian white (PW), NaxFe[Fe(CN)(6)](y)center dot nH(2)O has stood out as one of the most promising Na-host materials due to its low cost, facile synthesis and competitive electrochemical capacity. Despite this, there are concerns that this material will thermally decompose at relatively low temperatures to form cyanogen gas, which is a safety hazard. Thus, low vacancy NaxFe[Fe(CN)(6)](y)center dot nH(2)O (x = 1.5, 1, 0.5 and 0) has been synthesized, and the influence of x on its thermal behavior systematically investigated. It is demonstrated that the thermal decomposition temperature, water content and moisture sensitivity of the samples strongly depend on the sodium content. The sample with x = 1.5 is found to be the most thermally stable and has the highest water content under the same experimental conditions. In addition, the sodium-rich samples (x = 1.5, 1 and 0.5) have higher surface water than the sodium-deficient one (x = 0). The local structure for this sample is also very different to the sodium-rich ones. Our findings offer new insights into the profound implications of proper material handling and safer operating conditions for practical Na-ion batteries and may be extended to analogous systems.
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| 8. |
- Slawinski, Wojciech Andrzej, 1980, et al.
(författare)
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Neutron Pair Distribution Function Study of FePO4 and LiFePO4
- 2019
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 1520-5002 .- 0897-4756. ; 31:14, s. 5024-5034
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Tidskriftsartikel (refereegranskat)abstract
- Neutron powder diffraction studies of the compounds FePO4 and LiFePO4 are reported. Rietveld refinement of the diffraction data provides averaged structures for both materials that are in good agreement with the published structures. In addition, detailed investigations of the short-range ion-ion correlations within each compound have been performed using the reverse Monte Carlo (RMC) modeling of the total scattering (Bragg plus diffuse) data. Although the short-range structural information for LiFePO4 is consistent with the long-range (averaged) picture, a small, but statistically significant, proportion of the anions is displaced away from their ideal sites within the RMC configurations of FePO4. These anion displacements are discussed in terms of a small concentration of Li+/Fe2+ occupying the empty octahedral sites, probably arising from incomplete delithiation of the LiFePO4 and/or antisite (Li+-Fe2+) defects introduced during the delithiation process.
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| 9. |
- van Ekeren, Wessel, et al.
(författare)
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A comparative analysis of the influence of hydrofluoroethers as diluents on solvation structure and electrochemical performance in non-flammable electrolytes
- 2023
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Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488 .- 2050-7496. ; 11:8, s. 4111-4125
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Tidskriftsartikel (refereegranskat)abstract
- To enhance battery safety, it is of utmost importance to develop non-flammable electrolytes. An emerging concept within this research field is the development of localized highly concentrated electrolytes (LHCEs). This type of liquid electrolyte relies on the concept of highly concentrated electrolytes (HCEs), but possesses lower viscosity, improved conductivity and reduced costs due to the addition of diluent solvents. In this work, two different hydrofluoroethers, i.e., bis(2,2,2-trifluoroethyl) ether (BTFE) and 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE), are studied as diluents in a phosphate-based non-flammable liquid electrolyte. These two solvents were added to a highly concentrated electrolyte of 3.0 M lithium bis(fluorosulfonyl)imide (LiFSI) in triethyl phosphate (TEP) whereby the salt concentration was diluted to 1.5 M. The solvation structures of the HCE and LHCE were studied by means of Raman spectroscopy and Nuclear Magnetic Resonance (NMR) spectroscopy, where the latter was shown to be essential to provide more detailed insights. By using molecular dynamics simulations, it was shown that a highly concentrated Li+-TEP solvation sheath is formed, which can be protected by the diluents TTE and BTFE. These simulations have also clarified the energetic interaction between the components in the LHCE, which supports the experimental results from the viscosity and the NMR measurements. By performing non-covalent interaction analysis (NCI) it was possible to show the main contributions of the observed chemical shifts, which indicated that TTE has a stronger effect on the solvation structure than BTFE. Moreover, the electrochemical performances of the electrolytes were evaluated in half-cells (Li|NMC622, Li|graphite), full-cells (NMC622|graphite) and Li metal cells (Li|Cu). Galvanostatic cycling has shown that the TTE based electrolyte performs better in full-cells and Li-metal cells, compared to the BTFE based electrolyte. Operando pressure measurements have indicated that no significant amount of gases is evolved in NMC622|graphite cells using the here presented LHCEs, while a cell with 1.0 M LiFSI in TEP displayed clear formation of gaseous products in the first cycles. The formation of gaseous products is accompanied by solvent co-intercalation, as shown by operando XRD, and quick cell failure. This work provides insights on understanding the solvation structure of LHCEs and highlights the relationship between electrochemical performance and pressure evolution.
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| 10. |
- Whittle, Thomas A., et al.
(författare)
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Novel insight into the structure and properties of lead-free dielectric Sr3TiNb4O15
- 2018
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Ingår i: Journal of Materials Chemistry C. - : The Royal Society of Chemistry. - 2050-7526 .- 2050-7534. ; 6:33, s. 8890-8896
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Tidskriftsartikel (refereegranskat)abstract
- Sr3TiNb4O15 has been synthesised and its structure and dielectric properties characterised. In contrast to previously reported results the compound has been found to form with Pna21 symmetry and unit cell dimensions a = 12.3631(19), b = 12.4027(19) and c = 7.7601(12) Å. Variable temperature studies show a phase transition from orthorhombic to tetragonal symmetry at approximately 625 K, much higher than previously reported. Temperature-dependent dielectric measurements have also been performed and these correlate very well with the observed phase transition temperature.
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