| 1. |
- Agostini, Marco, 1987, et al.
(författare)
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Designing a Safe Electrolyte Enabling Long‐Life Li/S Batteries
- 2019
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Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 12:18, s. 4176-4184
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Tidskriftsartikel (refereegranskat)abstract
- Lithium–sulfur (Li/S) batteries suffer from “shuttle” reactions in which soluble polysulfide species continuously migrate to and from the Li metal anode. As a consequence, the loss of active material and reactions at the surface of Li limit the practical applications of Li/S batteries. LiNO3 has been proposed as an electrolyte additive to reduce the shuttle reactions by aiding the formation of a stable solid electrolyte interphase (SEI) at the Li metal, limiting polysulfide shuttling. However, LiNO3 is continuously consumed during cycling, especially at low current rates. Therefore, the Li/S battery cycle life is limited by the LiNO3 concentration in the electrolyte. In this work, an ionic liquid (IL) [N-methyl-(n-butyl)pyrrolidinium bis(trifluoromethylsulfonyl)imide] was used as an additive to enable longer cycle life of Li/S batteries. By tuning the IL concentration, an enhanced stability of the SEI and lower flammability of the solutions were demonstrated, that is, higher safety of the battery. The Li/S cell built with a high sulfur mass loading (4 mg cm−2) and containing the IL-based electrolyte demonstrated a stable capacity of 600 mAh g−1 for more than double the number of cycles of a cell containing LiNO3 additive.
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| 2. |
- Liu, Qiao, et al.
(författare)
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Enhanced ionic conductivity and interface stability of hybrid solid-state polymer electrolyte for rechargeable lithium metal batteries
- 2019
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Ingår i: Energy Storage Materials. - : Elsevier BV. - 2405-8297. ; 23, s. 105-111
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Tidskriftsartikel (refereegranskat)abstract
- Compared to conventional organic liquid electrolyte, solid-state polymer electrolytes are extensively considered as an alternative candidate for next generation high-energy batteries because of their high safety, non-leakage and electrochemical stability with the metallic lithium (Li) anode. However, solid-state polymer electrolytes generally show low ionic conductivity and high interfacial impedance to electrodes. Here we report a hybrid solid-state electrolyte, presenting an ultra-high ionic conductivity of 3.27 mS cm −1 at room temperature, a wide electrochemical stability window of 4.9 V, and non-flammability. This electrolyte consists of a polymer blend matrix (polyethylene oxide and poly (vinylidene fluoride-co-hexafluoropropylene)), Li + conductive ceramic filler (Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 ) and a solvate ionic liquid (LiFSI in tetra ethylene glycol dimethyl ether, 1:1 in molar ratio) as plasticizer. The introduction of the solvate ionic liquid to the solid-state electrolyte not only improves its ionic conductivity but also remarkably enhances the stability of the interface with Li anode. When applied in Li metal batteries, a Li|Li symmetric cell can operate stably over 800 h with a minimal polarization of 25 mV and a full Li|LiFePO 4 cell delivers a high specific capacity of 158 mAh g −1 after 100 cycles at room temperature.
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| 3. |
- Liu, Yangyang, et al.
(författare)
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Insight into the Critical Role of Exchange Current Density on Electrodeposition Behavior of Lithium Metal
- 2021
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Ingår i: Advanced Science. - : Wiley. - 2198-3844 .- 2198-3844. ; 8:5
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Tidskriftsartikel (refereegranskat)abstract
- Due to an ultrahigh theoretical specific capacity of 3860 mAh g−1, lithium (Li) is regarded as the ultimate anode for high-energy-density batteries. However, the practical application of Li metal anode is hindered by safety concerns and low Coulombic efficiency both of which are resulted fromunavoidable dendrite growth during electrodeposition. This study focuses on a critical parameter for electrodeposition, the exchange current density, which has attracted only little attention in research on Li metal batteries. A phase-field model is presented to show the effect of exchange current density on electrodeposition behavior of Li. The results show that a uniform distribution of cathodic current density, hence uniform electrodeposition, on electrode is obtained with lower exchange current density. Furthermore, it is demonstrated that lower exchange current density contributes to form a larger critical radius of nucleation in the initial electrocrystallization that results in a dense deposition of Li, which is a foundation for improved Coulombic efficiency and dendrite-free morphology. The findings not only pave the way to practical rechargeable Li metal batteries but can also be translated to the design of stable metal anodes, e.g., for sodium (Na), magnesium (Mg), and zinc (Zn) batteries.
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| 4. |
- Rizell, Josef, 1996, et al.
(författare)
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Neutron Reflectometry Study of Solid Electrolyte Interphase Formation in Highly Concentrated Electrolytes
- 2023
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Ingår i: Small Structures. - : WILEY. - 2688-4062. ; 4:11
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Tidskriftsartikel (refereegranskat)abstract
- Highly concentrated electrolytes have been found to improve the cycle life and Coulombic efficiency of lithium metal anodes, as well as to suppress dendrite growth. However, the mechanism for these improvements is not well understood. Partly, this can be linked to the difficulty of accurately characterizing the solid electrolyte interphase (SEI), known to play an important role for anode stability and stripping/plating efficiency. Herein, in situ neutron reflectometry is used to obtain information about SEI formation in a highly concentrated ether-based electrolyte. With neutron reflectometry, the thickness, scattering length density (SLD), and roughness of the SEI layer formed on a Cu working electrode are nondestructively probed. The reflectivity data point to the formation of a thin (5 nm) SEI in the highly concentrated electrolyte (salt:solvent ratio 1:2.2), while a considerably thicker (13 nm) SEI is formed in an electrolyte at lower salt concentration (salt:solvent ratio 1:13.7). Further, the SEI formed in the electrolyte with high salt concentration has a higher SLD, suggesting that the chemical composition of the SEI changes. The results from neutron reflectometry correlate well with the electrochemical data from SEI formation.
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| 5. |
- Sadd, Matthew, 1994, et al.
(författare)
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Investigating microstructure evolution of lithium metal during plating and stripping via operando X-ray tomographic microscopy
- 2023
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723 .- 2041-1723. ; 14
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Tidskriftsartikel (refereegranskat)abstract
- Efficient lithium metal stripping and plating operation capable of maintaining electronic and ionic conductivity is crucial to develop safe lithium metal batteries. However, monitoring lithium metal microstructure evolution during cell cycling is challenging. Here, we report the development of an operando synchrotron X-ray tomographic microscopy method capable of probing in real-time the formation, growth, and dissolution of Li microstructures during the cycling of a Li||Cu cell containing a standard non-aqueous liquid electrolyte solution. The analyses of the operando X-ray tomographic microscopy measurements enable tracking the evolution of deposited Li metal as a function of time and applied current density and distinguishing the formation of electrochemically inactive Li from the active bulk of Li microstructures. Furthermore, in-depth analyses of the Li microstructures shed some light on the structural connectivity of deposited Li at different current densities as well as the formation mechanism of fast-growing fractal Li microstructures, which are ultimately responsible for cell failure.
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| 6. |
- Sadd, Matthew, 1994, et al.
(författare)
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Polysulfide Speciation and Migration in Catholyte Lithium−Sulfur Cells
- 2022
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Ingår i: ChemPhysChem. - : Wiley. - 1439-7641 .- 1439-4235. ; 23:4
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Tidskriftsartikel (refereegranskat)abstract
- Semi-liquid catholyte Lithium−Sulfur (Li−S) cells have shown to be a promising path to realize high energy density energy storage devices. In general, Li−S cells rely on the conversion of elemental sulfur to soluble polysulfide species. In the case of catholyte cells, the active material is added through polysulfide species dissolved in the electrolyte. Herein, we use operando Raman spectroscopy to track the speciation and migration of polysulfides in the catholyte to shed light on the processes taking place. Combined with ex-situ surface and electrochemical analysis we show that the migration of polysulfides is central in order to maximize the performance in terms of capacity (active material utilization) as well as interphase stability on the Li-metal anode during cycling. More specifically we show that using a catholyte where the polysulfides have the dual roles of active material and conducting species, e. g. no traditional Li-salt (such as LiTFSI) is present, results in a higher mobility and faster migration of polysulfides. We also reveal how the formation of long chain polysulfides in the catholyte is delayed during charge as a result of rapid formation and migration of shorter chain species, beneficial for reaching higher capacities. However, the depletion of ionic species during the last stage of charge, due to the conversion to and precipitation of elemental sulfur on the cathode support, results in polarization of the cell before full conversion can be achieved.
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