| 1. |
- Lindberg, Simon, 1987, et al.
(author)
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Charge storage mechanism of α-MnO2 in protic and aprotic ionic liquid electrolytes
- 2020
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In: Journal of Power Sources. - : Elsevier BV. - 0378-7753 .- 1873-2755. ; 460
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Journal article (peer-reviewed)abstract
- In this work we have investigated the charge storage mechanism of MnO2 electrodes in ionic liquid electrolytes. We show that by using an ionic liquid with a cation that has the ability to form hydrogen bonds with the active material (MnO2) on the surface of the electrode, a clear faradaic contribution is obtained. This situation is found for ionic liquids with cations that have a low pKa, i.e. protic ionic liquids. For a protic ionic liquid, the specific capacity at low scan rate rates can be explained by a densely packed layer of cations that are in a standing geometry, with a proton directly interacting through a hydrogen bond with the surface of the active material in the electrode. In contrast, for aprotic ionic liquids there is no interaction and only a double layer contribution to the charge storage is observed. However, by adding an alkali salt to the aprotic ionic liquid, a faradaic contribution is obtained from the insertion of Li+ into the surface of the MnO2 electrode. No effect can be observed when Li+ is added to the protic IL, suggesting that a densely packed cation layer in this case prevent Li-ions from reaching the active material surface.
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| 2. |
- Lindberg, Simon, 1985, et al.
(author)
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A VO2 based hybrid super-capacitor utilizing a highly concentrated aqueous electrolyte for increased potential window and capacity
- 2020
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In: Electrochimica Acta. - : Elsevier BV. - 0013-4686. ; 345
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Journal article (peer-reviewed)abstract
- In this work we demonstrate the application of a highly concentrated aqueous electrolyte to a hybrid supercapacitor cell. We combine an 8 m Sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) aqueous electrolyte with a nanostructured VO2-cathode to enhance the voltage widow up to 2.4 V in a full cell. With the enhanced potential window, we are able to exploit the full contribution of the VO2 material, where a part is outside the stability window of standard alkaline aqueous electrolytes. We show that the VO2 material in the highly concentrated electrolyte provides a faradaic contribution even at the highest current density (25 A/g) and in this way increases the energy content also in high power conditions. The full cell shows a good efficiency but also a capacity fade over 500 cycles (39%) which is most likely related to dissolution of VO2.
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| 3. |
- Agostini, Marco, 1987, et al.
(author)
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Designing Highly Conductive Functional Groups Improving Guest-Host Interactions in Li/S Batteries
- 2020
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In: Small. - : Wiley. - 1613-6810 .- 1613-6829. ; 16:2
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Journal article (peer-reviewed)abstract
- Li-sulfur batteries are of great interest due to their potential to surpass the energy densities of other battery types, but the low electronic conductivity of both sulfur and its discharge products requires the use of a conductive host material. The most common is the use of different porous carbons which normally are hydrophobic and hardly retain the polar discharge products of the Li/S reaction, such as Li2S and lithium polysulfides (LiPs), at the working electrode. Functionalized hosts have been proposed as a strategy to improve LiPs interactions, including the use of heteroatom doping, organic frameworks, metals, metal oxides, sulfide particles, and conductive polymers. Despite demonstrating an improved cycle life, the functionalized structures often have an intrinsic limitation related to a low electronic conductivity resulting in slow kinetics and poor rate capability of Li/S cells. Herein, recent research trends aimed at designing sulfur electrodes with highly conductive functional groups on nanostructured hosts surface are reviewed. The main concepts, key developments, and parameters for building 3D hosts architectures that enable fast charge rates and long cycle life at high sulfur loadings are discussed.
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| 4. |
- Calcagno, Giulio, 1990, et al.
(author)
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Effect of Nitrogen Doping on the Performance of Mesoporous CMK-8 Carbon Anodes for Li-Ion Batteries
- 2020
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In: Energies. - : MDPI AG. - 1996-1073 .- 1996-1073. ; 13:19
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Journal article (peer-reviewed)abstract
- Designing carbonaceous materials with heightened attention to the structural properties such as porosity, and to the functionalization of the surface, is a growing topic in the lithium-ion batteries (LIBs) field. Using a mesoporous silica KIT-6 hard template, mesoporous carbons belonging to the OMCs (ordered mesoporous carbons) family, namely 3D cubic CMK-8 and N-CMK-8 were synthesized and thoroughly structurally characterized. XPS analysis confirmed the successful introduction of nitrogen, highlighting the nature of the different nitrogen atoms incorporated in the structure. The work aims at evaluating the electrochemical performance of N-doped ordered mesoporous carbons as an anode in LIBs, underlining the effect of the nitrogen functionalization. The N-CMK-8 electrode reveals higher reversible capacity, better cycling stability, and rate capability, as compared to the CMK-8 electrode. Coupling the 3D channel network with the functional N-doping increased the reversible capacity to similar to 1000 mAh center dot g(-1) for the N-CMK-8 from similar to 450 mAh center dot g(-1) for the undoped CMK-8 electrode. A full Li-ion cell was built using N-CMK-8 as an anode, commercial LiFePO4, a cathode, and LP30 commercial electrolyte, showing stable performance for 100 cycles. The combination of nitrogen functionalization and ordered porosity is promising for the development of high performing functional anodes.
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| 5. |
- Calcagno, Giulio, 1990, et al.
(author)
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Fast charging negative electrodes based on anatase titanium dioxide beads for highly stable Li-ion capacitors
- 2020
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In: Materials Today Energy. - : Elsevier BV. - 2468-6069. ; 16
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Journal article (peer-reviewed)abstract
- Hybrid energy storage systems aim to achieve both high power and energy densities by combining supercapacitor-type and battery-type electrodes in tandem. The challenge is to find sustainable materials as fast charging negative electrodes, which are characterized by high capacity retention. In this study, mesoporous anatase beads are synthetized with tailored morphology to exploit fast surface redox reactions. The TiO2-based electrodes are properly paired with a commercial activated carbon cathode to form a Li-ion capacitor. The titania electrode exhibits high capacity and rate performance. The device shows extremely stable performance with an energy density of 27 mWh g-1 at a specific current of 2.5 A g−1 for 10,000 cycles. The remarkable stability is associated with a gradual shift of the potential during cycling as result of the formation of cubic LiTiO2 on the surface of the beads. This phenomenon renews the interest in using TiO2 as negative electrode for Li-ion capacitors.
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| 6. |
- Fretz, Samuel Joseph, 1987, et al.
(author)
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Amine- and Amide-Functionalized Mesoporous Carbons: A Strategy for Improving Sulfur/Host Interactions in Li-S Batteries
- 2020
-
In: Batteries and Supercaps. - : Wiley. - 2566-6223. ; 3:8, s. 757-765
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Journal article (peer-reviewed)abstract
- Lithium-sulfur (Li-S) batteries are of great interest due to their potentially high energy density, but the low electronic conductivity of both the sulfur (S-8) cathode active material and the final discharge product lithium sulfide (Li2S) require the use of a conductive host. Usually made of relatively hydrophobic carbon, such hosts are typically ill-suited to retain polar discharge products such as the intermediate lithium polysulfides (LiPs) and the final Li2S. Herein, we propose a route to increase the sulfur utilization by functionalizing the surface of ordered mesoporous carbon CMK3 with polar groups. These derivatized CMK3 materials are made using a simple two-step procedure of bromomethylation and subsequent nucleophilic substitution with amine or amide nucleophiles. We demonstrate that, compared to the unfunctionalized control, these modified CMK3 surfaces have considerably larger binding energies with LiPs and Li2S, which are proposed to aid the electrochemical conversion between S-8 and Li2S by keeping the LiPs species in close proximity to the carbon surface during Li-S battery cycling. As a result, the functionalized cathodes exhibit significantly improved specific capacities relative to their unmodified precursor.
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| 7. |
- Lindberg, Simon, 1985, et al.
(author)
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Electrochemical Behaviour of Nb-Doped Anatase TiO2 Microbeads in an Ionic Liquid Electrolyte
- 2020
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In: Batteries and Supercaps. - : Wiley. - 2566-6223. ; 3:11, s. 1233-1238
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Journal article (peer-reviewed)abstract
- TiO(2)is a promising material for high-power battery and supercapacitor applications. However, in general TiO(2)suffers from an initial irreversible capacity that limits its use in different applications. A combination of a microbead morphology, Nb-doping, and the use of an ionic liquid electrolyte is shown to significantly decrease the irreversible capacity loss. A change in the electrochemical response in the first cycles indicates formation of a solid-electrolyte interphase (SEI) or a modification of the structure of the surface layer of the TiO2/Nb microbeads, which apparently stabilises the performance. The change in the response is manifested in an increased charge transfer resistance and the presence of two charge transfer contributions. During prolonged cycling the TiO2/Nb electrode shows an excellent stability over 5000 cycles. Ex situ analysis after cycling shows that the overall microbead morphology is intact and that there are no changes in the crystal structure. However, a decrease in the intensity of the XRD pattern can point to a decrease in size of the nanocrystals building up the microbeads or the formation of amorphous phases.
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| 8. |
- Liu, Yangyang, et al.
(author)
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Promoted rate and cycling capability of Li–S batteries enabled by targeted selection of co-solvent for the electrolyte
- 2020
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In: Energy Storage Materials. - : Elsevier BV. - 2405-8297. ; 25, s. 131-136
-
Journal article (peer-reviewed)abstract
- Lithium sulfur (Li–S) batteries are considered as promising candidates for high-energy-density battery systems owing to the high theoretical capacity of sulfur (1675 mAh g−1) and low cost of raw materials. However, their practical application is hampered by low rate capability and rapid degradation of capacity, arising from the passivation of the cathode by lithium sulfides (Li2S2/Li2S) deposited during discharge and low interfacial stability of the Li anode. Herein, we report on a comprehensive strategy to select co-solvent to the electrolyte to regulate the deposition of lithium sulfides during charge-discharge process. We show that addition of a co-solvent with high solubility, and strong interaction with Li2S to a conventional electrolyte effectively mitigates the formation of a passivating layer on the sulfur cathode and dramatically improves the interfacial stability of the Li anode. We demonstrate that Sulfolane (SL) has these properties and that a Li–S cell with an electrolyte containing 6 vol% SL exhibits outstanding cyclic performance (0.083% decay per cycle) and rate capability (capacity density of 765 mAh g−1 at rate of 1.0C). Thus, we provide a facile strategy for the selection of co-solvent for improved performance of Li–S batteries, realizing their practical application for high-energy-density battery systems.
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| 9. |
- Liu, Yangyang, et al.
(author)
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Stable Li metal anode by crystallographically oriented plating through in-situ surface doping
- 2020
-
In: Science China Materials. - : Springer Science and Business Media LLC. - 2199-4501 .- 2095-8226. ; 63:6, s. 1036-1045
-
Journal article (peer-reviewed)abstract
- Lithium (Li) metal is regarded as the holy grail anode material for high-energy-density batteries owing to its ultrahigh theoretical specific capacity. However, its practical application is severely hindered by the high reactivity of metallic Li against the commonly used electrolytes and uncontrolled growth of mossy/dendritic Li. Different from widely-used approaches of optimization of the electrolyte and/or interfacial engineering, here, we report a strategy of in-situ cerium (Ce) doping of Li metal to promote the preferential plating along the [200] direction and remarkably decreased surface energy of metallic Li. The in-situ Ce-doped Li shows a significantly reduced reactivity towards a standard electrolyte and, uniform and dendrite-free morphology after plating/stripping, as demonstrated by spectroscopic, morphological and electrochemical characterizations. In symmetric half cells, the in-situ Ce-doped Li shows a low corrosion current density against the electrolyte and drastically improved cycling even at a lean electrolyte condition. Furthermore, we show that the stable Li LiCoO2 full cells with improved coulombic efficiency and cycle life are also achieved using the Ce-doped Li metal anode. This work provides an inspiring approach to bring Li metal towards practical application in high energy-density batteries.
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| 10. |
- Munoz-Garcia, Ana Belen, et al.
(author)
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Structural evolution of disordered LiCo(1/3)Fe(1/3)Mn(1/3)PO(4)in lithium batteries uncovered
- 2020
-
In: Journal of Materials Chemistry A. - : Royal Society of Chemistry (RSC). - 2050-7496 .- 2050-7488. ; 8:37, s. 19641-19653
-
Journal article (peer-reviewed)abstract
- In this study we address the Li-ion de-insertion/insertion mechanisms from/into the lattice of the mixed olivine LiCo1/3Fe1/3Mn1/3PO4(LCFMP). This mechanism is driven by a subtle interplay of structural, electronic and thermodynamic features. We aim at dissecting this complex landscape that is tightly connected to the long-term electrochemical performance of this material as a positive electrode in lithium-ion cells. To this end, we report advanced structural characterization, based onex situsynchrotronradiation diffraction on samples at different lithium contents. We couple this analysis with first-principles simulations, for a directvis-a-viscomparison. Our results show that (1) the mixing of the three transition-metal (TM) cations in the olivine lattice leads to a solid solution, providing the olivine lattice with the necessary flexibility to retain its single-phase structure during cell operation; (2) the electronic features of the three TMs are responsible for the observed electrochemical performance; (3) the de-lithiation of the olivine lattice is a thermodynamically driven process. Last but not least, our integrated experimental and theoretical results reveal the subtle features behind the formation of antisite defects that selectively involve Li-Co couples. In conclusion, our study provides the necessary scientific foundations to understand the structure-property-function relationships in LCFMP olivines, paving the way for further development and optimization of this material for application in Li-ion batteries.
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