Ismael Gracia - Academia.edu (original) (raw)

Papers by Ismael Gracia

Solid Electrolytes for Advanced Applications, 2019

Polymer electrolytes are of prime importance for advanced lithium-based batteries in terms of hig... more Polymer electrolytes are of prime importance for advanced lithium-based batteries in terms of high-energy density, design flexibility and safety. In this chapter, we summarize the fundamental property requirements of materials for polymer electrolyte application. State of the art polymer hosts, salts and additives are reviewed along with the challenges faced in the current state of the art. Finally, the fabrication process (scaling-up) of Li metal polymer battery components, along with an overview of the current status of Li metal polymer batteries (Industrial), is presented. A brief conclusion and perspective for Li metal polymer batteries are also discussed.

Journal of Power Sources, 2018

Inverse vulcanization copolymers (p(S-DVB)) from the radical polymerization of elemental sulfur a... more Inverse vulcanization copolymers (p(S-DVB)) from the radical polymerization of elemental sulfur and divinylbenzene (DVB) have been studied as cathode active materials in poly(ethylene oxide) (PEO)-based all-solidstate Li-S cells. The Li-S cell comprising the optimized p(S-DVB) cathode (80:20 w/w S/DVB ratio) and lithium bis(fluorosulfonyl)imide/PEO (LiFSI/PEO) electrolyte shows high specific capacity (ca. 800 mAh g −1) and high Coulombic efficiency for 50 cycles. Most importantly, polysulfide (PS) shuttle is highly mitigated due to the strong interactions of PS species with polymer backbone in p(S-DVB). This is demonstrated by the stable cycling of the p(S-DVB)-based cell using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)/PEO electrolyte, where successful charging cannot be achieved even at the first cycle with plain elemental S-based cathode material due to the severe PS shuttle phenomenon. These results suggest that inverse vulcanization copolymers are promising alternatives to elemental sulfur for enhancing the electrochemical performance of PEO-based all-solid-state Li-S cells.

ChemElectroChem, 2018

Aluminum oxide (Al2O3) is a well-known electrolyte filler for stabilizing Li-metal (Li°) anode in... more Aluminum oxide (Al2O3) is a well-known electrolyte filler for stabilizing Li-metal (Li°) anode in all-solid-state Liº-based batteries. However, its strong interaction with lithium polysulfides (PS) hinders the direct application of Al2O3-added electrolytes in all-solid-state lithium-sulfur batteries (ASSLSBs). Herein, the role of Al2O3 in ASSLSBs both as electrolyte filler and cathode additive is studied. The combination of Al2O3-added electrolyte and Al2O3-added S8 cathode with optimum cell configuration could deliver an unprecedented discharge capacity of 0.85 mAh cm-2 (C/10, 30 cycles) for polymer-based ASSLSBs. These results suggest that the rational incorporation of Al2O3 can lead simultaneously to PS anchoring and Li° anode stabilizing benefits from the ceramic filler, thus improving the electrochemical performance of ASSLSBs.

Journal of the American Chemical Society, Jan 8, 2018

With a remarkably higher theoretical energy density compared to lithium-ion batteries (LIBs) and ... more With a remarkably higher theoretical energy density compared to lithium-ion batteries (LIBs) and abundance of elemental sulfur, lithium sulfur (Li-S) batteries have emerged as one of the most promising alternatives among all the post LIB technologies. In particular, the coupling of solid polymer electrolytes (SPEs) with the cell chemistry of Li-S batteries enables a safe and high-capacity electrochemical energy storage system, due to the better processability and less flammability of SPEs compared to liquid electrolytes. However, the practical deployment of all solid-state Li-S batteries (ASSLSBs) containing SPEs is largely hindered by the low accessibility of active materials and side reactions of soluble polysulfide species, resulting in a poor specific capacity and cyclability. In the present work, an ultrahigh performance of ASSLSBs is obtained via an anomalous synergistic effect between (fluorosulfonyl)(trifluoromethanesulfonyl)imide anions inherited from the design of lithium ...

Chemistry, an Asian journal, Jan 23, 2018

Owing to their resource abundance and hence reduction in cost, wider global distribution, environ... more Owing to their resource abundance and hence reduction in cost, wider global distribution, environmental benignity, and sustainability, sodium (Na) - based rechargeable batteries are believed to be the most feasible and enthralling energy storage devices. Accordingly, they have recently attracted the attention of both from the scientific and industry communities. However, in order to vie and go afar the dominating Li-ion technologies, a breakthrough research is urgently needed. Amongst all non-electrode components of the Na-based battery system, the electrolyte is considered as the most critical element, and its tailored design and formulation requests a top priority. The incorporation of a small dose of foreign molecules, called additives, brings a huge salient benefit to the electrolytes. Thus, this review presents the progress in the electrolyte additives for room temperature Na-based rechargeable batteries, enlisting Na-ion, Na-O2/air, Na-S and Na-intercalated cathode type-based ...

Chemistry - A European Journal, 2012

The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bri... more The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au 2 (mes) 2 (μ-LL)] (LL = dppe: 1,2-Bis(diphenylphosphano)ethane 1a, and water-soluble dppy: 1,2-Bis(di-3-pyridylphosphano)ethane 1b) with Ag + and Cu + lead to the formation of a family of heterometallic clusters with mesityl bridging ligands of the general formula [Au 2 M(μ-mes) 2 (μ-LL)]A (M = Ag, A = ClO 4 − , L-L = dppe 2a, dppy 2b; M = Ag, A = SO 3 CF 3 − , L-L = dppe 3a, dppy 3b; M = Cu, A = PF 6 − , L-L = dppe 4a, dppy 4b). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au 2 (mes) 2 (μ-dppy)] 1b and [Au 2 Ag(μ-mes) 2 (μdppe)]SO 3 CF 3 3a were determined by a single-crystal X-ray diffraction study. 3a in solid state is not a cyclic trinuclear Au 2 Ag derivative but it gives an open polymeric structure instead, with the {Au 2 (μ-dppe)} fragments "linked" by Ag(μ-mes) 2 units. The very short distances of 2.7559(6) Å (Au-Ag) and 2.9229(8) Å (Au-Au) are indicative of gold-silver (metallophillic) and aurophilic interactions. A systematic study of their luminescence properties revealed that all compounds are brightly luminescent in solid state, at room temperature (RT) and at 77 K, or in frozen DMSO solutions with lifetimes in the microsecond range and probably due to the self-aggregation of [Au 2 M(μ-mes) 2 (μ-LL)]+ units (M= Ag or Cu; LL= dppe or dppy) into an extended chain structure, through Au-Au and/or Au-M metallophylic interactions, as that observed for 3a. In solid state the heterometallic Au 2 M complexes with dppe (2a-4a) show a shift of emission maxima (from ca. 430 to the range of 520-540 nm) as compared to the parent dinuclear organometallic product 1a while the complexes with dppy (2b-4b) display a more moderate shift (505 for 1b to a max of 563 nm for 4b). More importantly, compound [Au 2 Ag(μ-mes) 2 (μ-dppy)]ClO 4 2b resulted luminescent in diluted DMSO solution at room temperature. Previously reported compound [Au 2 Cl 2 (μ-LL

Solid Electrolytes for Advanced Applications, 2019

Polymer electrolytes are of prime importance for advanced lithium-based batteries in terms of hig... more Polymer electrolytes are of prime importance for advanced lithium-based batteries in terms of high-energy density, design flexibility and safety. In this chapter, we summarize the fundamental property requirements of materials for polymer electrolyte application. State of the art polymer hosts, salts and additives are reviewed along with the challenges faced in the current state of the art. Finally, the fabrication process (scaling-up) of Li metal polymer battery components, along with an overview of the current status of Li metal polymer batteries (Industrial), is presented. A brief conclusion and perspective for Li metal polymer batteries are also discussed.

Journal of Power Sources, 2018

Inverse vulcanization copolymers (p(S-DVB)) from the radical polymerization of elemental sulfur a... more Inverse vulcanization copolymers (p(S-DVB)) from the radical polymerization of elemental sulfur and divinylbenzene (DVB) have been studied as cathode active materials in poly(ethylene oxide) (PEO)-based all-solidstate Li-S cells. The Li-S cell comprising the optimized p(S-DVB) cathode (80:20 w/w S/DVB ratio) and lithium bis(fluorosulfonyl)imide/PEO (LiFSI/PEO) electrolyte shows high specific capacity (ca. 800 mAh g −1) and high Coulombic efficiency for 50 cycles. Most importantly, polysulfide (PS) shuttle is highly mitigated due to the strong interactions of PS species with polymer backbone in p(S-DVB). This is demonstrated by the stable cycling of the p(S-DVB)-based cell using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)/PEO electrolyte, where successful charging cannot be achieved even at the first cycle with plain elemental S-based cathode material due to the severe PS shuttle phenomenon. These results suggest that inverse vulcanization copolymers are promising alternatives to elemental sulfur for enhancing the electrochemical performance of PEO-based all-solid-state Li-S cells.

ChemElectroChem, 2018

Aluminum oxide (Al2O3) is a well-known electrolyte filler for stabilizing Li-metal (Li°) anode in... more Aluminum oxide (Al2O3) is a well-known electrolyte filler for stabilizing Li-metal (Li°) anode in all-solid-state Liº-based batteries. However, its strong interaction with lithium polysulfides (PS) hinders the direct application of Al2O3-added electrolytes in all-solid-state lithium-sulfur batteries (ASSLSBs). Herein, the role of Al2O3 in ASSLSBs both as electrolyte filler and cathode additive is studied. The combination of Al2O3-added electrolyte and Al2O3-added S8 cathode with optimum cell configuration could deliver an unprecedented discharge capacity of 0.85 mAh cm-2 (C/10, 30 cycles) for polymer-based ASSLSBs. These results suggest that the rational incorporation of Al2O3 can lead simultaneously to PS anchoring and Li° anode stabilizing benefits from the ceramic filler, thus improving the electrochemical performance of ASSLSBs.

Journal of the American Chemical Society, Jan 8, 2018

With a remarkably higher theoretical energy density compared to lithium-ion batteries (LIBs) and ... more With a remarkably higher theoretical energy density compared to lithium-ion batteries (LIBs) and abundance of elemental sulfur, lithium sulfur (Li-S) batteries have emerged as one of the most promising alternatives among all the post LIB technologies. In particular, the coupling of solid polymer electrolytes (SPEs) with the cell chemistry of Li-S batteries enables a safe and high-capacity electrochemical energy storage system, due to the better processability and less flammability of SPEs compared to liquid electrolytes. However, the practical deployment of all solid-state Li-S batteries (ASSLSBs) containing SPEs is largely hindered by the low accessibility of active materials and side reactions of soluble polysulfide species, resulting in a poor specific capacity and cyclability. In the present work, an ultrahigh performance of ASSLSBs is obtained via an anomalous synergistic effect between (fluorosulfonyl)(trifluoromethanesulfonyl)imide anions inherited from the design of lithium ...

Chemistry, an Asian journal, Jan 23, 2018

Owing to their resource abundance and hence reduction in cost, wider global distribution, environ... more Owing to their resource abundance and hence reduction in cost, wider global distribution, environmental benignity, and sustainability, sodium (Na) - based rechargeable batteries are believed to be the most feasible and enthralling energy storage devices. Accordingly, they have recently attracted the attention of both from the scientific and industry communities. However, in order to vie and go afar the dominating Li-ion technologies, a breakthrough research is urgently needed. Amongst all non-electrode components of the Na-based battery system, the electrolyte is considered as the most critical element, and its tailored design and formulation requests a top priority. The incorporation of a small dose of foreign molecules, called additives, brings a huge salient benefit to the electrolytes. Thus, this review presents the progress in the electrolyte additives for room temperature Na-based rechargeable batteries, enlisting Na-ion, Na-O2/air, Na-S and Na-intercalated cathode type-based ...

Chemistry - A European Journal, 2012

The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bri... more The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au 2 (mes) 2 (μ-LL)] (LL = dppe: 1,2-Bis(diphenylphosphano)ethane 1a, and water-soluble dppy: 1,2-Bis(di-3-pyridylphosphano)ethane 1b) with Ag + and Cu + lead to the formation of a family of heterometallic clusters with mesityl bridging ligands of the general formula [Au 2 M(μ-mes) 2 (μ-LL)]A (M = Ag, A = ClO 4 − , L-L = dppe 2a, dppy 2b; M = Ag, A = SO 3 CF 3 − , L-L = dppe 3a, dppy 3b; M = Cu, A = PF 6 − , L-L = dppe 4a, dppy 4b). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au 2 (mes) 2 (μ-dppy)] 1b and [Au 2 Ag(μ-mes) 2 (μdppe)]SO 3 CF 3 3a were determined by a single-crystal X-ray diffraction study. 3a in solid state is not a cyclic trinuclear Au 2 Ag derivative but it gives an open polymeric structure instead, with the {Au 2 (μ-dppe)} fragments "linked" by Ag(μ-mes) 2 units. The very short distances of 2.7559(6) Å (Au-Ag) and 2.9229(8) Å (Au-Au) are indicative of gold-silver (metallophillic) and aurophilic interactions. A systematic study of their luminescence properties revealed that all compounds are brightly luminescent in solid state, at room temperature (RT) and at 77 K, or in frozen DMSO solutions with lifetimes in the microsecond range and probably due to the self-aggregation of [Au 2 M(μ-mes) 2 (μ-LL)]+ units (M= Ag or Cu; LL= dppe or dppy) into an extended chain structure, through Au-Au and/or Au-M metallophylic interactions, as that observed for 3a. In solid state the heterometallic Au 2 M complexes with dppe (2a-4a) show a shift of emission maxima (from ca. 430 to the range of 520-540 nm) as compared to the parent dinuclear organometallic product 1a while the complexes with dppy (2b-4b) display a more moderate shift (505 for 1b to a max of 563 nm for 4b). More importantly, compound [Au 2 Ag(μ-mes) 2 (μ-dppy)]ClO 4 2b resulted luminescent in diluted DMSO solution at room temperature. Previously reported compound [Au 2 Cl 2 (μ-LL