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Kanai, Yamato, Koji Hiraoka, Mutsuhiro Matsuyama e Shiro Seki. "Chemically and Physically Cross-Linked Inorganic–Polymer Hybrid Solvent-Free Electrolytes". Batteries 9, n. 10 (26 settembre 2023): 492. http://dx.doi.org/10.3390/batteries9100492.
Testo completoAbstract (sommario):
Safe, self-standing, all-solid-state batteries with improved solid electrolytes that have adequate mechanical strength, ionic conductivity, and electrochemical stability are strongly desired. Hybrid electrolytes comprising flexible polymers and highly conductive inorganic electrolytes must be compatible with soft thin films with high ionic conductivity. Herein, we propose a new type of solid electrolyte hybrid comprising a glass–ceramic inorganic electrolyte powder (Li1+x+yAlxTi2−xSiyP3−yO12; LICGC) in a poly(ethylene)oxide (PEO)-based polymer electrolyte that prevents decreases in ionic conductivity caused by grain boundary resistance. We investigated the cross-linking processes taking place in hybrid electrolytes. We also prepared chemically cross-linked PEO/LICGC and physically cross-linked poly(norbornene)/LICGC electrolytes, and evaluated them using thermal and electrochemical analyses, respectively. All of the obtained electrolyte systems were provided with homogenous, white, flexible, and self-standing thin films. The main ionic conductive phase changed from the polymer to the inorganic electrolyte at low temperatures (close to the glass transition temperature) as the LICGC concentration increased, and the Li+ ion transport number also improved. Cyclic voltammetry using [Li metal|Ni] cells revealed that Li was reversibly deposited/dissolved in the prepared hybrid electrolytes, which are expected to be used as new Li+-conductive solid electrolyte systems.
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Lv, Wenjing, Kaidong Zhan, Xuecheng Ren, Lu Chen e Fan Wu. "Comparing Charge Dynamics in Organo-Inorganic Halide Perovskite: Solid-State versus Solid-Liquid Junctions". Journal of Nanoelectronics and Optoelectronics 19, n. 2 (1 febbraio 2024): 121–28. http://dx.doi.org/10.1166/jno.2024.3556.
Testo completoAbstract (sommario):
In this study, we explore the dynamics of a perovskite-electrolyte photoelectrochemical cell, pivotal for advancing electrolyte-gated field effect transistors, water-splitting photoelectrochemical and photocatalytic cells, supercapacitors, and CO2 capture and reduction technologies. The instability of hybrid perovskite materials in aqueous electrolytes presents a significant challenge, yet recent breakthroughs have been achieved in stabilizing organo-inorganic halide perovskite films. This stabilization is facilitated by employing liquid electrolytes, specifically those formed by dissolving tetrabutylammoniumperchlorate in dichloromethane. A critical aspect of this research is the comparative analysis of charge and ion kinetics at the perovskite/liquid electrolyte interface versus the perovskite/solid charge transport layer interface. Employing Intensity Modulated Photocurrent Spectroscopy (IMPS), Open-Circuit Voltage Decay (OCVD), and Capacitance-Frequency (C-F) methods, the study scrutinizes charge dynamics in both perovskite/electrolyte and perovskite/solid interfaces. Furthermore, the investigation extends to contrasting the properties of solid–liquid and solid-state junctions, focusing on mobile ions, electric field impacts, and electron-hole transport. The research also examines variations in recombination resistance and ionic double layer charging in perovskite-based devices, aiming to elucidate the operational mechanisms and kinetic complexities at the hybrid perovskite/electrolyte interface.
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Choi, Kyoung Hwan, Eunjeong Yi, Kyeong Joon Kim, Seunghwan Lee, Myung-Soo Park, Hansol Lee e Pilwon Heo. "(Invited) Pragmatic Approach and Challenges of All Solid State Batteries: Hybrid Solid Electrolyte for Technical Innovation". ECS Meeting Abstracts MA2023-01, n. 6 (28 agosto 2023): 988. http://dx.doi.org/10.1149/ma2023-016988mtgabs.
Testo completoAbstract (sommario):
For the growth of electric vehicle market, lithium-ion batteries (LIBS) used in the EVs still requires safety and reliability. Unfortunately, large-scale application of the LIBs is being challenged due to the fact that the use of flammable liquid electrolytes has caused safety issues such as leakage and fire explosion. In this respect, all-solid-state batteries (ASSBs) have been intensively studied to ensure the safety and mileage that are superior to the current LIBs. In terms of solid electrolytes, oxide electrolytes not only shows high ionic conductivity (10-4 ~ 10-3 S/cm) but also high mechanical strength to suppress surface dendrite formation. In addition, the oxide electrolytes possess advantages such as non-flammability, high thermal stability, and excellent electrochemical stability (~ 6 V), enabling high temperature/high voltage operations of oxide-based ASSBs. However, most of oxide materials require a sintering process at high temperatures to form a planar solid electrolyte. And a lack of flexibility results in non-uniform electrolyte/electrode contact in the battery, which makes it difficult to apply the rigid oxide electrolyte directly. On the other hand, solid polymer electrolytes have also been actively investigated due to no leakage, good electrolyte/electrode contact, easy processing, flexibility, and good film formability. However, the solid polymer electrolytes have critical disadvantages such as low ionic conductivity at room temperature and low thermal/mechanical stability, which precludes commercialization of solid polymer-based ASSBs despite their advantages. To overcome each disadvantages of oxide and polymer electrolytes, we developed hybrid electrolytes for improved ionic conductivity, easy processing, and formation of continuous electrolyte/electrode interface. In this presentation, pragmatic approach and current challenges related to solid batteries will be discussed including innovative manufacturing process. Hybrid electrolytes and their synergistic effect on the battery performance as a promissing solution will be presented [Fig. 1]
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Liao, Cheng Hung, Chia-Chin Chen, Ru-Jong Jeng e Nae-Lih (Nick) Wu. "Application of Artificial Interphase on Ni-Rich Cathode Materials Via Hybrid Ceramic-Polymer Electrolyte in All Solid State Batteries". ECS Meeting Abstracts MA2023-01, n. 6 (28 agosto 2023): 1050. http://dx.doi.org/10.1149/ma2023-0161050mtgabs.
Testo completoAbstract (sommario):
Among many cathode materials, nickel-rich LiNi0.83Co0.12Mn0.05O2 (NCM 831205) has been spotlighted as one of the most feasible candidates for next-generation LIBs because of its high discharge capacity (~200 mAh/g). However, NCM 831205 shows significant performance degradation, which is mostly attributed to cation mixing, surface side reactions, and intrinsic structural instability originating from the large volume changes during repeated cycling. Conventional lithium ion batteries (LIB) normally use flammable nonaqueous liquid electrolytes, resulting in a serious safety issue in use. In this respect, all-solid-state batteries (ASSB) are regarded as a fundamental solution to address the safety issue by using a solid state electrolyte in place of the conventional liquid one. This work employed lithium sulfonate (SO3Li) tethered polymer, obtained from sulfonation of commercial polymer, to serve as the artificial protective coating on the active NCM831205 of the cathode for ASSB based on hybrid PEO-ceramic solid electrolyte. The coating layer should prevent direct contact of electrolyte with the cathode, thus avoid the negative effects such as microcracks of NCM831205 and undesired CEI formation. The preparation of hybrid ceramic-polymer electrolyte through a solvent-free process. The hybrid electrolytes exhibit good flexibility and processability with respect to pure ceramic and pure PEO polymer electrolyte. It is demonstrated that the hybrid electrolytes can penetrate into cathode under 60°C, providing a good Li+ transfer channel inside the battery. Moreover, the sulfone based polymer protective coating could effectively improve the electrochemical stability of the NCM831205 without sacrificing the battery performance. Keywords: NCM831205, Artificial Polymer Coating, All-Solid-State Batteries
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LI, X. D., X. J. YIN, C. F. LIN, D. W. ZHANG, Z. A. WANG, Z. SUN e S. M. HUANG. "INFLUENCE OF I2 CONCENTRATION AND CATIONS ON THE PERFORMANCE OF QUASI-SOLID-STATE DYE-SENSITIZED SOLAR CELLS WITH THERMOSETTING POLYMER GEL ELECTROLYTE". International Journal of Nanoscience 09, n. 04 (agosto 2010): 295–99. http://dx.doi.org/10.1142/s0219581x10006831.
Testo completoAbstract (sommario):
Thermosetting polymer gel electrolytes (TPGEs) based on poly(acrylic acid)-poly(ethylene glycol) (PAA-PEG) hybrid were prepared and applied to fabricate dye-sensitized solar cells (DSCs). N-methylpyrrolidone (NMP) and γ-butyrolactone (GBL) were used as solvents for liquid electrolytes and LiI and KI as iodide source, separately. The microstructure of PAA-PEG shows a well swelling ability in liquid electrolyte and excellent stability of the swollen hybrid. The TPGE was optimized in terms of the liquid electrolyte absorbency and ionic conductivity photovoltaic performance. Quasi-solid-state DSCs containing TPGE with optimized KI electrolyte show higher efficiency, voltage, fill factor, and lower photocurrent than those with LiI electrolyte. The related mechanism was discussed. A quasi-solid-state DSC fabricated with optimized polymer gel electrolyte obtained an overall energy conversion efficiency of 4.90% under irradiation of 100 mW/cm2 (AM1.5).
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Zahiri, Beniamin, Chadd Kiggins, Dijo Damien, Michael Caple, Arghya Patra, Carlos Juarez Yescaz, John B. Cook e Paul V. Braun. "Hybrid Halide Solid Electrolytes and Bottom-up Cell Assembly Enable High Voltage Solid-State Lithium Batteries". ECS Meeting Abstracts MA2022-01, n. 2 (7 luglio 2022): 327. http://dx.doi.org/10.1149/ma2022-012327mtgabs.
Testo completoAbstract (sommario):
Interface between halide based solid electrolytes and layered transition metal oxide cathodes has been found to be electro-chemically stable due to stability of chloride compounds, in particular, at >4V range. The extent of interfacial stability is correlated with the type of cationic and anionic species in the solid electrolyte compound, a fact supported by theoretical prediction and yet, not accurately measured in composite cathode mixtures. By altering the architecture of cathode into a dense additive-free structure, we have identified differences in interfacial stability of chloride compounds which are hidden in composite cathode formats. In this work, we report the use of dense cathode to track the electrochemical evolution of interface between a hybrid halide solid electrolyte composed of chloride and fluoride species. Introducing fluoride compounds is known to be a promising method to expand the oxidation stability while the nature of such expansion is found to be related to kinetics rather than thermodynamics, we report. Furthermore, fluorination of solid electrolyte is generally accompanied with loss of ionic conductivity due to strong electronegative fluoride ions. We demonstrate a fundamental change of solid-state battery assembly from conventional electrolyte pelletizing followed by electrode placement, to a bottom-up assembly route starting with dense cathode, thin (<20µm) layer of SE and anode addition, which compensates for the suppressed conductivity of fluorinated halide solid electrolytes. Through extensive characterization, compositional optimization, and electrochemical interfacial analysis, we demonstrate stable cycling of LiCoO2/hybrid halide solid electrolyte up to 4.4V vs. Li. Our findings pave the way for expanding the voltage stability of solid electrolytes without compromising the cell performance due to ionic conductivity overpotential issues.
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Zhai, Yanfang, Wangshu Hou, Zongyuan Chen, Zhong Zeng, Yongmin Wu, Wensheng Tian, Xiao Liang et al. "A hybrid solid electrolyte for high-energy solid-state sodium metal batteries". Applied Physics Letters 120, n. 25 (20 giugno 2022): 253902. http://dx.doi.org/10.1063/5.0095923.
Testo completoAbstract (sommario):
Exploring solid electrolytes with promising electrical properties and desirable compatibility toward electrodes for safe and high-energy sodium metal batteries remains a challenge. In this work, these issues are addressed via an in situ hybrid strategy, viz., highly conductive and thermally stable 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide is immobilized in nanoscale silica skeletons to form ionogel via a non-hydrolytic sol-gel route, followed by hybridizing with polymeric poly(ethylene oxide) and inorganic conductor Na3Zr2Si2PO12. Such hybrid design yields the required solid electrolyte, which shows not only a stable electrochemical stability window of 5.4 V vs Na/Na+ but also an extremely high ionic conductivity of 1.5 × 10−3 S cm−1 at 25 °C, which is demonstrated with the interacted and monolithic structure of the electrolyte by SEM, XRD, thermogravimetric (TG), and XPS. Moreover, the capabilities of suppressing sodium metal dendrite growth and enabling high-voltage cathode Mg-doped P2-type Na0.67Ni0.33Mn0.67O2 are verified. This work demonstrates the potential to explore the required solid electrolytes by hybridizing an in situ ionogel, a polymer, and an inorganic conductor for safe and high-energy solid-state sodium metal batteries.
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Vargas-Barbosa, Nella Marie, Sebastian Puls e Henry Michael Woolley. "Hybrid Material Concepts for Thiophosphate-Based Solid-State Batteries". ECS Meeting Abstracts MA2023-01, n. 6 (28 agosto 2023): 984. http://dx.doi.org/10.1149/ma2023-016984mtgabs.
Testo completoAbstract (sommario):
Solid-state batteries (SSBs) could replace conventional lithium-ion batteries due to the possibility of increasing the energy density of the cells by using lithium metal as the anode material.[1] Among the many electrolyte candidates for lithium SSBs, the lithium thiophosphates are particularly interesting due to their high ionic conductivities at room temperature (>1 mS/cm). However, the (electro)chemical stability of these solid electrolytes is limited and not fully compatible with state-of-the-art high-potential cathode active materials[2] or the lithium metal anode.[3] At the cell level, the formation of interparticle voids between the various battery components (solid electrolyte, cathode active material, anode material, additives, decomposition interphases) hinder the net transport during cycling. To address the latter electro-chemo-mechanical challenges, we are exploring hybrid material approaches, in which we combine established materials (solid electrolytes, liquid electrolytes and/or polymer additives) with state-of-the-art cathode active materials and test their electrochemical performance in solid-state battery (half-)cells. Such cycling results are complimented by detailed electrochemical transport studies in symmetrical cells using DC polarization and electrochemical impedance spectroscopy, including transmission-line modeling. ex.situ chemically-specific spectroscopic methods are used to support our hypotheses and interpretation of the electrochemical results. Taken together, we attain a better picture on the positive (or negative) role hybrid materials play in SSBs. In this talk, we will showcase two hybrid systems, namely ionic liquid/thiophosphate lithium hybrid electrolytes and conductive polymers additives in NMC-based catholyte composites for Li6PS5Cl cells. The first part of the talk we will discuss the results in which we evaluate the performance of liquid electrolyte-solid electrolyte materials against lithium metal using galvanostatic electrochemical impedance spectroscopy. In the second part, we elucidate the partial ionic and electronic transport in polymer electrolyte-Li6PS5Cl-NMC catholytes as a function of polymer content using impedance spectroscopy and its effect in the cycling performance, both the stability as well as the magnitude of the discharge capacities. These systems serve as a good starting point for the further development and incorporation of hybrid materials in SSBs. Literature: [1] W. G. Zeier and J. Janek Nature Energy, 2016, 1, 16141. [2] G.F. Dewald, S. Ohno, M.A. Kraft, R. Kroever, P. Till, N.M. Vargas-Barbosa, J. Janek, W.G. Zeier Chem. Mater. 2019, 31, 8328. [3] L. M. Riegger, R. Schlem, J. Sann, W. G. Zeier, J. Janek, Angew. Chem. Int Ed 2021, 60, 6718. Figure 1
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Zaman, Wahid, Nicholas Hortance, Marm B. Dixit, Vincent De Andrade e Kelsey B. Hatzell. "Visualizing percolation and ion transport in hybrid solid electrolytes for Li–metal batteries". Journal of Materials Chemistry A 7, n. 41 (2019): 23914–21. http://dx.doi.org/10.1039/c9ta05118j.
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Mohanty, Debabrata, Shu-Yu Chen e I.-Ming Hung. "Effect of Lithium Salt Concentration on Materials Characteristics and Electrochemical Performance of Hybrid Inorganic/Polymer Solid Electrolyte for Solid-State Lithium-Ion Batteries". Batteries 8, n. 10 (9 ottobre 2022): 173. http://dx.doi.org/10.3390/batteries8100173.
Testo completoAbstract (sommario):
Lithium-ion batteries are popular energy storage devices due to their high energy density. Solid electrolytes appear to be a potential replacement for flammable liquid electrolytes in lithium batteries. This inorganic/hybrid solid electrolyte is a composite of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, (poly(vinylidene fluoride-hexafluoro propylene) (PVDF-HFP) polymer and sodium superionic conductor (NASICON)-type Li1+xAlxTi2−x(PO4)3 (LATP) ceramic powder. The structure, morphology, mechanical behavior, and electrochemical performance of this composite solid electrolyte, based on various amounts of LiTFSI, were investigated. The lithium-ion transfer and conductivity increased as the LiTFSI lithium salt concentration increased. However, the mechanical strength apparently decreased once the percentage of LITFSI was over 60%. The hybrid electrolyte with 60% LiTFSI content showed high ionic conductivity of 2.14 × 10−4 S cm−1, a wide electrochemical stability window (3–6 V) and good electrochemical stability. The capacity of the Li|60% LiTFSI/PVDF-HFP/LATP| LiFePO4 solid-state lithium-metal battery was 103.8 mA h g−1 at 0.1 C, with a high-capacity retention of 98% after 50 cycles.
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Spencer Jolly, Dominic, Dominic L. R. Melvin, Isabella D. R. Stephens, Rowena H. Brugge, Shengda D. Pu, Junfu Bu, Ziyang Ning et al. "Interfaces between Ceramic and Polymer Electrolytes: A Comparison of Oxide and Sulfide Solid Electrolytes for Hybrid Solid-State Batteries". Inorganics 10, n. 5 (26 aprile 2022): 60. http://dx.doi.org/10.3390/inorganics10050060.
Testo completoAbstract (sommario):
Hybrid solid-state batteries using a bilayer of ceramic and solid polymer electrolytes may offer advantages over using a single type of solid electrolyte alone. However, the impedance to Li+ transport across interfaces between different electrolytes can be high. It is important to determine the resistance to Li+ transport across these heteroionic interfaces, as well as to understand the underlying causes of these resistances; in particular, whether chemical interphase formation contributes to giving high resistances, as in the case of ceramic/liquid electrolyte interfaces. In this work, two ceramic electrolytes, Li3PS4 (LPS) and Li6.5La3Zr1.5Ta0.5O12 (LLZTO), were interfaced with the solid polymer electrolyte PEO10:LiTFSI and the interfacial resistances were determined by impedance spectroscopy. The LLZTO/polymer interfacial resistance was found to be prohibitively high but, in contrast, a low resistance was observed at the LPS/polymer interface that became negligible at a moderately elevated temperature of 50 °C. Chemical characterization of the two interfaces was carried out, using depth-profiled X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry, to determine whether the interfacial resistance was correlated with the formation of an interphase. Interestingly, no interphase was observed at the higher resistance LLZTO/polymer interface, whereas LPS was observed to react with the polymer electrolyte to form an interphase.
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Spencer Jolly, Dominic, Dominic L. R. Melvin, Isabella D. R. Stephens, Rowena H. Brugge, Shengda D. Pu, Junfu Bu, Ziyang Ning et al. "Interfaces between Ceramic and Polymer Electrolytes: A Comparison of Oxide and Sulfide Solid Electrolytes for Hybrid Solid-State Batteries". Inorganics 10, n. 5 (26 aprile 2022): 60. http://dx.doi.org/10.3390/inorganics10050060.
Testo completoAbstract (sommario):
Hybrid solid-state batteries using a bilayer of ceramic and solid polymer electrolytes may offer advantages over using a single type of solid electrolyte alone. However, the impedance to Li+ transport across interfaces between different electrolytes can be high. It is important to determine the resistance to Li+ transport across these heteroionic interfaces, as well as to understand the underlying causes of these resistances; in particular, whether chemical interphase formation contributes to giving high resistances, as in the case of ceramic/liquid electrolyte interfaces. In this work, two ceramic electrolytes, Li3PS4 (LPS) and Li6.5La3Zr1.5Ta0.5O12 (LLZTO), were interfaced with the solid polymer electrolyte PEO10:LiTFSI and the interfacial resistances were determined by impedance spectroscopy. The LLZTO/polymer interfacial resistance was found to be prohibitively high but, in contrast, a low resistance was observed at the LPS/polymer interface that became negligible at a moderately elevated temperature of 50 °C. Chemical characterization of the two interfaces was carried out, using depth-profiled X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry, to determine whether the interfacial resistance was correlated with the formation of an interphase. Interestingly, no interphase was observed at the higher resistance LLZTO/polymer interface, whereas LPS was observed to react with the polymer electrolyte to form an interphase.
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Gu, Sui, Xiao Huang, Qing Wang, Jun Jin, Qingsong Wang, Zhaoyin Wen e Rong Qian. "A hybrid electrolyte for long-life semi-solid-state lithium sulfur batteries". Journal of Materials Chemistry A 5, n. 27 (2017): 13971–75. http://dx.doi.org/10.1039/c7ta04017b.
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Villaluenga, Irune, Kevin H. Wujcik, Wei Tong, Didier Devaux, Dominica H. C. Wong, Joseph M. DeSimone e Nitash P. Balsara. "Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries". Proceedings of the National Academy of Sciences 113, n. 1 (22 dicembre 2015): 52–57. http://dx.doi.org/10.1073/pnas.1520394112.
Testo completoAbstract (sommario):
Despite high ionic conductivities, current inorganic solid electrolytes cannot be used in lithium batteries because of a lack of compliance and adhesion to active particles in battery electrodes as they are discharged and charged. We have successfully developed a compliant, nonflammable, hybrid single ion-conducting electrolyte comprising inorganic sulfide glass particles covalently bonded to a perfluoropolyether polymer. The hybrid with 23 wt% perfluoropolyether exhibits low shear modulus relative to neat glass electrolytes, ionic conductivity of 10−4 S/cm at room temperature, a cation transference number close to unity, and an electrochemical stability window up to 5 V relative to Li+/Li. X-ray absorption spectroscopy indicates that the hybrid electrolyte limits lithium polysulfide dissolution and is, thus, ideally suited for Li-S cells. Our work opens a previously unidentified route for developing compliant solid electrolytes that will address the challenges of lithium batteries.
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Woolley, Henry Michael, e Nella Vargas-Barbosa. "Electrochemical Characterization of Thiophosphate- Ionic Liquid Hybrid Lithium Electrolytes Against Li Metal". ECS Meeting Abstracts MA2023-01, n. 6 (28 agosto 2023): 986. http://dx.doi.org/10.1149/ma2023-016986mtgabs.
Testo completoAbstract (sommario):
(Almost) solid-state batteries that utilize thiophosphate solid electrolytes (SE) are an exciting technology emerging as a potential alternative to lithium-ion batteries. When used alongside a lithium metal anode they can offer the high energy densities [1] required to meet the increasing demand for energy storage. However, they suffer from numerous issues which predominately occur at the cathode- or anode-SE interface. Issues include dendrite propagation through gaps, pores and grain boundaries of the solid electrolyte which can eventually puncture electrolyte crystallites and lead to cell failure. [2] Thiophosphate electrolytes are also unstable both chemically and electrochemically. As a result of the SEs having a low electrochemical stability window reduction or oxidation can occur at the anode or cathode interface, forming a resistive solid electrolyte interphase (SEI). [3] Finally, the ionic contact between Li metal anode and electrolyte is poor and thus high interfacial impedances can arise. These impedances can be dynamic which increase during stripping of the lithium and decrease during plating. [4] To solve some of the interfacial issues there is the option to add a small of amount of liquid electrolyte at the lithium metal-electrolyte interface. The liquid electrolyte can fill in the gaps and pores at the interface thus improving the ionic contact whilst allowing a more stable interface. Whilst the ionic contact can be improved the inherent instability of thiophosphate electrolytes against the liquid electrolyte means that a new interphase known as the solid-liquid electrolyte interphase (SLEI) can form. The presence of this interphase can therefore lower the energy density and round-trip efficiencies of cells which utilize hybrid electrolytes meaning that minimizing the SLEI resistance and maximizing total ionic conductivities is important in hybrid cells. [5] In this work a hybrid of the thiophosphate argyrodite Li6PS5Cl and the ionic liquid x-LiTFSI-1-butyl 1-methylpiperidinium TFSI (BMPipTFSI) with LiTFSI concentrations of 0.25 M and 0.5 M was studied. The choice of SE and liquid electrolyte boils down to the high ionic conductivity of the SE and the electrochemical and thermal stability of the ionic liquid. Temperature-dependent ionic conductivity measurements showed that hybrid systems exhibit lower in room temperature ionic conductivities and higher total activation energies. This hints at the presence of a SLEI forming between the LE and SE. To study how the SLEI resistances changes over time, ion blocking potential impedance spectroscopy measurements were performed. These measurements were performed at 10 °C to allow for the resistance contributions to be better resolved and showed a SLEI resistance of around 45-50 Ω cm2 for both hybrids. Over the period of 130 hours this resistance changed minimally (around 5 Ω cm2 on average) indicating good stability of the SLEI. To further test the suitability of this hybrid alongside lithium metal anodes impedance measurements in symmetrical lithium cells (Li0|LE|LPCL|LE|Li0) were undertaken. In this case galvanostatic impedance spectroscopy (GEIS) with an applied current density of ±0.4 mA cm-2 was used to probe the changes in resistance contributions in the system over the period of stripping (positive current) and plating (negative current). For cells with just SE a large change in the resistance owing to the electrochemical reaction (ECR) (Li0 ↔ Li+ + e-) occurred during stripping and plating indicating the dynamic nature of the ionic contact at the interface. For the hybrid electrolyte cells, this ECR resistance is decreased and becomes more stable however a larger interphase resistance is present. This resistance is a combination of the resistances of both the SLEI (the interphase between the LE and SE) and the SEI (the interphase between LE and Li anode) and it changes over stripping and plating showing that the S(L)EIs which are present are dynamic. Finally, post-mortem SEM/EDX of the surface of samples show a change in morphology and the presence of decomposition products from both the liquid and solid electrolytes. These studies show that the LPCL-BMPipTFSI hybrid is stable and improve ionic contact at the lithium metal anode interface. Further testing in half Li-S cells will determine the suitability of the use of the ionic liquid at the cathode side of the cell. References [1] J. Janek and W. G. Zeier, Nat Energy, 2016, 1, 16141. [2] M. B. Dixit et al. Matter, 2020, 3, 2138-2159 [3] G. Dewald et al. Chem Mater, 2019, 31, 8328-8337. [4] T. Krauskopf et al. Chem. Rev, 2020, 7745-7794. [5] H. M. Woolley and N. M. Vargas-Barbosa, under review.
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Lim, Seung, Juyoung Moon, Uoon Baek, Jae Lee, Youngjin Chae e Jung Park. "Shape-Controlled TiO2 Nanomaterials-Based Hybrid Solid-State Electrolytes for Solar Energy Conversion with a Mesoporous Carbon Electrocatalyst". Nanomaterials 11, n. 4 (3 aprile 2021): 913. http://dx.doi.org/10.3390/nano11040913.
Testo completoAbstract (sommario):
One-dimensional (1D) titanium dioxide (TiO2) is prepared by hydrothermal method and incorporated as nanofiller into a hybrid polymer matrix of polyethylene glycol (PEG) and employed as a solid-electrolyte in dye-sensitized solar cells (DSSCs). Mesoporous carbon electrocatalyst with a high surface area is obtained by the carbonization of the PVDC-g-POEM double comb copolymer. The 1D TiO2 nanofiller is found to increase the photoelectrochemical performance. As a result, for the mesoporous carbon-based DSSCs, 1D TiO2 hybrid solid-state electrolyte yielded the highest efficiencies, with 6.1% under 1 sun illumination, in comparison with the efficiencies of 3.9% for quasi solid-state electrolyte and 4.8% for commercial TiO2 hybrid solid-state electrolyte, respectively. The excellent photovoltaic performance is attributed to the improved ion diffusion, scattering effect, effective path for redox couple transfer, and sufficient penetration of 1D TiO2 hybrid solid-state electrolyte into the electrode, which results in improved light-harvesting, enhanced electron transport, decreased charge recombination, and decreased resistance at the electrode/electrolyte interface.
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Song, Shufeng, Masashi Kotobuki, Feng Zheng, Qibin Li, Chaohe Xu, Yu Wang, Wei Dong Z. Li, Ning Hu e Li Lu. "Al conductive hybrid solid polymer electrolyte". Solid State Ionics 300 (febbraio 2017): 165–68. http://dx.doi.org/10.1016/j.ssi.2016.12.023.
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CHENG, Xiong, Man LI, Yang Li, Seunghyun Song, Sowjanya Vallem e Joonho Bae. "Novel DNA-Based Polymer Solid Electrolytes for Lithium-Ion Batteries". ECS Meeting Abstracts MA2024-01, n. 2 (9 agosto 2024): 350. http://dx.doi.org/10.1149/ma2024-012350mtgabs.
Testo completoAbstract (sommario):
Solid electrolytes are becoming increasingly popular due to their safety [1], and the application of organic biomolecules in electrochemical devices is also an important strategy for sustainable development [2]. Recently, we have studied the application of DNA in electrochemical energy storage devices [3]. A novel PVDF@DNA solid polymer electrolyte was designed in this work, we studied the effect of different DNA addition amounts on polymer solid electrolytes. DNA as a plasticizer-like additive, reduces the crystallinity of the polymer solid electrolyte and improves its ionic conductivity [4]. At the same time, due to the Lewis acid effect of DNA, it can promote the dissociation of lithium salt when interacting with lithium salt anions, and it can also fix the anions, causing more free lithium ions in the electrolyte, thus improving its ionic conductivity. The polymer solid electrolyte with DNA shows relatively better performance. Hence, the DNA-based polymer solid electrolyte fabricated in this study has substantial potential for application in LSBs. Acknowledgement This work was supported by the National Research Foundation of Korea (NRF-2021R1A2C1008272). This work was supported by Ministry of Trade, Industry and Energy, KEIT, under the project title "International standard development of evaluation methods for nano-carbon-based high-performance supercapacitors for electric vehicles" (project # 20016144). References [1] Liang J. et al. Recent progress on solid-state hybrid electrolytes for solid-state lithium batteries. Energy Storage Materials 21 (2019) 308-334. [2] Dutta, D. et al. N7-(carboxymethyl)guanine-Lithium Crystalline Complex: A Bioinspired Solid Electrolyte. Scientific Reports 6 (2016) 24499. [3] Xue Y. et al. DNA-directed fabrication of NiCo2O4 nanoparticles on carbon nanotubes as electrodes for high-performance battery-like electrochemical capacitive energy storage device. Nano Energy 56 (2019) 751–758. [4] Li Z. et al. Ionic Conduction in Polymer-Based Solid Electrolytes. Advanced Science 10 (2023) 2201718.
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Kim, Jae-Kwang, Young Jun Lim, Hyojin Kim, Gyu-Bong Cho e Youngsik Kim. "A hybrid solid electrolyte for flexible solid-state sodium batteries". Energy & Environmental Science 8, n. 12 (2015): 3589–96. http://dx.doi.org/10.1039/c5ee01941a.
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Méry, Adrien, Steeve Rousselot, David Lepage, David Aymé-Perrot e Mickael Dollé. "Limiting Factors Affecting the Ionic Conductivities of LATP/Polymer Hybrid Electrolytes". Batteries 9, n. 2 (28 gennaio 2023): 87. http://dx.doi.org/10.3390/batteries9020087.
Testo completoAbstract (sommario):
All-Solid-State Lithium Batteries (ASSLB) are promising candidates for next generation lithium battery systems due to their increased safety, stability, and energy density. Ceramic and solid composite electrolytes (SCE), which consist of dispersed ceramic particles within a polymeric host, are among the preferred technologies for use as electrolytes in ASSLB systems. Synergetic effects between ceramic and polymer electrolyte components are usually reported in SCE. Herein, we report a case study on the lithium conductivity of ceramic and SCE comprised of Li1.4Al0.4Ti1.6(PO4)3 (LATP), a NASICON-type ceramic. An evaluation of the impact of the processing and sintering of the ceramic on the conductive properties of the electrolyte is addressed. The study is then extended to Poly(Ethylene) Oxide (PEO)-LATP SCE. The presence of the ceramic particles conferred limited benefits to the SCE. These findings somewhat contradict commonly held assumptions on the role of ceramic additives in SCE.
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Shah, Rajesh, Vikram Mittal e Angelina Mae Precilla. "Challenges and Advancements in All-Solid-State Battery Technology for Electric Vehicles". J 7, n. 3 (27 giugno 2024): 204–17. http://dx.doi.org/10.3390/j7030012.
Testo completoAbstract (sommario):
Recent advances in all-solid-state battery (ASSB) research have significantly addressed key obstacles hindering their widespread adoption in electric vehicles (EVs). This review highlights major innovations, including ultrathin electrolyte membranes, nanomaterials for enhanced conductivity, and novel manufacturing techniques, all contributing to improved ASSB performance, safety, and scalability. These developments effectively tackle the limitations of traditional lithium-ion batteries, such as safety issues, limited energy density, and a reduced cycle life. Noteworthy achievements include freestanding ceramic electrolyte films like the 25 μm thick Li0.34La0.56TiO3 film, which enhance energy density and power output, and solid polymer electrolytes like the polyvinyl nitrile boroxane electrolyte, which offer improved mechanical robustness and electrochemical performance. Hybrid solid electrolytes combine the best properties of inorganic and polymer materials, providing superior ionic conductivity and mechanical flexibility. The scalable production of ultrathin composite polymer electrolytes shows promise for high-performance, cost-effective ASSBs. However, challenges remain in optimizing manufacturing processes, enhancing electrode-electrolyte interfaces, exploring sustainable materials, and standardizing testing protocols. Continued collaboration among academia, industry, and government is essential for driving innovation, accelerating commercialization, and achieving a sustainable energy future, fully realizing the transformative potential of ASSB technology for EVs and beyond.
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Thangadurai, Venkataraman. "(Invited) Garnet Solid Electrolytes for Advanced All-Solid-State Li Metal Batteries". ECS Meeting Abstracts MA2022-02, n. 47 (9 ottobre 2022): 1759. http://dx.doi.org/10.1149/ma2022-02471759mtgabs.
Testo completoAbstract (sommario):
These days, Li metal anode-based battery has been arisen as one of the key energy storage technologies due to its high theoretical energy density compared to conventional lithium and sodium ion-based batteries. The present Li-S batteries suffer due to Li dendrite formation and capacity decay due to polysulfide dissolution effect, because of organic electrolytes used in the current research. Solid state (ceramic) electrolytes are promising to prevent Li dendrite growth and polysulfide dissolution. Among different ceramic electrolytes garnet-type structure solid inorganic electrolytes are very promising because of its high lithium-ion conductivity and stability with elemental Li. However, the high interfacial resistance with the electrode is the major bottleneck for the practical use of ceramic electrolyte. Polymer and ceramic hybrid electrolytes exhibit low interfacial resistance. In this talk, we will present development of electrolytes for all-solid-state Li metal batteries.
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Ryu, Kun, Kyungbin Lee, Hyun Ju, Jinho Park, Ilan Stern e Seung Woo Lee. "Ceramic/Polymer Hybrid Electrolyte with Enhanced Interfacial Contact for All-Solid-State Lithium Batteries". ECS Meeting Abstracts MA2022-02, n. 7 (9 ottobre 2022): 2621. http://dx.doi.org/10.1149/ma2022-0272621mtgabs.
Testo completoAbstract (sommario):
All solid-state lithium batteries (ASSLBs) with a high energy density are challenging, yet desired by the rising energy demands. Its intrinsic safety of solid-state electrolytes (SSEs) compared to flammable liquid electrolytes makes ASSLBs a modern-day necessity. NASICON-type Li1.5Al0.5Ge1.5P3O12 (LAGP) has high ionic conductivity, high stability against air and water, and a wide electrochemical window. However, the application of LAGP is significantly hindered by its slow interfacial kinetics and brittle nature. In addition, the ionic conductivity of LAGP is relatively low at room temperature compared to that obtained at elevated temperatures. In our study, LAGP was incorporated into a polymer matrix to accelerate charge transport at the electrode-electrolyte interface to form LAGP-poly-DOL (LAGP-pDOL) hybrid electrolyte. The in-situ cationic ring-opening polymerization of DOL decreases the interfacial contact impedance and improves the mechanical properties of the SSE. LAGP-pDOL electrolyte exhibits prolonged cycle stability in symmetric cells (> 200 h) and in Li|LiFePO4 full cells (99% retention after 50 cycles) at room temperature. This study demonstrates the effective utilization of conductive polymer matrix into LAGP to enhance mechanical strength, interfacial contact, and room temperature electrochemical performance.
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SHIMANO, Satoshi, e Itaru HONMA. "Organic-Inorganic Nano-Hybrid Solid-State-Electrolyte". Kobunshi 56, n. 3 (2007): 141. http://dx.doi.org/10.1295/kobunshi.56.141.
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Giffin, Guinevere A., Mara Goettlinger, Hendrik Bohn, Simone Peters, Mario Weller, Alexander Naßmacher, Timo Brändel e Alex Friesen. "Development of a Polymer-Based Silicon-NMC Solid-State Cell". ECS Meeting Abstracts MA2023-02, n. 2 (22 dicembre 2023): 373. http://dx.doi.org/10.1149/ma2023-022373mtgabs.
Testo completoAbstract (sommario):
Solid-state batteries are seen as the next generation of battery technology with the promise of high energy density and improved safety as compared to conventional lithium-ion batteries. To achieve these goals, high-capacity negative electrodes, e.g., silicon or lithium, need to be combined with high capacity and high voltage positive electrodes, e.g., Ni-rich NMC. This combination of active materials provides a number of significant challenges for the solid-state electrolyte. If silicon is used as the anode active material, significant volume changes during lithiation/delithiation occur. These volume changes lead to a variety of problems including irreversible loss of lithium and eventual disintegration of the electrodes, resulting in capacity fade. Therefore, the electrolyte must be sufficiently elastic to buffer these changes. If Ni-rich NMC is used as a cathode active material, then the electrolyte must be stable at voltages up to at least 4.2 V. There are currently few, if any, electrolyte solutions that can address these challenges simultaneously. In the ASTRABAT project, a silicon-NMC solid-state cell has been developed based on two tailored polymer electrolytes, which allows the specific challenges of each cell compartment to be addressed separately. A vinylidene fluoride copolymer-based electrolyte has been developed for use as a catholyte and a hybrid inorganic-organic polymer electrolyte as the anolyte. This work will report a characterization of both electrolytes, along with their electrochemical performance in solid-state half-cells and full-cells.
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Kim, Ji Sook, Sun Hwa Lee e Dong Wook Shin. "Fabrication of Hybrid Solid Electrolyte by LiPF6 Liquid Electrolyte Infiltration into Nano-Porous Na2O-SiO2-B2O3 Glass Membrane". Solid State Phenomena 124-126 (giugno 2007): 1027–30. http://dx.doi.org/10.4028/www.scientific.net/ssp.124-126.1027.
Testo completoAbstract (sommario):
To improve ion mobility in solid inorganic electrolyte for lithium ion battery, the hybrid electrolytes were developed in the form of the organic-inorganic meso-scale hybridization by the infiltration of liquid electrolyte into meso-porous inorganic glass membrane. Glass electrolyte membranes with nanopores were prepared by spinodal decomposition and subsequent acid leaching. The most suitable glass electrolyte membranes could be fabricated from the 7.5Na2O-46.25B2O3 -46.25SiO2 (mol%). The effect of leaching temperature, leaching time and leaching acids on the preparation of the membranes were investigated. The microstructure of the cross-section of 7.5Na2O-46.25B2O3-46.25SiO2 glass electrolytes were examined with a scanning electron microscope. Then, liquid electrolyte was infiltrated by dipping method into etched glasses electrolyte. Full cells were fabricated by LiCoO2 for cathode materials and MCMB for anode materials. Conductivity and charge-discharge test of the porous glass electrolyte membrane was measured.
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Thangadurai, Venkataraman. "(Invited) Lithium – Sulfur Batteries". ECS Meeting Abstracts MA2022-02, n. 4 (9 ottobre 2022): 545. http://dx.doi.org/10.1149/ma2022-024545mtgabs.
Testo completoAbstract (sommario):
These days, Li-S battery has been arisen as one of the key energy storage technologies due to its high theoretical energy density compared to conventional lithium and sodium ion-based batteries. The present Li-S batteries suffer due to Li dendrite formation and capacity decay due to polysulfide dissolution effect, due to organic electrolytes used in the current research. Solid state (ceramic) electrolytes are promising to prevent Li dendrite growth and polysulfide dissolution. Among different ceramic electrolytes garnet-type structure solid inorganic electrolytes are very promising because of its high lithium-ion conductivity and stability with elemental Li. However, the high interfacial resistance with the electrode is the major bottleneck for the practical use of ceramic electrolyte. Polymer and ceramic hybrid electrolytes exhibit low interfacial resistance. In this talk, we will present development of novel hybrid electrolytes for all-solid-state Li-S batteries, along with new methods to produce S cathodes with minimal polysulfide shuttle effect.
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Ji, Xiaoyu, Yiruo Zhang, Mengxue Cao, Quanchao Gu, Honglei Wang, Jinshan Yu, Zi-Hao Guo e Xingui Zhou. "Advanced inorganic/polymer hybrid electrolytes for all-solid-state lithium batteries". Journal of Advanced Ceramics 11, n. 6 (13 maggio 2022): 835–61. http://dx.doi.org/10.1007/s40145-022-0580-8.
Testo completoAbstract (sommario):
AbstractSolid-state batteries have become a frontrunner in humankind’s pursuit of safe and stable energy storage systems with high energy and power density. Electrolyte materials, currently, seem to be the Achilles’ heel of solid-state batteries due to the slow kinetics and poor interfacial wetting. Combining the merits of solid inorganic electrolytes (SIEs) and solid polymer electrolytes (SPEs), inorganic/polymer hybrid electrolytes (IPHEs) integrate improved ionic conductivity, great interfacial compatibility, wide electrochemical stability window, and high mechanical toughness and flexibility in one material, having become a sought-after pathway to high-performance all-solid-state lithium batteries. Herein, we present a comprehensive overview of recent progress in IPHEs, including the awareness of ion migration fundamentals, advanced architectural design for better electrochemical performance, and a perspective on unconquered challenges and potential research directions. This review is expected to provide a guidance for designing IPHEs for next-generation lithium batteries, with special emphasis on developing high-voltage-tolerance polymer electrolytes to enable higher energy density and three-dimensional (3D) continuous ion transport highways to achieve faster charging and discharging.
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Jiang, Wen, Lingling Dong, Shuanghui Liu, Bing Ai, Shuangshuang Zhao, Weimin Zhang, Kefeng Pan e Lipeng Zhang. "Improvement of the Interface between the Lithium Anode and a Garnet-Type Solid Electrolyte of Lithium Batteries Using an Aluminum-Nitride Layer". Nanomaterials 12, n. 12 (12 giugno 2022): 2023. http://dx.doi.org/10.3390/nano12122023.
Testo completoAbstract (sommario):
The next generation of all-solid-state batteries can feature battery safety that is unparalleled among conventional liquid batteries. The garnet-type solid-state electrolyte Li7La3Zr2O12 (LLZO), in particular, is widely studied because of its high Li-ion conductivity and stability in air. However, the poor interface-contact between Li and the electrolyte (garnet) severely limits the development of solid electrolytes. In this study, we synthesize cubic phase Li6.4La3Zr1.4Ta0.6O12 (LLZTO) using a secondary sintering method. In addition, a thin aluminum nitride (AlN) layer is introduced between the metal (Li) and the solid electrolyte. Theoretical calculations show that AlN has a high affinity for Li. Furthermore, it is shown that the AlN coating can effectively reduce the interface impedance between Li and the solid electrolyte and improve the lithium-ion transport. The assembled symmetric Li cells can operate stably for more than 3600 h, unlike the symmetric cells without AlN coating, which short-circuited after only a few cycles. The hybrid solid-state battery with a modified layer, which is assembled using LiFePO4 (LFP), still has a capacity of 120 mAh g−1 after 200 cycles, with a capacity retention rate of 98%. This shows that the introduction of an AlN interlayer is very helpful to obtain a stable Li/solid-electrolyte interface, which improves the cycling stability of the battery.
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Teshima, Katsuya, Hajime Wagata e Shuji Oishi. "All-Crystal-State Lithium-Ion Batteries: Innovation Inspired by Novel Flux Coating Method." Additional Conferences (Device Packaging, HiTEC, HiTEN, and CICMT) 2013, CICMT (1 settembre 2013): 000187–91. http://dx.doi.org/10.4071/cicmt-wp41.
Testo completoAbstract (sommario):
All-solid-state lithium-ion rechargeable batteries (LIBs) consisting of solid electrolyte materials have attracted a number of research interests because no use of organic liquid electrolyte increases packaging density and intrinsic safety of LIB, which contribute the development on environmentally-friendly automobiles such as electric vehicle (EV), hybrid vehicle (HV), and plug-in hybrid vehicle (HEV), in addition to efficient utilization of electric energy in smart grid. Among various solid electrolytes, inorganic electrolyte materials have achieved relatively high lithium-ion conductivity and better stability at an ambient atmosphere. Nevertheless, there is a drawback that is relatively high internal resistance owing to relatively slow Li ion movement caused by low crystallinity of materials, scattering at interfaces such as current collector/electrode active materials and electrode active materials/electrolyte materials. In this context, we have proposed a concept, all-crystal-state LIB, in which all the component materials have high crystallinity and those interfaces are effective for Li ion diffusion. Here, we present the fabrication of oxide crystals and crystal layers via flux method and flux coating. Flux method is one of the solution processes in which idiomorphic highly crystalline materials can be obtained under the melting point of the target ones. In addition, it provides simple, low-cost and environmentally-benign pathway compared to conventional solid-state-reaction method. Flux coating method is developed to fabricate high-quality crystal layers (films) on various substrates. High-quality crystals and crystal layers of cathode, anode and electrolyte materials were successfully fabricated.
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Kirchberger, Anna Maria, Patrick Walke e Tom Nilges. "Effect of Nanostructured Inorganic Ceramic Filler on Poly(ethylene oxide)-Based Solid Polymer Electrolytes". ECS Meeting Abstracts MA2023-01, n. 6 (28 agosto 2023): 991. http://dx.doi.org/10.1149/ma2023-016991mtgabs.
Testo completoAbstract (sommario):
In view of the ongoing changes in energy science and technology, the possibilities of energy storage are getting increasingly important. In particular, storing electrical energy is more complex than with fossil fuels. Lithium-Ion batteries are the most commonly used media for energy storage, but they also have some safety-related problems: toxic decomposition products can leak out and the devices can catch fire. Research is underway to find alternatives to minimize this potential hazards. Great improvements in safety matters can be achieved by replacing liquid electrolytes with ceramic/polymer hybrid electrolytes. These hybrid electrolytes combine the advantages of polymer electrolytes with the benefits of inorganic ceramic fillers.1 Flexibility, good contact ability and in addition the good processability is provided through the polymer. The inorganic ceramic filler in contrast adds mechanical stability, opens new pathways for the Lithium-Ions and can enhance the stability of the electrolyte. Figure 1: different Lithium-ion pathways in ceramic/polymer hybrid electrolytes dependent on different filler amounts. 2 In this work the impact of the manufacturing method on the conductivity of a series of electrolytes was examined. Therefore, hot pressing, solution casting and electrospinning were tested. Also, different distribution methods for the particles in the material were tested to monitor the influence of agglomeration on the conductivity. The materials were characterized regarding the crystallinity using X-Ray diffraction, the surface and particle distribution was monitored with SEM/EDX, the thermal character was investigated using DSC, the conductivity was determined using impedance spectroscopy and the electrochemical behavior was tested using cyclic voltammetry. Furthermore, the Arrhenius equation was used to interpret the results of impedance spectroscopy regarding their activation energy. The addition of inorganic ceramic fillers leads to an enhancement of the ionic conductivity in PEO based electrolytes and increases processability and stability of the electrolyte. In this work conductivities of 10-5 S/cm were reached at room temperature. The performance of the electrolyte was increased above three orders of magnitude compared to a PEO electrolyte without inorganic ceramic fillers. Walke, P.; Kirchberger, A.; Reiter, F.; Esken, D.; Nilges, T., Effect of nanostructured Al2O3 on poly(ethylene oxide)-based solid polymer electrolytes. Zeitschrift für Naturforschung B 2021, 76 (10-12), 615-624. Chen, L.; Li, Y.; Li, S.-P.; Fan, L.-Z.; Nan, C.-W.; Goodenough, J. B., PEO/garnet composite electrolytes for solid-state lithium batteries: From “ceramic-in-polymer” to “polymer-in-ceramic”. Nano Energy 2018, 46, 176-184. Figure 1
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Peng, Shihao, Jiakun Luo, Wenwen Liu, Xiaolong He e Fang Xie. "Enhanced Capacity Retention of Li3V2(PO4)3-Cathode-Based Lithium Metal Battery Using SiO2-Scaffold-Confined Ionic Liquid as Hybrid Solid-State Electrolyte". Molecules 28, n. 13 (21 giugno 2023): 4896. http://dx.doi.org/10.3390/molecules28134896.
Testo completoAbstract (sommario):
Li3V2(PO4)3 (LVP) is one of the candidates for high-energy-density cathode materials matching lithium metal batteries due to its high operating voltage and theoretical capacity. However, the inevitable side reactions of LVP with a traditional liquid-state electrolyte under high voltage, as well as the uncontrollable growth of lithium dendrites, worsen the cycling performance. Herein, a hybrid solid-state electrolyte is prepared by the confinement of a lithium-containing ionic liquid with a mesoporous SiO2 scaffold, and used for a LVP-cathode-based lithium metal battery. The solid-state electrolyte not only exhibits a high ionic conductivity of 3.14 × 10−4 S cm−1 at 30 °C and a wide electrochemical window of about 5 V, but also has good compatibility with the LVP cathode material. Moreover, the cell paired with a solid-state electrolyte exhibits good reversibility and can realize a stable operation at a voltage of up to 4.8 V, and the discharge capacity is well-maintained after 100 cycles, which demonstrates excellent capacity retention. As a contrast, the cell paired with a conventional liquid-state electrolyte shows only an 87.6% discharge capacity retention after 100 cycles. In addition, the effectiveness of a hybrid solid-state electrolyte in suppressing dendritic lithium is demonstrated. The work presents a possible choice for the use of a hybrid solid-state electrolyte compatible with high-performance cathode materials in lithium metal batteries.
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Muñoz, Bianca K., Jorge Lozano, María Sánchez e Alejandro Ureña. "Hybrid Solid Polymer Electrolytes Based on Epoxy Resins, Ionic Liquid, and Ceramic Nanoparticles for Structural Applications". Polymers 16, n. 14 (18 luglio 2024): 2048. http://dx.doi.org/10.3390/polym16142048.
Testo completoAbstract (sommario):
Solid polymer electrolytes (SPE) and composite polymer electrolytes (CPE) serve as crucial components in all-solid-state energy storage devices. Structural batteries and supercapacitors present a promising alternative for electric vehicles, integrating structural functionality with energy storage capability. However, despite their potential, these applications are hampered by various challenges, particularly in the realm of developing new solid polymer electrolytes that require more investigation. In this study, novel solid polymer electrolytes and composite polymer electrolytes were synthesized using epoxy resin blends, ionic liquid, lithium salt, and alumina nanoparticles and subsequently characterized. Among the formulations tested, the optimal system, designated as L70P30ILE40Li1MAl2 and containing 40 wt.% of ionic liquid and 5.7 wt.% of lithium salt, exhibited exceptional mechanical properties. It displayed a remarkable storage modulus of 1.2 GPa and reached ionic conductivities of 0.085 mS/cm at 60 °C. Furthermore, a proof-of-concept supercapacitor was fabricated, demonstrating the practical application of the developed electrolyte system.
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Wang, Linsheng. "Development of Novel High Li-Ion Conductivity Hybrid Electrolytes of Li10GeP2S12 (LGPS) and Li6.6La3Zr1.6Sb0.4O12 (LLZSO) for Advanced All-Solid-State Batteries". Oxygen 1, n. 1 (15 luglio 2021): 16–21. http://dx.doi.org/10.3390/oxygen1010003.
Testo completoAbstract (sommario):
A lithium superionic conductor of Li10GeP2S12 that exhibits the highest lithium ionic conductivity among the sulfide electrolytes and the most promising oxide electrolytes, namely, Li6.6La3Sr0.06Zr1.6Sb0.4O12 and Li6.6La3Zr1.6Sb0.4O12, are successfully synthesized. Novel hybrid electrolytes with a weight ratio of Li6.6La3Zr1.6Sb0.4O12 to Li10GeP2S12 from 1/1 to 1/3 with the higher Li-ion conductivity than that of the pure Li10GeP2S12 electrolyte are developed for the fabrication of the advanced all-solid-state Li batteries.
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Gerstenberg, Jessica, Dominik Steckermeier, Arno Kwade e Peter Michalowski. "Effect of Mixing Intensity on Electrochemical Performance of Oxide/Sulfide Composite Electrolytes". Batteries 10, n. 3 (7 marzo 2024): 95. http://dx.doi.org/10.3390/batteries10030095.
Testo completoAbstract (sommario):
Despite the variety of solid electrolytes available, no single solid electrolyte has been found that meets all the requirements of the successor technology of lithium-ion batteries in an optimum way. However, composite hybrid electrolytes that combine the desired properties such as high ionic conductivity or stability against lithium are promising. The addition of conductive oxide fillers to sulfide solid electrolytes has been reported to increase ionic conductivity and improve stability relative to the individual electrolytes, but the influence of the mixing process to create composite electrolytes has not been investigated. Here, we investigate Li3PS4 (LPS) and Li7La3Zr2O12 (LLZO) composite electrolytes using electrochemical impedance spectroscopy and distribution of relaxation times. The distinction between sulfide bulk and grain boundary polarization processes is possible with the methods used at temperatures below 10 °C. We propose lithium transport through the space-charge layer within the sulfide electrolyte, which increases the conductivity. With increasing mixing intensities in a high-energy ball mill, we show an overlay of the enhanced lithium-ion transport with the structural change of the sulfide matrix component, which increases the ionic conductivity of LPS from 4.1 × 10−5 S cm−1 to 1.7 × 10−4 S cm−1.
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Zhang, L. X., Y. Z. Li, L. W. Shi, R. J. Yao, S. S. Xia, Y. Wang e Y. P. Yang. "Electrospun Polyethylene Oxide (PEO)-Based Composite polymeric nanofiber electrolyte for Li-Metal Battery". Journal of Physics: Conference Series 2353, n. 1 (1 ottobre 2022): 012004. http://dx.doi.org/10.1088/1742-6596/2353/1/012004.
Testo completoAbstract (sommario):
Abstract Composite polymer electrolytes (CPEs) based on polyethylene oxide (PEO) offer manufacturing feasibility and outstanding mechanical flexibility. However, the low ionic conductivity of the CPEs at room temperature, as well as the poor mechanical properties, have hindered their commercialization. In this work, Solid-state electrolytes based on polyethylene oxide (PEO) with and without fumed SiO2 (FS) nanoparticles are prepared by electrostatic spinning process. The as-spun PEO hybrid nanofiber electrolyte with 6.85 wt% FS has a relatively high lithium ion conductivity and electrochemical stability, which is 4.8 × 10-4 S/cm and up to 5.2 V vs. Li+/Li, respectively. Furthermore, it also shows a higher tensile strength (2.03 MPa) with % elongation at break (561.8). Due to the superior electrochemical and mechanical properties, it is promising as high-safety and all-solid-state polymer electrolyte for advanced Li-metal battery.
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Zhang, Mi, A.-Man Zhang, Yifa Chen, Jin Xie, Zhi-Feng Xin, Yong-Jun Chen, Yu-He Kan, Shun-Li Li, Ya-Qian Lan e Qiang Zhang. "Polyoxovanadate-polymer hybrid electrolyte in solid state batteries". Energy Storage Materials 29 (agosto 2020): 172–81. http://dx.doi.org/10.1016/j.ensm.2020.04.017.
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Yan, Shuo, Chae-Ho Yim, Ali Merati, Elena A. Baranova, Yaser Abu-Lebdeh e Arnaud Weck. "Interfacial Challenge for Solid-State Lithium Batteries- Liquid Addition". ECS Meeting Abstracts MA2023-01, n. 6 (28 agosto 2023): 1010. http://dx.doi.org/10.1149/ma2023-0161010mtgabs.
Testo completoAbstract (sommario):
All solid-state lithium batteries with garnet electrolytes (Li7La3Zr2O12, LLZO) are promising energy storage devices that have gained increasing attention due to their huge potential towards non-flammability and higher energy density. However, reported solid-state lithium batteries cannot achieve the projected energy density (> 500 Wh/kg at the cell level) mainly due to insufficient contact and poor compatibility between LLZO and electrodes. The use of liquid electrolytes in small quantities has been suggested as a component in the quasi-solid hybrid electrolytes to address these two issues. However, the working principle of liquid electrolytes added as the interface inside the batteries is not clear yet. This study added 10L carbonate-based liquid electrolyte between LLZO and LiNi0.6Mn0.6Co0.2O2 (NMC 622) cathode. The assembled Li|LLZO|NMC 622 cell exhibited an initial discharge capacity of 168 mAh g-1 with a capacity retention ratio of ~82 % after 28 cycles. Scanning Transmission X-ray Microscopy revealed the reaction of LE with garnet and NMC 622. More importantly, the LE decomposed and solidified during the cycling process. Decomposed LE participated in the formation of a newly-identified solid-liquid electrolyte interface (SLEI) just after the 1st cycle. Furthermore, the X-ray Absorption Spectroscopy results indicated that the SLEI consisted predominantly of LiF, LaF3, Li2O, and Li2CO3 species. Overall, this study proved the solidification of liquid electrolytes at the garnet/cathode interface. The formation of SLEI effectively suppressed the degradation of the garnet electrolyte and stabilized the battery cycling performance. More efforts are required to optimize the liquid and establish a more stable SLEI that could expand the cycling life of the batteries.
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Lee, Yan Ying, e Andre Weber. "Harmonization of Testing Procedures for All Solid State Batteries". ECS Meeting Abstracts MA2023-02, n. 2 (22 dicembre 2023): 340. http://dx.doi.org/10.1149/ma2023-022340mtgabs.
Testo completoAbstract (sommario):
All Solid State Batteries (ASSBs) with lithium-ion based conducting solid state electrolytes are considered the next generation high performance batteries. They enable high power densities due to their single ion conducting solid electrolyte, eliminating salt concentration gradients and related polarization losses in the cell, and ensuring an unrivalled level of safety due to their non-combustibility. Currently, a variety of ASSBs based on different solid state electrolytes such as polymers, thiophosphates, oxides and combinations thereof are being developed. One general problem with ASSBs is establishing and maintaining contact between the solid electrolyte and the active material phase during production and cycling, respectively. In conventional lithium-ion batteries (LiBs), this contact is ensured by the liquid state of the electrolyte, but in ASSBs, chemical expansion and contraction of the active material during lithiation and delithiation can detach this contact, resulting in decreased capacity due to the loss of active material. As a consequence, ASSBs are often operated under pressurized conditions, applying pressures significantly exceeding those in conventional LiBs. The same holds for the operating temperature window. Especially for polymer electrolyte-based ASSBs, they are often operated at higher temperatures to compensate for the low ionic conductivity of polymers at room temperature. With respect to cell testing, such operating requirements must be considered, and testing protocols are designed according to the individual requirements of the tested cell. This contribution aims to provide an overview of testing protocols for various types of ASSBs applied to different cells with polymer-, thiophosphate-, oxide-, and hybrid-electrolytes. These protocols will be compared with standardized testing routines for conventional LiBs. Based on this compilation, a harmonized testing procedure that covers the special requirements of the individual cell types and enables a fair comparison of different ASSBs is suggested. Additionally, examples of ASSB testing results will be discussed, taking into consideration the harmonization of different testing parameters.
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Shah, Vaidik, e Yong Lak Joo. "Rationally Designed in-Situ Gelled Polymer-Ceramic Hybrid Electrolyte Enables Superior Performance and Stability in Quasi-Solid-State Lithium-Sulfur Batteries". ECS Meeting Abstracts MA2023-02, n. 4 (22 dicembre 2023): 535. http://dx.doi.org/10.1149/ma2023-024535mtgabs.
Testo completoAbstract (sommario):
Despite boasting giant leaps in performance improvement over the years, the current commercial standard, Li-ion batteries, are fast approaching their theoretical limits. Meanwhile, Lithium-Sulfur (Li-S) batteries offering ultra-high theoretical energy density (～2600 Whkg-1), cost-effectiveness, and nontoxicity are being seen as promising alternatives. Despite their plentiful advantages, the practicality of Li-S batteries has been largely stymied by several challenges: a) deleterious polysulfide dissolution and ‘shuttle effect’, b) significant volume change of S cathodes during cycling, c) safety concerns with flammable traditional glyme-based electrolyte, and d) the instability of Li anode. To mitigate these challenges, researchers have explored all-solid-state electrolytes, but their poor Li-ion conductivity, high interfacial impedance, and need for expensive, exotic materials and complex fabrication procedures severely limit their practical application. To overcome these challenges, we propose an in-situ gelled polymer-ceramic hybrid silsesquioxane-based electrolyte system. The gelled matrix, thermally crosslinked post cell fabrication, immobilizes the glyme-based liquid electrolyte and exhibits high liquid-like ionic conductivities (1.03 mS.cm-1), low interfacial impedance, and high oxidative potential (>4.5V vs. Li/Li+) . In this study, in addition to vastly decreased flammability, we report superior Li-ion conductivity compared to state-of-art solid-state Li-S electrolytes. This high ionic conductivity translated to a significantly improved specific capacity of 1050 mAh.gS-1 at 0.2 C, elevated Coulombic efficiencies (>98.5%), and elevated rate kinetics. The gelled electrolytes exhibited stable cycling in a large temperature range (-10oC - 60 oC). Moreover, polysulfide permeation studies and subsequent DFT calculations revealed that the gelled electrolyte exhibited strong chemical absorptivity to lithium polysulfides due to the polar silsesquioxane core, which translated to superior capacity retention (>80% over 200 cycles). Further, post- mortem XPS characterization studies revealed the formation of stable SEI at the anode and cathode, and SEM of cycled anodes showed reduced dendritic formations. Finally, the electrolyte was tested in practical pouch cell architecture, and the cells demonstrated excellent reliability even under mechanical stress. This work successfully reports a robust, rationally designed gelled electrolyte system for developing safe and high-performance quasi-solid state Li-S batteries.
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Kim, Jae-Kwang, Johan Scheers, Tae Joo Park e Youngsik Kim. "Superior Ion-Conducting Hybrid Solid Electrolyte for All-Solid-State Batteries". ChemSusChem 8, n. 4 (13 novembre 2014): 636–41. http://dx.doi.org/10.1002/cssc.201402969.
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Foran, Gabrielle, Nina Verdier, David Lepage, Cédric Malveau, Nicolas Dupré e Mickaël Dollé. "Use of Solid-State NMR Spectroscopy for the Characterization of Molecular Structure and Dynamics in Solid Polymer and Hybrid Electrolytes". Polymers 13, n. 8 (8 aprile 2021): 1207. http://dx.doi.org/10.3390/polym13081207.
Testo completoAbstract (sommario):
Solid-state NMR spectroscopy is an established experimental technique which is used for the characterization of structural and dynamic properties of materials in their native state. Many types of solid-state NMR experiments have been used to characterize both lithium-based and sodium-based solid polymer and polymer–ceramic hybrid electrolyte materials. This review describes several solid-state NMR experiments that are commonly employed in the analysis of these systems: pulse field gradient NMR, electrophoretic NMR, variable temperature T1 relaxation, T2 relaxation and linewidth analysis, exchange spectroscopy, cross polarization, Rotational Echo Double Resonance, and isotope enrichment. In this review, each technique is introduced with a short description of the pulse sequence, and examples of experiments that have been performed in real solid-state polymer and/or hybrid electrolyte systems are provided. The results and conclusions of these experiments are discussed to inform readers of the strengths and weaknesses of each technique when applied to polymer and hybrid electrolyte systems. It is anticipated that this review may be used to aid in the selection of solid-state NMR experiments for the analysis of these systems.
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Okos, Alexandru, Cristina Florentina Ciobota, Adrian Mihail Motoc e Radu-Robert Piticescu. "Review on Synthesis and Properties of Lithium Lanthanum Titanate". Materials 16, n. 22 (8 novembre 2023): 7088. http://dx.doi.org/10.3390/ma16227088.
Testo completoAbstract (sommario):
The rapid development of portable electronic devices and the efforts to find alternatives to fossil fuels have triggered the rapid development of battery technology. The conventional lithium-ion batteries have reached a high degree of sophistication. However, improvements related to specific capacity, charge rate, safety and sustainability are still required. Solid state batteries try to answer these demands by replacing the organic electrolyte of the standard battery with a solid (crystalline, but also polymer and hybrid) electrolyte. One of the most promising solid electrolytes is Li3xLa2/3−xTiO3 (LLTO). The material nevertheless presents a set of key challenges that must be resolved before it can be used for commercial applications. This review discusses the synthesis methods, the crystallographic and the ionic conduction properties of LLTO and the main limitations encountered through a number of selected studies on this material.
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Tang, Jiantao, Leidanyang Wang, Longzhen You, Xiang Chen, Tao Huang, Lan Zhou, Zhen Geng e Aishui Yu. "Effect of Organic Electrolyte on the Performance of Solid Electrolyte for Solid–Liquid Hybrid Lithium Batteries". ACS Applied Materials & Interfaces 13, n. 2 (8 gennaio 2021): 2685–93. http://dx.doi.org/10.1021/acsami.0c19671.
Testo completo
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Tsurumaki, Akiko, Rossella Rettaroli, Lucia Mazzapioda e Maria Assunta Navarra. "Inorganic–Organic Hybrid Electrolytes Based on Al-Doped Li7La3Zr2O12 and Ionic Liquids". Applied Sciences 12, n. 14 (21 luglio 2022): 7318. http://dx.doi.org/10.3390/app12147318.
Testo completoAbstract (sommario):
Organic–inorganic hybrid electrolytes based on Al-doped Li7La3Zr2O12 (LLZO) and two different ionic liquids (ILs), namely N-ethoxyethyl-N-methylpiperidinium bis(fluorosulfonyl)imide (FSI IL) and N-ethoxyethyl-N-methylpiperidinium difluoro(oxalato)borate (DFOB IL), were prepared with the aim of improvement of inherent flexibilities of inorganic solid electrolytes. The composites were evaluated in terms of thermal, spectroscopical, and electrochemical properties. In the impedance spectra of LLZO composites with 15 wt% ILs, a semi-circle due to grain boundary resistances was not observed. With the sample merely pressed with 1 ton, without any high-temperature sintering process, the ionic conductivity of 10−3 S cm−1 was achieved at room temperature. Employing a ternary composite of LLZO, FSI IL, and LiFSI as an electrolyte, all-solid-state lithium metal batteries having LiFePO4 as a cathode were assembled. The cell exhibited a capacity above 100 mAh g−1 throughout the course of charge–discharge cycle at C/20. This confirms that FSI IL is an effective additive for inorganic solid electrolytes, which can guarantee the ion conduction.
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Lin, Ruifan, Yingmin Jin, Yumeng Li, Xuebai Zhang e Yueping Xiong. "Recent Advances in Ionic Liquids—MOF Hybrid Electrolytes for Solid-State Electrolyte of Lithium Battery". Batteries 9, n. 6 (6 giugno 2023): 314. http://dx.doi.org/10.3390/batteries9060314.
Testo completoAbstract (sommario):
Li-ion batteries are currently considered promising energy storage devices for the future. However, the use of liquid electrolytes poses certain challenges, including lithium dendrite penetration and flammable liquid leakage. Encouragingly, solid electrolytes endowed with high stability and safety appear to be a potential solution to these problems. Among them, ionic liquids (ILs) packed in metal organic frameworks (MOFs), known as ILs@MOFs, have emerged as a hybrid solid-state material that possesses high conductivity, low flammability, and strong mechanical stability. ILs@MOFs plays a crucial role in forming a continuous interfacial conduction network, as well as providing internal ion conduction pathways through the ionic liquid. Hence, ILs@MOFs can not only act as a suitable ionic conduct main body, but also be used as an active filler in composite polymer electrolytes (CPEs) to meet the demand for higher conductivity and lower cost. This review focuses on the characteristic properties and the ion transport mechanism behind ILs@MOFs, highlighting the main problems of its applications. Moreover, this review presents an introduction of the advantages and applications of Ils@MOFs as fillers and the improvement directions are also discussed. In the conclusion, the challenges and suggestions for the future improvement of ILs@MOFs hybrid electrolytes are also prospected. Overall, this review demonstrates the application potential of ILs@MOFs as a hybrid electrolyte material in energy storage systems.
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Kim, Hyun Woo, Palanisamy Manikandan, Young Jun Lim, Jin Hong Kim, Sang-cheol Nam e Youngsik Kim. "Hybrid solid electrolyte with the combination of Li7La3Zr2O12 ceramic and ionic liquid for high voltage pseudo-solid-state Li-ion batteries". Journal of Materials Chemistry A 4, n. 43 (2016): 17025–32. http://dx.doi.org/10.1039/c6ta07268b.
Testo completoAbstract (sommario):
Concerning the safety aspects of high-voltage Li-ion batteries, a pelletized hybrid solid electrolyte (HSE) was prepared by blending Li7La3Zr2O12 (LLZO) ceramic particles and an ionic liquid electrolyte (ILE) for use in pseudo-solid-state Li-ion batteries.
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Luo, Wen-Bin, Shu-Lei Chou, Jia-Zhao Wang, Yong-Mook Kang, Yu-Chun Zhai e Hua-Kun Liu. "A hybrid gel–solid-state polymer electrolyte for long-life lithium oxygen batteries". Chemical Communications 51, n. 39 (2015): 8269–72. http://dx.doi.org/10.1039/c5cc01857a.
Testo completoAbstract (sommario):
A gel–solid state polymer electrolyte has been used as the separator and an electrolyte for lithium oxygen batteries, which can not only avoid electrolyte evaporation but also protect the lithium metal anode during reactions over long-term cycling.
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Bi, Jiaying, Daobin Mu, Borong Wu, Jiale Fu, Hao Yang, Ge Mu, Ling Zhang e Feng Wu. "A hybrid solid electrolyte Li0.33La0.557TiO3/poly(acylonitrile) membrane infiltrated with a succinonitrile-based electrolyte for solid state lithium-ion batteries". Journal of Materials Chemistry A 8, n. 2 (2020): 706–13. http://dx.doi.org/10.1039/c9ta08601c.
Testo completo
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Babkova, Tatiana, Rudolf Kiefer e Quoc Bao Le. "Hybrid Electrolyte Based on PEO and Ionic Liquid with In Situ Produced and Dispersed Silica for Sustainable Solid-State Battery". Sustainability 16, n. 4 (19 febbraio 2024): 1683. http://dx.doi.org/10.3390/su16041683.
Testo completoAbstract (sommario):
This work introduces the synthesis of hybrid polymer electrolytes based on polyethylene oxide (PEO) and electrolyte solution bis(trifluoromethane)sulfonimide lithium salt/ionic liquid 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (LiTFSI/EMIMTFSI) with in situ produced and dispersed silica particles by the sol–gel method. Conventional preparation of solid polymer electrolytes was followed by desolvation of lithium salt in a polymer matrix of PEO, which, in some cases, additionally contains plasticizers. This one-pot synthesis is an alternative route for fabricating a solid polymer electrolyte for solid-state batteries. The presence of TFSI- reduces the crystallinity of the PEO matrix (plasticizing effect), increases the dissociation and solubility of LiTFSI in the PEO matrix because of a highly delocalized charge distribution, and reveals excellent thermal, chemical, and electrochemical stability. Tetraethylorthosilicate (TEOS) was chosen due to the slow reaction rate, with the addition of (3-glycidyoxypropyl)trimethoxysilane (GLYMO), which contributes to the formation of a silica network. FTIR studies confirmed the interactions between the silica, the polymer salt, and EMIMTFSI. Impedance spectroscopy measurements were performed in a wide range of temperatures from 25 to 70 °C. The electrochemical performance was explored by assembling electrolytes in LiCoO2 (LCO), NMC(811), and LiFePO4 (LFP) coin half-cells. The HPEf15 shows a discharge capacity of 143 mA/g for NMC(811) at 0.1 C, 134 mA/g for LCO, and 139 mA/g for LFP half-cells at 0.1 C and 55 °C. The LFP half-cell with a discharge capacity of 135 mA/g at 0.1 C (safety potential range of 2.8 to 3.8) obtained a cyclability of 97.5% at 55 °C after 100 cycles. Such a type of electrolyte with high safety and good electrochemical performance provides a potential approach for developing a safer lithium-ion battery.