Figure - uploaded by Kang Xu
Content may be subject to copyright.
Scheme 30. Schematic Illustration of Lithium Ion Transport in Polyether Media (Redrawn from Ref 536)
Source publication
The late 1990s witnessed an explosive growth in lithium ion technology research, and essentially all aspects of lithium ion technology were explored with state-of-the-art techniques, while the main excitement revoved around developing new materials such as carbonaceous anode and metal oxide cathode materials and the electrolyte solvents and salts c...
Similar publications
The vulnerability of the shallow aquifer system for saline water intrusion has been evaluated using the classical tools at a coastal area, southern India. Groundwater samples (N=144) from Quaternary aquifer system within 25 km 2 area in pre-and post-monsoon seasons were analyzed for major ion chemistry including Electrical Conductivity (EC). The hy...
A discussion is given of the reason for the sharp fall-off observed in Dissociative Recombination (DR) cross sections above about 0.1 eV and of the need for accurate branching ratios being used in complex models of molecular ion chemistry. New measurements from TSR have shown that stored ions are not as cold as they were once thought to be and a ne...
The mass spectra and the ion molecule reactions of methylphosphine, dimethylphosphine and dimethyldeuterophosphine have been studied by ion cyclotron resonance spectrometry. About 50 ion molecule reaction are observed for each compound. The product ions can be classified as ions with two phosphorus atoms : P2R5+, P2R3+, P2R2.+ and P2R+ (R = CH3 or...
The FT-IR spectrum of chemically pure (C.P.) NO was obtained while the gas was being irradiated by radiation at 121.5 nm. A novel cell design allows the ultraviolet radiation and the infrared probe beam to be colinear. The exposure time of the gas to the UV radiation ranged from 0 to 100 minutes. Spectra were collected at evenly spaced time interva...
Citations
... The electrolytes currently in use are considerably limited due to their low flexibility, high fire risk, inefficient mass production processes, and environmental pollution from uncontrolled disposal (7)(8)(9). However, the electrolytes in biological systems are nontoxic, chemically stable, exhibit good ionic conductivity, and provide excellent energy storage performance (10)(11)(12). ...
Intrinsic impediments, namely weak mechanical strength, low ionic conductivity, low electrochemical performance, and stability have largely inhibited beyond practical applications of hydrogels in electronic devices and remains as a significant challenge in the scientific world. Here, we report a biospecies-derived genomic DNA hybrid gel electrolyte with many synergistic effects, including robust mechanical properties (mechanical strength and elongation of 6.98 MPa and 997.42%, respectively) and ion migration channels, which consequently demonstrated high ionic conductivity (73.27 mS/cm) and superior electrochemical stability (1.64 V). Notably, when applied to a supercapacitor the hybrid gel-based devices exhibit a specific capacitance of 425 F/g. Furthermore, it maintained rapid charging/discharging with a capacitance retention rate of 93.8% after ∼200,000 cycles while exhibiting a maximum energy density of 35.07 Wh/kg and a maximum power density of 193.9 kW/kg. This represents the best value among the current supercapacitors and can be immediately applied to minicars, solar cells, and LED lightning. The widespread use of DNA gel electrolytes will revolutionize human efforts to industrialize high-performance green energy.
... However, the chemical and thermodynamic stability of LiPF6, especially toward Li 0 , is insufficient. PF6 − rapidly decomposes at elevated temperatures and is hydrolytically sensitive, limiting its use in advanced batteries [40]. Alternatives to LiPF6, like LiBOB and LiDFOB, offer better thermal stability and can passivate Al foil, yet their low conductivity and solubility fail to satisfy battery system requirements [41]. ...
Asymmetric lithium salts, such as lithium (difluoromethanesulfonyl)(trifluoromethanesulfonyl)imide (LiDFTFSI), have been demonstrated to surpass traditional symmetric lithium salts with improved Li+ conductivity and the capacity to generate a stable solid electrolyte interphase (SEI) while maintaining compatibility with an aluminum (Al0) current collector. However, the intrinsic reductive mechanism through which LiDFTFSI influences battery performance remains unclear and under debate. Herein, detailed SEI reactions of LiDFTFSI–based electrolytes were investigated by combining density functional theory and molecular dynamics, aiming to clarify the formation process and atomic structure of the SEI. Our results show that asymmetric DFTFSI− weakens the interaction between carbonate solvents and Li+, and substantially alters the solvation structure, exhibiting a well-balanced coordination capacity compared to bis(trifluoromethanesulfonyl)imide (TFSI−). Nanosecond hybrid molecular dynamics simulation further reveals that preferential decomposition of LiDFTFSI produces sufficient LiF and Li2O to facilitate a robust SEI. Moreover, abundant F− generated from LiDFTFSI decomposition accumulates on the Al surface and subsequently combines with Al3+ from the current collector to form AlF3, potentially inhibiting corrosion of the current collector. Overall, these findings elucidate how LiDFTFSI regulates the solvation sheath and SEI structure, advancing the development of high-performance electrolytes compatible with current collectors.
... The electrolyte provides ionic conductivity between the electrodes: the cathode (positive) and the anode (negative). 4 There are other materials in alkaline batteries like plastics, coal particles (used as a binder in the cathode) and metals such as iron (Fe) or aluminum (Al) in trace amounts. 5 The ground mixture of the anode, cathode, and electrolyte is known as black mass (BM), and in the case of alkaline batteries, the BM is mainly composed of Zn, Mn, and K compounds. ...
BACKGROUND
Batteries play a vital role in meeting global energy needs. When their life cycle concludes, improperly discarded spent batteries can pose environmental risks primarily due to their metal content. In this sense, the recycling of metals contained in spent batteries could mean a huge advantage if they are extracted and purified using environmentally friendly processes.
RESULTS
In this study, the recovery of potassium (K), zinc (Zn) and manganese (Mn) from alkaline batteries was performed using a hydrometallurgical process consisting of neutral, acid and acid reductive leaching steps at room temperature and atmospheric pressure to extract K, Zn and Mn. In the neutral leaching step, 76.8 ± 3.4 (wt. %) of the K present in the spent batteries was extracted. Thus, in the acid leaching step, 90.9 ± 0.1 (wt. %) of the initial Zn and 36.7 ± 0.4 (wt. %) of the initial Mn was extracted using sulfuric acid (H2SO4) 2 M. In a subsequent acid reductive leaching step using H2SO4 2 M and oxygen peroxide (H2O2) 0.8 M as reducing agent, 8.7 ± 0.1 (wt. %) of the initial Zn and up to 49.4 ± 0.2 (wt. %) of the initial Mn were extracted.
CONCLUSION
The three‐unit process led to an overall extraction of 99.6 ± 0.3 (wt. %) of Zn and 86.1 ± 0.1 (wt. %) of Mn. Regarding the latter step, the extraction was not 100% because Mn complexes which are nearly insoluble were generated. This shows that extraction of valuable minerals from industrial residues is possible by hydrometallurgical processes. © 2024 The Authors. Journal of Chemical Technology and Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry (SCI).
... Li metal is susceptible to dendrite growth due to the presence of inorganic materials such as Li 2 O, LiOH, and Li 2 CO 3 covering its surface 9,10 . The physical and chemical heterogeneity of these materials causes an uneven distribution of surface currents, consequently leading to uncontrolled Li deposition after plating 11,12 . This phenomenon increases the risk factors such as explosiveness, ammability, and safety hazards of Li metal. ...
The development of Li metal batteries with increased lifespan and energy density is crucial for next-generation energy storage systems. To achieve this, it is necessary to control the growth of Li dendrites, which can lead to cycle performance issues and safety concerns. One approach to increasing the energy density of large-scale Li metal-based batteries is to use thin Li metal anodes. However, fabricating thin Li metal anodes from natural oxide layers can be difficult. In this study, we used pure Li metal powder to fabricate thin Li metal anodes, which do not possess a natural oxide layer. This resulted in Li plating with a low overpotential on the unprotected Li metal surface. Our fabricated LiMP symmetric cell maintained a stable cycle for over 170 hours at a current density of 1.0 mA/cm ² , demonstrating superior performance compared to bare Li metal foil. Furthermore, we evaluated the performance of an all-solid-state battery (ASSB) using a polymer solid electrolyte and an oxide-based solid electrolyte in the fabricated LiMP symmetric cell. At 0.1mA/cm ² , the conventional Li symmetric cell experienced polarization after 200 hours, while the LiMP symmetric cell remained stable even after 600 hours. Taken together, these results provide new insights into the development of high-performance Li metal batteries.
... However, the chemical and thermodynamic stability of LiPF6, especially toward Al 0 , is insufficient. PF6 -rapidly decomposes at elevated temperatures and is hydrolytically sensitive, limiting its use in advanced batteries [33]. Alternatives to LiPF6, like LiBOB and LiDFOB, offer better thermal stability and can passivate Al foil, yet their low conductivity and solubility fail to satisfy battery system requirements [34]. ...
Asymmetric lithium salts, such as Lithium (difluoromethanesulfonyl)(trifluoromethanesulfonyl)imide (LiDFTFSI), have been demonstrated to surpass traditional symmetric lithium salts with improved Li+ conductivity and the capacity to generate stable solid electrolyte interphase (SEI) while maintaining compatibility with aluminum (Al0) current collector. However, the intrinsic reductive mechanism through which LiDFTFSI influences battery performance remains unclear and under debate. Herein, the detailed SEI reactions of LiDFTFSI-based electrolytes were investigated by combining density functional theory and molecular dynamics, aiming to clarify the formation process and atomic structure of SEI. Our results show that asymmetric DFTFSI– weakens the interaction between carbonate solvents and Li+, and substantially alter the solvation structure, exhibiting a well-balanced coordination capacity to bis(trifluoromethanesulfonyl)imide (TFSI–). Nanoseconds hybrid molecular dynamics simulation further reveals that the preferential decomposition of LiDFTFSI produces sufficient LiF and Li2O to facilitate a robust SEI. Moreover, the abundant F– generated from LiDFTFSI decomposition accumulates on the Al surface and subsequently combines with Al3+ from the current collector to form AlF3, potentially inhibiting corrosion of the current collector. Overall, these findings elucidate how LiDFTFSI regulates the solvation sheath and SEI structure, advancing the development of high-performance electrolytes compatible with current collector.
... Nowadays, the electrolyte of LIB consists in lithium salts, that are dissolved in ammable organic solvents, such as diethyl carbonate or tetrahydrofuran. 3 From a safety point of view, the presence of these organic solvents is an open issue since they are highly ammable and volatile. When a LIB is fast charged, it oen develops an important generation of heat, that cannot easily be dissipated, resulting in possible thermal runways and explosions. ...
The hexagonal structure of LiBH4 at room temperature can be stabilised by substituting the BH4⁻ anion with I⁻, leading to high Li-ion conductive materials. A thermodynamic description of the pseudo-binary LiBH4–LiI system is presented. The system has been explored investigating several compositions, synthetized by ball milling and subsequently annealed. X-ray diffraction and Differential Scanning Calorimetry have been exploited to determine structural and thermodynamic features of various samples. The monophasic zone of the hexagonal Li(BH4)1−x(I)x solid solution has been experimentally defined equal to 0.18 ≤ x ≤ 0.60 at 25 °C. In order to establish the formation of the hexagonal solid solution, the enthalpy of mixing was experimentally determined, converging to a value of 1800 ± 410 J mol⁻¹. Additionally, the enthalpy of melting was acquired for samples that differ in molar fraction. By merging experimental results, literature data and ab initio theoretical calculations, the pseudo-binary LiBH4–LiI phase diagram has been assessed and evaluated across all compositions and temperature ranges by applying the CALPHAD method.
... Physical properties of some solvents[52]. ...
... Physical properties of some salts used in electrolytes[52]. ...
The reliability and efficiency of the energy storage system used in electric vehicles (EVs) is very important for consumers. The use of lithium-ion batteries (LIBs) with high energy density is preferred in EVs. However, the long range user needs and security issues such as fire and explosion in LIB limit the widespread use of these batteries. This review discusses the working principle, performance and failures of LIB. It provides an overview of LIB with particular emphasis on the factors that affect their performance and the factors that cause failures. Finally, potential batteries to replace lithium batteries in EVs are evaluated. In addition, the challenges of these future batteries are discussed. In this paper, we review studies in the field of batteries used in EVs, general problems and future battery technologies. Methods related to such topics are compared in terms of their advantages, disadvantages and qualitative factors. The authors believe that EVs will be the transportation vehicle of the future such that battery systems should be developed and academic studies should be carried out. The authors think this study will contribute to the EV and will provide a perspective to designers, researchers, manufacturers and companies working in the field of batteries.
... Lithium oxide (Li 2 O) is the second major ionic phase present in all model descriptions of the SEI 9, 10 . In Li-ion batteries, Li 2 O is the fully reduced form of typical carbonate solvents and is thus presumed to play a role in the passivation of graphite 23,24 . On Li, however, Li 2 O has received less focus, especially compared with LiF. ...
... often corrosive and toxic due to their high fluorine content. Whereas the particular blends reported herein are not optimal for full cells due the instability of non-fluorinated ethers at cathode potentials ( Supplementary Fig. 48), safety concerns associated with strongly oxidizing salts such as LiClO 4 24 , and limited high rate performance due to solvent viscosity ( Supplementary Fig. 49), these challenges motivate further research on non-fluorinated but cathodically stable salts and solvents such as sulfates and carbonates 24 . ...
Current electrolyte design for Li metal anodes emphasizes fluorination as the pre-eminent guiding principle for high Coulombic efficiency (CE) based largely on perceived benefits of LiF in the solid–electrolyte interphase (SEI). However, the lack of experimental techniques that accurately quantify SEI compositional breakdown impedes rigorous scrutiny of other potentially key phases. Here we demonstrate a quantitative titration approach to reveal Li2O content in cycled Li anodes, enabling this previously titration-silent phase to be compared statistically with a wide range of other leading SEI constituents including LiF. Across diverse electrolytes, CE correlates most strongly with Li2O above other phases, reaching its highest values when Li2O particles order along the SEI, demonstrating integrated chemical–structural function. The beneficial role of Li2O was exploited to create entirely fluorine-free electrolytes that breach >99% CE, highlighting electrolyte/SEI oxygenation as an underexplored design strategy.
... In such cases, the solute demonstrates higher solubility in a binary solvent compared to pure solvents [31][32][33] . However, the large diversity of potential solvent mixtures also renders the screening process more time-consuming and expensive, even with HTE systems 33,34 . A strategic approach would be to develop an ML-guided HTE system for targeted and efficient solubility data generation for ROMs in organic solvent systems. ...
Solubility of redox-active molecules is an important determining factor of the energy density in redox flow batteries. However, the advancement of electrolyte materials discovery has been constrained by the absence of extensive experimental solubility datasets, which are crucial for leveraging data-driven methodologies. In this study, we design and investigate a highly automated workflow that synergizes a high-throughput experimentation platform with a state-of-the-art active learning algorithm to significantly enhance the solubility of redox-active molecules in organic solvents. Our platform identifies multiple solvents that achieve a remarkable solubility threshold exceeding 6.20 M for the archetype redox-active molecule, 2,1,3-benzothiadiazole, from a comprehensive library of more than 2000 potential solvents. Significantly, our integrated strategy necessitates solubility assessments for fewer than 10% of these candidates, underscoring the efficiency of our approach. Our results also show that binary solvent mixtures, particularly those incorporating 1,4-dioxane, are instrumental in boosting the solubility of 2,1,3-benzothiadiazole. Beyond designing an efficient workflow for developing high-performance redox flow batteries, our machine learning-guided high-throughput robotic platform presents a robust and general approach for expedited discovery of functional materials.
... Currently, the stable working voltage of aqueous electrolytes is generally limited by the thermodynamic decomposition voltage of water (1.23 V). 26,27 Organic electrolytes (≥2 V) and ionic liquids (≥3 V) can achieve a higher operating voltage window. 28 Although they have broadened the operating voltage window, the high flammability and volatility of organic electrolytes cause serious safety issues, while ionic liquids are expensive and suffer from low ionic conductivity, hindering their large-scale applications. Therefore, there is ongoing research aiming to explore new electrolytes that outperform traditional ones. ...
The rapid advancement in the miniaturization, integration, and intelligence of electronic devices has escalated the demand for customizable micro-supercapacitors (MSCs) with high energy density. However, efficient micro-fabrication of safe and high-energy MXene MSCs for integrating microelectronics remains a significant challenge due to the low voltage window in aqueous electrolytes (typically ≤0.6 V) and limited areal mass loading of MXene microelectrodes. Here, we tackle these challenges by developing a high-concentration (18 mol kg −1) "water-in-LiBr" (WiB) gel electrolyte for MXene symmetric MSCs (M-SMSCs), demonstrating a record high voltage window of 1.8 V. Subsequently, additive-free aqueous MXene ink with excellent rheological behavior is developed for three-dimensional (3D) printing customizable all-MXene microelectrodes on various substrates. Leveraging the synergy of a high-voltage WiB gel electrolyte and 3D-printed microelectrodes, quasi-solid-state M-SMSCs operating stably at 1.8 V are constructed, and achieve an ultrahigh areal energy density of 1772 μWh cm −2 and excellent low-temperature tolerance, with a long-term operation at −40°C. Finally, by extending the 3D printing protocol, M-SMSCs are integrated with humidity sensors on a single planar substrate, demonstrating their reliability in miniaturized integrated microsystems. Carbon Energy. 2024;e481. wileyonlinelibrary.com/journal/cey2 |
