A proton pseudocapacitor, which benefits from the synergy effect between high ionic conductivity of electrolyte and pseudocapacitive electrode materials with open crystal structures to realize fast ...Grotthuss proton conduction, delivers a maximum energy density of 39 Wh kg−1 and a broadened electrochemical window of 0∼2.3 V at −60 °C.
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•A lower freezing point of high-concentration phosphoric acid electrolyte is achieved owing to the broken hydrogen bond network.•Pseudocapacitive WO3 anodes and VHCF cathodes achieve excellent electrochemical performance in this electrolyte from − 60 to 25 °C.•Proton pseudocapacitor delivers a maximum energy density of 39 Wh kg−1 and a broadened electrochemical window of 0 ∼ 2.3 V at − 60 °C.
A critical current challenge in the development of proton pseudocapacitors is developing antifreezing electrolytes and high-performance proton storage materials in extreme environments. Here, we design an antifreezing proton pseudocapacitor using a high-concentration phosphoric acid electrolyte and pseudocapacitive electrode materials, which delivers an outstanding rate capacity and cycle life below − 40 °C. Comprehensive physical characterization techniques and theoretical simulations demonstrate that the solvation structure of the electrolyte defines the freezing point and electrochemical stability window, which is crucial for achieving fast charge carrier mobility and avoiding side effects. The pseudocapacitive hydrated tungsten oxide anodes and Prussian blue analogue cathodes with their open crystal structures achieve fast proton transport and storage, resulting in excellent electrochemical performance from − 60 to 25 °C (1000 cycles with no capacity fading at − 40 °C). Benefiting from the synergistic effect between the electrolyte and electrode materials, the fabricated proton pseudocapacitors exhibit remarkable low-temperature electrochemical performance. It achieves a maximum energy density of 39 Wh kg−1 and a broadened electrochemical window from 1.7 V at 25 °C to 2.3 V at − 60 °C. This work provides a comprehensive strategy to develop high-performance proton energy storage devices under ultralow-temperature conditions.
•The whole process and technology of preparing suspended fertilizer by wet process phosphoric acid have been determined.•The types and optimal dosage of additives for suspended fertilizer were ...determined by comparing various methods.•The prepared suspension fertilizer performed well at different pH and temperature.•Various fitting models were used to fit the rheological properties of the suspended fertilizer, and the model parameters were obtained.
New water-soluble fertilizer can be applied to modern irrigation systems and has significant advantages. This study uses wet-process phosphoric acid as raw material and chelation and suspension technology to prepare water-soluble fertilizer containing high-concentration ammonium phosphate.
First, the composition and viscosity of the wet-process phosphoric acid was analyzed, and the ammoniation and chelation processes were explored. Subsequently, four suspension formulations were compared and selected after product analysis. The final process conditions are: 42 wt % (P2O5 %) phosphoric acid, 20 wt % chelating agent, pH = 4.5, 0.03 wt % xanthan gum or 0.02 wt % carboxymethyl cellulose of respectively, and obtain suspension fertilizer by high-speed shearing.
The Bingham model and Casson model were used to fit the rheological data of the two, and R2 values were greater than 0.94. The thixotropic loops of the two were measured using the triangular shear rate variation method mode, and the Huang equation and MBM models were used to fit the thixotropic loop data of the two respectively. In addition, at different pH and temperature, the suspended fertilizer performed well.
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Photocatalysis technology has been proved to be a promising strategy to eliminate antibiotic pollution from wastewater, in spite of arduous challenges such as insufficient utilization of sunlight, ...high recombination of photogenerated charges, low efficiency of high-concentration antibiotics, and infrequent investigation on new antibiotics. Herein, we synthesized a visible-light-driven (VLD) photocatalyst by modifying dodecyl benzene sulfonate (DBS) onto graphitic carbon nitride nanosheet (CNNS), and studied its photocatalytic performance for removing high-concentration moxifloxacin (MOX), a fourth-generation quinolone antibiotic. Compared with other studies (Table S1), this catalyst broke through the bottleneck of degradation of high concentration MOX, which could remove 100 mg L−1 MOX under 30 min of irradiation. The hydrophobic dodecyl benzene group and the formed sulfonyl group with strong electron-withdrawing property were beneficial to boost the MOX enrichment from the bulk solution and suppress the recombination of photogenerated charges. The effect of pH value, MOX concentration and photocatalyst dosage was also studied in order to explore the best photocatalytic reaction condition. The superior photocatalytic durability and practical application prospects of DBS/CNNS were also demonstrated. By revealing the band structure of the DBS/CNNS hybrid, as well as the active species and the intermediate products generated in the photocatalytic process, a plausible photocatalytic mechanism was proposed. This study indicates that the DBS/CNNS hybrid is a potential VLD photocatalyst for efficient elimination of high-concentration antibiotics in wastewater.
•Dodecyl benzene sulfonate was firstly grafted onto g-C3N4 nanosheet.•Electron-withdrawing effect was promoted by sulfonyl.•Pollutants enriched by hydrophobic dodecyl benzene group.•Photocatalytic degradation of high-concentration moxifloxacin.•Excellent photocatalytic stability for multiple uses.
Directly using aluminum (Al) foil as anode material offers a streamlined manufacturing process by eliminating the need for conductive additives, binders, and casting procedures. Nonetheless, ...monolithic Al foil anodes often suffer from mechanical failure and poor cyclability, posing challenges for practical adoption. In this study, a high‐concentration ether‐based electrolyte is employed to boost the durability of the Al foil anode. In contrast to traditional low‐concentration electrolytes, the use of 5 m lithium bis(fluorosulfonyl)imide in 1,2‐dimethoxyethane promotes the priority decomposition of anions, leading to the creation of a fluoride‐rich solid electrolyte interphase (SEI) layer with exceptional structural modulus and high ion conductivity. These outcomes, coupled with Al's superior compatibility in the chosen electrolyte, enable a record‐breaking cycle life of up to 400 cycles for Li//Al half‐cells, when operated at a high areal capacity of 1 mAh cm−2. In full‐cell configurations, an outstanding capacity retention is also observed, with 96.9% after 150 cycles even under practical conditions involving a 40 µm thin Al foil and a 7.4 mg cm−2 LiFePO4 cathode. These results not only mark the pioneering use of high‐concentration ether‐based electrolyte systems in Al foil anodes but also showcase the high potential for developing low‐cost and high‐energy Al foil‐based LIBs.
A record‐breaking cycle life of both Li//Al half‐cell and Al//LiFePO4 full‐cell under challenging conditions, is first reported by simply introducing high concentration ether‐based electrolyte into monolithic Al foil anode. This work highlights the pivotal role played by the composition and properties of the SEI in maintaining the structural stability of the Al foil anode, which is helpful to restart the practical adoption of the low‐cost and high‐energy Al foil‐based LIBs in a wide range of energy storage systems.
Li||NMC811 battery, with lithium‐metal (high specific capacity and low redox potential) as anode and LiNi0.8Co0.1Mn0.1O2 (NMC811) as cathode, has been widely accepted to be a good candidate as one of ...the high‐energy‐density batteries. However, its cyclability needs improvement to fulfill the requirement for its future commercial use, especially under practical conditions. Electrolyte plays a key role in improving the cycling performance of Li||NMC811 batteries, where a high voltage/electrochemical window and good stability with the electrodes of the electrolyte are required. Herein, a localized high‐concentration electrolyte with an additive of lithium difluoro(oxalate)borate (LiDFOB) is reported that improves the cycling performance of Li||NMC811 cells under crucial conditions with Li foil thickness of 50 µm, cathode areal loading of 4 mAh cm−2, the areal capacity ratio between the negative and positive electrodes (N/P ratio) of 2.6 and the electrolyte/cell capacity ratio (E/C ratio) of 3.0 g (Ah)−1. These cells can maintain 80% of the capacity after 195 cycles.
The cyclability for Li||NMC811 battery needs improvement to fill the gap between the current battery performance and that needed for its future commercial use, especially under practical conditions. The authors propose a localized high‐concentration electrolyte with lithium difluoro(oxalate)borate additive, which improves the cycling performance of Li||NMC811 cells with a high cathode loading and minimized excess components of anode and electrolyte.
High‐nickel layered oxide cathodes and lithium‐metal anode are promising candidates for next‐generation battery systems due to their high energy density. Nevertheless, the instability of the ...electrode–electrolyte interphase is hindering their practical application. Localized high‐concentration electrolytes (LHCEs) present a promising solution for achieving uniform lithium deposition and a stable cathode–electrolyte interphase. However, the limited choice of diluents and their high cost are restricting their implementation. Four novel cost‐effective diluents and their performance with highly reactive LiNiO2 cathode and Li‐metal anode are reported here. The results show that all the LHCE cells exhibit a Coulombic efficiency of >99.38% in Li | Cu cells and a capacity retention of >85% in Li | LiNiO2 cells after 250 cycles. Advanced characterizations unveil that the stable cell operation is due to well‐tuned electrode–electrolyte interphases and Li deposition morphology. In addition, online electrochemical mass spectroscopy and differential scanning calorimetry reveal that the gas generation and heat‐release are greatly reduced with the LHCEs presented. Overall, the study provides new insights into the role of diluents in LHCEs and offers valuable guidance for further optimization of LHCEs for high energy density lithium‐metal batteries.
Four novel, lower‐cost diluents have been developed for localized high‐concentration electrolytes that exhibit good compatibility with both lithium‐metal anode and LiNiO2 cathode, reflecting superior electrochemical performance with reduced gas generation and heat‐release.
High‐concentrated non‐flammable electrolytes (HCNFE) in lithium metal batteries prevent thermal runaway accidents, but the microstructure of their solid electrolyte interphase (SEI) remains largely ...unexplored, due to the lack of direct imaging tools. Herein, cryo‐HRTEM is applied to directly visualize the native state of SEI at the atomic scale. In HCNFE, SEI has a uniform laminated crystalline‐amorphous structure that can prevent further reaction between the electrolyte and lithium. The inorganic SEI component, Li2S2O7, is precisely identified by cryo‐HRTEM. Density functional theory (DFT) calculations demonstrate that the final Li2S2O7 phase has suitable natural transmission channels for Li‐ion diffusion and excellent ionic conductivity of 1.2 × 10‐5 S cm‐1.
The native state of solid electrolyte interphase (SEI) has been observed directly using Cryo‐HRTEM. In high‐concentrated non‐flammable electrolytes, SEI forms a uniform laminated crystalline‐amorphous structure that effectively inhibits further reaction between electrolytes and lithium. The stable dual‐layer SEI contributes to higher coulombic efficiency and excellent ionic conductivity.
The key to realize long‐life high energy density lithium batteries is to exploit functional electrolytes capable of stabilizing both high voltage cathode and lithium anode. The emergence of localized ...high‐concentration electrolytes (LHCEs) shows great promise for ameliorating the above‐mentioned interfacial issues. In this work, a lithium difluoro(oxalate)borate (LiDFOB) based nonflammable dual‐anion LHCE is designed and prepared. Dissolving in the mixture of trimethyl phosphate (TMP) /1,1,2,2‐tetrafluoroethyl‐2,2,3,3‐tetrafluoropropylether (D2), the continuously consumption of LiDFOB is suppressed by simply introducing lithium nitrate (LiNO3). Meantime, as most of the TMP molecular are coordinated with Li+, the electrolyte does not show incompatibility issue between neither metal lithium nor graphite anode. Therefore, it demonstrates excellent capability in stabilizing the interface of Ni‐rich cathode and regulating lithium deposition morphology. The Li||LiNi0.87Co0.08Mn0.05O2 (NCM87) batteries exhibit high capacity retention of more than 90% after 200 cycles even under the high cutoff voltage of 4.5 V, 1 C rate. This study offers a prospective method to develop safe electrolytes suitable for high voltage applications, thus providing higher energy densities.
A dual‐anion phosphate‐based nonflammable electrolyte was designed and prepared. Taking advantage of synergistic effect of LiDFOB and LiNO3, the electrolyte shows good compatibility with both high voltage cathode and lithium metal anode; meantime, the continuous consumption of LiDFOB is restrained by LiNO3. Thus, it shows impressive capacity retention of 97.8% after 200 cycles under high cutoff voltage of 4.5 V.
We designed a carboxylate-based localized high-concentration electrolyte that could enable the low-temperature and high-voltage operation of LiNi1.5Mn0.5O4 (LNMO)||Li batteries. Over 80% of the ...room-temperature discharge capacity at −50°C and reversibly cycling at −40°C were realized.
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•Stable LHCE enable low-temperature and high-voltage operation of LNMO||Li battery.•Realize discharging at −50 °C and reversible cycling at −40 °C.•Explain the influences of solvents and diluents on the solvation energy.•Propose a LHCE design principle with low-temperature and high-voltage properties.
Using localized high-concentration electrolytes (LHCEs), which have high oxidation resistance and low viscosity, in high-voltage lithium-ion batteries can facilitate the low-temperature operation of the batteries. In this study, a new short-chain fluorinated diluent 1,1,2,2-tetrafluoroethyl methyl ether is used to prepare a methyl acetate-based LHCE that shows good stability against a LiNi0.5Mn1.5O4 (LNMO) cathode. Furthermore, an LNMO||Li battery (3–4.9 V vs. Li/Li+) with the LHCE shows good cycling stability at room temperature at 1C. Owing to the excellent low-temperature performance of the LHCE, the battery can discharge 80.85% of its room temperature capacity at 0.2C at the temperature of −50 °C and show reversible charge/discharge behavior at 0.1C at the temperature of −40 °C. In this study, LHCEs are successfully used to realize a high-voltage battery that could operate with a relatively high current density (≥0.1C) at a low temperature (-50 °C).
Lithium‐metal batteries (LMB) employing cobalt‐free layered‐oxide cathodes are a sustainable path forward to achieving high energy densities, but these cathodes exhibit substantial transition‐metal ...dissolution during high‐voltage cycling. While transition‐metal crossover is recognized to disrupt solid‐electrolyte interphase (SEI) formation on graphite anodes, experimental evidence is necessary to demonstrate this for lithium‐metal anodes. In this work, advanced high‐resolution 3D chemical analysis is conducted with time‐of‐flight secondary‐ion mass spectrometry (TOF‐SIMS) to establish spatial correlations between the transition metals and electrolyte decomposition products found on cycled lithium‐metal anodes. Insights into the localization of various chemistries linked to crucial processes that define LMB performance, such as lithium deposition, SEI growth, and transition‐metal deposition are deduced from a precise elemental and spatial analysis of the SEI. Heterogenous transition‐metal deposition is found to perpetuate both heterogeneous SEI growth and lithium deposition on lithium‐metal anodes. These correlations are confirmed across various lithium‐metal anodes that are cycled with different cobalt‐free cathodes and electrolytes. An advanced electrolyte that is stable to higher voltages is shown to minimize transition‐metal crossover and its effects on lithium‐metal anodes. Overall, these results highlight the importance of maintaining uniform SEI coverage on lithium‐metal anodes, which is disrupted by transition‐metal crossover during operation at high voltages.
Transition metals that cross over from the cathode and deposit on the lithium‐metal anode during high‐voltage cycling (4.6 V) are shown to localize solid‐electrolyte interphase (SEI) formation and lithium deposition on cycled lithium‐metal anodes through advanced, high‐resolution 3D chemical analysis conducted with time‐of‐flight secondary‐ion mass spectrometry (TOF‐SIMS).
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