The lifespan of high‐energy‐density lithium metal batteries (LMBs) is hindered by heterogeneous solid electrolyte interphase (SEI). The rational design of electrolytes is strongly considered to ...obtain uniform SEI in working batteries. Herein, a modification of nitrate ion (NO3−) is proposed and validated to improve the homogeneity of the SEI in practical LMBs. NO3− is connected to an ether‐based moiety to form isosorbide dinitrate (ISDN) to break the resonance structure of NO3− and improve the reducibility. The decomposition of non‐resonant −NO3 in ISDN enriches SEI with abundant LiNxOy and induces uniform lithium deposition. Lithium–sulfur batteries with ISDN additives deliver a capacity retention of 83.7 % for 100 cycles compared with rapid decay with LiNO3 after 55 cycles. Moreover, lithium–sulfur pouch cells with ISDN additives provide a specific energy of 319 Wh kg−1 and undergo 20 cycles. This work provides a realistic reference in designing additives to modify the SEI for stabilizing LMBs.
The modification of NO3− is achieved by connecting NO3− to an ether‐based moiety. The broken resonance structure of −NO3 improves its reducibility compared with NO3−. The decomposition of −NO3 forms a LiNxOy‐rich solid electrolyte interphase (SEI) and induces uniform Li deposition.
High‐energy‐density Li metal batteries suffer from a short lifespan under practical conditions, such as limited lithium, high loading cathode, and lean electrolytes, owing to the absence of ...appropriate solid electrolyte interphase (SEI). Herein, a sustainable SEI was designed rationally by combining fluorinated co‐solvents with sustained‐release additives for practical challenges. The intrinsic uniformity of SEI and the constant supplements of building blocks of SEI jointly afford to sustainable SEI. Specific spatial distributions and abundant heterogeneous grain boundaries of LiF, LiNxOy, and Li2O effectively regulate uniformity of Li deposition. In a Li metal battery with an ultrathin Li anode (33 μm), a high‐loading LiNi0.5Co0.2Mn0.3O2 cathode (4.4 mAh cm−2), and lean electrolytes (6.1 g Ah−1), 83 % of initial capacity retains after 150 cycles. A pouch cell (3.5 Ah) demonstrated a specific energy of 340 Wh kg−1 for 60 cycles with lean electrolytes (2.3 g Ah−1).
A solid electrolyte interphase (SEI) was proposed for practical high‐energy‐density Li batteries. The intrinsic uniformity and the constant supplements of building blocks of SEI jointly afford a sustainable SEI. A pouch cell with a specific energy of 340 Wh kg−1 underwent 60 cycles with a retention of 90 %.
Single‐atom catalysts (SACs) with highly active sites atomically dispersed on substrates exhibit unique advantages regarding maximum atomic efficiency, abundant chemical structures, and extraordinary ...catalytic performances for multiple important reactions. In particular, M–N–C SACs (M=transition metal atom) demonstrate optimal electrocatalytic activity for the oxygen reduction reaction (ORR) and have attracted extensive attention recently. Despite substantial efforts in fabricating various M–N–C SACs, the principles for regulating the intrinsic electrocatalytic activity of their active sites have not been sufficiently studied. In this Review, we summarize the regulation strategies for promoting the intrinsic electrocatalytic ORR activity of M–N–C SACs by modulation of the center metal atoms, the coordinated atoms, the environmental atoms, and the guest groups. Theoretical calculations and experimental investigations are both included to afford a comprehensive understanding of the structure–performance relationship. Finally, future directions of developing advanced M–N–C SACs for electrocatalytic ORR and other analogous reactions are proposed.
Regulation strategies for enhancing the intrinsic electrocatalytic oxygen reduction reaction activity of M–N–C single‐atom catalysts are summarized in this review. Four components are considered in the optimization of the catalyst: the center metal atoms, the coordinated atoms, the environmental atoms, and the guest groups.
Lithium–sulfur (Li–S) batteries promise great potential as high‐energy‐density energy‐storage devices due to their ultrahigh theoretical energy density of 2600 Wh kg−1. Evaluation and analysis on ...practical Li–S pouch cells are essential for achieving actual high energy density under working conditions and affording developing directions for practical applications. This review aims to afford a comprehensive overview of high‐energy‐density Li–S pouch cells regarding 7 years of development and to point out further research directions. Key design parameters to achieve actual high energy density are addressed first, to define the research boundaries distinguished from coin‐cell‐level evaluation. Systematic analysis of the published literature and cutting‐edge performances is then conducted to demonstrate the achieved progress and the gap toward practical applications. Following that, failure analysis as well as promotion strategies at the pouch cell level are, respectively, discussed to reveal the unique working and failure mechanism that shall be accordingly addressed. Finally, perspectives toward high‐performance Li–S pouch cells are presented regarding the challenges and opportunities of this field.
High‐energy‐density lithium–sulfur pouch cells are cpomprehensively reviewed regarding the key design parameters, the current performances, and recent advances on failure analysis and promotion strategies on cathode, electrolyte, and anode.
Safe and rechargeable lithium metal batteries have been difficult to achieve because of the formation of lithium dendrites. Herein an emerging electrolyte based on a simple solvation strategy is ...proposed for highly stable lithium metal anodes in both coin and pouch cells. Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO3) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions, and forming a uniform solid electrolyte interphase (SEI), with an abundance of LiF and LiNxOy on a working lithium metal anode with dendrite‐free lithium deposition. Ultrahigh Coulombic efficiency (99.96 %) and long lifespans (1000 cycles) were achieved when the FEC/LiNO3 electrolyte was applied in working batteries. The solvation chemistry of electrolyte was further explored by molecular dynamics simulations and first‐principles calculations. This work provides insight into understanding the critical role of the solvation of lithium ions in forming the SEI and delivering an effective route to optimize electrolytes for safe lithium metal batteries.
Not dead ′Li′: Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO3) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions and forming a uniform solid electrolyte interphase (SEI). An abundance of LiF and LiNxOy is formed on the working lithium metal anode and contributes to dendrite‐free lithium deposition.
Stable operation at elevated temperature is necessary for lithium metal anode. However, Li metal anode generally has poor performance and safety concerns at high temperature (>55 °C) owing to the ...thermal instability of the electrolyte and solid electrolyte interphase in a routine liquid electrolyte. Herein a Li metal anode working at an elevated temperature (90 °C) is demonstrated in a thermotolerant electrolyte. In a Li|LiFePO4 battery working at 90 °C, the anode undergoes 100 cycles compared with 10 cycles in a practical carbonate electrolyte. During the formation of the solid electrolyte interphase, independent and incomplete decomposition of Li salts and solvents aggravate. Some unstable intermediates emerge at 90 °C, degenerating the uniformity of Li deposition. This work not only demonstrates a working Li metal anode at 90 °C, but also provides fundamental understanding of solid electrolyte interphase and Li deposition at elevated temperature for rechargeable batteries.
A Li metal anode working at 90 °C is demonstrated in a thermotolerant liquid electrolyte. The anode undergoes 100 cycles in a Li|LiFePO4 battery at 90 °C (10 cycles in a practical carbonate electrolyte). High operation temperature promotes independent and incomplete decomposition of Li salts and solvents to form a distinctive solid electrolyte interphase.
The aim of this study was to analyze the clinical data, discharge rate, and fatality rate of COVID‐19 patients for clinical help. The clinical data of COVID‐19 patients from December 2019 to February ...2020 were retrieved from four databases. We statistically analyzed the clinical symptoms and laboratory results of COVID‐19 patients and explained the discharge rate and fatality rate with a single‐arm meta‐analysis. The available data of 1994 patients in 10 literatures were included in our study. The main clinical symptoms of COVID‐19 patients were fever (88.5%), cough (68.6%), myalgia or fatigue (35.8%), expectoration (28.2%), and dyspnea (21.9%). Minor symptoms include headache or dizziness (12.1%), diarrhea (4.8%), nausea and vomiting (3.9%). The results of the laboratory showed that the lymphocytopenia (64.5%), increase of C‐reactive protein (44.3%), increase of lactic dehydrogenase (28.3%), and leukocytopenia (29.4%) were more common. The results of single‐arm meta‐analysis showed that the male took a larger percentage in the gender distribution of COVID‐19 patients 60% (95% CI 0.54, 0.65), the discharge rate of COVID‐19 patients was 52% (95% CI 0.34,0.70), and the fatality rate was 5% (95% CI 0.01,0.11).
Research Highlights
Our study explored the clinical and epidemiological characteristics of COVID‐19 patients, and proposed the need to focus on other systemic symptoms such as the gastrointestinal tract firstly, which could be of use for clinical work.
Hydrogen peroxide (H2O2) is a green oxidizer widely involved in a vast number of chemical reactions. Electrochemical reduction of oxygen to H2O2 constitutes an environmentally friendly synthetic ...route. However, the oxygen reduction reaction (ORR) is kinetically sluggish and undesired water serves as the main product on most electrocatalysts. Therefore, electrocatalysts with high reactivity and selectivity are highly required for H2O2 electrosynthesis. In this work, a synergistic strategy is proposed for the preparation of H2O2 electrocatalysts with high ORR reactivity and high H2O2 selectivity. A Co−Nx−C site and oxygen functional group comodified carbon‐based electrocatalyst (named as Co–POC–O) is synthesized. The Co–POC–O electrocatalyst exhibits excellent catalytic performance for H2O2 electrosynthesis in O2‐saturated 0.10 m KOH with a high selectivity over 80% as well as very high reactivity with an ORR potential at 1 mA cm−2 of 0.79 V versus the reversible hydrogen electrode (RHE). Further mechanism study identifies that the Co−Nx−C sites and oxygen functional groups contribute to the reactivity and selectivity for H2O2 electrogeneration, respectively. This work affords not only an emerging strategy to design H2O2 electrosynthesis catalysts with remarkable performance, but also the principles of rational combination of multiple active sites for green and sustainable synthesis of chemicals through electrochemical processes.
A synergistic strategy of rational combination of multiple active sites is proposed for high‐performance H2O2 electrosynthesis. Comodification of atomic Co–Nx–C sites and oxygen functional groups on noble‐metal‐free nanocarbon electrocatalysts synergistically renders high reactivity for oxygen reduction and high selectivity for the two‐electron pathway. Consequently, high H2O2 productivity is achieved through a green and sustainable electrochemical approach.
The construction of active sites with intrinsic oxygen evolution reaction (OER) is of great significance to overcome the limited efficiency of abundant sustainable energy devices such as fuel cells, ...rechargeable metal–air batteries, and in water splitting. Anionic regulation of electrocatalysts by modulating the electronic structure of active sites significantly promotes OER performance. To prove the concept, NiFeS electrocatalysts are fabricated with gradual variation of atomic ratio of S:O. With the rise of S content, the overpotential for water oxidation exhibits a volcano plot under anionic regulation. The optimized NiFeS‐2 electrocatalyst under anionic regulation possesses the lowest OER overpotential of 286 mV at 10 mA cm−2 and the fastest kinetics being 56.3 mV dec−1 to date. The anionic regulation methodology not only serves as an effective strategy to construct superb OER electrocatalysts, but also enlightens a new point of view for the in‐depth understanding of electrocatalysis at the electronic and atomic level.
Anionic regulation of NiFe (oxy)sulfide electrocatalysts by modulating the electronic structure of oxygen evolution reaction (OER) active sites significantly promotes the water oxidation performance. Antagonistic S/O anions polarize the NiFe active sites, rendering the OER reactivity dependent on the anionic composition. The as‐obtained electrocatalyst exhibits superb OER performance with an ultralow overpotential of 286 mV at an OER current density of 10.0 mA cm−2.
The lithium–sulfur (Li–S) battery is regarded as a promising secondary battery. However, constant parasitic reactions between the Li anode and soluble polysulfide (PS) intermediates significantly ...deteriorate the working Li anode. The rational design to inhibit the parasitic reactions is plagued by the inability to understand and regulate the electrolyte structure of PSs. Herein, the electrolyte structure of PSs with anti‐reductive solvent shells was unveiled by molecular dynamics simulations and nuclear magnetic resonance. The reduction resistance of the solvent shell is proven to be a key reason for the decreased reactivity of PSs towards Li. With isopropyl ether (DIPE) as a cosolvent, DIPE molecules tend to distribute in the outer solvent shell due to poor solvating power. Furthermore, DIPE is more stable than conventional ether solvents against Li metal. The reactivity of PSs is suppressed by encapsulating PSs into anti‐reductive solvent shells. Consequently, the cycling performance of working Li–S batteries was significantly improved and a pouch cell of 300 Wh kg−1 was demonstrated. The fundamental understanding in this work provides an unprecedented ground to understand the electrolyte structure of PSs and the rational electrolyte design in Li–S batteries.
The electrolyte structure of lithium polysulfides (PSs) with anti‐reductive solvent shells was unveiled. The reduction resistance of the solvent shell is proven to be a key reason for the decreased reactivity of PSs towards Li. With isopropyl ether as a cosolvent, the reactivity of PSs is suppressed by encapsulating PSs into anti‐reductive solvent shells. The stability of practical Li–S batteries was improved and a pouch cell of 300 Wh kg−1 was demonstrated.
PDF
