Rechargeable lithium-sulfur (Li-S) batteries are promising for high-energy storage. However, conventional redox reactions involving sulfur (S) and lithium (Li) can lead to unstable intermediates. Over the past decade, many strategies have emerged to address this challenge, enabling nonconventional electrochemical reactions in Li-S batteries. In our Perspective, we provide a brief review of these strategies and highlight their potential benefits. Specifically, our group has pioneered a top-down approach, investigating Li-S reactions at molecular and subatomic levels, as demonstrated in our recent work on stable S isotopes. These insights not only enhance understanding of charge transfer and storage properties but also offer exciting opportunities for advancements in battery materials research.
The formation of a solid electrolyte interphase on carbon anodes causes irreversible loss of Na+ ions, significantly compromising the energy density of Na-ion full cells. Sodium compensation additives can effectively address the irreversible sodium loss but suffer from high decomposition voltage induced by low electrochemical activity. Herein, we propose a universal electrocatalytic sodium compensation strategy by introducing a carbon nanotube (CNT)/MnO2 catalyst to realize full utilization of sodium compensation additives at a much-reduced decomposition voltage. The well-organized CNT/MnO2 composite with high catalytic activity, good electronic conductivity, and abundant reaction sites enables sodium compensation additives to decompose at significantly reduced voltages (from 4.40 to 3.90 V vs Na+/Na for sodium oxalate, 3.88 V for sodium carbonate, and even 3.80 V for sodium citrate). As a result, sodium oxalate as the optimal additive achieves a specific capacity of 394 mAh g-1, almost reaching its theoretical capacity in the first charge, increasing the energy density of the Na-ion full cell from 111 to 158 Wh kg-1 with improved cycle stability and rate capability. This work offers a valuable approach to enhance sodium compensation efficiency, promising high-performance energy storage devices in the future.
Graphite has been serving as the key anode material of rechargeable Li-ion batteries, yet is difficultly charged within a quarter hour while maintaining stable electrochemistry. In addition to a defective edge structure that prevents fast Li-ion entry, the high-rate performance of graphite could be hampered by co-intercalation and parasitic reduction of solvent molecules at anode/electrolyte interface. Conventional surface modification by pitch-derived carbon barely isolates the solvent and electrons, and usually lead to inadequate rate capability to meet practical fast-charge requirements. Here we show that, by applying a MoOx-MoNx layer onto graphite surface, the interface allows fast Li-ion diffusion yet blocks solvent access and electron leakage. By regulating interfacial mass and charge transfer, the modified graphite anode delivers a reversible capacity of 340.3â mAh g-1 after 4000â cycles at 6â C, showing promises in building 10-min-rechargeable batteries with a long operation life.
The inherently huge volume expansion during Li uptake has hindered the use of Si-based anodes in high-energy lithium-ion batteries. While some pore-forming and nano-architecting strategies show promises to effectively buffer the volume change, other parameters essential for practical electrode fabrication, such as compaction density, are often compromised. Here we propose a new in situ Mg doping strategy to form closed-nanopore structure into a micron-sized SiOx particle at a high bulk density. The doped Mg atoms promote the segregation of O, so that high-density magnesium silicates form to generate closed nanopores. By altering the mass content of Mg dopant, the average radii (ranged from 5.4 to 9.7â nm) and porosities (ranged from 1.4 % to 15.9 %) of the closed pores are precisely adjustable, which accounts for volume expansion of SiOx from 77.8 % to 22.2 % at the minimum. Benefited from the small volume variation, the Mg-doped micron-SiOx anode demonstrates improved Li storage performance towards realization of a 700-(dis)charge-cycle, 11-Ah-pouch-type cell at a capacity retention of >80 %. This work offers insights into reasonable design of the internal structure of micron-sized SiOx and other materials that undergo conversion or alloying reactions with drastic volume change, to enable high-energy batteries with stable electrochemistry.
The high-capacity advantage of lithium metal anode was compromised by common use of copper as the collector. Furthermore, lithium pulverization associated with "dead" Li accumulation and electrode cracking deteriorates the long-term cyclability of lithium metal batteries, especially under realistic test conditions. Here, we report an ultralight, integrated anode of polyimide-Ag/Li with dual anti-pulverization functionality. The silver layer was initially chemically bonded to the polyimide surface and then spontaneously diffused in Li solid solution and self-evolved into a fully lithiophilic Li-Ag phase, mitigating dendrites growth or dead Li. Further, the strong van der Waals interaction between the bottommost Li-Ag and polyimide affords electrode structural integrity and electrical continuity, thus circumventing electrode pulverization. Compared to the cutting-edge anode-free cells, the batteries pairing LiNi0.8Mn0.1Co0.1O2 with polyimide-Ag/Li afford a nearly 10% increase in specific energy, with safer characteristics and better cycling stability under realistic conditions of 1× excess Li and high areal-loading cathode (4 milliampere hour per square centimeter).
Sulfur in nature consists of two abundant stable isotopes, with two more neutrons in the heavy one (34S) than in the light one (32S). The two isotopes show similar physicochemical properties and are usually considered an integral system for chemical research in various fields. In this work, a model study based on a Li-S battery was performed to reveal the variation between the electrochemical properties of the two S isotopes. Provided with the same octatomic ring structure, the cyclo-34S8 molecules form stronger S-S bonds than cyclo-32S8 and are more prone to react with Li. The soluble Li polysulfides generated by the Li-34S conversion reaction show a stronger cation-solvent interaction yet a weaker cation-anion interaction than the 32S-based counterparts, which facilitates quick solvation of polysulfides yet hinders their migration from the cathode to the anode. Consequently, the Li-34S cell shows improved cathode reaction kinetics at the solid-liquid interface and inhibited shuttle of polysulfides through the electrolyte so that it demonstrates better cycling performance than the Li-32S cell. Based on the varied shuttle kinetics of the isotopic-S-based polysulfides, an electrochemical separation method for 34S/32S isotope is proposed, which enables a notably higher separation factor than the conventional separation methods via chemical exchange or distillation and brings opportunities to low-cost manufacture, utilization, and research of heavy chalcogen isotopes.
Solid-state lithium-sulfur batteries have shown prospects as safe, high-energy electrochemical storage technology for powering regional electrified transportation. Owing to limited ion mobility in crystalline polymer electrolytes, the battery is incapable of operating at subzero temperature. Addition of liquid plasticizer into the polymer electrolyte improves the Li-ion conductivity yet sacrifices the mechanical strength and interfacial stability with both electrodes. In this work, we showed that by introducing a spherical hyperbranched solid polymer plasticizer into a Li+ -conductive linear polymer matrix, an integrated dynamic cross-linked polymer network was built to maintain fully amorphous in a wide temperature range down to subzero. A quasi-solid polymer electrolyte with a solid mass content >90 % was prepared from the cross-linked polymer network, and demonstrated fast Li+ conduction at a low temperature, high mechanical strength, and stable interfacial chemistry. As a result, solid-state lithium-sulfur batteries employing the new electrolyte delivered high reversible capacity and long cycle life at 25 °C, 0 °C and -10 °C to serve energy storage at complex environmental conditions.
Anode-free rechargeable sodium batteries represent one of the ultimate choices for the 'beyond-lithium' electrochemical storage technology with high energy. Operated based on the sole use of active Na ions from the cathode, the anode-free battery is usually reported with quite a limited cycle life due to unstable electrolyte chemistry that hinders efficient Na plating/stripping at the anode and high-voltage operation of the layered oxide cathode. A rational design of the electrolyte toward improving its compatibility with the electrodes is key to realize the battery. Here, we show that by refining the volume ratio of two conventional linear ether solvents, a binary electrolyte forms a cation solvation structure that facilitates flat, dendrite-free, planar growth of Na metal on the anode current collector and that is adaptive to high-voltage Na (de)intercalation of P2-/O3-type layered oxide cathodes and oxidative decomposition of the Na2C2O4 supplement. Inorganic fluorides, such as NaF, show a major influence on the electroplating pattern of Na metal and effective passivation of plated metal at the anode-electrolyte interface. Anode-free batteries based on the refined electrolyte have demonstrated high coulombic efficiency, long cycle life, and the ability to claim a cell-level specific energy of >300 Wh/kg.
The prosperity of the lithium-ion battery market is dialectically accompanied by the depletion of corresponding resources and the accumulation of spent batteries. It is an urgent priority to develop green and efficient battery recycling strategies for helping ease resources and environmental pressures at the current stage. Here, we propose a mild and efficient lithium extracting strategy based on potential controllable redox couples. Active lithium in the spent battery without discharging is extracted using a series of tailored aprotic solutions comprised of polycyclic aromatic hydrocarbons and ethers. This ensures a safe yet efficient recycling process with nearly ≈100 % lithium recovery. We further investigate the Li+ -electron concerted redox reactions and the effect of solvation structure on kinetics during the extraction, and broaden the applicability of the Li-PAHs solution. This work can stimulate new inspiration for designing novel solutions to meet efficient and sustainable demands in recycling batteries.
Single-crystalline nickel-rich layered oxides are promising cathode materials for building high-energy lithium-ion batteries because of alleviated particle cracking and irreversible phase transitions upon cycling, compared with their polycrystalline counterparts. Under a high state of charge, parasitic reactions tend to occur at the cathode-electrolyte interface, which could result in sluggish Li-ion diffusion kinetics and quickly faded electrochemical performance of cathodes. In this work, a concentration-gradient niobium-doping strategy was applied to modify the single-crystal LiNi0.83Co0.12Mn0.05O2 cathode, with Nb concentration decreasing linearly from the surface to the core of the particle. As a result, the Nb-rich surface functions as an electrochemically active protective layer against electrolyte corrosion and transition metal dissolution, while the Nb-deficient core contributes to a higher capacity. The linear concentration gradient also minimizes structural transition from the surface to the core and helps to maintain structural integrity during repeated Li (de)intercalation. In addition, Nb-doping also assists to alleviate Li+/Ni2+ mixing and increases the interlayer distance to enable faster Li-ion diffusion kinetics. By taking these advantages, the Nb-doped cathode materials (containing 1.0 atom% Nb) demonstrate a high reversible capacity, a high capacity retention, and improved rate capabilities. This work provides a general and facile approach to improve the storage performance of layered-oxide cathode materials by rationally tuning the bulk structure and interface with the electrolyte.
Lithium-sulfur batteries are considered a promising "beyond Li-ion" energy storage technology. Currently, the practical realization of Li-S batteries is plagued by rapid electrochemical failure of S cathodes due to aggravated polysulfide dissolution and shuttle in the conventional liquid ether-based electrolytes. A gel polymer electrolyte obtained by in situ polymerization of liquid electrolyte solvent at the cathode-electrolyte interface has been proven an effective strategy to prevent polysulfide shuttle. However, notably reduced polysulfide solubility in the gel electrolyte leads to enrichment of poorly conductive sulfide species, which hinders charge migration across the interface and therefore accounts for retarded polysulfide conversion and a low capacity/energy output of batteries. Here, we show that thioacetamide, as a cathode additive, inhibits interfacial polymerization of ether molecules while assisting dissolution of polysulfides and Li2S at the cathode/electrolyte interface. In this way, a layer of liquid, sulfide-soluble electrolyte is preserved between the highly gelled electrolyte and the S particle surface, avoiding interfacial sulfide accumulation and improving polysulfide conversion kinetics. A Li-S battery with the controllably solidified interface demonstrates, without adding other performance-boosting agents or catalysts, a high reversible capacity, a long cycle life, and a favorable rate performance, showing promises for the next-generation storage applications.
The uncontrollable dendrite growth and unstable solid electrolyte interphase have long plagued the practical application of Li metal batteries. Herein, a dual-layered artificial interphase LiF/LiBO-Ag is demonstrated that is simultaneously reconfigured via an electrochemical process to stabilize the lithium anode. This dual-layered interphase consists of a heterogeneous LiF/LiBO glassy top layer with ultrafast Li-ion conductivity and lithiophilic Li-Ag alloy bottom layer, which synergistically regulates the dendrite-free Li deposition, even at high current densities. As a result, Li||Li symmetric cells with LiF/LiBO-Ag interphase achieve an ultralong lifespan (4500 h) at an ultrahigh current density and area capacity (20 mA cm-2 , 20 mAh cm-2 ). LiF/LiBO-Ag@Li anodes are successfully applied in quasi-solid-state batteries, showing excellent cycling performances in symmetric cells (8 mA cm-2 , 8 mAh cm-2 , 5000 h) and full cells. Furthermore, a practical quasi-solid-state pouch cell coupling with a high-nickel cathode exhibits stable cycling with a capacity retention of over 91% after 60 cycles at 0.5 C, which is comparable or even better than that in liquid-state pouch cells. Additionally, a high-energy-density quasi-solid-state pouch cell (10.75 Ah, 448.7 Wh kg-1 ) is successfully accomplished. This well-orchestrated interphase design provides new guidance in engineering highly stable interphase toward practical high-energy-density lithium metal batteries.
Safety concerns related to the abuse operation and thermal runaway are impeding the large-scale employment of high-energy-density rechargeable lithium batteries. Here, we report that by incorporating phosphorus-contained functional groups into a hydrocarbon-based polymer, a smart risk-responding polymer is prepared for effective mitigation of battery thermal runaway. At room temperature, the polymer is (electro)chemically compatible with electrodes, ensuring the stable battery operation. Upon thermal accumulation, the phosphorus-containing radicals spontaneously dissociate from the polymer skeleton and scavenge hydrogen and hydroxyl radicals to terminate the exothermic chain reaction, suppressing thermal generation at an early stage. With the smart risk-responding strategy, we demonstrate extending the time before thermal runaway for a 1.8-Ah Li-ion pouch cell by 100% (~9 hours) compared with common cells, creating a critical time window for safety management. The temperature-triggered automatic safety-responding strategy will improve high-energy-density battery tolerance against thermal abuse risk and pave the way to safer rechargeable batteries.
In overcoming the Li+ desolvation barrier for low-temperature battery operation, a weakly-solvated electrolyte based on carboxylate solvent has shown promises. In case of an organic-anion-enriched primary solvation sheath (PSS), we found that the electrolyte tends to form a highly swollen, unstable solid electrolyte interphase (SEI) that shows a high permeability to the electrolyte components, accounting for quickly declined electrochemical performance of graphite-based anode. Here we proposed a facile strategy to tune the swelling property of SEI by introducing an inorganic anion switch into the PSS, via LiDFP co-solute method. By forming a low-swelling, Li3 PO4 -rich SEI, the electrolyte-consuming parasitic reactions and solvent co-intercalation at graphite-electrolyte interface are suppressed, which contributes to efficient Li+ transport, reversible Li+ (de)intercalation and stable structural evolution of graphite anode in high-energy Li-ion batteries at a low temperature of -20 °C.
BACKGROUND: There is no available viable treatment for Sepsis-Induced Cardiomyopathy (SIC), a common sepsis complication with a higher fatality risk. The septic patients showed an abnormal activation of the renin angiotensin (Ang) aldosterone system (RAAS). However, it is not known how the Ang II and Ang-(1-7) affect SIC. METHODS: Peripheral plasma was collected from the Healthy Control (HC) and septic patients and Ang II and Ang-(1-7) protein concentrations were measured. The in vitro and in vivo models of SIC were developed using Lipopolysaccharide (LPS) to preliminarily explore the relationship between the SIC state, Ang II, and Ang-(1-7) levels, along with the protective function of exogenous Ang-(1-7) on SIC. RESULTS: Peripheral plasma Ang II and the Ang II/Ang-(1-7) levels in SIC-affected patients were elevated compared to the levels in HC and non-SIC patients, however, the HC showed higher Ang-(1-7) levels. Furthermore, peripheral plasma Ang II, Ang II/Ang-(1-7), and Ang-(1-7) levels in SIC patients were significantly correlated with the degree of myocardial injury. Additionally, exogenous Ang-(1-7) can attenuate inflammatory response, reduce oxidative stress, maintain mitochondrial dynamics homeostasis, and alleviate mitochondrial structural and functional damage by inhibiting nuclear factor-kappa B (NF-κB) and mitogen-activated protein kinase (MAPK) signaling pathways, thus alleviating SIC. CONCLUSIONS: Plasma Ang-(1-7), Ang II, and Ang II/Ang-(1-7) levels were regarded as significant SIC biomarkers. In SIC, therapeutic targeting of RAAS, for example with Ang-(1-7), may exert protective roles against myocardial damage.
Cardiomyopathies , Sepsis , Humans , NF-kappa B/metabolism , Mitogen-Activated Protein Kinases , Cells, Cultured , Angiotensin II/metabolism , Cardiomyopathies/drug therapy , Cardiomyopathies/etiology , Sepsis/complications , Sepsis/drug therapy
The interfacial stability is highly responsible for the longevity and safety of sodium ion batteries (SIBs). However, the continuous solid-electrolyte interphase(SEI) growth would deteriorate its stability. Essentially, the SEI growth is associated with the electron leakage behavior, yet few efforts have tried to suppress the SEI growth, from the perspective of mitigating electron leakage. Herein, we built two kinds of SEI layers with distinct growth behaviors, via the additive strategy. The SEI physicochemical features (morphology and componential information) and SEI electronic properties (LUMO level, band gap, electron work function) were investigated elaborately. Experimental and calculational analyses showed that, the SEI layer with suppressed growth delivers both the low electron driving force and the high electron insulation ability. Thus, the electron leakage is mitigated, which restrains the continuous SEI growth, and favors the interface stability with enhanced electrochemical performance.
Lithium-sulfur batteries are promising candidates of energy storage devices. Both adjusting salt/solvent ratio and applying quasi-solid-state electrolytes are regarded as effective strategies to improve the lithium (Li) anode performance. However, reaction mechanisms and interfacial properties in quasi-solid-state lithium-sulfur (QSSLS) batteries with high salt concentration are not clear. Here we utilize in-situ characterizations and molecular dynamics simulations to unravel aforesaid mysteries, and construct relationships of electrolyte structure, interfacial behaviour and performance. The generation mechanism, formation process, and mechanical/chemical/electrochemical properties of the anion-derived solid electrolyte interphase (SEI) are deeply explored. Li deposition uniformity and dissolution reversibility are further tuned by the sustainable SEI. These straightforward evidences and deepgoing studies would guide the electrolyte design and interfacial engineering of QSSLS batteries.
Sepsis-induced cardiomyopathy (SIC) is a serious complication of sepsis with high mortality but no effective treatment. The renin angiotensin (Ang) aldosterone system (RAAS) is activated in patients with sepsis but it is unclear how the Ang II/Ang II type 1 receptor (AT1R) axis contributes to SIC. This study examined the link between the Ang II/AT1R axis and SIC as well as the protective effect of AT1R blockers (ARBs). The Ang II level in peripheral plasma and AT1R expression on monocytes were significantly higher in patients with SIC compared with those in non-SIC patients and healthy controls and were correlated with the degree of myocardial injury. The ARB losartan reduced the infiltration of neutrophils, monocytes, and macrophages into the heart and spleen of SIC mice. Additionally, losartan regulated macrophage polarization from the M1 to the M2 subtype via nuclear factor-kappa B (NF-κB) and mitogen-activated protein kinase (MAPK) signaling pathways, thereby maintaining the mitochondrial dynamics balance in cardiomyocytes and reducing oxidative stress and cardiomyocyte apoptosis. In conclusion, the plasma Ang II level and AT1R expression on plasma monocytes are an important biomarker in SIC. Therapeutic targeting of AT1R, for example with losartan, can potentially protect against myocardial injury in SIC.
Cardiomyopathies , Sepsis , Mice , Animals , Losartan/pharmacology , Losartan/therapeutic use , NF-kappa B/metabolism , Angiotensin Receptor Antagonists , Toll-Like Receptor 4 , Angiotensin II Type 1 Receptor Blockers/pharmacology , Angiotensin II Type 1 Receptor Blockers/therapeutic use , Mitogen-Activated Protein Kinases , Angiotensin-Converting Enzyme Inhibitors , Receptor, Angiotensin, Type 1/metabolism , Angiotensin II/pharmacology , Sepsis/complications , Sepsis/drug therapy , Cardiomyopathies/drug therapy , Cardiomyopathies/etiology , Macrophages/metabolism
In Li-ion batteries, functional cosolvents could significantly improve the specific performance of the electrolyte, for example, the flame retardancy. In case the cosolvent shows strong Li+-coordinating ability, it could adversely influence the electrochemical Li+-intercalation reaction of the electrode. In this work, a noncoordinating functional cosolvent was proposed to enrich the functionality of the electrolyte while avoiding interference with the Li storage process. Hexafluorocyclotriphosphazene, an efficient flame-retardant agent with proper physicochemical properties, was chosen as a cosolvent for preparing functional electrolytes. The nonpolar phosphazene molecules with low electron-donating ability do not coordinate with Li+ and thus are excluded from the primary solvation sheath. In graphite-anode-based Li-ion batteries, the phosphazene molecules do not cointercalate with Li+ into the graphite lattice during the charging process, which helps to maintain integral anode structure and interface and contributes to stable cycling. The noncoordinating cosolvent was also applied to other types of electrode materials and batteries, paving a new way for high-performance electrochemical energy storage systems with customizable functions.
Acute myocardial infarction (AMI) is one of the leading causes of death globally, with a mortality rate of over 20%. However, the diagnostic biomarkers frequently used in current clinical practice have limitations in both sensitivity and specificity, likely resulting in delayed diagnosis. This study aimed to identify potential diagnostic biomarkers for AMI and explored the possible mechanisms involved. Datasets were retrieved from the Gene Expression Omnibus. First, we identified differentially expressed genes (DEGs) and preserved modules, from which we identified candidate genes by LASSO (least absolute shrinkage and selection operator) regression and the SVM-RFE (support vector machine-recursive feature elimination) algorithm. Subsequently, we used ROC (receiver operating characteristic) analysis to evaluate the diagnostic accuracy of the candidate genes. Thereafter, functional enrichment analysis and an analysis of immune infiltration were implemented. Finally, we assessed the association between biomarkers and biological processes, infiltrated cells, clinical traits, tissues and time points. We identified nine preserved modules containing 1,016 DEGs and managed to construct a diagnostic model with high accuracy (GSE48060: AUC = 0.923; GSE66360: AUC = 0.973) incorporating two genes named S100A9 and SOCS3. Functional analysis revealed the pivotal role of inflammation; immune infiltration analysis indicated that eight cell types (monocytes, epithelial cells, neutrophils, CD8+ T cells, Th2 cells, NK cells, NKT cells and platelets) were likely involved in AMI. Furthermore, we observed that S100A9 and SOCS3 were correlated with inflammation, variably infiltrated cells, clinical traits of patients, sampling tissues and sampling time points. In conclusion, we suggested S100A9 and SOCS3 as diagnostic biomarkers of AMI and discovered their association with inflammation, infiltrated immune cells and other factors.
Calgranulin B , Gene Expression Profiling , Myocardial Infarction , Suppressor of Cytokine Signaling 3 Protein , Biomarkers , Calgranulin B/genetics , Gene Expression Profiling/methods , Gene Expression Regulation , Humans , Inflammation , Myocardial Infarction/diagnosis , Myocardial Infarction/genetics , Suppressor of Cytokine Signaling 3 Protein/genetics
