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1.
Nature ; 624(7992): 557-563, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37913815

RESUMO

Perovskite solar cells with the formula FA1-xCsxPbI3, where FA is formamidinium, provide an attractive option for integrating high efficiency, durable stability and compatibility with scaled-up fabrication. Despite the incorporation of Cs cations, which could potentially enable a perfect perovskite lattice1,2, the compositional inhomogeneity caused by A-site cation segregation is likely to be detrimental to the photovoltaic performance of the solar cells3,4. Here we visualized the out-of-plane compositional inhomogeneity along the vertical direction across perovskite films and identified the underlying reasons for the inhomogeneity and its potential impact for devices. We devised a strategy using 1-(phenylsulfonyl)pyrrole to homogenize the distribution of cation composition in perovskite films. The resultant p-i-n devices yielded a certified steady-state photon-to-electron conversion efficiency of 25.2% and durable stability.

2.
Proc Natl Acad Sci U S A ; 121(29): e2400898121, 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-38980900

RESUMO

Precise electrochemical synthesis of commodity chemicals and fuels from CO2 building blocks provides a promising route to close the anthropogenic carbon cycle, in which renewable but intermittent electricity could be stored within the greenhouse gas molecules. Here, we report state-of-the-art CO2-to-HCOOH valorization performance over a multiscale optimized Cu-Bi cathodic architecture, delivering a formate Faradaic efficiency exceeding 95% within an aqueous electrolyzer, a C-basis HCOOH purity above 99.8% within a solid-state electrolyzer operated at 100 mA cm-2 for 200 h and an energy efficiency of 39.2%, as well as a tunable aqueous HCOOH concentration ranging from 2.7 to 92.1 wt%. Via a combined two-dimensional reaction phase diagram and finite element analysis, we highlight the role of local geometries of Cu and Bi in branching the adsorption strength for key intermediates like *COOH and *OCHO for CO2 reduction, while the crystal orbital Hamiltonian population analysis rationalizes the vital contribution from moderate binding strength of η2(O,O)-OCHO on Cu-doped Bi surface in promoting HCOOH electrosynthesis. The findings of this study not only shed light on the tuning knobs for precise CO2 valorization, but also provide a different research paradigm for advancing the activity and selectivity optimization in a broad range of electrosynthetic systems.

3.
Chem Rev ; 124(5): 2839-2887, 2024 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-38427022

RESUMO

The popularity of portable electronic devices and electric vehicles has led to the drastically increasing consumption of lithium-ion batteries recently, raising concerns about the disposal and recycling of spent lithium-ion batteries. However, the recycling rate of lithium-ion batteries worldwide at present is extremely low. Many factors limit the promotion of the battery recycling rate: outdated recycling technology is the most critical one. Existing metallurgy-based recycling methods rely on continuous decomposition and extraction steps with high-temperature roasting/acid leaching processes and many chemical reagents. These methods are tedious with worse economic feasibility, and the recycling products are mostly alloys or salts, which can only be used as precursors. To simplify the process and improve the economic benefits, novel recycling methods are in urgent demand, and direct recycling/regeneration is therefore proposed as a next-generation method. Herein, a comprehensive review of the origin, current status, and prospect of direct recycling methods is provided. We have systematically analyzed current recycling methods and summarized their limitations, pointing out the necessity of developing direct recycling methods. A detailed analysis for discussions of the advantages, limitations, and obstacles is conducted. Guidance for future direct recycling methods toward large-scale industrialization as well as green and efficient recycling systems is also provided.

4.
Proc Natl Acad Sci U S A ; 120(51): e2314264120, 2023 Dec 19.
Artigo em Inglês | MEDLINE | ID: mdl-38100418

RESUMO

The separator with high Young's modulus can avoid the danger of large-sized dendrites, but regulating the chemical behavior of lithium (Li) at the separator/anode interface can effectively eliminate the dendrite issue. Herein, a polyimine aerogel (PIA) with accurate nitrogen (N) functional design is used as the functional separator in Li metal batteries to promote uniform Li nucleation and suppress the dendrite growth. Specifically, the imine (N1) and protonated tertiary amine (N2) sites in the molecular structure of the PIA are significantly different in electron cloud density (ECD) distribution. The N1 site with higher ECD and the N2 site with lower ECD tend to attract and repulse Li+ through electrostatic interactions, respectively. This synergy effect of the PIA separator accelerates the interfacial Li+ diffusion on the Li anode to sustain a uniform two-dimensional Li nucleation behavior. Meanwhile, the well-defined nanochannels of the PIA separator show high affinity to electrolyte and bring uniform Li+ flux for Li plating/stripping. Consequently, the dendrites are effectively suppressed by the PIA separator in routine carbonate electrolyte, and the Li metal batteries with the PIA separator exhibit high Coulombic efficiency and stable high-rate cycling. These findings demonstrate that the ingenious marriage of special chemical structure designs and hierarchical pores can enable the separator to affect the interfacial Li nucleation behavior.

5.
Nano Lett ; 24(12): 3694-3701, 2024 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-38411584

RESUMO

A functional coating layer (FCL) is widely applied in fast-charging lithium-ion batteries to improve the sluggish Li+ transport kinetics of traditional graphite anodes. However, blindly increasing the Li+ conductivity for FCL reduces the overall electron conductivity of the anodes. Herein, we decoupled the effect of La-doping on TiNb2O7 (TNO) in terms of the phase evolution, Li+/electron transport, and lithiation behavior, and then proposed a promising La0.1TNO FCL with balanced Li+/electron transport for a fast-charging graphite anode. By optimizing the doping concentration of La, more holes are introduced into the TNO as electron carriers without causing lattice distortion, thus maintaining the fast Li+ diffusion channel in TNO. As a result, the graphite with La0.1TNO FCL delivers an excellent capacity of 220.2 mAh g-1 (96.3% retention) after 450 cycles at 3 C, nearly twice that of the unmodified one.

6.
Small ; 20(36): e2402197, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-38682612

RESUMO

The conjugation of terminal ammonium salt groups with perovskite surfaces is a frequently employed technique that aims to enhance the overall performance of perovskite materials, encompassing both bulk and surface properties. Particularly, it exhibits heightened efficacy when applied to surface modification, due to its ability to mitigate defect accumulation and facilitate facile binding with the receptive sites inherent to the perovskite structure. However, the interaction of the bulk ammonium group with PbI2 has the potential to form a low-dimensional phase of perovskite, which may obstruct carrier extraction at the interface. Therefore, the surface passivators (MeO-PFACl) are designed through intramolecular potential manipulation. The combinations of the electron-donating methoxy group and π-π conjugation of the phenyl ring reduce the local potential at the reactive site of formamidinium group, making it less likely to form a low-dimension phase with perovskite. This surface passivation strategy effectively suppresses the surface nonradiative recombination and promotes the interface carrier extraction. The devices treated with MeO-PFACl have demonstrated exceptional performance, achieving a peak power conversion efficiency (PCE) of 25.88%, with an average PCE of 25.37%. These works offer a novel principle for enhancing both the efficiency and stability of PSCs using ammonium-incorporated molecules without the induction of an additional phase layer.

7.
Brain Behav Immun ; 119: 84-95, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38552922

RESUMO

Autism spectrum disorder (ASD) is a neurodevelopmental disorder that severely affects individuals' daily life and social development. Unfortunately, there are currently no effective treatments for ASD. Dexmedetomidine (DEX) is a selective agonist of α2 adrenergic receptor (α2AR) and is widely used as a first-line medication for sedation and hypnosis in clinical practice. In recent years, there have been reports suggesting its potential positive effects on improving emotional and cognitive functions. However, whether dexmedetomidine has therapeutic effects on the core symptoms of ASD, namely social deficits and repetitive behaviors, remains to be investigated. In the present study, we employed various behavioral tests to assess the phenotypes of animals, including the three-chamber, self-grooming, marble burying, open field, and elevated plus maze. Additionally, electrophysiological recordings, western blotting, qPCR were mainly used to investigate and validate the potential mechanisms underlying the role of dexmedetomidine. We found that intraperitoneal injection of dexmedetomidine in ASD model mice-BTBR T+ Itpr3tf/J (BTBR) mice could adaptively improve their social deficits. Further, we observed a significant reduction in c-Fos positive signals and interleukin-6 (IL-6) expression level in the prelimbic cortex (PrL) of the BTBR mice treated with dexmedetomidine. Enhancing or inhibiting the action of IL-6 directly affects the social behavior of BTBR mice. Mechanistically, we have found that NF-κB p65 is a key pathway regulating IL-6 expression in the PrL region. In addition, we have confirmed that the α2AR acts as a receptor switch mediating the beneficial effects of dexmedetomidine in improving social deficits. This study provides the first evidence of the beneficial effects of dexmedetomidine on core symptoms of ASD and offers a theoretical basis and potential therapeutic approach for the clinical treatment of ASD.


Assuntos
Agonistas de Receptores Adrenérgicos alfa 2 , Transtorno do Espectro Autista , Dexmedetomidina , Modelos Animais de Doenças , Interleucina-6 , NF-kappa B , Receptores Adrenérgicos alfa 2 , Comportamento Social , Animais , Dexmedetomidina/farmacologia , Camundongos , Transtorno do Espectro Autista/tratamento farmacológico , Transtorno do Espectro Autista/metabolismo , Masculino , Receptores Adrenérgicos alfa 2/metabolismo , Receptores Adrenérgicos alfa 2/efeitos dos fármacos , Agonistas de Receptores Adrenérgicos alfa 2/farmacologia , NF-kappa B/metabolismo , Interleucina-6/metabolismo , Transdução de Sinais/efeitos dos fármacos , Camundongos Endogâmicos C57BL , Comportamento Animal/efeitos dos fármacos , Regulação para Baixo/efeitos dos fármacos , Inflamação/metabolismo , Inflamação/tratamento farmacológico
8.
Chemphyschem ; 25(13): e202400239, 2024 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-38578164

RESUMO

Currently, lithium sulfur (Li-S) battery with high theoretical energy density has attracted great research interest. However, the diffusion and loss process of intermediate lithium polysulfide during charge-discharge hindered the application of the Li-S battery in modern life. To overcome this issue, metal organic frameworks (MOFs) and their composites have been regarded as effective additions to restrain the LiPS diffusion process for Li-S battery. Benefiting from the unique structure with rich active sites to adsorb LiPS and accelerate the LiPS redox, the Li-S batteries with MOFs modified exhibit superior electrochemical performance. Considering the rapid development of MOFs in Li-S battery, this review summarizes the recent studies of MOFs and their composites as the sulfur host materials, functional interlayer, separator coating layer, and separator/solid electrolyte for Li-S batteries in detail. In addition, the promising design strategies of functional MOF materials are proposed to improve the electrochemical performance of Li-S battery.

9.
Langmuir ; 40(27): 13984-13994, 2024 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-38913777

RESUMO

Strong metal-support interaction (SMSI), which has drawn widespread attention in heterogeneous catalysis, is thought to significantly affect the catalytic performance for volatile organic chemical (VOC) abatement. In the present study, strong interactions between platinum and ceria are constructed by modulating the oxygen vacancy concentration of CeO2 through a NaBH4 reduction method. For a catalyst with higher content of oxygen vacancy, more electrons would transfer from ceria to Pt, which is attributed to the stronger effect of SMSI. The obtained electron-richer Pt sites exhibit higher ability for toluene activation, contributing to better performance for toluene oxidation. On the other hand, the stronger metal-support interaction would facilitate CeOx species migrating to the Pt nanoparticle surface and forming an encapsulated structure. Smaller Pt dispersion leads to fewer sites for toluene adsorption and activation, which is to the disadvantage of the reaction. Therefore, taking the negative and positive effects together, the Pt/CeO2-0.5 catalyst has the highest catalytic performance for toluene abatement. Our study provides new insights into strong metal-support interaction on toluene oxidation and contributes to designing noble metal catalysts for VOC abatement.

10.
J Gastroenterol Hepatol ; 39(7): 1256-1266, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38638082

RESUMO

Magnetic compression anastomosis (MCA) is a new method that provides sutureless passage construction for tubular organs. Due to the high recurrence rate of conventional endoscopic treatment and the high morbidity and mortality of surgical procedures, the MCA technique shows promise. The aim of this review is to comprehensively examine the literature related to the use of MCA in different gastrointestinal diseases over the past few years, categorizing them according to the anastomotic site and describing in detail the various methods of magnet delivery and the clinical outcomes of MCA. MCA is an innovative technique, and its use represents an advancement in the field of minimally invasive interventions. Comparison studies have shown that the anastomosis formed by MCA is comparable to or better than surgical sutures in terms of general appearance and histology. Although most of the current research has involved animal studies or studies with small populations, the safety and feasibility of MCA have been preliminarily demonstrated. Large prospective studies involving populations are still needed to guarantee the security of MCA. For technologies that have been initially used in clinical settings, effective measures should also be implemented to identify, even prevent, complications. Furthermore, specific commercial magnets must be created and optimized in this emerging area.


Assuntos
Anastomose Cirúrgica , Imãs , Humanos , Anastomose Cirúrgica/métodos , Endoscopia Gastrointestinal/métodos , Gastroenteropatias/cirurgia , Animais , Magnetismo , Resultado do Tratamento , Procedimentos Cirúrgicos sem Sutura/métodos , Pressão
11.
Phys Chem Chem Phys ; 26(41): 26304-26313, 2024 Oct 23.
Artigo em Inglês | MEDLINE | ID: mdl-39380540

RESUMO

Photocatalytic water splitting for hydrogen production offers a feasible solution to the problems of energy shortages and environmental pollution. However, its low photocatalytic efficiency limits the application of this technology in real world scenarios. In this study, a two-dimensional AlN/PSi-GaS-I van der Waals heterojunction is constructed and the properties of water photolysis are studied based on first-principles calculations. The results demonstrate that AlN/PSi-GaS-I exhibits exceptional photocatalytic performance with good stability, a narrow bandgap, appropriate band-edge position, a broader light absorption range and efficient separation of photogenerated electron-hole pairs. Moreover, the Gibbs free energies of different intermediates throughout the entire reaction process are calculated based on type-II and Z-scheme reaction mechanisms. By comparing the free energy barriers of the two pathways, it is observed that the Z-scheme reaction pathway has a lower energy barrier. Consequently, it can be concluded that AlN/PSi-GaS-I belongs to the direct Z-scheme heterojunction. These findings suggest that AlN/PSi-GaS-I exhibits an enhanced redox capacity, efficiently driving the water splitting reaction. More excitingly, the AlN/PSi-GaS-I can undergo spontaneous photocatalytic reactions under acidic conditions when provided with adequate optical driving force. This study not only proves that AlN/PSi-GaS-I is a promising high-efficiency photocatalyst for water splitting, but also describes a method for determining direct Z-scheme heterojunctions, which offers theoretical guidance for the design of efficient and stable photocatalysts.

12.
Nano Lett ; 23(20): 9609-9617, 2023 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-37843362

RESUMO

Lithium (Li) dendrite growth in a routine carbonate electrolyte (RCE) is the main culprit hindering the practical application of Li metal anodes. Herein, we realize the regulation of the LiPF6 decomposition pathway in RCE containing 1.0 M LiPF6 by introducing a "self-polymerizing" additive, ethyl isothiocyanate (EITC), resulting in a robust LiF-rich solid electrolyte interphase (SEI). The effect of 1 vol % EITC on the electrode/electrolyte interfacial chemistry slows the formation of the byproduct LixPOFy. Such a LiF-rich SEI with EITC polymer winding exhibits a high Young's modulus and a uniform Li-ion flux, which suppresses dendrite growth and interface fluctuation. The EITC-based Li metal cell using a Li4Ti5O12 cathode delivers a capacity retention of 81.4% over 1000 cycles at 10 C, outperforming its counterpart. The cycling stability of 1 Ah pouch cells was further evaluated under EITC. We believe that this work provides a new method for tuning the interfacial chemistry of Li metal through electrolyte additives.

13.
Int J Mol Sci ; 25(20)2024 Oct 16.
Artigo em Inglês | MEDLINE | ID: mdl-39456893

RESUMO

Nonalcoholic steatohepatitis (NASH) is a form of chronic liver disease that is characterized by liver inflammation and steatosis, with possible progression to fibrosis. Currently, no drugs have been approved for the treatment of NASH. In this study, we isolated a polysaccharide from Atractylodes lancea rhizome (AP) and established a methionine- and choline-deficient (MCD) diet -induced NASH mouse model to investigate the preventive effect and potential mechanism of AP on NASH. The results showed that AP effectively reduced liver lipid accumulation and inflammation and reduced autophagy and ferroptosis in hepatocytes, thereby preventing the development of NASH. These findings suggest that AP may be a promising natural candidate for the treatment of NASH.


Assuntos
Atractylodes , Hepatopatia Gordurosa não Alcoólica , Polissacarídeos , Rizoma , Transdução de Sinais , Serina-Treonina Quinases TOR , Proteína Supressora de Tumor p53 , Animais , Hepatopatia Gordurosa não Alcoólica/tratamento farmacológico , Hepatopatia Gordurosa não Alcoólica/metabolismo , Hepatopatia Gordurosa não Alcoólica/etiologia , Hepatopatia Gordurosa não Alcoólica/patologia , Polissacarídeos/farmacologia , Polissacarídeos/uso terapêutico , Polissacarídeos/química , Atractylodes/química , Rizoma/química , Camundongos , Serina-Treonina Quinases TOR/metabolismo , Transdução de Sinais/efeitos dos fármacos , Masculino , Proteína Supressora de Tumor p53/metabolismo , Modelos Animais de Doenças , Metionina/deficiência , Camundongos Endogâmicos C57BL , Autofagia/efeitos dos fármacos , Hepatócitos/efeitos dos fármacos , Hepatócitos/metabolismo , Fígado/metabolismo , Fígado/efeitos dos fármacos , Fígado/patologia , Ferroptose/efeitos dos fármacos , Dieta , Deficiência de Colina/complicações
14.
Int J Mol Sci ; 25(19)2024 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-39409181

RESUMO

Leonurine is a natural product unique to the Lamiaceae plant Leonurus japonicus Houtt., and it has attracted attention due to its anti-oxidative stress, anti-apoptosis, anti-fibrosis, and metabolic regulation properties. Also, it plays an important role in the prevention and treatment of nonalcoholic fatty liver disease (NAFLD) through a variety of biological mechanisms, but its mechanism of action remains to be elucidated. Therefore, this study aims to preliminarily explore the mechanisms of action of leonurine in NAFLD. Mice were randomly divided into four groups: the normal control (NC) group, the Model (M) group, the leonurine treatment (LH) group, and the fenofibrate treatment (FB) group. The NAFLD model was induced by a high-fat high-sugar diet (HFHSD) for 12 weeks, and liver pathological changes and biochemical indices were observed after 12 weeks. Transcriptomic analysis results indicated that leonurine intervention reversed the high-fat high-sugar diet-induced changes in lipid metabolism-related genes such as stearoyl-CoA desaturase 1 (Scd1), Spermine Synthase (Sms), AP-1 Transcription Factor Subunit (Fos), Oxysterol Binding Protein Like 5 (Osbpl5), and FK506 binding protein 5 (Fkbp5) in liver tissues. Kyoto Encyclopedia of Genes and Genomes (KEGG) enrichment analysis results suggest that leonurine may exert its lipid-lowering effects through the AMP-activated protein kinase (AMPK) signaling pathway. Liver lipidomic analysis showed that leonurine could alter the abundance of lipid molecules related to fatty acyl (FAs) and glycerophospholipids (GPs) such as TxB3, carnitine C12-OH, carnitine C18:1-OH, and LPC (20:3/0:0). Molecular biology experiments and molecular docking techniques verified that leonurine might improve hepatic lipid metabolism through the alpha-1A adrenergic receptor (ADRA1a)/AMPK/SCD1 axis. In summary, the present study explored the mechanism by which leonurine ameliorated NAFLD by inhibiting hepatic lipid synthesis via the ADRA1a/AMPK/SCD1 axis.


Assuntos
Proteínas Quinases Ativadas por AMP , Ácido Gálico , Metabolismo dos Lipídeos , Fígado , Hepatopatia Gordurosa não Alcoólica , Estearoil-CoA Dessaturase , Hepatopatia Gordurosa não Alcoólica/tratamento farmacológico , Hepatopatia Gordurosa não Alcoólica/metabolismo , Hepatopatia Gordurosa não Alcoólica/etiologia , Hepatopatia Gordurosa não Alcoólica/patologia , Animais , Camundongos , Ácido Gálico/análogos & derivados , Ácido Gálico/farmacologia , Estearoil-CoA Dessaturase/metabolismo , Estearoil-CoA Dessaturase/genética , Proteínas Quinases Ativadas por AMP/metabolismo , Metabolismo dos Lipídeos/efeitos dos fármacos , Fígado/metabolismo , Fígado/efeitos dos fármacos , Fígado/patologia , Masculino , Dieta Hiperlipídica/efeitos adversos , Lipogênese/efeitos dos fármacos , Transdução de Sinais/efeitos dos fármacos , Camundongos Endogâmicos C57BL , Modelos Animais de Doenças
15.
Beijing Da Xue Xue Bao Yi Xue Ban ; 56(5): 890-895, 2024 Oct 18.
Artigo em Zh | MEDLINE | ID: mdl-39397470

RESUMO

OBJECTIVE: To compare the effects of unilateral thoracic paravertebal block with lidocaine on hemodynamic and the level of consciousness during double lumen endotracheal intubation. METHODS: From June to october 2021, a total of 40 patients American Society of Anesthesiologists (ASA) physical status Ⅰ-Ⅱ, aged 19-65 years, scheduled for elective thoracic sugeries in Peking University International Hospital block with under general anesthesia requiring orotracheal intubation were recruited and divided into two groups: The double-lumen endobronchial intubation (group C) and double-lumen endobronchial intubation after thoracic paravertebal block with lidocaine (group P). After an intravenous anesthetic induction, the orotracheal double-lumen intubation was performed using a Macintosh direct laryngoscopy, respectively. Invasive blood pressure (BP) and heart rate (HR) were recorded before and after anesthetic induction, immediately after intubation and 5 min after intubation with 1-minute interval and the intubation time was also noted. Rate-pressure product (RPP) were calculated. RESULTS: After anesthetic induction, BP and RPP in the two groups decreased significantly compared with their preinduction values. As comparison with their postinduction values, the orotracheal intubation in the two groups caused significant increases in BP, HR and RPP. Diastolic blood pressure (DBP) and mean arterial pressure (MAP) increased significantly and lasted for 1-minute in group C compared with the baseline values. Systolic blood pressure (SBP) was not significant change and DBP increased significantly immediately after intubation in group P.HR of both groups after intubation were significantly higher than their baseline values and lasted for 4 min in group C, HR increased significantly immediately after intubation in group P. SBP, DBP, MAP, HR and RPP after intubation in group P were significantly lower than those of group C during the observation period. The value of BIS was similar between the two groups. Compared with group C, the incidence of SBP greater than 30% and RPP greater than 22 000 was significantly lower in group P in the observation period, and no patient in group P developed RPP greater than 22 000. At the end of the incidence of SBP less than 30% of the basal value and HR less than 30% of the baseline, no severe bradycardia occurred in both groups. CONCLUSION: During double-lumen endobronchial intubation, unilateral thoracic paravertebal block with lidocaine can provide less hemodynamic response and level of conscionsness.


Assuntos
Pressão Sanguínea , Hemodinâmica , Intubação Intratraqueal , Lidocaína , Humanos , Intubação Intratraqueal/métodos , Pessoa de Meia-Idade , Adulto , Masculino , Lidocaína/administração & dosagem , Feminino , Pressão Sanguínea/efeitos dos fármacos , Frequência Cardíaca/efeitos dos fármacos , Anestesia Geral/métodos , Idoso , Laringoscopia/métodos , Bloqueio Nervoso/métodos
16.
Angew Chem Int Ed Engl ; 63(3): e202316839, 2024 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-38014862

RESUMO

Reasonably elevating the working voltage (≥4.4 V vs. Li/Li+ ) of the cathode is one of the efficient approaches to maximize the energy density of lithium-ion batteries (LIBs). As a preferred partner for high-voltage LIB systems, localized high-concentration electrolyte (LHCE), characterized by a stronger Li solvation structure, less free solvent, and robust electrode/electrolyte interphase has attracted much attention in academic circles. Herein, we systematically studied the role of the diluent in LHCE on the formation of the cathode electrolyte interphase (CEI) and elucidated that the existing anion-diluent pairing in the inner Helmholtz plane (IHP) results in an uneven CEI and subsequent battery degradation under high voltage. A m-fluorotoluene (mFT) diluent was further employed in the LHCE containing lithium difluoro(oxalato)borate (LiDFOB) to facilitate a uniform and rich-anion-derived CEI, since the weaker interaction of HmFT -BDFOB - , as compared to the HHhydrofluoroether -BDFOB - , reduces the influence of mFT in IHP or initial CEI formation. Consequently, the mFT-dominated LHCE propels the high-voltage performance of LIBs one step forward, endowing a 4.6 V-class 1.2-Ah graphite||LiNi0.8 Co0.1 Mn0.1 O2 pouch cells a 90.4 % capacity retention after 130 cycles. Our study thus describes a new index affecting the CEI formation and proposes novel strategies to deeply optimize the high-voltage LIBs.

17.
Angew Chem Int Ed Engl ; : e202411933, 2024 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-39212463

RESUMO

Hydrofluoric acid (HF)-induced electrode and interfacial structure degeneration poses a significant challenge for high-voltage lithium metal batteries (LMBs). To address this issue, we propose a separator strategy that involves decorating a regular polyethylene (PE) separator with molecular sieves (TW) impregnated with piperidine (PI). The porous structure of the TW serves as a reaction chamber for PI and HF. As a result, the HF content in the controlled electrolyte with 500 ppm H2O (ELE-500) is notably reduced when using TW@PI-PE separators, thereby shielding nickel-rich cathodes from HF etching. Simultaneously, due to the hydrolysis of Li salts, and the inertness of PI towards H2O, a uniform lithium fluoride (LiF)-rich solid electrolyte interphase can form on the Li metal anode, further mitigating dendrite formation. The lifespan of the symmetric Li cell using the TW@PI-PE separator is doubled in ELE-500, exhibiting stable 500-hour cycles at 3 mA cm-2 and 3 mAh cm-2. Additionally, with the effective limitation of transition metal (TM) dissolution, the 4.6-V LMBs employing a LiNi0.8Co0.1Mn0.1O2 cathode maintain an 81 % capacity retention over 100 cycles, even in ELE-1000. The innovative TW@PI system presented here offers a fresh perspective for future research aimed at eliminating HF in LMBs.

18.
J Am Chem Soc ; 145(13): 7288-7300, 2023 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-36876987

RESUMO

Recycling spent lithium-ion batteries (LIBs) has become an urgent task to address the issues of resource shortage and potential environmental pollution. However, direct recycling of the spent LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode is challenging because the strong electrostatic repulsion from a transition metal octahedron in the lithium layer provided by the rock salt/spinel phase that is formed on the surface of the cycled cathode severely disrupts Li+ transport, which restrains lithium replenishment during regeneration, resulting in the regenerated cathode with inferior capacity and cycling performance. Here, we propose the topotactic transformation of the stable rock salt/spinel phase into Ni0.5Co0.2Mn0.3(OH)2 and then back to the NCM523 cathode. As a result, a topotactic relithiation reaction with low migration barriers occurs with facile Li+ transport in a channel (from one octahedral site to another, passing through a tetrahedral intermediate) with weakened electrostatic repulsion, which greatly improves lithium replenishment during regeneration. In addition, the proposed method can be extended to repair spent NCM523 black mass, spent LiNi0.6Co0.2Mn0.2O2, and spent LiCoO2 cathodes, whose electrochemical performance after regeneration is comparable to that of the commercial pristine cathodes. This work demonstrates a fast topotactic relithiation process during regeneration by modifying Li+ transport channels, providing a unique perspective on the regeneration of spent LIB cathodes.

19.
Small ; 19(20): e2207480, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36840656

RESUMO

Mixed lead-tin (PbSn) perovskite solar cells (PSCs) possess low toxicity and adjustable bandgap for both single-junction and all-perovskite tandem solar cells. However, the performance of mixed PbSn PSCs still lags behind the theoretical efficiency. The uncontrollable crystallization and the resulting structural defect are important reasons. Here, the bidirectional anions gathering strategy (BAG) is reported by using Methylammonium acetate (MAAc) and Methylammonium thiocyanate (MASCN) as perovskite bulk additives, which Ac- escapes from the perovskite film top surface while SCN- gathers at the perovskite film bottom in the crystallization process. After the optoelectronic techniques, the bidirectional anions movement caused by the top-down gradient crystallization is demonstrated. The layer-by-layer crystallization can collect anions in the next layer and gather at the broader, enabling a controllable crystallization process, thus getting a high-quality perovskite film with better phase crystallinity and lower defect concentration. As a result, PSCs treated by the BAG strategy exhibit outstanding photovoltaic and electroluminescent performance with a champion efficiency of 22.14%. Additionally, it demonstrates excellent long-term stability, which retains ≈92.8% of its initial efficiency after 4000 h aging test in the N2 glove box.

20.
Plant Cell ; 32(9): 2823-2841, 2020 09.
Artigo em Inglês | MEDLINE | ID: mdl-32699171

RESUMO

Zeins are the predominant storage proteins in maize (Zea mays) seeds, while Opaque2 (O2) is a master transcription factor for zein-encoding genes. How the activity of O2 is regulated and responds to external signals is yet largely unknown. Here, we show that the E3 ubiquitin ligase ZmRFWD3 interacts with O2 and positively regulates its activity by enhancing its nuclear localization. Ubiquitination of O2 enhances its interaction with maize importin1, the α-subunit of Importin-1 in maize, thus enhancing its nuclear localization ability. We further show that ZmRFWD3 can be phosphorylated by a Suc-responsive protein kinase, ZmSnRK1, which leads to its degradation. We demonstrated that the activity of O2 responds to Suc levels through the ZmSnRK1-ZmRFWD3-O2 signaling axis. Intriguingly, we found that Suc levels, as well as ZmRFWD3 levels and the cytonuclear distribution of O2, exhibit diurnal patterns in developing endosperm, leading to the diurnal transcription of O2-regulated zein genes. Loss of function in ZmRFWD3 disrupts the diurnal patterns of O2 cytonuclear distribution and zein biosynthesis, and consequently changes the C/N ratio in mature seeds. We therefore identify a SnRK1-ZmRFWD3-O2 signaling axis that transduces source-to-sink signals and coordinates C and N assimilation in developing maize seeds.


Assuntos
Nitrogênio/metabolismo , Proteínas de Plantas/metabolismo , Zea mays/metabolismo , Núcleo Celular/metabolismo , Ritmo Circadiano/fisiologia , Endosperma/crescimento & desenvolvimento , Endosperma/metabolismo , Regulação da Expressão Gênica de Plantas , Lisina/metabolismo , Fosforilação , Filogenia , Proteínas de Plantas/genética , Plantas Geneticamente Modificadas , Estabilidade Proteica , Serina/metabolismo , Transdução de Sinais , Sacarose/metabolismo , Ubiquitina-Proteína Ligases/genética , Ubiquitina-Proteína Ligases/metabolismo , Ubiquitinação , Zea mays/genética , Zea mays/crescimento & desenvolvimento , Zeína/genética , Zeína/metabolismo
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