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1.
Adv Mater ; 33(13): e2008194, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33645858

RESUMO

Oxygen-redox of layer-structured metal-oxide cathodes has drawn great attention as an effective approach to break through the bottleneck of their capacity limit. However, reversible oxygen-redox can only be obtained in the high-voltage region (usually over 3.5 V) in current metal-oxide cathodes. Here, we realize reversible oxygen-redox in a wide voltage range of 1.5-4.5 V in a P2-layered Na0.7 Mg0.2 [Fe0.2 Mn0.6 □0.2 ]O2 cathode material, where intrinsic vacancies are located in transition-metal (TM) sites and Mg-ions are located in Na sites. Mg-ions in the Na layer serve as "pillars" to stabilize the layered structure during electrochemical cycling, especially in the high-voltage region. Intrinsic vacancies in the TM layer create the local configurations of "□-O-□", "Na-O-□" and "Mg-O-□" to trigger oxygen-redox in the whole voltage range of charge-discharge. Time-resolved techniques demonstrate that the P2 phase is well maintained in a wide potential window range of 1.5-4.5 V even at 10 C. It is revealed that charge compensation from Mn- and O-ions contributes to the whole voltage range of 1.5-4.5 V, while the redox of Fe-ions only contributes to the high-voltage region of 3.0-4.5 V. The orphaned electrons in the nonbonding 2p orbitals of O that point toward TM-vacancy sites are responsible for reversible oxygen-redox, and Mg-ions in Na sites suppress oxygen release effectively.

2.
Molecules ; 26(4)2021 Feb 11.
Artigo em Inglês | MEDLINE | ID: mdl-33670379

RESUMO

A p-type thermoelectric conjugated polymer based on indacenodithiophene and benzothiadiazole is designed and synthesized by replacing normal aliphatic side chains (P1) with conjugated aromatic benzene substituents (P2). The introduced bulky substituent on P2 is detrimental to form the intensified packing of polymers, therefore, it hinders the efficient transporting of the charge carriers, eventually resulting in a lower conductivity compared to that of the polymers bearing aliphatic side chains (P1). These results reveal that the modification of side chains on conjugated polymers is crucial to rationally designed thermoelectric polymers with high performance.


Assuntos
Benzeno/química , Compostos Orgânicos/química , Polímeros/química , Centrais Elétricas
3.
Bioorg Med Chem Lett ; 33: 127749, 2021 02 01.
Artigo em Inglês | MEDLINE | ID: mdl-33340663

RESUMO

In an in-house screening, 1H-pyrrolo[2,3-b]pyridine scaffold was found to have high inhibition on TNIK. Several series of compounds were designed and synthesized, among which some compounds had potent TNIK inhibition with IC50 values lower than 1 nM. Some compounds showed concentration-dependent characteristics of IL-2 inhibition. These results provided new applications of TNIK inhibitors and new prospects of TNIK as a drug target.

4.
ACS Nano ; 14(11): 15669-15677, 2020 Nov 24.
Artigo em Inglês | MEDLINE | ID: mdl-33147406

RESUMO

Materials storing energy via an alloying reaction are promising anode candidates in rechargeable lithium-ion batteries (LIBs) due to their much higher energy density than the current graphite anode. Until now, the volumetric expansion of such electrode particles during lithiation has been considered as solely responsible for cycling-induced structural failure. In this work, we report different structural failure mechanisms using single-crystalline bismuth nanowires as the alloying-based anode. The Li-Bi alloying process exhibits a two-step transition, that is, Bi-Li1Bi and Li1Bi-Li3Bi. Interestingly, the Bi-Li1Bi phase transition occurs not only in the bulk Bi nanowire but also on the particle surface showing its characteristic behavior. The bulk alloying kinetics favors a Bi-(012)-facilitated anisotropic lithiation, whose mechanism and energetics are further studied using the density functional theory calculations. More importantly, the protrusion of Li1Bi nanograins as a result of anisotropic Li-Bi alloying is found to dominate the surface morphology of Bi particles. The growth kinetics of Li1Bi protrusions is understood atomically with the identification of two different controlling mechanisms, that is, the dislocation-assisted strain relaxation at the Bi/Li1Bi interface and the short-range migration of Bi supporting the off-Bi growth of Li1Bi. As loosely rooted to the bulk substrate and easily peeled off and detached into the electrolyte, these nanoscale protrusions developed during battery cycling are believed to be an important factor responsible for the capacity decay of such alloying-based anodes at the electrode level.

5.
Nature ; 585(7823): 63-67, 2020 09.
Artigo em Inglês | MEDLINE | ID: mdl-32879503

RESUMO

Rechargeable lithium-ion batteries with high energy density that can be safely charged and discharged at high rates are desirable for electrified transportation and other applications1-3. However, the sub-optimal intercalation potentials of current anodes result in a trade-off between energy density, power and safety. Here we report that disordered rock salt4,5 Li3+xV2O5 can be used as a fast-charging anode that can reversibly cycle two lithium ions at an average voltage of about 0.6 volts versus a Li/Li+ reference electrode. The increased potential compared to graphite6,7 reduces the likelihood of lithium metal plating if proper charging controls are used, alleviating a major safety concern (short-circuiting related to Li dendrite growth). In addition, a lithium-ion battery with a disordered rock salt Li3V2O5 anode yields a cell voltage much higher than does a battery using a commercial fast-charging lithium titanate anode or other intercalation anode candidates (Li3VO4 and LiV0.5Ti0.5S2)8,9. Further, disordered rock salt Li3V2O5 can perform over 1,000 charge-discharge cycles with negligible capacity decay and exhibits exceptional rate capability, delivering over 40 per cent of its capacity in 20 seconds. We attribute the low voltage and high rate capability of disordered rock salt Li3V2O5 to a redistributive lithium intercalation mechanism with low energy barriers revealed via ab initio calculations. This low-potential, high-rate intercalation reaction can be used to identify other metal oxide anodes for fast-charging, long-life lithium-ion batteries.

6.
J Am Chem Soc ; 142(35): 14966-14973, 2020 Sep 02.
Artigo em Inglês | MEDLINE | ID: mdl-32786761

RESUMO

The search for batteries with high energy density has highlighted lithium-rich manganese-based layered oxides due to their exceptionally high capacity. Although it is clear that both cationic and anionic redox are present in the charge compensation mechanism, the microstructural evolution of the Li2MnO3-like phase during anionic redox and its role in battery performance and structural stability are still not fully understood. Here, we systematically probe microstructural evolution using spatially resolved synchrotron X-ray measurements and reveal an underlying interaction between the Li2MnO3-like domains and bulk rhombohedral structure. Mn ion activation and a previously unobserved structural distortion are discovered at high voltages, and can be related to structural strain present in the Li2MnO3-like phase upon substantial lithium ion extraction. Moreover, we elucidate a correlation between this structural distortion and irreversible phase transitions by thermally perturbing delithiated samples. These insights highlight a pathway toward achieving high capacity cathode materials required for future commercial applications.

7.
Adv Sci (Weinh) ; 7(16): 2001002, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32832356

RESUMO

There are growing interests in metal-free heteroatom-doped carbons for electrochemical CO2 reduction. Previous studies extensively focus on the effect of N-doping, and their products severely suffer from low current density (mostly <2 mA cm-2) and limited selectivity (<90%). Here, it is reported that heteroatom codoping offers a promising solution to the above challenge. As a proof of concept, N,P-codoped mesoporous carbon is prepared by annealing phytic-acid-functionalized ZIF-8 in NH3. In CO2-saturated 0.5 m NaHCO3, the catalyst enables CO2 reduction to CO with great selectivity close to 100% and large CO partial current density (≈8 mA cm-2), which are, to the best of knowledge, superior to all other relevant competitors. Theoretical simulations show that the improved activity and selectivity are stemmed from the enhanced surface adsorption of *COOH and *CO intermediates as a result of the synergy of N and P codoping.

8.
Polymers (Basel) ; 12(7)2020 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-32629831

RESUMO

π-conjugated backbones play a fundamental role in determining the thermoelectric (TE) properties of organic semiconductors. Understanding the relationship between the structure-property-function can help us screen valuable materials. In this study, we designed and synthesized a series of conjugated copolymers (P1, P2, and P3) based on an indacenodithiophene (IDT) building block. A copolymer (P3) with an alternating donor-acceptor (D-A) structure exhibits a narrower band gap and higher carrier mobility, which may be due to the D-A structure that helps reduce the charge carrier transport obstacles. In the end, its power factor reaches 4.91 µW m-1 K-2 at room temperature after doping, which is superior to those of non-D-A IDT-based copolymers (P1 and P2). These results indicate that moderate adjustment of the polymer backbone is an effective way to improve the TE properties of copolymers.

9.
ACS Nano ; 14(7): 9117-9124, 2020 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-32584544

RESUMO

Sodium-ion batteries have attracted widespread attention for cost-effective and large-scale electric energy storage. However, their practical deployment has been largely retarded by the lack of choice of efficient anode materials featuring large capacity and electrochemical stability and robustness. Herein, we report a durian-inspired design and template-free fabrication of a robust sodium anode based on triangular pyramid arrays of Bi0.75Sb0.25 alloy electrodeposited on Cu substrates. The Bi0.75Sb0.25 arrays exhibit an appreciable electrochemical robustness for sodium storage, sustaining a reversible capability 335 mAh g-1 at a high rate of 2.5 A g-1 and 87% of the initial capacity over 2000 cycles. We further demonstrate the applicability of the Bi0.75Sb0.25 array anode in sodium full cells by pairing it with a Na3V2(PO4)3/C cathode. This full cell achieves a high specific energy of 203 Wh kg-1 (based on both active electrodes). Such an enhanced performance is attributed to the thorny-durian-like architecture and bimetallic alloy composition. The pyramid tip induces ion enrichment for rapid charge-transfer reaction, while the alloy design reduces the electrode volume swelling for stable Na cycling.

10.
Adv Mater ; 32(30): e2000992, 2020 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-32538508

RESUMO

Palladium is a promising material for electrochemical CO2 reduction to formate with high Faradaic efficiency near the equilibrium potential. It unfortunately suffers from problematic operation stability due to CO poisoning on surface. Here, it is demonstrated that alloying is an effective strategy to alleviate this problem. Mesoporous PdAg nanospheres with uniform size and composition are prepared from the co-reduction of palladium and silver precursors in aqueous solution using dioctadecyldimethylammonium chloride as the structure-directing agent. The best candidate can initiate CO2 reduction at zero overpotential and achieve high formate selectivity close to 100% and great stability even at <-0.2 V versus reversible hydrogen electrode. The high selectivity and stability are believed to result from the electronic coupling between Pd and Ag, which lowers the d-band center of Pd and thereby significantly enhances its CO tolerance, as evidenced by both electrochemical analysis and theoretical simulations.

11.
Nat Commun ; 11(1): 3050, 2020 Jun 16.
Artigo em Inglês | MEDLINE | ID: mdl-32546760

RESUMO

Single-crystal cathode materials for lithium-ion batteries have attracted increasing interest in providing greater capacity retention than their polycrystalline counterparts. However, after being cycled at high voltages, these single-crystal materials exhibit severe structural instability and capacity fade. Understanding how the surface structural changes determine the performance degradation over cycling is crucial, but remains elusive. Here, we investigate the correlation of the surface structure, internal strain, and capacity deterioration by using operando X-ray spectroscopy imaging and nano-tomography. We directly observe a close correlation between surface chemistry and phase distribution from homogeneity to heterogeneity, which induces heterogeneous internal strain within the particle and the resulting structural/performance degradation during cycling. We also discover that surface chemistry can significantly enhance the cyclic performance. Our modified process effectively regulates the performance fade issue of single-crystal cathode and provides new insights for improved design of high-capacity battery materials.

12.
Polymers (Basel) ; 12(4)2020 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-32272620

RESUMO

Composite films of indacenodithiophene-bezothiadazole copolymers bearing polar side chains (P1) and single wall carbon nanotubes (SWCNTs) are found to show a competitive thermoelectric performance compared to their analogous polymers with aliphatic side chains (P2). The enhanced power factors could be attributed to the stronger interfacial interactions between the P1/SWCNTs compared to that of P2/SWCNTs containing the same ratio of SWCNTs. A maximum power factor of 161.34 µW m-1 K-2 was obtained for the composite films of P1/SWCNTs for a filler content of 50 wt%, which is higher than that of P2/SWCNTs (139.06 µW m-1 K-2, 50 wt%). Our work sheds light on the design of side-chains in efficient conjugated polymers/SWCNTs thermoelectric materials and contributes to the understanding of their thermoelectric properties.

13.
Nano Lett ; 20(4): 2416-2422, 2020 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-32046493

RESUMO

Electrocatalytic activity of alloy nanocatalytsts can be manipulated effectively by tuning their physical properties (ensemble, geometric, and ligand effects) to afford optimal surface structure and compositions for proton exchange membrane fuel cell (PEMFC) application. Herein, highly catalytic platinum-palladium nanowires (PtnPd100-n NWs) with a subtle lattice strain and Boerdijk-Coxeter helix type morphology are synthesized through a surfactant-free, thermal single phase solvent method. X-ray diffraction results show that PtnPd100-n NWs are exposed through the (111) facets and their shrinking or expanding lattice parameters can be modulated by the alloy compositions. Electrochemical results reveal that their high catalytic activity correlates with the lattice shrinking, facets, and bimetallic compositions, showing higher activity when the ratio of Pt and Pd is ∼78:22, which is further supported by DFT results. Compared to the nanoparticle type platinum-palladium alloyed catalysts with similar metal compositions (PtnPd100-n NPs), the PtnPd100-n NWs exhibit significantly improved electrocatalytic activity and stability for the oxygen reduction reaction. These findings open new strategies to design the highly active and stable alloy nanocatalysts with controllable compositions.

14.
Chem Soc Rev ; 49(6): 1688-1705, 2020 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-32101182

RESUMO

Lithium-ion batteries have proven themselves to be indispensable among modern day society. Demands stemming from consumer electronics and renewable energy systems have pushed researchers to strive for new electrochemical technologies. To this end, the advent of anionic redox, that is, the sequential or simultaneous redox of the cation and anion in a transition metal oxide based cathode for a Li-ion battery, has garnered much attention due to the enhanced specific capacities. Unfortunately, the higher energy densities are plagued with problems associated with the irreversibility of anionic redox. Much effort has been placed on finding a suitable composition of transition metal oxide, with some groups identifying the underlying features and relationship for anion redox and cationic redox to occur reversibly. Accordingly, it is timely to review anionic redox in terms of what anionic redox is with emphasis on the mechanism and the evidence underlying its discovery and validation. To follow will be a section defining the nature of the transition metal and oxygen bond accompanied by three subsequent sections bridging the redox spectrum from pure anionic, to a mix of cationic and anionic and pure cationic.

15.
Proc Natl Acad Sci U S A ; 117(6): 2815-2823, 2020 Feb 11.
Artigo em Inglês | MEDLINE | ID: mdl-31996477

RESUMO

Existing lithium-ion battery technology is struggling to meet our increasing requirements for high energy density, long lifetime, and low-cost energy storage. Here, a hybrid electrode design is developed by a straightforward reengineering of commercial electrode materials, which has revolutionized the "rocking chair" mechanism by unlocking the role of anions in the electrolyte. Our proof-of-concept hybrid LiFePO4 (LFP)/graphite electrode works with a staged deintercalation/intercalation mechanism of Li+ cations and PF6 - anions in a broadened voltage range, which was thoroughly studied by ex situ X-ray diffraction, ex situ Raman spectroscopy, and operando neutron powder diffraction. Introducing graphite into the hybrid electrode accelerates its conductivity, facilitating the rapid extraction/insertion of Li+ from/into the LFP phase in 2.5 to 4.0 V. This charge/discharge process, in turn, triggers the in situ formation of the cathode/electrolyte interphase (CEI) layer, reinforcing the structural integrity of the whole electrode at high voltage. Consequently, this hybrid LFP/graphite-20% electrode displays a high capacity and long-term cycling stability over 3,500 cycles at 10 C, superior to LFP and graphite cathodes. Importantly, the broadened voltage range and high capacity of the hybrid electrode enhance its energy density, which is leveraged further in a full-cell configuration.

16.
Nat Commun ; 10(1): 4721, 2019 10 17.
Artigo em Inglês | MEDLINE | ID: mdl-31624258

RESUMO

Historically long accepted to be the singular root cause of capacity fading, transition metal dissolution has been reported to severely degrade the anode. However, its impact on the cathode behavior remains poorly understood. Here we show the correlation between capacity fading and phase/surface stability of an LiMn2O4 cathode. It is revealed that a combination of structural transformation and transition metal dissolution dominates the cathode capacity fading. LiMn2O4 exhibits irreversible phase transitions driven by manganese(III) disproportionation and Jahn-Teller distortion, which in conjunction with particle cracks results in serious manganese dissolution. Meanwhile, fast manganese dissolution in turn triggers irreversible structural evolution, and as such, forms a detrimental cycle constantly consuming active cathode components. Furthermore, lithium-rich LiMn2O4 with lithium/manganese disorder and surface reconstruction could effectively suppress the irreversible phase transition and manganese dissolution. These findings close the loop of understanding capacity fading mechanisms and allow for development of longer life batteries.

17.
Adv Mater ; 31(39): e1903852, 2019 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-31397028

RESUMO

The Li-CO2 battery is a promising energy storage device for wearable electronics due to its long discharge plateau, high energy density, and environmental friendliness. However, its utilization is largely hindered by poor cyclability and mechanical rigidity due to the lack of a flexible and durable catalyst electrode. Herein, flexible fiber-shaped Li-CO2 batteries with ultralong cycle-life, high rate capability, and large specific capacity are fabricated, employing bamboo-like N-doped carbon nanotube fiber (B-NCNT) as flexible, durable metal-free catalysts for both CO2 reduction and evolution reactions. Benefiting from high N-doping with abundant pyridinic groups, rich defects, and active sites of the periodic bamboo-like nodes, the fabricated Li-CO2 battery shows outstanding electrochemical performance with high full-discharge capacity of 23 328 mAh g-1 , high rate capability with a low potential gap up to 1.96 V at a current density of 1000 mA g-1 , stability over 360 cycles, and good flexibility. Meanwhile, the bifunctional B-NCNT is used as the counter electrode for a fiber-shaped dye-sensitized solar cell to fabricate a self-powered fiber-shaped Li-CO2 battery with overall photochemical-electric energy conversion efficiency of up to 4.6%. Along with a stable voltage output, this design demonstrates great adaptability and application potentiality in wearable electronics with a breath monitor as an example.

18.
Acc Chem Res ; 52(8): 2201-2209, 2019 Aug 20.
Artigo em Inglês | MEDLINE | ID: mdl-31180201

RESUMO

Lithium ion batteries (LIBs) not only power most of today's hybrid electric vehicles (HEV) and electric vehicles (EV) but also are considered as a promising system for grid-level storage. Large-scale applications for LIBs require substantial improvement in energy density, cost, and lifetime. Layered lithium transition metal (TM) oxides, in particular, Li(NixMnyCoz)O2 (NMC, x + y + z = 1) are the most promising candidates as cathode materials with the potential to increase energy densities and lifetime, reduce costs, and improve safety. In order to further boost Li storage capacity, a great deal of attention has been directed toward developing Ni-rich layered TM oxides. However, structural disorder as a result of Ni/Li exchange in octahedral sites becomes a critical issue when Ni content increases to high values, as it leads to a detrimental effect on Li diffusivity, cycling stability, first-cycle efficiency, and overall electrode performance. Increasing effort has been dedicated to improving the electrochemical performance of layered TM oxides via reduction of cationic mixing. Therefore, it is important to summarize this research field and provide in-depth insight into the impact of Ni/Li disordering on electrochemical characteristics in layered TM oxides and its origin to accelerate the future development of layered TM oxides with high performance. In this Account, we start by introducing the Ni/Li disordering in LiNiO2, the experimental characterization of Ni/Li disordering, and analyzing the impact of Ni/Li disordering on electrochemical characteristics of layered TM oxides. The antisite Ni in the Li layer can limit the rate performance by impeding the Li ion transport. It will also degrade the cycling stability by inducing anisotropic stress in the bulk structure. Nevertheless, the antisite Ni ions do not always bring drawbacks to the electrochemical performance; some studies including our works found that it can improve the thermal stability and the cycling structure stability of Ni-rich NMC materials. We next discuss the driving forces and the kinetic advantages accounting for the Ni/Li exchange and conclude that the steric effect of cation size and the magnetic interactions between TM cations are the two main driving forces to promote the Ni/Li exchange during synthesis and the electrochemical cycling, and the low energy barrier of Ni2+ migration from the 3a site in the TM layer to the 3b site in the Li layer further provides a kinetic advantage. Based on this understanding, we then review the progress made to control the Ni/Li disordering through three main ways: (i) suppressing the driving force from the steric effect by ion exchange; (ii) tuning the magnetic interaction by cationic substitution; (iii) kinetically controlling Ni migration. Finally, our brief outlook on the future development of layered TM oxides with controlled Ni/Li disordering is provided. It is believed that this Account will provide significant understanding and inspirations toward developing high-performance layered TM oxide cathodes.

19.
Macromol Rapid Commun ; 40(12): e1900082, 2019 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-30942939

RESUMO

The molecular structure of polymers has a great influence on their thermoelectric properties; however, the relationship between the molecular structure of a polymer and its thermoelectric properties remains unclear. In this work, two benzo[1,2-b:4,5-b']dithiophene (BDT)-based conjugated polymers are designed and synthesized, which contain alkyl side chains or polar side chains. The effects of the polymer side chain on the physicochemical properties are systematically investigated, especially the thermoelectric performance of the polymers after doping with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane. It is found that the BDT-based conjugated polymer with polar side chains exhibits good miscibility with the dopants, leading to higher thermoelectric properties than those of the polymer with alkyl side chains. This work can serve as a reference for the future design of high-performance organic thermoelectric polymers.


Assuntos
Polímeros/química , Temperatura , Tiofenos/química , Condutividade Elétrica , Estrutura Molecular , Tamanho da Partícula , Polímeros/síntese química , Propriedades de Superfície , Tiofenos/síntese química
20.
Bioorg Med Chem Lett ; 29(6): 844-847, 2019 03 15.
Artigo em Inglês | MEDLINE | ID: mdl-30713023

RESUMO

Tranylcypromine moiety extracted from LSD1 inhibitors and 6-trifluoroethyl thienopyrimidine moiety from menin-MLL1 PPI inhibitors were merged to give new chemotypes for medicinal chemistry study. Among 15 new compounds prepared in this work, some exhibited nanomolar LSD1 activity and good selectivity over MAO-A/B, low micromolar menin-MLL1 PPI inhibitory activity, as well as submicromolar MV4-11 antiprofilative activities. Intracellular LSD1 engagement of compounds with higher enzymatic and antiproliferative activities was confirmed by CD86 mRNA up-regulation experiments.


Assuntos
Antineoplásicos/farmacologia , Histona Desmetilases/antagonistas & inibidores , Inibidores da Monoaminoxidase/farmacologia , Pirimidinas/farmacologia , Tranilcipromina/farmacologia , Antineoplásicos/síntese química , Antígeno B7-2/genética , Linhagem Celular Tumoral , Humanos , Monoaminoxidase/metabolismo , Inibidores da Monoaminoxidase/síntese química , Pirimidinas/síntese química , RNA Mensageiro/metabolismo , Tiofenos/síntese química , Tiofenos/farmacologia , Tranilcipromina/análogos & derivados , Tranilcipromina/síntese química , Regulação para Cima/efeitos dos fármacos
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