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1.
Chemphyschem ; 25(8): e202300833, 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38289035

RESUMO

Biomass-based materials have emerged as a promising alternative to the conventional graphite anode in Li-ion batteries due to their renewability, low cost, and environmental friendliness. Therefore, a facile synthesis method for porous hard carbons based on cellulose acetate microspheres and bead cellulose is used, and their application as anode materials in Li-ion batteries is discussed. The resulting porous carbons exhibit promising electrochemical characteristics, including a reversible capacity of about 300 mAh g-1 at 0.1 C (37 mA g-1) after 50 cycles, and stable capacities up to 210 mAh g-1 over 1000 cycles at 1 C (372 mA g-1) in half-cells for cellulose acetate microspheres carbonised at 1200 °C. Moreover, at 60 °C cellulose-derived carbons show higher specific capacities than graphite (300 mAh g-1 vs 240 mAh g-1 at 1 C after 500 cycles), indicating their potential for use in high-temperature applications. The different charge storage mechanisms of the prepared hard carbon materials and graphite are observed. While capacity of graphite is mainly controlled by the Faradaic redox process, the cellulose-derived carbons combine Faradaic intercalation and capacitive charge adsorption.

2.
Small ; 17(12): e2005527, 2021 03.
Artigo em Inglês | MEDLINE | ID: mdl-33599055

RESUMO

Titanium and its alloys are frequently used to replace structural components of the human body due to their high mechanical strength, low stiffness, and biocompatibility. In particular, the use of porous materials has improved implant stabilization and the promotion of bone. However, it remains unclear which material properties and geometrical cues are optimal for a proper osteoinduction and osseointegration. To that end, transparent tubular microscaffolds are fabricated, mimicking the typical pores of structural implants, with the aim of studying early bone formation and cell-material interactions at the single cell level. Here, a ß-stabilized alloy Ti-45Nb (wt%) is used for the microscaffold's fabrication due to its elastic modulus close to that of natural bone. Human mesenchymal stem cell migration, adhesion, and osteogenic differentiation is thus investigated, paying particular attention to the CaP formation and cell-body crystallization, both analyzed via optical and electron microscopy. It is demonstrated that the developed platform is suited for the long-term study of living single cells in an appropriate microenvironment, obtaining in the process deeper insights on early bone formation and providing cues to improve the stability and biocompatibility of current structural implants.


Assuntos
Materiais Biocompatíveis , Osteogênese , Ligas , Humanos , Teste de Materiais , Óxidos , Titânio
3.
Molecules ; 25(11)2020 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-32512837

RESUMO

Ternary mixed oxide systems CuO/ZnO/ZrO2 and CuO/NiO/ZrO2 were synthesized by one-pot synthesis for a better understanding of the synthesis-property relationships of zirconium oxide-based catalyst materials. The prepared mixed oxide samples were analysed by a broad range of characterisation methods (XRD, N2-physisorption, Temperature-Programmed Ammonia Desorption (TPAD), and XPS) to examine the structural and surface properties, as well as to identify the location of the potential catalytically active sites. By XPS analysis, it could be shown that a progressive enrichment of the surface composition with copper takes place by changing from ZnO to NiO as a promoter. Thus, by addition of the second component, not only electronic but also the geometric properties of active sites, i.e., copper species distribution within the catalyst surface, can be affected in a desired way.


Assuntos
Amônia/química , Eletrônica , Níquel/química , Zircônio/química , Adsorção , Catálise , Propriedades de Superfície , Temperatura
4.
Langmuir ; 35(30): 9721-9731, 2019 07 30.
Artigo em Inglês | MEDLINE | ID: mdl-31280571

RESUMO

Bioactive peptides, such as isoleucyl-tryptophan (IW), exhibit a high potential to inhibit the angiotensin-converting enzyme (ACE). Adsorption on carbon materials provides a beneficial method to extract these specific molecules from the complex mixture of an α-lactalbumin hydrolysate. This study focuses on the impact of nitrogen functionalization of porous carbon adsorbents, either via pre- or post-treatment, on the adsorption behavior of the ACE-inhibiting peptide IW and the essential amino acid tryptophan (W). The commercially activated carbon Norit ROX 0.8 is compared with pre- and postsynthetically functionalized N-doped carbon in terms of surface area, pore size, and surface functionality. For prefunctionalization, a covalent triazine framework was synthesized by trimerization of an aromatic nitrile under ionothermal conditions. For the postsynthetic approach, the activated carbon ROX 0.8 was functionalized with the nitrogen-rich molecule melamine. The batch adsorption results using model mixtures containing the single components IW and W could be transferred to a more complex mixture of an α-lactalbumin hydrolysate containing a huge number of various peptides. For this purpose, reverse-phase high-pressure liquid chromatography with fluorescence detection was used for identification and quantification. The treatment with the three different carbon materials leads to an increase in the ACE-inhibiting effect in vitro. The modified surface structure of the carbon via pre- or post-treatment allows separation of IW and W due to the certain selectivity for either the amino acid or the dipeptide.


Assuntos
Inibidores da Enzima Conversora de Angiotensina/química , Carbono/química , Nitrogênio/química , Peptídeos/química , Peptidil Dipeptidase A/metabolismo , Adsorção , Hidrólise , Lactalbumina/metabolismo , Porosidade , Triptofano/química
5.
Phys Chem Chem Phys ; 19(19): 12414-12424, 2017 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-28470318

RESUMO

Nowadays, the development of highly efficient routes for the low cost synthesis of nitrides is greatly growing. Mechanochemical synthesis is one of those promising techniques which is conventionally employed for the synthesis of nitrides by long term milling of metallic elements under a pressurized N2 or NH3 atmosphere (A. Calka and J. I. Nikolov, Nanostruct. Mater., 1995, 6, 409-412). In the present study, we describe a versatile, room-temperature and low-cost mechanochemical process for the synthesis of nanostructured metal nitrides (MNs), carbonitrides (MCNs) and carbon nitride (CNx). Based on this technique, melamine as a solid nitrogen-containing organic compound (SNCOC) is ball milled with four different metal powders (Al, Ti, Cr and V) to produce nanostructured AlN, TiCxN1-x, CrCxN1-x, and VCxN1-x (x ∼ 0.05). Both theoretical and experimental techniques are implemented to determine the reaction intermediates, products, by-products and finally, the mechanism underling this synthetic route. According to the results, melamine is polymerized in the presence of metallic elements at intermediate stages of the milling process, leading to the formation of a carbon nitride network. The CNx phase subsequently reacts with the metallic precursors to form MN, MCN or even MCN-CNx nano-composites depending on the defect formation energy and thermodynamic stability of the corresponding metal nitride, carbide and C/N co-doped structures.

6.
Inorg Chem ; 55(14): 7079-89, 2016 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-27367435

RESUMO

Layered Li(M,Li)O2 (where M is a transition metal) ordered rock-salt-type structures are used in advanced metal-ion batteries as one of the best hosts for the reversible intercalation of Li ions. Besides the conventional redox reaction involving oxidation/reduction of the M cation upon Li extraction/insertion, creating oxygen-located holes because of the partial oxygen oxidation increases capacity while maintaining the oxidized oxygen species in the lattice through high covalency of the M-O bonding. Typical degradation mechanism of the Li(M,Li)O2 electrodes involves partially irreversible M cation migration toward the Li positions, resulting in gradual capacity/voltage fade. Here, using LiRhO2 as a model system (isostructural and isoelectronic to LiCoO2), for the first time, we demonstrate an intimate coupling between the oxygen redox and M cation migration. A formation of the oxidized oxygen species upon electrochemical Li extraction coincides with transformation of the layered Li1-xRhO2 structure into the γ-MnO2-type rutile-ramsdellite intergrowth LiyRh3O6 structure with rutile-like [1 × 1] channels along with bigger ramsdellite-like [2 × 1] tunnels through massive and concerted Rh migration toward the empty positions in the Li layers. The oxidized oxygen dimers with the O-O distances as short as 2.26 Å are stabilized in this structure via the local Rh-O configuration reminiscent to that in the µ-peroxo-µ-hydroxo Rh complexes. The LiyRh3O6 structure is remarkably stable upon electrochemical cycling illustrating that proper structural implementation of the oxidized oxygen species can open a pathway toward deliberate employment of the anion redox chemistry in high-capacity/high-voltage positive electrodes for metal-ion batteries.

7.
Pharm Res ; 32(6): 2132-43, 2015 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-25537340

RESUMO

PURPOSE: Preparation of Nanographene oxide (NGO) - Gelatin hybrids for efficient treatment of Neuroblastoma. METHODS: Nanohybrids were prepared via non-covalent interactions. Spectroscopic tools have been used to discriminate the chemical states of NGO prior and after gelatin coating, with UV visible spectroscopy revealing the maximum binding capacity of gelatin to NGO. Raman and X-ray photoelectron spectroscopy (XPS) demonstrated NGO and Gelatin_NGO nanohybrids through a new chemical environments produced after noncovalent interaction. Microscopic analyses, atomic force microscopy (AFM) and scanning electron microscopy (SEM) are used to estimate the thickness of samples and the lateral width in the nanoscale, respectively. RESULTS: The cell viability assay validated Gelatin_NGO nanohybrids as a useful nanocarrier for Carboplatin (CP) release and delivery, without obvious signs of toxicity. The nano-sized NGO (200 nm and 300 nm) did not enable CP to kill the cancer cells efficiently, whilst the CP loaded Gel_NGO 100 nm resulted in a synergistic activity through increasing the local concentration of CP inside the cancer cells. CONCLUSIONS: The nanohybrids provoked high stability and dispersibility in physiological media, as well as enhanced the anticancer activity of the chemotherapy agent Carboplatin (CP) in human neuroblastoma cells.


Assuntos
Antineoplásicos/farmacologia , Carboplatina/farmacologia , Portadores de Fármacos , Gelatina/química , Grafite/química , Nanopartículas , Neuroblastoma/tratamento farmacológico , Óxidos/química , Antineoplásicos/administração & dosagem , Antineoplásicos/química , Antineoplásicos/metabolismo , Carboplatina/administração & dosagem , Carboplatina/química , Carboplatina/metabolismo , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Química Farmacêutica , Relação Dose-Resposta a Droga , Humanos , Microscopia de Força Atômica , Microscopia Eletrônica de Varredura , Nanomedicina , Neuroblastoma/metabolismo , Neuroblastoma/patologia , Espectroscopia Fotoeletrônica , Espectrofotometria Ultravioleta , Análise Espectral Raman , Tecnologia Farmacêutica/métodos
8.
Phys Chem Chem Phys ; 17(38): 24956-67, 2015 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-26343297

RESUMO

Silicon is a promising negative electrode for secondary lithium-based batteries, but the electrochemical reversibility of particularly nanostructured silicon electrodes drastically depends on their interfacial characteristics, commonly known as the solid electrolyte interface (SEI). The beneficial origin of certain electrolyte additives or different binders is still discussed controversially owing to the challenging peculiarities of interfacial post-mortem investigations of electrodes. In this work, we address the common difficulties of SEI investigations of porous silicon/carbon nanostructures and study the addition of a fluoroethylene carbonate (FEC) as a stabilizing additive as well as the use of two different binders, carboxymethyl cellulose/styrene-butadiene rubber (CMC/SBR) and polyacrylic acid (PAA), for the SEI formation. The electrode is composed of silicon nanocrystallites below 5 nm diameter allowing a detailed investigation of interfacial characteristics of silicon owing to the high surface area. We first performed galvanostatic long-term cycling (400 times) and carried out comprehensive ex situ characterization of the cycled nanocrystalline silicon electrodes with XRD, EDXS, TEM and XPS. We modified the preparation of the electrode for post-mortem characterization to distinguish between electrolyte components and the actual SEI. The impact of the FEC additive and two different binders on the interfacial layer is studied and the occurrence of diverse compounds, in particular LiF, Li2O and phosphates, is discussed. These results help to understand general issues in SEI formation and to pave the way for the development of advanced electrolytes allowing for a long-term performance of nanostructured Si-based electrodes.

9.
J Am Chem Soc ; 134(24): 10089-101, 2012 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-22550936

RESUMO

A novel catalyst design for the conversion of mono- and disaccharides to lactic acid and its alkyl esters was developed. The design uses a mesoporous silica, here represented by MCM-41, which is filled with a polyaromatic to graphite-like carbon network. The particular structure of the carbon-silica composite allows the accommodation of a broad variety of catalytically active functions, useful to attain cascade reactions, in a readily tunable pore texture. The significance of a joint action of Lewis and weak Brønsted acid sites was studied here to realize fast and selective sugar conversion. Lewis acidity is provided by grafting the silica component with Sn(IV), while weak Brønsted acidity originates from oxygen-containing functional groups in the carbon part. The weak Brønsted acid content was varied by changing the amount of carbon loading, the pyrolysis temperature, and the post-treatment procedure. As both catalytic functions can be tuned independently, their individual role and optimal balance can be searched for. It was thus demonstrated for the first time that the presence of weak Brønsted acid sites is crucial in accelerating the rate-determining (dehydration) reaction, that is, the first step in the reaction network from triose to lactate. Composite catalysts with well-balanced Lewis/Brønsted acidity are able to convert the trioses, glyceraldehyde and dihydroxyacetone, quantitatively into ethyl lactate in ethanol with an order of magnitude higher reaction rate when compared to the Sn grafted MCM-41 reference catalyst. Interestingly, the ability to tailor the pore architecture further allows the synthesis of a variety of amphiphilic alkyl lactates from trioses and long chain alcohols in moderate to high yields. Finally, direct lactate formation from hexoses, glucose and fructose, and disaccharides composed thereof, sucrose, was also attempted. For instance, conversion of sucrose with the bifunctional composite catalyst yields 45% methyl lactate in methanol at slightly elevated reaction temperature. The hybrid catalyst proved to be recyclable in various successive runs when used in alcohol solvent.


Assuntos
Carbono/química , Dissacarídeos/química , Lactatos/síntese química , Monossacarídeos/química , Dióxido de Silício/química , Álcoois/química , Catálise , Lactatos/química , Ácido Láctico/síntese química , Ácido Láctico/química , Porosidade
10.
ACS Appl Mater Interfaces ; 14(1): 439-451, 2022 Jan 12.
Artigo em Inglês | MEDLINE | ID: mdl-34942074

RESUMO

Additive manufacturing is a promising technology for the fabrication of customized implants with complex geometry. The objective of this study was to investigate the initial cell-material interaction of degradable Fe-30Mn-1C-0.02S stent structures in comparison to conventional 316L as a reference, both processed by laser powder bed fusion. FeMn-based alloys have comparable mechanical properties with clinically applied AISI 316L for a corrosion-resistant stent material. Different corrosion stages of the as-built Fe-30Mn-1C-0.02S stent surfaces were simulated by pre-conditioning in DMEM under cell culture conditions for 2 h, 7 days, and 28 days. Human umbilical vein endothelial cells (HUVECs) were directly seeded onto the pre-conditioned samples, and cell viability, adherence, and morphology were analyzed. These studies were accompanied by measurements of iron and manganese ion release and Auger electron spectroscopy to evaluate the influence of corrosion products and degradation on the cells. In the initial phase (2 h of pre-conditioning), HUVECs were able to attach but the cell number decreased over the cultivation period of 14 days and the CD31 staining pattern of intercellular contacts was disordered. At later time points of corrosion (7 and 28 days of pre-conditioning), CD31 staining was distinctly located at the intercellular contacts, and the cell density increased after seeding and was stable for up to 14 days. Formation of a complex degradation layer, which had a composition and thickness dependent on the pre-conditioning time, led to a reduced ion release and finally showed a positive effect on cell survival. Concluding, our data suggest the suitability of Fe-30Mn-1C-0.02S for in vivo applications.


Assuntos
Materiais Biocompatíveis/metabolismo , Células Endoteliais da Veia Umbilical Humana/metabolismo , Ferro/metabolismo , Lasers , Manganês/metabolismo , Materiais Biocompatíveis/química , Células Cultivadas , Células Endoteliais da Veia Umbilical Humana/química , Humanos , Íons/química , Íons/metabolismo , Ferro/química , Manganês/química , Teste de Materiais
11.
Sci Adv ; 8(51): eadd6596, 2022 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-36542707

RESUMO

Advancing the lithium-ion battery technology requires the understanding of electrochemical processes in electrode materials with high resolution, accuracy, and sensitivity. However, most techniques today are limited by their inability to separate the complex signals from slurry-coated composite electrodes. Here, we use a three-dimensional "Swiss-roll" microtubular electrode that is incorporated into a micrometer-sized lithium battery. This on-chip platform combines various in situ characterization techniques and precisely probes the intrinsic electrochemical properties of each active material due to the removal of unnecessary binders and additives. As an example, it helps elucidate the critical role of Fe substitution in a conversion-type NiO electrode by monitoring the evolution of Fe2O3 and solid electrolyte interphase layer. The markedly enhanced electrode performances are therefore explained. Our approach exposes a hitherto unexplored route to tracking the phase, morphology, and electrochemical evolution of electrodes in real time, allowing us to reveal information that is not accessible with bulk-level characterization techniques.

12.
Nat Commun ; 12(1): 2839, 2021 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-33990573

RESUMO

A combination of complementary high-energy X-ray diffraction, containerless solidification during electromagnetic levitation and transmission electron microscopy is used to map in situ the phase evolution in a prototype Cu-Zr-Al glass during flash-annealing imposed at a rate ranging from 102 to 103 K s-1 and during cooling from the liquid state. Such a combination of experimental techniques provides hitherto inaccessible insight into the phase-transformation mechanism and its kinetics with high temporal resolution over the entire temperature range of the existence of the supercooled liquid. On flash-annealing, most of the formed phases represent transient (metastable) states - they crystallographically conform to their equilibrium phases but the compositions, revealed by atom probe tomography, are different. It is only the B2 CuZr phase which is represented by its equilibrium composition, and its growth is facilitated by a kinetic mechanism of Al partitioning; Al-rich precipitates of less than 10 nm in a diameter are revealed. In this work, the kinetic and chemical conditions of the high propensity of the glass for the B2 phase formation are formulated, and the multi-technique approach can be applied to map phase transformations in other metallic-glass-forming systems.

13.
J Am Chem Soc ; 132(15): 5413-21, 2010 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-20345137

RESUMO

The row of endohedral fullerenes is extended by a new type of sulfur-containing clusterfullerenes: the metal sulfide (M(2)S) has been stabilized within a fullerene cage for the first time. The new sulfur-containing clusterfullerenes M(2)S@C(82)-C(3v)(8) have been isolated for a variety of metals (M = Sc, Y, Dy, and Lu). The UV-vis-NIR, electrochemical, and FTIR spectroscopic characterization and extended DFT calculations point to a close similarity of the M(2)S@C(82) cage isomeric and electronic structure to that of the carbide clusterfullerenes M(2)C(2)@C(2n). The bonding in M(2)S@C(82) is studied in detail by molecular orbital analysis as well as with the use of quantum theory of atom-in-molecules (QTAIM) and electron localization function (ELF) approaches. The metal sulfide cluster formally transfers four electrons to the carbon cage, and metal-sulfur and metal-carbon cage bonds with a high degree of covalency are formed. Molecular dynamics simulations show that Sc(2)S cluster exhibits an almost free rotation around the C(3) axis of the carbon cage, resulting thus in a single line (45)Sc NMR spectrum.

14.
ACS Appl Mater Interfaces ; 12(33): 37227-37238, 2020 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-32687305

RESUMO

Lithium-ion batteries (LIBs) are nowadays widely used in many energy storage devices, which have certain requirements on size, weight, and performance. State-of-the-art LIBs operate very reliably and with good performance under restricted and controlled conditions but lack in efficiency and safety when these conditions are exceeded. In this work, the influence of outranging conditions in terms of charging rate and operating temperature on electrochemical characteristics was studied on the example of lithium titanate (Li4Ti5O12, LTO) electrodes. Structural processes in the electrode, cycled with ultrafast charge and discharge, were evaluated by operando synchrotron powder diffraction and ex situ X-ray absorption spectroscopy. On the basis of the Rietveld refinement, it was shown that the electrochemical storage mechanism is based on the Li-intercalation process at least up to current rates of 5C, meaning full battery charge within 12 min. For applications at temperatures between -30 and 60 °C, four carbonate-based electrolyte systems with different additives were tested for cycling performance in half-cells with LTO and metallic lithium as electrodes. It was shown that the addition of 30 wt % [PYR14][PF6] to the conventional LP30 electrolyte, usually used in LIBs, significantly decreases its melting point, which enables the successful low-temperature application at least down to -30 °C, in contrast to LP30, which freezes below -10 °C, making battery operation impossible. Moreover, at elevated temperatures up to 60 °C, batteries with the LP30/[PYR14][PF6] electrolyte exhibit stable long-term cycling behavior very close to LP30. Our findings provide a guideline for the application of LTO in LIBs beyond conventional conditions and show how to overcome limitations by designing appropriate electrolytes.

15.
Materials (Basel) ; 13(9)2020 Apr 27.
Artigo em Inglês | MEDLINE | ID: mdl-32349440

RESUMO

Ti-Al thin films with a thickness of 200 nm were prepared either by co-sputtering from elemental Ti and Al targets or as Ti/Al multilayers with 10 and 20 nm individual layer thickness on thermally oxidized Si substrates. Some of the films were covered with a 20-nm-thick SiO 2 layer, which was used as an oxidation protection against the ambient atmosphere. The films were annealed at up to 800 ∘ C in high vacuum for 10 h, and the phase formation as well as the film architecture was analyzed by X-ray diffraction, cross section, and transmission electron microscopy, as well as Auger electron and X-ray photoelectron spectroscopy. The results reveal that the co-sputtered films remained amorphous after annealing at 600 ∘ C independent on the presence of the SiO 2 cover layer. In contrast to this, the γ -TiAl phase was formed in the multilayer films at this temperature. After annealing at 800 ∘ C, all films were degraded completely despite the presence of the cover layer. In addition, a strong chemical reaction between the Ti and SiO 2 of the cover layer and the substrate took place, resulting in the formation of Ti silicide. In the multilayer samples, this reaction already started at 600 ∘ C.

16.
ACS Appl Mater Interfaces ; 12(48): 53827-53840, 2020 Dec 02.
Artigo em Inglês | MEDLINE | ID: mdl-33201669

RESUMO

Electrode materials with a high performance and stable cycling have been commercialized, but the utilization of state-of-the-art Li-ion batteries in high-current rate applications is restricted because of limitations in other battery components, in particular, the lack of an efficient binder. Herein, a novel multicomponent polymer gel binder (PGB) is presented, comprising the biopolymer chitosan as the host, embedded with the 1-butyl-1-methylpyrrolidinium dicyanamide (PYR14DCA) ionic liquid and the lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. The multicomponent approach leads to carbon black arrangement along well-distributed chitosan chains in the electrodes, forming a highly electronic conductive network. Furthermore, the plasticizing effect of the ionic liquid leads to an enhanced ionic conductivity. As a result, shorter charge-transfer paths are enabled, leading to an exceptionally high rate capability in LiFePO4 and Li4Ti5O12 half cells, up to 50C. LiFePO4||Li4Ti5O12 full cells using the PGB for both electrodes also demonstrated stable cycling at 10C, with an impressively high discharge capacity of 173 mA h·g-1 after 1000 cycles. In addition, freestanding electrodes could also be realized and functioning flexible Li-ion cells were successfully demonstrated. Thus, the novel water-processable binder offers multifaceted advantages, making the approach highly promising for industrial implementation.

17.
Adv Mater ; 32(4): e1905681, 2020 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-31788883

RESUMO

The intrinsic advantages of metallic Zn, like high theoretical capacity (820 mAh g-1 ), high abundance, low toxicity, and high safety have driven the recent booming development of rechargeable Zn batteries. However, the lack of high-voltage electrolyte and cathode materials restricts the cell voltage mostly to below 2 V. Moreover, dendrite formation and the poor rechargeability of the Zn anode hinder the long-term operation of Zn batteries. Here a high-voltage and durable Zn-graphite battery, which is enabled by a LiPF6 -containing hybrid electrolyte, is reported. The presence of LiPF6 efficiently suppresses the anodic oxidation of Zn electrolyte and leads to a super-wide electrochemical stability window of 4 V (vs Zn/Zn2+ ). Both dendrite-free Zn plating/stripping and reversible dual-anion intercalation into the graphite cathode are realized in the hybrid electrolyte. The resultant Zn-graphite battery performs stably at a high voltage of 2.8 V with a record midpoint discharge voltage of 2.2 V. After 2000 cycles at a high charge-discharge rate, high capacity retention of 97.5% is achieved with ≈100% Coulombic efficiency.

18.
ACS Nano ; 14(9): 11753-11764, 2020 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-32877171

RESUMO

Sluggish conversion reactions severely impair the rate capability for lithium storage, which is the main disadvantage of the conversion-type anode materials. Here, the microplatform based on a single microelectrode is designed and utilized for the fundamental understanding of the conversion reaction. The kinetic-favorable layered structure of the anode material is on-site synthesized in the microplatform. The in situ characterization reveals that introducing an oxygen network distortion in the layered oxide anode effectively circumvents the severe passivation of the electrode material by lithium oxide, thus leading to highly reversible conversion reactions. As a result, the high-rate capability of the conversion-type anode materials is realized. The on-site synthesis strategy is further applied in the large-scale synthesis of nanomaterials for lithium-ion batteries. As such, oxide nanorods with the layered structure are synthesized by a facile chemical strategy, showing high rate performance (574 mAh g-1 at 10 A g-1). This work unveils the beneficial effect of oxygen network distortion in the layered anode for conversion reactions over cycling, thus providing an alternative strategy to enhance the rate capability of conversion-type anodes for lithium storage.

19.
Adv Mater ; 31(14): e1807712, 2019 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-30767311

RESUMO

Supercapacitors have aroused considerable attention due to their high power capability, which enables charge storage/output in minutes or even seconds. However, to achieve a high energy density in a supercapacitor has been a long-standing challenge. Here, graphite is reported as a high-energy alternative to the frequently used activated carbon (AC) cathode for supercapacitor application due to its unique Faradaic pseudocapacitive anion intercalation behavior. The graphite cathode manifests both higher gravimetric and volumetric energy density (498 Wh kg-1 and 431.2 Wh l-1 ) than an AC cathode (234 Wh kg-1 and 83.5 Wh l-1 ) with peak power densities of 43.6 kW kg-1 and 37.75 kW l-1 . A new type of Li-ion pseudocapacitor (LIpC) is thus proposed and demonstrated with graphite as cathode and prelithiated graphite or Li4 Ti5 O12 (LTO) as anode. The resultant graphite-graphite LIpCs deliver high energy densities of 167-233 Wh kg-1 at power densities of 0.22-21.0 kW kg-1 (based on active mass in both electrodes), much higher than 20-146 Wh kg-1 of AC-derived Li-ion capacitors and 23-67 Wh kg-1 of state-of-the-art metal oxide pseudocapacitors. Excellent rate capability and cycling stability are further demonstrated for LTO-graphite LIpCs.

20.
Materials (Basel) ; 12(17)2019 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-31438479

RESUMO

Developing advanced thin film materials is the key challenge in high-temperature applications of surface acoustic wave sensor devices. One hundred nanometer thick (Mo-La 2 O 3 ) multilayer systems were fabricated at room temperature on thermally oxidized (100) Si substrates (SiO 2 /Si) to study the effect of lanthanum oxide on the electrical resistivity of molybdenum thin films and their high-temperature stability. The multilayer systems were deposited by the magnetron sputter deposition of extremely thin (≤1 nm) La interlayers in between adjacent Mo layers. After deposition of each La layer the process was interrupted for 25 to 60 min to oxidize the La using the residual oxygen in the high vacuum of the deposition chamber. The samples were annealed at 800 ∘ C in high vacuum for up to 120 h. In case of a 1 nm thick La interlayer in-between the Mo a continuous layer of La 2 O 3 is formed. For thinner La layers an interlayer between adjacent Mo layers is observed consisting of a (La 2 O 3 -Mo) mixed structure of molybdenum and nm-sized lanthanum oxide particles. Measurements show that the (Mo-La 2 O 3 ) multilayer systems on SiO 2 /Si substrates are stable at least up to 800 ∘ C for 120 h in high vacuum conditions.

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