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1.
Nature ; 598(7882): 590-596, 2021 10.
Artículo en Inglés | MEDLINE | ID: mdl-34671167

RESUMEN

Although solid-state lithium (Li)-metal batteries promise both high energy density and safety, existing solid ion conductors fail to satisfy the rigorous requirements of battery operations. Inorganic ion conductors allow fast ion transport, but their rigid and brittle nature prevents good interfacial contact with electrodes. Conversely, polymer ion conductors that are Li-metal-stable usually provide better interfacial compatibility and mechanical tolerance, but typically suffer from inferior ionic conductivity owing to the coupling of the ion transport with the motion of the polymer chains1-3. Here we report a general strategy for achieving high-performance solid polymer ion conductors by engineering of molecular channels. Through the coordination of copper ions (Cu2+) with one-dimensional cellulose nanofibrils, we show that the opening of molecular channels within the normally ion-insulating cellulose enables rapid transport of Li+ ions along the polymer chains. In addition to high Li+ conductivity (1.5 × 10-3 siemens per centimetre at room temperature along the molecular chain direction), the Cu2+-coordinated cellulose ion conductor also exhibits a high transference number (0.78, compared with 0.2-0.5 in other polymers2) and a wide window of electrochemical stability (0-4.5 volts) that can accommodate both the Li-metal anode and high-voltage cathodes. This one-dimensional ion conductor also allows ion percolation in thick LiFePO4 solid-state cathodes for application in batteries with a high energy density. Furthermore, we have verified the universality of this molecular-channel engineering approach with other polymers and cations, achieving similarly high conductivities, with implications that could go beyond safe, high-performance solid-state batteries.

2.
Nano Lett ; 22(1): 255-262, 2022 01 12.
Artículo en Inglés | MEDLINE | ID: mdl-34932367

RESUMEN

Chemically ordered intermetallic nanoparticles are promising candidates for energy-related applications such as electrocatalysis. However, the synthesis of intermetallics generally requires long annealing (several hours) to achieve the ordered structure, which causes nanoparticles agglomeration and diminished performance, particularly for catalysis. Herein, we demonstrate a new rapid Joule heating approach that can synthesize highly ordered and well-dispersed intermetallic nanoparticles. As a proof-of-concept, we synthesized fully ordered Pd3Pb intermetallic nanoparticles that feature small size distribution (∼6 nm). Computational analysis of the L12 Pd3Pb material suggests that this rapid atomic ordering transformation can be attributed to a vacancy-mediated diffusion mechanism. Moreover, the nanoparticles demonstrate excellent electrocatalytic activity and exceptional stability for the oxygen reduction reaction (ORR), retaining >95% of the current density over 10 h of chronoamperometry test with negligible structural and compositional changes. This study demonstrates a new strategy of providing a new direction for intermetallic synthesis and catalyst discovery.


Asunto(s)
Nanopartículas , Catálisis
3.
Nano Lett ; 21(14): 6163-6170, 2021 Jul 28.
Artículo en Inglés | MEDLINE | ID: mdl-34259523

RESUMEN

The use of solid-state electrolyte may be necessary to enable safe, high-energy-density Li metal anodes for next-generation energy storage systems. However, the inhomogeneous local current densities during long-term cycling result in instability and detachment of the Li anode from the electrolyte, which greatly hinders practical application. In this study, we report a new approach to maintain a stable Li metal | electrolyte interface by depositing an amorphous carbon nanocoating on garnet-type solid-state electrolyte. The carbon nanocoating provides both electron and ion conducting capability, which helps to homogenize the lithium metal stripping and plating processes. After coating, we find the Li metal/garnet interface displays stable cycling at 3 mA/cm2 for more than 500 h, demonstrating the interface's outstanding electro-chemomechanical stability. This work suggests amorphous carbon coatings may be a promising strategy for achieving stable Li metal | electrolyte interfaces and reliable Li metal batteries.

4.
Proc Natl Acad Sci U S A ; 115(15): 3770-3775, 2018 04 10.
Artículo en Inglés | MEDLINE | ID: mdl-29581262

RESUMEN

The increasing demands for efficient and clean energy-storage systems have spurred the development of Li metal batteries, which possess attractively high energy densities. For practical application of Li metal batteries, it is vital to resolve the intrinsic problems of Li metal anodes, i.e., the formation of Li dendrites, interfacial instability, and huge volume changes during cycling. Utilization of solid-state electrolytes for Li metal anodes is a promising approach to address those issues. In this study, we use a 3D garnet-type ion-conductive framework as a host for the Li metal anode and study the plating and stripping behaviors of the Li metal anode within the solid ion-conductive host. We show that with a solid-state ion-conductive framework and a planar current collector at the bottom, Li is plated from the bottom and rises during deposition, away from the separator layer and free from electrolyte penetration and short circuit. Owing to the solid-state deposition property, Li grows smoothly in the pores of the garnet host without forming Li dendrites. The dendrite-free deposition and continuous rise/fall of Li metal during plating/stripping in the 3D ion-conductive host promise a safe and durable Li metal anode. The solid-state Li anode shows stable cycling at 0.5 mA cm-2 for 300 h with a small overpotential, showing a significant improvement compared with reported Li anodes with ceramic electrolytes. By fundamentally eliminating the dendrite issue, the solid Li metal anode shows a great potential to build safe and reliable Li metal batteries.

5.
J Biol Chem ; 294(27): 10638-10648, 2019 07 05.
Artículo en Inglés | MEDLINE | ID: mdl-31138647

RESUMEN

The envelope protein of Zika virus (ZIKV) exists as a dimer on the mature viral surface and is an attractive antiviral target because it mediates viral entry. However, recombinant soluble wild-type ZIKV envelope (wtZE) might preferentially exist as monomer (monZE). Recently, it has been shown that the A264C substitution could promote formation of dimeric ZIKV envelope protein (ZEA264C), requiring further characterization of purified ZEA264C for its potential applications in vaccine development. We also noted that ZEA264C, connected by disulfide bond, might be different from the noncovalent native envelope dimer on the virion surface. Because the antibody Fc fragment exists as dimer and is widely used for fusion protein construction, here we fused wtZE to human immunoglobulin G1 (IgG1) Fc fragment (ZE-Fc) for noncovalent wtZE dimerization. Using a multistep purification procedure, we separated dimeric ZEA264C and ZE-Fc, revealing that they both exhibit typical ß-sheet-rich secondary structures and stabilities similar to those of monZE. The binding activities of monZE, ZEA264C, and ZE-Fc to neutralizing antibodies targeting different epitopes indicated that ZEA264C and ZE-Fc could better mimic the native dimeric status, especially in terms of the formation of tertiary and quaternary epitopes. Both ZEA264C and ZE-Fc recognize a ZIKV-sensitive cell line as does monZE, indicating that the two constructs are still functional. Furthermore, a murine immunization assay disclose that ZEA264C and ZE-Fc elicit more neutralizing antibody responses than monZE does. These results suggest that the two immunogen candidates ZEA264C and ZE-Fc have potential utility for neutralizing antibody selection and vaccine design against ZIKV.


Asunto(s)
Anticuerpos Neutralizantes/inmunología , Anticuerpos Antivirales/inmunología , Proteínas del Envoltorio Viral/inmunología , Virus Zika/metabolismo , Animales , Anticuerpos Neutralizantes/metabolismo , Anticuerpos Antivirales/metabolismo , Dimerización , Epítopos/genética , Epítopos/inmunología , Epítopos/metabolismo , Femenino , Ratones , Ratones Endogámicos BALB C , Ingeniería de Proteínas , Estabilidad Proteica , Estructura Secundaria de Proteína , Proteínas Recombinantes de Fusión/biosíntesis , Proteínas Recombinantes de Fusión/genética , Proteínas Recombinantes de Fusión/inmunología , Anticuerpos de Cadena Única/biosíntesis , Anticuerpos de Cadena Única/genética , Anticuerpos de Cadena Única/inmunología , Proteínas del Envoltorio Viral/genética , Proteínas del Envoltorio Viral/metabolismo , Vacunas Virales/inmunología , Virus Zika/inmunología
6.
Proc Natl Acad Sci U S A ; 114(14): 3584-3589, 2017 04 04.
Artículo en Inglés | MEDLINE | ID: mdl-28320936

RESUMEN

Lithium metal anode with the highest capacity and lowest anode potential is extremely attractive to battery technologies, but infinite volume change during the Li stripping/plating process results in cracks and fractures of the solid electrolyte interphase, low Coulombic efficiency, and dendritic growth of Li. Here, we use a carbonized wood (C-wood) as a 3D, highly porous (73% porosity) conductive framework with well-aligned channels as Li host material. We discovered that molten Li metal can infuse into the straight channels of C-wood to form a Li/C-wood electrode after surface treatment. The C-wood channels function as excellent guides in which the Li stripping/plating process can take place and effectively confine the volume change that occurs. Moreover, the local current density can be minimized due to the 3D C-wood framework. Therefore, in symmetric cells, the as-prepared Li/C-wood electrode presents a lower overpotential (90 mV at 3 mA⋅cm-2), more-stable stripping/plating profiles, and better cycling performance (∼150 h at 3 mA⋅cm-2) compared with bare Li metal electrode. Our findings may open up a solution for fabricating stable Li metal anode, which further facilitates future application of high-energy-density Li metal batteries.

7.
J Biol Chem ; 293(49): 19127-19135, 2018 12 07.
Artículo en Inglés | MEDLINE | ID: mdl-30327432

RESUMEN

Therapeutic monoclonal antibodies and Fc-fusion proteins containing antibody Fc fragment may tend to destabilize (e.g. unfold and aggregate), which leads to loss of functions and increase of adverse risks. Although engineering of an additional disulfide bond has been performed in Fc or Fc domains for optimization, the relationships between introduced disulfide bond and alteration of the stability, aggregation propensity and function were still unclear and should be addressed for achievement of better therapeutic outcome. Here, we constructed three human IgG1 Fc mutants including FcCH2-s-s- (one engineered disulfide bond in CH2 domain), FcCH3-s-s- (one engineered disulfide bond in CH3 domain), and FcCH3-s-s-CH2-s-s- (two engineered disulfide bonds in CH2 and CH3 domains, respectively) for evaluation. As expected, each mutated domain shows obviously increased stability during thermo-induced unfolding, and FcCH3-s-s-CH2-s-s- is most thermo-stable among wildtype Fc (wtFc) and three mutants. The order of overall stability against denaturant is FcCH3-s-s-CH2-s-s- > FcCH2-s-s- > FcCH3-s-s- > wtFc. Then the aggregation propensity was compared among these four proteins. Under conditions of incubation at 60 °C, their aggregation resistance is in the order of FcCH3-s-s-CH2-s-s- > FcCH2-s-s- > FcCH3-s-s- ≈ wtFc. In contrast, the order is FcCH3-s-s-CH2-s-s- > FcCH3-s-s- > FcCH2-s-s- ≈ wtFc under acidic conditions. In addition, the Fc-mediated functions are not obviously affected by engineered disulfide bond. Our results give a comprehensive elucidation of structural and functional effects caused by additional disulfide bonds in the Fc fragment, which is important for Fc engineering toward the desired clinical performance.


Asunto(s)
Disulfuros/química , Fragmentos Fc de Inmunoglobulinas/química , Inmunoglobulina G/química , Línea Celular , Disulfuros/metabolismo , Antígenos de Histocompatibilidad Clase I/metabolismo , Humanos , Fragmentos Fc de Inmunoglobulinas/genética , Fragmentos Fc de Inmunoglobulinas/metabolismo , Mutación , Desnaturalización Proteica , Dominios Proteicos , Ingeniería de Proteínas , Multimerización de Proteína , Estabilidad Proteica , Receptores Fc/metabolismo
8.
Mol Pharm ; 16(8): 3647-3656, 2019 08 05.
Artículo en Inglés | MEDLINE | ID: mdl-31282682

RESUMEN

The IgG1 CH2 domain is involved in Fc-mediated effector functions and is a promising scaffold for development of novel therapeutics. We previously reported that removal of seven unstructured N-terminal residues of an autonomous human IgG1 CH2 domain significantly increased its stability and aggregation resistance. However, the way in which the C-terminal residues affect folding is unclear. Here, we found that the CH2 C-terminus is highly sensitive to truncation although these residues adopt a random coil conformation according to the crystal structure of a CH2 domain. To optimize the C-terminus, we used a phage display platform for high-throughput screening of mutants with improved physicochemical properties. After panning of the CH2 mutant library at high temperature against a CH2-specific antibody recognizing a conformational epitope, we obtained two candidates, B3 and D9, with markedly increased thermal stability. We found that substitution of K338 (EU numbering) by isoleucine is crucial for the increased stability, which might be due to enhanced hydrophobic interactions involving W313. However, the aggregation propensity was also increased. To reduce the aggregation propensity, we further mutated the last two residues A339 and K340 adjacent to residue I338 at the C-terminus by rational design and identified a mutant, CH2-IKS (K338I, A339K, and K340S), with high stability and aggregation resistance. In summary, the C-terminus of CH2 is important for its folding and could be further optimized toward better potential applications for CH2-based therapeutics. Our strategy might be also useful for stabilization of other Ig-like proteins.


Asunto(s)
Anticuerpos Monoclonales/genética , Inmunoglobulina G/genética , Mutagénesis Sitio-Dirigida , Secuencia de Aminoácidos/genética , Sustitución de Aminoácidos , Anticuerpos Monoclonales/aislamiento & purificación , Anticuerpos Monoclonales/metabolismo , Anticuerpos Monoclonales/uso terapéutico , Inmunoglobulina G/aislamiento & purificación , Inmunoglobulina G/metabolismo , Inmunoglobulina G/uso terapéutico , Biblioteca de Péptidos , Agregado de Proteínas/genética , Dominios Proteicos/genética , Pliegue de Proteína , Estabilidad Proteica , Proteínas Recombinantes/genética , Proteínas Recombinantes/aislamiento & purificación , Proteínas Recombinantes/metabolismo , Proteínas Recombinantes/uso terapéutico
9.
Nano Lett ; 18(1): 297-301, 2018 01 10.
Artículo en Inglés | MEDLINE | ID: mdl-29272134

RESUMEN

Li metal anodes, which have attracted much attention for their high specific capacity and low redox potential, face a great challenge in realizing their practical application. The fatal issue of dendrite formation gives rise to internal short circuit and safety hazards and needs to be addressed. Here we propose a rational strategy of trapping Li within microcages to confine the deposition morphology and suppress dendrite growth. Microcages with a carbon nanotube core and porous silica sheath were prepared and proved to be effective for controlling the electrodeposition behavior. In addition, the insulative coating layer prevents concentrated electron flow and decreases the possibility of "hot spots" formation. Because of the Li trapper and uniform electron distribution, the electrode with delicate structure exhibits a dendrite-free morphology after plating 2 mA h cm-2 of Li. As the dendrite growth is suppressed, the as-obtained electrode maintains a high plating/stripping efficiency of 99% over 200 cycles. This work delivers new insights into the design of rational Li metal anodes and hastens the practical application of Li metal batteries.

10.
Nano Lett ; 18(6): 3926-3933, 2018 06 13.
Artículo en Inglés | MEDLINE | ID: mdl-29787678

RESUMEN

Solid-state electrolytes (SSEs) have been widely considered as enabling materials for the practical application of lithium metal anodes. However, many problems inhibit the widespread application of solid state batteries, including the growth of lithium dendrites, high interfacial resistance, and the inability to operate at high current density. In this study, we report a three-dimensional (3D) mixed electron/ion conducting framework (3D-MCF) based on a porous-dense-porous trilayer garnet electrolyte structure created via tape casting to facilitate the use of a 3D solid state lithium metal anode. The 3D-MCF was achieved by a conformal coating of carbon nanotubes (CNTs) on the porous garnet structure, creating a composite mixed electron/ion conductor that acts as a 3D host for the lithium metal. The lithium metal was introduced into the 3D-MCF via slow electrochemical deposition, forming a 3D lithium metal anode. The slow lithiation leads to improved contact between the lithium metal anode and garnet electrolyte, resulting in a low resistance of 25 Ω cm2. Additionally, due to the continuous CNT coating and its seamless contact with the garnet we observed highly uniform lithium deposition behavior in the porous garnet structure. With the same local current density, the high surface area of the porous garnet framework leads to a higher overall areal current density for stable lithium deposition. An elevated current density of 1 mA/cm2 based on the geometric area of the cell was demonstrated for continuous lithium cycling in symmetric lithium cells. For battery operation of the trilayer structure, the lithium can be cycled between the 3D-MCF on one side and the cathode infused into the porous structure on the opposite side. The 3D-MCF created by the porous garnet structure and conformal CNT coating provides a promising direction toward new designs in solid-state lithium metal batteries.

11.
J Am Chem Soc ; 140(1): 82-85, 2018 01 10.
Artículo en Inglés | MEDLINE | ID: mdl-29232123

RESUMEN

The key bottleneck troubling the application of solid electrolyte is the contradictory requirements from Li-metal and cathode, which need high modulus to block Li-dendrite penetration and flexibility to enable low interface resistance, respectively. This study describes a thin asymmetrical design of solid electrolyte to address these shortcomings. In this architecture, a rigid ceramic-layer modified with an ultrathin polymer is toward Li-metal to accomplish dendrite-suppression of Li-anode, and a soft polymer-layer spreads over the exterior and interior of cathode to endow connected interface simultaneously. This ingenious arrangement endows solid Li-metal batteries with extremely high Coulombic efficiency and cyclability. This work will open up one avenue for realizing safe and long-life energy storage systems.

12.
Nano Lett ; 17(6): 3792-3797, 2017 06 14.
Artículo en Inglés | MEDLINE | ID: mdl-28463514

RESUMEN

Room-temperature Na ion batteries (NIBs) have attracted great attention because of the widely available, abundant sodium resources and potentially low cost. Currently, the challenge of the NIB development is due primarily to the lack of a high-performance anode, while the Na metal anode holds great promise considering its highest specific capacity of 1165 mA h/g and lowest anodic potential. However, an uneven deposit, relatively infinite volume change, and dendritic growth upon plating/stripping cycles cause a low Coulombic efficiency, poor cycling performance, and severe safety concerns. Here, a stable Na carbonized wood (Na-wood) composite anode was fabricated via a rapid melt infusion (about 5 s) into channels of carbonized wood by capillary action. The channels function as a high-surface-area, conductive, mechanically stable skeleton, which lowers the effective current density, ensures a uniform Na nucleation, and restricts the volume change over cycles. As a result, the Na-wood composite anode exhibited flat plating/stripping profiles with smaller overpotentials and stable cycling performance over 500 h at 1.0 mA/cm2 in a common carbonate electrolyte system. In sharp comparison, the planar Na metal electrode showed a much shorter cycle life of 100 h under the same test conditions.

13.
Nano Lett ; 17(8): 4917-4923, 2017 08 09.
Artículo en Inglés | MEDLINE | ID: mdl-28714694

RESUMEN

High-temperature batteries require the battery components to be thermally stable and function properly at high temperatures. Conventional batteries have high-temperature safety issues such as thermal runaway, which are mainly attributed to the properties of liquid organic electrolytes such as low boiling points and high flammability. In this work, we demonstrate a truly all-solid-state high-temperature battery using a thermally stable garnet solid-state electrolyte, a lithium metal anode, and a V2O5 cathode, which can operate well at 100 °C. To address the high interfacial resistance between the solid electrolyte and cathode, a rapid thermal annealing method was developed to melt the cathode and form a continuous contact. The resulting interfacial resistance of the solid electrolyte and V2O5 cathode was significantly decreased from 2.5 × 104 to 71 Ω·cm2 at room temperature and from 170 to 31 Ω·cm2 at 100 °C. Additionally, the diffusion resistance in the V2O5 cathode significantly decreased as well. The demonstrated high-temperature solid-state full cell has an interfacial resistance of 45 Ω·cm2 and 97% Coulombic efficiency cycling at 100 °C. This work provides a strategy to develop high-temperature all-solid-state batteries using garnet solid electrolytes and successfully addresses the high contact resistance between the V2O5 cathode and garnet solid electrolyte without compromising battery safety or performance.

14.
Angew Chem Int Ed Engl ; 57(10): 2625-2629, 2018 03 01.
Artículo en Inglés | MEDLINE | ID: mdl-29346707

RESUMEN

The interaction between metal nanoparticles (NPs) and their substrate plays a critical role in determining the particle morphology, distribution, and properties. The pronounced impact of a thin oxide coating on the dispersion of metal NPs on a carbon substrate is presented. Al2 O3 -supported Pt NPs are compared to the direct synthesis of Pt NPs on bare carbon surfaces. Pt NPs with an average size of about 2 nm and a size distribution ranging between 0.5 nm and 4.0 nm are synthesized on the Al2 O3 coated carbon nanofiber, a significant improvement compared to those directly synthesized on a bare carbon surface. First-principles modeling verifies the stronger adsorption of Pt clusters on Al2 O3 than on carbon, which attributes the formation of ultrafine Pt NPs. This strategy paves the way towards the rational design of NPs with enhanced dispersion and controlled particle size, which are promising in energy storage and electrocatalysis.

15.
J Am Chem Soc ; 137(6): 2215-8, 2015 Feb 18.
Artículo en Inglés | MEDLINE | ID: mdl-25650588

RESUMEN

In contrast to the extensive studies of the electrochemical behavior of conventional cyclic S8 molecules in Li-S batteries, there has been hardly any investigation of the electrochemistry of S chains. Here we use S chains encapsulated in single- and double-walled carbon nanotubes as a model system and report the electrochemical behavior of 1D S chains in Li-S batteries. An electrochemical test shows that S chains have high electrochemical activity during lithiation and extinctive electrochemistry compared with conventional S8. The confined steric effect provides Li(+) solid-phase diffusion access to insert/egress reactions with S chains. During lithiation, the long S chains spontaneously become short chains, which show higher discharge plateaus and better kinetics. The unique electrochemistry of S chains supplements the existing knowledge of the S cathode mechanism and provides avenues for rational design of S cathode materials in Li-S batteries.

16.
Adv Sci (Weinh) ; : e2402497, 2024 Jun 17.
Artículo en Inglés | MEDLINE | ID: mdl-38884340

RESUMEN

Catalysis is crucial to improve redox kinetics in lithium-sulfur (Li-S) batteries. However, conventional catalysts that consist of a single metal element are incapable of accelerating stepwise sulfur redox reactions which involve 16-electron transfer and multiple Li2Sn (n = 2-8) intermediate species. To enable fast kinetics of Li-S batteries, it is proposed to use high-entropy alloy (HEA) nanocatalysts, which are demonstrated effective to adsorb lithium polysulfides and accelerate their redox kinetics. The incorporation of multiple elements (Co, Ni, Fe, Pd, and V) within HEAs greatly enhances the catalytically active sites, which not only improves the rate capability, but also elevates the cycling stability of the assembled batteries. Consequently, HEA-catalyzed Li-S batteries achieve a high capacity up to 1364 mAh g-1 at 0.1 C and experience only a slight capacity fading rate of 0.054% per cycle over 1000 cycles at 2 C, while the assembled pouch cell achieves a high specific capacity of 1192 mAh g-1. The superior performance of Li-S batteries demonstrates the effectiveness of the HEA catalysts with maximized synergistic effect for accelerating S conversion reactions, which opens a way to catalytically improving stepwise electrochemical conversion reactions.

17.
Adv Mater ; 36(21): e2312959, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38332502

RESUMEN

Ternary strategyopens a simple avenue to improve the power conversion efficiency (PCE) of organic solar cells (OSCs). The introduction of wide bandgap polymer donors (PDs) as third component canbetter utilize sunlight and improve the mechanical and thermal stability of active layer. However, efficient ternary OSCs (TOSCs) with two PDs are rarely reported due to inferior compatibility and shortage of efficient PDs match with acceptors. Herein, two PDs-(PBB-F and PBB-Cl) are adopted in the dual-PDs ternary systems to explore the underlying mechanisms and improve their photovoltaic performance. The findings demonstrate that the third components exhibit excellent miscibility with PM6 and are embedded in the host donor to form alloy-like phase. A more profound mechanism for enhancing efficiency through dual mechanisms, that are the guest energy transfer to PM6 and charge transport at the donor/acceptor interface, has been proposed. Consequently, the PM6:PBB-Cl:BTP-eC9 TOSCs achieve PCE of over 19%. Furthermore, the TOSCs exhibit better thermal stability than that of binary OSCs due to the reduction in spatial site resistance resulting from a more tightly entangled long-chain structure. This work not only provides an effective approach to fabricate high-performance TOSCs, but also demonstrates the importance of developing dual compatible PD materials.

18.
J Colloid Interface Sci ; 673: 628-637, 2024 Jun 15.
Artículo en Inglés | MEDLINE | ID: mdl-38897064

RESUMEN

The aqueous zinc ion battery (AZIB) has been widely studied due to its rapid kinetics and high specific capacity attributed to the chemical insertion of H+ protons. However, the current research landscape lacks comprehensive investigations into copper-based sulfide materials and the intricate co-embedding/extraction mechanism of H+/Zn2+. In this study, we employed an innovative in-situ etching method to synthesize a current collector-integrated Cu@Cu31S16 cathode material. Cu31S16 not only exhibits excellent stability and conductivity but also activates proton insertion chemistry. Consequently, we have demonstrated, for the first time, efficient and reversible co-embedding/extraction behavior of H+/Zn2+ in Zn-Cu31S16 batteries. Specifically, owing to the lower charging and discharging plateaus of zinc ions (0.65 V, 0.45 V) compared to H+ (0.97 V, 0.84 V) in Zn-Cu31S16 batteries, two distinct plateaus were observed. Moreover, we delved into the mechanism of ion co-embedding/extraction by exploring different ions (Zn2+, H+/Zn2+, H+) within varying voltage ranges. This exploration led to the development of three types of ion batteries, where Zn2+, H+/Zn2+, and H+ exhibit co-embedding/extraction within voltage ranges of 0.3-0.9 V, 0.3-1.05 V, and 0.5-1.05 V, respectively. These batteries have achieved impressive performance with specific capacities of 282.74 mAh g-1, 587.4 mAh g-1 and 687.3 mAh g-1, respectively. Introducing the concept of "Voltage-Selective Ion Co-Embedding/Extraction", this study broadens the research scope of AZIBs. This research not only offers a feasible solution and theoretical guidance for future proton batteries but also underscores the tremendous potential of AHPB.

19.
ACS Nano ; 17(1): 668-677, 2023 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-36534047

RESUMEN

The aqueous zinc (Zn) battery is a safe and eco-friendly energy-storage system. However, the use of Zn metal anodes is impeded by uncontrolled Zn deposition behavior. Herein, we regulate the Zn-ion deposition process for dendrite-free Zn metal anodes using an aminosilane molecular layer with high zincophilic sites and narrow molecule channels. The aminosilane molecular layer causes Zn ions to undergo consecutive processes including being captured by the amine functional groups of aminosilane and diffusing through narrow intermolecular channels before electroplating, which induces partial dehydration of hydrated Zn ions and uniform Zn ion flux, promoting reversible Zn stripping/plating. Through this molecule-induced capture-diffusion-deposition procedure of Zn ions, smooth and compact Zn electrodeposited layers are obtained. Hence, the aminosilane-modified Zn anode has high Coulombic efficiency (∼99.5%), long lifespan (∼3000 h), and high capacity retention in full cells (88.4% for 600 cycles). This strategy not only has great potential for achieving dendrite-free Zn anodes in practical Zn batteries but also suggests an interface-modification principle at the molecular level for other alternative metallic anodes.

20.
Nat Commun ; 14(1): 4211, 2023 Jul 14.
Artículo en Inglés | MEDLINE | ID: mdl-37452049

RESUMEN

Aqueous zinc batteries are ideal candidates for grid-scale energy storage because of their safety and low-cost aspects. However, the production of large-format aqueous Zn batteries is hindered by electrolyte consumption, hydrogen gas evolution and accumulation, and Zn dendrites growth. To circumvent these issues, here we propose an "open" pouch cell design for large-format production of aqueous Zn batteries, which can release hydrogen gas and allow the refilling of the electrolyte components consumed during cell cycling. The cell uses a gel electrolyte containing crosslinked kappa (k)-carrageenan and chitosan. It bonds water molecules and hinders their side reaction with Zn, preventing electrolyte leakage and fast evaporation. As a proof-of-concept, we report the assembly and testing of a Zn | |ZnxV2O5·nH2O multi-layer "open" pouch cell using the carrageenan/chitosan gel electrolyte, which delivers an initial discharge capacity of 0.9 Ah and 84% capacity retention after 200 cycles at 200 mA g‒1, 370 kPa and 25 °C.


Asunto(s)
Quitosano , Zinc , Carragenina , Metales , Electrólitos , Hidrógeno , Agua
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