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1.
Porous proton exchange membranes (PEMs) with abundant porous structures show enhanced phosphoric acid (PA) doping levels and proton transport capability. However, the high PA loss rate and serious hydrogen cross-over lead to poor membrane stability. Enhancing the stability of PA-doped porous PEMs is therefore crucial for obtaining high-performance proton exchange membrane fuel cells. Herein, a porous polybenzimidazole membrane with dense double skin layers is reported using amino tris (methylene phosphonic acid) (ATMP) constructed. This membrane effectively alleviates hydrogen permeation and PA loss in a water/anhydrous environment and exhibits enhanced stability. Surprisingly, as an organic proton conductor, ATMP has strong hydrogen bonding with PA, leading to the formation of more continuous proton transport channels. Due to the dense double skin layers protection and the synergistic mass transfer of ATMP and PA, the porous membrane shows excellent proton conductivity (0.112 S cm−1) and a H2-O2 fuel cell peak power density of 0.98 W cm−2 at 160 °C. Moreover, it presents excellent fuel cell stability, with a voltage decay rate of only 5.46 µV h−1. In addition, the porous membrane surpasses the traditional working temperature range, operating in the range of 80–220 °C. This study provides new insight into developing high-performance porous PEMs.  相似文献   

2.
Alkaline water electrolysis (AWE) is the promising technical pathway of large-scale green hydrogen production. The sluggish oxygen evolution reaction seriously hampers the water decomposition reaction kinetics for AWE, especially at high current density above 500 mA cm−2. It is closely related with bubbles removal dynamic performance of porous electrodes. In this study, the multi-stage porous nickel–iron oxide electrode is prepared by a two-step electro-deposition method. The electrode shows good oxygen evolution reaction performance at high current densitiy of 1000 mA cm−2, which is attributed to both the good electro-catalytic performance of NiFeOx with nano-cone structure and good bubbles removal performance of porous Ni interlayer with the curved pore channels. Bubbles motion inside the pore channels is deeply analyzed by Lattice Boltzmann simulation of gas–liquid two-phase flows, combining with the experiments. The results indicate that bubbles motion speed is faster in curved pore channels than that in straight pore channels due to the role of bubble buoyancy. It illuminates the effects of pore channel curvature on bubbles motion for porous electrodes prepared by electro-deposition. It provides the possibility of designing porous electrodes with both good electro-catalytic performance and good bubbles removal performance by the electro-deposition method, from the view of industrial applications.  相似文献   

3.
Aqueous Zn ion batteries (ZIBs) are one of the most promising battery chemistries for grid-scale renewable energy storage. However, their application is limited by issues such as Zn dendrite formation and undesirable side reactions that can occur in the presence of excess free water molecules and ions. In this study, a nanocellulose-carboxymethylcellulose (CMC) hydrogel electrolyte is demonstrated that features stable cycling performance and high Zn2+ conductivity (26 mS cm−1), which is attributed to the material's strong mechanical strength (≈70 MPa) and water-bonding ability. With this electrolyte, the Zn-metal anode shows exceptional cycling stability at an ultra-high rate, with the ability to sustain a current density as high as 80 mA cm−2 for more than 3500 cycles and a cumulative capacity of 17.6 Ah cm−2 (40 mA cm−2). Additionally, side reactions, such as hydrogen evolution and surface passivation, are substantially reduced due to the strong water-bonding capacity of the CMC. Full Zn||MnO2 batteries fabricated with this electrolyte demonstrate excellent high-rate performance and long-term cycling stability (>500 cycles at 8C). These results suggest the cellulose-CMC electrolyte as a promising low-cost, easy-to-fabricate, and sustainable aqueous-based electrolyte for ZIBs with excellent electrochemical performance that can help pave the way toward grid-scale energy storage for renewable energy sources.  相似文献   

4.
Membrane with ordered channels is the key to controlling ion sieving and proton conductivity in flow batteries. However, it remains a great challenge for finely controlling the nanochannels of polymeric membranes. Herein, two types of acid-stable Zr-metal organic framework (MOF-801 and MOF-808) with variable pore structures and channel properties are introduced as fillers into a non-fluorinated sulfonated poly (ether ether ketone) (SPEEK). The membrane incorporated with MOF-801 of a smaller triangular window (≈3.5 Å) successfully translates the molecular sieving property into the flow battery membrane, resulting in enhanced coulombic efficiency (98.5–99.2%) at 40–120 mA cm−2 compared with the pristine SPEEK membrane (97.1–98.5%). In contrast, more protophilic internal interconnected channels of MOF-808 yield faster proton highway, leading to a significant increase of voltage efficiency (93.7–84.1%) at 40–120 mA cm−2 compared with the pristine SPEEK membrane (91.7–78.9%). By regulating the ion sieving and proton conductivity, MOF-801/MOF-808 binary composite membrane exhibits synchronously improved performance in the vanadium redox flow battery system. The revealed structure–property relationship in the Zr-MOFs-based membranes provides a general guideline to design new proton exchange membranes with ordered channels for flow battery application.  相似文献   

5.
A 3D hierarchical porous catalyst architecture based on earth abundant metals Ni, Fe, and Co has been fabricated through a facile hydrothermal and electrodeposition method for efficient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The electrode is comprised of three levels of porous structures including the bottom supermacroporous Ni foam (≈500 μm) substrate, the intermediate layer of vertically aligned macroporous NiCo2O4 nanoflakes (≈500 nm), and the topmost NiFe(oxy)hydroxide mesoporous nanosheets (≈5 nm). This hierarchical architecture is binder‐free and beneficial for exposing catalytic active sites, enhancing mass transport and accelerating dissipation of gases generated during water electrolysis. Serving as an anode catalyst, the designed hierarchical electrode displays excellent OER catalytic activity with an overpotential of 340 mV to achieve a high current density of 1200 mA cm?2. Serving as a cathode catalyst, the catalyst exhibits excellent performance toward HER with a moderate overpotential of 105 mV to deliver a current density of 10 mA cm?2. Serving as both anode and cathode catalysts in a two‐electrode water electrolysis system, the designed electrode only requires a potential of 1.67 V to deliver a current density of 10 mA cm?2 and exhibits excellent durability in prolonged bulk alkaline water electrolysis.  相似文献   

6.
Achieving efficient and robust hydrogen evolution reaction (HER) electrocatalysts under all-pH conditions is significant for clean hydrogen production. Herein, an ultralow Pt-decorated hierarchical Ni-Mo porous hybrid, consisting of Ni3Mo3N on MoO2 microcolumns, is developed for all-pH HER with remarkable catalytic performances, owing to the porous structure, strong metal-support interaction, along with ultralow Pt nanoparticles and multichannel nickel foam support. The superhydrophilic and aerophilic surfaces favor mass transport during the HER process. Consequently, the porous Pt/Ni-Mo-N-O microcolumns present remarkable HER activity and durability with low overpotentials of 40.6, 101.1, and 89.5 mV to obtain 100 mA cm−2 in basic, neutral, and acid media, respectively. Moreover, the excellent performance in alkaline seawater (40.4 mV@100 mA cm−2) even suppresses most of over-reported catalysts. More importantly, the two-electrode cell, assembled with Pt/Ni-Mo-N-O and NiMoO4 as cathode and anode, exhibits excellent performance towards overall-water electrolysis with an ultralow cell voltage of 1.56 V@100 mA cm−2.  相似文献   

7.
High-energy-density Li–S batteries are considered one of the next-generation energy storage systems, but the uncontrolled Li-dendrite growth in Li metal anodes and the shuttling of polysulfides in S cathode severely impede the commercial development of Li–S batteries. Herein, a conductive composite architecture that is made up of bio-derived N-doped porous carbon fiber bundles (N-PCFs) with co-imbedded cobalt and niobium carbide nanoparticles is employed as a multifunctional integrated host for simultaneously addressing the challenges in both Li anodes and S cathodes. The implantation of Co and NbC nanoparticles bestows the N-PCFs matrix with synergistically enhanced degree of graphitization, electrical conductivity, hierarchical porosity, and surface polarization. Theoretical calculations and experimental results show that NbC with specific lithiophilic and sulfiphilic features can synchronously regulate the Li and S electrochemistry by realizing homogeneous lithium deposition with suppressed Li-dendrite growth and exerting catalytic effects for promoting the polysulfide conversion together with fast Li2S nucleation. Hence, the assembled Li–S full batteries exhibit a superb rate capability (704 mAh g−1 at 5 C) and cycling life (≈82.3% capacity retention after 500 cycles) at a sulfur loading over 3.0 mg cm−2, as well as high reversible areal capacity (>6.0 mAh cm−2) even at a higher sulfur loading of 6.7 mg cm−2.  相似文献   

8.
Ion conductive membranes (ICMs) with robust sub-2-nm channels show high proton transport rate in flow battery, but it remains a great challenge to precisely control the ion sieving of the membranes. Herein, as a promising proton-selective carrier, sulfonated piperazine covalent triazine framework (s-pCTF) with the channel size of ≈1.5 nm and abundant fast proton hopping sites is introduced into sulfonated poly(ether ether ketone) (SPEEK) to fabricate advanced ICM for vanadium flow battery (VFB) application. The interior protoplasmic channels of s-pCTF demonstrate significant Donnan exclusion effect, resulting in a high proton/vanadium ion selectivity in theory (6.22 × 105). Meanwhile, the nitrogen-rich sub-2-nm channels yield fast proton highway, and exterior-grafted sulfonic acid groups further facilitate the proton transfer. By regulating the ion sieving and proton conductivity, the optimal hybrid membrane exhibits synchronously improved battery performance with an enhanced energy efficiency (92.41% to 78.53% at 40–200 mA cm−2) and long-term stability for 900 cycles over 400 h (EE: 87.2–85% at 120 mA cm−2), outperforming pure SPEEK and Nafion212 membranes. This study validates the applicability of organic porous CTF with sub-2-nm channels and desired functionality in ICMs for high-performance VFB application.  相似文献   

9.
Aqueous rechargeable zinc–iodine batteries have received increasing attention in the field of portable electronics due to their high safety, low-cost, and great electrochemical performance. However, the insulated nature of iodine and the unrestricted shuttle effect of soluble triiodide seriously limit the lifespan and Coulombic efficiency (CE) of the batteries. Herein, a high-performance zinc–iodine energy storage system based on the hydrothermal reduced graphene oxide (rGO) and a high concentration zinc chloride water-in-salt electrolyte are promoted. The 3D microporous structures and outstanding electrical conductivity of rGO make it an excellent host for iodine, while the water-in-salt electrolyte effectively suppresses the shuttle effect of triiodide and improves the CE of the system. As a result, an ultra-high I2 mass loading of 25.33 mg cm−2 (loading ratio of 71.69 wt.%) is realized during the continuous charging/discharging process. The batteries deliver a high capacity of 6.5 mAh cm−2 at 2 mA cm−2 with a much-improved CE of 95% and a prominent rate performance with capacity of 1 mAh cm−2 at 80 mA cm−2. A stable long-term cycling performance is also achieved with capacity retention of 2 mAh cm−2 after 2000 cycles at 50 mA cm−2.  相似文献   

10.
Moisture–electric generator (MEG)-based blue energy is widely studied. There is still a significant challenge in improving the power of the MEGs system and expanding its application in self-powered electronic skin. Inspired by the structure of ferns, a biomimetic moisture–electric aerogel is designed to collect energy. Polyvinyl alcohol dendritic colloids act as “roots” and “stems” to provide support and channels to transport water molecules. Meanwhile, “leaf-like” graphene oxide sheets generate electricity through direct interaction with water. Besides, based on the above biomimetic structure, this work further enhances the output performance of MEGs by increasing the specific surface area (120.4 m2 g−1) and introducing an ultra-high ion density gradient (from −35 to +37 mV). Meanwhile, due to the excellent water absorption, the MEGs show good salt resistance and cyclic stability. By constructing unique biomimetic structures, ultra-high ion density gradient, and regulating environmental conditions, a high-performance MEG is obtained, including ultra-high open-circuit voltage (1.9 V) and short-circuit current (82.5 µA), the industry-leading power density among MEGs with continuous output is reported in the literature (22.55 µW cm−2). Besides, the MEGs can accurately respond to environmental and pressure changes, showing its application potential in self-powered electronic skin.  相似文献   

11.
3D organic-inorganic metal halide perovskites are excellent materials for optoelectronic applications due to their exceptional properties, solution processability, and cost-effectiveness. However, the lack of environmental stability highly restricts them from practical applications. Herein, a stable centimeter-long 2D hybrid perovskite (N-MPDA)[PbBr4] single crystal using divalent N1-methylpropane-1,3-diammonium (N-MPDA) cation as an organic spacer, is reported. The as-grown single crystal exhibits stable optoelectronic performance, low threshold random lasing, and multi-photon luminescence/multi-harmonic generation. A photoconductive device fabricated using (N-MPDA)[PbBr4] single crystal exhibits an excellent photoresponsivity (≈124 AW−1 at 405 nm) that is ≈4 orders of magnitudes higher than that of monovalent organic spacer-assisted 2D perovskites, such as (BA)2PbBr4 and (PEA)2PbBr4, and large specific detectivity (≈1012 Jones). As an optical gain media, the (N-MPDA)[PbBr4] single crystal exhibits a low threshold random lasing (≈6.5 µJ cm−2) with angular dependent narrow linewidth (≈0.1 nm) and high-quality factor (Q ≈ 2673). Based on these results, the outstanding optoelectronic merits of (N-MPDA)[PbBr4] single crystal will offer a high-performance device and act as a dynamic material to construct stable future electronics and optoelectronic-based applications.  相似文献   

12.
Achieving rapid ion transport through nanochannels is essential for both biological and artificial membrane systems. Covalent organic frameworks (COFs) with well-defined nanostructures hold great promise for addressing the above challenge. However, due to the limited processability and inadequate interlamellar interaction of COF materials, it is extremely difficult to integrate them to prepare high-performance proton conductors. Herein, inspired by the ingenious bio-adhesion strategy in nature, ultrafast proton conduction is achieved by taking advantage of COF membranes where TP-COF nanosheets are linked by subnanometer nanowires/lignocellulosic nanofibrils composites (SNWs/LCNFs) through electrostatic and π-π interactions to form an ordered and robust structure. Notably, the synthesized SNWs exhibited impressive proton conductivity and adhesion capacity due to their inbuilt phosphotungstic acid (HPW) molecules and multidimensional interactions. Therefore, attributed to the synergistic contribution of TP-COFs and SNWs, the composite membrane achieves ultrahigh proton conductivity (0.395 S cm−1 at 80 °C and 100% RH), superior mechanical property (109.8 MPa), exceptional fuel cell performance (71.6 mW cm−2), and superior operational stability (OCV decay rate is about 1.5 mV h−1), demonstrating outstanding competitiveness. More importantly, the proposed design concept has the potential to be applied in membranes for various electrochemical devices and molecular separations.  相似文献   

13.
Developing a feasible and efficient separation membrane for the purification of highly emulsified oily wastewater is of significance but challenging due to the critical limitations of low flux and serious membrane fouling. Herein, a biomimetic and superwettable nanofibrous skin on an electrospun fibrous membrane via a facile strategy of synchronous electrospraying and electrospinning is created. The obtained nanofibrous skin possesses a lotus‐leaf‐like micro/nanostructured surface with intriguing superhydrophilicity and underwater superoleophobicity, which are due to the synergistic effect of the hierarchical roughness and hydrophilic polymeric matrix. The ultrathin, high porosity, sub‐micrometer porous skin layer results in the composite nanofibrous membranes exhibiting superior performances for separating both highly emulsified surfactant‐free and surfactant‐stabilized oil‐in‐water emulsions. An ultrahigh permeation flux of up to 5152 L m?2 h?1 with a separation efficiency of >99.93% is obtained solely under the driving of gravity (≈1 kPa), which was one order of magnitude higher than that of conventional filtration membranes with similar separation properties, showing significant applicability for energy‐saving filtration. Moreover, with the advantage of an excellent antioil fouling property, the membrane exhibits robust reusability for long‐term separation, which is promising for large‐scale oily wastewater remediation.  相似文献   

14.
K-metal batteries have become one of the promising candidates for the large-scale energy storage owing to the virtually inexhaustible and widely potassium resources. The uneven K+ deposition and dendrite growth on the anode causes the batteries prematurely failure to limit the further application. An integrated K-metal anode is constructed by cold-rolling K metal with a potassiphilic porous interconnected mediator. Based on the experimental results and theoretical calculations, it demonstrates that the potassiphilic porous interconnected mediator boosts the mass transportation of K-metal anode by the K affinity enhancement, which decreases the concentration polarization and makes a dendrite-free K-metal anode interface. The interconnected porous structure mitigates the internal stress generated during repetitive deposition/stripping, enabling minimized the generation of electrode collapse. As a result, a durable K-metal anode with excellent cycling ability of exceed 1, 000 h at 1 mA cm−2/1 mAh cm−2 and lower polarization voltage in carbonate electrolyte is obtained. This proposed integrated anode with fast K+ kinetics fabricated by a repeated cold rolling and folding process provides a new avenue for constructing a high-performance dendrites-free anode for K-metal batteries.  相似文献   

15.
The hierarchical combination of mineral and biopolymer building blocks is advantageous for the notable properties of structural materials. Integrating silane and cellulose nanofibers into high-performance hybrid aerogels is promising yet remains challenging due to the unsatisfied interface connections. Here, an interfacial engineering strategy is introduced via freeze–drying-induced wetting and mineralization to reinforce the hierarchical porous cellulose network, resulting in mineral-coated nanocellulose hybrid aerogels in a simple and consecutive bottom-up assembly process. With optimized multiscale interfacial engineering between the stiff and soft components, the resulting cellulose-based hybrid aerogels are endowed with lightweight (>0.7 mg cm−3), superior enhanced mechanical compressibility (>99% strain) within a wide temperature range, as well as super-hydrophobicity (≈168°) and moisture stability under high humidity (95% relative humidity). Benefiting from these superior characters, the multifunctional hybrid aerogels as effective oil/water absorbents with excellent recyclability, thermal insulators in extreme conditions, and sensitive strain sensors are demonstrated. This assembly approach with optimized interfacial features is scalable and efficient, affording high-performance cellulose-based aerogels for various applications.  相似文献   

16.
Cross-linking is widely accepted as an effective method to improve the mechanical strength and durability of phosphoric acid (PA) doped polybenzimidazole (PBI) membranes. However, the cross-linked membranes generally exhibit compromised overall performance since their compact network structures decrease the free volumes of membranes, leading to poor proton conductivity. In this study, a locally high-density cross-linked polybenzimidazole network based on pillar[5]arene bearing multiple alkyl bromide is constructed for the first time to achieve high proton conductivity, desired mechanical properties, and excellent fuel cell performance. The pillar[5]arene-cross-linked network considerably enhances the mechanical strength of membrane (14.6 MPa), particularly with high PA uptake, and provides loose PBI chain segment packing to retain PA (315.9%). Surprisingly, the pillar[5]arene-cross-linked PBI membrane displays a high-power density of 1,084.1 mW cm−2 at 180 °C and 0.6 mg cm−2 Pt loading without backpressure and humidification, that is the highest value reported in cross-linked membranes for high-temperature proton exchange membrane fuel cells.  相似文献   

17.
Functionalized porous aromatic frameworks (PAFs) are excellent candidate materials for hybrid membrane fabrication. However, tailoring PAFs for membrane CO2 separation with desirable performance is still a challenge. Here, facile fabrication of functional hybrid alkylamine-modified PAF-1 containing membranes with high compatibility for efficient CO2/N2 separation is reported. The methylamino groups are installed on PAF-1 resulting in PAF-1-CH2NH2 that has a high surface area of over 1400 m2 g–1 and unique CO2 adsorption with CO2/N2 thermodynamic selectivity of over 1000. Amidation reaction is developed for PAF-1-CH2NH2 cross linking with cPIM-1 (carboxylic polymer of intrinsic microporosity), giving a homogenous compatible membrane of PAF-1-CH2NH2—cPIM-1 with outstanding CO2 permeability (≈10790 Barrer) and high CO2/N2 permselectivity (≈43). This membrane outperforms the counterparts derived from parent PAF-1 and phenylamine PAF-1 and possesses superior performance to other relevant membranes for CO2/N2 separation. Such a membrane can selectively and stably separate CO2 from N2 in a simulated flue gas mixture, demonstrating its huge potential in carbon capture.  相似文献   

18.
Natural biotissues like muscles, ligaments, and nerves have highly aligned structures, which play critical roles in directional signal transport, sensing, and actuation. Inspired by anisotropic biotissues, composite hydrogels with outstanding mechanical properties and conductivity are developed by compositing thermo-responsive poly (N-isopropylacrylamide) (PNIPAM) hydrogels with highly aligned carbon fibers (CFs). The anisotropic hydrogels show superior tensile strength (3.0 ± 0.3), modulus (74 ± 7.0 MPa), excellent electrical conductivity (≈670 S m−1), and ultra-high sensitivity (gauge factor up to 647) along CFs, with an anisotropic ratio (AR) up to 740 over those in perpendicular direction. The extremely high AR in conductivity (more than 400) produces high-level output in parallel direction and low-level output in perpendicular direction with a direct current (DC) power supply, which is used to fabricate AND and OR gates. Moreover, the composite hydrogels are converted into thermo-responsive actuators with CFs twisted before compositing with PNIPAM/clay network. The pre-twisted CF helices impart internal stress that drives reversible actuation of hydrogel helices upon thermo-stimulating. The actuation is self-sensed due to the extremely high sensitivity of the composite hydrogels. Such biomimetic anisotropic self-sensing hydrogel actuators resemble natural biotissues with both actuation and sensing capabilities, and have promise applications for artificial robotics.  相似文献   

19.
Potassium metal as anode is an ideal material for the assembly of high specific energy batteries. However, safety issues caused by unrestricted dendrite growth and “dead K” generation severely limit their application. Here, based on the concept of waste recycling, a structural engineering strategy (chemical exfoliation and enzyme-assisted synergistic method) is proposed to prepare oxygen-containing functionalized porous carbon microbelts (OPCMs) as freestanding K metal hosts. The porous structure, uniformly distribution of carbon nanospheres, and the presence of oxygen-containing functional groups reduce the energy barrier of K nucleation and promote the deposition kinetics. Benefitting from these advantages of OPCMs, the OPCMs-based K composite anodes (K-OPCMs) are free of obvious dendrite growth during the plating process. Symmetric cells assembled with K-OPCMs maintain a stable overpotential of 40 mV after cycling for more than 800 h at 1 mA cm−2. In addition, the K-OPCMs//organic cathode (PTCDA) full cell exhibits excellent rate capability (96% capacity retention, 100–2000 mA g−1, which is superior to most reported potassium metal batteries) and ultralong lifespan (97.8 mA h g−1, after 1500 cycles at 2000 mA g−1). This study illustrates the effectiveness of structure-engineered and provides a guiding insight for achieving high-performance rechargeable batteries.  相似文献   

20.
Transition-metal selenides are considered as one of the promising anode materials for potassium ion batteries (PIBs) due to their high theoretical capacities. However, addressing the issue of irreversibility caused by the large volume changes during potassiation/depotassiation, especially at high rates, remains a major challenge. This challenge is tackled by constructing nickel-iron selenide (NFS) with a unique hierarchically porous donut-like morphology using a simple template-free solvothermal strategy. With the bimetallic strategy and well-designed architecture, the donut-like NFS displays outstanding potassium storage performance, exhibiting a high reversible capacity (458 mAh g−1 even after 100 cycles at a slow rate of 0.1 A g−1), an impressive rate capability up to 10 A g−1 (≈10 mA cm−2), and an excellent capacity retention over 1000 cycles at 2 A g−1. By combining theoretical and experimental techniques, a two-stage intercalation-conversion reaction mechanism is put forward. This work provides an effective approach to develop bimetallic selenides electrode materials for applications in PIBs and potentially for other energy storage devices.  相似文献   

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