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1.
One of the main bottlenecks that limit the performance of reversible protonic ceramic electrochemical cells (R-PCECs) is the sluggish kinetics of the oxygen reduction and evolution reactions (ORR and OER). Here, the significantly enhanced ORR and OER kinetics and stability of a conventional La0.6Sr0.4Co0.2Fe0.8O3–δ (LSCF) air electrode by an efficient catalyst coating of barium cobaltite (BCO) is reported. The polarization resistance of a BCO-coated LSCF air electrode at 600 ° C is 0.16  Ω  cm2, about 30% of that of the bare LSCF air electrode under the same conditions. Further, an R-PCEC with the BCO-coated LSCF air electrode shows exceptional performance in both fuel cell (peak power density of 1.16 W cm−2 at 600 ° C) and electrolysis (current density of 1.80 A cm−2 at 600 ° C at 1.3 V) modes. The performance enhancement is attributed mainly to the facilitated rate of oxygen surface exchange.  相似文献   

2.
Solid oxide fuel cell (SOFC) is regarded as an environmentally friendly energy conversion device, which can directly convert the chemical energy stored in the fuel to the electrical energy. However, the degradation of cathodes caused by Cr-containing steel interconnects is a major problem that limits the broader application of SOFC. Herein, a novel A-site high entropy oxide, based on the cobalt-free PrBaFe2O5+δ (PBF) cathode, La0.2Pr0.2Nd0.2Sm0.2Gd0.2BaFe2O5+δ (LPNSGBF), is proposed as a high catalyst activity and Cr-tolerance cathode for SOFC. The anode-supported cell with the LPNSGBF cathode exhibits an excellent peak power density of 1020.69 mW cm−2 at 800 °C, which is better than that of the PBF (794.96 mW cm−2). Moreover, under the Cr-containing atmosphere, the outstanding stability of the single cell with the LPNSGBF for 100 h with a degradation rate of 0.17% h−1, is much lower than the 0.79% h−1 for that of the PBF cathode. The study provides a new strategy for achieving the enhanced oxygen reduction reaction and high Cr-tolerance of the cobalt-free cathode by high entropy doping.  相似文献   

3.
Transition metal single atoms anchored on nitrogen-doped carbon (M-N-C) matrix with M-N-C active sites have shown to be promising catalysts for both hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR). Herein, a hybrid catalyst with low-level loading of atomic Pt and Co species encapsulated in nitrogen-doped graphene (Pt@CoN4-G) is developed. The Pt@CoN4-G shows low overpotential for HER in wide-pH electrolyte and manifests improved mass activity with almost eight times greater than that of Pt/C at an overpotential of 50 mV. The Pt@CoN4-G also exhibits a top-level ORR activity (half-wave potential, E1/2 = 0.893 V) and robust stability (>200 h) in alkaline medium. Using theoretical calculations and comprehensive characterizations , the strong metal–support interactions between Pt species and CoN4-G support and synergistical cooperation of multiple active sites are clarified. A flow alkali-Al/acid hybrid fuel cell using Pt@CoN4-G as cathode catalyst delivers a large power density of 222 mW cm−2 with excellent stability to achieve simultaneously hydrogen evolution and electricity generation. In addition, Pt@CoN4-G endows a flow Zn-air battery with high power density (316 mW cm−2), good stability under large current density (>100 h at 100 mA cm−2), and long cycle life (over 600 h at 5 mA cm−2).  相似文献   

4.
Freezing electrolyte and sluggish ionic migration kinetics limited the low-temperature performance of rechargeable batteries. Here, an aqueous proton battery is developed, which achieves both high power density and energy density at the ultralow temperature conditions. Electrolyte including 2 m HBF4  +  2 m Mn(BF4)2 is used for the ultralow freezing point of below − 160  ° C and high ionic conductivity of 0.21 mS cm−1 at − 70  ° C. Spectroscopic and nuclear magnetic resonance analysis demonstrate the introduction of BF4 anions efficiently break the hydrogen-bond networks of original water molecules, resulting in ultralow freezing point. Based on H+ uptake/removal reaction in alloxazine (ALO) anode and MnO2/Mn2+ conversion in carbon felt cathode, the aqueous proton battery can operate regularly even at − 90  ° C and obtain a high specific discharge capacity of 85 mA h g−1. Benefiting from the rapid diffusion of proton and the pseudocapacitive character of ALO electrolyte, this battery shows a high specific energy density of 110 Wh kg−1 at a specific power density of 1650 W kg−1 at − 60  ° C. This work presents a new way of developing low-temperature batteries.  相似文献   

5.
Lowering the operating temperature (ideally below 400 °C) for solid oxide fuel cell (SOFC) technology deployment has been an important transition that introduces the benefit of reduced operational costs and system durability. However, the key technical issue limiting the transition is the sluggish cathodic performance, namely the oxygen reduction reaction (ORR) rate of the conventional sponge-like cathode dramatically drops as the temperature reduces. In this paper, 3D engineering of a cathode is conducted on a protonic ceramic fuel cell to obtain an enhanced ORR between 400 and 600 °C. Compared with a cell using a conventional sponge-like cathode, 3D engineering improves the cathode ORR by 41% at 400 °C with a peak power density of 0.410 W cm−2. A phase field simulation is applied to assist the engineering by understanding the competition between the cathode mass and charge transfer with different cathode porosities. The results show that structural engineering of existing well-developed cathodes is a simple and effective method to promote cathode ORR for low temperature SOFC by regulating the mass and charge transfer.  相似文献   

6.
Aqueous Zn-ion batteries (AZIBs) are promising due to their high theoretical energy density and intrinsic safety, and the natural abundance of Zn. Since low voltage is an intrinsic shortage of AZIBs, achieving super-high capacity of cathode materials is a vital way to realize high practical energy density, which however remains a huge challenge. Herein, the capacity increase of classical vanadium oxide cathode is predicted via designing atomic thickness of 2D structure to introduce abundant Zn2+ storage sites based on density functional theory (DFT) calculation; then graphene-analogous V2O5·nH2O (GAVOH) with only few atomic layers is fabricated, realizing a record capacity of 714 mAh g−1. Pseudocapacitive effect is unveiled to mainly contribute to the super-high capacity due to the highly exposed GAVOH external surface. In situ Raman and synchrotron X-ray techniques unambiguously uncover the Zn2+ storage mechanism. Carbon nanotubes (CNTs) are further introduced to design GAVOH-CNTs gel ink for large-scale cathode fabrication. The hybrid cathode demonstrates ultra-stable cycling and excellent rate capability and delivers a high energy density of 476 Wh kg−1 at 76 W kg−1; 228 Wh kg−1 is still retained at high mass loading of 10.2 mg cm−2. This work provides inspiration for breaking the capacity limit of cathode in AZIBs.  相似文献   

7.
Solid-state lithium metal batteries (SSLMBs) are highly desirable for energy storage because of the urgent need for higher energy density and safer batteries. However, it remains a critical challenge for stable cycling of SSLMBs at low temperature. Here, a highly viscoelastic polyether-b-amide (PEO-b-PA) based composite solid-state electrolyte is proposed through a one-pot melt processing without solvent to address this key process. By adjusting the molar ratio of PEO-b-PA to lithium bis(trifluoromethanesulphonyl)imide (ethylene oxide:Li = 6:1) and adding 20 wt.% succinonitrile, fast Li+ transport channel is conducted within the homogeneous polymer electrolyte, which enables its application at ultra-low temperature (−20 to 25 °C). The composite solid-state electrolyte utilizes dynamic hydrogen-bonding domains and ion-conducting domains to achieve a low interfacial charge transfer resistance (<600 Ω) at −20 °C and high ionic conductivity (25 °C, 3.7 × 10−4 S cm−1). As a result, the LiFePO4|Li battery based on composite electrolyte exhibits outstanding electrochemical performance with 81.5% capacity retention after 1200 cycles at −20 °C and high discharge specific capacities of 141.1 mAh g−1 with high loading (16.1 mg cm−2) at 25 °C. Moreover, the solid-state SNCM811|Li cell achieves excellent safety performance under nail penetration test, showing great promise for practical application.  相似文献   

8.
Solid-state lithium metal batteries (SSLMBs) are promising next-generation high-energy rechargeable batteries. However, the practical energy densities of the reported SSLMBs have been significantly overstated due to the use of thick solid-state electrolytes, thick lithium (Li) anodes, and thin cathodes. Here, a high-performance NASICON-based SSLMB using a thin (60 µm) Li1.5Al0.5Ge1.5(PO4)3 (LAGP) electrolyte, ultrathin (36 µm) Li metal, and high-loading (8 mg cm−2) LiFePO4 (LFP) cathode is reported. The thin and dense LAGP electrolyte prepared by hot-pressing exhibits a high Li ionic conductivity of 1 × 10−3 S cm−1 at 80 °C. The assembled SSLMB can thus deliver an increased areal capacity of ≈1 mAh cm−2 at C/5 with a high capacity retention of ≈96% after 50 cycles under 80 °C. Furthermore, it is revealed by synchrotron X-ray absorption spectroscopy and in situ high-energy X-ray diffraction that the side reactions between LAGP electrolyte and LFP cathode are significantly suppressed, while rational surface protection is required for Ni-rich layered cathodes. This study provides valuable insights and guidelines for the development of high-energy SSLMBs towards practical conditions.  相似文献   

9.
High-performance rechargeable Zn-air batteries with long-life stability are desirable for power applications in electric vehicles. The key component of the Zn-air batteries is the bifunctional oxygen electrocatalyst, however, designing a bifunctional oxygen electrocatalyst with high intrinsic reversibility and durability is a challenge. Through density functional theory calculations, it is found that the catalytic activity originated from the electronic and geometric coordination structures synergistic effect of the Fe and Co dual-sites with metal-N4 coordination environment, assisting the stronger hybridization of electronic orbitals between Co (dxz, dz2) and OO* (px, pz), thus making the stronger O2 active ability of Co active site. These findings enable to development of a fancy dual single-atom catalyst comprising adjacent Fe N4 and Co N4 sites on N-doped carbon matrix (FeCo-NC). FeCo-NC exhibits extraordinary bifunctional activities for oxygen reduction and evolution reaction (ORR/OER), which displays high half-wave potential (0.893 V) for the ORR, and low overpotential (343 mV) at 10 mA cm−2 for the OER. The assembled FeCo-NC air-electrode works well in the flexible solid-state Zn-air battery with a high specific capacity of 747.0 mAh g−1, a long-time stability of more than 400 h (30 °C), and also a superior performance at extreme temperatures (−30 °C–60 °C).  相似文献   

10.
The formation of lithiophobic inorganic solid electrolyte interphase (SEI) on Li anode and cathode electrolyte interphase (CEI) on the cathode is beneficial for high-voltage Li metal batteries. However, in most liquid electrolytes, the decomposition of organic solvents inevitably forms organic components in the SEI and CEI. In addition, organic solvents often pose substantial safety risks due to their high volatility and flammability. Herein, an organic-solvent-free eutectic electrolyte based on low-melting alkali perfluorinated-sulfonimide salts is reported. The exclusive anion reduction on Li anode surface results in an inorganic, LiF-rich SEI with high capability to suppress Li dendrite, as evidenced by the high Li plating/stripping CE of 99.4% at 0.5  mA cm−2 and 1.0 mAh cm−2, and 200-cycle lifespan of full LiNi0.8Co0.15Al0.05O2 (2.0 mAh cm−2) || Li (20 µm) cells at 80 °C. The proposed eutectic electrolyte is promising for ultrasafe and high-energy Li metal batteries.  相似文献   

11.
Solid-state sodium batteries have garnered considerable interest. However, their electrochemical performance is hampered by severe interfacial resistance between sodium metal and inorganic solid electrolytes, as well as Na dendrite growth within the electrolytes. To address these issues, a uniform and compact SnF2 film is first introduced onto the surface of the inorganic solid electrolyte Na3.2Zr1.9Ca0.1Si2PO12 (NCZSP) to improve contact through an effective and straightforward process. Through experiments and computations, the in situ conversion reaction between SnF2 and molten Na is adequately confirmed, resulting in a composite conductive layer containing NaxSn alloys and NaF at the interface. As a result, the interfacial resistance of Na/NCZSP is significantly decreased from 813 to 5 Ω cm2, and the critical current density is dramatically increased to 1.8 mA cm−2, as opposed to 0.2 mA cm−2 with bare NCZSP. The symmetric cell is able to cycle stably at 0.2 mA cm−2 for 1300 h at 30 °C and exhibits excellent current tolerance of 0.3 and 0.5 mA cm−2. Moreover, the Na3V2(PO4)3/SnF2-NCZSP/Na full cell displays excellent rate performance and cycling stability. The SnF2-induced interlayer proves significant in improving interfacial contact and restraining sodium dendrite propagation, thus promoting the development of solid-state sodium batteries.  相似文献   

12.
Fluorine-doped tin oxide (FTO) films were prepared by an improved sol-gel process, in which FTO films were deposited on glass substrates using evaporation method, with the precursors prepared by the conventional sol-gel method. The coating and sintering processes were combined in the evaporation method, with the advantage of reduced probability of films cracking and simplified preparation process. The effects of F-doping contents and structure of films on properties of films were analyzed. The results showed the performance index (ΦTC=3.535×10−3 Ω−1 cm) of the film was maximum with surface resistance (Rsh) of 14.7 Ω cm−1, average transmittance (T) of 74.4% when F/Sn=14 mol%, the reaction temperature of the sol was 50 °C, and the evaporation temperature was 600 °C in muffle furnace, and the film has densification pyramid morphology and SnO2−xFx polycrystalline structure with tetragonal rutile phase. Compared with the commercial FTO films (ΦTC=3.9×10−3 Ω−1 cm, Rsh=27.4 Ω cm−1, T=80%) produced by chemical vapor deposition (CVD) method, the ΦTC value of FTO films prepared by an improved sol-gel process is close to them, the electrical properties are higher, and the optical properties are lower.  相似文献   

13.
Compatible p- and n-type materials are necessary for high-performance GeTe thermoelectric modules, where the n-type counterparts are in urgent need. Here, it is reported that the p-type GeTe can be tuned into n-type by decreasing the formation energy of Te vacancies via AgBiTe2 alloying. AgBiTe2 alloying induces Ag2Te precipitates and tunes the carrier concentration close to the optimal level, leading to a high-power factor of 6.2 µW cm−1 K−2 at 423 K. Particularly, the observed hierarchical architectural structures, including phase boundaries, nano-precipitates, and point defects, contribute an ultralow lattice thermal conductivity of 0.39 W m−1 K−1 at 423 K. Correspondingly, an increased ZT of 0.5 at 423 K is observed in n-type (GeTe)0.45(AgBiTe2)0.55. Furthermore, a single-leg module demonstrates a maximum η of 6.6% at the temperature range from 300 to 500 K. This study indicates that AgBiTe2 alloying can successfully turn GeTe into n-type with simultaneously optimized thermoelectric performance.  相似文献   

14.
Developing solid-state electrolytes with good compatibility for high-voltage cathodes and reliable operation of batteries over a wide-temperature-range are two bottleneck requirements for practical applications of solid-state metal batteries (SSMBs). Here, an in situ quasi solid-state poly-ether electrolyte (SPEE) with a nano-hierarchical design is reported. A solid-eutectic electrolyte is employed on the cathode surface to achieve highly-stable performance in thermodynamic and electrochemical aspects. This performance is mainly due to an improved compatibility in the electrode/electrolyte interface by nano-hierarchical SPEE and a reinforced interface stability, resulting in superb-cyclic stability in Li || Li symmetric batteries ( > 4000 h at 1 mA cm−2/1 mAh cm−2; > 2000 h at 1 mA cm−2/4 mAh cm−2), which are the same for Na, K, and Zn batteries. The SPEE enables outstanding cycle-stability for wide-temperature operation (15–100 ° C) and 4 V-above batteries (Li || LiCoO2 and Li || LiNi0.8Co0.1Mn0.1O2). The work paves the way for development of practical SSMBs that meet the demands for wide-temperature applicability, high-energy density, long lifespan, and mass production.  相似文献   

15.
To improve the Li-ion diffusion and extreme-environment performance of LiFePO4 (LFP) lithium-ion batteries, a composite cathode material is fabricated using ultra-fine nano-Mg(OH)2 (MH). First, a flexible confined space is designed in the local area of the cathode surface, through the transition of charged xanthan gum polymer molecules under electric field force and the self-assembly of the xanthan gum network. Then, the 20 nm nano-Mg(OH)2 is prepared through cathodic electrodeposition within the local flexible confined space, and subsequent in situ surface modification as it traverses the xanthan gum network under gravity. LFP-MH significantly changes the density and homogeneity of the cathode electrolyte interphase film and improves the electrolyte affinity. The Li||LFP-MH half-cell demonstrates excellent rate capability (110 mAh g−1 at 5 C) and long-term cycle performance (116.6 mAh g−1 at 1 C after 1000 cycles), and maintains over 100 mAh g−1 after 150 cycles at 60 °C, as well as no structural collapse of the cathode material after 400 cycles at 5 V high cut-off voltage. The cell also shows an obvious decrease in inner resistance after 100 cycles (99.53/133.12 Ω). This work provides a significant advancement toward LiFePO4 lithium-ion batteries with excellent electrochemical performance and tolerance to extreme-environment.  相似文献   

16.
Multifunctional electrocatalysts play an increasingly crucial role in various practical electrochemical energy conversion devices. Especially, on the air cathode of rechargeable zinc–air batteries (ZABs), oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), requiring efficient bifunctional electrocatalysts, are switched during discharging and charging process. Here, supported by the theoretical computations, a facile strategy for the in situ assembly of NiFe-MOFs nanosheets on heteroatoms-doped porous activated carbon spheres is developed. The newly designed electrocatalyst (NP-ACSs@NiFe-MOFs) shows excellent performance toward bifunctional oxygen electrocatalysis. Specifically, a remarkable low value of potential gap (ΔE = 0.61 V), which is the difference between the potential to reach an OER current density of 10 mA cm−2 and ORR half-wave potential, is achieved in 0.1 m KOH. Notably, the aqueous ZAB based on NP-ACSs@NiFe-MOFs shows super cycle stability with small voltage gap of only 0.79 V when cycled for 450 h at 10 mA cm−2. Also, the quasi-solid-state ZAB indicates excellent flexibility and cycling stability. This study presents a facile strategy for the rational integration of different catalytically active components, and can be extended to prepare other strongly competitive multifunctional electrocatalysts.  相似文献   

17.
We have investigated the contact resistivity of GeCu2Te3 (GCT) phase change material to a W electrode using the circular transfer length method (CTLM). The contact resistivity ρc of as-deposited amorphous GCT to W was 3.9×10−2 Ω cm2. The value of ρc drastically decreased upon crystallization and crystalline GCT that annealed at 300 °C showed a ρc of 4.8×10−6 Ω cm2. The ρc contrast between amorphous (as-deposited) and crystalline (annealed at 300 °C) states was larger in GCT than in conventional Ge2Sb2Te5 (GST). Consequently, it was suggested from a calculation based on a simple vertical structure memory cell model that a GCT memory cell shows a four times larger resistance contrast than a GST memory cell.  相似文献   

18.
Semiconductors based on Bi element show large attenuation coefficients to X-ray photons and have been recognized as candidates for X-ray detectors. However, the application of stable Bi-based oxide materials to X-ray detectors has been rarely investigated. In this research, the X-ray response of a BiVO4 pellet has been studied. It has been found that the BiVO4 pellet has a large resistivity of 1.3 × 1012 Ω cm, negligible current drift of 6.18 × 10−8 nA cm−1 s−1 V−1 under electrical bias and mobility lifetime product, µτ, of 1.75 × 10−4 cm2 V−1, which renders the pellet with an X-ray sensitivity of 241.3 µC Gyair−1 cm−2 and a detection limit of 62 nGyair s−1 under 40 KVp X-ray illumination and 40 V bias voltage. The BiVO4 pellet also shows operational stability under steady X-ray illumination with total dose of 2.01 Gyair, equal to the dose of 20 000 medical chest X-ray inspections. This research reveals the potential application of BiVO4 in X-ray detection devices and inspires further research in this area.  相似文献   

19.
A unique strain-mediated lattice rotation strategy is introduced via nanocompositing to upsurge the optimized limits in the composition-to-structural pathway on rationally engineering the efficient thermoelectric material. In this study, a special lattice rotation via strain engineering is realized to optimize the desired electronic and chemical environment for enhancing thermoelectric properties in n-type Bi2S2Se. This approach results in a unique transport phenomenon to assist high-energy electrons in transferring through the optimized transport channels, and appropriate structure disparity to significantly localize phonons. As a result, Sb over Cl doping in Bi2S2Se gently reduces Eg and introduces defect states in bandgap with shifting down the Fermi level, thus causing increase in carrier concentration, which contributes to a higher power factor of ≈7.18 µW cm−1 K−2 (at T = 773 K). Besides, a lower thermal conductivity of ≈0.49 W m−1 K−1 is driven through lattice strain and defect engineering. Consequently, an ultra-high ZTmax = 1.13 (at T = 773 K) and a high ZTave = 0.54 (323 K-773 K) are realized. This study not only leads to an extraordinary thermoelectric performance but also reveals a unique paradigm for electron transportation and phonon localization via lattice strain engineering.  相似文献   

20.
The practical use of polyethylene oxide polymer electrolyte in the solid-state sodium metallic batteries (SSMBs) suffers from the retard Na+ diffusion at the room temperature, mechanical fragility as well as the oxidation tendency at high voltages. Herein, a hetero-layered composite polymeric electrolyte (CPE) is proposed to enable the simultaneous interfacial stability with the high voltage cathodes (till 4.2 V) and Na metallic anode. Being incorporated within the polymer matrix, the sand-milled Na3Zr2Si2PO12 nanofillers and nanocellulose scaffold collectively endow the thin-layer (25 µm), ultralightweight (1.65 mg cm−2) CPE formation with an order of magnitude enhancement of the mechanical strength (13.84 MPa) and ionic conductivity (1.62 × 10−4 S cm−1) as compared to the pristine polymer electrolyte, more importantly, the improved dimension stability up to 180 °C. Upon the integration of the hetero-layered CPE with the iron hexacyanoferrate FeHCF cathode (1 mAh cm−2) and the Na foil, the cell model can achieve the room-temperature cycling stability (93.73% capacity retention for 200 cycles) as well as the high temperature tolerance till 80 °C, which inspires a quantum leap toward the surface-wetting-agent-free, energy-dense, wide-temperature-range SSMB prototyping.  相似文献   

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