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1.
The reduction in electronic recombination losses by the passivation of surfaces is a key factor enabling high‐efficiency solar cells. Here a strategy to passivate surface trap states of TiO2 films used as cathode interlayers in organic photovoltaics (OPVs) through applying alumina (Al2O3) or zirconia (ZrO2) insulating nanolayers by thermal atomic layer deposition (ALD) is investigated. The results suggest that the surface traps in TiO2 are oxygen vacancies, which cause undesirable recombination and high electron extraction barrier, reducing the open‐circuit voltage and the short‐circuit current of the complete OPV device. It is found that the ALD metal oxides enable excellent passivation of the TiO2 surface followed by a downward shift of the conduction band minimum. OPV devices based on different photoactive layers and using the passivated TiO2 electron extraction layers exhibit a significant enhancement of more than 30% in their power conversion efficiencies compared to their reference devices without the insulating metal oxide nanolayers. This is a result of significant suppression of charge recombination and enhanced electron extraction rates at the TiO2/ALD metal oxide/organic interface.  相似文献   

2.
A homologous Ni–Co based nanowire system, consisting of both nickel cobalt oxide and nickel cobalt sulfide nanowires, is developed for efficient, complementary water splitting. The spinel‐type nickel cobalt oxide (NiCo2O4) nanowires are hydrothermally synthesized and can serve as an excellent oxygen evolution reaction catalyst. Subsequent sulfurization of the NiCo2O4 nanowires leads to the formation of pyrite‐type nickel cobalt sulfide (Ni0.33Co0.67S2) nanowires. Due to the 1D nanowire morphology and enhanced charge transport capability, the Ni0.33Co0.67S2 nanowires function as an efficient, stable, and robust nonnoble metal electrocatalyst for hydrogen evolution reaction (HER), substantially exceeding CoS2 or NiS2 nanostructures synthesized under similar methods. The Ni0.33Co0.67S2 nanowires exhibit low onset potential of ?65, ?39, and ?50 mV versus reversible hydrogen electrode, Tafel slopes of 44, 68, and 118 mV dec?1 at acidic, neutral, and basic conditions, respectively, and excellent stability, comparable to the best reported non‐noble metal‐based HER catalysts. Furthermore, the homologous Ni0.33Co0.67S2 nanowires and NiCo2O4 nanowires are assembled into an all‐nanowire based water splitting electrolyzer with a current density of 5 mA cm?2 at a voltage as 1.65 V, thus suggesting a unique homologous, earth abundant material system for water splitting.  相似文献   

3.
We show enhanced efficiency and stability of a high performance organic solar cell (OPV) when the work‐function of the hole collecting indium‐tin oxide (ITO) contact, modified with a solution‐processed nickel oxide (NiOx) hole‐transport layer (HTL), is matched to the ionization potential of the donor material in a bulk‐heterojunction solar cell. Addition of the NiOx HTL to the hole collecting contact results in a power conversion efficiency (PCE) of 6.7%, which is a 17.3% net increase in performance over the 5.7% PCE achieved with a poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) HTL on ITO. The impact of these NiOx films is evaluated through optical and electronic measurements as well as device modeling. The valence and conduction band energies for the NiOx HTL are characterized in detail through photoelectron spectroscopy studies while spectroscopic ellipsometry is used to characterize the optical properties. Oxygen plasma treatment of the NiOx HTL is shown to provide superior contact properties by increasing the ITO/NiOx contact work‐function by 500 meV. Enhancement of device performance is attributed to reduction of the band edge energy offset at the ITO/NiOx interface with the poly(N‐9′‐heptadecanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothidiazole) (PCDTBT):[6,6]‐phenyl‐C61 butyric acid methyl ester PCBM and [6,6]‐phenyl‐C71 butyric acid methyl ester (PC70BM) active layer. A high work‐function hole collecting contact is therefore the appropriate choice for high ionization potential donor materials in order to maximize OPV performance.  相似文献   

4.
Highly efficient and stable organic photovoltaic (OPV) cells are demonstrated by incorporating solution‐processed hydrogen molybdenum bronzes as anode interlayers. The bronzes are synthesized using a sol‐gel method with the critical step being the partial oxide reduction/hydrogenation using an alcohol‐based solvent. Their composition, stoichiometry, and electronic properties strongly correlate with the annealing process to which the films are subjected after spin coating. Hydrogen molybdenum bronzes with moderate degree of reduction are found to be highly advantageous when used as anode interlayers in OPVs, as they maintain a high work function similar to the fully stoichiometric metal oxide, whereas they exhibit a high density of occupied gap states, which are beneficial for charge transport. Enhanced short‐circuit current, open‐circuit voltage and, fill factor, relative to reference devices incorporating either PEDOT‐PSS or a solution processed stoichiometric molybdenum oxide, are obtained for a variety of bulk heterojunction mixtures based on different polymeric donors and fullerene acceptors. In particular, high power conversion efficiencies are obtained in devices that employed the s‐HxMoO2.75 as the hole extraction layer.  相似文献   

5.
Hierarchical nanostructures with highly exposed active surfaces for high‐performance pseudocapacitors have attracted considerable attention. Herein, a one‐step growth of (Ni xCo1?x)9Se8 solid solution series in various conductive substrates as advanced electrodes for flexible, foldable supercapacitors is developed. The formation of (NixCo1?x)9Se8 solid solution is confirmed by Vegard's law. Interestingly, the as‐grown (NixCo1?x)9Se8 solid solution series spontaneously crystallized into nanodendrite arrays with hierarchical morphology and fractal feature. The optimized (Ni0.1Co0.9)9Se8 nanodendrites deliver a specific capacitance of 3762 F g?1 at a current density of 5 A g?1 and remains 94.8% of the initial capacitance after 5000 cycles, owing to the advantage from fractal feature with numerous exposed () surface as well as fast ion diffusion. The as‐assembled flexible (Ni0.1Co0.9)9Se8@carbon fiber cloth (CFC)//PVA/KOH//reduced graphene oxide@CFC device exhibits an ultrahigh energy density of 17.0 Wh kg?1@ 3.1 kW kg?1, outperforming recently reported pseudocapacitors based on nickel‐cobalt sulfide and selenide counterparts. This study provides rational guidance toward the design of fractal feature with superior electrochemical performances due to the significantly increased electrochemical active sites. The resulting device can be easily folded, pulled, and twisted, enabling potential applications in high‐performance wearable and gadget devices.  相似文献   

6.
In an attempt to overcome the problems associated with LiNiO2, the solid solution series of lithium nickel‐metal oxides, Li[Ni1–xMx]O2 (with M = Co, Mn, Al, Ti, Mg, etc.), have been investigated as favorable cathode materials for high‐energy and high‐power lithium‐ion batteries. However, along with the improvement in the electrochemical properties in Ni‐based cathode materials, the thermal stability has been a great concern, and thus violent reaction of the cathode with the electrolyte needs to be avoided. Here, we report a heterostructured Li[Ni0.54Co0.12Mn0.34]O2 cathode material which possesses both high energy and safety. The core of the particle is Li[Ni0.54Co0.12Mn0.34]O2 with a layered phase (R3‐m) and the shell, with a thickness of < 0.5 μm, is a highly stable Li1+x[CoNixMn2–x]2O4 spinel phase (Fd‐3m). The material demonstrates reversible capacity of 200 mAhg‐1 and retains 95% capacity retention under the most severe test condition of 60 °C. In addition, the amount of oxygen evolution from the lattice in the cathode with two heterostructures is reduced by 70%, compared to the reference sample. All these results suggest that the bulk Li[Ni0.54Co0.12Mn0.34]O2 consisting of two heterostructures satisfy the requirements for hybrid electric vehicles, power tools, and mobile electronics.  相似文献   

7.
In aqueous alkaline Zn batteries (AZBs), the Co3+/Co4+ redox pair offers a higher voltage plateau than its Co2+/Co3+ counterpart. However, related studies are scarce, due to two challenges: the Co3+/Co4+ redox pair is more difficult to activate than Co2+/Co3+; once activated, the Co3+/Co4+ redox pair is unstable, owing to the rapid reduction of surplus Co3+ to Co2+. Herein, CoSe2?x is employed as a cathode material in AZBs. Electrochemical analysis recognizes the principal contributions of the Co3+/Co4+ redox pair to the capacity and voltage plateau. Mechanistic studies reveal that CoSe2?x initially undergoes a phase transformation to derived CoxOySez, which has not been observed in other Zn//cobalt oxide batteries. The Se doping effect is conducive to sustaining abundant and stable Co3+ species in CoxOySez. As a result, the battery achieves a 10 000‐cycle ultralong lifespan with 0.02% cycle?1 capacity decay, a 1.9‐V voltage plateau, and an immense areal specific capacity compared to its low‐valence oxide counterparts. When used in a quasi‐solid‐state electrolyte, as‐assembled AZB delivers 4200 cycles and excellent tailorability, a promising result for wearable applications. The presented effective strategy for obtaining long‐cyclability cathodes via a phase transformation‐induced heteroatom doping effect may promote high‐valence metal species mediation toward highly stable electrodes.  相似文献   

8.
A multicompositional particulate Li[Ni0.9Co0.05Mn0.05]O2 cathode in which Li[Ni0.94Co0.038Mn0.022]O2 at the particle center is encapsulated by a 1.5 µm thick concentration gradient (CG) shell with the outermost surface composition Li[Ni0.841Co0.077Mn0.082]O2 is synthesized using a differential coprecipitation process. The microscale compositional partitioning at the particle level combined with the radial texturing of the refined primary particles in the CG shell layer protracts the detrimental H2 → H3 phase transition, causing sharp changes in the unit cell dimensions. This protraction, confirmed by in situ X‐ray diffraction and transmission electron microscopy, allows effective dissipation of the internal strain generated upon the H2 → H3 phase transition, markedly improving cycling performance and thermochemical stability as compared to those of the conventional single‐composition Li[Ni0.9Co0.05Mn0.05]O2 cathodes. The compositionally partitioned cathode delivers a discharge capacity of 229 mAh g?1 and exhibits capacity retention of 88% after 1000 cycles in a pouch‐type full cell (compared to 68% for the conventional cathode). Thus, the proposed cathode material provides an opportunity for the rational design and development of a wide range of multifunctional cathodes, especially for Ni‐rich Li[NixCoyMn1‐x‐y]O2 cathodes, by compositionally partitioning the cathode particles and thus optimizing the microstructural response to the internal strain produced in the deeply charged state.  相似文献   

9.
Boron‐doped Li[Ni0.90Co0.05Mn0.05]O2 cathodes are synthesized by adding B2O3 during the lithiation of the hydroxide precursor. Density functional theory confirms that boron doping at a level as low as 1 mol% alters the surface energies to produce a highly textured microstructure that can partially relieve the intrinsic internal strain generated during the deep charging of Li[Ni0.90Co0.05Mn0.05]O2. The 1 mol% B‐Li[Ni0.90Co0.05Mn0.05]O2 cathode thus delivers a discharge capacity of 237 mAh g?1 at 4.3 V, with an outstanding capacity retention of 91% after 100 cycles at 55 °C, which is 15% higher than that of the undoped Li[Ni0.90Co0.05Mn0.05]O2 cathode. This proposed synthesis strategy demonstrates that an optimal microstructure exists for extending the cycle life of Ni‐rich Li[Ni1‐xyCoxMny]O2 cathodes that have an inadequate cycling stability in electric vehicle applications and indicates that an optimal microstructure can be achieved through surface energy modification.  相似文献   

10.
Safety has been a major technological concern hindering the deployment of lithium‐ion batteries for automobile applications. We investigated the decomposition mechanism of delithiated cathode materials at thermal abuse conditions using Li1.1[Ni1/3Mn1/3Co1/3]0.9O2 as a model cathode material. An in‐situ high‐energy X‐ray diffraction technique was established as an alternative to conventional thermal analysis techniques like differential scanning calorimetry and accelerating rate calorimetry. The X‐ray diffraction data revealed that the thermal decomposition pathway of delithiated Li1‐x[Ni1/3Mn1/3Co1/3]0.9O2 strongly depended on the exposed chemical environment, like solvents and lithium salts. A phase transformation of dry delithiated Li1‐x[Ni1/3Mn1/3Co1/3]0.9O2 was observed at about 278 °C, and its onset temperature was reduced to about 197°C with the presence of the electrolyte. It is suggested that the reduction in thermal stability is possibly related to proton intercalation into the delithiated material.  相似文献   

11.
Investigations on the impact of interfacial modification on organic optoelectronic device performance often attribute the improved device performance to the optoelectronic properties of the modifier. A critical assumption of such conclusions is that the organic active layer deposited on top of the modified surface (interface) remains unaltered. Here the validity of this assumption is investigated by examining the impact of substrate surface properties on the morphology of poly(3‐hexylthiophene):1‐(3‐methoxycarbonyl)‐propyl‐1‐phenyl‐[6,6]C61 (P3HT:PCBM) bulk‐heterojunction (BHJ). A set of four nickel oxide and poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transport layers (HTL) with contrasting surface properties and performance in organic photovoltaic (OPV) devices is studied. Differences in vertical composition variation and structural morphologies are observed across the samples, but only in the near‐interface region of <~20 nm. Near‐interface differences in morphology are most closely correlated with surface polarity and surface roughness of the HTL. Surface polarity is more influenced by surface composition than surface roughness and crystal structure. These findings corroborate the previously mentioned conclusions that the differences in device performance observed in solar cells employing these HTLs are dominated by the electronic properties of the HTL/organic photoactive active layer interface and not by unintentional alteration in the BHJ active layer morphology.  相似文献   

12.
A efficient indium tin oxide (ITO)‐free transparent electrode based on an improved Ag film is designed by introducing small amount of Al during co‐deposition, producing ultrathin and smooth Ag film with low loss. A transparent electrode as thin as 4 nm is achieved by depositing the film on top of Ta2O5 layer, and organic solar cells based on such ultrathin electrode are built, producing power conversion efficiency over 7%. The device efficiency can be optimized by simply tuning Ta2O5 layer thickness external to the organic photovoltaic (OPV) structure to create an optical cavity resonance inside the photoactive layer. Therefore Ta2O5/Al‐doped Ag films function as a high‐performance electrode with high transparency, low resistance, improved photon management capability and mechanical flexibility.  相似文献   

13.
Nickel‐rich layered oxide cathodes with the composition LiNi1?x?yCoxMnyO2 (NCM, (1?x?y) ≥ 0.6) are under intense scrutiny recently to contend with commercial LiNi0.8Co0.15Al0.05O2 (NCA) for high‐energy‐density batteries for electric vehicles. However, a comprehensive assessment of their electrochemical durability is currently lacking. Herein, two in‐house cathodes, LiNi0.8Co0.15Al0.05O2 and LiNi0.7Co0.15Mn0.15O2, are investigated in a high‐voltage graphite full cell over 1500 charge‐discharge cycles (≈5–10 year service life in vehicles). Despite a lower nickel content, NCM shows more performance deterioration than NCA. Critical underlying degradation processes, including chemical, structural, and mechanical aspects, are analyzed via an arsenal of characterization techniques. Overall, Mn substitution appears far less effective than Al in suppressing active mass dissolution and irreversible phase transitions of the layered oxide cathodes. The active mass dissolution (and crossover) accelerates capacity decline with sustained parasitic reactions on the graphite anode, while the phase transitions are primarily responsible for cell resistance increase and voltage fade. With Al doping, on the other hand, secondary particle pulverization is the more limiting factor for long‐term cyclability compared to Mn. These results establish a fundamental guideline for designing high‐performing Ni‐rich NCM cathodes as a compelling alternative to NCA and other compositions for electric vehicle applications.  相似文献   

14.
Ni‐rich Li[NixCoyMn1?x?y]O2 (x ≥ 0.8) layered oxides are the most promising cathode materials for lithium‐ion batteries due to their high reversible capacity of over 200 mAh g?1. Unfortunately, the anisotropic properties associated with the α‐NaFeO2 structured crystal grains result in poor rate capability and insufficient cycle life. To address these issues, a micrometer‐sized Ni‐rich LiNi0.8Co0.1Mn0.1O2 secondary cathode material consisting of radially aligned single‐crystal primary particles is proposed and synthesized. Concomitant with this unique crystallographic texture, all the exposed surfaces are active {010} facets, and 3D Li+ ion diffusion channels penetrate straightforwardly from surface to center, remarkably improving the Li+ diffusion coefficient. Moreover, coordinated charge–discharge volume change upon cycling is achieved by the consistent crystal orientation, significantly alleviating the volume‐change‐induced intergrain stress. Accordingly, this material delivers superior reversible capacity (203.4 mAh g?1 at 3.0–4.3 V) and rate capability (152.7 mAh g?1 at a current density of 1000 mA g?1). Further, this structure demonstrates excellent cycling stability without any degradation after 300 cycles. The anisotropic morphology modulation provides a simple, efficient, and scalable way to boost the performance and applicability of Ni‐rich layered oxide cathode materials.  相似文献   

15.
Layered lithium–nickel–cobalt–manganese oxide (NCM) materials have emerged as promising alternative cathode materials owing to their high energy density and electrochemical stability. Although high reversible capacity has been achieved for Ni‐rich NCM materials when charged beyond 4.2 V versus Li+/Li, full lithium utilization is hindered by the pronounced structural degradation and electrolyte decomposition. Herein, the unexpected realization of sustained working voltage as well as improved electrochemical performance upon electrochemical cycling at a high operating voltage of 4.9 V in the Ni‐rich NCM LiNi0.895Co0.085Mn0.02O2 is presented. The improved electrochemical performance at a high working voltage at 4.9 V is attributed to the removal of the resistive Ni2+O rock‐salt surface layer, which stabilizes the voltage profile and improves retention of the energy density during electrochemical cycling. The manifestation of the layered Ni2+O rock‐salt phase along with the structural evolution related to the metal dissolution are probed using in situ X‐ray diffraction, neutron diffraction, transmission electron microscopy, and X‐ray absorption spectroscopy. The findings help unravel the structural complexities associated with high working voltages and offer insight for the design of advanced battery materials, enabling the realization of fully reversible lithium extraction in Ni‐rich NCM materials.  相似文献   

16.
17.
Prussian blue analogs (PBAs) are especially investigated as superior cathodes for sodium‐ion batteries (SIBs) due to high theoretical capacity (≈170 mA h g?1) with 2‐Na storage and low cost. However, PBAs suffer poor cyclability due to irreversible phase transition in deep charge/discharge states. PBAs also suffer low crystallinity, with considerable [Fe(CN)6] vacancies, and coordinated water in crystal frameworks. Presently, a new chelating agent/surfactant coassisted crystallization method is developed to prepare high‐quality (HQ) ternary‐metal NixCo1?x[Fe(CN)6] PBAs. By introducing inactive metal Ni to suppress capacity fading caused by excessive lattice distortion, these PBAs have tunable limits on depth of charge/discharge. HQ‐NixCo1?x[Fe(CN)6] (x = 0.3) demonstrates the best reversible Na‐storage behavior with a specific capacity of ≈145 mA h g?1 and a remarkably improved cycle performance, with ≈90% capacity retention over 600 cycles at 5 C. Furthermore, a dual‐insertion full cell on the cathode and NaTi2(PO4)3 anode delivers reversible capacity of ≈110 mA h g?1 at a current rate of 1.0 C without capacity fading over 300 cycles, showing promise as a high‐performance SIB for large‐scale energy‐storage systems. The ultrastable cyclability achieved in the lab and explained herein is far beyond that of any previously reported PBA‐based full cells.  相似文献   

18.
The difficulty in finding positive electrode materials for sodium‐ion (Na‐ion) batteries with a large specific energy has slowed down their commercialization. Layered transition metal (M) oxides NaxMO2 with a two‐layer oxygen stacking (P2, 0.6 ≤ x ≤ 0.75), are promising candidates. However, the high average metal oxidation state needed during synthesis means that P2 NaxMO2 cathodes often require the introduction of high‐valent cations (Mn4+, Ti4+, Sn5+, or Te6+), limiting the cathode's performance. Using a combination of first‐principles calculations and experiments, the feasibility of P2 cathodes containing only electrochemically active nickel and cobalt cations is investigated. It is found that P2 NaxNiyCo1–yO2 materials with x = 0.66, 0.75, and 0 ≤ y ≤ 0.33 are either thermodynamically stable or metastable yet close to the convex hull at typical P2 synthesis temperatures (≈1000 K). It is demonstrated that a novel P2 compound with y = 0.22 and both Ni3+/4+ and Co3+/4+ can be successfully synthesized. It is studied electrochemically and structurally, using in situ and ex situ X‐ray diffraction. It is demonstrated that the chemical space of P2 layered compounds is not fully explored yet and that ab initio phase diagrams allow the determination of new high‐specific energy positive electrodes to be targeted experimentally.  相似文献   

19.
Understanding and optimizing the temperature effects of Li‐ion diffusion by analyzing crystal structures of layered Li(NixMnyCoz)O2 (NMC) (x + y + z = 1) materials is important to develop advanced rechargeable Li‐ion batteries (LIBs) for multi‐temperature applications with high power density. Combined with experiments and ab initio calculations, the layer distances and kinetics of Li‐ion diffusion of LiNixMnyCozO2 (NMC) materials in different states of Li‐ion de‐intercalation and temperatures are investigated systematically. An improved model is also developed to reduce the system error of the “Galvanostatic Intermittent Titration Technique” with a correction of NMC particle size distribution. The Li‐ion diffusion coefficients of all the NMC materials are measured from ?25 to 50 °C. It is found that the Li‐ion diffusion coefficient of LiNi0.6Mn0.2Co0.2O2 is the largest with the minimum temperature effect. Ab initio calculations and XRD measurements indicate that the larger Li slab space benefits to Li‐ion diffusion with minimum temperature effect in layered NMC materials.  相似文献   

20.
The role of the contacts in thin‐film, blended heterojunctions (<100 nm thick) organic photovoltaics is explored, specifically considering concepts of carrier selectivity, injection, and extraction efficiency, relative to recombination. Contact effects are investigated by comparing two hole‐collecting interlayers: a phosphonic acid monolayer on indium tin oxide (ITO) and a nickel oxide thin film. The interlayers have equivalent work functions (≈5.4 eV) but widely variant energy band offsets relative to the lowest unoccupied molecular orbital of the acceptor (electron blocking versus not), which are coupled to large differences in carrier density. Trends in open‐circuit voltages (VOC) as a function of light intensity and temperature are compared and it is concluded that the dominant mechanism limiting VOC for high density of states contacts is free carrier injection, not surface recombination or extraction barriers. Transient photocurrent decay measurements confirm excess reinjected carriers decrease the extraction efficiency via increased recombination and decrease free carrier lifetime, even at high internal electric fields, due to space charge accumulation. These results demonstrate that the energetics and injection dynamics of the interface between interlayers and high carrier density electrodes (typically ITO and metals) must be considered with fabrication and processing of interlayers, in addition to possible carrier selectivity and the interface with the active layer.  相似文献   

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