首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 171 毫秒
1.
The synthesis of in situ polymer‐functionalized anatase TiO2 particles using an anchoring block copolymer with hydroxamate as coordinating species is reported, which yields nanoparticles (≈11 nm) in multigram scale. Thermal annealing converts the polymer brushes into a uniform and homogeneous carbon coating as proven by high resolution transmission electron microscopy and Raman spectroscopy. The strong impact of particle size as well as carbon coating on the electrochemical performance of anatase TiO2 is demonstrated. Downsizing the particles leads to higher reversible uptake/release of sodium cations per formula unit TiO2 (e.g., 0.72 eq. Na+ (11 nm) vs only 0.56 eq. Na+ (40 nm)) while the carbon coating improves rate performance. The combination of small particle size and homogeneous carbon coating allows for the excellent electrochemical performance of anatase TiO2 at high (134 mAh g?1 at 10 C (3.35 A g?1)) and low (≈227 mAh g?1 at 0.1 C) current rates, high cycling stability (full capacity retention between 2nd and 300th cycle at 1 C) and improved coulombic efficiency (≈99.8%).  相似文献   

2.
A novel nanocomposite cathode consisting of sulfur and hollow‐mesoporous titania (HMT) embedded within carbon nanotubes (CNT), which is designated as S‐HMT@CNT, has been obtained by encapsulating elemental sulfur into the pores of hollow‐mesoporous, spherical TiO2 particles that are connected via CNT. A carbon‐paper interlayer, referred to as dual functional porous carbon wall (DF‐PCW), has been obtained by filling the voids in TiO2 spheres with carbon and then etching the TiO2 template with a chemical process. The DF‐PCW interlayer provides a medium for scavenging the lithium polysulfides and suppressing them from diffusing to the anode side when it is inserted between the sulfur cathode and the separator. Lithium–sulfur cells fabricated with the thus prepared S‐HMT@CNT cathode and the DF‐PCW interlayer exhibit superior performance due to the containment of sulfur in TiO2 and improved lithium–ion and electron transports. The Li–S cells display high capacity with excellent capacity retention at rates as high as 1C, 2C, and 5C rates.  相似文献   

3.
Recently, a consensus has been reached that using lithium metal as an anode in rechargeable Li‐ion batteries is the best way to obtain the high energy density necessary to power electronic devices. Challenges remain, however, with respect to controlling dendritic Li growth on these electrodes, enhancing compatibility with carbonate‐based electrolytes, and forming a stable solid–electrolyte interface layer. Herein, a groundbreaking solution to these challenges consisting in the preparation of a Li2TiO3 (LT) layer that can be used to cover Li electrodes via a simple and scalable fabrication method, is suggested. Not only does this LT layer impede direct contact between electrode and electrolyte, thus avoiding side reactions, but it assists and expedites Li‐ion flux in batteries, thus suppressing Li dendrite growth. Other effects of the LT layer on electrochemical performance are investigated by scanning electron microscopy, electrochemical impedance spectroscopy, and galvanostatic intermittent titration technique analyses. Notably, LT layer‐incorporating Li cells comprising high‐capacity/voltage cathodes with reasonably high mass loading (LiNi0.8Co0.1Mn0.1O2, LiNi0.5Mn1.5O4, and LiMn2O4) show highly stable cycling performance in a carbonate‐based electrolyte. Therefore, it is believed that the approach based on the LT layer can boost the realization of high energy density lithium metal batteries and next‐generation batteries.  相似文献   

4.
A 3D polymer‐network‐membrane (3D‐PNM) electrolyte is described for highly stable, solid‐state dye‐sensitized solar cells (DSCs) with excellent power‐conversion efficiency (PCE). The 3D‐PNM electrolyte is prepared by using one‐pot in situ cross‐linking polymerization on the surface of dye‐sensitized TiO2 particles in the presence of redox species. This method allows the direct connection of the 3D‐PNM to the surface of the TiO2 particles as well as the in situ preparation of the electrolyte gel during device assembly. There are two junction areas (liquid and solid‐state junctions) in the DSCs that employ conventional polymer electrolytes, and the major interface is at the liquid‐state junction. The solid‐state junction is dominant in the DSCs that employ the 3D‐PNM electrolyte, which exhibit almost constant performance during aging at 65 °C for over 700 h (17.0 to 17.2 mA cm–2). The best cell performance gives a PCE of 9.1%; this is slightly better than the performance of a DSC that employs a liquid electrolyte.  相似文献   

5.
In this work, a new strategy to design low‐temperature (≤200 °C) sintered dye‐sensitized solar cells (lt‐DSSC) is reported to enhance charge collection efficiencies (ηcoll), photoconversion efficiencies (η), and stabilities under continuous operation conditions. Realization of lt‐DSSC is enabled by the integration of hybrid nanoparticles based on TiO2‐Ru(II) complex (TiO2_Ru_IS)—obtained by in situ bottom‐up construction of Ru(II) N3 dye‐sensitized titania—into the photoelectrode. Incentives for the use of TiO2_Ru_IS are i) dye stability due to its integration into the TiO2 anatase network and ii) enhanced charge collection yield due to its significant resistance toward electron recombination with electrolytes. It is demonstrated that devices with single‐layer photoelectrodes featuring blends of P25 and TiO2_Ru_IS give rise to a 60% ηcoll relative to a 46% ηcoll for devices with P25‐based photoelectrodes. Responsible for this trend is a better charge transport and a reduced electron recombination. When using a multilayered photoelectrode architecture with a top layer based only on TiO2_Ru_IS, devices with an even higher ηcoll (74%) featuring a η of around 8.75% and stabilities of 600 h are achieved. This represents the highest values reported for lt‐DSSC to date.  相似文献   

6.
Surface properties of cathode particles play important roles in the transport of ions and electrons and they may ultimately dominate cathode's performance and stability in lithium‐ion batteries. Through the use of carefully prepared Li1.2Ni0.13Mn0.54Co0.13O2 crystal samples with six distinct morphologies, surface transition‐metal redox activities and crystal structural transformation are investigated as a function of surface area and surface crystalline orientation. Complementary depth‐profiled core‐level spectroscopy, namely, X‐ray absorption spectroscopy, electron energy loss spectroscopy, and atomic‐resolution scanning transmission electron microscopy, are applied in the study, presenting a fine example of combining advanced diagnostic techniques with a well‐defined model system of battery materials. The present study reports the following findings: (1) a thin layer of defective spinel with reduced transition metals, similar to what is reported on cycled conventional secondary particles in the literature, is found on pristine oxide surface even before cycling, and (2) surface crystal structure and chemical composition of both pristine and cycled particles are facet dependent. Oxide structural and cycling stabilities improve with maximum expression of surface facets stable against transition‐metal reduction. The intricate relationships among morphology, surface reactivity and structural transformation, electrochemical performance, and stability of the cathode materials are revealed.  相似文献   

7.
Optimizing the interfacial contacts between the photoactive layer and the electrodes is an important factor in determining the performance of organic solar cells (OSCs). A charge‐selective layer with tailored electrical properties enhances the charge collection efficiency and interfacial stability. Here, the potential of hydrogenated TiO2 nanoparticles (H‐TiO2 NPs) as an efficient electron‐selective layer (ESL) material in OSCs is reported for the first time. The H‐TiO2 is synthesized by discharge plasma in liquid at atmospheric pressure, which has the benefits of a simple one‐pot synthesis process, rapid and mild reaction conditions, and the capacity for mass production. The H‐TiO2 exhibits high conductivity and favorable energy level formation for efficient electron extraction, providing a basis for an efficient bilayer ESL system composed of conjugated polyelectrolyte/H‐TiO2. Thus, the enhanced charge transport and extraction efficiency with reduced recombination losses at the cathode interfacial contacts is achieved. Moreover, the OSCs composed of H‐TiO2 are almost free of light soaking, which has been reported to severely limit the performance and stability of OSCs based on conventional TiO2 ESLs. Therefore, H‐TiO2 as a new efficient, stable, and cost‐effective ESL material has the potential to open new opportunities for optoelectronic devices.  相似文献   

8.
High‐performance flexible energy‐storage devices have great potential as power sources for wearable electronics. One major limitation to the realization of these applications is the lack of flexible electrodes with excellent mechanical and electrochemical properties. Currently employed batteries and supercapacitors are mainly based on electrodes that are not flexible enough for these purposes. Here, a three‐dimensionally interconnected hybrid hydrogel system based on carbon nanotube (CNT)‐conductive polymer network architecture is reported for high‐performance flexible lithium ion battery electrodes. Unlike previously reported conducting polymers (e.g., polyaniline, polypyrrole, polythiophene), which are mechanically fragile and incompatible with aqueous solution processing, this interpenetrating network of the CNT‐conducting polymer hydrogel exibits good mechanical properties, high conductivity, and facile ion transport, leading to facile electrode kinetics and high strain tolerance during electrode volume change. A high‐rate capability for TiO2 and high cycling stability for SiNP electrodes are reported. Typically, the flexible TiO2 electrodes achieved a capacity of 76 mAh g–1 in 40 s of charge/discharge and a high areal capacity of 2.2 mAh cm–2 can be obtained for flexible SiNP‐based electrodes at 0.1C rate. This simple yet efficient solution process is promising for the fabrication of a variety of high performance flexible electrodes.  相似文献   

9.
Li‐ion hybrid supercapacitors (Li‐HSCs) hold great promise in future electrical energy storage due to their relatively high power and energy density. However, a major challenge lies in the slow kinetics of Li‐ion intercalation/extraction within metal‐oxide electrodes. Here, it is shown that ultrafast charge storage is realized by confining anatase TiO2 nanoparticles in carbon nanopores to enable a high‐rate anode for Li‐HSCs. The porous carbon with interconnected pore walls and open channels not only works as a conductive host to protect TiO2 from structural degradation but also provides fast pathways for ion/electron transport. As a result, the assembled cells exhibit remarkable rate capabilities with a specific capacity of ≈140 mAh g?1 at a slow charge and ≈60 mAh g?1 at a 3.5 s fast charge. While the charge/discharge process can be completed as fast as that of state‐of‐the‐art electrical double‐layer capacitors (EDLCs), the produced nanocomposites show three to seven times higher volumetric capacitance than activated carbons used in commercial EDLCs with acetonitrile‐based electrolytes. Equally important for some applications in cold climates or the space, the Li‐HSCs can operate at subzero temperatures as low as ?40 °C, which is likely only limited by thermal properties of the acetonitrile (melting point of ?45 °C).  相似文献   

10.
With the rapid growth of the lithium‐ion battery (LIBs) market, recycling and re‐use of end‐of‐life LIBs to reclaim lithium (Li) and transition metal (TM) resources (e.g., Co, Ni), as well as eliminating pollution from disposal of waste batteries, has become an urgent task. Here, for the first time the ambient‐pressure relithiation of degraded LiNi0.5Co0.2Mn0.3O2 (NCM523) cathodes via eutectic Li+ molten‐salt solutions is successfully demonstrated. Combining such a low‐temperature relithiation process with a well‐designed thermal annealing step, NCM523 cathode particles with significant Li loss (≈40%) and capacity degradation (≈50%) can be successfully regenerated to achieve their original composition and crystal structures, leading to effective recovery of their capacity, cycling stability, and rate capability to the levels of the pristine materials. Advanced characterization tools including atomic resolution electron microscopy imaging and electron energy loss spectroscopy are combined to demonstrate that NCM523's original layered crystal structure is recovered. For the first time, it is shown that layer‐to‐rock salt phase change on the surfaces and subsurfaces of the cathode materials can be reversed if lithium can be incorporated back to the material. The result suggests the great promise of using eutectic Li+ molten–salt solutions for ambient‐pressure relithiation to recycle and remanufacture degraded LIB cathode materials.  相似文献   

11.
A composite separator membrane (CSM) with an A/B/A type layered structure, composed of a microporous electrolyte‐philic poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVdF‐HFP) gel layer (A) and a submicrometer porous polyethylene (PE) or a macroporous poly(ethylene terephthalate) (PET) non‐woven matrix (B), is introduced in a dye‐sensitized solar cell (DSSC). Commercially available PE and PET separator membranes (SMs) act as matrices that provide mechanical stability to the DSSC and permanent pore structures for facilitated ion transport. PVdF‐HFP is used as a microporous gelator for improved interfacial contact between the solid SM and the electrodes. The PVdF‐HFP gel impedes the charge recombination process between electron and I3 ? at the TiO2/electrolyte interface, resulting in improved electron lifetimes. The DSSC assembled with the CSM exhibits high initial solar energy conversion efficiency (η, 6.1%) and stable η values over 1400 h, demonstrating good long term stability. The behaviors of the DSSC are attributed to the synergistic factors of the CSM, such as improved ion conductivity, electrolyte affinity, electrolyte retention capability, effective interfacial contact, and plausible passivation of the dyes. This study demonstrates a practical combination of short‐ and long‐term DSSC performance through the introduction of the CSM.  相似文献   

12.
Enhanced power conversion efficiency (PCE) is reported in inverted polymer solar cells when an electron‐rich polymer nanolayer (poly(ethyleneimine) (PEI)) is placed on the surface of an electron‐collecting buffer layer (ZnO). The active layer is made with bulk heterojunction films of poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]] (PTB7) and [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM). The thickness of the PEI nanolayer is controlled to be 2 nm to minimize its insulating effect, which is confirmed by X‐ray photoelectron spectroscopy and optical absorption measurements. The Kelvin probe and ultraviolet photoelectron spectroscopy measurements demonstrate that the enhanced PCE by introducing the PEI nanolayer is attributed to the lowered conduction band energy of the ZnO layer via the formation of an interfacial dipole layer at the interfaces between the ZnO layer and the PEI nanolayer. The PEI nanolayer also improves the surface roughness of the ZnO layer so that the device series resistance can be noticeably decreased. As a result, all solar cell parameters including short circuit current density, open circuit voltage, fill factor, and shunt resistance are improved, leading to the PCE increase up to ≈8.9%, which is close to the best PCE reported using conjugated polymer electrolyte films.  相似文献   

13.
In spite of the satisfactory advancement in preparing TiO2‐based hybrid structures, most methods rely on additional template‐based multistep reactions for engineering the given structure. Herein, a unique self‐template and in situ recrystallization strategy is explored to synthesize uniform flowerlike multicompositional structures of nitrogen‐doped porous carbon nanosheet networks immobilizing TiO2 nanoparticles (TiO2∩NPCSs) via a self‐prepared single precursor and subsequent thermal treatment. Depending on the unique coordination ability of 2,4‐dihydroxybenzoic acid with metal ions under alkaline conditions to form a flowerlike network, a self‐produced single precursor can be achieved. Careful investigations of the self‐prepared precursor reveal a high practicability of the present synthetic scheme. Because of the novel structural and compositional features, these TiO2∩NCSN flowers indicate superior sodium storage properties when evaluated as anodes for sodium‐ion batteries. Impressively, the TiO2∩NCSN flowers deliver high reversible capacities of 152 mAh g?1 at 2C for 3000 cycles and 114 mAh g?1 at 10C for 10000 cycles, as well as an ultrahigh rate capability up to 50C with a capacity of 101 mAh g?1. The facile method could stimulate further capability in precise construction of complex architectures with complicated compositions for different device applications.  相似文献   

14.
Functioning quantum dot (QD) sensitized solar cells have been fabricated using the vacuum deposition technique atomic layer deposition (ALD). Utilizing the incubation period of CdS growth by ALD on TiO2, we are able to grow QDs of adjustable size which act as sensitizers for solid‐state QD‐sensitized solar cells (ssQDSSC). The size of QDs, studied with transmission electron microscopy (TEM), varied with the number of ALD cycles from 1‐10 nm. Photovoltaic devices with the QDs were fabricated and characterized using a ssQDSSC device architecture with 2,2',7,7'‐tetrakis‐(N,N‐di‐p methoxyphenylamine) 9,9'‐spirobifluorene (spiro‐OMeTAD) as the solid‐state hole conductor. The ALD approach described here can be applied to fabrication of quantum‐confined structures for a variety of applications, including solar electricity and solar fuels. Because ALD provides the ability to deposit many materials in very high aspect ratio substrates, this work introduces a strategy by which material and optical properties of QD sensitizers may be adjusted not only by the size of the particles but also in the future by the composition.  相似文献   

15.
Compact TiO2 is widely used as an electron transport material in planar‐perovskite solar cells. However, TiO2‐based planar‐perovskite solar cells exhibit low efficiencies due to intrinsic problems such as the unsuitable conduction band energy and low electron extraction ability of TiO2. Herein, the planar TiO2 electron transport layer (ETL) of perovskite solar cells is modified with ionic salt CuI via a simple one‐step spin‐coating process. The p‐type nature of the CuI islands on the TiO2 surface leads to modification of the TiO2 band alignment, resulting in barrier‐free contacts and increased open‐circuit voltage. It is found that the polarity of the CuI‐modified TiO2 surface can pull electrons to the interface between the perovskite and the TiO2, which improves electron extraction and reduces nonradiative recombination. The CuI solution concentration is varied to control the electron extraction of the modified TiO2 ETL, and the optimized device shows a high efficiency of 19.0%. In addition, the optimized device shows negligible hysteresis, which is believed to be due to the removal of trap sites and effective electron extraction by CuI‐modified TiO2. These results demonstrate the hitherto unknown effect of p‐type ionic salts on electron transport material.  相似文献   

16.
Lithium‐sulfur (Li‐S) batteries are being considered as the next‐generation high‐energy‐storage system due to their high theoretical energy density. However, the use of a lithium‐metal anode poses serious safety concerns due to lithium dendrite formation, which causes short‐circuiting, and possible explosions of the cell. One feasible way to address this issue is to pair a fully lithiated lithium sulfide (Li2S) cathode with lithium metal‐free anodes. However, bulk Li2S particles face the challenges of having a large activation barrier during the initial charge, low active‐material utilization, poor electrical conductivity, and fast capacity fade, preventing their practical utility. Here, the development of a self‐supported, high capacity, long‐life cathode material is presented for Li‐S batteries by coating Li2S onto doped graphene aerogels via a simple liquid infiltration–evaporation coating method. The resultant cathodes are able to lower the initial charge voltage barrier and attain a high specific capacity, good rate capability, and excellent cycling stability. The improved performance can be attributed to the (i) cross‐linked, porous graphene network enabling fast electron/ion transfer, (ii) coated Li2S on graphene with high utilization and a reduced energy barrier, and (iii) doped heteroatoms with a strong binding affinity toward Li2S/lithium polysulfides with reduced polysulfide dissolution based on first‐principles calculations.  相似文献   

17.
Anatase TiO2 is an extensively studied anode material for lithium‐ion batteries because of its superior capability of storing Li+ electrochemically. Here reversible lithium storage of TiO2 is achieved chemically using redox targeting reactions. In the presence of a pair of redox mediators, bis(pentamethylcyclopentadienyl)cobalt (CoCp* 2) and cobaltocene (CoCp2) in an electrolyte, TiO2 and its lithiated form Li x TiO2 can be reduced and oxidized by CoCp* 2 and CoCp2 +, respectively, which accompany Li+ insertion and extraction, albeit without attaching the TiO2 onto the electrode. The reversible chemical lithiation/delithiation and the involved phase transitions are unambiguously confirmed using density functional theory (DFT) calculations, UV‐vis spectroscopy, X‐ray photoelectron spectoscopy (XPS), and Raman spectroscopy. A redox flow lithium‐ion battery (RFLB) half‐cell is assembled and evaluated, which is a critical step towards the development of RFLB full cells.  相似文献   

18.
This article reports a novel category of coating structure SiO2@Eu(MABA‐Si) luminescence nanoparticles (NPs) consisting of a unique organic shell, composed of perchlorate europium(III) complex, and an inorganic core, composed of silica. The binary complex Eu(MABA‐Si)3·(ClO4)3·5H2O was synthesized using HOOCC6H4N(CONH(CH2)3Si(OCH2CH3)3)2 (MABA‐Si) and was used as a ligand. Furthermore, the as‐prepared silica NPs were successfully coated with the ‐Si(OCH2CH3)3 group of MABA‐Si to form Si–O–Si chemical bonds by means of the hydrolyzation of MABA‐Si. The binary complexes were characterized by elemental analysis, molar conductivity and coordination titration analysis. The results indicated that the composition of the binary complex was Eu(MABA‐Si)3·(ClO4)3·5H2O. Coating structure SiO2@Eu(MABA‐Si) NPs were characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and infrared (IR) spectra. Based on the SEM and TEM measurements, the diameter of core‐SiO2 particles was ~400 and 600 nm, and the thickness of the cladding layer Eu(MABA‐Si) was ~20 nm. In the binary complex Eu(MABA‐Si)3·(ClO4)3·5H2O, the fluorescence spectra illustrated that the energy of the ligand MABA‐Si transferred to the energy level for the excitation state of europium(III) ion. Coating structure SiO2@Eu(MABA‐Si) NPs exhibited intense red luminescence compared with the binary complex. The fluorescence lifetime and fluorescence quantum efficiency of the binary complex and of the coating structure NPs were also calculated. The way in which the size of core‐SiO2 spheres influences the luminescence was also studied. Moreover, the luminescent mechanisms of the complex were studied and explained.  相似文献   

19.
Perovskite solar cells (PSCs) are of great interest in current photovoltaic research due to their extraordinary power conversion efficiency of ≈20% and boundless potentialities. The high efficiency has been mostly obtained from TiO2‐based PSCs, where TiO2 is utilized as a hole‐blocking, mesoporous layer. However, trapped charges and the light‐induced photocatalytic effect of TiO2 seriously degrade the perovskite and preclude PSCs from being immediately commercialized. Herein, a simplified PSC is successfully fabricated by eliminating the problematic TiO2 layers, using instead a fluorine‐doped tin oxide (FTO)/perovskite/hole–conductor/Au design. Simultaneously, the sluggish charge extraction at the FTO/perovskite interface is overcome by modifying the surface of the FTO to a porous structure using electrochemical etching. This surface engineering enables a substantial increase in the photocurrent density and mitigation of the hysteretic behavior of the pristine FTO‐based PSC; a remarkable 19.22% efficiency with a low level of hysteresis is obtained. This performance is closely approaching that of conventional PSCs and may facilitate their commercialization due to improved convenience, lower cost, greater stability, and potentially more efficient mass production.  相似文献   

20.
Three‐dimensional mesoporous TiO2‐Sn/C core‐shell nanowire arrays are prepared on Ti foil as anodes for lithium‐ion batteries. Sn formed by a reduction of SnO2 is encapsulated into TiO2 nanowires and the carbon layer is coated onto it. For additive‐free, self‐supported anodes in Li‐ion batteries, this unique core‐shell composite structure can effectively buffer the volume change, suppress cracking, and improve the conductivity of the electrode during the discharge‐charge process, thus resulting in superior rate capability and excellent long‐term cycling stability. Specifically, the TiO2‐Sn/C nanowire arrays display rechargeable discharge capacities of 769, 663, 365, 193, and 90 mA h g?1 at 0.1C, 0.5C, 2C 10C, and 30C, respectively (1C = 335 mA g?1). Furthermore, the TiO2‐Sn/C nanowire arrays exhibit a capacity retention rate of 84.8% with a discharge capacity of over 160 mA h g?1, even after 100 cycles at a high current rate of 10C.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号