Isomer‐Pure Bis‐PCBM‐Assisted Crystal Engineering of Perovskite Solar Cells Showing Excellent Efficiency and Stability

A fullerene derivative (α‐bis‐PCBM) is purified from an as‐produced bis‐phenyl‐C₆₁‐butyric acid methyl ester (bis‐[60]PCBM) isomer mixture by preparative peak‐recycling, high‐performance liquid chromatography, and is employed as a templating agent for solution processing of metal halide perovskite films via an antisolvent method. The resulting α‐bis‐PCBM‐containing perovskite solar cells achieve better stability, efficiency, and reproducibility when compared with analogous cells containing PCBM. α‐bis‐PCBM fills the vacancies and grain boundaries of the perovskite film, enhancing the crystallization of perovskites and addressing the issue of slow electron extraction. In addition, α‐bis‐PCBM resists the ingression of moisture and passivates voids or pinholes generated in the hole‐transporting layer. As a result, a power conversion efficiency (PCE) of 20.8% is obtained, compared with 19.9% by PCBM, and is accompanied by excellent stability under heat and simulated sunlight. The PCE of unsealed devices dropped by less than 10% in ambient air (40% RH) after 44 d at 65 °C, and by 4% after 600 h under continuous full‐sun illumination and maximum power point tracking, respectively.     

Versatility of Carbon Enables All Carbon Based Perovskite Solar Cells to Achieve High Efficiency and High Stability

Carbon‐based perovskite solar cells (PVSCs) without hole transport materials are promising for their high stability and low cost, but the electron transporting layer (ETL) of TiO₂ is notorious for inflicting hysteresis and instability. In view of its electron accepting ability, C₆₀ is used to replace TiO₂ for the ETL, forming a so‐called all carbon based PVSC. With a device structure of fluorine‐doped tin oxide (FTO)/C₆₀/methylammonium lead iodide (MAPbI₃)/carbon, a power conversion efficiency (PCE) is attained up to 15.38% without hysteresis, much higher than that of the TiO₂ ones (12.06% with obvious hysteresis). The C₆₀ ETL is found to effectively improve electron extraction, suppress charge recombination, and reduce the sub‐bandgap states at the interface with MAPbI₃. Moreover, the all carbon based PVSCs are shown to resist moisture and ion migration, leading to a much higher operational stability under ambient, humid, and light‐soaking conditions. To make it an even more genuine all carbon based PVSC, it is further attempted to use graphene as the transparent conductive electrode, reaping a PCE of 13.93%. The high performance of all carbon based PVSCs stems from the bonding flexibility and electronic versatility of carbon, promising commercial developments on account of their favorable balance of cost, efficiency, and stability.     

Simplified Perovskite Solar Cell with 4.1% Efficiency Employing Inorganic CsPbBr3 as Light Absorber

Perovskite solar cells with cost‐effectiveness, high power conversion efficiency, and improved stability are promising solutions to the energy crisis and environmental pollution. However, a wide‐bandgap inorganic–semiconductor electron‐transporting layer such as TiO₂ can harvest ultraviolet light to photodegrade perovskite halides, and the high cost of a state‐of‐the‐art hole‐transporting layer is an economic burden for commercialization. Here, the building of a simplified cesium lead bromide (CsPbBr₃) perovskite solar cell with fluorine‐doped tin oxide (FTO)/CsPbBr₃/carbon architecture by a multistep solution‐processed deposition technology is demonstrated, achieving an efficiency as high as 4.1% and improved stability upon interfacial modification by graphene quantum dots and CsPbBrI₂ quantum dots. This work provides new opportunities of building next‐generation solar cells with significantly simplified processes and reduced production costs.     

Peapod‐like Li3VO4/N‐Doped Carbon Nanowires with Pseudocapacitive Properties as Advanced Materials for High‐Energy Lithium‐Ion Capacitors

Lithium ion capacitors are new energy storage devices combining the complementary features of both electric double‐layer capacitors and lithium ion batteries. A key limitation to this technology is the kinetic imbalance between the Faradaic insertion electrode and capacitive electrode. Here, we demonstrate that the Li₃VO₄ with low Li‐ion insertion voltage and fast kinetics can be favorably used for lithium ion capacitors. N‐doped carbon‐encapsulated Li₃VO₄ nanowires are synthesized through a morphology‐inheritance route, displaying a low insertion voltage between 0.2 and 1.0 V, a high reversible capacity of ≈400 mAh g^?1 at 0.1 A g^?1, excellent rate capability, and long‐term cycling stability. Benefiting from the small nanoparticles, low energy diffusion barrier and highly localized charge‐transfer, the Li₃VO₄/N‐doped carbon nanowires exhibit a high‐rate pseudocapacitive behavior. A lithium ion capacitor device based on these Li₃VO₄/N‐doped carbon nanowires delivers a high energy density of 136.4 Wh kg^?1 at a power density of 532 W kg^?1, revealing the potential for application in high‐performance and long life energy storage devices.     

A Novel Conductive Mesoporous Layer with a Dynamic Two‐Step Deposition Strategy Boosts Efficiency of Perovskite Solar Cells to 20%

Lead halide perovskite solar cells (PSCs) with the high power conversion efficiency (PCE) typically use mesoporous metal oxide nanoparticles as the scaffold and electron‐transport layers. However, the traditional mesoporous layer suffers from low electron conductivity and severe carrier recombination. Here, antimony‐doped tin oxide nanorod arrays are proposed as novel transparent conductive mesoporous layers in PSCs. Such a mesoporous layer improves the electron transport as well as light utilization. To resolve the common problem of uneven growth of perovskite on rough surface, the dynamic two‐step spin coating strategy is proposed to prepare highly smooth, dense, and crystallized perovskite films with micrometer‐scale grains, largely reducing the carrier recombination ratio. The conductive mesoporous layer and high‐quality perovskite film eventually render the PSC with a remarkable PCE of 20.1% with excellent reproducibility. These findings provide a new avenue to further design high‐efficiency PSCs from the aspect of carrier transport and recombination.     

Pyridinic‐N Protected Synthesis of 3D Nitrogen‐Doped Porous Carbon with Increased Mesoporous Defects for Oxygen Reduction

Nitrogen (N)‐doped carbons are potential nonprecious metal catalysts to replace Pt for the oxygen reduction reaction (ORR). Pyridinic‐N‐C is believed to be the most active N group for catalyzing ORR. In this work, using zinc phthalocyanine as a precursor effectively overcomes the serious loss of pyridinic‐N, which is commonly regarded as the biggest obstacle to catalytic performance enhancement upon adopting a second pyrolysis process, for the preparation of a 3D porous N‐doped carbon framework (NDCF). The results show only ≈14% loss in pyridinic‐N proportion in the Zn‐containing sample during the second pyrolysis process. In comparison, a loss of ≈72% pyridinic‐N occurs for the non‐Zn counterpart. The high pyridinic‐N proportion, the porous carbon framework produced upon NaCl removal, and the increased mesoporous defects in the second pyrolysis process make the as‐prepared catalyst an excellent electrocatalyst for ORR, exhibiting a half‐wave potential (E_1/2 = 0.88 V) up to 33 mV superior to state‐of‐the‐art Pt/C and high four‐electron selectivity (n > 3.83) in alkaline solution, which is among the best ORR activities reported for N‐doped carbon catalysts. Furthermore, only ≈18 mV degradation in E_1/2 occurs after an 8000 cycles' accelerating stability test, manifesting the outstanding stability of the as‐prepared catalyst.     

A High‐Performance Lithium‐Ion Capacitor Based on 2D Nanosheet Materials

Lithium‐ion capacitors (LICs) are promising electrical energy storage systems for mid‐to‐large‐scale applications due to the high energy and large power output without sacrificing long cycle stability. However, due to the different energy storage mechanisms between anode and cathode, the energy densities of LICs often degrade noticeably at high power density, because of the sluggish kinetics limitation at the battery‐type anode side. Herein, a high‐performance LIC by well‐defined ZnMn₂O₄‐graphene hybrid nanosheets anode and N‐doped carbon nanosheets cathode is presented. The 2D nanomaterials offer high specific surface areas in favor of a fast ion transport and storage with shortened ion diffusion length, enabling fast charge and discharge. The fabricated LIC delivers a high specific energy of 202.8 Wh kg^?1 at specific power of 180 W kg^?1, and the specific energy remains 98 Wh kg^?1 even when the specific power achieves as high as 21 kW kg^?1.     

Trash into Treasure: δ‐FAPbI3 Polymorph Stabilized MAPbI3 Perovskite with Power Conversion Efficiency beyond 21%

Effective passivation and stabilization of both the inside and interface of a perovskite layer are crucial for perovskite solar cells (PSCs), in terms of efficiency, reproducibility, and stability. Here, the first formamidinium lead iodide (δ‐FAPbI₃) polymorph passivated and stabilized MAPbI₃ PSCs are reported. This novel MAPbI₃/δ‐FAPbI₃ structure is realized via treating a mixed organic cation MA _x FA_{1‐ x} PbI₃ perovskite film with methylamine (MA) gas. In addition to the morphology healing, MA gas can also induce the formation of δ‐FAPbI₃ phase within the perovskite film. The in situ formed 1D δ‐FAPbI₃ polymorph behaves like an organic scaffold that can passivate the trap state, tunnel contact, and restrict organic‐cation diffusion. As a result, the device efficiency is easily boosted to 21%. Furthermore, the stability of the MAPbI₃/δ‐FAPbI₃ film is also obviously improved. This δ‐FAPbI₃ phase passivation strategy opens up a new direction of perovskite structure modification for further improving stability without sacrificing efficiency.     

Highly Efficient 2D/3D Hybrid Perovskite Solar Cells via Low‐Pressure Vapor‐Assisted Solution Process

The fabrication of multidimensional organometallic halide perovskite via a low‐pressure vapor‐assisted solution process is demonstrated for the first time. Phenyl ethyl‐ammonium iodide (PEAI)‐doped lead iodide (PbI₂) is first spin‐coated onto the substrate and subsequently reacts with methyl‐ammonium iodide (MAI) vapor in a low‐pressure heating oven. The doping ratio of PEAI in MAI‐vapor‐treated perovskite has significant impact on the crystalline structure, surface morphology, grain size, UV–vis absorption and photoluminescence spectra, and the resultant device performance. Multiple photoluminescence spectra are observed in the perovskite film starting with high PEAI/PbI₂ ratio, which suggests the coexistence of low‐dimensional perovskite (PEA₂MA_n?1Pb_nI_3n+1) with various values of n after vapor reaction. The dimensionality of the as‐fabricated perovskite film reveals an evolution from 2D, hybrid 2D/3D to 3D structure when the doping level of PEAI/PbI₂ ratio varies from 2 to 0. Scanning electron microscopy images and Kelvin probe force microscopy mapping show that the PEAI‐containing perovskite grain is presumably formed around the MAPbI₃ perovskite grain to benefit MAPbI₃ grain growth. The device employing perovskite with PEAI/PbI₂ = 0.05 achieves a champion power conversion efficiency of 19.10% with an open‐circuit voltage of 1.08 V, a current density of 21.91 mA cm^?2, and a remarkable fill factor of 80.36%.     

Reduced Interface‐Mediated Recombination for High Open‐Circuit Voltages in CH3NH3PbI3 Solar Cells

Perovskite solar cells with all‐organic transport layers exhibit efficiencies rivaling their counterparts that employ inorganic transport layers, while avoiding high‐temperature processing. Herein, it is investigated how the choice of the fullerene derivative employed in the electron‐transporting layer of inverted perovskite cells affects the open‐circuit voltage (V_OC). It is shown that nonradiative recombination mediated by the electron‐transporting layer is the limiting factor for the V_OC in the cells. By inserting an ultrathin layer of an insulating polymer between the active CH₃NH₃PbI₃ perovskite and the fullerene, an external radiative efficiency of up to 0.3%, a V_OC as high as 1.16 V, and a power conversion efficiency of 19.4% are realized. The results show that the reduction of nonradiative recombination due to charge‐blocking at the perovskite/organic interface is more important than proper level alignment in the search for ideal selective contacts toward high V_OC and efficiency.     

Sugar Blowing‐Induced Porous Cobalt Phosphide/Nitrogen‐Doped Carbon Nanostructures with Enhanced Electrochemical Oxidation Performance toward Water and Other Small Molecules

Rational design of high active and robust nonprecious metal catalysts with excellent catalytic efficiency in oxygen evolution reaction (OER) is extremely vital for making the water splitting process more energy efficient and economical. Among these noble metal‐free catalysts, transition‐metal‐based nanomaterials are considered as one of the most promising OER catalysts due to their relatively low‐cost intrinsic activities, high abundance, and diversity in terms of structure and morphology. Herein, a facile sugar‐blowing technique and low‐temperature phosphorization are reported to generate 3D self‐supported metal involved carbon nanostructures, which are termed as Co₂P@Co/nitrogen‐doped carbon (Co₂P@Co/N‐C). By capitalizing on the 3D porous nanostructures with high surface area, homogeneously dispersed active sites, the intimate interaction between active sites, and 3D N‐doped carbon, the resultant Co₂P@Co/N‐C exhibits satisfying OER performance superior to CoO@Co/N‐C, delivering 10 mA cm^?2 at overpotential of 0.32 V. It is worth noting that in contrast to the substantial current density loss of RuO₂, Co₂P@Co/N‐C shows much enhanced catalytic activity during the stability test and a 1.8‐fold increase in current density is observed after stability test. Furthermore, the obtained Co₂P@Co/N‐C can also be served as an excellent nonprecious metal catalyst for methanol and glucose electrooxidation in alkaline media, further extending their potential applications.     

Nonconfinement Structure Revealed in Dion–Jacobson Type Quasi‐2D Perovskite Expedites Interlayer Charge Transport

Dion–Jacobson (DJ) type 2D perovskites with a single organic cation layer exhibit a narrower distance between two adjacent inorganic layers compared to the corresponding Ruddlesden–Popper perovskites, which facilitates interlayer charge transport. However, the internal crystal structures in 2D DJ perovskites remain elusive. Herein, in a p‐xylylenediamine (PDMA)‐based DJ perovskite bearing bifunctional NH₃⁺ spacer, the compression from confinement structure (inorganic layer number, n = 1, 2) to nonconfinement structure (n > 3) with the decrease of PDMA molar ratio is unraveled. Remarkably, the nonconfined perovskite displays shorter spacing between 2D quantum wells, which results in a lower exciton binding energy and hence promotes exciton dissociation. The significantly diminishing quantum confinement promotes interlayer charge transport leading to a maximum photovoltaic efficiency of ≈11%. Additionally, the tighter interlayer packing arising from the squeezing of inorganic octahedra gives rise to enhanced ambient stability.     

General and Scalable Fabrication of Core–Shell Metal Sulfides@C Anchored on 3D N‐Doped Foam toward Flexible Sodium Ion Batteries

Flexible self‐standing transitional metal sulfides (TMSs)/carbon nanoarchitectures have attracted widespread research interests for sodium ion batteries (SIBs), thanks to their enormous capability to address intrinsic issues of TMSs for SIBs applications. However, controllable synthesis of hierarchical hybrid structures is always laborious and involves complicated procedures. Herein, a simple yet general and scalable adsorption‐annealing strategy is first devised to finely construct core–shell carbon‐coated TMSs (TMSs@C, including Co₉S₈@C, FeS@C, Ni₃S₂@C, MnS@C, and ZnS@C) nanoparticles anchored on 3D N‐doped carbon foam (3DNCF) via the coordination and hydrogen‐bond adsorption. Benefiting from synergistic contributions from strong chemical affinity between nanodimensional TMSs and 3DNCF, efficient electronic/ionic transport channels, as well as a uniform carbon accommodating layer, the resulted self‐standing TMSs@C/3DNCF electrodes exhibit distinguished sodium storage performances, including large reversible capacities, high rate behaviors, and exceptional long‐span cycle stability in both half cells and flexible full devices. More significantly, the smart methodology developed holds huge promise for commercialization of binder‐free TMSs@C/3DNCF anodes toward advanced flexible SIBs.     

Improving Polysulfides Adsorption and Redox Kinetics by the Co4N Nanoparticle/N‐Doped Carbon Composites for Lithium‐Sulfur Batteries

Improved conductivity and suppressed dissolution of lithium polysulfides is highly desirable for high‐performance lithium‐sulfur (Li‐S) batteries. Herein, by a facile solvent method followed by nitridation with NH₃, a 2D nitrogen‐doped carbon structure is designed with homogeneously embedded Co₄N nanoparticles derived from metal organic framework (MOF), grown on the carbon cloth (MOF‐Co₄N). Experimental results and theoretical simulations reveal that Co₄N nanoparticles act as strong chemical adsorption hosts and catalysts that not only improve the cycling performance of Li‐S batteries via chemical bonding to trap polysulfides but also improve the rate performance through accelerating the conversion reactions by decreasing the polarization of the electrode. In addition, the high conductive nitrogen‐doped carbon matrix ensures fast charge transfer, while the 2D structure offers increased pathways to facilitate ion diffusion. Under the current density of 0.1C, 0.5C, and 3C, MOF‐Co₄N delivers reversible specific capacities of 1425, 1049, and 729 mAh g^?1, respectively, and retains 82.5% capacity after 400 cycles at 1C, as compared to the sample without Co₄N (MOF‐C) values of 61.3% (200 cycles). The improved cell performance corroborates the validity of the multifunctional design of MOF‐Co₄N, which is expected to be a potentially promising cathode host for Li‐S batteries.     

Charge transfer enhancement of TiO2/perovskite interface in perovskite solar cells

In the conventional perovskite solar cells (PSCs) structure, TiO₂ is the most commonly used electron transport layer (ETL) as it has good energy-level matching with perovskite layer. However, oxygen vacancy defects will appear when TiO₂ is exposed to ultraviolet light for a long time, which would reduce its carrier extraction ability. Here, we report a simple and effective interface engineering method for TiO₂ ETL to achieve a highly efficient PSCs. An ultra-thin [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) layer is used to modify the mesoporous TiO₂/perovskite layer interface. The PCBM effectively passivates defects on the TiO₂ surface, promotes the extraction of electrons, and improves the quality of the perovskite film. Finally, a high efficiency of 16.4% was achieved for the modified device, much higher than 13.5% of the reference devices. After storing for 12 days in an atmosphere with an air humidity of 30?±?5%, the efficiency of the PSCs maintains more than 60% of its initial level. This strategy is beneficial to enhance the efficiency and working stability of PSCs.

     

Plant Sunscreen and Co(II)/(III) Porphyrins for UV‐Resistant and Thermally Stable Perovskite Solar Cells: From Natural to Artificial

The poor UV, thermal, and interfacial stability of perovskite solar cells (PSCs) makes it highly challenging for their technological application, and has drawn increasing attention to resolving the above issues. In nature, plants generally sustain long exposure to UV illumination without damage, which is attributed to the presence of the organic materials acting as sunscreens. Inspired by the natural phenomenon, a natural plant sunscreen, sinapoyl malate, an ester derivative of sinapic acid, is employed to modify the surface of electron transport materials (ETMs). The interfacial modification successfully resolved the UV stability and reduced the poor interfacial contact between ETM and perovskite. The best efficiency of fabricated PSCs is up to 19.6%. Furthermore, we employed a mixture of Co(II) and Co(III)‐based porphyrin compounds containing the excellent Co(II)/Co(III) redox couple to substitute the commonly used hole transport material, 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐9,9‐spiro‐bifluorene (spiro‐OMeTAD), to resolve the thermal degradation of PSCs noted at and above 80 °C that originates from ion diffusion of I^? and CH₃NH₃⁺ (MA⁺) ions from perovskite into spiro‐OMeTAD. Finally, the stable PSCs with the best efficiency up to 20.5% are successfully fabricated.     

Divalent Anionic Doping in Perovskite Solar Cells for Enhanced Chemical Stability

The chemical stabilities of hybrid perovskite materials demand further improvement toward long‐term and large‐scale photovoltaic applications. Herein, the enhanced chemical stability of CH₃NH₃PbI₃ is reported by doping the divalent anion Se^2? in the form of PbSe in precursor solutions to enhance the hydrogen‐bonding‐like interactions between the organic cations and the inorganic framework. As a result, in 100% humidity at 40 °C, the 10% w/w PbSe‐doped CH₃NH₃PbI₃ films exhibited >140‐fold stability improvement over pristine CH₃NH₃PbI₃ films. As the PbSe‐doped CH₃NH₃PbI₃ films maintained the perovskite structure, a top efficiency of 10.4% with 70% retention after 700 h aging in ambient air is achieved with an unencapsulated 10% w/w PbSe:MAPbI₃‐based cell. As a bonus, the incorporated Se^2? also effectively suppresses iodine diffusion, leading to enhanced chemical stability of the silver electrodes.     

Boosting High‐Rate Sodium Storage Performance of N‐Doped Carbon‐Encapsulated Na3V2(PO4)3 Nanoparticles Anchoring on Carbon Cloth

The further development of high‐power sodium‐ion batteries faces the severe challenge of achieving high‐rate cathode materials. Here, an integrated flexible electrode is constructed by smart combination of a conductive carbon cloth fiber skeleton and N‐doped carbon (NC) shell on Na₃V₂(PO₄)₃ (NVP) nanoparticles via a simple impregnation method. In addition to the great electronic conductivity and high flexibility of carbon cloth, the NC shell also promotes ion/electron transport in the electrode. The flexible NVP@NC electrode renders preeminent rate capacities (80.7 mAh g^?1 at 50 C for cathode; 48 mAh g^?1 at 30 C for anode) and superior cycle performance. A flexible symmetric NVP@NC//NVP@NC full cell is endowed with fairly excellent rate performance as well as good cycle stability. The results demonstrate a powerful polybasic strategy design for fabricating electrodes with optimal performance.     

Graphdiyne: A Brilliant Hole Accumulator for Stable and Efficient Planar Perovskite Solar Cells

Traditional carbon materials have demonstrated immense potential in perovskite solar cells (PSCs) owing to their superior electrical properties and environmental stability. Graphdiyne (GDY), as an emerging carbon allotrope, features uniformly distributed pores, endless design flexibility, and unique electronic character compared with traditional carbon materials. Herein, graphdiyne is introduced into the upper part of the perovskite (CH₃NH₃PbI₃) layer by utilizing a GDY‐containing antisolvent during the one‐step synthesis of perovskite. Intriguingly, GDY plays an essential role in hole accumulation and transportation because of its higher Fermi level than perovskite. As a result, the automatic separation of photogenerated carriers inside the perovskite film is achieved. Furthermore, the Schottky barrier formed on the interface between perovskite and GDY guarantees the unidirectional hole transport from perovskite to GDY, thereby benefiting further extraction to the hole transport layer. Consequently, GDY‐modified perovskite‐based planar PSCs exhibit a boosted J_sc of 24.21 mA cm^?2 and up to 19.6% power conversion efficiency owing to the increased efficient light utilization and charge extraction. The device with GDY modification exhibits less than 10% shrinkage after a month in ambience. Overall, this work demonstrates an easy method for the utilization of GDY to boost the charge extraction and environmental stability in PSCs.     

Fine Multi‐Phase Alignments in 2D Perovskite Solar Cells with Efficiency over 17% via Slow Post‐Annealing

Layered Ruddlesden–Popper (RP) phase (2D) halide perovskites have attracted tremendous attention due to the wide tunability on their optoelectronic properties and excellent robustness in photovoltaic devices. However, charge extraction/transport and ultimate power conversion efficiency (PCE) in 2D perovskite solar cells (PSCs) are still limited by the non‐eliminable quantum well effect. Here, a slow post‐annealing (SPA) process is proposed for BA₂MA₃Pb₄I₁₃ (n = 4) 2D PSCs by which a champion PCE of 17.26% is achieved with simultaneously enhanced open‐circuit voltage, short‐circuit current, and fill factor. Investigation with optical spectroscopy coupled with structural analyses indicates that enhanced crystal orientation and favorable alignment on the multiple perovskite phases (from the 2D phase near bottom to quasi‐3D phase near top regions) is obtained with SPA treatment, which promotes carrier transport/extraction and suppresses Shockley–Read–Hall charge recombination in the solar cell. As far as it is known, the reported PCE is so far the highest efficiency in RP phase 2D PSCs based on butylamine (BA) spacers (n = 4). The SPA‐processed devices exhibit a satisfactory stability with <4.5% degradation after 2000 h under N₂ environment without encapsulation. The demonstrated process strategy offers a promising route to push forward the performance in 2D PSCs toward realistic photovoltaic applications.