Design Strategies for Aqueous Zinc Metal Batteries with High Zinc Utilization: From Metal Anodes to Anode-Free Structures

Aqueous zinc metal batteries(AZMBs)are promising candidates for next-generation energy storage due to the excellent safety, environmental friendliness, natural abundance, high theoretical specific capacity, and low redox potential of zinc(Zn) metal. However,several issues such as dendrite formation, hydrogen evolution, corrosion, and passivation of Zn metal anodes cause irreversible loss of the active materials. To solve these issues, researchers often use large amounts of excess Zn to ensure a continuous supply of active materials for Zn anodes. This leads to the ultralow utilization of Zn anodes and squanders the high energy density of AZMBs. Herein, the design strategies for AZMBs with high Zn utilization are discussed in depth, from utilizing thinner Zn foils to constructing anode-free structures with theoretical Zn utilization of 100%, which provides comprehensive guidelines for further research. Representative methods for calculating the depth of discharge of Zn anodes with different structures are first summarized. The reasonable modification strategies of Zn foil anodes, current collectors with pre-deposited Zn, and anode-free aqueous Zn metal batteries(AF-AZMBs) to improve Zn utilization are then detailed. In particular, the working mechanism of AF-AZMBs is systematically introduced. Finally, the challenges and perspectives for constructing high-utilization Zn anodes are presented.

Inkjet-Printing Controlled Phase Evolution Boosts the Efficiency of Hole Transport Material Free and Carbon-Based CsPbBr_(3) Perovskite Solar Cells Exceeding 9%

Hole transport material free carbon-based all-inorganic CsPbBr_(3)perovskite solar cells(PSCs)are promising for commercialization due to its low-cost,high open-circuit voltage(V_(oc))and superior stability.Due to the different solubility of PbBr_(2)and CsBr in conventional solvents,CsPbBr_(3)films are mainly obtained by multi-step spin-coating through the phase evolution from PbBr_(2)to CsPb_(2)Br_(5)and then to CsPbBr_(3).The scalable fabrication of high-quality CsPbBr_(3)films has been rarely studied.Herein,an inkjet-printing method is developed to prepare high-quality CsPbBr_(3)films.The formation of long-range crystalline CsPb_(2)Br_(5)phase can effectively improve phase purity and promote regular crystal stacking of CsPbBr_(3).Consequently,the inkjet-printed CsPbBr_(3)C-PSCs realized PCEs up to 9.09%,8.59%and 7.81%with active areas of 0.09,0.25,and 1 cm^(2),respectively,demonstrating the upscaling potential of our fabrication method and devices.This high performance is mainly ascribed to the high purity,strong crystal orientation,reduced surface roughness and lower trap states density of the as-printed CsPbBr_(3)films.This work provides insights into the relationship between the phase evolution mechanisms and crystal growth dynamics of cesium lead bromide halide films.

Highly Efficient and Stable FAPbI_(3) Perovskite Solar Cells and Modules Based on Exposure of the(011)Facet

Perovskite crystal facets greatly impact the performance and stability of their corresponding photovoltaic devices.Compared to the(001)facet,the(011)facet yields better photoelectric properties,including higher conductivity and enhanced charge carrier mobility.Thus,achieving(011)facet-exposed films is a promising way to improve device performance.However,the growth of(011)facets is energetically unfavorable in FAPbI_(3) perovskites due to the influence of methylammonium chloride additive.Here,1-butyl-4-methylpyridinium chloride([4MBP]Cl)was used to expose(011)facets.The[4MBP]^(+)cation selectively decreases the surface energy of the(011)facet enabling the growth of the(011)plane.The[4MBP]^(+)cation causes the perovskite nuclei to rotate by 45°such that(011)crystal facets stack along the out-of-plane direction.The(011)facet has excellent charge transport properties and can achieve better-matched energy level alignment.In addition,[4MBP]Cl increases the activation energy barrier for ion migration,suppressing decomposition of the perovskite.As a result,a small-size device(0.06 cm2)and a module(29.0 cm2)based on exposure of the(011)facet achieved power conversion efficiencies of 25.24%and 21.12%,respectively.

Fixed-Time Stabilization of a Class of Strict-Feedback Nonlinear Systems via Dynamic Gain Feedback Control

This paper presents a novel fixed-time stabilization control(FSC)method for a class of strict-feedback nonlinear systems involving unmodelled system dynamics.The key feature of the proposed method is the design of two dynamic parameters.Specifically,a set of auxiliary variables is first introduced through state transformation.These variables combine the original system states and the two introduced dynamic parameters,facilitating the closed-loop system stability analyses.Then,the two dynamic parameters are delicately designed by utilizing the Lyapunov method,ensuring that all the closed-loop system states are globally fixed-time stable.Compared with existing results,the“explosion of complexity”problem of backstepping control is avoided.Moreover,the two designed dynamic parameters are dependent on system states rather than a time-varying function,thus the proposed controller is still valid beyond the given fixedtime convergence instant.The effectiveness of the proposed method is demonstrated through two practical systems.

Leader-follower Consensus of Upper-triangular Nonlinear Multi-agent Systems

This paper is concerned with the leader-follower consensus problem by using both state and output feedback for a class of nonlinear multi-agent systems. The agents considered here are all identical upper-triangular nonlinear systems which satisfy the Lipschitz growth condition. First, it is shown that the leader-follower consensus problem is equivalent to the control design problem of a high-dimensional multi-variable system.Second, by introducing an appropriate state transformation, the control design problem can be converted into the problem of finding a constant parameter, which can be obtained by solving the Lyapunov equation and estimating the nonlinear terms of the given system. At last, an example is given to verify effectiveness of the proposed consensus algorithms.

Heteroatom engineering on spiro-type hole transporting materials for perovskite solar cells

A series of spiro-type hole transporting materials, spiro-OMe TAD, spiro-SMe TAD and spiro-OSMe TAD,with methoxy, methylsulfanyl or half methoxy and half methylsulfanyl terminal groups are designed and prepared. The impact of varied terminal groups on bulk properties, such as photophysical, electrochemical, thermal, hole extraction, and photovoltaic performance in perovskite solar cells is investigated.It is noted that the terminal groups of the hole transporting material with half methoxy and half methylsulfanyl exhibit a better device performance and decreased hysteresis compared with all methoxy or methylsulfanyl counterparts due to better film-forming ability and improved hole extraction capability.Promisingly, the spiro-OSMe TAD also shows comparable performance than high-purity commercial spiro-OMe TAD. Moreover, the highest power conversion efficiency of the optimized device employing spiro-OSMe TAD exceeding 20% has been achieved.

C≡N-based carbazole-arylamine hole transporting materials for perovskite solar cells: Substitution position matters

Hole transporting materials(HTMs)containing passivating groups for perovskite materials have attracted much attention for efficient and stable perovskite solar cells(PSCs).Among them,C≡N-based molecules have been proved as efficient HTMs.Herein,a series of novel C≡N functionalized carbazole-arylamine derivatives with variable C≡N substitution positions(para,meta,and ortho)on benzene-carbazole skeleton(on the adjacent benzene of carbazole)were synthesized(p-HTM,m-HTM and o-HTM).The experimental results exhibit that the substitution positions of the Ctriple bondN unit on HTMs have minor difference on the HOMO energy level and hydrophobicity.m-HTM has a relatively lower glass transition temperature compared with that of p-HTM and o-HTM.The functional theory calculations show that the C≡N located on meta position exposed very well,and the exposure direction is also the same with the methoxy.Upon applying these molecules as HTMs in PSCs,their device performance is found to sensitively depend on the substitution position of the C≡N unit on the molecule skeleton.The devices using m-HTM and o-HTM exhibit better performance than that of p-HTM.Moreover,m-HTM-based devices exhibit better light-soaking performance and long-term stability,which could be resulted from better interaction with the perovskite according to DFT results.Moreover,we further prepared a HTM with two C≡N units on the symmetrical meta position of molecular skeleton(2m-HTM).Interestingly,2m-HTM-based devices exhibit relatively inferior performance compared with that of the m-HTM,which could be resulted from weak negative electrical character of C≡N unit on 2m-HTM.The results give some new insights for designing ideal HTM for efficient and stable PSCs.

Pyridine-triphenylamine hole transport material for inverted perovskite solar cells

In the light of superior interaction between pyridine unit and perovskite,a facile star-shaped triphenylamine-based hole transport material(HTM)incorporating pyridine core(coded as H-Pyr)is designed and synthesized.A reference HTM with benzene core,coded as H-Ben,is also prepared for a comparative study.The effects of varying core on HTMs are investigated by comparing the photophysical,electrochemical and hole mobility properties.It is found that pyridine core exhibits better conjunction and decreased dihedral angles with triphenylamine side arms than that of benzene,leading to obviously better hole mobility and well-matched work function.The perovskite film prepared on H-Pyr also shows improved crystallization than on H-Ben.Photoluminescence and electrochemical impedance studies indicate improved charge extraction and reduced recombination in the H-Pyr-based perovskite solar cells.Consequently,H-Pyr-based device exhibits higher efficiency than H-Ben-based one.After doping with a Lewis acid,tris(pentafluorophenyl)borane,H-Pyr-based device delivers a champion efficiency of 17.09%,which is much higher compared with 12.14% of the device employing conventional poly(3,4-ethy lenedioxythiophene)polystyrene sulfonate(PEDOT:PSS)as HTM.Moreover,the H-Pyr-based device displays good long-term stability that the power conversion efficiency remains over 80% of the initial value after storage in ambient(relative humidity=50±5%)for 20 days.

钙钛矿太阳电池中螺环小分子空穴传输材料

空穴传输材料的性能直接影响钙钛矿太阳电池中空穴在电池中的传输和电子-空穴的复合,从而决定电池性能。螺环结构特殊的正交分子构象使分子易于在钙钛矿薄膜上形成良好的接触、具有均匀的电荷传输特性、较高的玻璃化转变温度等优点,该材料已广泛作为高效空穴传输材料骨架单元应用于钙钛矿太阳电池。本论文概述了小分子螺环空穴传输材料的研究进展,主要从分子末端官能团优化和螺环核调控两个方面总结了分子结构变化对材料光物理、电化学、热稳定性、空穴传输特性及在钙钛矿太阳电池中的性能等的影响,同时本论文也对该领域的发展和高性能螺环空穴传输材料的发展和研究趋势进行了预测。

自组装单分子空穴传输层在反式钙钛矿太阳电池的研究进展

空穴传输层在钙钛矿太阳电池(Perovskite solar cell, PSC)中起着抽取和传输钙钛矿层产生的光生空穴、抑制电子回流等重要作用,是构成高性能器件的重要组成部分.经典的空穴传输材料,如2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴(spiro-OMe TAD)、聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)等,空穴迁移率低、价格昂贵等缺点限制了其规模化应用.近年来,在反式PSC中自组装单分子层(self-assembledmonolayers,SAM)作为空穴传输层广泛应用,提升了器件性能.SAM分子结构中含有锚定官能团,可以在衬底上形成单分子薄膜,有着材料消耗小、无需添加剂、寄生吸收低、能够兼容叠层器件和有利于大面积制造等优点,已成为PSC领域的研究热点.本综述结合PSC发展,按照SAM分子结构中锚定基团的不同,对近年来基于SAM的空穴传输层的研究进行了分类和归纳,结合分子骨架变化分析了结构变化对其特性及器件性能的影响.最后,对SAM作为空穴传输层的发展做了总结和展望.

Pathological basal ganglia oscillations with time delays:a memoryless feedback control strategy

Pathological basal ganglia oscillations are associated with the hypokinetic motor symptoms of Parkinson’s disease.In this paper,a memoryless feedback control strategy is proposed to suppress pathological oscillations in the basal ganglia.In the most of closed-loop control strategies,the excitatory subthalamic nucleus populations are both monitored and stimulated targets,neglecting the important contribution of the external globus pallidus populations in suppressing pathological oscillations.To this end,we transform the original model into a time-delay system with a lower-triangular structure,and construct a memoryless state feedback controller utilizing the gain scaling method.It is proved by the Lyapunov–Krasovskii functional method that all the signals of the resulting closed-loop system are bounded,and the system states converge to an adjustable region of the origin.In addition,the input delay in stimulating the target is considered and a corresponding controller is designed to achieve convergence of the states in the resulting closed-loop system with both state delays and input delay.Moreover,simulation tests are conducted to explore the performance of the control strategy.This paper further explores the intrinsic dynamics in the neural system,and provides an effective strategy for closed-loop deep brain stimulation control.

Dynamic event-triggered bipartite consensus for uncertain high-order nonlinearmulti-agentsystems

In this paper,the bipartite consensus problem is studied for a class of uncertain high-order nonlinear multi-agent systems.A signed digraph is presented to describe the collaborative and competitive interactions among agents.For each agent with lower triangular structure,a time-varying gain compensator is first designed by relative output information of neighboring agents.Subsequently,a distributed controller with dynamic event-triggered mechanism is proposed to drive the bipartite consensus error to zero.It is worth noting that an internal dynamic variable is introduced in triggering function,which plays an essential role in excluding the Zeno behavior and reducing energy consumption.Furthermore,the dynamic event-triggered control protocol is developed for upper triangular multi-agent systems to realize the bipartite consensus without Zeno behavior.Finally,simulation examples are provided to illustrate the effectiveness of the presented results.

Adaptive feedback control for nonlinear triangular systems subject to uncertain asymmetric dead-zone input

In this paper,an adaptive control strategy is proposed to investigate the issue of uncertain dead-zone input for nonlinear triangular systems with unknown nonlinearities.The considered system has no precise priori knowledge about the dead-zone feature and growth rate of nonlinearity.Firstly,a dynamic gain is introduced to deal with the unknown growth rate,and the dead-zone characteristic is processed by the adaptive estimation approach without constructing the dead-zone inverse.Then,by virtue of hyperbolic functions and sign functions,a new adaptive state feedback controller is proposed to guarantee the global boundedness of all signals in the closed-loop system.Moreover,the uncertain dead-zone input problem for nonlinear upper-triangular systems is solved by the similar control strategy.Finally,two simulation examples are given to verify the effectiveness of the control scheme.

Self-assembled α-MnO2 urchin-like microspheres as a high-performance cathode for aqueous Zn-ion batteries

Aqueous Zn-ion batteries(AZIBs)are one of the promising battery technologies for the green energy storage and electric vehicles.As one attractive cathode material for AZIBs,α-MnO2 materials exhibit superior electrochemical properties.However,their long-term reversibility is still in great suspense.Considering the decisive effect of the structure and morphology on theα-MnO2 materials,hierarchicalα-MnO2 materials would be promising to improve the cycle performance of AZIB.Here,we synthesized theα-MnO2 urchin-like microspheres(AUM)via a self-assembled method.The porous microspheres composed of one-dimensionalα-MnO2 nanofibers with high crystallinity,which improved the surface area and active sites for Zn2+intercalation.The AUM-based AZIB realized a high initial capacity of 308.0 mA hg-1,and the highest energy density was 396.7 W hkg-1.The kinetics investigation confirmed the high capacitive contribution and fast ion diffusion of the AUM.Ex-situ XRD measurement further verified the synergistic insertion/extraction of H+and Zn2+ions during the charge/discharge process.The superiority of the AUM guaranteed good electrochemical performance and reversible phase evolution,and this application would promote the follow-up research on the advanced AZIB.

Consensus control of feedforward nonlinear multi-agent systems:a time-varying gain method

In this paper,the leader–follower consensus of feedforward nonlinear multi-agent systems is achieved by designing the distributed output feedback controllers with a time-varying gain.The agents dynamics are assumed to be in upper triangular structure and satisfy Lipschitz conditions with an unknown constant multiplied by a time-varying function.A time-varying gain,which increases monotonously and tends to infinity,is proposed to construct a compensator for each follower agent.Based on a directed communication topology,the distributed output feedback controller with a time-varying gain is designed for each follower agent by only using the output information of the follower and its neighbors.It is proved by the Lyapunov theorem that the leader–follower consensus of the multi-agent system is achieved by the proposed consensus protocol.The effectiveness of the proposed time-varying gain method is demonstrated by a circuit system.

Bipartite consensus for nonlinear time-delay multiagent systems via time-varying gain control method

The bipartite consensus problem is addressed for a class of nonlinear time-delay multiagent systems in this paper.Therein,the uncertain nonlinear dynamics of all agents satisfy a Lipschitz growth condition with unknown constants,and part of the state information cannot be measured.In this case,a time-varying gain compensator is constructed,which only utilizes the output information of the follower and its neighbors.Subsequently,a distributed output feedback control protocol is proposed on the basis of the compensator.According to Lyapunov stability theory,it is proved that the bipartite consensus can be guaranteed by means of the designed control protocol.Different from the existing literature,this paper studies the leader-follower consensus problem under a weaker connectivity condition,i.e.,the signed directed graph is structurally balanced and contains a directed spanning tree.Two simulation examples are carried out to show the feasibility of the proposed control strategy.

H_(∞)output feedback control for large-scale nonlinear systems with time delay in both state and input

The H_(∞)output feedback control problem for a class of large-scale nonlinear systems with time delay in both state and input is considered in this paper.It is assumed that the interconnected nonlinearities are limited by constant multiplied by unmeasured states,delayed states and external disturbances.Different from existing methods to study the H_(∞)control of large-scale nonlinear systems,the static gain control technique is utilized to obtain an observer-based output feedback control strategy,which makes the closed-loop system globally asymptotically stable and attenuates the effect of external disturbances.An example is finally carried out to show the feasibility of the proposed control strategy.

Boosting optoelectronic performance of MAPbI3 perovskite solar cells via ethylammonium chloride additive engineering

The quality of the perovskite light absorption layer plays a dynamic role in the photovoltaic properties of solar cells.The existing methods to prepare methylammonium lead iodide(MAPbI3)films render substantial structural defect density,particularly at the grain boundaries and film surface,constituting a challenge that hinders the further optoelectronic enhancement of perovskite solar cells.Herein,a unique approach was introduced:using a simple ethylammonium chloride(EACl)additive in perovskite precursor mixture to produce high-quality MAPbI3 thin films.The results indicated that EACl could encourage perovskite crystal growth without experiencing the intermediate phase formation and would evaporate from the perovskite after annealing.Additionally,a gradient perovskite structure was achieved using this technique,which impressively enhanced the performance of the perovskite films.A high power conversion efficiency(PCE)of 20.03%was achieved under the optimal amount of EACl,and the resultant efficient device could retain over 89%of the original PCE after aging for 1000 h at room temperature.This novel technique leads to a facile fabrication of highquality and less-defect perovskite thin films for competent and stable devices.

Behavioural responses of ex-situ captive hippopotamus (Hippopotamus amphibius) in lactation season: Maternal investment and plasticity of infant self-independence

In order to promote hippopotamus manage-ment in the captive and ex-situ environment,especially the control of behavioural and physiological status during breeding and lactation seasons,we conducted a prelimin-ary study on behavioural responses of a pair of hippos including both mother and infant in Hangzhou Wildlife Park,China.The study of the captive hippos for about 1-month in the lactation season was carried out during August and September,2009.The behavioural patterns were identified by all occurrence sampling and instanta-neous scanning sampling methods with 5–10 min inter-vals.As a result,mother-offspring conflicts and interactions did occur throughout the whole study period.Early maternal investment showed a positive trend in activity rhythms(slope=0.0014,Z=0.3027,P<0.001)and a negative trend(slope=–0.0066,Z=0.8807,P<0.001)in territorial occupation of water,all of which supported our hypotheses that the mother hippo might exert less care for the infant and cut down on her own obligations in nursing.For infant self-independence,during the whole lactation season,the primary trends of activities and territorial occupation dynamics of the infant hippo were slightly different from before,judging from linear models(slope=–0.0017,Z=0.3309,P<0.001).However,the frequencies of activities were not stable,especially at around 12 days of age.The trends of territorial occupation(slope=–0.0071,Z=0.904,P<0.001)also showed negative dynamics in water body occupation by the time the infant hippo grew up.The general trend(slope=–0.005,Z=0.06,P<0.001)of suckling dynamics was demonstrably negative,with an upwardsfluctuation at period 3(10–15th day).This also illustrated that as the infant developed,the dependency on the mother was reduced at the end of the lactation season.In addition,a sharp decline between P3 and P4 also supported the mother-offspring conflict theory.In general,time budgets of hippos in active behaviour were(31.8�2.1)%for the mother and(32.1�2.6)%for the infant.Spatial distribu-tions in water within temporal limitations were(80.1�2.7)%for the mother and(81.8�2.7)%for the infant.Behavioural dynamics showed strong synchronous relations between maternal investment and infant inde-pendence.Our current short-term investigation proves to be a key in management and conservation of hippopotami during the lactation season.