A Room-Temperature Chloride-Conducting Metal-Organic Crystal[Al(DMSO)_(6)]Cl_(3) for Potential Solid-State Chloride-Shuttle Batteries

The growing demand for substitutes of lithium chemistries in battery leads to a surge in budding novel anion-based electrochemical energy storage,where the chloride ion batteries(CIBs)take over the role.The application of CIBs is limited by the dissolution and side reaction of chloride-based electrode materials in a liquid electrolyte.On the flipside,its solid-state electrolytes are scarcely reported due to the challenge in realizing fast Cl^(-)conductivity.The present study reports[Al(DMSO)_(6)]Cl_(3),a solid-state metal-organic material,allows chloride ion transfer.The strong Al-Cl bonds in AlCl_(3)are broken down after coordinating of Al^(3+)by ligand DMSO,and Cl^(-)in the resulting compound is weakly bound to complexions[Al(DMSO)_(6)]^(3+),which may facilitate Cl^(-)migration.By partial replacement of Cl^(-)with PF_(6)^(-),the room-temperature ionic conductivity of as-prepared electrolyte is increased by one order of magnitude from 2.172×10^(-5)S cm^(-1)to 2.012×10^(-4)S cm^(-1).When they are assembled with Ag(anode)/Ag-AgCl(cathode)electrode system,reversible electrochemical redox reactions occur on both sides,demonstrating its potential for solid-state chloride ion batteries.The strategy by weakening the bonding interaction using organic ligands between Cl^(-)and central metallic ions may provide new ideas for developing solid chloride-ion conductors.

A gel polymer electrolyte based on IL@NH_(2)-MIL-53(Al)for high-performance all-solid-state lithium metal batteries

Solid polymer composite electrolytes possess the benefits of superior compatibility with electrodes and good thermal characteristics for more secure energy storage equipment.Herein,a new gel polymer electrolyte(GPE)containing NH_(2)-MIL-53(Al),[PP_(13)][TFSI],LiTFSI,and PVDF-HFP was prepared using a simple method of solution casting.The effects of encapsulating different ratios of ionic liquid([PP_(13)][TFSI])into the micropores of functionalized metal-organic frameworks(NH_(2)-MIL-53(Al))on the electrochemical properties were compared.XRD,SEM,nitrogen adsorption-desorption isotherms,and electrochemical measurements were conducted.This GPE demonstrates a superior ionic conductivity of 8.08×10^(-4)S·cm^(-1)at 60℃and can sustain a discharge specific capacity of 156.6 mA·h·g^(-1)at 0.2 C for over 100 cycles.This work might offer a potential approach to alleviate the solid-solid contact with the solid-state electrolyte and electrodes and broaden a new window for the creation of all-solid-state batteries.

Paper-based aqueous Al ion battery with water-in-salt electrolyte

Low-cost,flexible and safe battery technology is the key to the widespread usage of wearable electronics,among which the aqueous Al ion battery with water-in-salt electrolyte is a promising candidate.In this work,a flexible aqueous Al ion battery is developed using cellulose paper as substrate.The water-in-salt electrolyte is stored inside the paper,while the electrodes are either printed or attached on the paper surface,leading to a lightweight and thin-film battery prototype.Currently,this battery can tolerate a charge and discharge rate as high as 4 A g^(-1) without losing its storage capacity.The charge voltage is around 2.2 V,while the discharge plateau of 1.6–1.8 V is among the highest in reported aqueous Al ion batteries,together with a high discharge specific capacity of~140 mAh g^(-1).However,due to the water electrolysis side reaction,the faradaic efficiency can only reach 85%with a cycle life of 250 due to the dry out of electrolyte.Benefited from using flexible materials and aqueous electrolyte,this paper-based Al ion battery can tolerate various deformations such as bending,rolling and even puncturing without losing its performance.When two single cells are connected in series,the battery pack can provide a charge voltage of 4.3 V and a discharge plateau as high as 3–3.6 V,which are very close to commercial Li ion batteries.Such a cheap,flexible and safe battery technology may be widely applied in low-cost and large-quantity applications,such as RFID tags,smart packages and wearable biosensors in the future.

Solid-state Al-air battery with an ethanol gel electrolyte

Hydrogel electrolyte is especially suitable for solid-state Al-air batteries targeted for various portable applications, which may, however, lead to continuous Al corrosion during battery standby. To tackle this issue, an ethanol gel electrolyte is developed for Al-air battery for the first time in this work, by using KOH as solute and polyethylene oxide as gelling agent. The ethanol gel is found to effectively inhibit Al corrosion compared with the water gel counterpart, leading to stable Al storage. When assembled into an Al-air battery, the ethanol gel electrolyte achieves a much improved discharge lifetime and specific capacity, which are 5.3 and 4.1 times of the water gel electrolyte at 0.1 mA cm^(-2), respectively.By studying the gel properties, it is found that a lower ethanol purity can improve the battery power output, but at the price of decreased discharge efficiency. On the contrary, a higher polymer concentration will decrease the power output, but can bring extra benefit to the discharge efficiency. As for the gel thickness, a moderate value of 1 mm is preferred to balance the power output and energy efficiency. Finally, to cater the increasing market of flexible electronics, a flexible Al-air battery is developed by impregnating the ethanol gel into a paper substrate, which can function normally even under serious deformation or damage.

Al-Ga-In-Sn-Si合金阳极及海水溶解氧电池的电化学性能

通过Ga、In和Sn低熔点合金元素改性,成功制备了高负电位高活化Al-Ga-In-Sn-Si合金阳极,通过材料表征和电化学测试研究了Al-Ga-In-Sn-Si合金的腐蚀行为和电化学性能,并与碳纤维刷-石墨烯-铂(Pt-G@CFB)催化阴极搭建了海水溶解氧电池,考察了室内静态海水环境和实际海洋环境下电池不同恒电阻的长周期放电性能。结果表明,Al-Ga-In-Sn-Si合金的自腐蚀电位为-1.613 V(vs.Ag/AgCl),自腐蚀电流密度为1.431 mA/cm^(2)。随着负载电阻的增加,电池电压上升,在室内静态和实海动态海水中2000Ω的负载下海水溶解氧电池平均放电电压最高,分别为1.73和1.78 V,在1000Ω的负载下平均能量密度最大,分别为549.85和653.44 Wh/kg。

海水电池AgO电极性能改善研究

采用化学合成法制备AgO粉末,通过控制适当的反应物浓度和反应温度,制备得到96%纯度以上的AgO粉末。使用不同粘合剂和不同结构导电骨架制备电极,进一步组装成海水电池测试不同制备方法下电池的电性能,结果显示当添加1%含量的PVDF作为粘合剂,使用多层蜂窝状银网作为导电骨架时,AgO电极的电性能提升较明显。

电解液组成对Al/AgO电池性能的影响

用恒电流放电技术和扫描电子显微镜(SEM)研究了添加缓蚀剂Na2SnO3的含量和反应产物NaAlO2的浓度对Al/AgO电池在20%NaOH溶液中的电压、析氢速率和铝阳极表面形貌的影响。结果表明:在NaOH溶液中添加Na2SnO3,可以降低铝阳极的析氢速率,减少铝的阳极极化,改变铝阳极的腐蚀形貌;加入NaAlO2阻碍铝阳极的溶解,降低了Al/AgO电池的电压,不利于Sn的析出,使铝阳极的析氢速率增大。

Al/AgO电池的制备及性能研究

采用化学方法制备AgO,并组装成实验电池。通过恒电流放电技术研究了在4 mol/L NaOH电解质溶液中加入不同浓度的NaAlO2对Al/AgO电池性能的影响,并考察了放电倍率和温度对Al/AgO电池性能的影响。用扫描电子显微镜(SEM)研究了电池放电前后AgO的表观形貌。结果表明:在NaOH溶液中加入适量NaAlO2可以提高电池的比容量。随着温度的提高,电池的比容量增大。随着放电倍率增加,电池的比容量降低。当NaAlO2浓度为2.5 mol/L,温度为80℃时,以0.1 C放电,终止电压为1.0 V时,Al/AgO电池的比容量达到292mA.h/g。

铝酸盐浓度对Al/AgO电池的影响

Al/AgO电池放电过程中产生铝酸盐,它对AgO正极和铝负极均有不利影响,但对铝负极影响更大。铝酸盐最大允许浓度约为2.8M。

All-carbon positive electrodes for stable aluminium batteries

For addressing the critical problems in current collectors in the aluminium batteries,a variety of carbonbased current collectors,including carbon fiber textiles and three-dimensional(3D)biomass-derivative carbon(BDC)networks,are employed for serving as lightweight non-metal current collectors.The results indicate that all the carbon-based current collectors have electrochemical stability in the acidic electrolyte environments.In the assembled aluminium batteries with all-carbon positive electrodes,thermal annealing process on the carbon-based current collectors has substantially promoted the entire electrochemical energy storage performance.Additionally,both the structure configuration and chemical components of the current collectors have also great impact on the rate capability and cycling stability,implying that the 3D BDC networks are more favorable to offer promoted energy storage capability.Implication of the results from suggests that the carbon-based current collectors and all-carbon positive electrodes are able to deliver more advantages in energy storage behaviors in comparison with the traditional positive electrodes with metal Mo current collectors.Such novel strategy promises a new route for fabricating highperformance positive electrodes for stable advanced aluminium batteries.

Regeneration of Al-doped LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cathode material by simulated hydrometallurgy leachate of spent lithium-ion batteries

A uniform Al-doped LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cathode material was prepared using a coprecipitation method to take advantage of the positive effect of Al on regenerated NCM(Ni,Co,Mn)cathode materials and ameliorate cumbersome and high-cost impurity removal processes during lithium-ion battery recycling.When the Al^(3+) content in the leachate was 1 at.%with respect to the total amount of transition metals(Ni,Co,and Mn),the produced Al-doped NCM cathode material increased concentrations of lattice oxygen and Ni^(2+).The initial specific capacity at 0.1C was 167.4 mA·h/g,with a capacity retention of 79.1%after 400 cycles at 1C.Further,this Al-doped sample showed improved rate performance and a smaller electrochemical impedance.These findings provide a reference for developing industrial processes to resynthesize cathode materials with improved electrochemical performance by incorporating Al^(3+) impurities produced during lithium-ion battery recycling.

Effect of Ga on microstructure and electrochemical performance of Al−0.4Mg−0.05Sn−0.03Hg alloy as anode for Al−air batteries

The effects of 0.01 wt.%Ga on microstructure and electrochemical performance of Al−0.4Mg−0.05Sn−0.03Hg anodes in NaOH solutions were investigated.Potentiodynamic polarization,electrochemical impedance spectroscopy,and galvanostatic discharge tests were used to assess the electrochemical performance of the Al−Mg−Sn−Hg−Ga anodes.The results show that the addition of 0.01 wt.%Ga in Al−0.4Mg−0.05Sn−0.03Hg anode enhances its corrosion resistance and discharge activity.It is benefited from the refined second phases and homogenous microstructure of Al−Mg−Sn−Hg−Ga anode,which restrains the local crystallographic corrosion and chunk effect.Compared with Al−Mg−Sn−Hg anode,the corrosion current density and the mass loss rate of Al−Mg−Sn−Hg−Ga anode decrease by 57%and 93%,respectively.When discharging at the current density of 20 mA/cm^(2),the discharge voltage,current efficiency and specific capacity of the single Al−air battery with Al−0.4Mg−0.05Sn−0.03Hg−0.01Ga anode are 1.46 V,33.1%,and 1019.2 A·h·kg^(−1),respectively.The activation mechanism of Ga on Al−Mg−Sn−Hg−Ga anode materials was also discussed.

Hierarchically porous N-doped carbon derived from biomass as oxygen reduction electrocatalyst for high-performance Al–air battery

Developing large-scale and highly efficient oxygen reduction reaction(ORR)catalysts acts a vital role in realizing wide application of metal–air batteries.Here,we propose a gas-foaming strategy to fabricate sustainable and 3D hierarchically porous N-doped carbon with high specific surface area and abundant defects sites derived from biomass.The obtained catalyst exhibits prominent ORR property with higher half-wave potential(0.861 V)and slightly lower kinetic current density(32.44 m A cm^-2),compared to Pt/C(0.856 V and 43.61 m A cm^-1).Furthermore,employing it as catalyst of air cathode,the Al–air battery delivers remarkable discharge performance with excellent power density of 401 m W cm^-2,distinguished energy density of 2453.4 Wh kg^-1 and extremely high open-circuit voltage of 1.85 V among the reported metal–air batteries in the literatures.This gas-foaming strategy for full utilization of biomass affords a chance to explore scalable advanced catalysts in metal–air battery.

AgO/Al_2O_3催化剂选择还原氮氧化物的研究

对浸渍法和水热共沉淀法制备的AgO/Al2O3催化剂进行了选择还原氮氧化物的研究。结果表明:催化剂制备方法对催化剂的催化效果起重要作用,水热共沉淀法制备的AgO/Al2O3催化剂要比浸渍法制备的更有活性;引入不同的还原剂表现出不同的还原性能,水热共沉淀法制备的AgO/Al2O3催化剂具有更强的抗水抗硫性能。AgO与高比表面积Al2O3之间的强相互作用是水热共沉淀法制备的AgO/Al2O3催化剂具有高选择还原活性的原因所在。催化剂表面吸附的氧气很大程度上促进了氮氧化物的选择性氧化过程。

Emerging rechargeable aqueous aluminum ion battery:Status,challenges,and outlooks

Aluminum ion battery(AIB)technology is an exciting alternative for post-lithium energy storage.AIBs based on ionic liquids have enabled advances in both cathode material development and fundamental understanding on mechanisms.Recently,unlocking chemistry in rechargeable aqueous aluminum ion battery(AAIB)provides impressive prospects in terms of kinetics,cost,safety considerations,and ease of operation.To review the progress on AAIB,we discuss the critical issues on aluminum electrochemistry in aqueous system,cathode material design to overcome the drawbacks by multivalent aluminum ions,and challenges on electrolyte design,aluminum stripping/plating,solid-electrolyte interface(SEI)formation,and design of cathode materials.This review aims to stimulate exploration of high-performance AAIB and rationalize feasibility grounded on underlying reaction mechanisms.

固溶温度对Al-Mg-Sn-Ga-Bi合金显微组织及电化学性能的影响

通过扫描电镜、静态腐蚀、电化学腐蚀以及恒流放电测试,研究固溶温度对新型Al-Mg-Sn-Ga-Bi合金显微组织、电化学性能的影响。选择合适温度的固溶处理可以有效调控析出相的形貌、数量和分布,进而显著改善合金的耐蚀性和放电性能。经过540℃固溶处理的合金的自腐蚀速率为0.25 mg/(cm^(2)·min),比铸态合金低一个数量级;在以100 mA/cm^(2)的电流密度放电时,放电电压能达到1.157 V,阳极利用率高达89.49%。

Significantly enhanced oxygen reduction activity of Cu/CuN_xC_y co-decorated ketjenblack catalyst for Al–air batteries

Highly efficient and non-precious catalysts are imperative for oxygen reduction reaction（ORR） to replace Pt/C. Anchoring efficient active species to carbon supports is a promising and scalable strategy. Here we synthesize Cu nanoparticles and noncrystalline CuNxCy species co-decorated ketjenblack（KB） carbon catalyst（denoted as Cu-N-KB-acid） by a facile and scalable method using copper sulfate, melamine, and KB as raw materials. An initial one-pot hydrothermal treatment is designed before pyrolysis process to achieve the good distribution of Cu and melamine on KB via a possible chelation effect. Owing to the synergistic effect of Cu and CuNxCy on KB, this composite catalyst displays excellent ORR catalytic activity in alkaline solution, which is comparable to the commercial 20% Pt/C. When used as a catalyst in a home-made Al-air battery, it shows a stable discharge voltage of 1.47 V at a discharge density of 50 mA cm-2, a little higher than that of Pt/C（1.45 V）.

Al_2O_3 coating for improving thermal stability performance of manganese spinel battery

The synthesis of Al2O3-coated and uncoated LiMn2O4 by solid-state method and fabrication of LiMn2O4/graphite battery were described. The structure and morphology of the powders were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The electrochemical and overcharge performances of Al2O3-coated and uncoated LiMn2O4 batteries were investigated and compared. The uncoated LiMn2O4 battery shows capacity loss of 16.5% after 200 cycles, and the coated LiMn2O4 battery only shows 12.5% after 200 cycles. The uncoated LiMn2O4 battery explodes and creates carbon, MnO, and Li2CO3 after 3C/10 V overcharged test, while the coated LiMn2O4 battery passes the test. The steadier structure, polarization of electrode and modified layer are responsible for the safety performance.

Synthesis and electrochemical properties of Al-doped LiVPO_4F cathode materials for lithium-ion batteries

Al-doped LiVPO4F cathode materials LiAlxV1-xPO4F were prepared by two-step reactions based on a car-bothermal reduction （CTR） process. The properties of the Al-doped LiVPO4F were investigated by X-ray diffraction （XRD）,scanning electron microscopy （SEM）,and electrochemical measurements. XRD studies show that the Al-doped LiVPO4F has the same triclinic structure （space group p-↑1 ） as the undoped LiVPO4F. The SEM images exhibit that the particle size of Al-doped LiVPO4F is smaller than that of the undoped LiVPO4F and that the smallest particle size is only about 1 μm. The Al-doped LiVPO4F was evaluated as a cathode material for secondary lithium batteries,and exhibited an improved reversibility and cycleability,which may be attributed to the addition of Al^3＋ ion by stabilizing the triclinic structure.

Self-standing 3D nanoporous Ag_(2)Al with abundant surface oxygen species facilitating oxygen electroreduction for efficient hybrid Zn battery

The hybrid battery integrating a typical Zn redox battery and a Zn-air battery is a promising green technology for energy storage,and the cathode integrating the redox reaction and electrocatalytic oxygen reduction is a key point for efficient electrochemical energy conversion.Herein,we report a scalable strategy to fabricate nanoporous Ag2 Al internetallic compound as a self-standing cathode for the hybrid Zn battery.The abundant surface oxygen species,the Ag-Al intermetallic interaction and the npAg_(2)Al@AgAlOx interface cooperatively contributed to the catalytic ORR activity.The electrode endows efficient catalytic oxygen reduction(a Tafel slope of 38.0 mV/dec and an onset potential of 0.998 V)and regulated redox activity as compared with Ag.The nanoporous channels allow efficient ion transport,interface charge exchange and gas molecular diffusion.Significantly,the assembled hybrid Zn-Ag_(2) Al/air battery delivers a high capacity of 3.23 mAh/cm^(2) as compared with recent reports.As far as we know,this is the first exploration for the electrochemical property of Ag2 Al,and it would inspire more exploration in developing multifunctional materials and robust hybrid batteries for practical applications.