Recent Advances on Challenges and Strategies of Manganese Dioxide Cathodes for Aqueous Zinc-Ion Batteries

Aqueous zinc-ion batteries(AZIBs)are regarded as promising electrochemical energy storage devices owing to its low cost,intrinsic safety,abundant zinc reserves,and ideal specific capacity.Compared with other cathode materials,manganese dioxide with high voltage,environmental protection,and high theoretical specific capacity receives considerable attention.However,the problems of structural instability,manganese dissolution,and poor electrical conductivity make the exploration of high-performance manganese dioxide still a great challenge and impede its practical applications.Besides,zinc storage mechanisms involved are complex and somewhat controversial.To address these issues,tremendous efforts,such as surface engineering,heteroatoms doping,defect engineering,electrolyte modification,and some advanced characterization technologies,have been devoted to improving its electrochemical performance and illustrating zinc storage mechanism.In this review,we particularly focus on the classification of manganese dioxide based on crystal structures,zinc ions storage mechanisms,the existing challenges,and corresponding optimization strategies as well as structure-performance relationship.In the final section,the application perspectives of manganese oxide cathode materials in AZIBs are prospected.

Carbon-coated manganese dioxide nanoparticles and their enhanced electrochemical properties for zinc-ion battery applications

In this study, we report the cost-effective and simple synthesis of carbon-coated α-MnOnanoparticles(α-MnO@C) for use as cathodes of aqueous zinc-ion batteries(ZIBs) for the first time. α-MnO@C was prepared via a gel formation, using maleic acid(CHO) as the carbon source, followed by annealing at low temperature of 270 °C. A uniform carbon network among the α-MnOnanoparticles was observed by transmission electron microscopy. When tested in a zinc cell, the α-MnO@C exhibited a high initial discharge capacity of 272 m Ah/g under 66 m A/g current density compared to 213 m Ah/g, at the same current density, displayed by the pristine sample. Further, α-MnO@C demonstrated superior cycleability compared to the pristine samples. This study may pave the way for the utilizing carbon-coated MnOelectrodes for aqueous ZIB applications and thereby contribute to realizing high performance eco-friendly batteries.

Preparation and Application of Manganese Dioxide/Graphene Composite in Lithium Sulfur Batteries

Graphene/manganese dioxide composites and grapheme/manganese dioxide/sulfur(G/MnO2/S) composite cathode were prepared by hydrothermal method and by vapor permeation, respectively. Their structure, morphology and specific surface area were characterized by X-ray diffraction, electron microanalysis and nitrogen adsorption analysis. The composites show morphology of nanosheets, high specific surface area and even distribution of sulfur. The sulfur accounts for 75% in the G/MnO2/S composite by thermogravimetric analysis. The electrochemical performance of G/S and G/MnO2/S cathode were investigated. The G/MnO2/S composite cathodes show excellent rate performance and cycle stability. At a 0.2C current density, initial discharge specific capacity is 1 061 m A·h·g^-1 and maintains 698 m A·h·g^-1 after 100 cycles;At a 1C current density, maximum discharge capacity reaches 816 m A·h·g^-1 and average capacity decreasing rate is only 0.073%/cycle after running over 400 cycles. Electrochemical mechanism of the composites cathodes was analyzed. The sulfur adsorption of Mn O2 inhibited the loss of active material sulfur, so, the electrochemical performance of the complex was improved.

Flexible Zinc-Manganese Dioxide Alkaline Batteries Based on Kelp Electrolytes

Flexible energy-storage devices play a critical role in the development of portable, flexible and wearable electronics. In addition, biological materials including plants or plant-based materials are known for their safety, biodegradability, biocompatibility, environmental benignancy, and low cost. With respect to these advances, a flexible alkaline zinc-manganese dioxide (Zn-MnO2) battery is fabricated with a kelp-based electrolyte in this study. To the best of our knowledge, pure kelp is utilized as a semi-solid electrolyte for flexible Zn-MnO2 alkaline batteries for the first time, with which the as-assembled battery exhibited a specific capacity of 60 mA·h and could discharge for 120 h. Furthermore, the as-assembled Zn-MnO2 battery can be bent into a ring-shape and power a light-emitting diode screen, showing promising potential for the practical application in the future flexible, portable and biodegradable electronic devices.

Manganese Dioxide with High Specific Surface Area for Alkaline Battery

The authors reported a facile method for the synthesis of manganese dioxide without any template and catalyst at a low-temperature. The prepared sample was characterized with X-ray diffraction（XRD）, scanning electron microscopy（SEM）, Brunauer-Emmett-Teller（BET） surface analysis, Fourier transform infrared（FTIR） spectrometry, cyclic voltammetry, alternative current（AC） impedance test and battery discharge test. It is found that the prepared sample belongs to α-MnO2 and has a microsphere morphology and a large BET surface area. The electrochemical characterization indicates that the prepared sample displays a larger electrochemical capacitance than the commercial electrolytic manganese dioxides（EMD） in Na2SO4 solution, and exhibits larger discharge capacity than EMD, especially at a high rate discharge condition when it is used as cathode of alkaline Zn/MnO2 battery.

Oxygen-deficient titanium dioxide supported cobalt nano-dots as efficient cathode material for lithium-sulfur batteries

Lithium sulfur(Li-S)batteries demonstrate great promise for efficient energy storage systems once the lithium polysulfide(LPS)shuttling and sluggish redox kinetics can be well addressed.Herein,we developed a sea urchin-structured oxygen-deficient titanium dioxide semiconductor anchored with cobalt nano-dots(Co@TiO2-x)as a high-performance multifunctional sulfur host material for Li-S batteries.The sea urchin-structured Co@TiO2-x offers strong structural stability and strengthened chemical interaction towards LPS.Meanwhile,the incorporation of Co nano-dots into TiO2 leads to increased oxygen vacancies,which augments the electrical conduction and benefits LPS conversion acceleration as well.As a result,the oxygen vacancy-rich Co@TiO2-x composite exhibits excellent conductivity,strong LPS confinement and promoted sulfur electrochemical kinetics,rendering enhanced LPS shuttling inhibition and rapid redox reaction.Attributed to these features,the Co@TiO2-x/S cathode exhibits a discharge capacity of 803 mAh g-1at 1 C and a good cyclic stability upon 500 cycles with a low capacity fading rate of 0.07%per cycle.This synergistic design of conductive multifunctional LPS barrier is also promising to enlighten the material engineering in other energy storage applications.

Tuning the crystalline and electronic structure of ZrO_(2)via oxygen vacancies and nano-structuring for polysulfides conversion in lithium-sulfur batteries

The recent emergence of tetragonal phases zirconium dioxide(ZrO_(2))with vacancies has generated significant interest as a highly efficient and stable electrocatalyst with potential applications in trapping polysulfides and facilitating rapid conversion in lithium-sulfur batteries(LSBs).However,the reduction of ZrO_(2)is challenging,even under strong reducing atmospheres at high temperatures and pressures.Consequently,the limited presence of oxygen vacancies results in insufficient active sites and reaction interfaces,thereby hindering practical implementation.Herein,we successfully introduced abundant oxygen vacancies into ZrO_(2)at the nanoscale with the help of carbon nanotubes(CNTs-OH)through hydrogen-etching at lower temperatures and pressures.The introduced oxygen vacancies on ZrO_(2-x)/CNTs-OH can effectively rearrange charge distribution,enhance sulfiphilicity and increase active sites,contributing to high ionic and electronic transfer kinetics,strong binding energy and low redox barriers between polysulfides and ZrO_(2-x).These findings have been experimentally validated and supported by theory calculations.As a result,LSBs assembled with the ZrO_(2-x)/CNTs-OH modified separators demonstrate excellent rate performance,superior cycling stability,and ultra-high sulfur utilization.Especially,at high sulfur loading of 6 mg cm^(-2),the area capacity is still up to 6.3 mA h cm^(-2).This work provides valuable insights into the structural and functional optimization of electrocatalysts for batteries.

The Future Trend of E-Mobility in Terms of Battery Electric Vehicles and Their Impact on Climate Change: A Case Study Applied in Hungary

The transportation sector is responsible for 25% of the total Carbon dioxide (CO2) emissions, whereas 60.6% of this sector represents small and medium passenger cars. However, as noted by the European Union Long-term strategy, there are two ways to reduce the amount of CO2 emissions in the transportation sector. The first way is characterized by creating more efficient vehicles. In contrast, the second way is characterized by changing the fuel used. The current study addressed the second way, changing the fuel type. The study examined the potential of battery electric vehicles (BEVs) as an alternative fuel type to reduce CO2 emissions in Hungarys transportation sector. The study used secondary data retrieved from Statista and stata.com to analyze the future trends of BEVs in Hungary. The results showed that the percentage of BEVs in Hungary in 2022 was 0.4% compared to the total number of registered passenger cars, which is 3.8 million. The simple exponential smoothing (SES) time series forecast revealed that the number of BEVs is expected to reach 84,192 in 2030, indicating a percentage increase of 2.21% in the next eight years. The study suggests that increasing the number of BEVs is necessary to address the negative impact of CO2 emissions on society. The Hungarian Ministry of Innovation and Technologys strategy to reduce the cost of BEVs may increase the percentage of BEVs by 10%, resulting in a potential average reduction of 76,957,600 g/km of CO2 compared to gasoline, diesel, hybrid electric vehicles (HEVs), and plug-in hybrid vehicles (PHEVs).

A Binder-Free Amorphous Manganese Dioxide for Aqueous Zinc-Ion Battery

Aqueous zinc-ion battery has attracted much attention due to its low price, high safety, and high theoretical specific capacity. However, most of their performances are limited by the unsatisfied architecture of cathodes. Herein, we fabricated amorphous manganese dioxide by an in situ deposition method. The amorphous manganese dioxide can directly serve as the cathode of an aqueous zinc-ion battery without a binder. The resultant cathode exhibits a high specific capacity of 133.9 mAh/g at 200 mA/g and a capacity retention of 82% over 50 cycles at 1 A/g.

Effects of current density on preparation of grainy electrolytic manganese dioxide

Grainy electrolytic manganese dioxide was prepared by electrodeposition in a 0.9 mol/L MnSO4 and 2.5 mol/LH2SO4 solution. The structure, particle size and appearance of the grainy electrolytic manganese dioxide were determined by powder X-ray diffraction, laser particle size analysis and scanning electron micrographs measurements. Current density has important effects on cell voltage, anodic current efficiency and particle size of the grainy electrolytic manganese dioxide, and the optimum current density is 30 A/dm2. The grainy electrolytic manganese dioxide electrodeposited under the optimum conditions consists of γ-MnO2 with an orthorhombic lattice structure; the grainy electrolytic manganese dioxide has a spherical or sphere-like appearance and a narrow particle size distribution with an average particle diameter of 7.237 μm.

Preparation and electrochemical properties of nanosized tin dioxide electrode material by sol-gel process

Nanosized SnO 2 powders were prepared by sol gel process using inorganic salt as a precursor. The tin oxide powders obtained at different calcinating temperatures (300700 ℃) were investigated by means of X ray diffraction(XRD), infrared spectrum (IR), thermogravimetric analysis (TGA), differential thermal analysis (DTA) and transmission electron microscopy (TEM) as well. The results indicate that well crystallized nanosized SnO 2 powders with a structure of rutile and uniform size about 10 nm can be obtained when the calcinating is carried out at 550 ℃ for 3 h using the method. The electrochemical properties of nanosized SnO 2 powders as anode material for lithium ion batteries were also studied in detail. The results show that nanosized SnO 2 is a candidate of anode material for lithium ion batteries with reversible capacity more than 372 mA·h/g after ten cycles and low voltage for Li + intercalation and de intercalation.

Effects of temperature and concentration of sulfuric acid on the electrodeposition of grainy electrolytic manganese dioxide

The effects of temperature and the concentration of sulfuric acid on the cell voltage, the anode current efficiency of electrodeposition and the particle size of grainy electrolytic manganese dioxide （EMD） were investigated. The structure, particle size and appearance of grainy EMD were determined by powder X-ray diffraction, laser particle size analysis and scanning electron micrograph measurements. As the concentration of sulfuric acid increases, both the cell voltage and the average anode current efficiency decrease. With the increase of electrolysis temperature in the range of 30-60℃, the cell voltage, average anode current efficiency and particle size decrease. The optimum temperature of 30℃ and concentration of sulfuric acid of 2.5 mol/L for electrodeposition of the grainy EMD were obtained. XRD patterns show that the grainy EMD electrodeposited under the optimum conditions consists of γ-MnO2 and has an orthorhombic lattice structure. According to the results of SEM, the grainy EMD has a spherical or sphere-like appearance and a narrow particle size distribution with an average size of about 7μm. The grainy EMD is a promising cathode of rechargeable alkaline batteries for high energy density and a prospective precursor for production of the LiMn2O4 cathode of lithium ion batteries.

Rechargeable Na-MnO_(2) battery with modified cell chemistry

High voltage,high energy density,nominal cycle life,and low cost are the most critical requirements of rechargeable batteries for their widespread energy storage applications in electric vehicles and renewable energy technologies.Na-MnO_(2) battery could be a low-cost contender,but it suffers extensively from its low cell voltage and poor rechargeability.In this study,we modified the conventional cell structure of Na-MnO_(2) battery and established altered cell chemistry through a hybrid electrochemical process consisting of Na striping/plating at the anode and Zn^(2+) insertion/de-insertion along with MnO_(2) dissolution/deposition at the cathode.After the modification,Na-MnO_(2) battery exhibits a discharge capacity of 267.10 mA h/g and a cell voltage of 3.30 V(vs.Na/Na^(+)),resulting in a high specific energy density of 881.43 Wh/kg.After 300 cycles,the battery retains 98% of its first-cycle discharge capacity with100% coulombic efficiency.Besides,Na metal-free battery assembled using sodium biphenyl as a safer anode also delivers an excellent energy density of 810.0 Wh/kg.This work could provide a feasible method to develop an advanced Na-MnO_(2) battery for real-time energy storage applications.

In-situ cation-inserted MnO_(2) with selective accelerated intercalation of individual H^(+) or Zn^(2+) ions in aqueous zinc ion batteries

The recognized energy storage mechanism of neutral aqueous zinc-manganese batteries is the co-insertion/extrusion of H^(+) and Zn^(2+) ions.However,modulating the kinetics of a single H^(+) or Zn^(2+) ion is scarce,which can provide meaningful insights into the energy storage mechanism of Zn ion batteries.Herein,a distinctive doubly electric field in-situ induced cationic anchoring of two-dimensional layered MnO_(2) is successfully constructed to modulate the insertion/extrusion of a single H^(+) or Zn^(2+) ion.As a result,regulating the intercalation of different metal ions can precisely achieve the accelerated induction for the individual H^(+) or Zn^(2+) ions intercalation/deintercalation.Moreover,the introduction of metal ions stabilizes the lattice distortion and alleviates the irreparable structural collapse,leading to an increase in the H^(+)/Zn^(2+) storage sites,efficiently diminishing the stagnation of the ordered structure and creating the more open channels,which is conducive to facilitating the diffusion of ions.This work delivers some innovative insights into pre-embedding strategies,and also serves as a precious reference for the cathode development of advanced aqueous batteries.

Engineered nitrogen doping on VO_(2)(B)enables fast and reversible zinc-ion storage capability for aqueous zinc-ion batteries

Vanadium-based compounds with high theoretical capacities and relatively stable crystal structures are potential cathodes for aqueous zinc-ion batteries(AZIBs).Nevertheless,their low electronic conductivity and sluggish zinc-ion diffusion kinetics in the crystal lattice are greatly obstructing their practical application.Herein,a general and simple nitrogen doping strategy is proposed to construct nitrogen-doped VO_(2)(B)nanobelts(denoted as VO_(2)-N)by the ammonia heat treatment.Compared with pure VO_(2)(B),VO_(2)-N shows an expanded lattice,reduced grain size,and disordered structure,which facilitates ion transport,provides additional ion storage sites,and improves structural durability,thus presenting much-enhanced zinc-ion storage performance.Density functional theory calculations demonstrate that nitrogen doping in VO_(2)(B)improves its electronic properties and reduces the zinc-ion diffusion barrier.The optimal VO_(2)-N400 electrode exhibits a high specific capacity of 373.7 mA h g^(-1)after 100 cycles at 0.1 A g^(-1)and stable cycling performance after 2000 cycles at 5 A g^(-1).The zinc-ion storage mechanism of VO_(2)-N is identified as a typical intercalation/de-intercalation process.

一维多孔二氧化钛@碳纳米纤维复合材料的制备及储钠应用

通过静电纺丝法和浓碱水热刻蚀法原位制备出具有片状分枝结构的一维多孔二氧化钛@碳纳米纤维(P-TiO_(2)@CNFs)复合材料,并将其作为钠离子电池的负极材料。P-TiO_(2)@CNFs的片状分枝结构能够有效缩短离子扩散路径并增加电解液与活性物质的接触面积;多孔结构提供了更多的反应活性位点,从而加快了电荷转移动力学;二氧化钛与碳纳米纤维之间的化学键能够增加复合材料的结构稳定性。实验对P-TiO_(2)@CNFs的表面形貌、微观结构、晶体结构、比表面积、孔径、元素价态等进行了分析,并在新威尔电池测试系统上进行恒电流充放电测量和倍率性能测试,实验结果表明P-TiO_(2)@CNFs表现出优异的循环性能和倍率性能,在2.0A/g的电流密度下循环2000次仍能保持197mAh/g的比容量,在超大电流密度30.0A/g下电极仍然能够保持61.7mAh/g的比容量。

缓慢水解法制备纳米TiO_(2)及其作为锂离子电池负极材料的电化学性能研究

以四氯化钛为原料,在冰水浴,弱碱性条件下,将TiCl_(4)配制为0.5 mol/L水溶液,低温水解得到沉淀产物,将此沉淀在80℃的真空烘箱中干燥;低温400℃下焙烧12 h得到白色粉末。通过X射线衍射(XRD)进行结构表征;通过扫描电子显微镜(SEM)透射电镜(TEM)进行形貌表征。得到的烧结产物,结合金属锂对电极材料和聚乙稀隔膜搭建半电池系统,进行电池性能测试。结果表明,以四氯化钛为原料在低温的条件下实现缓慢水解,再经过长时间低温焙烧得到白色粉末为纳米级金红石型和锐钛矿型TiO_(2)的混合相,且具有粒径小、分散性好、粒径分布窄、球形度较好等优点;此产品在0.05充放电时首次放电比容量为370 mAh/g, 5 C的放电比容量达到69 mAh/g,容量保持率分别为91.69%,电化学性能远高于商业化TiO_(2)。研究表明,基于缓慢水解低温烧结机制制备TiO_(2)的方法是一种简单、低成本、适用于大规模生产的工艺。

椰壳碳@MnO_(2)纳米材料在水系锌离子电池中的应用

为解决MnO_(2)材料在水系锌离子电池(ZIBs)中存在的导电性差、材料利用率低等问题,以农业废弃物椰壳为原料,将低成本、来源丰富、绿色可再生的生物质资源引入到电极材料中,通过高温碳化得到导电性优异的椰壳碳,用水热法在椰壳碳表面生长MnO_(2)纳米粒子,获得椰壳碳@MnO_(2)复合纳米材料。借助扫描电子显微镜(SEM)、X射线衍射仪(XRD)、电化学技术等表征测试手段,分析该复合材料的形貌结构以及电化学性能。结果表明椰壳碳@MnO_(2)在100 mA g^(-1)的电流密度下,经过300次循环,比容量仍高达到344.6 mA h g^(-1),性能远高于商用MnO_(2)材料(64.3 mA h g^(-1));椰壳碳@MnO_(2)优异的导电性,纳米化的结构设计提高了材料利用率,减少了离子扩散路径,带来更快的离子扩散速率,提高了材料的倍率性能,具有良好的应用前景。

沙漠光伏电能外送技术综述

充分利用可再生能源是我国实现助力“双碳”目标的重要保障,然而,由于集中式光伏处于沙漠地区,光伏电能输送成为制约光伏发展的瓶颈问题。运输电池技术作为输送电能途径可为现有沙漠电能输送提供新的选择。首先,从沙漠集中式光伏输电方式的角度,重点讨论了现有的沙漠光伏输电的实际运行情况,分析了电池运输技术的工作原理;然后,整理了传统沙漠光伏输电和运输电池技术在投资成本、输电容量及应对沙漠气候能力等方面的差异;最后,论述了运输电池技术具有建设成本低、应对沙漠气候能力强等优势,以及存在的局限性。

超临界二氧化碳-高温热泵联合储能发电系统设计及分析

为解决可再生能源间歇性和波动性导致的电力供需不匹配问题,提出了一种基于超临界二氧化碳(S-CO_(2))循环和高温热泵的联合循环储能发电系统,该系统是卡诺电池形式的一种创新探索。通过熔盐储热装置和水储冷装置实现能量交换,有效联合了热泵循环加热过程和S-CO_(2)循环发电过程,获得了较高的储能发电系统往返效率。模拟计算了联合循环的典型工况参数和热力性能,分析了S-CO_(2)循环中主要参数对系统整体效率的影响。结果表明:提高膨胀机入口温度有助于提高整体循环效率,系统最优往返效率可达62.8%,同时储热熔盐需求量减少;提高主压缩机入口气体参数可使系统效率达到极限值,超过该值后整体循环效率不再提高;主再压缩机分流比为0.35时系统效率达到最优;确定了S-CO_(2)循环系统最佳运行工况,比同工况下简单布雷顿系统往返效率高7.98%。