Difficulties, strategies, and recent research and development of layered sodium transition metal oxide cathode materials for high-energy sodium-ion batteries

Energy-storage systems and their production have attracted significant interest for practical applications.Batteries are the foundation of sustainable energy sources for electric vehicles(EVs),portable electronic devices(PEDs),etc.In recent decades,Lithium-ion batteries(LIBs) have been extensively utilized in largescale energy storage devices owing to their long cycle life and high energy density.However,the high cost and limited availability of Li are the two main obstacles for LIBs.In this regard,sodium-ion batteries(SIBs) are attractive alternatives to LIBs for large-scale energy storage systems because of the abundance and low cost of sodium materials.Cathode is one of the most important components in the battery,which limits cost and performance of a battery.Among the classified cathode structures,layered structure materials have attracted attention because of their high ionic conductivity,fast diffusion rate,and high specific capacity.Here,we present a comprehensive review of the classification of layered structures and the preparation of layered materials.Furthermore,the review article discusses extensively about the issues of the layered materials,namely(1) electrochemical degradation,(2) irreversible structural changes,and(3) structural instability,and also it provides strategies to overcome the issues such as elemental phase composition,a small amount of elemental doping,structural design,and surface alteration for emerging SIBs.In addition,the article discusses about the recent research development on layered unary,binary,ternary,quaternary,quinary,and senary-based O3-and P2-type cathode materials for high-energy SIBs.This review article provides useful information for the development of high-energy layered sodium transition metal oxide P2 and O3-cathode materials for practical SIBs.

Designing ultrastable P2/O3-type layered oxides for sodium ion batteries by regulating Na distribution and oxygen redox chemistry

P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.

Ca_(2)MnO_(4)-layered perovskite modified by NaNO_(3)for chemical-looping oxidative dehydrogenation of ethane to ethylene

Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions.

Inhibiting Voltage Decay in Li-Rich Layered Oxide Cathode:From O3-Type to O2-Type Structural Design

Li-rich layered oxide(LRLO)cathodes have been regarded as promising candidates for next-generation Li-ion batteries due to their exceptionally high energy density,which combines cationic and anionic redox activities.However,continuous voltage decay during cycling remains the primary obstacle for practical applications,which has yet to be fundamentally addressed.It is widely acknowledged that voltage decay originates from the irreversible migration of transition metal ions,which usually further exacerbates structural evolution and aggravates the irreversible oxygen redox reactions.Recently,constructing O2-type structure has been considered one of the most promising approaches for inhibiting voltage decay.In this review,the relationship between voltage decay and structural evolution is systematically elucidated.Strategies to suppress voltage decay are systematically summarized.Additionally,the design of O2-type structure and the corresponding mechanism of suppressing voltage decay are comprehensively discussed.Unfortunately,the reported O2-type LRLO cathodes still exhibit partially disordered structure with extended cycles.Herein,the factors that may cause the irreversible transition metal migrations in O2-type LRLO materials are also explored,while the perspectives and challenges for designing high-performance O2-type LRLO cathodes without voltage decay are proposed.

Long-lasting growth regulation on cotton using mepiquat chloride adsorbed layered double hydroxide

Mepiquat chloride(1,1-dimethyl piperidinium chloride,DPC)is a representative plant growth regulator which can regulate the source-sink relationship for yield increase and shape ideal plant type for mechanical cultivation.Here we show a DPC adsorbed layered double hydroxide(DPC-LDH)architecture with enhanced controlled release property and soil distribution.By drip irrigation on cotton,it makes total dosage of DPC reduced from 270 to 90 g/ha,while the frequency decreased from 5 to 2 times.The unique supramolecular interaction is confirmed as the basis of controlled release behavior.Moreover,except for the physical resistance to the sedimentation brought by the lamellar LDH,the enhanced electrostatic interaction makes DPC-LDH the dominant distribution in soil.It improves the efficiency of DPC molecules absorbed by cotton plants and greatly saves the inputs in labor and chemicals.This method is expected to achieve the yield increase and agricultural sustainability by energy saving and emission reduction.

新生态MnO_2对水溶性阴离子染料废水的脱色研究

以各种水溶性染料,包括直接染料、酸性媒介染料、活性染料的废水为实验对象,系统研究了新生态MnO2在染料废水脱色过程中的作用。结果表明,受试染料的脱色效果均十分显著,最佳pH≤2.5,脱色作用的机理在于MnO2的表面羟基在酸性条件下发生质子化,可以与阴离子染料以库仑力结合而将其吸附除去。

超级电容器电极材料纳米α-MnO_2的制备及性能研究

用溶胶-凝胶法和沉淀法制备了具有纳米结构的α-MnO2,分别对其进行X-射线衍射(XRD)、扫描电镜(SEM)、循环伏安(CV)等测试,结果发现溶胶-凝胶法所合成的材料是由粒径为60nm的微粒组成,沉淀法所合成的材料粒径在80nm范围.并研究了不同配比的α-MnO2和活性炭组成的复合电极在各种浓度的电解液中的循环伏安性能,发现当电极中α-MnO2质量百分含量为40%～60%时,在0.5mol/LNa2SO4、2.0mol/L(NH4)2SO4、1.0mol/LKCl溶液中的比电容较高,其中在2.0mol/L(NH4)2SO4溶液中的比电容最高可达108.26F/g.

水热温度对MnO_2纳米线结构和电容性能的影响

以KMn O4和Mn SO4为原料,采用水热法合成超级电容器电极材料纳米MnO_2,采用X射线衍射（XRD）、扫描电镜（SEM）、比表面积测试、循环伏安、恒流充放电和电化学阻抗等方法测试MnO_2的结构和电容性能。结果表明,采用水热法可以合成直径为10~90 nm,长度为1~3 cm的α-MnO_2纳米线;水热温度对MnO_2纳米线的晶粒和形貌影响显著,但不改变MnO_2的晶型;随水热温度升高,MnO_2纳米线的晶粒逐渐长大,同时变长变粗,导致比表面逐渐降低;MnO_2纳米线的比电容随水热温度升高呈先增大后减小,当水热温度为140℃时比电容最大,为227 F/g,同时表现出良好的倍率性能。

空气条件下高温固相合成层状LiMnO_2及其离子交换的影响规律

在空气中高温固相反应合成了层状单斜结构前驱体 Na Mn O2 ,在不同条件下进行离子交换反应 ,得到Li Mn O2 .用 X射线衍射法表征了前驱体及交换产物的晶体结构 ,用电感耦合等离子体光谱进行元素含量分析 ,用扫描电镜测定晶体的形貌 .结果表明 ,离子交换反应条件对反应速率和产物的晶体结构与组成有重要影响 .

碱性Zn/MnO_2电池的技术进步与发展潜力(1)

介绍了近年来碱性Zn／MnO2电池的工艺进展，在正极中使用高活性MnOZ2较细的石墨粒子；在负极中使用细粒径Zn粉合金，去Hg、Cd、Pb，以及适宜的胶凝剂、缓蚀剂；在简壳上减小筒壁厚度，使用适宜涂层；使用多孔更薄加有表面活性剂的隔膜；以及其他可提高碱性Zn／MnO2电池性能的措施。指明碱性Zn／MnO2电池仍有较大的发展潜力。

非层状二维γ-In_(2)Se_(3)的各向异性生长及其光学特性

非层状二维(2D)γ-In_(2)Se_(3)具有优异的光学和电学性能,在超薄柔性器件和光电探测领域具有广泛的应用前景.然而,相较于层状的类石墨烯材料,非层状材料固有的各向同性化学键,使得其二维各向异性生长面临较大的挑战.本研究构建了一种新的化学气相沉积(CVD)生长策略,成功制备了高质量的2Dγ-In_(2)Se_(3).首次选用低熔点的铟粉为前驱体,有效降低了生长温度.此外,生长过程去除了CVD法合成二维硒化物时不可避免的危险气体H_(2),这不仅能有效抑制InSe副产物的形成,还降低了实验危险性.通过探究原料用量、生长温度及时间等参数对样品形貌和厚度的影响,获得了最佳生长窗口.详细表征了2Dγ-In_(2)Se_(3)的微观形貌、化学组分、晶体结构和光学特性等.结果表明,样品具有强烈的光致发光(PL)效应,与γ-In_(2)Se_(3)的直接带隙属性相吻合.随着厚度的减小,PL峰会发生蓝移,说明光学带隙随之增大.Raman光谱显示,不同厚度的样品其特征峰也会发生移动,说明厚度会影响2Dγ-In_(2)Se_(3)的分子振动行为.由此可见,通过生长参数调控2Dγ-In_(2)Se_(3)的厚度,可实现对其光学带隙和分子振动行为的调控,这将为相关的理论研究和光电器件应用提供基本的材料平台.

电沉积法制备PANI/MnO_2/石墨烯复合材料及其电化学性能研究

采用简便的脉冲电沉积方法一步合成了呈现层-层分布的三维立体结构的PANI/MnO_2/石墨烯三元复合材料,利用XRD和FT-IR等研究了复合物的结构和组成,SEM和TEM表征了复合物的形貌。同时,通过恒流充放电和循环伏安测试研究了该复合物的电化学性能。结果表明,0.5 A·g^(–1)电流密度下的比容量可达1 120 F·g^(–1),且1 000次循环的稳定性高达99%。出色的超电容性能主要源于石墨烯作为基体,其上均匀分布棒状结构的PANI,MnO_2纳米粒子均匀分布于PANI纳米棒上,形成了一种分级的特殊结构。

超级电容器用(RuO_2/MnO_2)·n H_2O复合电极的研究

采用电沉积法制备超级电容器用钽基(RuO_2/MnO_2)·n H_2O复合薄膜电极材料,制定钽箔基体的预处理方法、复合溶液主盐的配置比例、电沉积参数和热处理参数。重点研究了初始沉积液中Mn^(7+)与Ru^(3+)摩尔浓度比以及不同热处理参数对((RuO_2/MnO_2)·n H_2O复合薄膜附着力与电学性能的影响。借助扫描电镜、X射线衍射仪对薄膜的形貌和物相分析,用电化学工作站对该复合薄膜电化学性能进行测量。实验结果表明,当初始沉积液中Mn^(7+)与Ru^(3+)摩尔比为3:1,热处理温度为250℃,时间为2.5h,所制备出的复合电极薄膜具有较好的附着力和较高的比电容,分别为14.8MPa与418F/g。该复合薄膜在不同扫描速率下的循环伏安图具有高度可逆的氧化和还原曲线,说明其具有很明显的电容特性,是一种较为理想的RuO_2基复合薄膜。

新型稀土固体超强酸SO_4^(2-)/MnO_2/La^(3+)的合成研究

以硫酸锰和硝酸镧为原料,采用共沉淀-浸渍法制备不同比例的SO^(2-)_4/MnO_2/La^(3+)。以催化合成乙酸苄酯为探针反应,考察H_2SO_4浓度、La(NO_3)_3的质量分数、焙烧温度、焙烧时间等因素对其催化活性的影响。结果表明,催化剂制备的最佳条件为:硝酸镧的加人为硫酸锰的3%(质量分数),浸渍浓度为1 mol·L^(-1)的H_2SO_4,焙烧温度为450℃,焙烧时间3 h,酯化率到达最大,为89.7%。

λ-MnO_2及掺杂λ-MnO_2在LiNO_3电液中的电化学性质研究

利用恒电流放电、循环伏安、ＩＣＰ、ＸＲＤ 等技术研究了λＭｎＯ２ 及掺铋、掺钡λＭｎＯ２ 在５ ｍｏｌ·Ｌ－ １ＬｉＮＯ３ 水溶液中的放电性能。得出λＭｎＯ２ 在中性电液中的恒电流放电曲线为三个明显的放电平台，放电机理与λＭｎＯ２ 在有机电液中的放电机理相似。循环伏安测试表明放电的可逆性差，经过掺杂后样品在ＬｉＮＯ３ 中的循环性有一定的改善。

负载纳米MnO_2针织物分解溶液中甲醛效率分析

以高锰酸钾和乙醇为原料采用原位液相沉淀法制备了负载纳米MnO_2针织物,通过红外光谱、X-射线衍射光谱和扫描电镜对负载纳米MnO_2针织物进行了表征,分析了负载次数、甲醛初始浓度、反应时间、洗涤次数和重复使用对甲醛分解效率的影响。结果表明,负载纳米MnO_2针织物对甲醛具有较优的氧化分解性能;室温条件下,负载7次纳米MnO_2针织物17 h后即可将浓度为5.00 mg/L甲醛溶液中的甲醛全部分解去除;负载5次纳米MnO_2针织物反应24 h,甲醛去除率为96.5%,且随反应时间延长,所有样品都可将甲醛分解去除;经10次水洗后MnO_2脱落量较小,重复试验结果表明负载纳米MnO_2针织物可循环重复利用。

不同形貌MnO_2的制备及其电化学性能

用化学共沉淀法和水热法制备了海胆型和纳米线型的MnO_2。采用X射线衍射仪（XRD）、扫描电镜（SEM）对电极材料的物相和形貌进行表征。采用电化学阻抗、循环伏安和恒电流充放电对其进行电化学性能测试。结果表明，采用相同材料不同制备方法得到的MnO_2具有不同的形貌。化学共沉淀法制备的海胆型MnO_2，其直径约为300～500nm；水热法制备的纳米线型MnO_2，其直径约为10～30nm，长度约为100～500nm。两种形貌的MnO_2在6mol·L^-1KOH溶液中具有良好的电容特性，1A·g^-1的电流密度下，海胆型MnO_2的比电容为539F·g^-1；纳米线型MnO_2的比电容为375F·g^-1经过1000圈的循环后，海胆型MnO_2仅损失了15％的比容量。

α-MnO_2/石墨烯纳米复合物的合成及其电化学性能研究

通过回流原位复合方法制备了α-MnO2/石墨烯纳米复合物。通过X-射线衍射(XRD)和热重方法分别对样品进行晶体结构分析和石墨烯含量的计算。采用恒流充放电和交流阻抗法研究石墨烯的添加对α-MnO2负极材料电化学性能的影响,结果表明,在本实验条件下,添加13.5%石墨烯的纳米复合物具有最优的电化学性能,在电流密度为50mA/g时,循环15周之后,充放电容量分别比纯α-MnO2提高了94mAh/g和117mAh/g。随着石墨烯添加量的增加,复合电极的电荷转移电阻减小,交换电流密度增加,有利于电化学反应的进行。

超级电容器用MnO_2基纳米复合材料的进展

介绍二氧化锰(MnO_2)的结构及储能机理,综述近年来MnO_2作为赝电容材料,通过不同材料改性,以提高电化学性能的研究进展。这些材料主要有碳材料、导电聚合物、金属和金属氧化物/硫化物等。展望由MnO_2基纳米复合材料构建的核壳结构的发展趋势。

In sight of K-deficient layered K_(x)MnO_(2) cathode for potassium-ions batteries

Potassium-ions batteries(PIBs)are attracting increasing attention as up-and-coming youngster in largescale grid-level energy storage benefiting from its low-cost and high energy density.Nevertheless,enough researches regarding indispensable cathode materials for PIBs are badly absent.Herein,we synthesize K-deficient layered manganese-based oxides(P2-K_(0.21)MnO_(2) and P3-K_(0.23)MnO_(2))and investigate them as cathode of PIBs for the first time.As the newcomer of potassium-containing layered manganese-based oxides(K_(x)MnO_(2))group,P2-K_(0.21)MnO_(2) delivers high discharge capacity of 99.3 mAh g^(-1) and P3-K_(0.23)MnO_(2) exhibits remarkable capacity retention rate of 75.5%.Besides,in-situ XRD and ex-situ XRD measurements reveal the reversible phase transition of P2-K_(0.21)MnO_(2) and P3-K_(0.23)MnO_(2) with the potassium-ions extraction and reinsertion,respectively.This work contributes to a better understanding for the potassium storage in K-deficient layered K_(x)MnO_(2)(x≤0.23),possessing an important basic scientific significance for the exploitation and application of layered K_(x)MnO_(2) in PIBs.