MnO2

MnO2
  • 文章类型: Journal Article
    水在各种多相催化反应中普遍存在,它很容易被吸附,化学解离,并扩散到催化剂表面,不可避免地影响催化过程。然而,水在这些反应中的具体作用尚不清楚。在这项研究中,我们创新性地提出了在γ-MnO2中H2O驱动的表面晶格氧活化显著增强了低温NH3-SCR。来自水解离的质子激活了γ-MnO2中的表面晶格氧,从而使催化活性加倍(在100°C下实现90%的NO转化率)和显着的稳定性。全面的原位表征和计算表明,质子自发扩散到表面晶格氧减少了质子化氧原子与其相邻Mn原子之间的轨道重叠。因此,Mn-O键被削弱,表面晶格氧被有效激活,以提供可用于将O2转化为O2-的过量氧空位。因此,改善了Mn-H的氧化还原性能,导致增强的NH3氧化-脱氢和NO氧化过程,这对低温NH3-SCR至关重要。这项工作为低温NOx消除中的水促进机制提供了更深入的理解和新的观点。
    Water is ubiquitous in various heterogeneous catalytic reactions, where it can be easily adsorbed, chemically dissociated, and diffused on catalyst surfaces, inevitably influencing the catalytic process. However, the specific role of water in these reactions remains unclear. In this study, we innovatively propose that H2O-driven surface lattice oxygen activation in γ-MnO2 significantly enhances low-temperature NH3-SCR. The proton from water dissociation activates the surface lattice oxygen in γ-MnO2, giving rise to a doubling of catalytic activity (achieving 90% NO conversion at 100 °C) and remarkable stability. Comprehensive in situ characterizations and calculations reveal that spontaneous proton diffusion to the surface lattice oxygen reduces the orbital overlap between the protonated oxygen atom and its neighboring Mn atom. Consequently, the Mn-O bond is weakened and the surface lattice oxygen is effectively activated to provide excess oxygen vacancies available for converting O2 into O2-. Therefore, the redox property of Mn-H is improved, leading to enhanced NH3 oxidation-dehydrogenation and NO oxidation processes, which are crucial for low-temperature NH3-SCR. This work provides a deeper understanding and fresh perspectives on the water promotion mechanism in low-temperature NOx elimination.
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  • 文章类型: Journal Article
    甲醛(HCHO),室内环境中普遍存在的气态污染物,长期暴露会威胁人类健康,必须有效消除。由于其在增强传质和有效暴露活性位点方面的优势,具有三维(3D)互连网络结构的气凝胶有望在环境温度下实现高效稳定的HCHO分解。然而,如何实现过渡金属氧化物的自组装构建高纯度的三维网络气凝胶仍然是一个巨大的挑战。在这里,开发了阳离子诱导的自组装策略,以构建高纯度的自立3D网络二氧化锰气凝胶。阳离子和纳米线表面基团之间的相互作用对于成功的自组装至关重要,这导致纳米线彼此交叉缠绕,形成一个3D结构的网络。K+诱导的3D-MnO2对HCHO表现出优异的催化性能,在环境温度下可以连续稳定地将HCHO分解为CO2和H2O。得益于3D互连网络结构,一方面,它提供了一个大的比表面积和孔隙率,降低传质阻力,促进HCHO和O2分子的吸附。另一方面,更重要的是充分暴露活跃的网站,能产生更多的表面活性氧,实现有效的循环再生。重要的是,3D-MnO2具有很强的捕获和激活大气中水分子的能力,这可以进一步参与补充消耗的羟基。本研究提出了一种通过阳离子诱导自组装过渡金属氧化物的策略,为室温分解VOCs供给了新的催化剂设计办法。
    Formaldehyde (HCHO), a ubiquitous gaseous pollutant in indoor environments, threatens human health under long-term exposure, necessitating its effective elimination. Due to its advantages in enhancing mass transfer and effectively exposing active sites, aerogels with a three-dimensional (3D) interconnected network structure are expected to achieve efficient and stable decomposition of HCHO at ambient temperature. However, how to realize the self-assembly of transition metal oxides to construct high-purity 3D network aerogels is still a huge challenge. Herein, the cation-induced self-assembly strategy was developed to construct high-purity self-standing 3D network manganese dioxide aerogels. The interaction between cations and the surface groups of nanowires is crucial for successful self-assembly, which leads to the cross-winding of nanowires with each other, forming a 3D-structured network. The K+-induced 3D-MnO2 exhibited excellent catalytic performance for HCHO, which could continuously and steadily decompose HCHO into CO2 and H2O at ambient temperature. Thanks to the 3D interconnected network structure, on the one hand, it provides a large specific surface area and porosity, reducing mass transfer resistance and promoting the adsorption of HCHO and O2 molecules. On the other hand, it is more important to fully expose the active sites, which can generate more surface active oxygen species and achieve effective recycling and regeneration. Importantly, 3D-MnO2 has a strong ability to capture and activate water molecules in the atmosphere, which could be further involved in the replenishment of the consumed hydroxyl groups. This study proposes a strategy for self-assembly of transition metal oxides through cation-induction, which provides a new catalyst design approach for the room temperature decomposition of VOCs.
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  • 文章类型: Journal Article
    水中染料过多成为水污染的主要原因,这是非常重要的去除,因为它是有害的。染料污染的水正在通过各种方法进行处理。由于多种技术原因,吸附方法可以认为是研究染料去除的最佳方法。在这项研究中也强调了吸附方法。在目前的工作中,通过在丰富的纤维素番石榴叶粉上生长氧化锰纳米颗粒来制备纳米生物复合材料。这允许以标称成本大量制备纳米复合材料。表征技术证实了氧化锰纳米颗粒在番石榴叶粉上的不规则生长。在氧化锰纳米颗粒与番石榴叶粉的碳结构之间证实了静电和非静电相互作用。发现大量官能团存在于所制备的纳米生物复合材料中。制备的材料的晶粒尺寸在纳米范围内。开发的纳米生物复合材料用于从水中去除亚甲基蓝。这表明对亚甲基蓝具有非常好的吸附能力。分析的吸附数据通过等温线建模,动力学和热力学模型。确定吸附过程的性质是自发的和放热的。对五个吸附-解吸循环进行了可重用性测试。可重用性结果表明,前两个循环的去除效率(%)较好,去除效率(%)仅降低20%。浸出测试结果表明,MnO2/GL在中性pH值下具有良好的稳定性。这是一种独特而廉价的吸附剂,这是以前没有注意到的。
    Excessive number of dyes in water is becoming the main cause of water pollution, which is very important to remove because it is harmful. Dye contaminated water is being treated by various methods. Adsorption method can be considered best for the study of dye removal due to several technological reasons. The adsorption method has also been emphasized in this study. In the present work, a nano-bio-composite was fabricated by growing manganese oxide nanoparticles on abundant cellulosic guava leaf powder. This allows nanocomposite to be prepared in large quantities at nominal cost. The characterization technique confirmed the irregular growth of manganese oxide nanoparticles onto the guava leaf powder. The electrostatic and non-electrostatic interactions was confirmed in between manganese oxide nanoparticles and the carbon structure of guava leaf powder. The massive functional groups were found to be in the prepared nano-bio-composite. The grain size of prepared material was in nano range. The developed nano-bio-composite was used to remove methylene blue from water. This showed a very good adsorptive capacity for methylene blue. The analyzed adsorption data was modelled through isotherms, kinetics and thermodynamics models. The nature of the adsorption process was determined to be spontaneous and exothermic. The reusability test was carried out for five adsorption-desorption cycles. The reusability results suggested the better removal efficiency (%) in the first two cycles with only 20 % reduction in removal efficiency (%). The leaching test result revealed the good stability of MnO2/GL at neutral pH. It was a unique and cheap adsorbent of its kind, which had not been noticed anywhere before.
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  • 文章类型: Journal Article
    由于在高工作电压下令人着迷的额外容量,激活阴离子氧化还原反应(ARR)引起了Li/Na离子电池的极大兴趣。然而,在水性锌离子电池(AZIB)中很少报道ARR,并且尚未探索其在流行的MnO2基阴极中的可能性。在这里,通过低温(140°C)水热法制备了具有中间层“Ca2-支柱”(CaMnO-140)的新型缺锰MnO2微纳米球,其中Mn空位可以通过创建非键合O2p状态来触发ARR,预插层Ca2+可以增强层状结构,并通过形成Ca-O构型来抑制晶格氧的释放。定制的CaMnO-140阴极具有前所未有的高倍率性能(0.1Ag-1时为485.4mAhg-1,10Ag-1时为154.5mAhg-1)和出色的长期循环耐久性(在5000次循环中保持90.6%的容量)。伴随CF3SO3-(来自电解质)吸收/释放的可逆氧氧化还原化学,以及伴随H+/Zn2+共插入/萃取的锰氧化还原,通过先进的同步加速器表征和理论计算来阐明。最后,袋式CaMnO-140//Zn电池具有广阔的应用前景,长寿,宽温度适应性,和高操作安全性。这项研究为通过引发阴离子氧化还原化学来开发AZIB的高能阴极提供了新的视角。
    Activating anionic redox reaction (ARR) has attracted a great interest in Li/Na-ion batteries owing to the fascinating extra-capacity at high operating voltages. However, ARR has rarely been reported in aqueous zinc-ion batteries (AZIBs) and its possibility in the popular MnO2-based cathodes has not been explored. Herein, the novel manganese deficient MnO2 micro-nano spheres with interlayer \"Ca2+-pillars\" (CaMnO-140) are prepared via a low-temperature (140 °C) hydrothermal method, where the Mn vacancies can trigger ARR by creating non-bonding O 2p states, the pre-intercalated Ca2+ can reinforce the layered structure and suppress the lattice oxygen release by forming Ca-O configurations. The tailored CaMnO-140 cathode demonstrates an unprecedentedly high rate capability (485.4 mAh g-1 at 0.1 A g-1 with 154.5 mAh g-1 at 10 A g-1) and a marvelous long-term cycling durability (90.6% capacity retention over 5000 cycles) in AZIBs. The reversible oxygen redox chemistry accompanied by CF3SO3- (from the electrolyte) uptake/release, and the manganese redox accompanied by H+/Zn2+ co-insertion/extraction, are elucidated by advanced synchrotron characterizations and theoretical computations. Finally, pouch-type CaMnO-140//Zn batteries manifest bright application prospects with high energy, long life, wide-temperature adaptability, and high operating safety. This study provides new perspectives for developing high-energy cathodes for AZIBs by initiating anionic redox chemistry.
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  • 文章类型: Journal Article
    二氧化锰由于其丰富的晶体形状,是钠离子电池的理想阳极。然而,它的低电导率,低可逆放电容量,慢扩散动力学,循环稳定性差限制了其工业应用的潜力。各种形态的二氧化锰(MnO2)的设计,比如纳米线,纳米棒,和纳米花,已被证明有效地增强其电化学性能。堆叠纳米线结构是令人感兴趣的,因为它们通过形成互连网络来增加开放空间。从而促进钠离子的有利扩散途径。同时,电解质接触面积的显著增加有效地减轻了由与钠离子的重复迁移和插入相关的体积膨胀引起的应变。在前人研究的基础上,本文介绍了在碳布(CC)上组装的柔性MnO2/聚苯胺(MnO2/PANI)纳米线的结构设计,MnO2改性的创新。与传统的MnO2纳米线相比,MnO2/PANI纳米线表现出增强的结构稳定性和改进的动态性能,从而标志着他们的材料性能的显著进步。该MnO2/PANI复合材料在0.1Ag-1的电流密度下60次循环后表现出约200mAhg-1的倍率容量,并且即使在相同电流密度下200次循环后仍保持182mAhg-1的倍率容量。这项研究不仅为MnO2/PANI纳米线储能的潜在机制提供了新的见解,而且为其作为钠离子电池阳极的进一步开发和优化铺平了道路。从而为研究和应用开辟了新的途径。
    Manganese dioxide is an ideal anode for sodium-ion batteries due to its rich crystal shapes. However, its low conductivity, low reversible discharge capacity, slow diffusion kinetics, and poor cyclic stability limit its potential for industrial application. The design of manganese dioxide (MnO2) with various morphologies, such as nanowires, nanorods, and nanoflowers, has proven effective in enhancing its electrochemical performance. Stacking nanowire structures is of interest as they increase the open space by forming an interconnected network, thus facilitating favorable diffusion pathways for sodium ions. Concurrently, the substantial increase in the electrolyte contact area efficiently mitigates the strain induced by the volume expansion associated with the repetitive migration and insertion of sodium ions. Based on previous research, this work presents the structural design of flexible MnO2/polyaniline (MnO2/PANI) nanowires assembled on carbon cloth (CC), an innovation in MnO2 modification. Compared to conventional MnO2 nanowires, the MnO2/PANI nanowires exhibit enhanced structural stability and improved dynamic performance, thereby marking a significant advancement in their material properties. This MnO2/PANI composite exhibits a rate capacity of approximately 200 mA h g-1 after 60 cycles at a current density of 0.1 A g-1, and maintains a rate capacity of 182 mA h g-1 even after 200 cycles under the same current density. This study not only provides new insights into the underlying mechanisms governing energy storage in MnO2/PANI nanowires but also paves the way for their further development and optimization as anodes for sodium-ion batteries, thereby opening up fresh avenues for research and application.
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  • 文章类型: Journal Article
    通过使用电化学沉积在碳布(CC)(MoO3/rGO/CC)上的MoO3和氧化石墨烯(GO)的复合材料作为阴极,成功开发了一种柔性非对称超级电容器(ASC),将MnO2沉积在作为阳极的CC(MnO2/CC)上,和Na2SO4/聚乙烯醇(PVA)作为凝胶电解质。结果表明,GO层的引入可以显着提高MoO3的比电容从282.7Fg-1增加到341.0Fg-1。此外,这种良好的电极材料和中性凝胶电解质的组合使得在0.5molL-1Na2SO4水溶液中制造具有1.6V的大工作电位差的高性能ASC。此外,ASCs表现出优异的循环能力,6000次循环后电容可保持其初始值的87%。发光二极管可以被ASC点亮的事实表明该装置作为能量存储装置的潜在应用。令人鼓舞的结果表明,MoO3和GO的复合材料在储能器件中具有广阔的应用前景。
    A flexible asymmetric supercapacitor (ASC) is successfully developed by using the composite of MoO3 and graphene oxide (GO) electrochemically deposited on carbon cloth (CC) (MoO3/rGO/CC) as the cathode, the MnO2 deposited on CC (MnO2/CC) as the anode, and Na2SO4/polyvinyl alcohol (PVA) as the gel electrolyte. The results show that the introduction of the GO layer can remarkably increase the specific capacitance of MoO3 from 282.7 F g-1 to 341.0 F g-1. Furthermore, the combination of such good electrode materials and a neutral gel electrolyte renders the fabrication of high-performance ASC with a large operating potential difference of 1.6 V in a 0.5 mol L-1 Na2SO4 solution of water. Furthermore, the ASCs exhibit excellent cycle ability and the capacitance can maintain 87% of its initial value after 6000 cycles. The fact that a light-emitting diode can be lit up by the ASCs indicates the device\'s potential applications as an energy storage device. The encouraging results demonstrate a promising application of the composite of MoO3 and GO in energy storage devices.
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  • 文章类型: Journal Article
    随着可穿戴电子产品和人工智能的迅速发展,电子设备与人体的集成显着进步,导致增强的实时健康监测和远程疾病诊断。尽管在开发具有类似皮肤的机械性能的可拉伸材料方面取得了进展,仍然需要还表现出高光学透明度的材料。超级电容器,作为有前途的储能设备,具有便携性等优点,长循环寿命,和快速充电/放电速率,但是实现高容量,可拉伸性,同时,透明度仍然具有挑战性。这项研究结合了可拉伸的,透明聚合物PEDOT:PSS与MnO2纳米粒子发展高性能,可拉伸,透明超级电容器。PEDOT:PSS膜使用旋涂法沉积在PDMS衬底上,然后电化学沉积MnO2纳米颗粒。该方法确保纳米尺寸的MnO2颗粒均匀分布,保持PEDOT:PSS的透明性和拉伸性。使用LiCl/PVA凝胶电解质将所得的PEDOT:PSS/MnO2纳米颗粒电极聚集到对称装置中,在71.2%的透明度下实现1.14mFcm-2的面积电容,并在20%应变的5000次循环后保持89.92%的电容。这项工作提出了一种可扩展和经济的技术来制造结合高容量的超级电容器,透明度,和机械拉伸性,建议在可穿戴电子产品中的潜在应用。
    With the swift advancement of wearable electronics and artificial intelligence, the integration of electronic devices with the human body has advanced significantly, leading to enhanced real-time health monitoring and remote disease diagnosis. Despite progress in developing stretchable materials with skin-like mechanical properties, there remains a need for materials that also exhibit high optical transparency. Supercapacitors, as promising energy storage devices, offer advantages such as portability, long cycle life, and rapid charge/discharge rates, but achieving high capacity, stretchability, and transparency simultaneously remains challenging. This study combines the stretchable, transparent polymer PEDOT:PSS with MnO2 nanoparticles to develop high-performance, stretchable, and transparent supercapacitors. PEDOT:PSS films were deposited on a PDMS substrate using a spin-coating method, followed by electrochemical deposition of MnO2 nanoparticles. This method ensured that the nanosized MnO2 particles were uniformly distributed, maintaining the transparency and stretchability of PEDOT:PSS. The resulting PEDOT:PSS/MnO2 nanoparticle electrodes were gathered into a symmetric device using a LiCl/PVA gel electrolyte, achieving an areal capacitance of 1.14 mF cm-2 at 71.2% transparency and maintaining 89.92% capacitance after 5000 cycles of 20% strain. This work presents a scalable and economical technique to manufacturing supercapacitors that combine high capacity, transparency, and mechanical stretchability, suggesting potential applications in wearable electronics.
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  • 文章类型: Journal Article
    二维MXenes是微型超级电容器(MSC)的关键高电容电极材料,可满足集成微系统的需求。然而,常规水性电解质(≤1.23V)和对称MXeneMSC(通常≤0.6V)的窄电化学电压窗口基本上限制了它们的输出电压和能量密度。高浓度的水性电解质表现出较低的水分子活性,这抑制了水的分解,从而扩大了工作电压窗口。在这里,我们报道了以MXene(Ti3C2Tx)为负极,以MnO2纳米片为正极(MXene//MnO2-AMSCs),基于高浓度LiCl凝胶准固态电解质的超高压水性平面非对称MSCs(AMSCs).MXene//MnO2-AMSCs具有高达2.4V的高电压,达到53mWhcm-3的超高体积能量密度。此外,面内几何结构和准固态电解质使我们的AMSC的串联/并联连接包中具有出色的机械灵活性和性能均匀性。值得注意的是,基于MXene//MnO2-AMSC的集成微系统,结合太阳能电池和消费电子产品,可以有效地实现同步能量收集,storage,和转换。这项研究的结果为构建基于MXene的高压水性AMSC作为智能集成微系统中的安全和自给自足的微电源提供了见解。
    Two-dimensional MXenes are key high-capacitance electrode materials for micro-supercapacitors (MSCs) catering to integrated microsystems. However, the narrow electrochemical voltage windows of conventional aqueous electrolytes (≤ 1.23 V) and symmetric MXene MSCs (typically ≤ 0.6 V) substantially limit their output voltage and energy density. Highly concentrated aqueous electrolytes exhibit lower water molecule activity, which inhibits water splitting and consequently widens the operating voltage window. Herein, we report ultrahigh-voltage aqueous planar asymmetric MSCs (AMSCs) based on a highly concentrated LiCl-gel quasi-solid-state electrolyte with MXene (Ti3C2T x ) as the negative electrode and MnO2 nanosheets as the positive electrode (MXene//MnO2-AMSCs). The MXene//MnO2-AMSCs exhibit a high voltage of up to 2.4 V, attaining an ultrahigh volumetric energy density of 53 mWh cm-3. Furthermore, the in-plane geometry and the quasi-solid-state electrolyte enabled excellent mechanical flexibility and performance uniformity in the serially/parallel connected packs of our AMSCs. Notably, the MXene//MnO2-AMSC-based integrated microsystem, in conjunction with solar cells and consumer electronics, could efficiently realize simultaneous energy harvesting, storage, and conversion. The findings of this study provide insights for constructing high-voltage aqueous MXene-based AMSCs as safe and self-sufficient micropower sources in smart integrated microsystems.
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  • 文章类型: Journal Article
    作为关键绩效指标,陶瓷的吸水率和机械强度与烧结温度高度相关。较低的烧结温度,虽然有利于陶瓷生产的节能,通常会使所制备陶瓷的致密化程度和吸水率大幅下降和增加,分别。在目前的工作中,0.5wt.%MnO2,作为添加剂,在室温下使用机械搅拌与铝硅酸盐陶瓷混合,获得58.36MPa的弯曲强度和0.05%的吸水率,并同时将烧结温度降低50°C。根据TG-DSC的结果,XRD,MIP,XPS,等。,我们推测MnO2添加剂促进了陶瓷体中水蒸气的消除,有效地抑制了烧结过程中气孔的产生,促进了陶瓷在较低温度下的致密化。这可能是因为在烧结过程中转变为液相的MnO2流入晶粒之间的间隙,去除孔隙内的气体并填充孔隙,抑制气孔的产生和晶粒的异常生长。这项研究证明了一种在铝硅酸盐陶瓷的实际生产中降低孔隙率和提高致密化程度的简单而经济的方法。
    As key performance indicators, the water absorption and mechanical strength of ceramics are highly associated with sintering temperature. Lower sintering temperatures, although favorable for energy saving in ceramics production, normally render the densification degree and water absorption of as-prepared ceramics to largely decline and increase, respectively. In the present work, 0.5 wt.% MnO2, serving as an additive, was mixed with aluminosilicate ceramics using mechanical stirring at room temperature, achieving a flexural strength of 58.36 MPa and water absorption of 0.05% and lowering the sintering temperature by 50 °C concurrently. On the basis of the results of TG-DSC, XRD, MIP, and XPS, etc., we speculate that the MnO2 additive promoted the elimination of water vapor in the ceramic bodies, effectively suppressing the generation of pores in the sintering process and facilitating the densification of ceramics at a lower temperature. This is probably because the MnO2 transformed into a liquid phase in the sintering process flows into the gap between grains, which removed the gas inside pores and filled the pores, suppressing the generation of pores and the abnormal growth of grains. This study demonstrated a facile and economical method to reduce the porosity and enhance the densification degree in the practical production of aluminosilicate ceramics.
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  • 文章类型: Journal Article
    在这项研究中,引入了一种新颖的方法来解决与含水锌离子电池中δ-MnO2的结构不稳定性和缓慢反应动力学相关的挑战。通过利用两性离子甜菜碱(Bet)进行插层,与传统的阳离子插层方法不同,合成了Bet插层MnO2(MnO2-Bet)。Bet中带正电荷的季铵基团与δ-MnO2层中带负电荷的氧原子形成强烈的静电相互作用,增强结构稳定性,防止层坍塌。同时,Bet中带负电荷的羧酸盐基团通过它们的相互作用促进H+/Zn2+离子的快速扩散,从而改善反应动力学。所得的MnO2-Bet阴极显示出高的比容量,优异的倍率能力,快速反应动力学,和延长循环寿命。这种双功能嵌入策略显着优化了δ-MnO2的电化学性能,使其成为高级水性锌离子电池的有前途的正极材料。
    In this study, a novel approach is introduced to address the challenges associated with structural instability and sluggish reaction kinetics of δ-MnO2 in aqueous zinc ion batteries. By leveraging zwitterionic betaine (Bet) for intercalation, a departure from traditional cation intercalation methods, Bet-intercalated MnO2 (MnO2-Bet) is synthesized. The positively charged quaternary ammonium groups in Bet form strong electrostatic interactions with the negatively charged oxygen atoms in the δ-MnO2 layers, enhancing structural stability and preventing layer collapse. Concurrently, the negatively charged carboxylate groups in Bet facilitate the rapid diffusion of H+/Zn2+ ions through their interactions, thus improving reaction kinetics. The resulting MnO2-Bet cathode demonstrates high specific capacity, excellent rate capability, fast reaction kinetics, and extended cycle life. This dual-function intercalation strategy significantly optimizes the electrochemical performance of δ-MnO2, establishing it as a promising cathode material for advanced aqueous zinc ion batteries.
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