三维多孔铜和锌镀层协同构筑无枝晶锂金属电极

金属锂具有高理论比容量和低氧化还原电位, 被认为是高能量密度二次电池最理想的负极材料之一, 但其在循环过程中的枝晶生长和体积变化易造成电池失效和安全隐患. 以孔径为5 μm左右的自制三维多孔铜为基底, 在其表面电沉积锌层(3D Cu@Zn), 作为金属锂沉积的集流体, 构筑无枝晶锂金属电极. 三维多孔铜的孔结构稳定, 孔径大小适宜, 可有效降低局部电流密度和缓解体积变化. 锌镀层可降低锂金属的形核过电位, 诱导锂的均匀沉积, 有效抑制锂枝晶生长. 以3D Cu@Zn为集流体, 锂沉积面积容量为4 mAh•cm^–2, 电极表面仍无枝晶出现, 经过锂剥离后表面仍然光滑; 而铜箔上沉积的锂显示明显的枝晶和不均匀性, 3D Cu上沉积的锂显示局部不均匀性和一定量枝晶. 在电流密度为0.5和 1 mA•cm^–2, 面积容量为1 mAh•cm^–2条件下, Li||3D Cu@Zn半电池获得了稳定的库伦效率; 在2 mA•cm^–2的高电流密度和1 mAh•cm^–2的面积容量条件下, Li||3D Cu@Zn@Li对称电池可稳定循环700 h以上; 以3D Cu@Zn@Li为负极, LiFePO₄为正极的全电池, 在1 C倍率下, 经过150次循环后仍保持88 mAh•g^–1的容量, 均明显优于Cu片和3D Cu作为集流体的锂金属电极.     

纳米铜修饰三维锌网电极的制备及锌离子电池负极的电化学性能

设计构建了纳米铜修饰的三维锌网电极(Nano Cu@3D Zn Mesh, 简称3D Cu-Zn电极), 并将其作为锌沉积的宿主材料用作锌离子电池的负极, 获得了稳定的、 具有长循环寿命的锌负极材料. 3D Cu-Zn电极的三维(3D)锌网骨架和表面均匀分布的3D树枝状纳米铜可以降低局部电流密度, 并为锌的沉积提供结构支撑和容纳空间. 锌网表面具有的较强锌结合能力的铜和后续原位形成的铜锌合金, 可以有效降低锌形核的过电势, 并作为均匀分布的形核位点引导锌的均匀成核和沉积. 这种3D Cu-Zn电极宿主材料表现出较低的形核过电势和界面阻抗, 并在对称电池中表现出优异的循环稳定性, 在0.5 mA/cm²的电流密度下可以稳定循环超过1100 h. 3D Cu-Zn电极与MnO₂组装的全电池表现出更小的极化、 良好的倍率性能和循环性能.     

单液流锌镍电池锌负极性能及电池性能初步研究

对单液流锌镍电池锌电极在电解液流动状态下,电沉积锌形貌随电流密度的变化进行表征,结果表明,随充电电流密度的增大电沉积锌层逐渐致密化,没有枝晶生成.组装了容量为2Ah的电池,并进行长时间充放电性能研究.测试结果该电池的平均充电电压为1.84 V,平均放电电压1.65 V,平均库仑效率达到96%,能量效率达到了86%.     

电化学法制备Ni-W-P纳米线阵列电极及其催化析氢性能

采用二次氧化法制备了多孔阳极氧化铝(AAO)模板, 通过控制电位沉积技术在AAO模板内组装了Ni-W-P合金纳米线阵列. 在扫描电子显微镜(SEM)下观察到Ni-W-P纳米线表面光滑, 长约20 μm, 直径均匀(约为100 nm), 与AAO模板孔径基本一致. 阴极极化曲线和交流阻抗图谱(EIS)的测试结果表明, Ni-W-P合金纳米线阵列电极析氢反应(HER)电阻减小, 具有更高的催化析氢活性, 电流密度为10 mA·cm^-2时, 析氢极化电位较Ni-W-P合金电极正移约250 mV.     

水系锌电池Se@Zn负极的制备及性能

采用原位化学反应策略,在Zn电极表面生长出Se单质,通过XRD、XPS、SEM和能谱表征,结果表明Se在Zn电极表面的成功合成,且Se在锌电极表面均匀分布。将Se@Zn电极和裸Zn电极分别组装为对称电池和以MnO₂为正极的全电池进行性能比较,结果表明,Se@Zn对称电池在1 mA/cm²下可以运行1000小时以上,并保持27 mV的极化电压。Se@Zn||MnO₂全电池在2 A/g电流密度下容量为136 mA·h/g,在1000次循环后,Se@Zn||MnO₂全电池仍接有近100%的库仑效率,容量保持率为88%。     

轻质三维多孔泡沫铝用作高性能锂金属负极骨架

将轻质、三维多孔且亲锂的泡沫铝用作锂(Li)金属负极骨架,通过简单的机械挤压方法,将泡沫铝与金属Li复合,制得Al@Li复合负极。泡沫铝自身的高亲锂性,能够为Li金属成核提供丰富且均匀的活性位点,诱导Li在泡沫铝内部的快速成核和均匀电沉积。同时,泡沫铝的三维多孔结构,可以容纳Li金属负极在充放电过程中的巨大体积应变,降低局部电流密度,从而有效抑制Li枝晶的生长。因此,与纯Li金属负极相比,所获得的Al@Li复合负极在对称电池和LiFePO₄||Al@Li半电池中,均表现出了更加优异的循环稳定性。     

碳布负载高致密Sn/SnBi合金的电催化CO2还原性能

通过分步电沉积法制备碳布(CC)负载高致密Sn/SnBi合金催化剂：首先在CC上电沉积致密Sn颗粒,而后利用酸性电解液部分溶解Sn为Sn²⁺离子,实现在Sn颗粒表面共沉积SnBi合金枝晶,随后经过原位化学氧化及电化学还原步骤将SnBi合金枝晶转变为SnBi合金纳米颗粒(SnBi NPs)。得益于Sn提供形核位点,SnBi枝晶在碳织物表面垂直致密生长,并通过后续氧化还原转化实现了直径约20 nm的SnBi合金颗粒在CC上致密均匀生长。CC/Sn/SnBi NPs三维电极在-1.08 V(vs RHE)下显示出较高的电催化还原CO₂活性,电流密度高达36 mA·cm^-2且甲酸盐产物选择性为94.9%。同时,在连续12 h恒电压测试中性能未发生衰减,表明电极具有良好的稳定性。     

亲锂的三维二硫化锡@碳纤维布用于稳定的锂金属负极

金属锂由于其高的比容量,低的电极电势和轻质等特点被认为是下一代高能量密度锂金属二次电池负极材料的最佳选择。然而,充放电循环中不均匀的锂沉积会导致严重的体积变化和大量的锂枝晶形成,从而影响了电池的库伦效率甚至会带来严重的安全隐患。为此,本文设计了一种亲锂的三维二硫化锡@碳纤维布复合基底材料,并作为集流体将其应用于金属锂电池上。一者,高比表面积的三维碳纤维骨架可以适应充放电过程中的体积变化并且有效地降低局部电流密度,从而确保锂的均匀沉积。二者,表面修饰的SnS2层在锂沉积过程中可以形成Li-Sn合金界面层,诱导锂的沉积并降低过电势。最终,实验结果表明:使用所制备的复合集流体与金属锂搭配组成的半电池可以在5 mA·cm^-2的高电流密度下以>98%的库伦效率稳定循环100周以上。此外,在承载10 mAh·cm^-2的金属锂后,复合的锂负极无论是在对称电池还是与磷酸铁锂组装成的实际电池中,均可以在高的电流密度下实现稳定的循环。我们相信这一复合的集流体构建策略对于设计安全稳定的锂金属电池或器件具有重要意义。     

轻质三维多孔泡沫铝用作高性能锂金属负极骨架

将轻质、三维多孔且亲锂的泡沫铝用作锂(Li)金属负极骨架,通过简单的机械挤压方法,将泡沫铝与金属 Li复合,制得Al@Li复合负极。泡沫铝自身的高亲锂性,能够为Li金属成核提供丰富且均匀的活性位点,诱导Li在泡沫铝内部的快速成核和均匀电沉积。同时,泡沫铝的三维多孔结构,可以容纳Li金属负极在充放电过程中的巨大体积应变,降低局部电流密度,从而有效抑制Li枝晶的生长。因此,与纯Li金属负极相比,所获得的Al@Li复合负极在对称电池和LiFePO₄||Al@Li半电池中,均表现出了更加优异的循环稳定性。     

水系锌离子电池负极集流体关键问题及设计策略

水系锌离子电池具有成本低廉、环境友好、安全、能量密度较高等特点,有望应用于大规模电化学储能装置.然而,目前使用的商业化锌箔负极相对正极活性材料大大过量,显著降低了电池的能量密度,且存在严重的穿孔和极耳脱落等问题.使用集流体负载锌作为负极可有效提高放电深度,同时避免电极穿孔失效.但是,集流体界面易产生锌枝晶与副反应,严重影响电池的循环寿命.本综述首先分析了锌枝晶与副反应的产生原因及其对锌负极电化学性能的影响,并从集流体材料成分选择与结构构建两方面总结了锌负极集流体的设计思路,包括选择亲锌性材料、设计择优取向基底与构建三维集流体结构.设计合适的集流体可有效调控锌金属的沉积与剥离行为,从而推进水系锌离子电池的实用化.     

The Three‐Dimensional Dendrite‐Free Zinc Anode on a Copper Mesh with a Zinc‐Oriented Polyacrylamide Electrolyte Additive

Rechargeable aqueous zinc‐ion batteries have been considered as a promising candidate for next‐generation batteries. However, the formation of zinc dendrites are the most severe problems limiting their practical applications. To develop stable zinc metal anodes, a synergistic method is presented that combines the Cu‐Zn solid solution interface on a copper mesh skeleton with good zinc affinity and a polyacrylamide electrolyte additive to modify the zinc anode, which can greatly reduce the overpotential of the zinc nucleation and increase the stability of zinc deposition. The as‐prepared zinc anodes show a dendrite‐free plating/stripping behavior over a wide range of current densities. The symmetric cell using this dendrite‐free anode can be cycled for more than 280 h with a very low voltage hysteresis (93.1 mV) at a discharge depth of 80 %. The high capacity retention and low polarization are also realized in Zn/MnO₂ full cells.     

Interwoven nickel(II)-dimethylglyoxime nanowires in 3D nickel foam for dendrite-free lithium deposition

Metal skeletons, such as Nickel Foam (NF) has attracted worldwide interests as stable host for lithium metal anode because of its high stability, large specific surface area and high conductivity. However, most metal skeletons have lithophobic surface and uneven current distribution that result in sporadic lithium nucleation and uncontrolled dendrites growth. Herein, we describe a sequential immersing strategy to generate interwoven Nickel(II)-dimethylglyoxime (Ni-DMG) nanowires at NF to obtain composite skeleton (NDNF), which can be used as an stable host for Li metal storage. The Ni-DMG has proved effective to realize uniform lithium nucleation and dendrite-free lithium deposition. Combing with the three dimensional (3D) hierarchical porous structure, the composite host shows a significantly improved coulombic efficiency (CE) than pristine commercial nickel foam. Moreover, the corresponding Li||Li symmetrical cells can run more than 700 h with low voltage hysteresis 22 mV at 1.0 mA/cm², and Li@NDNF||LiFePO₄ full-cell exhibits a high capacity retention of 82.03% at 1.0 C during 630 cycles. These results proved the effectiveness of metal-organic complexes in governing Li metal growth and can be employed as a new strategy for dendrite-free Li metal anode and safe Li metal batteries (LMBs).     

Balancing Interfacial Reactions through Regulating p-Band Centers by an Indium Tin Oxide Protective Layer for Stable Zn Metal Anodes

Metallic zinc (Zn) is considered as one of the most attractive anode materials for the post-lithium metal battery systems owing to the high theoretical capacity, low cost, and intrinsic safety. However, the Zn dendrites and parasitic side reaction impede its application. Herein, we propose a new principle of regulating p-band center of metal oxide protective coating to balance Zn adsorption energy and migration energy barrier for effective Zn deposition and stripping. Experimental results and theoretical calculations indicate that benefiting from the uniform zincophilic nucleation sites and fast Zn transport on indium tin oxide (ITO), highly stable and reversible Zn anode can be achieved. As a result, the I−Zn symmetrical cell achieves highly reversible Zn deposition/stripping with an extremely low overpotential of 9 mV and a superior lifespan over 4000 h. The Cu/I−Zn asymmetrical cell exhibits a long lifetime of over 4000 cycles with high average coulombic efficiency of 99.9 %. Furthermore, the assembled I−Zn/AC full cell exhibits an excellent lifetime for 70000 cycles with nearly 100 % capacity retention. This work provides a general strategy and new insight for the construction of efficient Zn anode protection layer.     

Surface-tuned two-dimension MXene scaffold for highly reversible zinc metal anode

Zinc metal has aroused increasing interest as anode material of Zn-based batteries for their energy storage application. However, the uneven Zn stripping/plating processes induce severe dendrite growth, leading to low Coulombic efficiency and safety hazards. Herein, a surface-tuned two-dimensional (2D) MXene Ti₃C₂T_x scaffold as a robust skeleton is developed to facilitate the uniform Zn stripping/plating. The Ti₃C₂T_x with high electrical conductivity and unique structure provides fast ionic-transport paths, promising even Zn²⁺ stripping/plating processes. With suppressed Zn dendrite growth and uniform nucleation, the proposed 2D Ti₃C₂T_x scaffold for Zn metal anode delivers a low voltage hysteresis of 63 mV and long lifespan over 280 h. This surface-tuned engineering strategy demonstrates the potential application of Zn anode with MXene skeleton for next-generation Zn-based batteries.     

锂金属负极亲锂骨架的研究进展

随着电动汽车和便携式电子产品的快速发展, 人们对于高比能二次电池的需求越来越迫切. 锂金属以其极高的理论比容量和极低的电极电势被视为下一代高比能电池理想负极材料之一. 但是, 锂枝晶的生长及体积膨胀等问题限制了金属锂负极的实际应用. 在金属锂负极中引入三维骨架可以有效抑制锂枝晶生长, 缓解体积膨胀. 其中亲锂骨架可以降低锂的形核能垒, 诱导锂的均匀成核, 更加有效地调控锂沉积行为. 本文结合国内外的研究进展总结了锂金属负极中亲锂骨架的研究成果. 根据亲锂材料的不同对亲锂骨架进行了分类, 总结了各类亲锂骨架在调控锂沉积行为和提高电池性能方面取得的成果, 并对其今后的研究和发展进行了展望.     

多孔泡沫铜和硫脲协同作用构筑无枝晶锂负极

锂金属作为下一代储能电池的理想负极材料一直受到极大的关注,然而锂枝晶的不可控生长和负极副反应带来的低库伦效率问题严重限制了锂金属电池的发展。这里,我们提出了一种多孔泡沫铜和硫脲协同作用的策略,利用硫脲分子的超填充作用实现锂金属在多孔泡沫铜表面的均匀沉积。在电解液中添加0.02 mol·L^-1硫脲作为电解质添加剂,采用多孔泡沫铜的Li||Cu半电池在循环300圈以后,库伦效率仍保持在98%以上。此外,在5C的高倍率条件下,Li||Li FePO4全电池循环300圈以后仍有94%的容量保持率。本工作为锂金属负极保护提供了一种新的策略并且该策略也可以扩展到其他金属负极保护中,非常有利于下一代高能量密度储能电池的开发。     

Intrinsically zincophobic protective layer for dendrite-free zinc metal anode

Aqueous zinc anodes have attracted the attention of many researchers owing to their high safety, low cost, and high theoretical specific capacity. However, its practical application is severely limited by the dendrite growth on zinc anode. Herein, we develop an intrinsically zincophobic barium-titanate protective layer with a porous structure to suppress the zinc dendrite formation by homogenizing the ion distribution on the anode surface, increasing the nucleation sites, and limiting the irregu...