Direct-ink writing 3D printed energy storage devices: From material selectivity,design and optimization strategies to diverse applications

Additive manufacturing, also known as three-dimensional (3D) printing technology, has recently emerged as a promising fabrication technology for a variety of applications with diverse complex architectures, as it allows for simple printing of desired pattern, fast prototyping, reduced fabrication process and low cost. As an important type of 3D printing technology, direct ink writing (DIW) endows the electrochemical energy storage devices (EESDs) with excellent electrochemical performance with high areal energy density and excellent rate capability owing to enhanced ion/electron transportation and surface kinetics induced by the designed patterns and device architecture. In view of the current infancy and urgency, as well as the lack of in-depth discussion, we critically overview the DIW 3D printing technology for EESDs devices in terms of materials selectivity principle for ink formulation and rheology, technical challenges (design principles and optimization strategies) and various EESDs applications in a comprehensive yet concise fashion. In this review, firstly, we introduce the typical features of DIW 3D printing technology. Subsequently, we discuss the design and optimization strategies towards several key parameters of DIW, including printable ink formulation, printing process and post treatment, device configuration and electrode pattern, porosity and tortuosity, as well as the package. Thereafter, we summarize the advances and recent progress of various EESDs devices fabricated by DIW technology, including conventional lithium/sodium ion batteries, newly emerged lithium sulfur/selenide/oxygen batteries, lithium/sodium-metal batteries, Ni-Fe batteries, zinc-air batteries, zinc ion batteries and supercapacitors, with a detailed analysis of rational design mechanism of each EESD. At last, the remaining challenges and research orientations in this booming field are proposed to motivate the future research and development of 3D printed EESDs.     

Solubilities, Vapor Pressures, and Heat Capacities of the Water + Lithium Bromide + Lithium Nitrate + Lithium Iodide + Lithium Chloride System

The optimum mole ratio of lithium salts in the H₂O + LiBr + LiNO₃ + LiI + LiCl system was experimentally determined to be LiBr : LiNO₃ : LiI : LiCl = 5 : 1 : 1 : 2. The solubilities were measured at temperatures from 252.02 to 336.75 K. Regression equations on the solubility data were obtained with a least-squares method. Average absolute deviations of the calculated values from the experimental data were 0.15% at temperatures <285.18 K and 0.05% at temperatures 285.18 K. The vapor pressures were measured at concentrations ranging from 50.0 to 70.0 mass% and at temperatures from 330.13 to 434.88 K. The experimental data were correlated with an Antoine-type equation, and the average absolute deviation of the calculated values from the experimental data was 2.25%. The heat capacities were measured at concentrations from 50.0 to 65.0 mass% and temperatures from 298.15 to 328.15 K. The average absolute deviation of the values calculated by the regression equation from the experimental data was 0.24%.     

Silicon Decorated Cone Shaped Carbon Nanotube Clusters for Lithium Ion Battery Anodes

In this work, we report the synthesis of an three‐dimensional (3D) cone‐shape CNT clusters (CCC) via chemical vapor deposition (CVD) with subsequent inductively coupled plasma (ICP) treatment. An innovative silicon decorated cone‐shape CNT clusters (SCCC) is prepared by simply depositing amorphous silicon onto CCC via magnetron sputtering. The seamless connection between silicon decorated CNT cones and graphene facilitates the charge transfer in the system and suggests a binder‐free technique of preparing lithium ion battery (LIB) anodes. Lithium ion batteries based on this novel 3D SCCC architecture demonstrates high reversible capacity of 1954 mAh g^?1 and excellent cycling stability (>1200 mAh g^?1 capacity with ≈100% coulombic efficiency after 230 cycles).     

Synthesis of CDMO from LiOH and EMD and the Performances of Li/CDMO Rechargeable Batteries

The synthesis of CDMO from LiOH and EMD has been investigated by thermogravimetry and pow-der X-ray diffraction analysis.The results showed that it took place from below 100 to 400℃.Whenthe proportion of Li:Mn in the starting mixture was 3:7,the measured weight loss during this processwas 7.40% for heat-treated EMD and 8.33% for non-heat-treated EMD.Based on these data andX-ray diffraction results the obtained product would be 3LiMn204 - MnO2.This material was es-sentially amorphous.It can insert 4.7 Li per 3LiMn_2O_4·MnO_2,leading to a capacity of 170-200 mAh/g and demonstrated reasonable discharge and recharge cycle performance for both testcells and practical batteries.     

MoS2@GO三维絮状结构的制备及电化学储锂性能

以改良Hummers法制备了氧化石墨烯(GO),通过水热以及热处理制备了MoS_2@GO复合材料,探讨了MoS_2与GO物质的量比对复合材料结构、电化学性能的影响。结果表明,当MoS2与GO的物质的量比为1∶1时,所得复合材料呈现三维絮状结构并具有良好的电化学性能。其作为锂离子电池负极材料,在0.1A/g电流密度下,50次循环后放电比容量仍有879mAh/g,容量基本没有衰减。在2A/g的高电流密度下还能保持530mAh/g,当电流密度从2A/g恢复到0.1A/g,循环容量能恢复到0.1A/g时的水平,表现出优异的倍率性能。     

Weak-Coordination Electrolyte Enabling Fast Li+ Transport in Lithium Metal Batteries at Ultra-Low Temperature

Lithium metal batteries (LMBs) are promising for next-generation high-energy-density batteries owing to the highest specific capacity and the lowest potential of Li metal anode. However, the LMBs are normally confronted with drastic capacity fading under extremely cold conditions mainly due to the freezing issue and sluggish Li⁺ desolvation process in commercial ethylene carbonate (EC)-based electrolyte at ultra-low temperature (e.g., below −30 °C). To overcome the above challenges, an anti-freezing carboxylic ester of methyl propionate (MP)-based electrolyte with weak Li⁺ coordination and low-freezing temperature (below −60 °C) is designed, and the corresponding LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) cathode exhibits a higher discharge capacity of 84.2 mAh g⁻¹ and energy density of 195.0 Wh kg⁻¹_cathode than that of the cathode (1.6 mAh g⁻¹ and 3.9 Wh kg⁻¹_cathode) working in commercial EC-based electrolytes for NCM811‖ Li cell at −60 °C. Molecular dynamics simulation, Raman spectra, and nuclear magnetic resonance characterizations reveal that rich mobile Li⁺ and the unique solvation structure with weak Li⁺ coordination are achieved in MP-based electrolyte, which collectively facilitate the Li⁺ transference process at low temperature. This work provides fundamental insights into low-temperature electrolytes by regulating solvation structure, and offers the basic guidelines for the design of low-temperature electrolytes for LMBs.     

石墨烯及其聚合物复合材料在锂离子电池中的应用研究进展

石墨烯的出现为设计和构建新型功能复合材料提供了广阔的空间,文中详细综述了石墨烯及其聚合物复合材料在锂离子电池中的研究进展。石墨烯是一种极有发展潜力的负极材料,储锂性能受到结构特征、含氧官能团和杂质原子等多种因素影响,导致储锂行为和机理较为复杂。将具有储锂活性的聚合物与石墨烯复合作为正极材料,储锂性能受到聚合物氧化还原的可逆性和复合结构等因素影响。聚合物还作为晶格匹配剂和交联剂,有利于提高石墨烯与氧化物复合的结构稳定性。最后指出,聚合物种类和制备方法的选择是以改善储锂性能为原则,有针对性和预见性地设计和制备高性能锂离子电池电极材料。     

锂离子电容器性能分析及其应用

锂离子电容器作为一种新型的储能器件,不仅具有较高能量密度,还具有较为优异的功率密度和超长的循环寿命,在高功率和长寿命的应用场景具有极大的应用潜力。首先,从理论上分析了双电层电容器能量密度受限原理以及锂离子电容器性能提升的因素;其次,对比讨论了锂离子电容器和双电层电容器的性能差异;最后,对锂离子电容器在智能仪表、汽车节能减排、新能源汽车、可再生能源发电与功率储能的应用潜力进行了分析。研究结果为锂离子电容器能量密度的进一步提升提供了理论基础,为锂离子电容器的应用指明了方向。     

Recycling Bacteria for the Synthesis of LiMPO4 (M = Fe,Mn) Nanostructures for High‐Power Lithium Batteries

In this work, a novel waste‐to‐resource strategy to convert waste bacteria into a useful class of cathode materials, lithium metal phosphate (LiMPO₄; M = Fe, Mn), is presented. Escherichia coli (E. coli) bacteria used for removing phosphorus contamination from wastewater are harvested and used as precursors for the synthesis of LiMPO₄. After annealing, LiFePO₄ and LiMnPO₄ nanoparticles with dimensions around 20 nm are obtained. These particles are found to be enveloped in a carbon layer with a thickness around 3–5 nm, generated through the decomposition of the organic matter from the bacterial cell cytoplasm. The battery performance for the LiFePO₄ is evaluated. A high discharge capacity of 140 mAh g^?1 at 0.1 C with a flat plateau located at around 3.5 V is obtained. In addition, the synthesized particles display excellent stability and rate capabilities. Even under a high C rate of 10 C, a stable discharge capacity of 75.4 mAh g^?1 can still be achieved.     

Dendrite‐Free Lithium Deposition via Flexible‐Rigid Coupling Composite Network for LiNi0.5Mn1.5O4/Li Metal Batteries

Notorious lithium dendrite causes severe capacity fade and harsh safety issues of lithium metal batteries, which hinder the practical applications of lithium metal electrodes in higher energy rechargeable batteries. Here, a kind of 3D‐cross‐linked composite network is successfully employed as a flexible‐rigid coupling protective layer on a lithium metal electrode. During the plating/stripping process, the composite protective layer would enable uniform distribution of lithium ions in the adjacent regions of the lithium electrode, resulting in a dendrite‐free deposition at a current density of 2 mA cm^?2. The LiNi_0.5Mn_1.5O₄‐based lithium metal battery presents an excellent cycling stability at a voltage range of 3.5–5.0 V with the induction of 3D‐cross‐linked composite protective layer. From an industrial field application of view, thin lithium metal electrodes (40 µm, with 4 times excess lithium) can be used in LiNi_0.5Mn_1.5O₄ (with industrially significant loading of 18 mg cm^?2 and 2.6 mAh cm^?2)‐based lithium metal batteries, which reveals a promising opportunity for practical applicability in high energy lithium metal batteries.     

金属氰胺化合物的结构、合成及电化学储能应用

金属氰胺化合物M_x(NCN)_y作为类氧硫族化合物, 是一类新兴的无机功能材料。准线性[NCN]^2-阴离子赋予其空旷和具有孔道的晶体结构、独特的电子结构和新奇的物化性质, 金属氰胺化合物在固态发光、光/电催化及电化学储能等诸多领域展现出应用前景, 近年来逐渐成为研究热点。本文简要回顾了金属氰胺化合物的研究历史, 概述了金属氰胺化合物的晶体结构及物化性质, 总结了常见合成方法及策略, 探讨了金属氰胺化合物在电化学储能领域的应用, 重点论述了其作为锂钠离子电池新型负极材料的电化学性能及存储机制。     

3D打印石墨烯制备技术及其在储能领域的应用研究进展

石墨烯优异的力学和物理性能使其成为理想的储能材料。因结构精确可控,易实现规模化制备,3D打印石墨烯材料有望在储能领域得到广泛应用。本文全面综述了3D打印石墨烯制备技术及其在储能领域的应用研究进展。石墨烯墨水的黏度和可打印性是实现石墨烯3D打印的制约因素。实现工艺简单、浓度可控、无黏结剂石墨烯墨水的规模化打印将成为3D打印石墨烯制备技术未来的研究热点。石墨烯超级电容器、锂硫电池、锂离子电池等储能元件一体化打印成型是3D打印石墨烯在储能领域应用的发展方向。     

Peapod‐like Li3VO4/N‐Doped Carbon Nanowires with Pseudocapacitive Properties as Advanced Materials for High‐Energy Lithium‐Ion Capacitors

Lithium ion capacitors are new energy storage devices combining the complementary features of both electric double‐layer capacitors and lithium ion batteries. A key limitation to this technology is the kinetic imbalance between the Faradaic insertion electrode and capacitive electrode. Here, we demonstrate that the Li₃VO₄ with low Li‐ion insertion voltage and fast kinetics can be favorably used for lithium ion capacitors. N‐doped carbon‐encapsulated Li₃VO₄ nanowires are synthesized through a morphology‐inheritance route, displaying a low insertion voltage between 0.2 and 1.0 V, a high reversible capacity of ≈400 mAh g^?1 at 0.1 A g^?1, excellent rate capability, and long‐term cycling stability. Benefiting from the small nanoparticles, low energy diffusion barrier and highly localized charge‐transfer, the Li₃VO₄/N‐doped carbon nanowires exhibit a high‐rate pseudocapacitive behavior. A lithium ion capacitor device based on these Li₃VO₄/N‐doped carbon nanowires delivers a high energy density of 136.4 Wh kg^?1 at a power density of 532 W kg^?1, revealing the potential for application in high‐performance and long life energy storage devices.     

锂离子电池正极材料Li1+xV3O8合成技术研究进展

层状的Li1 xV3O8电池正极材料具有比容量高、循环寿命长、价格便宜等优点，有望成为新一代锂离子二次电池的正极材料。综述了层状的Lil xV3O8正极材料的结构、性质、制备技术、掺杂技术、电化学性能以及影响电极材料性能的各因素。其中重点总结了Li1 xV3O8正极材料的制备技术，包括高温固相合成技术、低温合成技术和掺杂技术。指出溶胶-凝胶法和经脱水处理的电极材料在综合性能上取得了一定突破，有望实现产业化生产。     

储能锂电池模组SoE运行区间评估方法研究

为提高电池储能单元控制精度,保证储能系统高效稳定运行,研究了储能锂电池模组能量状态（state of energy,SoE）运行区间。在分析跟踪计划发电、风光功率平滑运行模拟工况,以及电池电压极差、电池电压标准差系数等评估指标的基础上,提出了储能锂电池模组SoE运行区间评估方法。然后,对实际运行的锂电池模组进行了跟踪计划发电、风光功率平滑模拟工况试验,并通过分析电池电压极差、电池电压标准差系数的变化,确定了2种运行工况下锂电池模组的SoE运行区间。研究结果表明,采用分析模拟工况试验中电池电压极差、电池电压标准差系数的方法能有效评估储能锂电池模组的SoE运行区间,为提高储能单元能量利用率提供了技术手段,对于保证锂电池储能系统高效稳定运行具有指导意义。     

锂离子电池正极材料Li1+xV3O8的合成及性能研究

研究了一种新型制备锂离子电池正极材料Li_(1+x)V_3O_8的工艺方法.以NH_4VO_3为原料,通过淬火法制备出V_2O_5溶胶,加入LiOH溶液后,通过喷雾干燥法制备球形前驱体,再通过一定的热处理即制得锂离子电池正极材料Li_(1+x)V_3O_8.试验中,进行了前驱体的DTA/TGA分析;对产物进行了XRD、SEM及电化学性能测试研究.结果表明,经过350℃热处理24h后得到的样品颗粒细小、呈球形、粒径分布均匀、结晶度好,并且还表现出很好的电化学性能,其首次放电比容量高达378mAh·g~(-1),经过10次充放电循环后,其放电比容量为312mAh·g~(-1).     

Sn量子点/石墨烯复合材料的合成及储锂性能

Sn基材料是目前高容量锂离子电池电极材料研究的热点,但循环性能较差阻碍了其大规模应用.以氧化石墨烯为载体,通过化学还原法在载体表面成功均匀负载＜10 nm的Sn量子点,合成Sn量子点/石墨烯(SnQds/rGO)复合电极材料.结果 表明,Sn质量分数为90wt％的SnQds/rGO复合材料具有良好的综合电化学性能,首次...