An array of LiNi_1/3Mn_1/3Co_1/3O₂ (NMC 111) samples with a hollow‐sphere morphology enabling the use of binder‐free, millimeter‐thick electrodes in a battery are prepared by a combination of ball milling, hydrothermal treatment and calcination. Materials are studied by powder X‐ray diffraction, nitrogen adsorption measurements, X‐ray fluorescence analysis, and scanning electron microscopy. Their electrochemical performance for Li⁺ extraction/insertion is tested by cyclic voltammetry and galvanostatic chronopotentiometry on thin‐film electrodes. Optimized materials, prepared by mechanical and thermal treatment with surface areas of 7 to 10 m² g⁻¹, provide charge capacity values of 141 to 156 mAh g⁻¹. The concentration of the crystalline phase in NMC 111 materials with a hollow‐sphere morphology is found to be the decisive parameter for their galvanostatic cycling stability. Hollow spheres with well‐developed NMC nanocrystals and a low concentration of amorphous phase in the walls, exhibiting excellent cycling stability and charge capacity in thin‐film electrodes are incorporated into a NMC/graphite 3D‐battery module. This 122 Ah/451 Wh 3D‐battery provides 78% of theoretical capacity and 73% of theoretical energy after 10 formatting cycles. Additionally, the battery prototype exhibits stable performance over more than 200 cycles at C/10 rate. A series of analogous 3D Li accumulators, currently assembled and tested in a pilot plant, represent the first step toward large‐scale production of novel 3D Li accumulator.

中文翻译：

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为新概念的3D锂蓄电池优化了形态的LiNi1 / 3Mn1 / 3Co1 / 3O2

通过球的组合，制备了一系列具有空心球形形态的LiNi _1/3 Mn _1/3 Co _1/3 O ₂（NMC 111）样品，可在电池中使用无粘合剂的毫米厚电极研磨，水热处理和煅烧。通过粉末X射线衍射，氮吸附测量，X射线荧光分析和扫描电子显微镜研究材料。通过循环伏安法和恒电流计时电位法在薄膜电极上测试了它们对Li ⁺萃取/插入的电化学性能。通过机械和热处理制备的最佳材料，表面积为7至10 m ² g ^-1，提供141至156 mAh g ^-1的充电容量值。发现具有中空球形形态的NMC 111材料中的结晶相浓度是其恒电流循环稳定性的决定性参数。NMC /石墨3D电池模块中集成了具有良好NMC纳米晶体和壁中非晶相浓度低，在薄膜电极中表现出出色的循环稳定性和充电容量的空心球。这种122 Ah / 451 Wh 3D电池在10个格式化周期后可提供78％的理论容量和73％的理论能量。此外，电池原型在C / 10速率下在200多个循环中表现出稳定的性能。当前正在中试工厂中组装和测试的一系列类似的3D Li蓄电池代表了大规模生产新型3D Li蓄电池的第一步。