富锂锰基正极材料具有较高的可逆容量，被认为是下一代锂离子电池正极材料的重要选项。共沉淀是制备富锂前驱体最常用的方法，反应过程中通常需要氨作为络合剂来降低沉淀速率。然而氨及铵根离子在有氧条件下容易被氧化为亚硝酸根离子或硝酸根离子并产生含氮废水进而造成环境污染，增加废水处理成本。故开发新的绿色前驱体合成工艺具有重要意义。本论文借助微反应器在无络合剂条件下采用快速沉淀耦合水热老化的方式合成碳酸盐前驱体，探究该方法的可行性，以及反应物摩尔比、浓度、老化温度与时间等因素的影响，发展高效的锰镍碳酸盐前驱体绿色制备方法，进而探讨高温煅烧过程对材料形貌和电化学性能的影响，揭示其中的构效关系，获得高性能的富锂锰基正极材料。本论文主要进展和结论如下：揭示了快速沉淀结合水热老化制备碳酸盐前驱体的调变规律，发现在一定范围内增加Na2CO3的用量能够有效提升金属离子利用率且不会在前驱体中生成氢氧化镍杂质，从而使前驱体中的锰镍比接近设计比，有效降低富锂锰基晶体中的Li+/Ni2+混排程度；水热过程不充分会导致富锂晶体中的Li+/Ni2+混排程度很高，过高的水热温度则会导致前驱体中出现氢氧化镍杂质；Na2CO3过量10 %、80 ℃水热处理8 h是较优的前驱体制备条件，由所得产物制备的富锂材料在0.1 C、1 C、5 C下的放电比容量分别可达到253.6 mAh g-1，190.0 mAh g-1，141.0 mAh g-1，在1 C下经过100圈循环后容量保留率为92 %，在5 C下经过300圈循环后容量保留率为88.0 %。探究了煅烧温度对富锂形貌晶型和电化学性能的影响。发现当高温煅烧温度低于800 ℃时，富锂结晶度较差，倍率性能较差。当煅烧温度为850 ℃时，结晶度有了明显提升，倍率性能大大提升。继续上升至900 ℃时，结晶度进一步上升，Li+/Ni2+混排程度也继续降低，低倍率下放电比容量明显提升，但倍率性能出现明显下降。基于850 ℃和900 ℃煅烧各自的优势，提出两步煅烧策略，即在850 ℃煅烧时间为8 h，900 ℃下煅烧时间为4 h，所得材料在0.1 C，1 C，5 C下的放电比容量达到260 mAh g-1，201.4 mAh g-1，155.9 mAh g-1，1 C下循环100圈后容量保留率为90.89 %，5 C下循环300圈后容量保留率为90.35 %。这种新的煅烧策略有望成为提升锂离子正极材料电化学性能的通用策略。

Li-rich Mn-based cathode materials are regarded as an important alternative for next-generation lithium-ion battery cathode materials, owing to their high reversible capacity. The most common method to prepare precursors is co-precipitation, and ammonia is typically used as a complexing agent to reduce the precipitation rate during the reaction. However, under aerobic conditions, ammonia and ammonium ions can easily be oxidized to nitrite or nitrate ions, which produce nitrogen-containing wastewater, causing environmental pollution and increasing wastewater treatment costs. Therefore, it is crucial to develop a new green precursor synthesis process. In this thesis, we investigate the feasibility of the precursor synthesis by rapid precipitation with hydrothermal aging in a microreactor under complexing agent-free condition. We also explore the effects of the molar ratio, concentration, aging temperature and time of the reactants to develop an efficient green preparation method for manganese nickel carbonates, which can be used as precursors of cathode materials.The main progress and conclusions of this thesis are as follows:For preparing carbonate precursors by rapid precipitation combined with hydrothermal aging, it is found that increasing the amount of Na2CO3 within a certain range does not generate nickel hydroxide impurities in the precursors but effectively improve the metal ion utilization rate, resulting in the Mn-to-Ni ratio in the precursors being close to the design ratio as well as low Li+/Ni2+ mixing degree in the Li-rich Mn-based materials. However, insufficient hydrothermal process leads to high Li+/Ni2+ mixing in the final products, while too high hydrothermal temperature leads to nickel hydroxide impurities in the precursors. The best conditions for preparing the precursors are an excess of 10 % Na2CO3 and 8 h of hydrothermal treatment at 80 ℃. The specific capacities of the prepared Li-rich materials can reach 253.6 mAh g-1, 190.0 mAh g-1, 141.0 mAh g-1 and 5.0 mAh g-1 at 0.1 C, 1 C and 5 C, respectively. The capacity retention rate is 92 % after 100 cycles at 1 C and 88.0 % after 300 cycles at 5 C, respectively. The influence of calcination temperature on the crystalline morphology and electrochemical properties of Li-rich materials is investigated. The results show that the crystallinity of Li-rich materials is poor when the high-temperature calcination temperature is lower than 800 ℃. A significant improvement in the crystallinity is observed when the calcination temperature is 850 ℃. Further increasing the calcination temperature to 900 ℃, results in increased crystallinity and decreased Li+/Ni2+ mixing degree. The discharge specific capacity at low rate increases significantly, but the rate performance shows a significant decrease. To make use of the respective advantages of calcination at 850 °C and 900 °C, a two-step calcination strategy is proposed, consisting of 8 h at 850 °C followed by 4 h at 900 °C. The resulting materials have discharge specific capacities of 260 mAh g-1, 201.4 mAh g-1, 155.9 mAh g-1 at 0.1 C, 1 C, and 5 C, respectively. The capacity retention rates after 100 cycles at 1 C are 90.89 % and 90.35 % after 300 cycles at 5 C. This new calcination strategy is expected to enhance the electrochemical performance of lithium-ion cathode materials in general.