Abstract:Lithium ore smelting slag is a major bulk solid by-product generated from conventional pyro-hydrometallurgical lithium extraction processes. Developing efficient resource utilization and value-added technologies for this material is crucial for reducing China′s dependency on external lithium resources, ensuring the stability and security of the new energy industry chain, and promoting green, low-carbon development. Current research has employed various techniques, such as pyro-hydrometallurgy and alkali roasting, to enhance lithium leaching kinetics and enable the co-recovery of associated strategic metals such as rubidium, cesium, and aluminum. In the field of critical metal recovery, studies have focused on integrated pyro-hydrometallurgical processes, alkali roasting, and negative pressure distillation. Among these, the pyro-hydrometallurgical approach can achieve lithium leaching efficiencies exceeding 97%, while negative pressure distillation enables the production of metallic lithium with a purity over 98%, significantly reducing energy consumption and environmental pollution. Solvent extraction and electrochemical methods have also shown considerable potential for selective lithium recovery. For associated metals such as Rb, Cs, and Al, high-temperature roasting followed by acid leaching can achieve rubidium recovery rates up to 93.09%, although this method suffers from high energy consumption and limited product purity. While aluminum precipitation is a well-established separation technique, its industrial application remains constrained by inefficient silicon-aluminum separation. Simultaneously, lithium smelting slag shows promising potential for producing value-added products such as high-performance ternary geopolymers, cement, and molecular sieves. However, several key challenges persist, including incomplete lithium extraction, low recovery rates of strategic metals, limited product value addition, and the absence of standardized processing systems. In terms of value-added utilization, lithium slag is widely applied in building materials due to its pozzolanic activity. Incorporating 5% lithium slag can reduce the energy consumption of cement production and enhance the 28-day compressive strength of concrete to over 80 MPa, demonstrating excellent engineering applicability. Furthermore, lithium slag can be used to produce environmentally friendly materials such as ternary geopolymers and NaX zeolites. The former exhibits high immobilization efficiency for various heavy metals, while the latter possesses a well-defined structure and superior adsorption performance, opening new pathways for the high-value utilization of lithium slag. Accordingly, this review systematically analyzes the key physicochemical characteristics of lithium smelting slag, including its chemical composition and modes of occurrence. It summarizes mainstream recovery techniques for valuable metals such as Li, Rb, and Cs (covering leaching, selective adsorption, and electrochemical recovery) and evaluates recent advances and existing challenges in producing high-value-added products such as ternary geopolymers and cement. Furthermore, the study outlines a sustainable technology framework centered on "source reduction, low-carbon processing, and end-stage high-value conversion," with an emphasis on rapid activation, multi-component selective separation, and full-process system integration. This work aims to provide theoretical and mechanistic insights to support the development of green recycling and value-added technologies for lithium ore smelting slag. Close-