This study introduces mechanochemical activation–instantaneous carbon thermal shock (CTS) as a synergistic strategy for the high-value utilization of all components in retired crystalline-Si photovoltaic (PV) modules, addressing recycling bottlenecks such as limited metal recovery, high chemical consumption, and low-value treatment of Si. Mechanochemical ball milling effectively disrupts the Ag–Si interface and glassy interlayers, increasing the specific surface area and inducing lattice distortions. This lowers the reaction activation energy, enabling high leaching efficiencies for Ag (99.5%) and Al (94%) while markedly reducing the required nitric acid dosage. Subsequent CTS, with its ultrafast heating, overcomes the kinetic limitations of silica reduction, rapidly converting the acid-leached Si residue into high-purity, highly crystalline SiC. The synthesized SiC is well suited for high-temperature electronic devices and thermal management applications due to its excellent thermal stability, high thermal conductivity, and semiconducting properties. Life cycle and economic analyses indicate that, compared with conventional hydrometallurgical methods, the proposed process reduces the environmental footprint by 88.19% and lowers material treatment costs, offering an economically viable pathway for green, closed-loop recycling of PV waste.
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