To facilitate the transition of laboratory research to industrial applications, it is critical to establish a reliable protocol for the mass synthesis of high-quality graphene. Here, we present an efficient electrochemical intercalation-based exfoliation approach utilizing alternating current that allows for the production of sub-kilogram quantities of graphene. This strategy involves repeatedly intercalating foreign anions and cations into the interlayer gaps of dual-graphite electrodes, accelerating the graphite expansion process and maximizing the exfoliation efficiency of both electrodes while inhibiting excessive anodic oxidation. The exfoliation process leads to high-yield graphene nanosheets (92 %, primarily 1–3 layers) with minimal structural deterioration (ID/IG ratio of 0.05), high purity (2.1 at% oxygen), and outstanding electrical property (7.28 × 104 S m−1). Notably, our scaled-up manufacturing technique produces a record-breaking throughput of 135 g h−1, improving on the best-reported exfoliation efficiency with direct current by 35%. Furthermore, the as-made graphene demonstrates a large reversible capacity of 102 mF cm−2 for flexible supercapacitors, with robust cyclability with 99.5% after 10,000 cycles, excellent mechanical flexibility, and exceptional serial integration for adjustable voltage output. The efficient and scalable method presents a significant advancement in the large-scale manufacture of graphene, with potential for widespread industrial applications.