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Driven by the rapid growth of new energy vehicles and energy storage, development of lithium extraction technologies from salt lake brines has been considerably stimulated. This work introduces a novel method for structure and surface co-modification of the manganese-based lithium ion-sieve H1.6Mn1.6O4 (HMO-EtOH & SDS) sub-micron spheres, employing ethanol (EtOH) and sodium dodecyl sulfate (SDS) as the additives. The HMO-EtOH & SDS sub-micron spheres exhibit a uniform spherical morphology, narrow size distribution (300–600 nm), small average particle size (0.44 µm), large specific surface area (120.06 m2·g−1), super-hydrophilicity and relatively rich porous structure. When utilized as the adsorbents, HMO-EtOH & SDS sub-micron spheres demonstrate a high equilibrium adsorption capacity (qe = 56.71 mg·g−1) and a fast adsorption rate (te = 3.0 h), with a maximum adsorption capacity of 58.74 mg·g−1. After five cycles of adsorption, an excellent cycling performance (retention rate: 80.23 wt.%) and low manganese dissolution rate (below 5.25 wt.%) have been accomplished. Additionally, for extraction of lithium from the simulated salt brine, an equilibrium adsorption capacity of 25.41 mg·g-1 and relatively high separation coefficients (

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