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© 2020 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim.There is a long-standing consciousness that the rhombohedral NASICON-type compounds as promising cathodes for Li+ /Na+ batteries should have inactive M1(6b) sites with ion (de)intercalation occurring only in the M2 (18e) sites. Of particular significance is that M1 sites active for charge/discharge are commonly considered undesirable because the ion diffusion tends to be disrupted by the irregular occupation of channels, which accelerates the deterioration of battery. However, it is