This paper proposes a grant-free massive access scheme based on the millimeter wave (mmWave) extra-large-scale multiple-input multiple-output (XL-MIMO) to support massive Internet-of-Things (IoT) devices with low latency, high data rate, and high localization accuracy in the upcoming sixth-generation (6G) networks. The XL-MIMO consists of multiple antenna subarrays that are widely spaced over the service area to ensure line-of-sight (LoS) transmissions. First, we establish the XL-MIMO-based massive access model considering the near-field spatial non-stationary (SNS) property. Then, by exploiting the block sparsity of subarrays and the SNS property, we propose a structured block orthogonal matching pursuit algorithm for efficient active user detection (AUD) and channel estimation (CE). Furthermore, different sensing matrices are applied in different pilot subcarriers for exploiting the diversity gains. Additionally, a multi-subarray collaborative localization algorithm is designed for localization. In particular, the angle of arrival (AoA) and time difference of arrival (TDoA) of the LoS links between active users and related subarrays are extracted from the estimated XL-MIMO channels, and then the coordinates of active users are acquired by jointly utilizing the AoAs and TDoAs. Simulation results show that the proposed algorithms outperform existing algorithms in terms of AUD and CE performance and can achieve centimeter-level localization accuracy.

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