Shotcrete is one of the most important types of concrete used in engineering construction, and its properties are significantly influenced by accelerators. This study investigates the effects of aluminum sulfate series alkali-free accelerator (AKF) and alkali accelerator (ALK) on the strength, hydration process, characteristic hydration products, and microstructure properties of shotcrete. Techniques such as setting time measurement, isothermal calorimetry, simultaneous thermal analysis, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM–EDS), and mercury intrusion porosimetry (MIP) were utilized. The results indicate that both ALK and AKF significantly accelerate and increase the early hydration heat release rate and cumulative hydration heat of Portland cement, producing the characteristic hydration products hexagonal plate AFm and rod AFt, respectively. This acceleration notably speeds up the setting process of Portland cement. ALK negatively impacts the later-stage microstructural development and pore structure filling of hardened cement paste, leading to average reductions of 15.3% and 19.9% in flexural and compressive strengths at 28 days, respectively. Specifically, compared to ALK, AKF shows a faster hydration heat release rate during the induction period and a more significant increase in cumulative hydration heat during the hydration process; the cumulative hydration heat is on average 18.2% higher than AKF. Furthermore, AKF does not hinder the subsequent C3S hydration and C-S-H gel densification process. After 28 days of curing, EDS analysis indicates an average Ca/Si ratio of 1.171 for the AKF-treated shotcrete; the average Ca/Si ratio shows minimal variation from the reference group and is classified as the same type of C-S-H gel as the reference group. Therefore, the strength of hardened cement paste with AKF continues to increase steadily in the later stages. At 28 days, the average flexural strength increased by 10.2%, while the compressive strength decreased by only 3.0%. These findings suggest that AKF enhances the microstructural development and strength of shotcrete, making it a more effective accelerator for engineering applications.
