Ultra-reliable and low-latency communications (URLLC) have stringent requirements on quality-of-service and network availability. Due to path loss and shadowing, it is very challenging to guarantee the stringent requirements of URLLC with satisfactory communication range. In this paper, we first provide a quantitative definition of network availability in the short blocklength regime: the probability that the reliability and latency requirements can be satisfied when the blocklength of channel codes is short. Then, we establish a framework to maximize available range, defined as the maximal communication distance subject to the network availability requirement, by exploiting multi-connectivity. The basic idea is using both device-to-device (D2D) and cellular links to transmit each packet. The practical setup with correlated shadowing between D2D and cellular links is considered. Besides, since processing delay for decoding packets cannot be ignored in URLLC, its impacts on the available range are studied. By comparing the available ranges of different transmission modes, we obtained some useful insights on how to choose transmission modes. Simulation and numerical results validate our analysis, and show that multi-connectivity can improve the available ranges of D2D and cellular links remarkably.