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Heat dissipation involved safety issues are crucial for industrial applications of the high-energy density battery and fast charging technology.While traditional air or liquid cooling methods suffering from space limitation and possible leakage of electricity during charge process,emerging phase change materials as solid cooling media are of growing interest. Among them, paraffin wax(PW) with large latent heat capacity and low cost is desirable for heat dissipation and thermal management which mainly hindered by their relatively low thermal conductivity and susceptibility to leakage. Here, highly ordered and interconnected hexagonal boron nitride(h-BN) networks were established via ice template method and introduced into PW to enhance the thermal conductivity. The composite with 20 wt% loading amount of h-BN can guarantee a highly ordered network and exhibited high thermal conductivity(1.86 W m-1K-1) which was 4 times larger compared with that of random dispersed h-BN involved PW and nearly 8 times larger compared with that of bare PW. The optimal thermal conductive composites demonstrated ultrafast heat dissipation as well as leakage resistance for lithium-ion batteries(LIBs), heat generated by LIBs can be effectively transferred under the working state and the surface temperature kept 6.9℃ lower at most under 2–5℃ continuous charge-discharge process compared with that of bare one which illustrated great potential for industrial thermal management.