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A new family of chemical cross-linked ionogel is successfully synthesized by photopolymerization of hyperbranched aliphatic polyester with acrylate terminal groups in an ionic liquid of 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4). The microstructure, viscoelastic behavior, mechanical property thermal stability, and ionic conductivities of the ionogels are investigated systematically. The ionogels exhibit high mechanical strength (up to 1.6 MPa) and high mechanical stability even at temperatures up to 200 degrees C. It is found to be thermally stable up to 371.3 degrees C and electrochemically stable above 4.3 V. The obtained ionogels show superior ionic conductivity over a wide temperature range (from 1.2 x 10(-3) S cm(-1) at 20 degrees C up to 5.0 x 10(-2) S cm(-1) at 120 degrees C). Moreover, the Li/LiFePO4 batteries based on ionogel electrolyte with LiBF4 show a higher specific capacity of 153.1 mAhg(-1) and retain 98.1% after 100 cycles, exhibiting very stable charge/discharge behavior with good cycle performance. This work provides a new method for fabrication of novel advanced gel polymer electrolytes for applications in lithium-ion batteries.