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In the search for improved materials for rechargeable lithium batteries, LiFePO4 offers interesting possibilities because of its low raw materials cost, environmental friendliness and safety. The main drawback with using the material is its poor electronic conductivity and this limitation has to be overcome. Here Al-doped LiFePO4/C composite cathode materials were prepared by a polymer-network synthesis technique. Testing of X-ray diffraction, charge-discharge, and cyclic voltammetry were carried out for its performance. Results show that Al-doped LiFePO4/C composite cathode materials have a high initial capacity, good cycle stability and excellent low temperature performance. The electrical conductivity of LiFePO4 material can be obviously improved by doping Al. The better electrochemical performances of Al-doped LiFePO4/C composite cathode materials have a connection with its conductivity.