This paper reviews the recent research and development of graphene-based multilayers fabricated from layer-by-layer (LBL) self-assembly technique. Graphene multilayer films, due to their excellent performances and specific applications, have attracted widespread attention during recent decades. In this paper, the preparation and property of self-assembled graphene multilayer films are introduced. The application of different graphene multilayer films in transparent conducting films (TCFs), field effect transistors (FETs), lithium ion batteries (LIBs), supercapacitors, and solar cells are summarized and discussed. The perspectives for the future developments of self-assembled graphene multilayer films are proposed.
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