There are challenges of how to realize large-scale fabrication of high-quality graphene materials and large-size single crystal graphene domains, which are essential for mass applications and device applications since grain boundaries are believed to markedly degrade the quality and properties of grapbene.For these purposes, we developed a solid state intercalation-expansion-liquid phase exfoliation process with a prototype production line of 5 kg/day high-quality graphene material.We also developed an ambient pressure CVD to synthesize millimeter-size single crystal graphene grains and films on Pt substrates, and graphene materials in quantity on Ni particles and Ni foams as substrates.Interestingly, with a Ni foam as template, a 3D graphene macrostructre, which is called graphene foam (GF), can be synthesized.This porous graphene bulk material consists of an interconnected network of graphene, is flexible, and has outstanding electrical and mechanical properties.With those graphene materials obtained from the above-mentioned methods, applications in transparent conducting films, elastic conductors, sensors, lithium ion batteries, supercapacitors, and electromagnetic interference fielding, etc, have been explored.