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Statistical equilibrium configurations are important in the physics of macroscopic systems with a large number of constituent degrees of freedom. They are expected to be crucial also in discrete quantum gravity, where dynamical spacetime should emerge from the collective physics of the underlying quantum gravitational degrees of freedom. However, defining statistical equilibrium in a background independent system is a challenging open issue, mainly due to the absence of absolute notions of time and energy. This is especially so in non-perturbative quantum gravity frameworks that are devoid of usual space and time structures. In this thesis, we investigate aspects of a generalisation of statistical equilibrium, specifically Gibbs states, suitable for background independent systems. We emphasise on an information theoretic characterisation based on the maximum entropy principle. Subsequently, we explore the resultant generalised Gibbs states in a discrete quantum gravitational system composed of many candidate quanta of geometry, utilising their field theoretic formulation of group field theory and various many-body techniques. We construct several concrete examples of quantum gravitational generalised Gibbs states. We further develop inequivalent thermal representations based on entangled, two-mode squeezed, thermofield double vacua, induced by a class of generalised Gibbs states. In these representations, we define a class of thermal condensates which encode statistical fluctuations in a given observable, e.g. volume of the quantum geometry. We apply these states in the condensate cosmology programme of group field theory to study a relational effective cosmological dynamics extracted from a class of free models, for homogeneous and isotropic spacetimes. We find the correct classical limit of Friedmann equations at late times, with a bounce and accelerated expansion at early times.