Boron nitride (BN) aerogels materials have low density characteristics and stable three-dimensional network structure, which can be used as high thermal conductivity ultralight materials or thermal conductive polymer additives. The hexagonal boron nitride nanoribbons (BNNRs) aerogels material not only has a three-dimensional network structure with high specific surface area, but also has a two-dimensional band structure. It has ultra-low thermal conductivity along the in-plane direction, and has ultra-high aspect ratio and electrical insulation energy. However, the research on the thermoelectric properties of BN Aerogels and its composites is still blank. Therefore, it is of great significance to carry out the research on BN Aerogels, its thermoelectric composites, thermoelectric properties and the design of thermoelectric devices. In this paper, BN Aerogels were prepared by the combination of freeze-drying and high temperature thermal annealing, and the effects of 2-methyl-2-propanol (TBA) modification on the yield and quality of BN Aerogels were investigated. The experimental results show that TBA greatly reduces the width and thickness of BNNRs in BN Aerogels, and increases the aspect ratio of BNNRs. The composite thermoelectric particles were prepared by hot pressing to combine BN Aerogels and Bi2Te3 and the influence of the doping concentration of BN Aerogels on the thermoelectric parameters such as Seebeck coefficient and power factor of the thermoelectric battery was studied. The experimental results reveal that when the concentration of BN Aerogels is 1.48 wt%, the ZT value of BN Aerogels/p-Bi2Te3 composite thermoelectric particles is 0.719, while when the doping concentration of BN Aerogels is 1.96 wt%, the ZT value of BN Aerogels/n-Bi2Te3 composite thermoelectric particles is 0.577. And the TBA modified BN Aerogels/Bi2Te3 composite thermoelectric particles show that when the TBA doping concentration is 19.35 wt%, the ZT value of the TBA modified BN Aerogels/p-Bi2Te3 composite thermoelectric particles can reach 0.87, which is higher than that of BN aerogels/p-Bi2Te3 thermoelectric particles, and also much higher than that of the intrinsic p-Bi2Te3 thermoelectric particles. When the TBA doping concentration is 28.57 wt%, the ZT value of the BN Aerogels/n-Bi2Te3composite thermoelectric particles modified by TBA can reach 0.623, which is also higher than that of the BN aerogels/n-Bi2Te3 thermoelectric particles, and also much higher than that of the intrinsic n-Bi2Te3 thermoelectric particles. And based on the self-prepared TBA modified BN Aerogels/Bi2Te3 composite thermoelectric particles, the TEG thermoelectric battery was designed and manufactured. The Seebeck coefficient of the TEG thermoelectric battery can be reached 886.08 μV/K, the conductivity can be reached 9.74 × 104 S/m, and the thermoelectric power factor and power density are 7.65 × 104 μW/mK2 and 14.49 μW/cm3, respectively. This system reduces the need for physical space by using a common framework, which is conducive to the application of thermoelectric power generation technology in micro and small fields.