Energy density is the main property of rechargeable batteries that has driven the entire technology forward in past decades. Lithium-ion batteries (LIBs) now surpass other, previously competitive battery types (for example, lead-acid and nickel metal hydride) but still require extensive further improvement to, in particular, extend the operation hours of mobile IT devices and the driving mileages of all-electric vehicles. In this Review, we present a critical overview of a wide range of post-LIB materials and systems that could have a pivotal role in meeting such demands. We divide battery systems into two categories: near-term and long-term technologies. To provide a realistic and balanced perspective, we describe the operating principles and remaining issues of each post-LIB technology, and also evaluate these materials under commercial cell configurations.