The CompCert verified C compiler is "big" software, but not actually written in C, rather OCaml and Coq/Gallina.
also, what happens when the loop invariants can't be automatically proved? is there some way to manually prove invariants hold?
Coq has been used to formally verify a large body of classical mathematics. Coq can 'understand' what a prime number is and can be used to prove that there are infinitely many primes, can prove that sqrt(2) is irrational, etc. Coq can prove a recursive solver for the Towers of Hanoi actually solves the problem, etc. And thus Coq can prove a C program to solve the Towers of Hanoi correctly solves the problem, because Coq can reason about C programs.
I've been slowly working through the Software Foundations series on using Coq/Gallina:
https://softwarefoundations.cis.upenn.edu/
Another poster mentioned CBMC which I just started playing with. It is much less powerful than Frama-C, there isn't the ACSL specification capability and theorem proving, but it is much more automatic and much faster to get started with. For many cases if I just want to verify that a certain C file frees all its mallocs, doesn't have out-of-bounds accesses, and that all obviously bounded loops terminate, CBMC is much easier. Also, like Frama-C, it converts C functions into "goto programs" (removes the syntactic sugar of 'for' and 'while' loops to obtain a more pure Control-Flow-Graph (CFG)) for certain forms of analysis, and when I first encountered this in Frama-C there was no explanation why, whereas the manual for CBMC actually has an excellent gentle introduction: