Does a solar geometry library exist for satellites in LEO?
Almost certainly, but it's also almost certainly hidden. Your question can be broadened:
Does a generic, freely available geometry library exist for satellites in any orbit about any planet (or even in transit between planets)?
Here the answer is YES, not just a boring yes in the standard font and style, but yes in all-caps and bold-faced. That library would be the SPICE Toolkit. A good chunk of SPICE deals specifically with answering geometry questions such as "at time=T, where do I need point my interplanetary satellite so it can communicate with a ground station on the Earth?" SPICE also has a geometry finder subsystem that does the inverse: "At what times is the Earth in view for my satellite?" (Or, in your case, at what times is the Sun in view for my satellite?)
There's one gotcha that might well trip you up, which is that the geometry finder functions need you to describe the position of your satellite as a continuous function of time in the form of a SPICE SPK kernel. A brute force way to do this is to provide a dense time series of cartesian positions, dense enough such that linear interpolation between points in the series yields a sufficiently accurate estimate of the spacecraft position. It's possible to do much better than this brute force approach with higher order polynomials. Unless you know the mathematics of and the potential pitfalls of using higher order polynomials, I'd recommend the brute force approach.