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Josh,
Where do you plan on using this Peltier energy harvester?
Here is a circuit that is powered by a Peltier and senses temperature. Low power sensor applications would be a good use of the effect. The more of a difference in between two surfaces the better your project will work.
See more about this fully worked out project at Linear's site.
First of all, I recommend learning as much as you can about the Peltier. Build some projects that are already worked out, like the two above. Then, I would say, you know enough to venture out to build your unique project.
I have a project idea for you to try in the future:
Use the heat source from your furnace or water-heater to detect moisture on the basement floor. (If you live in a house.)
Or a similar heat source for detecting window condensation. (For high-rise apartments, window moisture is an issue.)
Cabe