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I'm not qualified to answer the question of if you can add more battery capacity to the Civic, but it wouldn't do much to improve the mpg of your car unless you could charge the batteries from an external source.
Charging batteries from power derived from your engine, and then using it to accelerate your car is less efficient than just using the engine to accelerate your car. The thing that makes a hybrid efficient is that it recaptures a small part of the energy that is normally wasted when you step on the brake; energy that is normally entirely wasted to heat.
I'm sure the Civic was engineered with a battery capacity that optimizes fuel economy, longevity, cost, weight and all of the factors that must be considered.
Now, adding battery capacity that can be plugged in and charged is a whole other topic, and I don't know how difficult it would be to adapt to the Civic.
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