I have a 5th gen 4Runner with a lot of lights. I installed an auxiliary lithium battery and the Orion XS to charge it, to run the lights separate from the led acid battery to start the 4Runner. Should I run a voltage booster (common thing on 4Runners) to make sure the lithium battery is being charged properly by the alternator?
You already installed an Orion XS to charge the additional LiFePo battery, why would you want to add another voltage booster? The Orion XS does that already, and if you set the charge parameters correctly, then the LiFePo will be charged correctly
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