Hi there. Offline refers to a power supply that derives its input power off of the AC power line. In that case off is used to mean from.
The expression offline might be considered idiomatic because as you are thinking, online might seem to be a better way to say something is connected to the mains power. Then it would be similar to the expression of a computer being online.
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Albert Szent-Györgyi: “discovery consists of seeing what everybody has seen and thinking what nobody has thought.”
Offline SMPS is a special type of ac-dc converter called an off-line converter or off-line power supply. In off-line converters the ac voltage is rectified to dc directly off the ac power line and filtered with no isolation transformer and then processed with a dc-dc converter that provides isolation at the switching frequency, wich is normaly 20khz or higher
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