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Well there are some things to keep in mind.
A.) Batteries can't stay at 100% when they are topped off. In fact the life cycle of a rechargeable battery is that the older they get they less they can hold a charge. So even though the screen may report the battery being topped off at 100% before you unplug, the reality is that it is holding 2% less(maybe even as much as 6% less) than what is being reported. It's unrealistic for new batteries to hold 100% charge after being topped off. You might ask why that's not true for some devices that report a 100% charge for batteries that have only gone through a month use, that leads to the second issue.
B.) Battery charge indicators are not 100% accurate. They use a collection of mathematical formlas and statistical algorithms to produce an estimated charge. Reading the volts from a volt meter is not how battery charges are indicated with. Instead, a collection of volt readings across time is used to produce an estimated charge percentage for a particular point in time.
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