Because higher voltage puts more stress on the chemical constituents of the battery. So does higher temperature, which is mostly produced during the last stage of charging, when the battery’s inner resistance to current in that direction is high.
Other batteries have different vulnerabilities. For instance, lead-acid batteries are the most stable when fully charged, and I think NiMH don’t really care.
Resistance in the cells goes up in the top 15-20% and also in the bottom 15-20%. It’s why your phone battery may get hot when charging or discharging in that zone. Most devices have an oversized battery that will keep your phone or other devices working when it’s near a full charge or discharge. Almost all devices designed to run on lithium batteries are designed to shut off before the cells are fully discharged to help prevent cell damage and possible fires.
Source: RC hobby and fear of fires forced me to do a lot of research on lipo batteries.
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