For 2,3,4 or even 5 cell batteries 24 volts is usually good enough (depending on the charger). But when you move up to the bigger packs, 6, 8 or 10 cells you start running up against the input current limitations of the charger and the only wany to get around that is to up the voltage.
The typical charger we're talking about has a built-in buck-boost regulator. When charging a 6 cell or larger battery at 30-40 amps the input currents can get quite large, which is why people with the these batteries & chargers are switching from 12V to 24V (or more) power supplies to power them. All of these devices have input & output limits on voltage, current & watts. So bumping up the voltage in some cases means you get full power out of your charger vs not getting full power out if you don't. It may seem trivial but a lot of folks want every last watt out of their charger as it reduces the time to charge and increases the time to fly.
Dean