I am also new to the Xbee world and also working through how the LT/H works. You may have resolved this already and be a few steps ahead of me, but this is what I have determined.
According to the reference manual %V only applies to modules configured as routers so I guess the results for an LT/H sensor is unclear.
I have been reviewing the DIGI python files (refer attached) to determine how the DIA tool manages the Xbee module and determines low battery on an LT/H sensor. These routines read DIO11 (set P1=3) and return true/false for low battery.
Attached is the py file from the DIGI DIA distribution which may help explain.
The “problem” with measuring supply voltage on a sleeping device it is leads to a small current leak at ALL times, meaning even when it sleeps so battery life falls - remember, the XBee is a daughter-module so has limited I/O options.
So most of the Digi products (all?) don’t offer direct access to the battery voltage, but offer the indirect comparator signal (the “low Battery” flag) which I think really just means the output of the voltage regulator has fallen below the expected voltage by some margin.