Don't expect your mcu to run at 3.9V, li-ion starts at 4.2V but quickly drops and stabilizes at ~3.7V.
Nope, My 18650 Li-on battery will never start to discharge at 4.2V, because of it is charged to 3.9Vmax

and this can extend its lifespan, since it can make more charge/discharge cycles.
Discharge voltage as low as around ~2.7V it is worst case when ATTiny85 with BOD enabled for 3.3Vcc powered directly from 18650 Li-on battery will stop working when Vcc will be as low as typical 2.7Vcc BOD level @ 3.3Vcc and it is slightly above flat Li-on battery 2.5Vbat minimum

So, Attiny85 BOD level for 3.3Vcc programmed by using AVR BOD fuse bit is is simply used as additional 18650 Li-on battery over discharge protection, because of MPU itself can sometimes from time to time make its Vcc voltage measurements and go into sleep mode eg. while running <3Vcc
