The battery pad on the back of XIAO is for 3.7V LiPo batteries only.
The charge current of the on-board charge controller is 370mA for C3, 120mA for C6, 110mA for S3, 200mA for MG24, and 100mA for nRF52840.
Unless a LiPo battery has a special built-in feature to limit the charge current, it will be charged at the above current. In general, it is recommended that a 180mAh battery be charged at 180mA or less. If a 180mAh battery is charged with C3, it will be charged at 370mA, which may reduce battery life.
The following link may also be helpful.
The following document may be helpful regarding the possibility of LED lighting during sleep.
ESP32-C3 Technical Reference Manual
5.9 Pin Hold Feature
32 LED PWM Controller (LEDC)
ESP32-C3 Series Datasheet
3.4.7 LED PWM Controller