Everything looks good except for that one value. I'd say HW Monitor is reading the sensor incorrectly.
Set your cpu to it's default speeds and volts and see if that value changes. If it drops down to a normal temperature then slowly start increasing your speeds and voltage again but this time see if you can determine at what speed and or voltage setting is causing the spike in temperature.
Set your cpu to it's default speeds and volts and see if that value changes. If it drops down to a normal temperature then slowly start increasing your speeds and voltage again but this time see if you can determine at what speed and or voltage setting is causing the spike in temperature.