NodeMCU - Vin pin as 5V output?
There is confusion about what is and what isn't possible with this board. This is because there are different versions with different power arrangements.
NodeMCU 0.9
In this board the USB's 5V and the 5V pin are directly connected together. The combined result is then fed through a diode before entering the 3.3V voltage regulator.
With this arrangement the 5V pin will provide the exact same voltage that the USB port feeds the board. However it is dangerous to connect that pin to any power source - it may kill (or at the very least disable) the USB port in your computer - when the board is also connected to a computer through the USB port.
NodeMCU 1.0 and 1.1
On this version the USB's power is first fed through the diode and then to the 5V pin and the 3.3V regulator together.  This means that the 5V pin will show about 0.5V below whatever voltage is fed in through USB. This isolates the USB from the 5V pin so it becomes safe to provide power through the 5V pin whilst at the same time having the board plugged in to the computer - at the cost of having a slightly lower output from the 5V pin.

Original answer:
The VIN pin not directly connected to the USB's 5V supply (at least on the LoLin v3 board). this means the pin cannot be used as a 5V supply output.

You cannot control that voltage. It is always on, and always 5V (or whatever your USB port happens to provide - 4.75v - 5.25v).
You must never ever connect VIN to a power source and connect the USB socket. That can destroy the USB port in your computer. There is zero back-powering protection on that board.
Drawing more than 500mA from the VIN pin could cause the USB port of your computer to be shut down.