Those 2 resisters could be a divider, but without a schematic there is really no way to tell.
The wroom-02 also has this in the datasheet for the ADC (TOUT) pin "Tests the power supply voltage of VDD3P3 (Pin3 and Pin4) and the input power voltage of TOUT (Pin6). However, these two functions cannot be used simultaneously. This interface is typically used in sensors." but I am not really sure what they are saying and again, without the schematic, there is no way to know what is between the Wroom-02 and that pin.
Have you tried contacting Wemos?
As far as measuring voltage on something like this, I have found using an ina219 on a separate ESP8266 works much better and will not draw on the battery further, you can also use that to monitor the power from the solar cell to see how effective it is. If you can get the ADC pin to work, that is easier, cheaper and probably a lot better long term, but the ina219 will also give you mA, which would be interesting for the solar cell, I think. I am using that on several to monitor batteries.
A couple of other notes:
This uses an AMS1117 regulator ( I refuse to call it an LDO, max of 39% of output is NOT low) which has between 1V and 1.3V dropout. If the battery is feeding in to this, you need 4.3 to 4.6V to get 3.3V! If there is a diode on this it will be even worse. This is fine for a 5V wall wart, but not so great for batteries. I assume these must be dirt cheap, because there are a lot of better voltage regulators out there.
I have several solar powered ESP units I am testing and I am still split between 18650 and 4 X AA Nimh. For the 18650 units, I use 6V solar cells (you never actually see 6V out of them, especially with a load.) feeding into an inexpensive TP4056, and a MCP1826 Voltage regulator with a shutdown pin. I have also started using a KA75330 voltage detector to turn off the regulator when the battery voltage drops below 3.3V. This winter will be a good test, as it gets very cloudy here, but the one unit outside ( not in a window) has never run down and as an example just before the sun came up today the battery voltage was 3.91V. This is on a ESP8285 with external antenna, BME280, 6V - 6 X 11 cm solar cell, 18650 battery set to sleep for 10 minutes, running ESPEasy 148 I think.
I had a problem of the ESP "locking" at low voltage and not resetting when the voltage comes back up, so I bought a bench power supply and started testing. If the input voltage drops to 2.0V the esp will not recover without a hard reset. With the MCP1826 and good Schotky diode, max dropout is about .5V, so at 3.3V battery I still get 2.8V to the ESP. I also have several capacitive soil moisture sensors where input voltage dramatically changes the moisture reading (860 at 3.3V and 760 at 3.0V). I can use the KA75330 to shut down if the output voltage from the voltage regulator falls below 3.3V. Of course this also keeps the batteries from getting drained to nothing hopefully extending their useful life.
While the modules like Node MCU and wemos work great, they are designed for a 5V wall wart and do not work on batteries very well (ams1117). The adafruit feather huzzah is an exception as it has a built in Lipo charging circuit and the voltage regulator is an AP2112 with a typical dropout of 250mv at 600 mA. If it had Solar charging built in, it would be almost perfect, although expensive.
The best solar charging circuit I have used is
https://learn.adafruit.com/usb-dc-and-s ... q?view=all . It really maximizes the amount of power from the sun. Unfortunately it is expensive and has more bells and whistles than I need for most projects. I also don't know if it will work on an 18650 battery. The chip it uses is not easy to solder so I have not tried to incorporate something like this into my design, yet. I have dreams of doing re-flow, but I probably need to find a job first, which would limit the time I have to work on these things.
