But doesn't the rectifier act as kind of a check valve?
Yes, it is a check valve for current.
Back up.
The battery is a DC (Direct Current) creature. It likes to take in current in a constant fashion, and it doles it out the same way.
The current in an alternator is constantly changing direction (Alternating Current) depending on which magnetic pole it is associated with at a given moment moment, and this changes several times in a rotation.
The rectifier blocks battery current from depleting into the stator coils. More importantly, when the alternator makes more voltage than the battery has, the rectifier allows only the current polarity acceptable to the battery, to pass through it.
Voltage is the potential to do work. Current is what happens when it its working.
12.6 V is a charged and resting voltage for a good battery. Depeletion (or on its way to depletion) is below that voltage. A battery that is accepting a charge can and should be above that voltage.
Would it confuse you to know that a battery doesn't actually store electricity? It converts electricity into a chemical reaction. This then produces electricity when the chemical reaction is reversed.
The bike's electrical system CAN see 14.5V only when the battery has been charged to that level. The electrical voltage level of the bike IS the battery voltage. The battery is normally slow to change it's level, and the charging system can only persuade it to reverse the chemical reaction. It cannot demand it. There is much more conversion power in the battery than the alternator can ever hope to make in an instantaneous time period.
If the voltage regulator is doing its job, it monitors the battery for signs of overcharge. When this occurs, the regulator tells the alternator to not make as much power (lowers the Field voltage). The alternator output is then usually below the usage level of the bike electricals, so the battery depletes and the voltage falls. The Regulator sees this and say's "OH my GOD the battery isn't full" and applies the whip to the alternator in the form of more voltage to the Alternator field coil. The cycle continues at a frequency governed by the electrical load, the power or rotational speed of the alternator rotor, and the conversion capacity of the battery.
You can never see this with the naked eye. Tools must be used to interpret voltage levels. These tools are not absolute. Some average, some sample, some have display update frequencies that beat against the Voltage Reg reaction frequencies. Few of us have oscilloscopes to monitor the goings on visually. But, that's okay. You can get the gist of what is going on with simple DMM and VOM measurements. And a good battery should act as a huge capacitor to filter/iron out rapid voltage oscillations at the battery. This is why the alternator connection should be made as close to the battery terminals as it possible.
If so, then couldn't you see the regulator kick back & forth between charging and maintenance by watching the headlight fluctuate between 14.5 & 12.whatever? Or is the incoming charge overwhelmed by the battery capacity, in effect acting as a dampening chamber?
That's a descent enough conceptual description. But, you probably shouldn't teach that way.
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You can see the effect of the regulator working on the White wires from the regulator, provided the frequency it is operating at is within the display range of your instrumentation. There may also be some small ripple currents wandering about the bike wiring, too, if you know what to look for.
Hope this helps,