3.65V is 'full' for LFP cells. By bringing all your cells to that voltage (usually in parallel), you're more sure they are at the same energy level (assuming capacity-balanced cells). This approach is referred to as 'top-balancing'.
The problem with 3.2V is that's on the very flat part of the charge/discharge curve for LFP chemistry. You could be at 20% SOC or 40% SOC, depending on very small voltage differences that would all read as 3.2V on a not-very-precise-or-accurate meter.
There is also an approach called bottom-balancing, which I've never used, that tries to achieve the same result by starting at 0% SOC (or some other very low number). I don't like bringing cells down that low (it can be hard on them), and it's not as well-defined of a voltage (2.5V, 2.75V, ...?). 100% SOC is easy to know you're at, based on the cells not accepting further charge beyond just a trickle (C/100 say).
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