Actually, they're much better than "just" 95%.
98-99.5% is realistic with at least non-isolated converters for each end.
And yeah, a DC grid needs active converters at connections points anyways, and the small voltage changes needed for steering power flow across redundant paths is also relatively cheap.
A big issue is just that a constant-power SMPS with an input voltage range/tolerance inherently offers a negative differential (aka incremental) resistance: within the supported input voltage range, reducing the input voltage causes the current consumption to increase inverse-proportionally (typically even a tiny bit worse because internal losses in the SMPS increase with current, requiring even more current to make up for the slight drop in efficiency (think 98% to 97%, for a sense of scale)).
In AC grids phase is comparatively easy to stabilize, and constant-power loads already need PFC that (for single-phase rectifiers) has to emulate a normal resistor who's resistance slowly drifts to accommodate changes in output power consumption. The only real issue is that this method requires an intermediate stage with large capacitors to feed the output stage while the input stage stops feeding near the zero crossing (the capacitors get smaller if you do away with the zero crossing (DC grid using the emulated resistance for stabilizing the grid), but the stages remain, along with their ~1% inefficiency per stage).
The main issue with LEDs is that you need electrolytic capacitors to buffer the zero crossing of single-phase AC, and electrolytic capacitors dry out/corrode when operated at high temperatures.
So unless you want the LED PSU to have a fan, those capacitors will severely affect how tightly integrated you can build a non-low-power LED light bulb.
And yeah, especially at a local scale DC grids are very useful, because you can skip expensive inverters and conversion losses for both battery(-backup) sources and solar panels/fuel cells.
You would typically still want an MPPT for a string of solar cells, but that's a compact and rather inexpensive DC/DC converter. Batteries only need a way to accurately limit the charge voltage/current per-pack, to prevent the voltage drop along the grid cables from affecting the maximum charge voltage/state of the pack's cells. Also a deep-discharge protection, but beyond those, a (mostly) solar-fed local DC grid can just let the MPPTs feed as much as they can up to a target voltage, from where they start to gradually throttle output current to only produce as much as is being used (once the batteries are full). If the batteries start to reach sufficiently low charge state, load shedding or alternative power has to be used (say, via telling PCs to reduce/disable Turbo Boost and similar, or lights/screens to limit brightness).