I am looking for a well insulated door to mount on the exterior of ICF walls. To help with passive solar heat they would be combined with mostly glass overhead doors mounted on the inside, the exterior doors would be open during the day and closed at night, hot days or bad weather. 10' x 10' or so.

Roll-up doors? Bi-fold? Brand? Any suggestions?

Depending on your particular design, there are several alternatives.
The most likely candidate would be a rollup door such as those used on mini-storage and commerical applications.
Most of these companies make a reverse roll door designed for outside mounting. These units can be insulated with radiant barrier (bubble wrap) insulation the an R value of about 7. Check out Trac-Rite Doors at www.tracrite.com.
An interesting solution I have seen on rural type designs is a sliding door similar to the type used on barns. These units can be insulated by different methods as well.

Any other info?

http://kierantimberlake.com/featured_projects/loblolly_2.html

I'm interested in this type concept as well.  to work in MN in a lakeside south facing lot.   Lot's of glass to lake(southern exposure) for views, passive solar but want to maximize thermal performance and minimize heat loss at night.

Those are nice doors, they double as awnings to block out the high sun, while up in the summer. But the architect firm do not say who made the doors. If you find any more info, please post here, as will I.

Schweiss in MN makes bifold doors like that.  I think I saw another company in wisconsin that does as well.

http://www.bifold.com/door-specialty.php

Those Schweiss doors look nice, and they are local. I wonder how much they cost? I could not find how much insulation they have.

How about insulating a sliding roller door, like barn doors?

http://www.barndoorhardware.com/400lbCapacitydoors.htm

With any of these solutions, the critical aspect will be forming an air seal on this second door as well, or the slightest breeze will blow behind the insulated door, and at that point it doesn't matter what kind of insulation the outer door has. I would shy away from roll up type doors. The barn doors like in the link won't have any sort of air-sealing provisions because they are for a barn. If you wanted to use a slider, it either needs to "sink in" to the frame to create an air-seal or have really accurate weatherstripping to brush against it when it is closed. The bifold type door looks like the best off the shelf solution, it wouldn't be as hard to get an air seal.

I saw the bi fold door and the motor and some of the hardware is more than 12" to the inside and therefore would hit the inner door.

I think I can have the sliding door, slide away from the house and be pulled in to the house, tight.

I got a quote on the bifold/hydraulic doors for my own curiosity, they are 5x the money of a standard insulated garage door. For the slider, are you planning on motorizing it, or will it be manual?

the bifold is expensive, but it goes on the outside like I need. The more I think about it, the better I like it. Is there a motorized opener/closer that would work?

Yes, the doors are available with a motorized opener.  After reading this thread, I requested quotes from www.bifold.com on a 8'h X 9'w door.  The bid for the bi-fold was around $5,800.  The hydraulic door was a little over 6k.  Each door came with an automatic opener.  It had a 1 HP motor that ran on 240V.

I had Schweiss bid 10x10 and 12x12 doors, they weren't that much but the doors did not include inside or outside "skin" or insulation. I saw them at the Minnesota State Fair, they are quality doors but the opener and hardware protrude to the inside more than I can use for this application.