With following command you are able to manually add an entry
| # ip -6 neigh add <IPv6 address> lladdr <link-layer address> dev <device> | 
Example:
| # ip -6 neigh add fec0::1 lladdr 02:01:02:03:04:05 dev eth0 | 
Like adding also an entry can be deleted:
| # ip -6 neigh del <IPv6 address> lladdr <link-layer address> dev <device> | 
Example:
| # ip -6 neigh del fec0::1 lladdr 02:01:02:03:04:05 dev eth0 | 
The tool “ip” is less documentated, but very strong. See online “help” for more:
| # ip -6 neigh help
Usage: ip neigh { add | del | change | replace } { ADDR [ lladdr LLADDR ] 
          [ nud { permanent | noarp | stale | reachable } ] 
          | proxy ADDR } [ dev DEV ] 
       ip neigh {show|flush} [ to PREFIX ] [ dev DEV ] [ nud STATE ] | 
Looks like some options are only for IPv4...if you can contribute information about flags and advanced usage, pls. send.