First of all, create a snapshot of your EBS volume. Then out of that snapshot you will be able to create your new volume.
However, when you detach the old one from your instance and attach the new one, you will still see the old available space with df
look at my /dev/xvdf/ available space (after mounting the new EBS volume)
ubuntu@ip-10-47-167-74:~$ df -h
Filesystem      Size  Used Avail Use% Mounted on
/dev/xvda1       16G  5.9G  9.1G  40% /
udev            7.4G   12K  7.4G   1% /dev
tmpfs           1.5G  176K  1.5G   1% /run
none            5.0M     0  5.0M   0% /run/lock
none            7.4G     0  7.4G   0% /run/shm
/dev/xvdf        20G   19G  1.7G  92% /media/ebs/data  <<< this one
still 20G, I mounted a 80G one!
This drive has been formatted to use an xfs file system. In order to resize it, this is the command I used:
sudo xfs_growfs -d /media/ebs/data
output should be something like this
ubuntu@ip-10-47-167-74:~$ sudo xfs_growfs -d /media/ebs/data
meta-data=/dev/xvdf              isize=256    agcount=4, agsize=1310720 blks
         =                       sectsz=512   attr=2
data     =                       bsize=4096   blocks=5242880, imaxpct=25
         =                       sunit=0      swidth=0 blks
naming   =version 2              bsize=4096   ascii-ci=0
log      =internal               bsize=4096   blocks=2560, version=2
         =                       sectsz=512   sunit=0 blks, lazy-count=1
realtime =none                   extsz=4096   blocks=0, rtextents=0
data blocks changed from 5242880 to 20971520
now let’s see the df -h output
ubuntu@ip-10-47-167-74:~$ df -h
Filesystem      Size  Used Avail Use% Mounted on
/dev/xvda1       16G  5.9G  9.1G  40% /
udev            7.4G   12K  7.4G   1% /dev
tmpfs           1.5G  176K  1.5G   1% /run
none            5.0M     0  5.0M   0% /run/lock
none            7.4G     0  7.4G   0% /run/shm
/dev/xvdf        80G   19G   62G  23% /media/ebs/data
