You need to work with AWS Powershell Module.
The trick here is work with 2 cmdlet function - Get-EC2instance and Get-EC2KeyPair. First of all, you need to get all the keys that in use right now.
Later, you need to get all key pairs and filter them by basic for each and if statement.
Take a look at the following code snippet :
Import-Module AWSPowerShell
$keysInUse = @()
$keysNotInUse = @()
#Set AWS Credential
Set-AWSCredential -AccessKey "AccessKey" -SecretKey "SecretKey"
#Get ec2 key name from each instance
$allInstancesKeys = (Get-EC2instance -Region "YourRegion").Instances.KeyName
#Get all key based on region and check if there's an instance who use this key
Get-EC2KeyPair -Region "YourRegion" | % {
if($_.KeyName -notin $allInstancesKeys)
{
$keysNotInUse += $_.KeyName
}
else
{
$keysInUse += $_.KeyName
}
}
Write-Output "Keys not in use: $($keysNotInUse -join ',')\n
Keys in use: $($keysInUse -join ',')"
The instances i own and key name :

Output :

How to create new AccessKey and SecretKey - Managing Access Keys for Your AWS Account.
AWSPowerShell Module installation.
More about Get-EC2KeyPair Cmdlet.
From the docs :
Describes the specified key pairs or all of your key pairs.
More about Get-EC2instance
Returns information about instances that you own.