Let’s Encrypt will probably not fit to your needs:
First of all you need to proof the possession of the domain - you could use another server to do so. Therefore you have to run the let’s encrypt client in the standalone mode and generate the certificate and copy it afterwards on to the ASA.
BUT this has to be done every 90 days.
The Let’s Encrypt client is designed automates the whole process including the renewal, on a webserver.
Cisco may support the ACME-Protocol in the future (Let’s Encrypt based on it), but for now you may use an alternative like WoSign: Install a certificate on Cisco ASA 5520