It's possible something like unplanned power off (or repeated power pulls to reboot) have simply screwed the filesystems up but those issues are normally resolved with the automated fsck on boot while presence of I/O errors normally indicates a dying card. It happens and the lottery these days is normally whether the 'name' brand card you buy from e.g. Amazon is a real 'name' card or a Chinese knock-off that's so accurately reproduced that nobody can tell. RPi boards are no better/worse than any other LE device in respect to read/write "wear" on the card and LE runs the core OS from a virtual filesystem in RAM on anything with 1GB or more so it's really only Kodi related read/write to /storage that is being made. TL/DR; LE should be lighter on the SD card than conventional distros that read/write to the full medium more frequently.
The backup folder will be (by default) /storage/backup which is in the second (STORAGE) partition of the SD card which is EXT4 format and thus not visible to Windows or macOS devices that cannot understand EXT4 filesystems. You will need to copy the backup from the \\LIBREELEC\Backup SMB share or use an SFTP client to copy the file off.
Once you have a copy of the file you can try reimaging the card and restoring the backup. If it was just screwed up filesystems you should be running again quickly. If it was a dying card you should quickly find similar issues.
I would avoid attempting to clone the card as if the card is truly dying it's going to fail, and either way it's a long process. It's also unnecessary if you backed up the data on the card.