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No, not without first suing her and getting a judgment against her. Someone can't file a lien unless they have a legal basis to do so and in this situation, it would have to be an order from the court or a legal judgment for some amount of money before he could file a lien on the vehicle.
No, if he sued his wife and got a judgment, he could lien the vehicle to the extent that she owned it. If you are both on the title, she owns half and you own half. So he could potentially lien it to the extent of half the equity value of the vehicle.
But since most people owe more on a vehicle than it is worth due to depreciation, it is unlikely that he would go through the time and thousands in attorney fees to sue her, get a judgment, and then lien a vehicle that likely doesn't have much if any equity in it because the purchase loan would have to be paid off first in any sale so there probably wouldn't be anything left to pay him.