When Captain America throws his mighty shield, all who oppose his mighty shield must yield! Well, apparently not everyone. Captain America's mighty vibranium shield is not only a staple of the Avengers team, but essentially symbolizes everything the good soldier stands for.
The mighty shield he uses is actually much more than a glorified frisbee. It is composed of vibranium, a powerful metal found in Wakanda that essentially absorbs the power of all impacts through vibrations. It's not quite as strong as adamantium, but it's still a force to be reckoned with. Because of the composure of the metal, the shield is also incredibly lightweight, and sometimes even defies the laws of physics (those of you who saw Civil War already will get the joke).
We've already seen in many of the MCU movies just how strong the shield is. It can take a hit from Thor's hammer without a single scratch, has deflected Loki's scepter, and can hold back Iron Man's repulsor blasts. However, the shield is not indestructible. Across the multiverse in Marvel history, there have been several instances where Cap's shield has been broken or shattered. Now, not all of these examples are from the main universe (Earth-616) simply because there weren't very many times it happened there according to my research. Regardless, Cap's shield was still broken, and here are eleven people that did it.
11 Doctor Doom
Doctor Doom is one of the most intelligent villains in the Marvel Universe, so much so that he was able to trick the Beyonder- a cosmic being with seemingly limitless power. Doom ended up stealing the Beyonder's power and laid waste to all of the Marvel superheroes. All we get after that is a lone panel with Captain America's shield - broken. Luckily for the Avengers, the Beyonder tricks Doom into resurrecting all of the heroes again, so they can live to fight another day. Oh yeah, Cap gets his shield back, too.
10 Molecule Man
As ridiculous as he looks and as campy as his name is, Molecule Man is not a villain you want to mess with. His special power is being able to manipulate molecules, so he can essentially control the entire world. When confronted by the Avengers, he demonstrates his power by disintegrating Thor's hammer, Silver Surfer's board, Iron Man's armor, and yes, Captain America's shield. He even did it all without breaking a single sweat. Still, the heroes end up finding a way to beat him and after doing so, he agrees to reassemble their disintegrated items.
During the Infinity Gauntlet storyline (which is what the MCU is taking inspiration from for the third Avengers film), the Avengers from all corners of the world find themselves face to face with the Mad Titan, Thanos, complete with the Infinity Gauntlet and all of the Infinity Stones. His powers become God-like, and of course, Steve Rogers isn't afraid. He rushes to Thanos with his mighty shield in hand, but Thanos, with a twisted smile, breaks the shield in one blow and then proceeds to kill the Captain where he stands. Sorry Chris Evans lovers, this doesn't bode well for him when Infinity War comes around.
8 King Thor
We've already seen that Thor himself is not strong enough to break Captain America's shield, but all of that changed when his father Odin died. Thor became the King of Asgard, and with it, inherited the Odin Force. The Odin Force gave Thor incredible power, but also an incredible attitude. During a rage-filled battle, King Thor goes up against Captain America. However, within minutes, he kills the Captain and destroys his shield. It says a lot about the scope of Odin's powers and whether or not Thor is truly ready to be a ruler. How's that for long live the king?
7 The Serpent
Another individual from Asgard, the Serpent is exactly as strong and menacing as he sounds. He is the God of Fear and was freed during an "event" comic. He begins to turn Marvel heroes into his mindless minions. Naturally, it's up to the Avengers to bring down this tyrant. During the epic battle, Captain America throws his mighty shield at the Serpent, but instead of taking a beating, Serpent just catches the shield and snaps it in half with his bare hands. Luckily for Cap, after Serpent is defeated, some dwarves repaired the shield which left a scar on it from then on.
I kid you not. Captain America's shield once got some sort of vibranium cancer. You see, vibranium can absorb almost any impact, but it's not without its limits. Once, Captain America essentially absorbed an impact that caused a molecular anomaly in the structure of the shield. The anomaly slowly progressed through the entire shield, infecting it to the point where it ended up shattering altogether. Then, in true comic book fashion, it got fixed after the supervillain Klaw blasted some sonic waves at it which turned out to be just the thing the shield needed to be restructured.
Here's where we start getting to the alternate Earths. In this Earth, the president of the United States despised the mutants, so he vowed to make them extinct through the use of Sentinels. After decades of war, the mutants were finally extinguished, but other heroes were out for vengeance. Captain America, knowing many of the mutants that were slain, decided to take the battle to the Sentinels himself. Unfortunately, he was no match for the robots and was killed in the process. The resulting damage on his shield removed a large chunk from one of its sides.
This earth is the epitome of anarchy. Superheroes and supervillains run amok with no laws or regulations. So the U.S. government made superpowers illegal, but that didn't stop the criminals from taking over. But how did it get to that point? Nine years before then, the sinister Hyperion sought to destroy the entire world with a powerful army behind him. The war was tough and many sacrifices were made. One of those sacrifices came from Captain America. In an attempt to stop Hyperion, he lost his life, and his shield became severely cracked in the aftermath.
This Earth sees an alternate form of Namor the Submariner (called Namora) take control of the entire Earth and crush anyone who stood in her way. Many heroes like Mister Fantastic lost their lives in the process. The result was an earth nearly submerged in water. She isn't without her enemies though. For example, Captain America was determined to put an end to her plans, but she didn't take too kindly to that. During their fight, she actually managed to chip the Captain's Shield. While it's not completely broken, that still counts for something. After all, it takes a lot to damage that particular frisbee.
Could you imagine if Tony Stark decided that he wanted to rule the world and shape it into his own image to protect it? That's exactly what this world is all about. Tony Stark manipulated the world into electing him as Emperor of the Planet until the day he dies. All who opposed his rule were killed without question. You can imagine there were many uprisings and wars during that time. One of these wars, called the Mutant Wars and started by Magneto, was a brutal event. Captain America was one of the heroes caught up in the war, and it cost him his life. And his shield fared no better. It was shown to have a giant hole melted through it. Although... we're never told exactly who did it.
This comes directly from the cartoon Avengers: Earth's Mightiest Heroes. During the episode "The Fall of Asgard," Loki is seeking to take over Asgard and finally put an end to his brother Thor. Naturally, the Avengers come to stop him from doing so. However, Loki gains access to the Odin Force, and when Captain America comes to fight him, the God of Mischief shatters the shield into tiny fragments. The Captain ends up using Lady Sif's shield for the rest of the fight, but it was a devastating defeat for Steve Rogers, nonetheless.