Gunpowder
The Chinese invented gunpowder on accident in the 9th Century. Alchemists were trying to make the elixer for immortality. They instead made a very explosive material. First, they mainly used it for fireworks. They then used it for Military uses.
They made small bombs that would be thrown by soilders and smoke bombs that poisoned enemies. They later also made landmines, bombs that were set up, grenades, and fire arrows. In the 12th Century there were cast iron grenades. These had gunpowder formulas that were powerful enough to burst through the metal container that held the gunpowder. Later there were rockets, the first guns, and flamethrowers that were made from a combination of oil and gunpowder.

Here are Mongol Soilders attacking Japanese Samurai with bombs.
Here is the link to the other pictures.