It was a double celebration for the British team who took silver as well as gold after 38-year-old Storey pipped compatriot Crystal Lane to the post in the C5 3,000m individual pursuit.
It is Storey's 23rd Paralympic medal over two sports and seven Paralympic Games, having made her debut in the 1992 Barcelona Games.
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Storey began her career as a swimmer but was forced to abandon the pool after suffering persistent ear infections after the 2004 Athens Games.
She returned as a cyclist at the 2008 and 2012 Games to win another six gold medals to add to her five for swimming, and has had considerable success outside the Paralympics including in able-bodied national competitions.
Her 12th gold medal edges her above Tanni Grey-Thompson, who won 11 gold Paralympic medals. The most decorated male paralympian is swimmer Mike Kenny who has 16 gold medals.
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