The highest-scoring shootout was Argentinos Juniors' 20-19 win over Racing Club in November 1988, when all drawn Argentine League games went to penalties, from 44 attempts overall.
However, the longest shootout, as recognised by the Guinness Book of Records, was 48 in the 2005 Namibian Cup final, when KK Palace won 17-16 against Civics after 15 kicks were missed.
Liverpool and their spirited Championship (second tier) opponents Middlesbrough were far more accurate, missing three between them out of 30 after their third round match at Anfield ended 2-2 after extra time.
The decisive spot kick was clipped wide in front of the famous Kop by Ghana international Albert Adomah, putting the home side through to the fourth round of the competition.
Liverpool manager Brendan Rodgers praised his team, saying: "Our players showed great resilience to keep going.
"And at the end, when it was needed, they showed wonderful composure with some of our young players stepping up."
While setting a new shootout mark for the competition, it also equalled the record between English professional clubs established when Dagenham & Redbridge beat Leyton Orient 14-13 on penalties after a 1-1 draw in a minor cup played between lower league teams in September 2011.
The previous longest League Cup shootout was 9-8 on three occasions: Arsenal v Rotherham in 2004 and Manchester City v Stoke City and Aston Villa versus Colchester United in 1982.
English non-League clubs Brockenhurst and Andover Town claim the best sequence of successive kicks scored, 29 in the former's 15-14 win in 2013 in the Hampshire Senior Cup.
Highest scoring shootouts at international level include the Netherlands' 13-12 win over England at the European Under-21 Championship in 2007 and the Ivory Coast's 12-11 victory against Cameroon in the 2006 African Nations Cup semi-finals.
(Editing by Mike Collett and Ken Ferris)
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