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She turned professional in 1999 at the age of sixteen.At the end of 2002, Li left the national tennis team to study part-time at Huazhong University of Science and Technology (HUST), where she completed her bachelor's degree in journalism in 2009. Some reported that the relationship between her and her teammate and future husband, Jiang Shan (姜山), was opposed by the national team's management, a day out from the 4th anniversary of her French Open win.Prior to this, she had already become the first player representing an Asian country to appear in a Grand Slam singles final, a milestone she achieved at the 2011 Australian Open.Li was also the runner-up at the 2013 Australian Open and 2013 WTA Tour Championships, a three-time quarterfinalist at Wimbledon and a semifinalist at the 2008 Beijing Olympic Games and 2013 US Open.Despite winning the first set, Li lost her first WTA singles match to Anna Zaporozhanova in three sets, but she captured the women's doubles title at Tashkent with Li Ting against Zaporozhanova and Iroda Tulyaganova.
Her mother didn't tell Li Na that her father had died for many weeks, thinking it would affect her game.
Li turned professional in 1999, and won three of the first four singles tournaments she entered on the ITF Circuit, two at Shenzhen and one at Westende, Belgium.
She also won all of her first seven ITF doubles tournaments she entered.
On the back of the ranking points accrued through this result, on 4 October 2004, she broke into the WTA top 100 for the first time.
To cap off her most successful year as a singles player yet, she competed in two ,000 ITF tournaments at Shenzhen, winning the first outright to bring her the 19th ITF singles title and 20th overall singles title of her career, but losing in the quarterfinals of the second to lower-ranked country-woman Yan Zi. 80 by the close of the year, a year in which she won 51 singles matches and lost just four.