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Li won the 2011 French Open singles title, making her the first player who represents an Asian country to win a Grand Slam in singles. With her performance at the 2011 Australian Open, Li is also the first player of an Asian nation to reach a Grand Slam final.
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When Li was 6 years old, she became a badminton player, but her coach kept noticing that she looked as if she were playing tennis. By the time she was 8, her coach asked her parents if she could switch to tennis, which she did at the age of 9. Li joined China's National Tennis Team in 1997 and turned pro in 1999.
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Li also frequently enters doubles tournaments at events alongside singles, and has won two WTA doubles titles and 16 further ITF doubles events. Her early success in doubles came mostly with Li Ting (no relation); but more recently she has made a habit of forming temporary women's doubles partnerships with players with whom she has previously enjoyed a healthy rivalry through repeated head-to-head meetings in singles tournaments, notably Liu Nan-Nan, Nicole Pratt, Yan Zi, Jelena Janković, and Peng Shuai.
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Li was the 9th seed at the 2011 Australian Open, where she reached her first Grand Slam singles final. On her way there, she ousted the No. 8 seed Victoria Azarenka in straight sets, 6–3 6–3. She then defeated world No. 1 Caroline Wozniacki in the semi-finals to reach her first Grand Slam final after saving a match point in the second set, 3–6 7–5 6–3. She became the first Chinese player to reach a Grand Slam singles final, facing No. 3 seed Kim Clijsters (whom she defeated at the Medibank International). Although Li claimed the first set, Clijsters was able to rally back and claim the championship, winning 3–6, 6–3, 6–3. Despite the loss, Li's ranking rose to a career high of world #7.
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Li's losing streak then continued when she was upset in the 2011 Sony Ericsson Open by Swede Johanna Larsson 5–7, 7–6(5), 6–7(5). With this loss, and Andy Murray's loss at Miami, both Australian Open finalists have yet to win a match since the first Grand Slam. Despite Li's successive losses, her #6 Ranking was ensured due to Samantha Stosur's inability to defend her clay season points. After a week, she fell back to #7. Li then broke her losing streak by winning her first round match against Anastasija Sevastova in Stuttgart, 6–2, 6–3. However, she subsequently lost to Sabine Lisicki in the second round, 4–6, 5–7. Even, though she was not able to defend all her Stuttgart ranking points,she rose back to #6, with Samantha Stosur's inability to defend her own Stuttgart points. However with her disappointing results Li Na sacked her husband as coach and hired the Dane Michael Mortensen.
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Li's resurgence continued in 2011 Internazionali BNL d'Italia. Seeded 4th, she received a bye in the first round. She won her opening match against Lourdes Domínguez Lino 6–4, 6–2. She defeated Jarmila Gajdošová 6–2, 6–1, and Gréta Arn 6–3, 6–1 in the next two rounds en route to her back-to-back semifinals on clay court.However, she lost to Samantha Stosur 7–6(6), 6–0.
Li won her first Grand Slam title and become the first Grand Slam singles champion born in an Asian country at the 2011 French Open. Seeded 6th, she defeated Barbora Záhlavová-Strýcová, Silvia Soler Espinosa, Sorana Cîrstea, 9th seed Petra Kvitova, 4th seed Victoria Azarenka, 7th seed Maria Sharapova and 5th seed and defending champion Francesca Schiavone in the final. After the match, Li Na was praised by the Chinese media and her popularity throughout China is expected to grow significantly in the following months, as she became the first ever Chinese singles player to win a tennis Grandslam title. Following the French Open, Li reached a career high ranking of World No. 4.
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Due to the withdrawal of Kim Clijsters, Li was the 3rd seed at the 2011 Wimbledon Championships. She beat Alla Kudryavtseva in the first round. She lost in the second round to Sabine Lisicki of Germany 3–6, 6–4, 8–6.
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In 2000, she won a total of 52 singles matches on the ITF circuit, more than any other player, notching another eight tournament titles including one at $50,000 level, two at $25,000, and an unbroken run of four successive $10,000 tournament wins in March and April.