摘要：Manganese tetravalent oxide(MnO_(2)),a superstar Faradic electrode material,has been investigated extensively for capacitive desalination,enabling higher salt adsorption capacity compared to the great majority of carbonous ***,few works paid attention on the relationship between the valences of manganese oxide and their desalination *** the first time,we prepared the spindle-like manganese oxides/carbon composites with divalent(MnO@C),trivalent(Mn_(2)O_(3)@C)and divalent/trivalent(Mn_(3)O_(4)@C)manganese by pyrolysis of manganese carbonate precursor under different condition,*** electrochemical behavior in three-electrode system and electrosorption performance obtained in hybrid membrane capacitive deionization(HMCDI)cells assembled with capacitive carbon electrodes were systematically evaluated,*** salt adsorption capacity(as large as 31.3,22.2,and 18.9 mg·g^(−1))and corresponding average salt adsorption rates(0.83,0.53,and 1.71 mg·g^(−1)min−1)were achieved in 500 mg·L^(−1) NaCl solution for MnO@C,Mn_(2)O_(3)@C,and Mn_(3)O_(4)@C,*** fifteen electrosorption-desorption cycles,ex-situ water contact angle and morphology comparison analysis demonstrated the superior cycling durability of the manganese oxide electrodes and subtle difference between their surface ***,density functional theory(DFT)was also conducted to elaborate the disparity among the valence states of manganese(+2,+3 and +2/+3)for in-depth *** work introduced manganese oxide with various valences to blaze new trails for developing novel Faradic electrode materials with high-efficiency desalination performance by valence engineering.