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)00)V(0)V(0 egatloVegatloV(yticapacegrahcsiD1-ghAm500th cycle 500th chgwithout TiOSO4500th cycle 500th chgwith TiOSO41.81.61Zn+0.1Mn 100th cycle 300th cycle 500th cycle 1000th cycle1.4 10th cycle 1.21.00.850100150Specific capacity (mAh g-1)2002503001.81.61.41Zn+0.1Mn+0.5Ti1.2 10th cycle 100th cycle 300th cycle 500th cycle 1000th cycle1.00.810050150Specific capacity (mAh g-1)200250300P1-22Solution: coat Zn with polyionic liquid polymer (PDADMA-TFSI)Effect: Cationic (+ve charged) surface modification to provide electrostatic shielding to enable uniform Zn depositionDuan et al. J. Power Sources (2023) 558, 232356. DOI: 10.1016/j.jpowsour.2022.232356591M ZnSO4MnO2Key Words: Rechargeable, low cost, Pb-acid battery replacementKey Words: Rechargeable, low cost, Pb-acid battery replacementTheme Suppresses phase change with TiOSO4 additivePolyionic liquid polymer (PDADMA-TFSI)Effect of Bi2O3 electrode additive[Without Bi2O3]<15% capacity retention after 100 cycles[With Bi2O3]~85% capacity retention after 100 cyclesZn dendrites caused by tip effect – inhomogeneous negative charge distribution on surfaceTip effect is reduced with cationic (PILZ) coatingWithout coatingWith PILZ coating(120 mins ＝ 30 m Zn deposition) Low-cost energy storage for renewables Replacement of Pb-acid batteries Improve long-term cycle performance Reduce gas generation Increase energy densityExtending cycle stability of MnO2 cathodeSolution１１: add Bi2O3 additive into MnO2 electrodeSolution２２: add TiOSO4 additive into the electrolyteEffect: increases cycle stability of MnO2 due to suppression of Zn-Mn-O phaseDuan et al. J. Power Sources (2022) 528, 231194 DOI: 10.1016/j.jpowsour.2022.231194Duan et al. Small (2024) 2404368. DOI:/10.1002/smll.202404368Enabling smooth deposition of ZnDirections of developmentApplications and prospects1200 mA g-1 1Zn 1Zn+0.1Mn 1Zn+0.1Mn+0.5Ti50010001500Cycle number200100Effect of TiOSO4 electrolyte additive300Improved cycle stability with MnSO4 and TiOSO4 electrolyte additivesMnO2gg-MnO2ZnMn2O4ZHSZnMn3O7 graphite10 20 30 40 50 60 70 801M ZnSO4 +0.1MnSO4pristineZnMn2O4gg-MnO22 (degree)1M ZnSO4+0.1MnSO4 +0.5%TiOSO4ZnThe aim of the project is to develop a low-cost rechargeable MnO2-Zn battery that can be used for large energy storage applications and replacement of Pb-acid batteries Advantages of MnO2-Zn batteries：• High capacity; low cost• Low toxicity, high safety (aqueous)Key issues:• Degradation of MnO2 cathode with cycling• Uneven Zn deposition leads to dendrite and cell short circuitingRechargeable Battery Materials Group, GREEN Denis Y. W. YUE-mail：： yu.denis@nims.go.jpIntroductionLow-cost rechargeable MnO2-Zn Low-cost rechargeable MnO2-Zn batteries for energy storage applicationsbatteries for energy storage applications