TY - JOUR
T1 - Partially methylated polybenzimidazoles as coating for alkaline zinc anodes
AU - Konovalova, Anastasiia
AU - Stock, Daniel
AU - Schröder, Steffen
AU - Park, Hyun S.
AU - Jang, Jong Hyun
AU - Kim, Hyoung Juhn
AU - Han, Jonghee
AU - Schröder, Daniel
AU - Henkensmeier, Dirk
N1 - Funding Information:
The work was supported by funding from KIST (internal budget and Global Mobility Program) and NRF . D.St. and D.S. gratefully acknowledge financial support by the BMBF (Federal Ministry of Education and Research) within the project ‘Zisabi’ ( 03XP0086 ) and by the DFG via the GRK (Research Training Group) 2204 "Substitute Materials for sustainable Energy Technologies".
Publisher Copyright:
© 2020 Elsevier B.V.
PY - 2020/9/1
Y1 - 2020/9/1
N2 - Hydroxide ion conductive polymer coatings with a low permeability for zinc species reduce shape change and dendrite formation of zinc anodes, and reduce the capacity fade over charge/discharge cycles. Herein we focus on the material properties and aim to minimize the permeability of polybenzimidazole (PBI) for zincate ions by methylating its imidazole NH groups. This reduces the volume swelling in 4 M KOH solution from 104% for PBI to 20% for a PBI with 1.3 methyl groups per repeat unit. Similarly, materials with a degree of methylation (DOM) between 0.96 and 1.2 show very low uptake of KOH. Above a DOM of 1.7 decreasing alkaline stability is observed, presumably because a fraction of the imidazole groups is permethylated to benzmidazolium ions. Most importantly, membranes with a DOM around 1–1.2 revealed the lowest permeation for zincate ions, with permeability coefficients P of 0.9–1.5 10−9 cm2 s−1, 3000 times lower than for PBI. At higher DOM slightly higher P values were observed. In a Zn/NiOOH cell an optimized anode coating with 0.96MePBI led to better cycling stability than with PBI, and an initial capacity of 265 mAh (g anode)−1.
AB - Hydroxide ion conductive polymer coatings with a low permeability for zinc species reduce shape change and dendrite formation of zinc anodes, and reduce the capacity fade over charge/discharge cycles. Herein we focus on the material properties and aim to minimize the permeability of polybenzimidazole (PBI) for zincate ions by methylating its imidazole NH groups. This reduces the volume swelling in 4 M KOH solution from 104% for PBI to 20% for a PBI with 1.3 methyl groups per repeat unit. Similarly, materials with a degree of methylation (DOM) between 0.96 and 1.2 show very low uptake of KOH. Above a DOM of 1.7 decreasing alkaline stability is observed, presumably because a fraction of the imidazole groups is permethylated to benzmidazolium ions. Most importantly, membranes with a DOM around 1–1.2 revealed the lowest permeation for zincate ions, with permeability coefficients P of 0.9–1.5 10−9 cm2 s−1, 3000 times lower than for PBI. At higher DOM slightly higher P values were observed. In a Zn/NiOOH cell an optimized anode coating with 0.96MePBI led to better cycling stability than with PBI, and an initial capacity of 265 mAh (g anode)−1.
KW - Alkylated polybenzimidazole
KW - Anode coating
KW - Hydroxide ion conductivity
KW - Zinc oxygen battery
KW - Zincate ion permeability
UR - http://www.scopus.com/inward/record.url?scp=85084844062&partnerID=8YFLogxK
U2 - 10.1016/j.memsci.2020.118254
DO - 10.1016/j.memsci.2020.118254
M3 - Article
AN - SCOPUS:85084844062
SN - 0376-7388
VL - 610
JO - Jornal of Membrane Science
JF - Jornal of Membrane Science
M1 - 118254
ER -