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@ARTICLE{Jo:903991,
author = {Jo, Chang-Heum and Voronina, Natalia and Kim, Hee Jae and
Yashiro, Hitoshi and Yaqoob, Najma and Guillon, Olivier and
Kaghazchi, Payam and Myung, Seung-Taek},
title = {{B}io‐{D}erived {S}urface {L}ayer {S}uitable for {L}ong
{T}erm {C}ycling {N}i‐{R}ich {C}athode for
{L}ithium‐{I}on {B}atteries},
journal = {Small},
volume = {17},
number = {47},
issn = {1613-6810},
address = {Weinheim},
publisher = {Wiley-VCH},
reportid = {FZJ-2021-05561},
pages = {2104532 -},
year = {2021},
abstract = {Since Ni-rich cathode material is very sensitive to
moisture and easily forms residual lithium compounds that
degrade cell performance, it is very important to pay
attention to the selection of the surface modifying media.
Accordingly, hydroxyapatite (Ca5(PO4)3(OH)), a tooth-derived
material showing excellent mechanical and thermodynamic
stabilities, is selected. To verify the availability of
hydroxyapatite as a surface protection material,
lithium-doped hydroxyapatite, Ca4.67Li0.33(PO4)3(OH), is
formed with ≈10-nm layer after reacting with residual
lithium compounds on Li[Ni0.8Co0.15Al0.05]O2, which
spontaneously results in dramatic reduction of surface
lithium residues to 2879 ppm from 22364 ppm. The
Ca4.67Li0.33(PO4)3(OH)-modified Li[Ni0.8Co0.15Al0.05]O2
electrode provides ultra-long term cycling stability,
enabling 1000 cycles retaining $66.3\%$ of its initial
capacity. Also, morphological degradations such as
micro-cracking or amorphization of surface are significantly
suppressed by the presence of Ca4.67Li0.33(PO4)3(OH) layer
on the Li[Ni0.8Co0.15Al0.05]O2, of which the
Ca4.67Li0.33(PO4)3(OH) is transformed to CaF2 via
Ca4.67Li0.33(PO4)3F during the long term cycles reacting
with HF in electrolyte. In addition, the authors’ density
function theory (DFT) results explain the reason of
instability of NCA and why CaF2 layers can delay the
micro-cracking during electrochemical reaction. Therefore,
the stable Ca4.67Li0.33(PO4)3F and CaF2 layers play a
pivotal role to protect the Li[Ni0.8Co0.15Al0.05]O2 with
ultra-long cycling stability.},
cin = {IEK-1},
ddc = {540},
cid = {I:(DE-Juel1)IEK-1-20101013},
pnm = {1221 - Fundamentals and Materials (POF4-122)},
pid = {G:(DE-HGF)POF4-1221},
typ = {PUB:(DE-HGF)16},
pubmed = {34677913},
UT = {WOS:000709875900001},
doi = {10.1002/smll.202104532},
url = {https://juser.fz-juelich.de/record/903991},
}