7 research outputs found
Mesoscopic Phase Transition Kinetics in Secondary Particles of Electrode-Active Materials in Lithium-Ion Batteries
Many compounds used
as battery storage electrodes undergo large
composition changes during use that are accompanied by a first-order
phase transition. Most studies of these phase transitions have focused
on the unit cell to single-crystallite scale, whereas real battery
electrodes are typically composed of mesoscopic assemblies of nanocrystallites,
for which phase transformation mechanisms are poorly understood. In
this work, a systematic study is conducted of the potentiostatic (constant
driving force) kinetics of phase transition in secondary particles
of representative intercalation compounds: LiFePO<sub>4</sub>, LiMn<sub>1–<i>x</i></sub>Fe<sub><i>x</i></sub>PO<sub>4</sub>, and Li<sub>4</sub>Ti<sub>5</sub>O<sub>7</sub>. Storage kinetics
are studied as a function of overpotential, material composition,
primary particle size, and temperature. We find that in regimes where
phase transformation occurs, the results can be self-consistently
explained as nucleation and growth kinetics within the framework of
the Johnson–Mehl–Avrami–Kolmogorov model. This
implies that despite the common secondary particle topology, the electrochemically
driven phase transformations occur by nucleation and growth with little
apparent resistance to phase propagation across the grain boundaries.
Growth appears to be one-dimensional in nature, consistent with a
hybrid growth model in which rapid surface propagation is followed
by slower growth into particles
Mesoscopic Phase Transition Kinetics in Secondary Particles of Electrode-Active Materials in Lithium-Ion Batteries
Many compounds used
as battery storage electrodes undergo large
composition changes during use that are accompanied by a first-order
phase transition. Most studies of these phase transitions have focused
on the unit cell to single-crystallite scale, whereas real battery
electrodes are typically composed of mesoscopic assemblies of nanocrystallites,
for which phase transformation mechanisms are poorly understood. In
this work, a systematic study is conducted of the potentiostatic (constant
driving force) kinetics of phase transition in secondary particles
of representative intercalation compounds: LiFePO<sub>4</sub>, LiMn<sub>1–<i>x</i></sub>Fe<sub><i>x</i></sub>PO<sub>4</sub>, and Li<sub>4</sub>Ti<sub>5</sub>O<sub>7</sub>. Storage kinetics
are studied as a function of overpotential, material composition,
primary particle size, and temperature. We find that in regimes where
phase transformation occurs, the results can be self-consistently
explained as nucleation and growth kinetics within the framework of
the Johnson–Mehl–Avrami–Kolmogorov model. This
implies that despite the common secondary particle topology, the electrochemically
driven phase transformations occur by nucleation and growth with little
apparent resistance to phase propagation across the grain boundaries.
Growth appears to be one-dimensional in nature, consistent with a
hybrid growth model in which rapid surface propagation is followed
by slower growth into particles
In Situ Observation of Random Solid Solution Zone in LiFePO<sub>4</sub> Electrode
Nanostructured LiFePO<sub>4</sub> (LFP) electrodes have attracted
great interest in the Li-ion battery field. Recently there have been
debates on the presence and role of metastable phases during lithiation/delithiation,
originating from the apparent high rate capability of LFP batteries
despite poor electronic/ionic conductivities of bulk LFP and FePO<sub>4</sub> (FP) phases. Here we report a potentiostatic in situ transmission
electron microscopy (TEM) study of LFP electrode kinetics during delithiation.
Using in situ high-resolution TEM, a Li-sublattice disordered solid
solution zone (SSZ) is observed to form quickly and reach 10–25
nm × 20–40 nm in size, different from the sharp LFP|FP
interface observed under other conditions. This 20 nm scale SSZ is
quite stable and persists for hundreds of seconds at room temperature
during our experiments. In contrast to the nanoscopically sharp LFP|FP
interface, the wider SSZ seen here contains no dislocations, so reduced
fatigue and enhanced cycle life can be expected along with enhanced
rate capability. Our findings suggest that the disordered SSZ could
dominate phase transformation behavior at nonequilibrium condition
when high current/voltage is applied; for larger particles, the SSZ
could still be important as it provides out-of-equilibrium but atomically
wide avenues for Li<sup>+</sup>/e<sup>–</sup> transport
Improving the Capacity of Sodium Ion Battery Using a Virus-Templated Nanostructured Composite Cathode
In this work we investigated an energy-efficient
biotemplated route to synthesize nanostructured FePO<sub>4</sub> for
sodium-based batteries. Self-assembled M13 viruses and single wall
carbon nanotubes (SWCNTs) have been used as a template to grow amorphous
FePO<sub>4</sub> nanoparticles at room temperature (the active composite
is denoted as Bio-FePO<sub>4</sub>-CNT) to enhance the electronic
conductivity of the active material. Preliminary tests demonstrate
a discharge capacity as high as 166 mAh/g at C/10 rate, corresponding
to composition Na<sub>0.9</sub>FePO<sub>4</sub>, which along with
higher C-rate tests show this material to have the highest capacity
and power performance reported for amorphous FePO<sub>4</sub> electrodes
to date
Azasilicon-bridged heterocyclic arylamines: syntheses, structures and photophysical properties
The lithium κ1-enamides, Me2NSiMe2CHC(Ph)-{2,6-(R1)2-4-(R2)C6H2}NLi·3THF (R1 = iPr, R2 = H L1; R1 = Et, R2 = H L2; R1 = Me, R2 = H L3; R1 = R2 = Me L4; R1 = Et, R2 = Me L5), in the presence of titanium tetrachloride, undergo intermolecular rearrangement cyclization reactions resulting in 1,3-migration of the silicon groups and the elimination of dimethylamine affording five examples of bis-azasilicon-bridged heterocyclic arylamines, [{2,6-(R1)2-4-(R2)C6H2}N(Ph)CCSiMe2]2 (R1 = iPr, R2 = H D1; R1 = Et, R2 = H D2; R1 = Me, R2 = H D3; R1 = R2 = Me D4; R1 = Et, R2 = Me D5) in good yield, respectively. The molecular structures of D1–D5 show the two fused N–Si–C–C–C rings to be co-planar indicative of extended π-conjugation, while their photophysical properties reveal them to be green/blue emitting with high luminescence quantum yields (ΦF range: 75–99%). Furthermore, the compounds D serve as versatile reactants undergoing ring opening on hydrolysis to afford the saturated 1,4-diimines [{2,6-(R1)2-4-(R2)C6H2}N(Ph)C-CH2]2 (R1 = iPr, R2 = H E1; R1 = Et, R2 = H E2; R1 = Me, R2 = H E3; R1 = R2 = Me E4; R1 = Et, R2 = Me E5). Alternatively, D can be employed in a redox-promoted cascade reaction to afford the conjugated 1,4-diimines, (E)-[{2,6-(R1)2-4-(R2)C6H2}N[double bond, length as m-dash]C(Ph)CH]2 (R1 = iPr, R2 = H F1; R1 = Et, R2 = H F2; R1 = Me, R2 = H F3; R1 = R2 = Me F4; R1 = Et, R2 = Me F5). In addition to D1–D5, E1–E3, E5, F2 and F3 have been the subject of single crystal X-ray diffraction studies
Engineering the Transformation Strain in LiMn<sub><i>y</i></sub>Fe<sub>1–<i>y</i></sub>PO<sub>4</sub> Olivines for Ultrahigh Rate Battery Cathodes
Alkali ion intercalation compounds
used as battery electrodes often exhibit first-order phase transitions
during electrochemical cycling, accompanied by significant transformation
strains. Despite ∼30 years of research into the behavior of
such compounds, the relationship between transformation strain and
electrode performance, especially the rate at which working ions (e.g.,
Li) can be intercalated and deintercalated, is still absent. In this
work, we use the LiMn<sub><i>y</i></sub>Fe<sub>1–<i>y</i></sub>PO<sub>4</sub> system for a systematic study, and
measure using operando synchrotron radiation powder X-ray diffraction
(SR-PXD) the dynamic strain behavior as a function of the Mn content
(<i>y</i>) in powders of ∼50 nm average diameter.
The dynamically produced strain deviates significantly from what is
expected from the equilibrium phase diagrams and demonstrates metastability
but nonetheless spans a wide range from 0 to 8 vol % with <i>y</i>. For the first time, we show that the discharge capacity
at high C-rates (20–50C rate) varies in inverse proportion
to the transformation strain, implying that engineering electrode
materials for reduced strain can be used to maximize the power capability
of batteries
Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO<sub>4</sub>
Virtually
all intercalation compounds exhibit significant changes
in unit cell volume as the working ion concentration varies. Na<sub><i>x</i></sub>FePO<sub>4</sub> (0 < <i>x</i> < 1, NFP) olivine, of interest as a cathode for sodium-ion batteries,
is a model for topotactic, high-strain systems as it exhibits one
of the largest discontinuous volume changes (∼17% by volume)
during its first-order transition between two otherwise isostructural
phases. Using synchrotron radiation powder X-ray diffraction (PXD)
and pair distribution function (PDF) analysis, we discover a new strain-accommodation
mechanism wherein a third, amorphous phase forms to buffer the large
lattice mismatch between primary phases. The amorphous phase has short-range
order over ∼1nm domains that is characterized by <i>a</i> and <i>b</i> parameters matching one crystalline end-member
phase and a <i>c</i> parameter matching the other, but is
not detectable by powder diffraction alone. We suggest that this strain-accommodation
mechanism may generally apply to systems with large transformation
strains