Dehydration rather than HF Capture Explains Performance Improvements of

Li-ion Cells by Ceramic Nanoparticles

Marco-Tulio F. Rodrigues, Chen Liao, Kaushik Kalaga, Ilya A. Shkrob, and Daniel P. Abraham*

Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois,

60439, USA

*Corresponding author: Daniel. P. Abraham, E-mail: abraham@anl.gov; Tel: (630)252-4332.

Abstract

Instability of nickel-rich layered oxides at high voltages is an impediment to their wider use in Li-

ion batteries. HF generated via LiPF6 hydrolysis accelerates corrosion, further destabilizing the

material. Ceramic particles are believed to interfere with this corrosion by scavenging HF. Here

we show that the likely mechanism is, in fact, disruption of the hydrolytic cycle due to adsorption

of water on ceramic particles, of which MgO performed the best. We suggest that hydrolysis

prevention rather than post factum remediation of hydrolytic damage makes a more efficient

strategy for protection of the high-voltage cathodes.

Keywords: NCM811, LiPF6 hydrolysis, water, HF, capacity fade, impedance rise
 Increasing the energy density of Li-ion batteries is highly desired, as it would extend the

driving range of electric vehicles.1 Although nickel-rich layered oxide cathodes such as

LiNi0.8Co0.1Mn0.1O2 (known commercially as NCM811) can potentially supply more energy at

high voltages, in their delithiated state they become thermodynamically unstable, undergoing

oxygen loss from the surface that contributes to impedance rise.2 High voltage exposure also

causes acidic dissolution of transition metal ions (in particular, Mn2+) to the electrolyte;3 these ions

migrate to the graphite (Gr) anode, where they deposit in the solid electrolyte interphase (SEI) and

catalyze detrimental reactions leading to capacity fade.4 This process is further exacerbated by the

formation of hydrofluoric acid in the electrolyte bulk.5-8 This acid is formed by the hydrolysis of

LiPF6, the commonly used electrolyte salt, as trace water present in the electrodes and electrolyte

stepwise converts the hexafluorophosphate (PF6-) anion to HF molecules and oxofluorophosphate

(e.g., PO2F2-) anions.9-11 As destructive as HF can be to the cathode, this acid also passivates the

aluminum current collector that in the absence of such protection undergoes anodic dissolution at

high voltages.12 This beneficial action is one of the reasons why LiPF6 remains prevalent in the

industry despite its low hydrolytic stability.

While it may be impossible to completely eliminate moisture (and thus HF) from the cell,

mitigation strategies can be pursued to reduce acidic dissolution of metal ions. These approaches

include creating physical barriers, such as protective coatings, that limit access to the oxide surface,

and HF capture with electrolyte additives and dopants.8, 13 Ceramic materials are well known in

this regard. Reports abound in the literature demonstrating benefits conferred by thin ceramic

coating on the cathodes,5-7, 14

anodes 15
and separators.16 Incorporating these materials into
14, 17
electrode slurries or using them as electrolyte additives have also been shown to improve
performance.18 Generally, it appears that having ceramic materials in the cell (regardless of their

physical form) is beneficial, and the prevalent view is that such materials react with HF thereby

preventing acidolysis of the cathode. However, not all observations fit into this scenario. For

example, it was reported that mere exposure of the carbonate electrolyte to ceramic nanoparticles

can improve the cycle life of LiCoO2//Li half-cells even after these particles are removed from the

electrolyte.19-20 These observations raise questions as to what aspect of chemical behavior plays

the most important role in the anti-aging action of these ceramics. In this study, we demonstrate

that removing water (thereby suppressing HF generation) is more important than the postulated

HF scavenging. Details of the experiments are provided in the Supporting Information (SI); the

figures referenced from the SI have designator “S”, as in Figure S1.

For this demonstration, ceramic nanoparticles (20-210 nm in diameter) were introduced

into the baseline (Gen2) electrolyte containing 1.2 mol/dm3 LiPF6 in a 3:7 wt/wt liquid mixture of

ethylene carbonate and ethyl methyl carbonate. After a week, the solutions were settled by gravity

and the particles were mostly removed by sedimentation. The top supernatant layers were then

used to fill NCM811//Gr cells. Galvanostatic cycling of the cells was conducted in the 3.0-4.4 V

range based on the protocol described by Long et al. 21. This protocol has four formation cycles at

a ~C/10 rate, followed by aging cycles at a ~C/3 rate that includes a 3h constant voltage hold at

4.4V. The aging cycles are interrupted periodically to obtain capacity and impedance data as

described in the SI. At the end of the test, each cell experiences ~120 cycles and ~300 h total

exposure to 4.4 V.

Electrochemical performance of the cells is briefly summarized in Figure 1 (see Figures

S1 and S2 for a more complete data set). For our baseline electrolyte (Figure 1a), the initial specific

discharge capacity was 204 mAh/g (the mass pertains to the active material in the cathode). The
capacity gradually decreased over time, resulting in a final capacity of 166 mAh/g. This capacity

fade (~19%) includes both the Li+ inventory loss (as the ions become trapped in the SEI) 4 and

slowdown of Li+ intercalation due to impedance rise.2

Turning to cells containing electrolytes pre-exposed to the nanoparticles, for some

materials (e.g. ZnO and Al2O3 in Figures 1b and 1c, respectively), the capacity fade is not

significantly affected by the pre-exposure, while for others (e.g., SiO2, Figure 1d) there is

significant capacity loss. When ZrO2 and CeO2 are used (Figures 1e-f), the final capacity is slightly

higher than for the baseline electrolyte, while for MgO and TiO2 (Figures 1g-h) it is slightly lower

(though with a higher capacity retention; see Figure S2). These trends are graphically summarized

in Figure 1i, in which the initial discharge capacities and capacity retention are plotted together.

Systems to the right of the vertical line in this chart (ZrO2, Al2O3, MgO, TiO2 and CeO2) have

better capacity retention than the baseline electrolyte. Only SiO2 lies to the left of the vertical line,

presumably because the SEI formation chemistry is affected. Figure 1j shows differential capacity

(dQ/dV) plots during the first charge for cells containing electrolyte exposed to SiO2 or ZnO (the

latter is representative of most other systems). For SiO2, the peak associated with electrolyte
22
reduction deviates from ~3 V indicating interference during SEI formation, whereas for ZnO

the peak is similar to that for the baseline electrolyte.

Figure 1. Influence of oxide nanoparticles on the electrochemical cycling of NCM811//Gr cells.
Panels a to h show the discharge capacity (per weight of active material in the cathode) in cells
containing the baseline electrolyte (in light gray) and in electrolytes pre-exposed to the
nanoparticles (in blue), with the materials indicated in each panel. The initial five cycles and the
terminal cycle were at a slow C/10 rate, while the remaining cycles are at a C/3 rate (1C
corresponding to full discharge in 1 h). The discontinuities in the plots indicate cycles at which
pulsed impedance measurements were carried out. (i) The initial discharge capacity plotted vs.
capacity retention for different cells. The cross corresponds to the baseline electrolyte (Gen2). (j)
Differential capacity vs. cell voltage for selected systems, showing delayed SEI formation in the
SiO2 cells.
Figure 2. Area specific impedance (ASI) plotted vs. cell voltage for cells shown in Figure 1. ASI
for baseline electrolyte (Gen2, panel a) is reproduced in gray in panels b-h for comparison. The
impedance was measured at the cycles indicated in Figure 1.

Impedance data acquired at various stages of aging (indicated by the blue numbers in

Figure 1a) are summarized in Figure 2 (test details in the SI). The pulsed current technique gives

the cell area specific impedance (ASI) at different depths of discharge. The ASI of the baseline

cells increases continuously as the cell ages (Figure 2a). After 100 cycles, the ASI at ~3.7 V

increases by a factor of six. Previous studies using reference microelectrodes showed that this

increase is predominantly from the cathode; negligible changes are observed in the graphite ASI.2

For the ceramic-modified electrolytes, the initial impedance was comparable to that observed in

the baseline cells. For ZnO and TiO2 (Figures 2b-c), no change was observed in the rate of

impedance rise, while for Al2O3 (Figure 2d), the impedance rise accelerated. More interestingly,

for ZrO2, CeO2, SiO2 and MgO (Figures 2e-h), the impedance rise slowed down. This beneficial

effect is particularly notable for MgO and SiO2 (see Figure S3 which plots the initial ASI vs. ASI

increase). The capacity retention and impedance rise for different oxides are graphically

summarized in Figure 3. It is seen that most of the nanomaterials have relatively little effect on
electrochemical performance with two outliers: SiO2 and MgO. Both of these materials halve the

rate of impedance rise, and MgO also improves capacity retention. These general trends and the

unique behavior of MgO and SiO2, can be explained by their ability to interfere with the hydrolytic

cycle of LiPF6 in the cell (cf. Scheme 1).

Figure 3. The impedance rise (defined as the difference between the initial and final ASI) obtained
at 3.7 V and capacity retention after 120 cycles for cells shown in Figures 1 and 2. The cross
indicates the baseline electrolyte (in gray). With the exception of SiO2 and MgO, electrolyte pre-
exposure to the oxides had little effect on cell performance.

We observe that all oxide ceramics chemisorb and dissociate water by hydroxylation of

their surfaces, forming thin hydrogel coatings. Additional water molecules then physisorb onto

these hydroxylated surfaces, increasing the net moisture uptake.23 At low-to-moderate fluoride

concentration, these modified surfaces undergo anion exchange, capturing and immobilizing the

fluoride anion.24-25 SiO2 is the exception to this general rule, as the fluorinated compounds

solubilize, exposing fresh surface that can react with more fluoride.10
 To estimate how the oxides interfere with the hydrolytic cycle responsible for the release

of HF acid, we intentionally added ~8,300 ppm of water to freshly prepared nanoparticle-

containing electrolytes. After 7 days of resting, the electrolyte samples were examined using

fluorine-19 and phosphorus-31 nuclear magnetic resonance (NMR). In the presence of water, PF6-

converts to HF, PO2F2- and PO3F2-, which display resonance lines in the NMR spectra.10 The

results of our analyses are summarized in Table 1. Advanced stages of hydrolysis are observed in

most samples, the oxide particles generally catalyzing PF6- hydrolysis rather than impeding it. The

behavior of silica is particularly illuminating in this respect: though less HF was detected (as can

be expected given the high reactivity of SiO2 towards HF), the high yield of oxofluorophosphate

anions indicated advanced stage of hydrolysis. Indeed, as we observed elsewhere,26 scavenging of

HF actually shifts the equilibrium towards additional hydrolysis, as water is reintroduced into the

bulk when HF reacts with the oxide (see Scheme 1a).

These analytical results suggest that the oxides benefit the cell primarily by removing water

from the hydrolytic cycle (Scheme 1b). This propensity readily explains what distinguishes MgO

from other oxides, as it is a well-known drying agent, readily dissociating water on its surface.23,
27
For magnesia, only traces of HF and other hydrolytic products are observed, suggesting that it

completely disrupts the hydrolytic cycle (Scheme 1b). When MgO was added to aged Gen2 doped

with water (compare the first and last rows in Table 1), the HF concentration before and after the

addition of MgO was nearly the same, suggesting low fluoride uptake by MgO. This simple

experiment demonstrates that MgO acts by removing water rather than HF from the hydrolytic

cycle. We conclude that active removal of water during aging of the cell significantly improves

long-term performance of cells cycled at high-voltage.

Scheme 1. Representation of the effect of oxide particles on cell performance. For a generic oxide
particle (panel a), the hydrolytic cycle converting between HF and water in the electrolyte is not
disrupted, and can even be facilitated by the ceramic nanoparticles. This cycle includes stepwise
hydrolysis of LiPF6 by water molecules in electrolyte and acidolysis and/or F-/OH- ion exchange
in the oxide materials (including the cathode and the ceramics added to the electrolyte) by
hydrofluoric acid reacting at the surface. For MgO particles, the water is locked in a stable hydrogel
on the particle surface, so LiPF6 hydrolysis is largely suppressed and the hydrolytic cycle is
disrupted (panel b).
 Table 1. Oxofluorophosphate and Hydrofluoric Acid yields obtained from NMR data after 1
week of aging in electrolyte containing 8,300 ppm water. The baseline electrolyte contained no
HF and trace amounts of hydrolysis products before water addition.

Electrolyte/ % LiPF6 b
ceramic
a % HF yield
hydrolyzed
baseline 4.0 9.7
SiO2 10.4 4.1
ZnO 9.9 9.0
ZrO2 7.4 13.5
TiO2 7.1 11.9
Al2O3 6.5 9.4
CeO2 4.8 9.0
MgO 0.1 0.0
MgO c 4.6 7.3
2- -
a) the total fraction of PO3F and PO2F2 anions relative to all phosphate anions; b) the atom
fraction of HF relative to all fluorine compounds; c) added after 1 week aging of the baseline
electrolyte.

At first glance, our conclusion appears to contradict the research literature, which suggests

that adding ~200-2000 ppm of water to the carbonate electrolyte has little effect on cell

performance.28-29 However, careful examination of the literature indicates that these previous

experiments were carried out with relatively low upper cut-off voltages (<4.25 V) compared to 4.4

V used in our cycling tests. To assess how water affects the cell operated at 4.4 V, we deliberately

introduced ~1,000 ppm H2O to our baseline electrolyte. In one series of experiments, the cells were

assembled and tested immediately after water addition. In another series, the electrolyte was aged

for 7 days before cell assembly to facilitate LiPF6 hydrolysis. The results of these two series of

tests are shown in Figure 4. While the baseline cells cycle reproducibly (Figures 4a,d), the “wet”

cells display non-reproducible and erratic behavior, demonstrating sudden capacity loss and
impedance rise (Figures 4b,e and 4c,f). Such erratic behaviors have been linked to transition metal

ions loss from the cathode surface, which then migrate to the anode and catalyze parasitic reactions

in the SEI.4 In fact, even the best-performing “wet” cells (Figures 4b,c) exhibit more capacity fade

than the baseline cells, and the initial capacities are consistently lower for the aged hydrated

electrolyte (see dashed lines along Figures 4a-c). While the typical Li-ion cells contain much less

water than these “wet” cells, our experiment proves that water can have highly detrimental effect

on the long-term electrochemical performance at higher voltages.

In regular Li-ion cells, the residual moisture is introduced mainly from the electrode

matrices.29-30 The typical water content of a dry electrolyte is <20 ppm, while fully dried electrodes

can still contain >100 ppm of water. We have recently shown that electrolyte in contact with dried

electrodes develops much higher levels of oxofluorophosphate anions than exhibited by the

electrolyte alone,2 indicating that the moisture carried by the electrodes also participate in the

hydrolytic cycle. The typical moisture levels listed above amounts to ~3 µg of water in our coin

cells. Considering the sorption capacity of MgO suggested by Table 1, only ~10 µg of MgO

nanoparticles would be sufficient to completely dehydrate the coin cell. Given this miniscule

amount, the behaviors shown in Figures 1 and 2 could be caused by dispersed nanoparticles carried

with electrolyte into the cell: even at a low concentration, MgO nanoparticles can dehydrate the

cell and stall the hydrolysis of LiPF6.

In conclusion, our experiments suggest that the beneficial effects of ceramic nanoparticles

on electrochemical performance originate mainly from their ability to chemisorb water, disrupting

the hydrolytic cycle that converts LiPF6 to HF acid (Scheme 1). Among the oxides examined, MgO

is the most effective anti-aging agent precisely because it is the most efficient drying agent. The

research literature indicates that the presence of water in the electrolyte has relatively little effect
on electrochemical performance at low cell voltages (< 4.2 V). Here we demonstrate that this is

not the case for 4.4 V operation; this is why removal of water is so important in this regime. While

the oxide nanoparticles are believed to act primarily as HF scavengers, our results suggest that by

the moment HF is generated, the battle is largely over, as this HF will be converted to water on

their surfaces that re-enters the hydrolytic cycle generating still more HF (Scheme 1a). The most

efficient way to protect the cathode is rather via the removal of water hydrolyzing LiPF6 (Scheme

1b). Using the dehydrating MgO particles can be a simple and cost-effective approach to building

longer-lasting Li-ion batteries.

Figure 4. The effect of added water on electrochemical performance of NCM811//Gr cells. Cycle
life (panels a, b, and c) and impedance rise (panels d, e, and f) for multiple cells containing baseline
electrolyte with (panels b, c, e, and f) or without (panels a and d) 1,000 ppm water. Different color
hues represent different cells. The hydrated electrolyte was used to fill these cells either promptly
(panels b and e) or after one week of aging (panels c and f). The dashed horizontal lines are visual
guides to compare different systems. While for baseline cells the cycling parameters were highly
reproducible, the hydrated cells often behaved erratically.

Supporting Information: A file containing additional figures and experimental details is

available to the reader. This material can be obtained free of charge at http://pubs.acs.org.
Acknowledgements

This work was supported by the Office of Vehicle Technologies at the U.S. Department of

Energy. The electrodes used in this article were fabricated at Argonne’s Cell Analysis, Modeling

and Prototyping (CAMP) Facility, which is supported within the core funding of the Applied

Battery Research (ABR) for Transportation Program.

This manuscript has been created by UChicago Argonne, LLC, Operator of Argonne

National Laboratory (“Argonne”). Argonne, a U. S. Department of Energy Office of Science

laboratory, is operated under Contract No. DE-AC02-06CH11357. The U. S. Government retains

for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in

said article to reproduce, prepare derivative works, distribute copies to the public, and perform

publicly and display publicly, by or on behalf of the Government.

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TOC graphic
 Supporting Information

Dehydration rather than HF Capture Explains Performance Improvements of

Li-ion Cells by Ceramic Nanoparticles
Marco-Tulio F. Rodrigues, Chen Liao, Kaushik Kalaga, Ilya A. Shkrob, and Daniel P. Abraham*
Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois,
60439, USA
*Corresponding author: Daniel. P. Abraham, E-mail: abraham@anl.gov; Tel: (630)252-4332.

Experimental Details
Materials. – Aluminum oxide (Al2O3, 80 nm) was obtained from Sigma-Aldrich; CeO2 (50-105
nm), MgO (40-60 nm), SiO2 (80 nm), TiO2 (100 nm), ZnO (90-210 nm) and ZrO2 (20 nm) were
obtained from Nanostructured & Amorphous Materials, Inc. The particle sizes were provided by
the manufacturer. The oxide powders were dried at 120 oC under vacuum for 48 h, and then stored
under argon.
Electrochemical tests were carried in 2032-type stainless steel cells, using a
LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode paired with a graphite anode (Gr). The positive electrode
contained 90 wt% of the active oxide (Targray), 5 wt% of a conductive carbon (C45, Timcal) and
5 wt% of poly(vinylidene difluoride) binder (PVdF, Solef 5130, Solvay). The anode comprised a
mixture of 91.8 wt% graphite (CGP-A12, Philips 66), 2 wt% C45 carbon, 6 wt% PVdF binder
(KF-9300, Kureha) and 0.17 wt% oxalic acid. The resulting thickness and porosity of the electrode
coatings were 44 µm and 38.4% for the cathode, and 32 µm and 36.3% for the anode, respectively.
The total coating loading was 8.3 mg/cm2 for the cathode, and 5.9 mg/cm2 for the anode. Electrodes
were fabricated at Argonne’s Cell Analysis, Modeling and Prototyping (CAMP) Facility, and were
balanced to achieve ~90% anode utilization when the full-cell is initially charged to 4.4 V (i.e.,
these are cathode-limited cells). Celgard 2325 was used as microporous separator. The electrolyte
was a mixture of 1.2 M LiPF6 in 3:7 wt/wt ethylene carbonate : ethylmethylcarbonate (“Gen2”,
supplied by Tomiyama, Inc.). In some experiments, this electrolyte was aged in the presence of
oxide particles (see below) or deliberately contaminated with water. Cell assembly followed the
recommendations outlined in ref. 1.
Electrolyte aging. – Dried oxide nanoparticles (300 mg) were mixed with 10 mL of Gen2 in
polypropylene vials for 7 days. The vials were vortexed for 1 min immediately after mixing, and
also on day 2 and 4 afterwards. The solution settled by gravity for 72 hours, and the top layer of
supernatant was removed and used as electrolyte. In certain tests, Gen2 contained ~1,000 ppm of
water. This electrolyte was prepared by combining 5 µL of water with 5 g of Gen2 in a stainless
steel container. The mixture was vortexed for 2 min and used to fill cells.
Electrochemical testing. – The cells were cycled between 3.0 V and 4.4 V, as discussed in refs. 1-
2
. The rate of 1C corresponds to full cell discharge in 1 h, which in our case is equivalent to 1.56
mA/cm2. The cells were initially charged to 1.5 V for 15 min, and then allowed to rest at open
circuit for 6 h. The formation cycling consisted of four constant-current, constant-voltage cycles
S1
at a C/10 rate, with the voltage held at 4.4 V for 3 h or until the current decreased to < C/20 rate.
Cells were then exposed to five series of aging cycles. Each series began with diagnostic tests.
These tests consisted of (i) a slow cycle at a C/10 rate (to estimate capacity loss), (ii) a fast cycle
that included charge at a C/3 rate followed by discharge at an 1C rate (to characterize polarization
in the cell), and then full charge at C/3, and (iii) a hybrid pulse power characterization step (HPPC)
with incremental discharge, also at a C/3 rate. The HPPC measurement was carried out using a 10
s long rectangular 2C charge and 1.5C discharge pulses forced through the cell to measure internal
resistance (imitating breaking and acceleration of an electric vehicle). HPPC is used to estimate
cell impedance at different states of charge, see 3-4. These diagnostic tests were followed by 20
cycles at a C/3 rate (with a potentiostatic hold for 3 h at 4.4 V after charging in order to increase
high voltage exposure). At the end of this test, each cell was subjected to 100 cycles at a C/3 rate
and 300 h of combined exposure to 4.4 V.
NMR analyses. – Fluorine-19 and phosphorus-31 Nuclear Magnetic Resonance (NMR) was used
to quantify LiPF6 hydrolysis and HF yield after treating the electrolyte with ceramic nanoparticles.
For these tests, 60 mg of oxide material was combined with 1.98 mL Gen2 containing 20 µL water
to obtain ~8,300 ppm solutions. A control sample without ceramic particles was also prepared.
The samples rested for 7 days before NMR analysis, being vortexed occasionally, as described
above. For this analysis, an aliquot was placed in a fluoropolymer insert (Bel-Art SP Scienceware,
Wilmad) sealed with a Teflon plug. The filled inserts were placed in the standard 5 mm borosilicate
NMR tubes containing acetonitrile-d3 or acetone-d6. 1H, 19F and 31P NMR spectra were collected
using a Bruker Avance III HD 300 MHz spectrometer.

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Supporting Figures

Figure S1. Same as Figures 1 panels a to h, with capacity measurements for diagnostic cycles at
a fast rate of 1C and a slow rate of C/10 indicated in the plot.

Figure S2. Similar to Figure S1, but showing discharge capacity retention (vs. cycle 5) instead of
discharge capacity.

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Figure S3. A correlation of the initial ASI at 3.7 V (y-axis) and the ASI rise (x-axis) for cells
shown in Figure 2, panels a to h. The crosshair indicates the baseline Gen2 electrolyte. As seen
from this plot, cells with the electrolyte exposed to MgO showed the lowest ASI increase.

Supporting References
1. Long, B. R.; Rinaldo, S. G.; Gallagher, K. G.; Dees, D. W.; Trask, S. E.; Polzin, B. J.;
Jansen, A. N.; Abraham, D. P.; Bloom, I.; Bareño, J.; Croy, J. R., Enabling High-Energy,
High-Voltage Lithium-Ion Cells: Standardization of Coin-Cell Assembly, Electrochemical
Testing, and Evaluation of Full Cells. J. Electrochem. Soc. 2016, 163, A2999-A3009.
2. Tornheim, A.; Peebles, C.; Gilbert, J. A.; Sahore, R.; Garcia, J. C.; Bareño, J.; Iddir, H.;
Liao, C.; Abraham, D. P., Evaluating Electrolyte Additives for Lithium-ion cells: A new
Figure of Merit Approach. J. Power Sources 2017, 365, 201-209.
3. Abraham, D. P.; Dees, D. W.; Christophersen, J.; Ho, C.; Jansen, A. N., Performance of
High-power Lithium-ion Cells under Pulse Discharge and Charge Conditions. Int. J.
Energy Res. 2010, 34, 190-203.
4. Abraham, D. P.; Poppen, S. D.; Jansen, A. N.; Liu, J.; Dees, D. W., Application of a
Lithium–tin Reference Electrode to Determine Electrode Contributions to Impedance Rise
in High-power Lithium-ion Cells. Electrochim. Acta 2004, 49, 4763-4775.

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