Articles

https://doi.org/10.1038/s41560-021-00852-3

Balancing interfacial reactions to achieve long

cycle life in high-energy lithium metal batteries
Chaojiang Niu   1, Dianying Liu1, Joshua A. Lochala   1, Cassidy S. Anderson1, Xia Cao   1, Mark E. Gross1,
Wu Xu   1, Ji-Guang Zhang   1, M. Stanley Whittingham2, Jie Xiao   1,3 ✉ and Jun Liu   1,3 ✉

The rechargeable lithium metal battery has attracted wide attention as a next-generation energy storage technology. However,
simultaneously achieving high cell-level energy density and long cycle life in realistic batteries is still a great challenge. Here
we investigate the degradation mechanisms of Li || LiNi0.6Mn0.2Co0.2O2 pouch cells and present fundamental linkages among Li
thickness, electrolyte depletion and the structure evolution of solid–electrolyte interphase layers. Different cell failure pro-
cesses are discovered when tuning the anode to cathode capacity ratio in compatible electrolytes. An optimal anode to cathode
capacity ratio of 1:1 emerges because it balances well the rates of Li consumption, electrolyte depletion and solid–electrolyte
interphase construction, thus decelerating the increase of cell polarization and extending cycle life. Contrary to conventional
wisdom, long cycle life is observed by using ultra-thin Li (20 µm) in balanced cells. A prototype 350 Wh kg−1 pouch cell (2.0 Ah)
achieves over 600 long stable cycles with 76% capacity retention without a sudden cell death.

R
echargeable lithium metal batteries (LMBs) have been consid-
ered one of the most promising next-generation, high-energy
battery technologies due to the light weight and high capacity
of Li metal anodes1–3. However, the development of LMBs has been
hindered by two fundamental problems, which dictate the cycle life
and cell safety. First, similar to other electroplated metals, Li deposi-
tion in an electrochemical cell always forms spiky microstructures
(dendrites) causing safety concerns4,5. The second problem is con-
tinuous side reactions that form a thick and mossy solid–electro-
lyte interphase (SEI) layer on Li surfaces6,7, which not only quickly
depletes the electrolyte in practical cells with very lean electrolyte8,
but also builds up the cell impedance9,10.
In the last few years, there have been intensive efforts to under-
stand and control the dendrites and SEI reactions11–13. Many strat-
egies and approaches have been reported to protect the Li metal
anode or stabilize the anode architectures to achieve long cycle
life14–16. Despite numerous reports using a variety of approaches,
including both liquid or solid electrolye configuations, high-energy
cells with a stable and long cycle life have not been demonstrated
in the literature. The dominant factor that dictates the cycle life of
LMBs at different cycling numbers remains very unclear, which
makes it challenging to effectively prolong the battery lifespan. More
importantly, most of these investigations are based on coin cells (or
single-layer pouch cells) using experimental parameters far from
what are practically required to achieve high energy. High cell-level
energy density cannot be achieved unless realistic conditions are
used17–20, including high cathode loading, low electrolyte amount to
cathode capacity (E/C) ratio and negative to positive areal capac-
ity (N/P) ratio. Therefore, many ‘promising’ results obtained under
unconstrained conditions may not be realized or repeated in realis-
tic high-energy batteries.
Recently, there have been a few reports on the electrochemi-
cal properties of full pouch cells based on LiNixMnyCo1–x–yO2
(NMC)21–26. For example, up to 200 stable cycles were reported for
1.0 Ah 300 Wh kg−1 Li || NMC pouch cells in 2019 (ref. 25); however,
these cells still suffered a sudden cell ‘death’ (sudden capacity drop/
plunge) after reaching approximately 80% of the original cell capac-
ity. In addition, Li-free-anode (also called anode-free) pouch cells
were investigated to improve cell safety27–30, while such cells show a
slow but continuous capacity decay throughout their entire lifespan.
New concepts such as dual salt electrolytes demonstrated improved
cycle life and safety8–10. Overall, the electrochemical reactions in
LMBs are very complex. Achieving reliable and long cycle life pro-
vides a good opportunity to control the reactivities of the different
components on the cell level and improve their properties, includ-
ing cell safety.
The cell-level energy of LMBs can be designed31,32, while the
cycle life of Li metal cells remains unpredictable. Sudden capacity
drop is commonly observed in LMBs and is attributed to a variety
of reasons25. However, the exact cause has not been identified, not
to mention providing useful strategies to avoid such premature cell
death in realistic batteries. Although high coulombic efficiencies
(CEs) are often cited as a measure of cycle life in Li metal cells, when
extra Li is present in the anode, CEs cannot be directly linked to
predict the cycle life in LMBs33. We reported earlier that the deple-
tion rates of Li and electrolyte, whichever comes first, potentially
determine the lifespan of a rechargeable LMB25, particularly when
an unstable electrolyte is used that aggressively reacts with and
‘consumes’ the Li. As is commonly recognized, a thicker Li anode
usually lasts longer than a thinner one with sufficient electrolyte
present8,34. However, when a ‘good’ electrolyte is used, the deple-
tion rate of Li is substantially reduced. The electrolyte drying up
and SEI build-up lead to an increase of cell impedance, especially
after extensive cycling, and ultimately dictate the end of cell life.
The underlying scientific questions are the following. First, how to
determine the desired amount of Li needed to balance the cathode
and interfacial reactions with electrolyte? Second, what fundamen-
tally determines the balanced interfacial reactions? And lastly, can
we design a balanced cell to compensate the continuous Li loss and
minimize the accumulation of SEI layers during cycling?

Energy and Environmental Directorate, Pacific Northwest National Laboratory, Richland, WA, USA. 2Materials Science and Engineering Program,
1

Binghamton University, Binghamton, NY, USA. 3Materials Science and Engineering Department, University of Washington, Seattle, WA, USA.
✉e-mail: jie.xiao@pnnl.gov; jun.liu@pnnl.gov

Nature Energy | www.nature.com/natureenergy

Articles Nature Energy

b 100 µm thick Li, N/P ratio 5:1 c

50 µm Li, N/P ratio 2.5:1

…
Al

…
−2
4 mAh cm NMC
Separator
100 µm Li
50 µm Li
Cu
a Li metal pouch cells
Separator

Al

…
…
d 20 µm thin Li, N/P ratio 1:1 e
Li-free anode, N/P ratio 0:1

…
20 µm Li
Bare Cu

…
…
Fig. 1 | Four types of 350 Wh kg−1 pouch cells. a, Schematic of Li metal pouch cells. The four types are based on Li || NMC622 chemistry with different Li
foil thicknesses in the anodes. b, One repeating layer (double-sided) of the thick-Li pouch cell configuration with 100 µm Li in the anode; the N/P ratio
is 5:1. c, The 50 µm Li pouch cell configuration with N/P ratio of 2.5:1. d, The thin-Li pouch cell configuration with 20 µm Li in the anode; the N/P ratio is
1:1 and the E/C ratio is 2.4 g Ah−1. e, The Li-free-anode pouch cell configuration without Li on the Cu foil; this cell is Cu || NMC622, so the N/P ratio is 0:1.
To achieve a high cell-level energy density of 350 Wh kg−1 in the very restricted volume and with limited weight, the cathode areal capacity must be at
least 4.0 mAh cm−2 on each side of the Al foil; the E/C ratios of the four pouch cells are similar since the Li is very light (details in the Methods). The total
capacity of each pouch cell is more than 2.0 Ah.

In this work, we investigate the electrochemical properties of
four types of 350 Wh kg−1 Li || LiNi0.6Mn0.2Co0.2O2 (Li || NMC622)
pouch cells (2.0 Ah). The cathodes and electrolytes35 used in all
the pouch cells are the same (details in Methods); the N/P ratios
are controlled by reducing the Li anode thickness from 100 µm to
50 µm, 20 µm and 0 (bare Cu), as schematically illustrated in Fig.
1. By tuning the Li reservoir in the pouch cells, we find that cell
degradation mechanisms depend on the competition between the
amount of available Li, speed of electrolyte depletion and rate of
SEI accumulation. This understanding helps explain the different
cycling behaviours of LMBs spanning from a thick-Li anode to a
thin-Li anode and finally to no Li in the anode (Li-free anode). This
study reveals that the evolution of SEI structures is determined not
only by the electrolyte. The available Li surfaces to accommodate
SEI layers also play an important role in balancing the interfacial
interactions and decelerate the generation of ‘dry SEI’ layers. The
fundamental linkage among Li metal thickness, SEI structures and
ultimate cycle life is revealed in this work.
Pouch cells consisting of excess Li
First, the pouch cells with thick Li metal (100 µm Li, N/P ratio 5:1)
in the anodes were examined. The cell energy and CE of this 100 µm
Li pouch cell remain almost flat until about 300 cycles (94% capac-
ity retention), and then a sudden capacity drop is observed (Fig.
2a). The initial stable cycling and sudden cell death seem to be a
signature failure characteristic of LMBs, in both coin cells7,8,36–40 and
pouch cells21–26, where excess Li exists. The initial stable and flat
cycling behaviour is understandable because there is plenty of Li
provided from the anode to compensate for the loss of Li originat-
ing from the cathode. Superficially, the cathode is able to maintain
the full capacity as long as a sufficient amount of Li+ ions come back
during each discharge. Therefore, for the first 300 cycles, the CE
is artificially high at almost 100%. Unfortunately, contrary to some
reports in the literature, this 100% CE in a full cell with excess Li
in the anode does not mean there is no Li loss or side reactions
occurring during cycling, and therefore, the CE in the LMB cannot
be linked to predict cell lifespan33. This situation is totally differ-
ent from the conventional Li-ion batteries where only the cathode
supplies Li. In fact, the side reactions in the pouch cells with a high
excess of Li may be intensified and will be discussed later.
From the charge–discharge curves (Fig. 2b and Supplementary
Fig. 1), the capacity fading of the 100 µm Li-anode pouch cell is pre-
dominantly caused by the continuous increase of polarization dur-
ing cycling. The polarization lowers the average discharge voltage,
causing the deliverable capacity to decrease, since the cut-off volt-
age is always 2.7 V during each discharge. A close inspection of the
voltage profiles also reveals that both IR drop and ohmic polariza-
tion (labelled by arrows in Fig. 2b) increase upon cycling. IR drop is
the difference between the cell output voltage and the open-circuit
voltage and relates to the internal resistance of cells; ohmic polar-
ization arises from contact between particles of active materials or
from a resistive film on the surface of the electrode. The concurrent
increase of both IR drop and ohmic polarization indicates the con-
tinuous growth of a resistive SEI film on the anode upon cycling,
resulting from the formation of insulating products in the SEI.
Balancing the interfacial reactions by tuning Li thickness
Although the addition of extra Li in the pouch cell initially shows
stable cycling, serious polarization still occurs due to the accumu-
lation of an insulating SEI. To mitigate this problem, 350 Wh kg−1
pouch cells with two thinner Li foils (50 µm and 20 µm) were fabri-
cated and investigated.
For the 50 µm Li cell, the N/P ratio is 2.5:1. Similar long stable
cycles are observed for the first 400 cycles (Fig. 2c), maintaining
almost 100% CE. However, after 400 cycles, the cell energy and
capacity begin to drop rapidly, and the CE decreases quickly. This
sudden capacity drop is similar to that observed in the 100 µm Li
pouch cell. Minimum polarization is seen during the first 400 cycles
(Fig. 2d and Supplementary Fig. 2), beyond which IR drop and
ohmic polarization increase drastically. These results indicate that

Nature Energy | www.nature.com/natureenergy

Nature Energy Articles
a b Specific capacity (mAh g–1)

All pouch cells: 0.1 C (~0.23 A) charge, 0.3 C (~0.7 A) discharge, 1 C equal to 4.0 mA cm–2 or 2.3 A 0 30 60 90 120 150 180
450 4.5 101
4.4
Cell energy density 100
400 4.0
Cell capacity 99
350 CE 3.5 98 4.0
Cell energy (Wh kg )
–1

Cell capacity (Ah)

300 3.0 97

Voltage (V)
96

CE (%)
250 2.5 3.6
95
200 2.0 94
80% 4th
150 1.5 93 3.2 100th
92 200th
100 1.0
91 300th
50 100 µm thick-Li pouch cell, N/P ratio 5:1 0.5 2.8 350th
90 370th
0 0 89
0 50 100 150 200 250 300 350 400 450 500 550 600 0 0.4 0.8 1.2 1.6 2.0 2.4
Cycle number Cell capacity (Ah)
–1
Specific capacity (mAh g )
c d 0 30 60 90 120 150 180
450 4.5 101
4.4
Cell energy density 100
400 4.0
Cell capacity 99
350 CE 3.5 98
Cell energy (Wh kg )

4.0
–1

Cell capacity (Ah)

300 3.0 97

Voltage (V)
96

CE (%)
250 2.5
95 3.6
80%
200 2.0 94
4th
150 1.5 93 3.2 100th
92 200th
100 1.0
91 300th
50 50 µm Li pouch cell, N/P ratio 2.5:1 0.5 90 2.8 400th
465th
0 0 89
0 50 100 150 200 250 300 350 400 450 500 550 600 0 0.4 0.8 1.2 1.6 2.0 2.4
Cycle number Cell capacity (Ah)
–1
e Time (month)
f Specific capacity (mAh g )
0 1 2 3 4 5 6 7 8 9 10 11 12 13 0 30 60 90 120 150 180
450 4.5 101
4.4
4.0 100
400
99
350 3.5 98 4.0
Cell energy (Wh kg )
–1

Cell capacity (Ah)

300 3.0 97
71%

Voltage (V)
96

CE (%)
250 2.5 3.6
95
200 81% 76% 2.0 4th
94 100th
150 1.5 93 3.2 200th
92 300th
100 Cell energy density 1.0 400th
Cell capacity 91
50 20 µm thin-Li pouch cell, N/P ratio 1:1 0.5 500th
2 cm CE 90 2.8
600th
0 0 89
0 50 100 150 200 250 300 350 400 450 500 550 600 0 0.4 0.8 1.2 1.6 2.0 2.4
Cycle number Cell capacity (Ah)

Specific capacity (mAh g–1)

g h 0 30 60 90 120 150 180
450 4.5 101
4.4
Cell energy density 4.0 100
400
Cell capacity 99
350 CE 3.5
98 4.0
Cell energy (Wh kg )
–1

Cell capacity (Ah)

300 3.0 97
Voltage (V)

96
CE (%)

250 2.5 3.6

95
200 80% 2.0
94
150 1.5 93 3.2 4th
100 1.0 92 100th
91 200th
50 Li-free-anode pouch cell, N/P ratio 0:1 0.5 2.8 300th
90
0 0 89
0 50 100 150 200 250 300 350 400 450 500 550 600 0 0.4 0.8 1.2 1.6 2.0 2.4
Cycle number Cell capacity (Ah)

Fig. 2 | Electrochemical performances of four types of 350 Wh kg−1 Li || NMC622 pouch cells at 2.0 Ah level. a,b, Cell-level energy density, cell capacity, CE
and charge–discharge curves of the pouch cell with 100 µm thick-Li in the anode; the N/P ratio is 5:1. c,d, Cycling performance and charge–discharge curves
of the 50 µm Li pouch cell; the N/P ratio is 2.5:1. e,f, Cycling performance and charge–discharge curves of the 20 µm thin-Li pouch cell; the N/P ratio is 1:1
and the E/C ratio is 2.4 g Ah−1. g,h, Cycling performance and charge–discharge curves of the Li-free-anode pouch cell, Cu || NMC622; the N/P ratio is 0:1.
All pouch cells were cycled at 0.1 C for two initial formation cycles, and then charged at 0.1 C (the electric current is ~0.23 A) and discharged at 0.3 C (the
electric current is ~0.7 A) in subsequent cycles (1 C equals 4.0 mA cm−2 or corresponds to 2.3 A, from 2.7 V to 4.4 V, 25 °C). The arrows indicate the voltage
changes during the charge–discharge processes. During the long testing of more than 13 months, these pouch cells suffered two power outages and one
period of oven maintenance, so some cycling behaviours show fluctuations. Note that the cell energy density is calculated based on the total weight of the
whole pouch cell, including all active and inactive parts in the pouch cell.

a 50 µm Li anode is enough for the compensation of the Li loss in cycles with a cell capacity retention as high as 76% (Fig. 2e). The
early cycles, but the resistive SEI build-up still accelerates during CE remains at almost 100% until reaching 600 cycles. Although the
later cycling and causes sudden cell death. CE is artificially inflated due to the presence of excess Li in the cell,
The most interesting result is obtained when the thickness of Li the extended long-term cycle life implies a good balance between a
is further reduced to 20 µm (thin-Li cell, the N/P ratio is 1:1). The timely supply of Li while minimizing the accumulation of ineffec-
stable cycling of the 350 Wh kg−1 pouch cell is extended to over 600 tive SEI layers. The charge–discharge curves of this thin-Li pouch

Nature Energy | www.nature.com/natureenergy

Articles
a c
After 600 cycles
70 µm
10 µm Al foil
50 µm
2 cm
b d
Pristine NMC622 electrode
96:2:2
Intensity (a.u.)
After 600 cycles
10 20 30 40 50 60 70
2θ (°)
Fig. 3 | Characterizations of the NMC622 electrodes after long cycling in 350 Wh kg−1 pouch cells. a, The cross-sectional SEM image of one cathode layer
(double-sided on Al foil) after 600 cycles in the 20 µm thin-Li pouch cell. The insert is a photograph of a piece of cathode after cycling. b, The X-ray
diffraction patterns of the cathode electrode before and after cycling in the pouch cell. The pristine electrode is composed of 96 wt% NMC622, 2 wt%
conductive carbon and 2 wt% PVDF binder. c,d, The cross-sectional TEM images of NMC622 secondary particles before and after cycling. e,f, High-angle
annular dark-field (HAADF)-STEM images of the surface layer of the NMC622 cathode before and after cycling.
cell remain very stable, as shown in Fig. 2f and Supplementary Fig. 3.
Different from the Li-free-anode and thick-Li pouch cells, no obvi-
ous voltage shift (that is, polarization) is found in the well balanced
20 µm Li cell throughout the entire 600 cycles. The cell-level energy
density of this 350 Wh kg−1 pouch cell with 20 µm Li maintains 71%
after 600 cycles. This result suggests SEI build-up is greatly reduced
in the thin-Li cell. The changes in SEI structures are also confirmed
by preliminary impedence measures. After extensive cycling, the
thin-Li pouch cell has the smallest interfacial charge transfer resis-
tance, followed by the 50 µm and 100 µm Li pouch cells (Fig. 5d).
Li-free-anode pouch cells
An extreme situation is to completely remove Li metal from the
anode (called a Li-free-anode cell). In this case, both cell energy
and cell capacity (Fig. 2g) show a slow steady decay throughout the
entire cycling (80% capacity retention at the 100th cycle). The slow
steady capacity degradation over long-term cycling is consistent
with previous studies27–30. However, a sudden capacity drop is absent
in the Li-free-anode cell. The cell lasts for almost 500 cycles before
the capacity reaches zero. The steady capacity fading is caused by the
irreversible Li consumption during each cycle. In the Li-free-anode
cell, all Li cations come from the cathode and no extra Li is avail-
able from the anode to compensate for the Li loss in side reactions.
The cell capacity is calculated based on the cathode; the amount of
reversible Li+ ions available to return back into the cathode directly
determines the cell capacity. The continuous loss of Li leads to the
continuous decrease of cell capacity, and thus a steady cell degrada-
tion is seen in the Li-free-anode cell.
The Li loss is also reflected in the obvious decrease of the charge
and discharge voltages upon cycling (Fig. 2h and Supplementary
Nature Energy
e
Before cycling Before cycling
5 µm 2 nm
f
After 600 cycles After cycling
Reconstruction layers
5 µm 2 nm
Fig. 4). The CE of the Li-free-anode cell can be used to monitor
the Li leftover and estimate the cycle life of the battery33. The prod-
uct of all CEs measured from the first cycle to the 500th cycle gives
4.95% (Fig. 2g), suggesting a very small amount of Li is left in the
cell after extensive cycling, which is consistent with the observed
capacity retention of ~4% at the 500th cycle. Therefore, the CE in
the Li-free-anode cell represents the strict scenario of Li metal cells
and is a good indicator for cell life prediction, provided that a com-
patible electrolyte is used.
SEI structures and cell degradation processes
First, the integrity of the cathode materials and structures were
evaluated. A scanning electron microscopy (SEM) image reveals
good integrity of the NMC622 electrode after 600 cycles in the
20 µm Li pouch cell (Fig. 3a and Supplementary Fig. 5). The
X-ray diffraction pattern reveals that the layer structure of the
NMC622 electrode remains stable and no new phases are gener-
ated after long cycling (Fig. 3b). Furthermore, as shown in the
cross-sectional transmission electron microscopy (TEM) of sec-
ondary particles (Fig. 3c,d), the primary crystalline particles are
intact without visible intergranular cracking, while some interpar-
ticle cracking is observed. High-resolution TEM study suggests
that the bulk crystalline structure is retained without visible cat-
ion mixing, although a very thin, ~3 nm thick, disordered rock-
salt phase can be seen on the surface (Fig. 3e,f). Based on these
observations and independent long cycling data of the cathode
materials under similar conditions, we conclude that electrochem-
ical properties of the cathode are largely maintained over the long
cycles. The main degradation should come from the anode side,
that is, the SEI reactions.
Nature Energy | www.nature.com/natureenergy
Nature Energy
100 µm Li anode 50 µm Li anode
a Before cycling d Before cycling
100 µm Li
50 µm Li
Cu Cu
2 cm 100 µm 100 µm
b After 370 cycles
e After 460 cycles
Intact Li
Intact Li
~130 µm
~180 µm
100 µm 100 µm
c f
5 µm 5 µm
Fig. 4 | Postmortem characterizations of the Li metal anodes before and after cycling in four types of 350 Wh kg−1 pouch cell. a–c, The cross-sectional
and top view SEM images of one anode layer (double-sided) in the 100 µm thick-Li pouch cell before (a) and after (b and c) cycling. d–f, SEM images
of the 50 µm Li anode before and after cycling. g–i, SEM images of one anode layer in the 20 μm thin-Li pouch cell before and after 600 cycles. j–l, SEM
images of one anode layer before (bare Cu foil) and after cycling in the Li-free-anode pouch cell. All insets are the corresponding photos.
To understand the nature of the SEI, the Li metal anodes of four
types of pouch cells before and after cycling were characterized (Fig.
4). With a thick 100 µm Li anode in the cell, the cycled Li contains an
unevenly distributed porous structure, and a large portion of intact/
dense Li is left in the cell (Fig. 4a–c). Therefore, the electrolyte is
depleted before the Li anode is consumed. At the same time, the
insulating SEI layers quickly increase cell impedance, which accel-
erates the cell polarization so that the cell always displays a sudden
capacity drop after a certain number of cycles. The depletion of the
electrolyte with thick Li is consistent with previous results in which
the cell capacity was partially recovered when the ‘dead’ cell was
refilled with additional electrolyte1. Additional experiments were
also conducted with coin cells using conditions similar to the pouch
cells (high cathode loading, controlled electrolyte amount and Li
thickness). Much longer cycle life can be obtained with flooded
electrolyte conditions as compared to lean electrolyte conditions
for thick Li. (A systematic comparison of the pouch cell and coin
cell results will be published separately.) The medium 50 µm Li cell
produces an approximately 100-µm-thick porous structure consist-
ing of Li and SEI (Fig. 4d–f), and about half of the original intact Li
is seen after long cycling, also indicating the electrolyte is depleted
before the Li is consumed.
For the pouch cell with ultra-thin 20 µm Li, the whole anode
structure is well maintained (as shown in the insert photos in Fig.
4); an approximately 70 µm porous SEI/Li layer is seen after 600
cycles (Fig. 4g–i and Supplementary Fig. 6), while almost no intact
Li is left on the anode side, indicating a complete utilization of the
20 µm Li after cycling. A Cu mesh is used as the anode current
Nature Energy | www.nature.com/natureenergy
Articles
20 µm Li anode Li-free anode
g Before cycling j Before cycling
Bare Cu
20 µm Li
Cu
100 µm 100 µm
h After 600 cycles k After 500 cycles
~40 µm
~70 µm
100 µm 100 µm
i l
5 µm 5 µm
collector to reduce the weight of the paraside weight from inactive
materials, but all Li on the anode is utilized and there is no evidence
of residual Li trapped in the large porosity of the Cu mesh. This is
a good indication of balanced interactions between the limited Li
source and lean electrolyte in realistic batteries.
For the Li-free-anode pouch cell, even though there is no Li on
the anode at the beginning, the cell utilizes Li from the cathode,
and the whole Li inventory is repeatedly cycled between the cathode
and the anode. In each cycle, a small amount of Li is trapped on the
anode, eventually leading to a porous entangled SEI/Li structure of
roughly 40 µm in thickness (Fig. 4k–l). Overall, an increased exces-
sive Li amount leads to increased reaction heterogeneity, thickening
the SEI and rough interfaces. The electrolyte is also depleted faster
than Li is consumed if Li is in large excess, for example, 100 µm.
Reducing the Li anode thickness to 50 µm helps extend the cycling.
A balanced Li thickness is identified at 20 µm in the compatible
electrolyte used in this work, which takes full advantage of both
thin Li and lean electrolyte while minimizing the accumulation of
SEI layers.
The cell thickness swelling of four types of pouch cells before
and after cycling are compared. In the experiments, all cell cycling
was terminated when the capacity reached about 60% of the original
capacity. No measurable gas release was detected under these con-
ditions. Since the different cells have different cycles, the data have
been normalized by the total number of cycles to yield the average
thickness increase per cycle (Fig. 5a). Noticeably, the cell volumetric
density of the Li-free-anode cell and thin-Li pouch cell can reach up
to 909 Wh l−1 and 802 Wh l−1, respectively, due to the reduced cell
Articles Nature Energy

a 10 100

Cell thickness average swelling (µm per cycle)

9 350 Wh kg –1 90
Thick-Li cell 20 µm thin Li
8 Previous 100 µm Li –1 80
350 Wh kg
300 Wh kg−1

Cell capacity retention (%)

7 50 µm Li 70
50 µm Li
6 60

5 50

4 40

3 30

2 Cell thickness average swelling (µm per cycle) 20

Li-free-anode cell
1 Cell capacity retention after cycling (%) 350 Wh kg–1 10

0 0
150 200 250 300 350 400 450 500 550 600 650
Cycle number

b Li-free-anode pouch cell

c 20 µm thin-Li pouch cell
d 0.2
20 µm Li pouch cell Before cycling
Before cycling Before cycling After cycling
0.1

0
0.2
3.7 mm 4.1 mm 50 µm Li pouch cell

Z ″ (Ω)
0.1

After 500 cycles After 600 cycles 0

0.2
100 µm Li pouch cell
0.1

4.9 mm, swell 32%, 2.4 µm per cycle 5.7 mm, swell 39%, 2.7 µm per cycle
0
0 0.1 0.2 0.3 0.4 0.5
Z ′ (Ω)

Fig. 5 | Pouch cell thickness average swelling comparison after cycling. a, The cell thickness average swelling rate and cell capacity retention of four
350 Wh kg−1 pouch cells after cycling, and compared with our previous reported 300 Wh kg−1 pouch cell with 50 µm Li (ref. 25). Since the different pouch
cells have different cycles, the cell swelling has been plotted as thickness increase upon cycling, and the data is normalized by the total number of cycles to
yield the average thickness increase per cycle. b, Photographs of the Li-free-anode pouch cell before and after cycling. The Li-free-anode pouch cell swells
by 32% with capacity retention at only 4% after 500 cycles, which corresponds to an average swelling of 2.4 µm per cycle. c, Photographs of the 20 µm
thin-Li pouch cell before and after cycling. The 20 µm thin-Li pouch cell swells a little bit more at 39%, but the cell capacity retention reaches up to 76%
even after 600 cycles; the average thickness swelling is 2.7 µm per cycle. d, The impedance measurements of 350 Wh kg−1 pouch cells before and after
cycling. Note that the contact area of the cathode and anode is more than 600 cm2 in each pouch cell, and an external uniform pressure of ~172 kPa had
initially been applied to the pouch cell before cycling. Therefore, the measured cell resistances of the pouch cells are much smaller than lab-scale coin cells
even with the same chemistry.

volume in these two cells. The 100 µm Li pouch cell has a ‘bulky’ capacity fading, making the comparison not very meaningful. Still,
volume due to the thick anode, and the percentage of total Li thick- the Li-free-anode pouch cell swells by 32% in thickness by the end
ness in the whole pouch cell is as high as 48.5%. After 370 cycles of its cycle life (Fig. 5b), due to the SEI thickening in the anode.
the cell swells by 41% (Fig. 5a), corresponding to an average cell Therefore, the Li-free-anode cell does not solve the cell swelling
swelling of ~7.3 µm per cycle. For the medium 50 µm Li pouch cell, issue, not to mention the steady capacity decay.
the percentage of Li is 30.8%; the cell swells by 46% but achieves a
longer 465 cycles, so the average cell swelling is ~5.2 µm per cycle. The degradation mechanisms
However, for the 20 µm thin-Li pouch cell, the percentage of total A fundamental question is why the SEI layer accumulation is
Li thickness in the whole pouch cell is 15.6%; the total swelling is decreased in the 20 µm Li pouch cell. Each pouch cell used the same
only 39%, even after 600 long cycles (Fig. 5a,c), and the average cell cathode loading, meaning that the same amount of Li (4 mAh cm−2,
swelling is only ~2.7 µm per cycle. Therefore, reducing the Li thick- equal to 20 µm Li) is being deposited and stripped during each
ness in the pouch cell mitigates cell swelling after extensive cycling. cycle. The same lean electrolyte was also used in these four types of
Compared with our previously reported 300 Wh kg−1 pouch cell25, pouch cells. For LMBs, SEI layers accumulated in the cells are the
which swells by 67% after only 200 cycles, resulting in an average by-products from the side reactions between the electrolyte and the
swelling of ~9 µm per cycle (Fig. 5a), the cell thickness swelling in Li. The electrolyte has to flow onto Li metal surfaces and react with
these 350 Wh kg−1 pouch cells has been greatly reduced. Li to produce SEI layers. Our results suggest that two different kinds
The Li-free-anode cell has an average swelling of ~2.4 µm per of SEI layers have been generated from the contact between the Li
cycle, seemingly less than that of the 20 µm Li pouch cell. However, and the electrolyte. One is the ‘wet SEI’ layers formed by the electro-
during each cycle, the plated Li amount in the Li-free-anode cell is lyte wetting the Li metal surfaces, on which some residual electro-
much less than that of the 20 µm Li pouch cell because of the steady lyte is left. Therefore, Li+ ions diffuse back and forth through these

Nature Energy | www.nature.com/natureenergy

Nature Energy Articles
Li-free-anode cell: continuous loss of the only Li inventory from cathode dominates thoughout the entire cycling

Entangled ‘dead’ Li and SEI

Bare Cu Cycling

Thick-Li cell: cell impedance builds up and gradually dominates towards the end of cycling, leading to sudden death
Capacity retention (%)

Dry SEI gradually dominates

50 µm or 100 µm Li

Dry SEI:
Wet SEI: electrolyte no residual
still available electrolyte

Thin-Li cell: produces a thin, uniform SEI layer (with less dry SEI), decelerates cell impedance build-up, smooths the end cycling

A thin and uniform SEI layer

20 µm thin Li

Cycle number

Fig. 6 | Schematic illustration of the degradation mechanisms and cell capacity fading models. In the Li-free-anode cell, although no Li is present in
the anode at the beginning, the Li from the cathode still gradually deposits on the anode, forming SEI layers and ‘dead’ Li, accompanied by continuous
slow capacity decay and cell swelling until all cathode Li is depleted. The number of cycles (with steady decay) can be monitored by the full cell CE if the
electrolyte is compatible with Li metal. In the thick-Li cells (100 µm and 50 µm Li, N/P ratio ≥2.5:1), an initial stable cycling behaviour is first seen with an
artificially high (~100%) full cell CE due to the extra Li in the anode, but this artificially high CE does not reflect the real loss of the Li during cycling, and
therefore cannot be used to predict cell life. As cycling continues, more pores are generated in cycled Li; the liquid electrolyte freely flows into those new
areas, and the amount of electrolyte is very lean in realistic batteries—a trace amount of liquid just barely touches new Li surfaces, which are immediately
converted to dry SEI layers without additional electrolyte to ‘wet’. These dry SEI layers cannot participate in the subsequent cycles but keep increasing the
cell impedance due to the lack of an ion conduction pathway. Therefore, a sudden capacity drop is usually seen once the polarization becomes sufficiently
high to turn off the electrochemical reactions within the same electrochemical window. An optimized thin-Li anode (20 µm Li, N/P ratio 1:1) produces a
thin, uniform SEI layer (with less dry SEI) and effectively balances the competition among the Li consumption rate, the speed of electrolyte depletion and
the rate of SEI accumulation under realistic constrained conditions. The end results are that the increase in impedance/polarization is decelerated due to
the prevention of SEI layer accumulation. The steep capacity drop towards the end of the cell cycle life is mitigated or smoothed, and a long stable cycle
life is obtained.

wetted SEI layers to continue the electrochemical reactions. Most
SEIs in thin-Li cells prove to be effective wet SEI layers. The sec-
ond type of SEI layer is considered ‘dry SEI’ layers. As more ‘pores’
are generated within the cycled Li, the liquid electrolyte freely flows
into those new areas; in realistic high-energy batteries, the amount
of electrolyte is very limited, and a trace amount of liquid just barely
touches the new Li surfaces, which are immediately converted to
dry SEI layers (as shown in Fig. 6). Therefore, these dry SEI layers
cannot participate in the subsequent electrochemical reactions due
to the lack of ion conduction pathways.
Compared with the thin-Li cell, the random flow of electrolyte
within a thick-Li anode provides more opportunity to produce dry
SEI layers. The thick, porous SEI structures with thick Li are pro-
duced by uneven reactions with the electrolyte. Due to the highly
reactive nature of Li metal, side reactions are unavoidable and
uneven on the Li metal surface, and many of those side reactions
also contribute electrons to the current collectors4. The electrons
from those irreversible side reactions are one-time-use only. In the
subsequent cycles, in order to compensate for the insufficiency of
electrons, either new side reactions occur, or new Li surfaces are
exposed to electrolyte to proceed with electrochemical reactions.
As a result, the Li anode becomes more and more porous and the
surface area increases. The thicker the Li, the more Li is available
for the side reactions, and thus the thicker the SEI layers. This
result is also supported by cell impedence measures (Fig. 5d and
Supplementary Fig. 7); the thick Li gives a high resistance, which
also increases more quickly during cycling, indicating the more
insulating nature of the SEI layers. The impedance of the thin-Li
pouch cell remains very small even after 600 cycles. In addition, a
thick-Li anode with a large volume also accelerates the electrolyte
depletion rate, especially in the practical pouch cells with lean elec-
trolyte. These above discussions explain why reducing the Li metal
thickness in the anode helps extend the cycling.
Much more research is needed on the detailed degradation mech-
anisms and molecular pathways of the SEI reactions, but it is worth-
while to schematically summarize the major findings based on the
experimental observations (Fig. 6). The Li-free-anode pouch cell is
characterized by a slow steady capacity decay because the Li (stored
in the cathode) inventory loss dominates from the beginning to the
end of cycle life. The cell capacity is based on the cathode, which con-
tinuously loses usable Li+ ions. The cell polarization increases sharply
during charge–discharge, and the Li trapped in the SEI cannot be
restored to the cathode materials during cycling, giving rise to the
steady capacity dacay. The number of cycles (with steady decay) can
be monitored by the full cell CE if the electrolyte is compatible with
Li metal. The resistance of the Li-free-anode cell is higher than other
cells (Supplementary Fig. 7), most likely due to the fact that the SEI
layer contains more insulating reaction products than in other cases.

Nature Energy | www.nature.com/natureenergy

Articles
For the thick-Li cells (100 µm Li), an initial stable cycling behav-
iour is always observed with an artificially inflated full cell CE, but
this artificially high CE does not reflect the real loss of Li during
cycling, and therefore cannot be used to predict the cell lifespan. As
cycling continues, a thick SEI is built up (mainly dry SEI) with rough
surfaces, which gives rise to cell polarization, particularly towards
the end of battery life. The cell capacity suddenly drops when the
polarization becomes sufficiently high to turn off the electrochemi-
cal reactions within the same electrochemical window. The SEI
build-up is further confirmed by impedance measurements (Fig.
5d). Reducing Li metal thickness to 50 µm Li helps extend the stable
cycle life but cannot get rid of the sudden capacity drop because
the SEI-induced cell impedance increases, as reflected by the polar-
ization, are still dominant. However, an optimized 20 µm thin-Li
produces a thin, uniform SEI layer (with less dry SEI), reduces
polarization and effectively balances the competition among the Li
consumption rate, the speed of electrolyte depletion and the rate of
SEI accumulation under the realistic limiting conditions. The end
results are that the impedance/polarization increasing is decelerated
due to the prevention of SEI layer accumulation. The steep capacity
drop towards the end of the cell cycle life is mitigated/smoothed,
and a long stable cycle life is obtained.
However, the properties of rechargeable LMBs are complex and
can change with the specific cell designs and selection of electrolytes.
A balanced Li metal cell not only means a reasonable N/P ratio, but
more importantly affects the distribution of lean electrolyte in the
reacted porous Li metal anode, which determines how much effec-
tive SEI layer will be left after each cycle. Therefore, for the current
design of a 350 Wh kg−1 pouch cell (that is, a high loading NMC
cathode (≥4.0 mAh cm−2), specific compatible electrolyte35 with
very limited amount (E/C ratio at 2.4 g Ah−1), PE separator, and so
on), there will be an optimized Li thickness to maximize the sta-
ble cycle life under realistic conditions. But the specific, optimum
N/P ratio may change depending on the specific cell conditions.
Currently, 50 μm and 20 μm Li foils can be obtained from commer-
cial sources. New manufacturing capabilities will be needed for uni-
form and high-purity Li if thinner Li foils are desired.
Discussion
LMBs are complex systems with high reactivity, sensitive electrode
materials and electrolytes. The SEI structures are mostly amorphous
or disordered. Nevertheless, our experimental results provide useful
answers to some key questions in the development of LMBs, includ-
ing what CE in full cells means, why the amount of Li matters, what
determines the optimum Li thickness and why some cells achieve
very long cycles but others die very quickly.
Another very important topic for LMBs is safety concerns.
Although excellent cycling stability is observed in this study, the
combination of the high reactivity of the Li metal, the electro-
lyte and the cathode materials still presents a great challenge for
practical applications. The Li metal challenge and the associated
safety concerns are far from being solved. Achieving reliable and
stable long cycle life is the first step, but our LMBs could serve as
a platform to conduct systematic investigations of the thermody-
namics and kinetics that control the thermal stability of the entire
battery system.
Future research should focus on strategies to further improve and
control the Li metal deposition and stripping processes. Currently,
more than 600 stable cycles can be achieved for high-energy Li
metal pouch cells with a stable electrolyte and optimized cell param-
eters, but the CE as measured by the Li-free-anode cell is still below
99.5%. A higher CE close to 100% could be enabled by an electrolyte
that produces a more stable SEI and less side reactions, or by an
anode that allows a more stable interface such as a surface protec-
tion layer so as to reduce the interactions with the liquid electrolyte.
For the NMC cells, the achievable energy density is still hindered by
Nature Energy
several factors, such as the limited cathode capacity, the capacity loss
including the first cycle loss and degradation over long cycles, and
the difficulty in extracting full capacity with a high cathode loading
and lean electrolyte conditions. In addition, a good cell design also
needs to strike a balance in achieving both high energy density and
long cycle life. Genuine material and performance breakthroughs
should be validated either in real high-energy cells or under realistic
testing conditions.
Conclusions
We systematically studied the competing degradation mechanisms
in different practical 350 Wh kg−1 Li metal pouch cells spanning
from the Li-free anode to the thin-Li and thick-Li regions. In the
Li-free-anode pouch cell (N/P ratio 0:1), continuous loss of Li is
accompanied by a steady capacity decay and cell swelling until all Li
stored in the cathode is completely depleted. The number of cycles
(with steady decay) can be monitored by the full cell CE if the elec-
trolyte is compatible with Li metal.
We show that in the thick-Li pouch cells (100 µm and 50 µm
Li, N/P ratio ≥2.5), initial cycles are always very stable; however,
as cycling continues, the build-up of dry SEI layers increases the
cell polarization, which gradually becomes dominant, especially
towards the end of cell life. Therefore, a sudden capacity drop is
usually seen once the polarization becomes sufficiently high to turn
off the electrochemical reactions within the same electrochemical
window. The CE in Li metal cells is artificially high at almost 100%
because the extra Li in the anode can compensate for the loss of Li
originating from the cathode; therefore, this CE does not reflect the
real loss of the Li during cycling, and thus cannot be used to predict
cell life. This situation is totally different from that of conventional
Li-ion batteries, where only the cathode supplies Li.
An optimized 20 µm thin-Li (N/P ratio 1:1) produces a thin,
uniform SEI layer (with less dry SEI) and effectively balances the
competition among the Li consumption rate, the speed of elec-
trolyte depletion and the rate of SEI accumulation under realistic
constrained conditions, thus minimizing the cell polarization upon
cycling and extending the cell cycle life. Contrary to the conven-
tional viewpoint that thicker Li usually produces a longer cycle life,
it is found that a longer cycle life is achieved by using a thin-Li anode
in realistic high-energy LMBs. A prototype 350 Wh kg−1 pouch cell
(2 Ah) achieved 600 stable cycles with a capacity retention at 76%, a
milestone in rechargeable high-energy LMBs.
Methods
Li metal pouch cell assembly. All pouch cells were assembled with a
semi-automated cell manufacturing line (MediaTech, Korea) in the dry room
(0.1% relative humidity, dew point controlled below −55 °C, temperature constant
at 19 °C) of the Advanced Battery Facility Lab at the Pacific Northwest National
Laboratory (PNNL). This includes the slurry mixing machine; coating machine;
calendaring machine; Z-stacking machine of the cathode, anode and separator;
grid-trim; ultrasonic welding for connection with Al (cathode) and Ni (anode)
external tabs; packaging; top and side sealing; and vacuum sealing with electrolyte
injection. To achieve 350 Wh kg−1 energy within the very restricted volume with
controlled weight, the cathode area capacity must be more than 4.0 mAh cm−2
NMC622 on each side of the Al foil, and the capacity of each pouch cell is more
than 2.0 Ah. Each pouch cell contains 16 layers of double-sided anodes, as well as
15 double-sided and 2 single-sided cathode layers. The Li-free-anode pouch cell
was assembled with bare Cu foil and NMC622, so the N/P ratio is 0:1 and the E/C
ratio is 2.6 g Ah−1. For the 20 µm Li pouch cell, the N/P ratio is 1:1 and the E/C
ratio is 2.4 g Ah−1. For the 50 µm Li pouch cell, the N/P ratio is 2.5:1 and the E/C
ratio is 2.2 g Ah−1. For the 100 µm Li pouch cell, the N/P ratio is 5:1, and the E/C
ratio is also kept at 2.2 g Ah−1, the same as the 50 µm Li pouch cell for comparison,
so the cell-level gravimetric energy of the 100 µm Li pouch cell is a little lower,
334 Wh kg−1. The 350 Wh kg−1 pouch cell fabrication was also combined with a
series of technological improvements compared with our previously reported
300 Wh kg−1 pouch cell.
Preparation of NMC cathode. NMC622 was received from Targray. The cathode
slurry was prepared by mixing 96 wt% NMC622, 2 wt% conductive carbon (Super
P C65, Timcal) and 2 wt% polyvinylidene difluoride (PVDF) binder (L1120 from
Nature Energy | www.nature.com/natureenergy
Nature Energy
Kureha) in N-methyl-2-pyrrolidone solution. Then, the slurry was coated onto
both sides of 10-μm-thick Al foil by using the coating machine (Mediatech) in
the dry room. After coating, the cathode was calendared and then punched into
rectangular pieces and dried in a vacuum oven (70 °C, 24 h) prior to cell assembly.
Preparation of Li metal anode. Both 50 μm and 100 μm free-standing Li foils
(Li content ≥99.9%) were ordered from China Energy Lithium. The 20 μm
free-standing Li (Li content ≥99.9%) foil was received from Honjo, and is the
thinnest commercially available free-standing Li foil currently. The Cu current
collector was from MTI. The free-standing Li foil was laminated onto both sides
of the Cu current collector in the dry room (0.1% relative humidity, dew point
controlled below −55 °C, temperature constant at 19 °C), and then was punched
into rectangular pieces prior to cell assembly.
Electrolyte. Battery-grade lithium bis(fluorosulfonyl)imide (LiFSI) was
provided by Nippon Shokubai and further dried at 120 °C under vacuum for
24 h before use; 1,2-dimethoxyethane (DME) was purchased from Gotion, Inc.;
1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE, 99%) was ordered
from SynQuest Laboratories and dried with molecular sieves before use. LiFSI
and DME were first mixed, and then TTE was added as the diluent to yield 1.5 M
LiFSI–DME–TTE electrolyte (DME/TTE molar ratio 1.2:3)35. All procedures were
performed in an MBraun LABmaster glove box filled with purified argon gas
(<0.1 ppm O2, <0.1 ppm H2O).
Characterization. Both cycled Li anodes and NMC622 cathodes were obtained
by disassembling the cycled pouch cells inside the glove box. Notably, the
disassembly of large-scale cycled pouch cells is high risk, and requires a standard
operating procedure that must be strictly observed. Samples were hermetically
sealed inside an air-tight bottle for transferring. SEM images were collected with
a Helios focused ion beam SEM instrument (FEI). Some samples were cut on the
pore part of the Cu mesh, while some were cut on the solid foil part. (The cycled
Li anodes show no obvious difference between that located on the solid foil
part and that on the pore part.) X-ray diffraction patterns were obtained on a
Rigaku MiniFlex II X-ray diffraction instrument (Cu Kɑ radiation, 30 kV, 15 mA
and scan rate 0.15° per minute with 0.02° step). The NMC622 electrodes were
transferred from the glove box to the FEI Helios Dual Beam system to prepare
the TEM samples. Several random secondary particles were picked, and the lift
out processes were started by coating a Pt layer. After that, a sample slice was
extracted, followed by welding onto the Cu TEM grid. The subsequent thinning
process was performed step by step using a voltage of 30 kV until reaching
electron-transparent thickness; the final polishing processes were carried out
at a voltage of 2 kV. The high-angle annular dark-field (HAADF)-STEM images
were collected on the aberration-corrected JEOL JEM-ARM200CF with an
operation voltage of 200 kV. Electrons ranging from 90 mrad to 370 mrad were
collected for imaging.
Electrochemical testing. All pouch cells were sandwiched in the stainless-steel
clamping device for testing, and the initial external pressure was optimized at
25 psi (~172 kPa). As is known, the Li metal pouch cell will expand upon cycling;
therefore, 172 kPa is supposed to be the minimum value. All Li metal pouch cells
were tested in a gas-detecting safety chamber (Cincinnati Sub-Zero) filled with
inner gas at 25 °C. Galvanostatic cycling tests were conducted within a voltage
window of 2.7 V to 4.4 V using Land battery testers (LANHE CT2001B, type
5V-10A-8C-110V, Wuhan Land), first charged–discharged at a constant current
rate of 0.1 C for two initial formation cycles, then charged at 0.1 C and discharged
at 0.3 C in subsequent cycles (1 C equals 4.0 mA cm−2 or corresponds to 2.3 A).
During the long testing of more than 13 months, these pouch cells suffered two
power outages and one period of oven maintenance, so some cycling behaviours
show some fluctuations. The cell impedance was measured using a Solartron
Frequency Response Analyzer (1255B); the initial set-up frequency was 105 Hz, and
the final frequency was 10−3 Hz.
Data availability
All data generated this study are included in the published article and its
Supplementary Information.
Received: 15 December 2020; Accepted: 30 April 2021;
Published: xx xx xxxx
References
1. Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal
batteries. Nat. Energy 4, 180–186 (2019).
2. Whittingham, M. S. Ultimate limits to intercalation reactions for lithium
batteries. Chem. Rev. 114, 11414–11443 (2014).
3. Whittingham, M. S. Lithium batteries and cathode materials. Chem. Rev. 104,
4271–4302 (2004).
4. Xiao, J. How lithium dendrites form in liquid batteries. Science 366,
426–427 (2019).
Nature Energy | www.nature.com/natureenergy
Articles
5. Xu, W. et al. Lithium metal anodes for rechargeable batteries. Energy Environ.
Sci. 7, 513–537 (2014).
6. Jiao, S. et al. Behavior of lithium metal anodes under various capacity
utilization and high current density in lithium metal batteries. Joule 2,
110–124 (2018).
7. Wu, B., Lochala, J., Taverne, T. & Xiao, J. The interplay between solid
electrolyte interface (SEI) and dendritic lithium growth. Nano Energy 40,
34–41 (2017).
8. Chen, S. et al. Critical parameters for evaluating coin cells and pouch cells of
rechargeable Li-metal batteries. Joule 3, 1094–1105 (2019).
9. Cao, X. et al. Monolithic solid–electrolyte interphases formed in fluorinated
orthoformate-based electrolytes minimize Li depletion and pulverization. Nat.
Energy 4, 796–805 (2019).
10. Ren, X. et al. High-concentration ether electrolytes for stable high-voltage
lithium metal batteries. ACS Energy Lett. 4, 896–902 (2019).
11. Fang, C. et al. Quantifying inactive lithium in lithium metal batteries. Nature
572, 511–515 (2019).
12. Yamada, Y., Wang, J., Ko, S., Watanabe, E. & Yamada, A. Advances and
issues in developing salt-concentrated battery electrolytes. Nat. Energy 4,
269–280 (2019).
13. Fan, X. et al. Non-flammable electrolyte enables Li-metal batteries with
aggressive cathode chemistries. Nat. Nanotechnol. 13, 715–722 (2018).
14. Shen, L. et al. Progress on lithium dendrite suppression strategies from the
interior to exterior by hierarchical structure designs. Small 27, 2000699 (2020).
15. Zhang, Y. et al. Towards better Li metal anodes: challenges and strategies.
Mater. Today 33, 56–74 (2020).
16. Lin, D., Liu, Y. & Cui, Y. Reviving the lithium metal anode for high-energy
batteries. Nat. Nanotechnol. 12, 194–206 (2017).
17. Niu, C. et al. Self-smoothing anode for achieving high-energy lithium metal
batteries under realistic conditions. Nat. Nanotechnol. 14, 594–601 (2019).
18. Kang, N. et al. Cathode porosity is a missing key parameter to optimize
lithium-sulfur battery energy density. Nat. Commun. 10, 4597 (2019).
19. Hwang, J. et al. Customizing a Li–metal battery that survives practical
operating conditions for electric vehicle applications. Energy Environ. Sci. 12,
2174–2184 (2019).
20. Ue, M., Sakaushi, K. & Uosaki, K. Basic knowledge in battery research
bridging the gap between academia and industry. Mater. Horiz. 7, 1937–1954
(2020).
21. Shi, P. et al. Electrochemical diagram of an ultrathin lithium metal anode in
pouch cells. Adv. Mater. 31, 1902785 (2019).
22. Palanisamy, M., Parikh, V. P., Parekh, M. H. & Pol, V. G. Lithium metal
battery pouch cell assembly and prototype demonstration using tailored
polypropylene separator. Energy Technol. 8, 2000094 (2020).
23. Zhang, X. et al. Rethinking how external pressure can suppress dendrites in
lithium metal batteries. J. Electrochem. Soc. 166, A3639–A3652 (2019).
24. Barai, P., Higa, K. & Srinivasan, V. Impact of external pressure and electrolyte
transport properties on lithium dendrite growth. J. Electrochem. Soc. 165,
A2654–A2666 (2018).
25. Niu, C. et al. High-energy lithium metal pouch cells with limited anode
swelling and long stable cycles. Nat. Energy 4, 551–559 (2019).
26. Lee, Y. G. et al. High-energy long-cycling all-solid-state lithium metal
batteries enabled by silver–carbon composite anodes. Nat. Energy 5,
299–308 (2020).
27. Weber, R. et al. Long cycle life and dendrite-free lithium morphology in
anode-free lithium pouch cells enabled by a dual-salt liquid electrolyte. Nat.
Energy 4, 683–689 (2019).
28. Louli, A. J. et al. Exploring the impact of mechanical pressure on the
performance of anode-free lithium metal cells. J. Electrochem. Soc. 166,
A1291–A1299 (2019).
29. Louli, A. J. et al. Diagnosing and correcting anode-free cell failure via
electrolyte and morphological analysis. Nat. Energy 5, 693–702 (2020).
30. Genovese, M. et al. Combinatorial methods for improving lithium metal
cycling efficiency. J. Electrochem. Soc. 165, A3000–A3013 (2018).
31. Xiao, J., Yang, Y., Liu, D. & Deng, Z. D. Li-Batt Design App (Pacific
Northwest National Laboratory, 2020).
32. Wu, B. et al. Good practices for rechargeable lithium metal batteries. J.
Electrochem. Soc. 166, A4141–A4149 (2019).
33. Xiao, J. et al. Understanding and applying coulombic efficiency in lithium
metal batteries. Nat. Energy 5, 561–568 (2020).
34. Zhu, Y. et al. Design principles for self-forming interfaces enabling stable
lithium metal anodes. Proc. Natl Acad. Sci. USA 117, 27195–27203 (2020).
35. Ren, X. et al. Enabling high-voltage lithium-metal batteries under practical
conditions. Joule 3, 1662–1676 (2019).
36. Lu, D. et al. Failure mechanism for fast-charged lithium metal batteries with
liquid electrolytes. Adv. Energy Mater. 5, 1400993 (2015).
37. Goodenough, J. B. & Park, K. S. The Li-ion rechargeable battery: a
perspective. J. Am. Chem. Soc. 135, 1167–1176 (2013).
38. Yang, S., Zavalij, P. Y. & Whittingham, M. S. Anodes for lithium batteries: tin
revisited. Electrochem. Commun. 5, 587–590 (2003).
Articles
39. Kim, D. et al. Porosity controlled carbon-based 3D anode for lithium metal
batteries by a slurry based process. Chem. Commun. 56, 13040–13043 (2020).
40. Kim, S. et al. Correlation of electrochemical and mechanical responses:
differential analysis of rechargeable lithium metal cells. J. Power Sources 463,
228180 (2020).
Acknowledgements
This research was supported by the Assistant Secretary for Energy Efficiency and
Renewable Energy, Office of Vehicle Technologies of the US Department of Energy
(DOE) through the Advanced Battery Materials Research Program (Battery500
Consortium). The SEM and TEM were conducted in the William R. Wiley
Environmental Molecular Sciences Laboratory, a national scientific user facility
sponsored by DOE’s Office of Biological and Environmental Research and located at
PNNL. PNNL is operated by Battelle for the DOE under contract DE-AC05-76RLO1830.
We thank L. Zou and C. Wang of PNNL for the TEM characterizations. We thank K.
Murata of Nippon Shokubai for providing the LiFSI salt.
Author contributions
J.L. directed and led the research. J.X. led the pouch cell design and fabrication. C.N.
assembled the pouch cells, performed the electrochemical measurements and carried out
Nature Energy
the characterizations. D.L., J.A.L. and C.S.A. participated in discussions. X.C., W.X. and
J.-G.Z. provided the electrolyte. M.E.G. helped on cell disassembly and safety protection.
M.S.W. provided advice for the research and for the analysis of the electrochemical
results. C.N., J.X. and J.L. cowrote the manuscript with input from all authors.
Competing interests
The authors declare no competing interests.
Additional information
Supplementary information The online version contains supplementary material
available at https://doi.org/10.1038/s41560-021-00852-3.
Correspondence and requests for materials should be addressed to J.X. or J.L.
Peer review information Nature Energy thanks Guohua Chen, Tetsuya Osaka and the
other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Reprints and permissions information is available at www.nature.com/reprints.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in
published maps and institutional affiliations.
© The Author(s), under exclusive licence to Springer Nature Limited 2021
Nature Energy | www.nature.com/natureenergy