MRS Energy & Sustainability (2022) 9:13–18

© National Technology & Engineering

Solutions of Sandia, LLC 2022
doi:10.1557/s43581-021-00018-4

LARGE-SCALE ENERGY STORAGE – PERSPECTIVE

Driving Zn‑MnO2 grid‑scale Erik D. Spoerke , Howard Passell, Timothy N. Lambert and

Babu Chalamala , Sandia National Laboratories, Albuquerque,

batteries: A roadmap
NM 87185, USA
Gabriel Cowles, Gautam G. Yadav , Jinchao Huang and

to cost‑effective energy Sanjoy Banerjee, Urban Electric Power, Pearl River, NY 10965, USA

Address all correspondence to Erik D. Spoerke at edspoer@sandia.gov

storage (Received: 4 September 2021; accepted: 28 October 2021;

published online: 16 February 2022)

ABSTRACT
Zn-MnO2 batteries promise safe, reliable energy storage, and this roadmap outlines a combination of manufacturing strategies and tech-
nical innovations that could make this goal achievable. Approaches such as improved efficiency of manufacturing and increasing active
material utilization will be important to getting costs as low as $100/kWh, but key materials innovations that facilitate the full 2-electron
capacity utilization of ­MnO2, the use of high energy density 3D electrodes, and the promise of a separator-free battery with greater than
2V potential offer a route to batteries at $50/kWh or less.

Large-scale energy storage is certain to play a significant, enabling role in the evolution of the emerging electrical grid. Battery-based storage,
while not a dominant form of storage today, has opportunity to expand its utility through safe, reliable, and cost-effective technologies. Here,
secondary Zn–MnO2 batteries are highlighted as a promising extension of ubiquitous primary alkaline batteries, offering a safe, environmentally
friendly chemistry in a scalable and practical energy dense technology. Importantly, there is a very realistic pathway to also making such bat-
teries cost-effective at price points of $50/kWh or lower. By examining manufacturing examples at the Zn–MnO 2 battery manufacturer Urban
Electric Power, a roadmap has been created to realize such low-cost systems. By focusing on manufacturing optimization through reduced
materials waste, scalable manufacturing, and effective materials selection, costs can be significantly reduced. Ultimately, though, coupling
these approaches with emerging research and development advances to enable full capacity active materials utilization and battery volt-
ages greater than 2V are likely needed to drive costs below a target of $50/kWh. Reaching this commercially important goal, especially with
a chemistry that is safe, well-known, and reliably effective stands to inject Zn–MnO 2 batteries in the storage landscape at a critical time in
energy storage development and deployment.

Keywords  energy storage · Zn · cost/cost-effective

Discussion
• What opportunities may there be to leverage extensive, existing
primary Zn-MnO2 battery manufacturing or supply chains to accel-
erate the large-scale deployment of secondary Zn-MnO2 batteries?
• While low cost makes Zn-MnO2 batteries market competitive, how
does the absence of flammable solvents in Zn-MnO2 batteries
impact or enable battery acceptance or deployment in applications
near high population density, where fire codes and safety policies
may prove limiting for other technologies?

Vol.:(0123456789)

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Introduction
Large-scale battery-based energy storage is a key enabler
in grid modernization for integration of intermittent renew-
able energy resources like wind and solar photovoltaics, for
efficient grid decarbonization, for improving the resiliency of
the grid infrastructure, and for providing grid operators with
a flexible resource that can offer multiple grid services in the
power and energy markets. At residential, commercial, and grid
scales, low-cost and efficient battery energy storage systems can
reduce the need for costly carbon-based electricity generation
and defer expensive upgrades to transmission and distribution
infrastructure. Storage stands to revolutionize electricity retail
and wholesale market dynamics with arbitrage, time shifting,
demand charge reductions, and other mechanisms.1,2
Installation of battery energy storage systems (BESSs) for
residential and commercial use and at grid scale have been
increasing rapidly in the last few years for a range of applica-
tions, primarily in the power markets and in markets with high
energy prices.3–5 The amount of installed energy storage capac-
ity is still miniscule, however. The United States has a grid with
nearly a 1 TW base load capacity, but the total amount of battery
energy storage on the grid is limited to approximately 0.1% of
that load capacity! The vast majority of storage capacity in the
USA comes from pumped hydroelectric storage, but in all, exist-
ing storage still only represents about 15 min of ride-through
energy. Clearly, there is a need for more storage, including bat-
tery storage.
Although the ultimate solution to grid-scale energy storage
will no doubt include a host of complementary technologies,
the limited amount of currently implemented storage cur-
rently reveals tremendous opportunity for under-represented
electrochemical (battery) energy storage to grow if key issues
around battery safety, long-term performance, and cost-effec-
tive production can be resolved. Here we describe a vision for
an emerging Zn–MnO2 battery technology with the potential to
change the face of large-scale energy storage as a safe, reliable,
and low-cost technology. Recognizing the value of batteries has
motivated the use of other battery chemistries, such as lithium-
ion, lead-acid, sodium metal, and flow batteries, but these tech-
nologies continue to confront roadblocks to widespread utiliza-
tion. Long-term reliability remains an issue for some systems,
and costs generally exceed $200/kWh delivered, making them
too expensive for widespread adoption at either residential or
grid scales.6 Fire safety is also a concern for some technolo-
gies7,8 as are supply chain issues9 and social and environmental
impacts.10
Zinc–manganese oxide (Zn–MnO2) batteries have the poten-
tial to overcome these obstacles.11 The basic constituents of
these batteries are already ubiquitous in the form of the com-
monly used disposable alkaline batteries. Both zinc and man-
ganese are geologically abundant, supply chains and manufac-
turing processes are well established, operating temperatures
for the Zn–MnO2 system are low, and fire danger is essentially
non-existent. Moreover, neither zinc nor manganese, as waste
products, present significant environmental problems.10,12–14
14         MRS ENERGY & SUSTAINABILITY // VOLUME 9 // www.mrs.org/energy-sustainability-journal
The traditional Zn–MnO2 battery, however, is a primary bat-
tery, one that is not rechargeable. Grid-scale energy storage
requires a secondary battery, reliably rechargeable thousands
of times. In the past 10 years, significant research and devel-
opment efforts have produced functional secondary Zn–MnO2
batteries utilizing Zn anodes and carefully engineered M ­ nO2
cathode chemistries.13,15–18 These batteries have advanced to
early stages of commercial development and implementation,
but challenges remain to increase the system value by improv-
ing power capacity, increasing the functional lifetime, and criti-
cally, increasing active material utilization while maintaining
rechargeability. These prior efforts have aimed to decrease bat-
tery cost to below $100/kWh, making them much more acces-
sible as deployable storage solutions.
This paper, however, will identify key challenges and outline
a research and development roadmap to develop a secondary
Zn–MnO2 battery cell manufacturable at an enabling cost of
$50/kWh, with performance characteristics making it competi-
tive with lead-acid and lithium-ion batteries in all markets. To
provide a baseline model for manufacture of these batteries, we
will explore the pilot-scale manufacturing currently utilized by
Urban Electric Power (UEP, Pearl River, NY), which produces up
to 500 300Ah, 1.3 V cells per day for a current cost of approxi-
mately $300/kWh.
An overview of Zn–MnO2 battery chemistry
Alkaline Zn–MnO 2 batteries typically comprise a Zn
anode and an M ­ nO2 cathode, separated by a porous polymer
membrane (separator) and an aqueous alkaline electrolyte
comprised of potassium hydroxide in water. In the simplest
terms, when the charged battery discharges, the Zn anode is
oxidized, leading to the formation of soluble ionic zinc spe-
cies, such as Zn(OH)42−. Meanwhile manganese in the ­MnO2
is reduced to form MnOOH or Mn(OH) 2 species, depending
on whether the M ­ n4+ is reduced to M­ n3+ or ­Mn2+, respectively.
In conventional primary cells, the formation of insulating,
electrochemically inactive spinel compounds in the cathode
occurs during the second-electron process, limiting cathode
capacity to essentially the first-electron of ­MnO2 (308 mAh/g).
These spinel compounds are hausmannite ­(Mn3O4) and hetae-
rolite ­(ZnMn2O4), the latter of which forms in the presence of
zincate [Zn(OH)4]2−, which is the soluble discharge product
of the Zn anode in alkaline electrolyte and can pass through
the separator to the cathode.11,19 Hydroxide ions in the elec-
trolyte shuttle through the separator to balance charge in the
system during these reactions. Understanding and engineer-
ing the specific chemistries behind these reactions are among
the keys to making this battery chemistry rechargeable. In a
recent review, Lim et al. have provided a more detailed discus-
sion of Zn–MnO 2 battery chemistry and a comparative sum-
mary of properties and performance metrics from research
and development efforts around Zn and M ­ nO 2 electrodes
published in the literature.11 As a point of clarification, the
batteries discussed here are alkaline batteries, distinct from
 Zn-ion batteries,20 which rely on divalent Z ­ n2+ transport and
intercalation, or non-alkaline (the so-called “mild”) aqueous
Zn–MnO2 batteries that do not use the highly alkaline aqueous
electrolytes described here.16 These alternative Zn–MnO2 bat-
teries are less commercially mature and are not the focus of the
present, practical roadmap to low-cost battery manufacturing
(Fig. 1).
The theoretical energy density of the Zn anode (820 mAh/g)
is higher than the M
­ nO2 in the cathode, which means that the
energy storing capacity of the cell is effectively limited by the
­M nO 2 cathode. Because the functional cost of a battery is
typically described in terms of the dollars per kWh of storable
energy, the energy density (the product of capacity and volt-
age, normalized by mass or volume) of these systems is impor-
tant, and that makes the capacity of the ­M nO 2  important.
When the manganese in the ­MnO2 cathode is reduced from
­Mn4+ to ­Mn3+ and only one electron—or the “first” electron—is
used, the theoretical capacity of this system is 308 mAh/g of
­MnO2. In contrast, if the ­Mn4+ can be reduced to ­Mn2+, access-
ing the “second” electron, then the capacity increases to a
tantalizing 616 mAh/g. Here, we will outline the challenges
to realizing cost-effective utilization of the first- and second-
electron chemistries.
Current state of the art
The current state of the art in the development of a recharge-
able Zn–MnO2 cell utilizes the first-electron capacity ­(1e−, theo-
retical energy density of 308 mAh/g) of ­MnO2. This chemistry
utilizes a relatively well-behaved proton insertion chemistry
that has proven highly reversible—one of the key innovations for
this rechargeable technology. This approach works, so long as
the battery only accesses approximately 20% of the ­1e− ­MnO2
capacity (referred to as 20% depth of discharge) and only approx-
imately 9% of the total Zn capacity.15,21 These inefficiencies,
however, result in added weight, volume, and cost from electro-
chemically inactive electrode materials with no contribution to
the useful storage capacity.
Figure 1.  Schematic depiction of a Zn–MnO2 battery showing theoretical
energy densities of the Zn anode (820 mAh/g) and M
­ nO2 cathode for both
one-electron (308 mAh/g) and two-electron (616 mAh/g) access.
MRS ENERGY & SUSTAINABILITY // VOLUME 9 //  www.mrs.org/energy-sustainability-journal                    15
In the UEP system, the current bill of materials (BOM) using
pilot-scale manufacturing is approximately $300/kWh for a 300
Ah, 1.3 V, 390 Wh battery. This battery can achieve 300 cycles
at 20% utilization of the first-electron capacity. This system
is already competitive with lead-acid cells for certain applica-
tions;22 however, reductions to this manufacturing costs are
required for the battery to be competitive in broader markets.
Roadmap to $50/kWh
To be commercially competitive with incumbent technolo-
gies, cell manufacturing costs need to be reduced from $300/
kWh to atmost $100/kWh. We argue in this paper that recharge-
able Zn–MnO2 cells can be produced in the near future at $50/
kWh. At a high level, this can be achieved through a combina-
tion of reduced production costs and increased cell capacity
(energy density). The product development roadmap described
in this paper provides a prospective path to improving the cost-
effectiveness of cell manufacturing both by reducing costs and
increasing capacity through a variety of enhancements to mate-
rial specifications, manufacturing processes, and electrochemi-
cal material interactions. Such changes are likely to be incremen-
tal and cooperative; no single change to the technology or the
manufacturing is likely to immediately drive down battery cost.
UEP’s continuous manufacturing process (Fig. 2) employs
paste coating of both anodes and cathodes, which are cut to
length and width as specified for the desired form factor. Tabs
are welded onto the dried electrodes, which are then wound into
a jellyroll format before being assembled into the cell container.
As an emerging technology, current cells are being produced at
pilot scale, which inherently contains inefficiencies that gen-
erate waste and increase costs. Estimates from 2019 indicate
material waste rates of up to 20% using the current pilot-scale
equipment and manufacturing processes.
Due to the innovative nature of the secondary (rechargeable)
Zn–MnO2 cell manufacturing, fully automated manufacturing
equipment is not currently available. Existing pilot facilities
utilize equipment designed for other battery chemistries and
rely heavily on manual labor. Further, pilot plants are limited
in production to 500 cells per day, only a small fraction of cur-
rent lead-acid or lithium-ion battery production. This small-scale
production model does not fully optimize labor or capital infra-
structure utilization. Utilizing a Lean Six Sigma process review,
basic improvements to the pilot production process have been
identified, including more precise electrode cutting and slitting,
paste recycling, and equipment repositioning. Such improve-
ments would be expected to reduce material waste rates at the
pilot scale from 20% to around 5%.
The electrode coating process is vital in determining a bat-
tery’s functional energy density, which is directly related to bat-
tery cost. Both the Zn anode and the M ­ nO2 cathode are coated
as slurries on copper and nickel current collectors, respectively.
These active materials, along with mixing additives that help
facilitate the coating process, represent nearly 30% of the bill of
Figure 2.  Schematic of UEP’s
battery manufacturing process as
developed at its pilot manufactur-
ing facility in New York.
material (BOM) cost, making efficiencies in the coating process
necessary to achieve competitive production costs. Cell capacity
is dictated, in part, by the amount of accessible active material
present on the current collector. Greater Zn and ­MnO2 avail-
ability, while in balance with one another, creates greater cell
capacity. Coating uniformity, active material dispersion, and
final areal density (possibly improved through subsequent com-
paction or calendaring) of the coated active material all impact
the electrode performance.
Finally, scaling of the optimized production line will dramati-
cally reduce the cost per unit of energy by more effectively uti-
lizing labor and capital costs. For example, increasing produc-
tion to 12,000 cells/day is expected to enable volume material
purchasing and provide the economy of scale that could reduce
overall BOM by up to 30%.
To successfully reach the $50/kWh target, it is necessary to
integrate lower cost materials that maintain or enhance cell per-
formance. One key target in this effort is to substitute lower cost
non-active materials, specifically current collectors and separa-
tors, which are both costly items in the BOM. Current collec-
tors generally represent a significant portion of material costs
associated with battery cell construction, as they must meet high
standards of conductivity, strength, flexibility, and active mate-
rial coatability. As an example, UEP employs cathodic nickel (Ni)
and anodic copper (Cu) current collectors in the Zn–MnO2 cell.
While effective, both the Ni and Cu current collectors, which are
in an expanded mesh form, are high-cost materials that repre-
sent approximately 28% of the cylindrical cell’s bill of materials.
Recent progress has shown that replacement of costly current
collectors with materials such as cold-rolled steel provides excel-
lent performance at a much lower cost.
Separators can also be high-cost items as they must allow for
ionic transfer while still providing a strong and flexible physical
barrier between electrodes. UEP utilizes regenerated cellulose
(i.e., cellophane) in the rechargeable Zn–MnO2 cell. Cellophane
is a relatively costly material, and it is still quite susceptible to
cell failure. The early failure rate of cells using only cellophane
separators can be as high as 20–30%, with more than two-thirds
of these failures attributable to short circuits between the anode
and cathode. Identifying effective alternatives to both current
16         MRS ENERGY & SUSTAINABILITY // VOLUME 9 // www.mrs.org/energy-sustainability-journal
collectors and separators that can reduce cost while maintaining
or even enhancing performance is a significant research focus
and is estimated to reduce the overall BOM by 20%.
By reducing waste, making inactive material substitutions,
and producing cells on a larger scale, it is reasonable to expect
the battery cost could be reduced to below $200/kWh. To make
the changes needed to drive the cost toward the game-chang-
ing $50/kWh, however, the accessible capacity of the active
material must be increased. As mentioned earlier, the current
rechargeable Zn–MnO2 cell accesses approximately 20% of the
first-electron capacity ­(1e−) of ­MnO2 and only approximately
9% of the total Zn capacity. If Zn utilization was doubled to 18%
and ­MnO2 utilization was doubled to 40%, cell capacity would
double, driving down the cost of storage to less than $100/kWh.
Even lower values are possible with significant reductions in
current collector and inactive material costs outlined above.
To date, however, increasing utilization of current materials
reduces cycle life. For example, utilizing 40% of the ­MnO2 cur-
rently reduces cycle life from hundreds to tens of cycles. Alterna-
tive materials solutions are necessary to improve this important
metric.
To address these issues, innovations on both the Zn anode and
the ­MnO2 cathode are needed. Consider first increasing Zn utili-
zation from 9 to 18%. Accessing high utilizations usually results
in rapid deterioration in capacity of Zn anodes because of loss
of active material during discharge, uneven dendritic formation
during charging that results in battery shorts, redistribution of
active material (shape change) that results in loss of material for
subsequent charge and discharge, and formation of passivated
ZnO around Zn, which results in loss of the needed electronic
network on the anode.
The UEP R&D team has discovered that charging the Zn
anode is the most critical step in ensuring repeatable high-
capacity utilization. In a recently published paper,23 the team
developed a method of nesting the Zn particles in a conductive
carbon framework which allows for efficient plating on charging
and dissolution on discharge. The newly developed anodes are
able to cycle at 810 mAh/g, very near the theoretical Zn capac-
ity of 820 mAh/g. Importantly, this development can be imple-
mented using existing production equipment.
Figure 3.  A pathway to $50/kWh realized through reduced cost, improvements in manufacturing efficiency, manufacture at scale, and advances in materials
chemistry.
In addition to the Zn anode, higher capacity must be avail-
able from the M ­ nO 2 cathode, and the most direct route to
this goal is by accessing the “second electron” of manganese.
Recent demonstrations have shown that modified ­MnO2 elec-
trodes cycle near theoretical second-electron capacity with the
strategic addition of bismuth oxide and copper.13,18 The bis-
muth oxide acts as a complexing additive to the cathode com-
position, which, through its dissolved ions in the electrolyte,
can prevent dissolved manganese ions from reacting to form
inactive spinel phases. The addition of copper to the cathode
reduces the charge transfer resistance between the M ­ nO2 parti-
cles and the electrolyte, which is usually associated with metal
oxide electrodes on account of their poor electronic properties.
The cathodes developed by UEP are able to cycle 80–100% of
the theoretical capacity over 3000 cycles. Implementation of
these promising electrodes in scalable battery assemblies offers
a route toward the high capacity needed for low-cost storage
implementation.
Another promising approach to improving active materials utili-
zation efficiency and overall capacity in both electrodes is the appli-
cation of three-dimensional (3D) electrode structures. Carefully
designed 3D frameworks allow for efficient ionic transport and
charge transfer. Prototype 3D Zn electrodes have shown discharge
and charge performance near theoretical capacity, and deleterious
dendrites have not been observed in this new design because of the
unique pore network created during the manufacturing of these
3D anodes.23,24 For 3D ­MnO2 electrodes, 3D cathodes can be
embedded with ultrahigh loadings of optimized M ­ nO2 to increase
cathodic energy density. Numerous 3D printing methods are in
development that may provide avenues to cost-effective manufac-
ture of the desired high-energy-density materials.
MRS ENERGY & SUSTAINABILITY // VOLUME 9 //  www.mrs.org/energy-sustainability-journal                    17
One forward-looking direction that holds tremendous prom-
ise toward low-cost battery production is increasing the voltage
of the battery. The energy density of the battery is directly tied to
this voltage, which means that if cost-effective strategies could
increase the battery voltage from 1.3 to over 2 V, the effective
energy cost of the battery could be dramatically reduced. A
recent paper by Yadav et al. describes breaking this “2 V” bar-
rier,24 by using a polymer gel electrolyte containing potassium
hydroxide (KOH) (coupled with an acidic cathode electrolyte)
that also allowed for elimination of costly separators and stabi-
lized the Zn anode. Meanwhile, this system also decreased zin-
cate crossover that can limit battery lifetimes (Fig. 3).
Along the road to low-cost storage, reduced materials waste,
large-scale manufacturing, and inactive materials, substitutions
are likely to reduce manufacturing costs from current values
near $300/kWh to approximately $200/kWh. Doubling the
usable capacity of the Zn anode and M ­ nO2 cathode with current
manufacturing is likely to cut that value to closer to $100/kWh.
The key to reaching or exceeding the goal of $50/kWh storage,
however, involves changes to access the full 2-electron capacity
of the ­MnO2, use of high-energy-density 3D electrodes, and the
promise of a separator-free battery with greater than 2 V poten-
tial. Based on ongoing research, these are accessible targets that
could be reached within a few years, and they could be integrated
into existing manufacturing lines, making large-scale implemen-
tation a tantalizing possibility. Few technologies can offer the
potential of large-scale manufacturing of batteries that can offer
storage at costs as low as $50/kWh. Zn–MnO2 batteries have the
potential to realize this goal in a safe, environmentally friendly,
and reliable package that could revolutionize large-scale energy
storage at a time when it is needed most.
Acknowledgements  2. S. Chu, Y. Cui, N. Liu, Nat. Mater. 16, 16 (2017). https://​doi.​org/​
This work was supported by the US Department of Energy’s
Office of Electricity Energy Storage Program managed by Dr.
Imre Gyuk. Sandia National Laboratories is a multimission
laboratory managed and operated by National Technology &
Engineering Solutions of Sandia, LLC, a wholly owned subsidi-
ary of Honeywell International Inc., for the US Department
of Energy’s National Nuclear Security Administration under
contract DE-NA0003525. This paper describes objective
technical results and analysis. Any subjective views or opin-
ions that might be expressed in the paper do not necessarily
represent the views of the US Department of Energy or the US
Government.
Data availability  age agenda,” Energy Storage News (2019), https://​www.​energy-​
The data that support the findings of this study are available
from Urban Electric Power, but restrictions apply to the avail-
ability of these data, which were used under license for the cur-
rent study, and so are not publicly available. Data are, however,
available from the authors upon reasonable request and with
permission of Urban Electric Power.
Declarations  5892A
Conflict of interest  The corresponding author states that authors
Spoerke, Passell, Lambert, and Chalamala have no conflict of
interest. Authors Cowles, Yadav, Huang, and Banerjee are em-
ployed by Urban Electric Power, which is developing Zn-MnO2
batteries as a commercial technology.
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22. G.G. Yadav, J. Huang, A.M. Augustus, V. De Angelis, S. Banerjee,
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