Zn MnO2 Aqueous battery_23 nov 22.docx

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HP Green R&D Centre, Bengaluru
Nanomaterials Lab
Research Project Proposal
__________________________________________________________________________________________
1. Project Details:
Project Name Development of Low Cost and High Energy Aqueous
Rechargeable Battery for Stationary Energy Storage
Application
Project Code
Team Krishnamurthy Narayanan, Malay Pramanik, Kushal Singh
Project Start Date November 2022
Project Duration 12 months (Nov 2022 to Nov 2023)
Objective Development of high-performance and low-cost Aqueous
Rechargeable Battery
2. Background:
Rechargeable batteries have been employed as energy storage devices in many areas of modern
life, including portable devices and electric vehicles.
1
. Although lithium-ion batteries have
gained great improvement in energy/power density and life span, the safety issues associated
with flammable organic electrolytes and the growing concerns about the price and availability
of Li resources impede their large-scale deployment. Battery chemistries based on
electrochemical intercalation/storage of Na+, K+
, Mg2+
, and Zn2+
in aqueous electrolytes have
been considered as promising alternatives, because of high safety, materials abundance, and
environmental friendliness2-4
. Rechargeable aqueous batteries have been commercially applied
in common life including nickel-cadmium (Ni/Cd), However, some inherent problems hamper
their further development in energy storage, such as the poor coulombic efficiency and poor
low-temperature performance of Ni/MH and the limited energy density (30 W h kg-1
) of
Pb/acid and Ni/Cd 5-7
. The energy density, cycle life of different kind of battery has tabulated
below. In 1994, the first ARLiB (Aqueous rechargeable Li ion battery) was introduced by Jeff
Dahn and co-workers with VO2//LiMn2O4 chemistry in 5 M LiNO3 aqueous solution,
delivering an energy density of 75 W h kg-1
, which was regarded as a breakthrough in energy
storage systems 8
. Aqueous rechargeable batteries also have drawn particular attention owing
to their facile manufacturing and high ionic conductivity (10-1
to 3.47 S cm-1
), which is almost
two orders of magnitude higher than those of non-aqueous electrolytes (3 x 10-3
to 2 x 10-2
S
cm-1
) 9
.

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The main ARBs (Aqueous rechargeable batteries) currently reported are based on quite
different charge carriers such as non-metallic ions (e.g., H+
, NH4+
), monovalent metal ions
(e.g., Li+
, Na+
, K+
) and multivalent metal ions (e.g., Zn2+
, Ca2+
, Mg2+
, Al3+
) where the latter
have the advantage of one ion carrying two/three charges. It is worth noting that ARBs may be
divided into four categories according to the energy storage mechanisms of the electroactive
materials: Systems with i) conventional ion insertion, ii) dual ion co-insertion, iii) conversion
reaction, and iv) coordination reaction. As expected, a considerable number of ARBs with
excellent electrochemical performance have been established 10-11
. The electtrochemical
performance of the differenct types of the battery has been mentioned in table 1.
Battery
Type
Specific
Energy
(Wh/kg)
Power
Density(W/kg)
Cycle
Life
Efficiency Energy Density
(Wh/kg)(Wh/l)
Lead-Acid 35 180 1000 80 % 25-35
Nickel-
Cadmium
50 200 2000 70 % 50-75
Nickel-
Metal
Hydride
90 300 <3000 75 % 70–95
Nickel-
Zinc
75 500 500 70 % 280
Li-ion 200 400 1500 93 % 100-265
VRFB 10-20 50 13000 85 % 10-50
Table 1: Electrochemical performance of difference types of battery
In the last three years, remarkable progress has been achieved in the case of ARZiBs (Aqueous
rechargeable zinc ion batteries), especially for aqueous Zn–MnO2 batteries through the
technical routines towards aqueous electrolytes such as hydrogel, salt concentrated, pH-
adjusting and decoupling electrolytes. Some representative works are exhibited with the
employed electrolytes and compared in terms of energy density and lifespan. The present
availability of zinc and manganese is 36.36 and 495.87 million tonnes respectively as per the
NMI database. The aqueous ZIBs with mild electrolytes have the advantages of high energy
density (~ 300 Wh kg-1
); low-cost materials (e.g., Zn/MnO2), manufacturing (air- and water-
inert Zn anode), and recycling (mild electrolytes); and excellent safety, making them
prospective batteries for large-scale grid storage 12-13
.

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Fig. 1. Performance comparison of recently reported Zn//MnO2 batteries based on various
aqueous electrolytes in terms of energy density and cyclic number 14
(Ref.: Energy Environ.
Sci., 2022, 15, 1805–1839)
In a recent study as-proposed low-cost Zn–Mn2+
chemistry pairs give a high voltage of 2.44 V
and ultrahigh specific energy density of 1503 Wh kg−1
based on the cathode active materials.
A stable cycling behavior of the Zn–Mn2+
battery was obtained with discharge capacity
retention of 97.5% after 1500 cycles at the current density of 2 mA cm−2
. Furthermore, through
a flow battery design, an extremely high cyclability of 99.5% discharge capacity retention for
6000 cycles at the current density of 2 mA cm−2
was achieved by effectively suppressing Zn
dendrites and decreasing polarization 15
.
As is well known, the electrochemical performance of ZIBs with MnO2 as cathode material
strongly depends on its crystallographic structures, which can be prepared under different
reaction conditions. Though Mn-based oxides are ideal materials for energy storage in aqueous
electrolytes, three main shortcomings impede their further development. Firstly, Mn3+
ions
have Jahn–Teller distortion16
, which introduces 5.6% of volume distortion and local plastic
deformation because of the difference of the bond length between the equatorial and axial Mn–
O bonds of the Mn octahedral coordination. Secondly, Mn3+
ions undergo a disproportionation
reaction and form Mn4+
ions and Mn2+
ions, especially in acidic aqueous solutions. Because of
the soluble Mn2+
, Mn2+
dissolves in the electrolyte and causes capacity degradation. Thirdly,
the inherent poor electrical conductivity of manganese oxides (e.g., electrical conductivity for
Mn3O4 (108
-ohm cm) greatly slows down ion diffusion and reduces power density12
. The
synthesis of MnO2 was always a challenging issues e.g. All manganese oxides generally suffer

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from structure transformation, serious structural damage and large volume change during the
repetitive intercalation/ deintercalation of hydrated H+
/Zn2+
ions, leading to capacity fading of
ZIBs. Mn+ ions are continuously dissolved from the manganese oxide cathodes into the
electrolyte. However, this problem has been overcome including construction of
nanostructures, compositing with conductive substrates, introduction of defects, adjustment of
interlayer
spacing, and optimization of electrolytes, have been reported. Kang et al.17
successfully
synthesized α-MnO2 composed of spherical nanoparticles and cylindrical nanorods by a
coprecipitation method, which delivered a specific surface area of 208 m2
/g and first discharge-
specific capacity of 234 mAh/g. However, compared with 0D structured nanoparticles, 1D
structured materials (eg, nanotube, nanowire, and nanorod) not only have short ion diffusion
distance in the radial direction, but also enable rapid electronic transmission in the ID direction.
Kim et al18
prepared MnO2 nanorod with a large specific surface area of 153 m2
/g via a simple
solvent-free synthesis method, achieving first discharge specific capacity of 323 mAh/g .
Another 1D-structured MnO2 nanowires were synthesized by Mai et al,19
which exhibited an
enhanced discharge capacity of 362.2 mA h/g . However, specific surface area and porosity of
1D structured materials are nonadjustable, limiting their application. Compared with 0D and
1D nanomaterials, 2D nanomaterials possess the wide interlayer spacing between nanosheets,
the large surface-to-volume ratio, and the atomic thickness, making them show more
effectively active sites and remarkable mechanical flexibility. Choi et al.20
synthesized layered
MnO2 nanosheets, which delivered a large discharge capacity of 350 mAh/g.
Last but not the least, except for MnO2 cathode, Zn-MnO2 battery are composed by Zn anode,
separator, electrolyte and other accessories. For example, the Mn2+
dissolution and subsequent
diffusion to Zn anode would result in the corrosion and shape change of Zn anode, leading to
the deterioration of electrochemical performance for Zn-MnO2 battery .Therefore, more effort
is needed in the collaborative design of battery system. For instance, the development of
Zn(CF3SO3)2-based electrolyte would suppress the Mn2+
dissolution and the utilization of new
electrolyte additives could protect the electrode/electrolyte interface from detrimental side
reactions through the formation of a dense passivation film. Furthermore, some issues
originated from the use of aqueous electrolytes, such as water splitting reactions during cycling,
water evaporation and liquid leakage would largely limit the future application of Zn-MnO2

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Nanomaterials Lab
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batteries because of their unfavorable electrochemical performance. The employment of
polymer electrolytes would be a promising alternative for the future development of Zn-MnO2
batteries. Subsequently, the flexible solid-state Zn-MnO2 batteries based on polymer
electrolytes are expected for wide-ranging applications in the future.
3. White Space Analysis:
White space analysis has been conducted using Innovation Q+
tool.
Main Concept Text: “Electrolyte for the Zn-MnO2 Aqueous Rechargeable Battery”
The total records found related to Zn-MnO2 Aqueous Rechargeable Battery area are: 29
Patent Filing trend

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Nanomaterials Lab
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CPC class by Enforceability
Classification of patents into different categories are given in the above chart. Top 3 research
areas are:
1. H01: Electricity- Basic electric elements
2. H01M: Process or means e.g., Batteries for the direct conversion of chemical energy to
electrical energy
3. H01G: Capacitors, rectifiers, detectors, switching device or light sensitive device of the
electrolytic type

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Nanomaterials Lab
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Country of Origin
The following chart shows the major countries contributing towards the development of Zn-
MnO2 Aqueous Rechargeable Battery
Patent count of each Assignee
The following image shows the major industries/institutions contribution towards the
development of Zn-MnO2 Aqueous Rechargeable Battery

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Nanomaterials Lab
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Patent Filing trend

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Nanomaterials Lab
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Related patents for Zn-MnO2 Aqueous Rechargeable Battery
S.No Ref Title Remarks
1 Korea Patent
KR102191807B1
A separator and Zinc-
Manganese dioxide(Zn-
MnO2) aqueous battery
system comprising the same
In the present invention, a
separator capable of
preventing a reduction in
capacity due to loss of an
active material due to elution
of manganese ions and a
zinc-manganese dioxide (Zn-
MnO2) aqueous battery
system including the same is
presented.
2 Korea patent:
KR20220036695
A
Surface treatment method of
electrode, surface-treated
electrode and Zinc-
Manganese dioxide(Zn-
MnO2) secondary battery
including the same
This work relates to a
surface-treated negative
electrode and a zinc-
manganese dioxide aqueous
secondary battery comprising
the same, and more
particularly, to a surface-
treated negative electrode
surface-treated with reduced
graphene oxide and a zinc-
manganese dioxide aqueous
secondary battery comprising
the same.
3 China Patent:
CN105390697B
A kind of porous
carbon/manganese dioxide
composite material electrode,
its preparation method and
In this work authors using
resulting porous
carbon/manganese dioxide
composite material as

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Nanomaterials Lab
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rechargeable type zinc-
manganese ion battery
electrode, secondary cell is
assembled as electrolyte
using the aqueous solution
containing zinc, manganese
ion, electrode specific
capacity has the
characteristics of high power
capacity, long-life in 200
more than mAh/g, it is green
and the preparation method
is easily operated
4. SWOT Analysis:
Strengths
 Expertise in electrolyte synthesis and
optimization
 Availability of in-house facilities for
characterization of the materials
 Availability of facilities for electrochemical
testing of the battery
Weaknesses
Opportunities
 Huge demand in the market for aqueous
battery containing low-cost
Threats
 To design Aqueous rechargeable
battery with low cost is a fast-
growing field and there may be other
players/competitors who enter the
market with more advanced in the
near future.
5. Gaps identified:
 In summary, Aqueous rechargeable Zn/MnO2 battery suitable to be industrialized than the other
types of ARBs at this stage in terms of reliable performance and cost. Aqueous energy storage

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Nanomaterials Lab
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systems have been extensively investigated through the development of novel
electrolyte concepts, while there are still challenges to be tackled before their large-
scale applications e.g. suitable cathode preparation and electrolyte formulation.
Particularly, Aqueous rechargeable Zn/MnO2 battery are almost ready for application in
portable electronic devices and large-scale energy storage stations, especially Zn/MnO2
batteries, but their energy density needs to be further improved for EV applications.
6. Scope:
 Development of facile and scalable synthesis method for producing battery grade MnO2
 Fabrication of prototype rechargeable Zn-MnO2 Battery, sp. Capacity (based on MnO2
weight) =220 mAh/g Cycle life =300
 Making a Battery Pack for demonstration of Rechargeable aqueous Battery Chemistry.
7. Research approach & Methodology:
 Literature review will be carried out on various synthesis methods for the fabrication
Aqueous rechargeable zinc ion battery and a suitable method will be finalized.
 Characterization of the as synthesized materials will be performed using SEM, XRD
and other spectroscopy techniques for establishment of the best synthesis procedure.
 Battery set up will be established in the battery lab, HPGRDC using the R&D
designed components.
8. Milestones:
Sl.
No
.
Milestones Activity Responsibility Duration R
e
m
ar
ks
1 Literature
Survey
Literature survey on various
synthesis procedures of the
electrolyte and cathode
Dr. K. Narayanan , Dr.
Kushal Singh
Till the
project
closure

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Nanomaterials Lab
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And
procuring
chemicals,
electrodes
material for the ARB and
finalization of the synthesis
process/discussion with various
vendors/ Purchasing Chemicals
2 Electrolyte
Preparation
Synthesis of Electrolyte
materials through optimized
synthesis method at different
experimental conditions and
parameters
Kushal Singh
3 Characterizati
on of the
materials
Structure, particle size,
morphology analysis using
XRD, SEM, TEM, EDS and
BET will be performed to
determine the material
properties
Kushal Singh
5 Developing
Aqueous
rechargeable
battery
To check the electrochemical
performance of the ARB
Kushal Singh
9. Deliverables:
 To develop for synthesis process for MnO2
 Zn-MnO2 battery assembly having sp capacity = 220 mAh/g and cycle life = 300
 Two Patents
10. Metrics for project selection:
Sl. No. Factor Marks (0-5)
1 Ease of research 4
2 Ease of development 4
3 Relevance to business 5
4 Value of the outcome 4

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Nanomaterials Lab
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5 Patentability 4
6 Novelty 3
7 Timelines 3
8 Strategic advantage 3
9 Competitor mapping (Indian/Global) 3
10 Indigenization 4
Total 37
11. References:
1. Wan, F.; Hao, Z.; Wang, S.; Ni, Y.; Zhu, J.; Tie, Z.; Bi, S.; Niu, Z.; Chen, J., A Universal
Compensation Strategy to Anchor Polar Organic Molecules in Bilayered Hydrated Vanadates
for Promoting Aqueous Zinc‐Ion Storage. Advanced Materials 2021, 33, 2102701.
2. Kim, H.; Hong, J.; Park, K.-Y.; Kim, H.; Kim, S.-W.; Kang, K., Aqueous Rechargeable
Li and Na Ion Batteries. Chemical reviews 2014, 114, 11788-11827.
3. Kundu, D.; Adams, B. D.; Duffort, V.; Vajargah, S. H.; Nazar, L. F., A High-Capacity
and Long-Life Aqueous Rechargeable Zinc Battery Using a Metal Oxide Intercalation
Cathode. Nature Energy 2016, 1, 1-8.
4. Pasta, M.; Wessells, C. D.; Huggins, R. A.; Cui, Y., A High-Rate and Long Cycle Life
Aqueous Electrolyte Battery for Grid-Scale Energy Storage. Nature communications 2012, 3,
1-7.
5. Fan, N.; Sun, C.; Kong, D.; Qian, Y., Chemical Synthesis of Pbo2 Particles with
Multiple Morphologies and Phases and Their Electrochemical Performance as the Positive
Active Material. Journal of Power Sources 2014, 254, 323-328.
6. Ovshinsky, S.; Fetcenko, M.; Ross, J., A Nickel Metal Hydride Battery for Electric
Vehicles. Science 1993, 260, 176-181.
7. Battlebury, D. R., A High Performance Lead–Acid Battery for Ev Applications. Journal
of power sources 1999, 80, 7-11.
8. Li, W.; Dahn, J. R.; Wainwright, D. S., Rechargeable Lithium Batteries with Aqueous
Electrolytes. Science 1994, 264, 1115-1118.
9. Wu, Y.; Dai, X.; Ma, J.; Chen, Y., Lithium Ion Batteries: Practice and Applications.
Chemical Industry, Beijing 2004.
10. Li, C.; Zhang, X.; He, W.; Xu, G.; Sun, R., Cathode Materials for Rechargeable Zinc-
Ion Batteries: From Synthesis to Mechanism and Applications. Journal of Power Sources 2020,
449, 227596.

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11. Ao, H.; Zhao, Y.; Zhou, J.; Cai, W.; Zhang, X.; Zhu, Y.; Qian, Y., Rechargeable
Aqueous Hybrid Ion Batteries: Developments and Prospects. Journal of Materials Chemistry
A 2019, 7, 18708-18734.
12. Gao, Y.; Yang, H.; Bai, Y.; Wu, C., Mn-Based Oxides for Aqueous Rechargeable Metal
Ion Batteries. Journal of Materials Chemistry A 2021, 9, 11472-11500.
13. Li, Y.; Wang, S.; Salvador, J. R.; Wu, J.; Liu, B.; Yang, W.; Yang, J.; Zhang, W.; Liu,
J.; Yang, J., Reaction Mechanisms for Long-Life Rechargeable Zn/Mno2 Batteries. Chemistry
of Materials 2019, 31, 2036-2047.
14. Chen, S.; Zhang, M.; Zou, P.; Sun, B.; Tao, S., Historical Development and Novel
Concepts on Electrolytes for Aqueous Rechargeable Batteries. Energy & Environmental
Science 2022, 15, 1805-1839.
15. Chao, D.; Ye, C.; Xie, F.; Zhou, W.; Zhang, Q.; Gu, Q.; Davey, K.; Gu, L.; Qiao, S. Z.,
Atomic Engineering Catalyzed Mno2 Electrolysis Kinetics for a Hybrid Aqueous Battery with
High Power and Energy Density. Advanced Materials 2020, 32, 2001894.
16. Yamaguchi, H.; Yamada, A.; Uwe, H., Jahn-Teller Transition of Limn 2 O 4 Studied
by X-Ray-Absorption Spectroscopy. Physical Review B 1998, 58, 8.
17. Wei, C.; Xu, C.; Li, B.; Du, H.; Kang, F., Preparation and Characterization of
Manganese Dioxides with Nano-Sized Tunnel Structures for Zinc Ion Storage. Journal of
Physics and Chemistry of Solids 2012, 73, 1487-1491.
18. Alfaruqi, M. H.; Islam, S.; Gim, J.; Song, J.; Kim, S.; Pham, D. T.; Jo, J.; Xiu, Z.;
Mathew, V.; Kim, J., A High Surface Area Tunnel-Type Α-Mno2 Nanorod Cathode by a
Simple Solvent-Free Synthesis for Rechargeable Aqueous Zinc-Ion Batteries. Chemical
Physics Letters 2016, 650, 64-68.
19. Wu, B.; Zhang, G.; Yan, M.; Xiong, T.; He, P.; He, L.; Xu, X.; Mai, L., Graphene
Scroll‐Coated Α‐Mno2 Nanowires as High‐Performance Cathode Materials for Aqueous Zn‐
Ion Battery. Small 2018, 14, 1703850.
20. Nam, K. W.; Kim, H.; Choi, J. H.; Choi, J. W., Crystal Water for High Performance
Layered Manganese Oxide Cathodes in Aqueous Rechargeable Zinc Batteries. Energy &
Environmental Science 2019, 12, 1999-2009.
12. Resources:
 For electrolyte synthesis: Hot plate, Oven, Furnace, Magnetic stirrer, Centrifuge,
ultra-sonicator, Chemicals
 Material characterization: XRD, FESEM, TEM, BET, XRF, XPS, EDS
 Electrochemical Characterization:
Manpower: Officer, RA and PA

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Project Proposed by Reviewed by Approved by
Name Dr. Kushal Singh Dr. K Narayanan Dr. B Ramachandra Rao
Signature
Date
Comments,
If Any
RRM dated:

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