Driver-E-Mobility Forecasts-Global & India

As of 2035, it is expected that there will be an on-road fleet of 140 million electric vehicles.
55% of all new car sales and 33% of global fleets are expected to be electric by 2040 1.
National Electric Mobility Mission Plan 2020 (NEMMP) predicts India will be able to save 9500
million litres of fuel, as well as 2 million tonnes of GHG emissions, by 20202. As per the
government’s think tank, NITI Aayog, India can save upto INR 3.9 trillion by switching to green
mobility by 2030. An efficient energy storage technology is essential for meeting the
Government of India’s targets with regards to electric mobility and renewable energy. Among
the different types of storage technologies, lithium-ion battery (LiB) is considered to be the
best suited for electric vehicles (EVs). LIBs can also address intermittency problems in
renewable energy integration with the grid.

LiB Technology & EMD

LiB consists of an anode, usually graphitic carbon, and a cathode, separated by a liquid organic
electrolyte. Inactive components include a polymer separator, Cu and Al current collectors,
as well as casing and packaging materials. Multiple cathode materials are in use for LIBs. Most
efficient and widely used are layered oxides in the LiMO2 family, where M is some
combination of Co, Ni, Al, and Mn. Manganese is utilised within two of the most prominent
batteries in production, being the Nickel Manganese Cobalt (NMC) and Lithium Manganese
Oxide (LMO) batteries. Within LMO batteries, there is approximately 61% manganese in the
cathode, being the majority mineral present. Whereas, the manganese in the cathode of an
NMC battery constitutes 20-30% of the total cathode material. More than 70% of cost of
manufacturing LiB results from Raw materials used. Of all the current transition metals used
within cathodic material, manganese is the cheapest by a significant margin. This gives LMO
batteries a significant cost advantage over other batteries. At least 25% of the cost in
producing an NMC battery is related to production of the cathodic material. LMO batteries
have a significant starting advantage with only 18% of the total cost being associated with
cathodic materials.3
Electrolytic Manganese Dioxide (EMD) is a form of Manganese oxide (MnO2), which is
produced by aqueous electrolysis method and has a gamma (γ-MnO2) crystalline structure.
EMD is used as cathode materials in almost all dry‐cell batteries, as they have been proven to
be superior than other forms of manganese dioxides, such as chemically synthesized one and
natural manganese dioxide (NMD). In the recent, as aforementioned EMD is becoming the
most competitive cathodic material for LiBs too. There are three grades of EMDs depending
upon intended battery applications are: (a) alkaline, (b) lithium and (c) zinc‐chloride.

Demand Global & India

Demand for batteries is growing exponentially as global sales of electric vehicles are expected
to increase from 1.1 million in 2017 to 30 million in 2030. In the same period, components of
lithium ion batteries will increase from approximately 0.7 million metric tonnes in 2018 to
over 10 million metric tonnes. As of 2035, it is expected that there will be an on-road fleet of
140 million electric vehicles. 55% of all new car sales and 33% of global fleets are expected to
be electric by 20404.
The demand for EMD has been booming recently is in tandem with Li- ion battery demand
surge. According to the International Manganese Institute global production of electrolytic
manganese dioxide (EMD) increased in 2017 to almost 400,000 metric tonne (MT) showing
net 4% YoY (year-on year) increase compared to 2016 production1.

In India, it is estimated that 13.8 GWh of battery capacity is required by 2020 for the EV sector
and 15 GWh battery capacity is needed for grid storage requirements2. The Indian lithium-ion
battery market is expected to grow at a robust CAGR of 29.26% during the forecast period,
2018-2023. The Indian automobile sector is one of the most prominent sectors of the country,
accounting for nearly 7.1% of the national GDP5. Indian overall consumption of EMD in 2019
may exceed 10,000 TPA (Tonnes Per Annum), with domestic production of about 800 TPA
(MOIL, Ltd. being the primary producer), indicating net import of 92% EMD demand
amounting to about 18 million USD annually. Indigenization of LiB manufacturing thus can
help to meet this large-scale demand more economically and efficiently.

Source & Production Global & India

Currently global EMD production is largely dependent on availability of Mn-ore grade with
high MnO2, low iron, adequate porosity and hardness. The user industry specification for ore
is MnO2 70% (min), Fe 6% (max), moisture 4% (max), Cu 0.02% (max) and Ni 0.02% (max)
(MOIL, 2016; U.S.I.T.C. 2014). The global output of Mn ore increased by 23% from 2016 to
18.6 mt (Mn Contained) in 2017. South Africa (5.3 Million tonnes), China (2.5 Million tonnes),
Australia (2.2 Million tonnes), Gabon (1.6 Million tonnes), Brazil (1.2 Million tonnes) and
India (0.79 Million tonnes) were among leading producers of Mn ore in 20174.

World Mn Ore Production (2011-2017)

Top 10 Ore Producing Countries, 2017 (Source: IMnI)

The global EMD capacity was 477, 700 tons in 2017, while the production was 397,959 tons
in 2017 and predicted to increase at compound annual growth rate (CAGR) of 6% between
2016 and 20224. The revenue of EMD was 430 million USD in 2016, and it will be 671 million
USD in 2022, with a CAGR of 7.7% between 2016 and 20226,7.

Global production of electrolytic manganese dioxide (EMD) increased in 2017 to almost

400,000 metric tonne (MT). This is a net 4% YoY (year-on year) increase compared to 2016
production4. Looking at the different grades, global production of Lithium Manganese Oxide
(LMO) grade EMD increased by 47% from 2016, while Alkaline & other (Li-primary) grade EMD
production saw a more moderated growth (+3%). Finally, Carbon-zinc (C-Zn) grade EMD
production contracted by 7% in 2017 compared to 20164. At present China leads in global
production capacity of EMD~326,725 tonnes (12 operating companies) followed by United
States ~68,894 tonnes (Tronox, Erachem & Everyday), Japan~36,376 tonnes (Tosoh), South
Africa~33,069 Tonnes (Delta), Greece (Tosoh) ~28,660 Tonnes, Spain~12,125 Tonnes
(Cegassa), Colombia ~6,614 tonnes (Quintal) and India ~800 tonnes (MOIL), total worldwide
EMD production~477,700 tonnes8.

 Alkaline and other (Li-primary) 67%

grade production
 Carbon-zinc (C-Zn) grade 22
production
 Lithium Manganese oxide (LMO) 11

Global EMD Production by Grade in 2017 (source: Citic Dameng, Tosoh, IMnl)

India is the 6th largest country in terms of Mn ore reserves; having an estimated 34 million
tonnes of metal deposits9. India has estimated resource for Mn is ~495.87 Million Tonnes out
of which ~93.47 Million tonnes are active reserves (of which~34% owned by MOIL). Also, as
majority of exploitable ore grade is of medium or low grade hence its critical to develop
extraction technologies for production of LiB suitable EMD from these ores as well.

Quality of Mn Ore Reserves & Production in India (Source: MOIL)

Mn Ore Production in India

However, the country produces just ~0.3% of global EMD. Global EMD market dynamics is
presented in Figure-2, which shows India is the 9th largest importer of EMD in 20174.
According to Indian Bureau of Mines Year Book, India imported about 7,284 tons of EMD in
2013, which has marginally increased up to 2017 as per Figure 2. However, keeping in view of
growing battery demand in automotive sectors (EVs, Solar, etc.), this will witness a stiff rise
in coming years as per the global trends, presented in Figure 310.

EMD import by countries in 2017 (in tonnes)

EMD Production Technology state of Art-Global & India

Recent global technology trend for EMD production such as by MESA Minerals Electro-fuel
Process11; Toc Tat Vietnam12, Galaxy Ventures, Australia & China13; American Manganese Inc.-
Kemetco Process14,15 are improvising upon advanced ore reduction, impurity removal, cell
house designs and augmented process automation for minimizing the overall energy
consumption, impurity content of EMDs and overall production cost.

At present Manganese Ore India Limited (MOIL) plant manufactures ~1,000 MT per annum of
EMD at Dongri Buzurg, Maharashtra. The EMD is being produced at MOIL using the 28 years
old technology comprising of high temperature carbo-thermal reduction of Mn ore, sulphuric
acid leaching, and impurity removal from leach solution followed by electrolysis11. Typical
specification of the EMD produced from this plant, although meets the IS standard for dry cell
battery applications but is inadequate for applications in the emerging Li- based/alkaline
battery sectors. As highlighted in the table the purity requirement for LiB are stringent as
compared with current MOIL’s EMD composition specially with respect to Iron (Fe), Lead (Pb)
and Copper (Cu). Also, close control over final product particle size would be crucial for final
use in the LiBs.
 Specification of EMD grades produced by different manufacturers
Grade => Alkaline grade Li-ion battery grade Zn chloride grade
Human Sunsine Tech
Supplier => Tronox, US Tosh Tosh, Japan MOIL*, India
China
Items Spec. Spec Typical LM05 LM10 LM25 Spec. Typical Guaranteed Typical
Chemical Analysis
MnO2 (%)
Mn (%)
H2O (%)
Fe (ppm) 30 100 72 34 35 37 70 Max 35 <1000 250
Pb (ppm) 5 <1 <1 <1 5 Max 0.37 <1500 15
SO42- (%) 1.23 NA 0.85 1.2 Max 1.08 - -
S (ppm) 3,600 3,400 3,500
Cu (ppm) 5 3 <1 <1 <1 5 Max 0.71 <300 4.9
Co (ppm) 1 5 Max 0.11
6 Max
Ni (ppm) 2 5 Max 0.31
Zn (ppm) <1 <1 <1
3500
Na (ppm) 2250 2550 170 160 200 3394
Max
K (ppm) 400 235 500 Max 81
Physical Properties
Bulk density,
1.62 1.2 - 1.6 1.35
g/cm2
Particle size 5µ 10µ 25µ
D10, µm 2.1 3.1 9.0
D50, µm 5.1 9.7 24.0
D90, µm 8.4 21.2 42.4

Particle size
mesh 100 99.5 99.99 >95 100
mesh 200 92 80 99.0 99.9
mesh 325 58 - 95.0 98 >80 81.3

Electrochemical Properties
pH (H2O) 6.5 6.7 5.0 -7.0 6.45 4-5.6 4
Potential , V 1.64 - 1.66 - 1.77 1.7

The evolving battery technologies require EMDs with stringent chemical, electrochemical and
physical characteristics, which MOIL has failed to produce by using the existing technology
and facilities. In this context, it is highly imperative that, MOIL’s EMD production technology
need a thorough revamping with respect to ore reduction, leaching and impurity control,
electrolysis cell re-designing, cathode-anode materials selection, materials of construction
(MOC) of reactors, etc. for MOIL to be globally competitive with respect to EMD quality and
cost of production.

The continual surge in demand for Manganese from steel industry and battery applications
has made it necessary to develop processes for recovery of manganese as well as EMD from
low grade and secondary resources. Attempts have been taken to produce EMD from
secondary sources such as spent household battery materials, manganiferous materials such
as anode mud, Mn cake, Mn leach residue, Cobalt Manganese Bromide (CMB) spent catalyst,
ferro/ silico-manganese alloy production slag etc.

R& D Intervention bridging the Technological Gap - India

CSIR-IMMT (CSIR- Institute of Minerals & Materials Technology) in collaboration with CSIR-
IMMT in the recent has entered into agreement with MOIL to function as Nodal Agency:

1-Provide basic engineering for facilitating the upscaling of MOIL EMD production capacity
from current 1000TPA to 10,000TPA with upgraded product quality

2-Further, the institutes will also customise the existing process or develop the alternative to
produce EMD suitable for LiB applications.

The total tenure of work is will be 14 months with following sub activities & their duration:

Months
Project activity Sub activity
Start End
Leaching with SO2 1 3
Development of alternate
Downstream operations 4 5
process for EMD production
Electrowinning studies 7 6
based on SO2 reduction
Flowsheet testing in lab scale 7 8
Design, MOC selection and Optimization of cell operating parameters 1 4
optimization of EMD cell with Studies on effect of impurities 1 2
improved efficiency and Cell design and MOC selection 3 6
characterization of EMD for Bench scale testing 3 6
Li-ion battery applications Characterization of EMD for Li-ion battery application 5 8
Optimization of leaching 1 2
Bench scale leaching
Impurity removal studies 1 4
optimization for improving
Mn recovery (> 90% Electrowinning studies 3 6
targeted) Flow sheet testing in bench scale 5 8
Exploring various reactor systems and reductants 1 2
Alternate reduction roasting
Optimization of suitable reactor and reductant system 2 5
process development using
Process up-scaling and data collection at 20 kg/h scale
gaseous reductant 3 8
reduction
Preparation of Basic Engineering Package for 10000 TPA EMD plant 9 14

CSIR-Institutes IMMT and NML have been working in the area of technology development for
most of the base metals for over past several decades. IMMT is capable of providing end-to-
end solutions for primary and secondary resource harnessing for extracting metal and mineral
values. IMMT’s experience and expertise ranges from developing, customising upscaling
(bench to pilot) the extraction process flow sheet to providing basic engineering packages for
establishing plants for transferable technologies in domain of metal/ metal values extraction.
In recent IMMT keeping in pace with the global state of the art IMMT has been building
capability in energy materials as Manganese, Nickle, Cobalt, Graphite.

Very recently, CSIR-IMMT, has successfully developed a process to recover manganese values
from the deep-sea polymetallic nodules as EMD; established and operated a 500 kg pilot plant
at HZL, Udaipur, India16. The institute has also developed a process to produce EMD from Co-
Mn bearing sludge for battery applications17,18,19. However, EMD generated have been in
necessity for refinement to be fit for LiB industry with respect to Iron and lead impurities
hence, in the present IMMT will extend the process technology for achieving the desired EMD
specifications.

1. Electrolytic Manganese Dioxide (EMD) Market 2017 Global Analysis, Opportunities and
Forecast To 2022, Pune, India - October 20, 2017 /MarketersMedia

2. Lithium-ion battery supply chain: enabling national electric vehicle and renewables targets ,
Epica Mandal Sarkar et al., Center for Study of Science, Technology and Policy, Bengaluru 560
094, India

3. www.moorestephens.com.au/Manganese. is it the forgotten battery minerals, July, 2018.

4. International Manganese Institute, IMnI, Statistics 2018

5. The "India Lithium-Ion Battery Market - Growth, Trends, and Forecast (2018 - 2023)”, Dublin-
-business wire), May 10, 2018.

6. Top Trends in the Global Electrolytic Manganese Dioxide Market ,Technavio, Feb.’18.

7. Electrolytic Manganese Dioxide (EMD) Market 2017 Global Analysis, Opportunities and
Forecast To 2022, Pune, India - October 20, 2017 /MarketersMedia.

8. www.usitc.gov/publications/701_731/pub4506.pdf

9. Manganese Ore Indian Minerals yearbook 2017, 56th Edition, Part-III Minerals Review.

10. https://www.businesswire.com/news/home/20180206006085/en/Top-Trends-Global-
Electrolytic-Manganese-Dioxide-Market.

11. http://mesaminerals.com.au/products/electrolytic-manganese-dioxide-emd/.

12. Anh Dao, Duy & Gieré, Reto. (2018). Leaching of manganese ore from northeastern Vietnam
by reduction with SO2 gas in an H2SO4 rich solution.
https://batteryuniversity.com/learn/archive/understanding_lithium_ion.
13. Galaxy Ventures Into Electrolytic Manganese Dioxide (EMD) Production, February 25, 2010

https://www.evwind.es/2010/02/25/galaxy-ventures-into-electrolytic-manganese-dioxide-
emd-production/4258.

14. US8460631B2-Processing of manganous sulphate/dithionate liquors derived from manganese

resource material.

15. Technical report and prefeasibility study artillery peak project, Mohave County, Arizona,
document no.: 1191630100-rep-r0001-06, American Manganese Inc.

16. Electrolytic manganese dioxide (EMD): a perspective on worldwide production, reserves and
its role in electrochemistry, Avijit Biswal, Bankim Chandra Tripathy, Kali Sanjay, Tondepu
Subbaiah and Manickam Minakshi,RSC Adv., 5, 58255–58283, 2015.

17. Recovery of Co metal and Electrolytic Manganese Dioxide (EMD) from Co–Mn sludge, A.
Biswal, S. Mahakud,Sandhyarani Bhuyan, B. Dash, C.K. Sarangi, Kali Sanjay, B.C. Tripathy, T.
Subbaiah, I.N. Bhattacharya, Sung-Ho Joo,Shun Myung Shin, K.H. Park, Hydrometallurgy, Vol
152, 159–168, 2015.

18. Influence of the microstructure and its stability on the electrochemical properties of EMD
produced from a range of precursors, A Biswal, BC Tripathy, K Sanjay, D Meyrick, T Subbaiah,
M Minakshi, Journal of Solid State Electrochemistry17 (12), 3191-3198, 2013.

19. Influence of alternative alkali reagents on Fe removal during recovery of Mn as Electrolytic

Manganese Dioxide (EMD) from Mn sludge, Avijit Biswal, Barsha Dash, BC Tripathy, T
Subbaiah, Shun Myung Shin, Kali Sanjay, BK Mishra, Hydrometallurgy 140, 151-162, 2013.