Future of Energy Storage System

DR. AYAN MUKHERJEE

ASSISTANT PROFESSOR
DEPARTMENT OF PHYSICS
PATLIPUTRA UNIVERSITY, PATNA
 Outline

 Why storage system is essential?

 Advantages and Disadvantages of Batteries
Comparison between Battery and Supercapacitor.
 Character of a good Supercapacitor Material
Current Research on Supercapacitor
Facilities available
All Renewable energy systems are incomplete without
efficient storage systems

In recent times we use Electrochemical

storage system to store energy of
renewable systems
4
Lithium ion battery
(1) There is continuous demand for miniaturization of portable electronic devices ( cell
phones, digital cameras, note book, computers, TV etc.) in which LIBs are emerging
as one of the most promising nanotechnology for energy storage.

(2) Today, this technology is applied to green transportation systems such as electric
vehicles (EVs) or hybrid EVs (HEVs). The increase in the demand of highly
functionalized applications always includes higher power density, higher energy
density, excellent charge-discharge cycling performance, and more safety.

(3) For (EVs) or hybrid EVs (HEVs) applications, the performance of LIBs, particularly their
energy density, safety, and cost, still need to be significantly improved and further
development of the LIB technology is urgently needed.
 Construction

• Li-ion cell has a four-layer structure.

• A positive electrode made with Lithium Cobalt Oxide has a
current collector made of thin aluminum foil - cathode

• A negative electrode made with specialty carbon has a current

collector of thin copper foil – anode

• A separator is a fine porous polymer film.

• An electrolyte made with lithium salt in an organic solvent.
 Electrodes with higher rate capability, higher charge capacity, and sufficiently high voltage
can improve the energy and power densities of Li batteries
 The key to success in the development of advanced LIBs to meet the emerging EVs market
demands is the electrode materials, especially the cathode.
 Present LIBs technology the working voltage, energy density, and rate capability are mainly
determined by the theoretical capacity and thermodynamics of the cathode material.
Therefore, it is critical to develop promising cathode materials for the current LIBs
technology.
 The cathode material is made up from Lithium liberating compounds, typically the three
electro-active oxide materials,
• Lithium Cobalt-oxide (LiCoO2 )

• Lithium Manganese-oxide (LiMn2O4 )

• Lithium Nickel-oxide (LiNiO2)

Advantage of Nanomaterial for LIBs

These nanostructured materials are the most promising

and provide multiple advantages such as a short path
distance for Li ions and electron transport, a higher
contact area with electrolyte and better
accommodation of the strain caused by lithiation or
delithiation. These are may be enable the realization of
charging speeds faster than those achieved using
conventional bulk materials, without significant
degradation in storage capacity.
 Lithium-ion battery disadvantages:

* Expensive 
* Protection required 
* Aging effect 
* Transportation problems 
* Deep discharge  .
* Safety concerns 
* Sensitivity to high temperature 

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So to supply renewable energy to a large portion we need
Grid Energy Storage system
Comparison between Battery and Capacitor system

Battery: High Energy Density Capacitor: High Power Density

 Obstacles to grow
• Relatively high cost
• Competition with batteries well established
on the market
• Consumer conservatism

“Global Supercapacitor Market is Set for a Rapid Growth

and is Expected to Reach USD 2,096.16 Million by 2022”

Supercapacitor market in INDIA

Factors to grow
• New market opportunities like HEVs, Smart
Grid, Alternative/Renewable Energy
• Growing ecology restrictions for competitors
• Operation in a wide temperature range
• Good prospects or a combined power supply

India supercapacitors market is projected to grow at a compound

annual growth rate (CAGR) of around 16% during 2017 – 2022
15
Ref: Zion Market Research,  http://www.zionmarketresearch.com
VISIBLE APPLICATIONS OF SUPERCAPACITORS IN INDIA

Mahindra e2O E-rickshaw 'Raahii' (Hero)

Travel cost Rs 0.50 per KM Travel cost Rs 0.15 per KM

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Capacitance of pseudocapacitor is about 10 times than EDLC 17
Electrostatic capacitance Influence of pseudo capacitance 18
APPLICATIONS

 They are used in electronic applications such as cellular electronics, power

conditioning, uninterruptable power supplies.
 They used in industrial lasers, medical equipment.
 They are used in wireless communication system.
 They are used in VCRs, CD players, electronic toys, computers, scanners, smoke
detectors and coffee makers.

Disadvantage

The amount of energy stored per unit weight is considerably lower than an
electrochemical battery.
The voltage varies with the energy stored. To effectively store and recover energy
requires electronic control and switching equipment.
It has highest dielectric absorption of all types of capacitors
Nickel Oxide (NiO) thin film for
supercapacitance property

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 Why Nickel Oxide ?

 Environmental friendliness

 Natural abundance

 Multiple oxidation states makes it fast redox material

 High theoretical specific capacitance

 Preparation

Four samples were prepared for different dipping cycle:

NiO1 (20), NiO2 (30), NiO3 (40) and NiO4 (50)

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 Structural Characterization

50 cycle
The diffraction peaks at 37.67°, 43.51°, 63.08° and
75.76° corresponds to (111), (200), (220), and (311)
40 cycle planes confirming formation of single cubic NiO
(JCPDS card no. 47-1049 )
Intensity (a.u.)

30 cycle
800 (a) 8

Thickness (nm)

G rain size (nm )

(200) 700 9
(111) 20 cycle Thickness
(220) (311) Grain size
10
600

11
20 30 40 50 60 70 80
500
2 theta (deg)
12

400
13
20 40 60
Deposition cycle

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 FTIR ANALYSIS
NiO-3

No significant change of peak position or intensity is observed for other deposited films

25
Surface morphology

Formation of well
adherent and porous
nano-flake like structure

For NiO3, the porosity

is maximum

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 TEM ANALYSIS
NiO-3

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Frequency
Gauusian Fit
12

10
Frequency

10 15 20
Particle size (nm)

TEM image
Particle size estimated ~ 14.6 nm.
SAED pattern
Confirms presence of (111), (200), (220), and
(311) planes of cubic NiO.

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 Cyclic voltammetry Analysis

Electrolyte 1M KOH

NiO  OH      NiOOH  e

ch arg e / disch arg e

Maximum Specific Capacitance value 1341 Fg−1

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 Galvanostatic Charge Discharge analysis

Maximum Specific Capacitance value 877 Fg−1 at current density 1 Ag-1

Contribution of resistive drop and slow kinetics of redox based faradic mechanism

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 Cycle retentivity and Ragone plot

Capacitance retentivity 90 % after 1000 cycle

It shows highest specific energy of 64.4Wh Kg-1 and specific power of 2.305 kW
Kg-1 and good coulombic efficiency is 95.4%.

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 OUTCOME

 Formation of well adherent. Porous, nano-flake like structure.

 Maximum specific capacitance of 1341 Fg-1 from CV analysis.

 Maximum specific capacitance of 877 Fg-1 from GCD analysis.

 Capacitance retentivity ~ 90% after 1000 cycles.

32
Copper Oxide (CuO) thin film for
supercapacitance property

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Structural Characterization
Prominent diffraction were peaks observed at
~35.94oo and ~39.16oo corresponding to (-111) and
(111) diffraction planes which can be associated
with monoclinic copper oxide [JCPDS file no. 48-
1548].
The values of lattice constant was ~0.4649nm,
~0.3369nm and ~0.5095nm

GOF ~ 1.1-1.2
Sample Thickness Grain size Starin
(nm) (nm)

CuO1 220 19.7 5.84

CuO2 295 24.3 4.21

CuO3 385 29.3 2.02
CuO4 410 25.1 3.14

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Surface morphology and EDS

formation of porous like

near-spheroidal structure

For CuO-3cauliflower like

spheroid morphology is
formed

EDS confirms present of Cd

and O

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 TEM ANALYSIS

TEM image
Particle size estimated ~ 31.2 nm.
SAED pattern
Confirms presence of (202), (-202), (111), (-
110) and (311) planes of Monoclinic CuO.
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 Cyclic voltammetry Analysis

Electrolyte 1M Na2SO4

 2CuO surface  2 A   2e _ 
 Cu 2 OOA 
surface

Maximum Specific Capacitance value 585 Fg–1

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 Cyclic voltammetry Analysis

Maximum Specific Capacitance value 554 Fg–1 at current density 1 Ag-1

Rapid discharge curve is due to IR drop and thereafter a slow decay

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 Performance parameters of supercapacitors
compared with electrolytic capacitors and lithium-ion batteries
Parameter Aluminium Supercapacitors Li-ion
electrolytic batteries
Double-layer Supercapacitor for Pseudo and hybrid
capacitor
capacitors for power application capacitors(Li-ion
memory backup capacitors

Temperature -40 to +125 -40 to +70 -20 to +70 -20 to +70 -20 to +60
range(°C)
Cell Voltage(V) 4 to 630 1.2 to 3.3 2.2 to 3.3 2.2 to 3.8 2.5 to 4.2
Charge/dis- unlimited 105 to 106 105 to 106 2×104 to 105 500 to 104
charge cycle
Capacitance ≤ 2.7 0.1 to 470 100 to 12000 300 to 3300 -
range(F)
Specific 0.01 to 0.3 1.5 to 3.9 4 to 9 10 to 15 100 to 265
energy(Wh/kg)
Specific > 100 2 to 10 3 to 10 3 to 14 0.3 to 1.5
power(Wh/kg)
Cell discharge Short Middle Middle Long Long
time at room (days) (weeks) (weeks) (months) (months)
temp.
Efficiency 99 95 95 90 90
Lifetime (years) >20 5 to 10 5 to 10 5 to 10 3 to 5
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Which one is Superior?

Battery
or
Supercapacitor

The answer is…………..

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42
Research Facilities in India for Supercapacitor
Materials
 Preparation Process

Nanomaterials

Thin Films

Different Physical and Chemical processes are

used
 Characterization
• XRD
• SEM
• TEM
• BET for porosity
• Cyclic Voltametry
• Galvanostatic Charge Discharge
 46

Electrostatic capacitance Influence of pseudo capacitance

 Energy Storage Laboratory in
 

Department of Physics, IIT Roorkee

Research expertise assosiated with this Facility:
Energy Storage, Li-ion Battery, Supercapacitor, Fuel cells, Solid State Ionics, Li-
Kinetics,
Electrochemical Impedance Spectroscopy, Nano-hybrids, Nano-Composites,
Functional Materials.

The Laboratory is equipped with following Systems:

•Battery Fabrication Facility
•Battery Testing and Troubleshooting Facility
•Transport Property Measurment Facility
•Material Development Facility
•Supercapacitor Fabrication Facility
Coordinator of the Lab: Prof. Y. K. Sharma
The link for External Website: Link Contact No. of Lab: +91-1332-286685
Advanced Functional Materials Research Group
Indian Institute of Technology, Indore
Dr. Parasharam M. Shirage
Associate Professor and Ramanujan Fellow
Discipline of Metallurgy Engineering and Materials Science and Discipline of Physics,

Email : [email protected], [email protected]

Phone : +91-787-52222-331
Indian Institute of Technology (IIT) Indore,
Simrol, Khandwa Road
Indore- 453552
Madhya Pradesh
INDIA

Department of Chemistry, IISER Bhopal

Electrochemistry of Nanomaterials
Dr. Amit Paul, Associate Professor

•Phone : +91 755 269 1343, 669 1343

•Email : [email protected]
•Fax : +91 755 669 2392
ENERGY AND ENVIRONMENT UNIT
Institute of Nano Science and Technology (INST), Mohali (Punjab),
an autonomous institution of Department of Science and Technology (DST),
Government of India

Dr. Ramendra Sundar Dey In-plane, on-chip micro-supercapacitor

Scientist-C Hybrid capacitor/nanohybrid capacitor
Hybrid Supercapacitor-biofuel cell/solar cell/nanogenerator

Jadavpur University

Dr. Sachindra Nath Das

Assistant Professor, Jadavpur University

Energy Storage System

Supercapacitor

CNT based materials and oxides for Energy Storage

Nanomaterials and Energy storage Research

Material Science Research Division

Ram Ratan Singh College, Mokama, Patna

Patliputra University, Patna

Contact: Dr. Ayan Mukherjee

[email protected]
8372098447

Dr. Laxman Singh

[email protected]
9910186046