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Energy Storage
Soorathep Kheawhom
Department of Chemical Engineering,
Faculty of Engineering
Chulalongkorn University THAILAND
Electricity
Biomass
114 USD/MWh
Geothermal
75 USD/MWh
Hydro
54 USD/MWh
Wind
38 USD/MWh
Solar
36 USD/MWh
0 30 60 90 120
Renewable energy sources
A total of 173,000 terawatts (trillions of

watts) of solar energy strikes the Earth
continuously
A total of 173,000 terawatts (trillions of watts) of solar energy strikes the Earth
continuously. That's more than 10,000 times the world's total energy use. And that
energy is completely renewable — at least, for the lifetime of the sun. "It's nite, but
we're talking billions of years.
Variability is the main limitation.
fi
Net load during the day is pushed further down as more solar is
added to the grid. [CAISO]
There is no inventory in power grid.

Energy storage is the key element for effective use of renewable energy.
Characteristics of electricity
• Time
Electricity is consumed at the same time as it is generated.
Time shifting.
Characteristics of electricity
• Location
The place where electricity is generated is usually located far from the locations where
it is consumed.
Backup during transmission failures.

Supplying electricity to mobile applications.
Needs for EES system
• Higher fraction of renewable energy
The fluctuation in the output of

renewable generation makes system
frequency control difficult.
Renewable energy output is
undependable.
In 2020, California produced unused

1.3 TWh of electricity from solar and
wind.
• Essential roles in the future smart grid
EES installed in customer-side can control power flow and mitigate congestion.
Electrification of existing equipment and integration with the smart grid.
Energy storage is a medium for energy management system.
• Rechargeable Batteries is the key

technology for electric vehicles
- Vehicles, ~50-100 kWh

- Charging station, level 2
charging, ~ 40 kW, level 3
charging ~350 kW
EV sold, in million units, worldwide, 2015-2030
Several announcement accelerate the growth

Norway, has set a target of only allowing sales of 100%
electric or plug-in hybrid cars by 2025 – Feb 2016
The Netherlands voted to ban all new petrol and diesel car
sales by 2025 – March 2016
“We would phase out the internal combustion engine in the

coming years” – Volvo, June 2017
“We are announcing an end to the sale of petrol and diesel

cars by 2040” Nicolas Hulot, French ecology
minister (July 2017)
Britain to Ban New Diesel and Gas Cars by 2040 (July 2017)
Germany’s Federal Council, which represents the country’s 16
states, had passed a resolution on banning
ICEs from 2030 onward
Three main applications of rechargeable batteries
• Power grid management and backup

Stable power
Emergency power supply
Time shifting/cost saving
• Transportation
• Portable devices
Energy storage systems
Pump Hydro Energy Storage (PHES) Electrochemical Energy Storage
Two reservoirs of different height

Potential energy Electricity
Two electrode of different potential
High initial capital cost and site-specific negative Chemical energy Electricity
environmental and ecological impacts
Batteries
Prof. Alessandro Volta

Battery
• Negative electrode: gives electrons to

the external circuit and oxidized
during electrochemical reaction.
• Positive electrode: accepts electrons
from the external circuit and reduced
during electrochemical reaction.
• Electrolyte: the ionic conductor
Battery
Negative: Pb
Positive: PbO2
Battery segmentation
Battery market (2016-2021), $bn
Main driver
- Population increase and city growth

- Shift in energy production with an
Primary increasing focus on renewable energy
Rechargeable
solutions
- Global awareness regarding global
warming pushing for adoption of green
solutions
Configurations of electrode materials in batteries
Traditional enclosed battery made of solid Flow batteries in which the electrode
electrode materials materials are made of liquids
Enclosed battery
Traditional enclosed battery made of solid Flow batteries in which the electrode
electrode materials materials are made of liquids
Flow battery
Anolyte
Catholyte
Positrolyte
Negatrolyte
Flow battery
Anode
A hybrid flow battery, in which half the cell is made of liquid A semi-solid flow battery in which the active
electrolyte, and half is made of solid electrode material materials are dispersed in electrolytes
Hybrid flow battery
Hybrid flow battery
Hybrid flow battery
Anode
A hybrid flow battery, in which half the cell is made of liquid A semi-solid flow battery in which the active
electrolyte, and half is made of solid electrode material materials are dispersed in electrolytes
Semi solid flow battery
Traditional enclosed battery
• All active materials are packed inside

the cell.
• Closed system
• Power and energy capacity are related.
Traditional enclosed battery made of solid

electrode materials
World rechargeable battery market
Lithium-Ion Battery: Highest growth & major part of the investments
Lead acid batteries: 50% market share in volume
World rechargeable battery market
10% AVERAGE GROWTH PER YEAR (2010-2021)
SLI: Start light and ignition batteries for cars, trucks, motors, boats, etc…
PORTABLE: consumer electronics (cellular, portable PCs, tablets, cameras, …), data collection & handy terminals,
POWER Tools: power tools but also gardening tools
INDUSTRIAL: Forklift (95%), Telecom, UPS, Energy Storage System, Medical, Others
(Emergency Lighting, Security, Railroad Signaling, Diesel Generator Starting, Control & Switchgear,
AUTOMOTIVE: HEV, P-HEV, EV
World rechargeable battery market in 2021
Worldwide battery sales
A 62% growth from 2020 to 2021

Li-ion battery
• Negative: carbon-based electrodes or lithium metal and lithium-metal alloys

• Positive: intercalation host materials i.e. LiCoO2, LiFePO4, Li(Ni1−x−yMnxCoy)O2 (NMC),
Li(Ni1−x−yCoxAly)O2 (NCA) and LiMn2O4
• Electrolyte: Non-aqueous
Li-ion battery
Advantages Limitations
• High specific energy and high power • Requires protection circuit to prevent
• Long cycle and extend shelf-life; thermal runaway
maintenance-free • Degrades at high temperature and high
• High capacity, low internal resistance, voltage
good coulombic efficiency • No rapid charge possible at freezing
• Low self-discharge temperatures (<0°C, <32°F)
• Transportation regulations required
when shipping in larger quantities
Lithium-ion battery
Lithium Cobalt Oxide — LCO
• High specific energy

• Popular choice for mobile phones, laptops and digital cameras
• A cobalt oxide cathode/ A graphite carbon anode
• Relatively short life span
• Low thermal stability
• Limited specific power
• Voltages: 3.6V nominal; typical operating range 3.0–4.2V
• Specific energy: 150–200Wh/kg
• Charge (C-rate): 0.7–1C, charges to 4.20V (most cells); 3h charge typical
• Discharge (C-rate): 1C; 2.50V cut off
• Cycle life: 500–1000, related to DOD, load, temperature
• Thermal runaway: 150°C, full charge promotes thermal runaway
• Applications: mobile phones, tablets, laptops, cameras
Lithium Manganese Oxide — LMO
• Fast charging and high-current discharging

• High power but less capacity
• Safer than LCO; commonly mixed with NMC to improve performance
• Voltages: 3.7-3.8V nominal; typical operating range 3.0–4.2V
• Charge (C-rate): 0.7–1C typical, 3C maximum, charges to 4.2V
• Discharge (C-rate): 1C; 10C (some cells), 2.5V cut-off
• Thermal runaway: 250°C, high charge promotes thermal runaway
• Applications: power tools, medical devices
Lithium Nickel Manganese Cobalt Oxide — NMC
• Cathode: one-third nickel, one-third manganese and one-third cobalt

• Lowers the raw material cost by replacing with Ni
• Ni-based systems have higher energy density, lower cost, and longer cycle life than
Co-based systems (but slightly lower voltage
• High capacity and high power
• Charge (C-rate): 0.7–1C, charges to 4.20V
• Discharge (C-rate): 1C; 2C possible on some cells; 2.50V cut-off
• Applications: E-bikes, medical devices, EVs, industrial
Lithium Iron Phosphate — LFP
• More tolerant to full charge conditions

• Lower nominal voltage of 3.2V
• Lower specific energy
• Replacement of lead acid battery
• Charge (C-rate): 1C typical, charges to 3.6V
• Discharge (C-rate): 1C, 25C (some cells)
• Cycle life: 2000 and higher, related to DOD, load, temperature
• Thermal runaway: 270°C, very safe even if fully charged
• Applications: portable and stationary needing high load currents and endurance
Lithium Nickel Cobalt Aluminum Oxide — NCA
• Similarities with NMC by offering high specific energy, reasonably good specific power
and a long life span
• Specific energy: 200-260Wh/kg
• Charge (C-rate): 0.7C, charges to 4.20V
• Discharge (C-rate): 1C typical; 3.0V cut-off; high discharge rate shortens battery life
• Cycle life: 500 and higher, related to DOD, load, temperature
• Applications: medical devices, industrial, electric powertrain
Lithium Titanate — LTO
• LTO replaces the graphite in the anode

• Long life
• Fast charge
• Wide temperature range
• Expensive
• Safest Li-ion batteries
• Low specific energy, rivalling NiCd
• Charge (C-rate): 1C typical; 5C maximum, charges to 2.8V
• Discharge (C-rate): 10C possible; 1.8V cut-off on LCO/LTO
• Cycle life: 3,000–7,000
• Applications: UPS, electric powertrain, solar-powered street lighting
Who is going to win?
Aging of Li-ion batteries
• The smaller the discharge (low

DoD), the longer the battery will
last.
• Exposing the battery to high temperature and dwelling in a full state-of-charge for an
extended time can be more stressful than cycling.
• Environmental conditions: the worst situation is keeping a fully charged battery at

elevated temperatures.
• Store Li-ion at partial charge in a cool place.
• Lower charge voltages prolong battery life.
• Always keep the airflow unobstructed when running electric devices with air-cooling
on a bed or pillow. A cool laptop extends battery life and safeguards the internal
components.
• The cells should be charged at 1C or less. Avoid using ultra-fast chargers that claim to
fully charge Li-ion in less than one hour.
• Avoid deep cycling. Each cycle wears the battery down by a small amount and a partial
discharge is better than a full discharge.
Recycle of Li-ion batteries
Recycle of Li-ion batteries
Zinc-based batteries
Higher potential
Lower potential
Two electrodes to store electrons

Preferable highly reversible reaction
Favorable redox potential, high stability,
and a high specific volumetric capacity
Low cost and abundant
Stable supply chain
100% Recyclable
Zinc-based battery
Primary batteries
Zinc-carbon battery
Alkaline battery
Anode: Zinc
Cathode: MnO2
Secondary batteries
Rechargeable alkaline battery

Zinc-nickel battery
Zinc-air battery
Zinc-bromine battery
Zinc-ion battery
Zinc-ion batteries
Non-aqueous electrolyte
Aqueous electrolyte •Organic electrolytes 10.1016/j.mtener.2021.100738
•Hydrogen evolution reaction (HER) •Room-temperature ionic liquid (RTIL) and
•Dendrite formation deep-eutectic solvent (DES) based
•Corrosion of Zn (HER) electrolytes 10.1149/2.0641906jes
•Passivation •Non-aqueous gel polymer electrolytes
Manganese-based oxide cathodes
Vanadium-based cathodes
Vanadium flow battery
• Negative electrode
• Graphite felt
• Vanadium solution (V2+)
• Positive electrode
• Graphite felt
• Vanadium solution (V6+)
Flow battery
• Very fast response time (millisecond)

• Efficiency 60-80%
• Long-duration
• 100% depth of discharge is possible
• Long life, > 25,000 cycles
• For long duration storage (4+ hours), vanadium flow battery is 2-3
times cheaper than Li-ion battery
• Parasitic loss because of pump
• Environmental concern because of leaking of the electrolyte
• Vanadium is expensive and toxic
• Low solubility of vanadium
Redox potential of various inorganic redox couples
Hybrid flow battery systems
Zinc-bromine battery system

Zinc-air batteries (ZABs)
Two electrodes
Zinc
Oxygen
Oxygen is virtually unlimited
Aqueos electrolyte
Zinc-air flow battery
• Active materials: zinc and oxygen from air

• Aqueous electrolyte
• 100% DOD is possible
• Much cheaper than vanadium flow battery
and zinc-bromine
• High safety and environmentally friendly
• Efficiency 60%
• Demonstrated in USA, Canada, France,
Spain, Indonesia
Semi-solid flow batteries
Zinc-bromine flow battery
• Active materials: zinc and bromine

• Aqueous electrolyte
• 100% DOD is possible
• Efficiency 60-70%
• Self-discharge: bromine crossing over.
• Lifetime: Corrosion of bromine.
• Bromine vapors are highly corrosive and
toxic.
• Temperature 20-50 C.
• Gassing concern
Zinc-iodine flow battery
Zinc-iodine flow battery
Anode:
Zinc
Cathode:
Iodine solution
Electrolyte:
Aqueous (neutral)
Key feature
- High safety
- High rate and high volumetric capacity
Organic flow battery
Hydrogen
solar automotive
H 2O wind fuel cells
hydro
nuclear/solar gas or consumer

thermochemical hydride electronics
cycles H2 storage H2
stationary
electricity/heat
Bio- and fossil fuel
generation
bioinspired reforming
use
production storage in fuel cells
4.4 MJ/L (Gas, 10,000 psi)
9M tons/yr 8.4 MJ/L (LH2) $3000/kW
40M tons/yr 9.72 MJ/L $35/kW

(Transportation only) (2015 FreedomCAR Target) (Internal Combustion Engine)

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Energy Storage

A total of 173,000 terawatts (trillions of

Variability is the main limitation.

There is no inventory in power grid.

Electricity is consumed at the same time as it is generated.

Backup during transmission failures.

• Higher fraction of renewable energy

The fluctuation in the output of

In 2020, California produced unused

• Essential roles in the future smart grid

• Rechargeable Batteries is the key

- Vehicles, ~50-100 kWh

Several announcement accelerate the growth

“We would phase out the internal combustion engine in the

“We are announcing an end to the sale of petrol and diesel

• Power grid management and backup

Two reservoirs of different height

Prof. Alessandro Volta

• Negative electrode: gives electrons to

- Population increase and city growth

• All active materials are packed inside

Traditional enclosed battery made of solid

A 62% growth from 2020 to 2021

• Negative: carbon-based electrodes or lithium metal and lithium-metal alloys

• High specific energy

• Fast charging and high-current discharging

• Cathode: one-third nickel, one-third manganese and one-third cobalt

• More tolerant to full charge conditions

• LTO replaces the graphite in the anode

• The smaller the discharge (low

• Environmental conditions: the worst situation is keeping a fully charged battery at

Two electrodes to store electrons

Rechargeable alkaline battery

• Very fast response time (millisecond)

Zinc-bromine battery system

• Active materials: zinc and oxygen from air

• Active materials: zinc and bromine

nuclear/solar gas or consumer

40M tons/yr 9.72 MJ/L $35/kW

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