LAB REPORT

8/19/2018

SYNTHESIS AND
CHARACTERISATION
OF CATHODE
MATERIALS FOR
SODIUM ION BATTERY

VINAY ARYA
18ES60R05
SCHOOL OF ENERGY SCIENCE AND ENGINEERING
IIT KHARAGPUR
OBJECTIVE: SYNTHESIS AND CHARACTERISATION OF
CATHODE MATERIALS FOR SODIUM ION BATTERY
THEORY:

Introduction to Battery
A battery consists of two or more than two electric cells joined together. Cells convert chemical
energy to electrical energy and vice versa. The cells consist of positive and negative electrodes
joined by an electrolyte. It is the chemical reaction between the electrodes and the electrolyte
that generates DC electricity. Cell is the building block of battery. Battery consists of multiple
cells in series.
Types of cells:
1. Primary cell
2. Secondary cell
Primary battery/cell:
In primary cell, the electrochemical reaction is not reversible. It means that after the chemical
reactions, active materials may not return to their original form. Primary batteries can supply
current immediately after assembly. They are like use and throw batteries. They create
hazardous waste. Primary batteries are assembled in charged state and they get discharged
during their lifetime. Some examples of primary battery are:
i. Dry cell
ii. Zinc carbon battery
iii. Daniel cell
Advantages:
a. High energy density
b. Low initial cost
c. Lighter and smaller
d. Wide availability of standard products
e. Best choice for single use like in guided missiles
Shortcomings:
a. Short life time
b. Single time use
c. Produce waste
Applications:
Consumer batteries used in-
a. Toys
b. Flashlights
c. Watches
d. Clocks
e. Hearing aids
f. Radios
 Specialist batteries used for-
a. Implanted medical devices
b. Missiles
c. Weapons systems

Secondary battery/cell:
Secondary batteries are also known as rechargeable batteries as they operate over multiple
charging and discharging cycles. Their chemical reactions are electrochemically reversible.
They are more useful in applications like inverter’s battery, battery in mobiles, batteries in
vehicles, etc. Some examples of secondary battery are:
i. Lithium ion battery
ii. Lead acid battery
iii. Sodium ion battery
iv. Nickel ion battery
v. Nickel zinc battery
Advantages:
a. More cost efficient in long term
b. Best solution for high power applications
Shortcomings:
a. High initial cost
b. Need special handling and disposal
c. Safety issues with mains power
d. Lower energy density than primary cells
e. Some custom designs have limited interchangeability
Applications:
a. Traction
b. Power tools
c. Motor drives
d. Laptop computers
e. Mobile phones
f. Camcorders
g. Toys

Considerations in selection of Cathode and Anode:

Anode material should exhibit the following properties

 Efficient reducing agent

 Good conductivity
 Stable
 Ease of fabrication
 Low cost
 Metals such as Zinc and Lithium are often used as anode materials.
Cathode material should exhibit the following properties

 Efficient oxidizing agent.

 Stable when in contact with electrolyte
 Useful working voltage
 Ease of fabrication
 Low cost
 Metallic oxides such as are often used as cathode materials

The most desirable anode-cathode material combinations are those that result in lightweight
cells with high voltage and capacity. Such combinations may not always be practical because
of extenuating factors such as material handling difficulty, reactivity with other cell
components, difficulty of fabrication, polarization tendencies, and cost prohibitive materials.

Why move from Lithium to Sodium:

However lithium is best choice for battery making, but there are significant drawbacks for
using lithium ion batteries: they are rather expensive and in addition the extraction of lithium
metal is problematic from an environmental point of view due to its high reactivity and
relatively low abundance in the Earth’s crust (only 20 ppm).

One option to avoid these drawbacks might be to replace lithium (Li) with sodium (Na) in
electrode materials for rechargeable batteries. Sodium is similar to lithium in terms of its
chemical properties, but approximately 1,000 times more abundant in the ground (26,000 ppm)
and in the form of salt (NaCl) in normal seawater (15,000 ppm). This makes sodium-based
batteries potentially more environmentally friendly and easier to recycle, as well as up to five
times less expensive. However, sodium ions are bigger and heavier than lithium ions and
nominally the operating voltage is somewhat lower. As a result, sodium-based batteries are
initially expected to have a lower energy density (Wh/kg), making them larger than present
lithium ion batteries. But this is obviously not a significant drawback for using them in
stationary energy storage applications such as batteries storing excess energy at a wind turbine
or solar panel.

Working Principle of Sodium Ion battery:

A Sodium-Ion (Na-Ion) Battery System is an energy storage system based on electrochemical
charge/discharge reactions that occur between a positive electrode (cathode) composed of
sodium-containing layered materials, and a negative electrode (anode) that is typically made
of hard carbons or intercalation compounds. The electrodes are separated by some porous
material which allow ionic flow between them and are immersed in an electrolyte that can be
made up of either aqueous solution (such as Na SO solution) or non-aqueous solution (e.g.
salts in propylene carbonate). When the battery is being charged, Na atoms in the cathode
release electrons to the external circuit and become ions which migrate through the electrolyte
toward the anode, where they combine with electrons from the external circuit while reacting
with the layered anode material. This process is reversed during discharge.
 Schematic illustration of Na-ion battery with a layered transition metal oxide cathode and
carbonaceous anode

Materials used
1. Sodium Carbonate (Na2CO3)
2. Nickel (II) Oxide (NiO)
3. Manganese Trioxide (Mn2O3)

4. Nickel (II) Sulfate hexahydrate (𝑁𝑖𝑆𝑂 .6 H2O)

5. Manganese (II) sulfate monohydrate (MnSO4. H2O)
6. Ammonium Hydroxide (NH4OH)
7. De-ionized Water

Equipments used

1. Weighing balance

2. Beaker

3. Graduated measuring cylinder

4. Micropipette and tip

5. Magnetic stirrer cum hotplate

6. Magnetic stir bar

7. Magnetic stir bar retriever

8. Filter paper

9. Glass filter funnel

10. Buchner flask

11. Petri dish

12. Hot air oven

13. Steel spatula

14. Mortar and pestle

15. Alumina crucible

16. Muffle furnace

17. Crucible tong

18. Heat Resistant Gloves

19. Vacuum desiccator

20. Film coating machine

21. Electrode punching machine

22. Coin cell (CR2032) components

23. Na-ion separator

24. Coin cell crimping machine

25. Glove-box

26. Electrochemical workstation

METHODOLOGY:
Co-precipitation synthesis procedure:

In Co-precipitation method, the required metal cations, taken as soluble salts (e.g. nitrates), are
co-precipitated from a common medium, usually as hydroxides, carbonates, oxalates or
citrates. In actual practice, one takes oxides or carbonates of the relevant metals, digests them
with an acid and then the precipitating reagent is added to the solution. The precipitate obtained
after drying is heated to the required temperature in appropriate atmosphere to produce the final
product.
Procedure:

1. Take two beakers, one 100ml and one 250ml and wash them properly with acetone.
Make them dry with tissue paper.
2. Weigh 5.6g of MnSO4.H2O and 4.4g of NiSO4.6H2O in weighing balance. Switch off
the machine.
3. Mix them in 250 ml beaker.
4. Add 50ml de-ionized water into it to prepare 1M mixed solution (Solution A).
5. Place this solution on a magnetic stirrer and stir it until homogeneous solution appears.
6. Weigh 5.3g of Na2CO3 and transfer it into 100ml beaker.
7. Add 50ml de-ionized water to prepare a homogeneous solution ( Solution B).
8. Now add Solution B dropwise into Solution A under continuous stirring on magnetic
stirrer.
9. Add 1.36 ml ammonia hydroxide solution through a micropipette. This is done to
maintain pH at around 12-14.
10. Put magnetic stirrer in the beaker.
11. Keep the solution under stirring at 600C for one hour. There will be typical light green
colour. This is precipitation.
12. Filter the precipitate by keeping filter paper on flask and rinse with water thoroughly.
13. Place the filter paper on a petri dish and keep it in a hot air oven at 1000C overnight.
14. Grind the dried powder and transfer into an alumina crucible.
15. Anneal the powder at 6000C for 3 hr.
16. Cool the annealed powder to room temperature.
17. Weigh the powder and mix Na2CO3 in it. The amount is to be calculated as per
stoichiometric ratios.
18. Grind the dried powder and transfer into an alumina crucible.
19. Place the crucible inside the muffle furnace.
20. Set the temperature at 9000C.
21. After 12h of heating, take a crucible tong and remove the crucible from furnace to room
temperature.
22. Wait until it cools down.
23. Grind the obtained powder and transfer it into a plastic container.
24. Store it in a vacuum desiccator to protect it from moisture.

Solid state synthesis procedure

1) Clean mortar and pestle with acetone and dry it in oven for 30 minutes.
2) Weigh these chemicals in weighing balance:
i) 1.1358g of Na2CO3
ii) 1.5318g of Mn2O3
iii) 0.3574g of NiO
3) Mix all these chemicals in mortar and grind for 1 hour. Mixture should not have any
granules and it should be uniform.
4) Place the mixture inside the oven and keep it around 1000C so that moisture will be
removed.
5) Transfer the ground powder in alumina crucible.
6) Place the crucible inside muffle furnace and set temperature at 9000C.
7) After 12h of heating, take a crucible tong and remove the crucible from the furnace to room
temperature.
8) Wait until it cools down.
9) Grind the obtained powder and transfer it into a plastic container.
10) Store it in a vacuum desiccator to protect it from moisture.

Surface Characterization

All the powder samples have been characterized using powder X-ray diffraction and data
havebeen collected using Bruker D2 PHASER diffractometer (Cu Kα radiation, λ = 1.540598
Å) withscanning from 10 to 80 ̊ two-theta region. The grain size and morphology have been
investigatedwith ZEISS EVO 60 scanning electron microscope.

Electrochemical Measurements

There are two electrodes:

Anode: Na metal

Cathode: Contains slurry on Al foil. The slurry contains

 70 wt% active material

 20 wt% activated carbon black
 10 wt% poly-vinylidene fluoride (PVDF) binder

Electrode discs are punched with a diameter of 16mm. Separator has 18mm diameter. The
loading mass on the Aluminium foil current collector is 1.5mg/cm2.

Assembly of Na-ion coin cell inside the glove box

Figure: Schematic representation of typical Na- ion coin cell

 1. Keep the casing bottom of the positive terminal.
2. Place the cathode disc (Al foil facing downward and slurry side upward )
3. Place the separator disc of suitable material and 18mm diameter onto it.
4. Soak the separator with 200µL of electrolyte [1 M NaClO4in Ethylene Carbonate:
Diethyl Carbonate (1:1 vol/vol)].
5. Place the anode Na metal disc (15 mm diameter) on top of it.
6. Place the stainless steel spacer and disc spring.
7. Close with the casing top of the negative terminal.
8. Press the coin cell with the help of crimper inside the glove box.

Cyclic voltammetry and Charge-discharge measurements

1.Wait for another 5 h to equilibrate the cell.
2.Set the scan rate at 1 mV/s and scan range 1.5 to 4.1 V for measuring cyclic voltammetry.
3.For measuring charge-discharge characteristics, calculate the theoretical capacity of the
material.
4.Set a certain capacity rate by inserting the current input calculated from theoretical
capacity.
5.Cycle the cell over a voltage range of 1.5– 4.1V at room temperature.
6. Record the charge and discharge capacity after each cycle.
7.Find out the Columbic efficiency of the cell.
8.Find out the capacity retention after each cycle.

Data Calculations:
1. Data Voltage range = 1.5 to 4.1 V
2. Scan Rate in Cyclic voltametry = 1 mV
3. Theoretical Capacity = (n * F)/(3600 * m)
n = Number of mobile ion
F = Faraday constant
m = Molecular weight of active material
4. Capacity rate = C/20
5. Columbic Efficiency = (Discharging capacity/Charging capacity*100) %
6. Capacity Retention= [100 - {( C1-Cn+1)/C1}*100] %
C 1= Discharge capacity of 1st cycle
C n+1 = Discharge capacity of (n+1)th Cycle

Weight of active material = 0.00371 g

Cycle Charge Discharge Charge Discharge Columbic Capacity
No. Point Point capacity capacity Efficiency retention
(mAh/g) = (mAh/g) =
Charge Discharge (%) (%)
Point/0.00371 Point/0.00371
1 0.539 0.466 113.4 124.4 - -

2 0.529 0.455 142.97 122.97 86.01 99.5

3 0.531 0.451 143.51 121.89 84.93 99.6

4 0.509 0.447 137.56 120.8 87.81 97.89

5 0.502 0.452 135.67 122.16 90.04 98.99

6 0.5 0.453 135.13 122.43 90.06 99.2

7 0.494 0.453 133.51 122.43 91.7 99.2

8 0.498 0.453 134.59 122.43 90.96 99.2

9 0.503 0.454 134.94 122.70 90.26 99.4