Enhancing the Anode Stability in Mild Aqueous Zinc-ion Batteries

through Additive Engineering

November 2023
Academic Year 2023

School of Chemical Engineering

University of New South Wales
Under the guidance of: Sydney 2033 Presented by:
Dr. Priyank Kumar Ravindra Kokate
Dr. Dipan Kundu (zID- 5426946)
 Outline

 Problem statement

 Strategies for anode protection

 Research plan
 Problem statement
 Dendrites (unwanted branch-like structures) form on the anode surface.
Zn2+ + 2e− → Zn

 Hydrogen Evolution Reaction (HER):evolution of H2 gas irreversible reaction, leading to gas bubbles.
2H2O + 2e− → H2 + 2OH−

 Corrosion Reaction: leading to the formation of zinc

oxide or hydroxide.
Zn+2H2​O+2e− →Zn(OH)2​+H2​
consumption of active zinc and the formation of undesirable
products.

 Thereby reducing the coulombic efficiency (CE) and

increasing in-cell pressure, impacting the reversibility and
efficiency of the zinc anode.
Figure 1. Schematic illustration of potential issues related to
the Zn metal anode cycling in AZIBs.
3
https://doi.org/10.1039/D2MH00973K
 Strategies for anode protection
Additives: Why important and working
Concentration of additive
• Organic additives promote formation of a
dynamic solid electrolyte interphase (SEI) on
the zinc surface, preventing hydrogen evolution
reaction (HER).

• Adsorption Mechanism: Additive molecules

adsorb onto surface, leveling the electric field,
and providing uniform metal deposition.

• Hydrophobic Nature: The filmed layer is

Figure 2. Schematic diagram of the material designs for
stabilizing Zn anodes in mild AZIBs.
https://dx.doi.org/10.20517/energymater.2022.08
hydrophobic, preventing water from metal
surface and enhancing stability.
4
Overcome challenges/Additives
Density Functional Theory (DFT) is a method used in physics
and chemistry to understand the behavior of atoms and
molecules. In simple terms, it's like a tool or a mathematical
model that scientists use to predict how atoms and molecules
will behave in different situations.
• Again finding new additives is a challenge, it’s really time consuming
and expensive to check additives in experimental labs, so we have
chosen a list of the additives and using DFT and machine learining
model we got 3 main descriptors which actually tells where the
additives are useful/good or not. However, again there is a high
computational cost since the calculation considers both Zn anode
surface and molecule, so to make it more efficient and cost effective
and less time consuming, we are trying to find some descriptors
which actually tells by just seeing the molecules if the molecule is
suitable for the good additive
What isfor the particular anode or not.
additive/descriptors/
 Research plan
• Additives performance is also depending on its composition.
Adsorption Energy: This descriptor quantifies the strength of
interaction between the additive and the anode surface. A higher to find additives with suitable properties, expensive and time taking
• Challenges:
adsorption energy typically indicates stronger binding, whichby experimental.
process
may enhance the stability and performance of the anode.
• Collection of list of additives and calculating their properties at a standard
conditions.

• 3 descriptors are important which can find the additives properties.

• Density Function Theory (DFT) using VASP.

• Machine learning modelling to predict new additives’ properties.

Certainly:

1. **Solvation Energy**:
- Measures the energy change when a molecule dissolves in a solvent.
- Indicates the strength of interaction between solute and solvent.
- Higher solvation energy suggests greater stability in solution.

2. **Boiling Point**:
- Temperature at which a substance transitions from liquid to gas.
Figure 4. Machine learning-based correlation of the - Reflects strength of intermolecular forces.
performance with the three performance descriptors. - Higher boiling point indicates stronger interactions within the substance.
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adsorption energies
A negative adsorption energy indicates that the adsorption
Zn (100) surface process is exothermic, meaning energy is released as the
molecule or atom binds to the surface. This suggests that the
adsorbed species is stable on the surface. Conversely, a positive
Zn+1-2-butanediol
adsorption energy indicates that the adsorption process is
endothermic, requiring energy input to bind the molecule or
atom to the surface. This implies that the adsorbed species may

→
not be stable on the surface under those conditions.
+

Adsorption energies:
1-2-butanediol
where , total electronic energy of a system
 Density of states

Explain d-band center Vs sp-band center

Adsorption energy Vs sp-band center plot
Second third and forth moment
• Milestones

1. Explore novel descriptors by conducting a detailed analysis of the sp-band plot, incorporating insights from the 2 nd (variance) and 3rd

(skewness) moment.

2. Writing a research paper presenting findings on the relationship between the properties of sp-band plot and the adsorption energies of

the additives.

3. Utilize machine learning methodologies to construct a predictive model correlating the Density of States (DOS) with the adsorption

energy of additive.
• Try to new descriptors by studying the sp-band plot in more detail with the help of 2nd and 3rd moment.

• Writing a paper using the obtained result data (regarding the correlation between the properties of sp-band plot and the adsorption of the additives) work.

• Machine learning techniques will be employed to develop a direct predictive model by corelating the Density of States (DOS) and the adsorption energy of the additive molecules.

• ………… descriptors… checking for the second moment and third moment using the sp-center band

• Writing a paper using the obtained result data (regarding the correlation between the properties of sp-band plot and the adsorption of the additives) work.

• Machine learning techniques will be employed to develop a direct predictive model by corelating the Density of States (DOS) and the adsorption energy of the additive molecules.

• … Learning machine techniques DOS direct model with the adsorption energy…? Create a model…

Machine learning techniques will be employed to develop a direct predictive model by corelating the Density of States (DOS) and the adsorption energy of the additive molecules.
COMSOL
Thank you
 Appendix
• The free energy of solvation () is determined through the following equation:

where the optimized geometries in gas and solution phases are denoted as and , respectively. represents the
nonelectrostatic component of the free energy of solvation.

• The adsorption energies were computed through the given formula:

where , , and represent the self-consistent field energies of the relaxed bulk, molecule, and molecule adsorbed
on the Zn surface, respectively.

• The interaction among different additives (association energy): Boiling point values of the additives were
utilized as a proxy for their association energies, given that accurate computation of association energies
would entail extensive exploration of intermolecular configurations.
Table 1. The boiling point and calculated adsorption and solvation energies of the various additives.
 Introduction
• Energy Storage challenges:
 Urgency to search new technologies in the field of energy storage.
• Lithium-ion batteries (LIBs):
 As a commercial battery, has played a great role in social production.
• Drawbacks of LIBs:
 Limited lithium resources.
 Security concerns hinder further development.
• Aqueous zinc ion batteries (AZIBs):
 Promising alternative to LIBs.
 Higher capacity density.
 More environmentally friendly, Safety, and relaxed assembly conditions.

• Challenges in AZIB Development:

 Irregular dendritic growth.
 Hydrogen evolution reaction (HER).
 Corrosion reactions pose obstacles. 16
 Why Zn-ion batteries?

 Abundance & distribution of Zn in earth crust.

 Competitive cost (approx. 2$ per kg (Zn), 19$ per kg (Li)).

 Stable redox potential (-0.78V vs SHE).

 Zinc exhibits high energy density, storing significant charges with a small amount of
active material.

 Ionic radius is comparable to Li+.

 More stable in aqueous electrolytes (less H2 evolution).

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 Working mechanism
• Work through reversible intercalation (similar to LIBs).

• Components include a zinc metal anode, zinc-containing

electrolyte (ZnSO4), cathode for Zn ion hosting, and
separator.

• Electrolyte Function: Helps ions move through the battery.

• Discharge Process:
 Zinc metal anode dissolves into Zn ions in the electrolyte.
 Cathode absorbs these zinc ions.
Electrolyte

Figure 1. Working of AZIBs. • Charging Process: Reverse of discharge.

Zn(s) ⇌ Zn2+(aq) + 2e−

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https://doi.org/10.1002/inf2.12306