CE60017 - Sustainable Energy Technologies Flashcards
What’s a redox reaction?
A reaction involving electron transfer, with a species being oxidised and another being reduced.
Define oxidation and reduction:
Oxidation: loss of e- and increase in oxidation state
Reduction: gain of e- and a decrease in oxidation state
What are the equations for:
Li-ion batteries
Electrolysers
Fuel cells
CO2 reduction
Li-ion batteries
LiCoO2 + C6 → CoO2 + LiC6
Electrolysers
2H2O → 2H2 + O2
Fuel cells
2H2 + O2 → 2H2O
CO2 reduction
CO2+H2 → HCOOH
Define anode and cathode:
During discharge, the positive is the cathode and the negative is the anode.
During charging, the positive is the anode and negative is the cathode.
Anode - where oxidation occurs
Cathode - where reduction occurs
What’s the difference between galvanic and electrolytic cells?
Galvanic:
Spontaneous reactions
dG < 0
Electrons are spontaneously formed at anode
Electrons are supplied by the reaction
Electrolytic:
Non spontaneous
dG > 0
Electrons supplied to cathode to drive reaction
Electrons supplied by an external battery
What is absolute potential?
The amount of electric potential energy carried by a unitary point charge located at a specific point.
Or
The Work needed to move a unit positive charge from infinity to a specific point
The absolute potential cannot be measured - we always use relative potentials, i.e. the difference between the potential at two electrodes
The most common “reference potential” is the Standard Hydrogen Electrode (SHE), which is the potential of the redox couple H+/H2
So, clearly, the potential at which hydrogen can be reduced or oxidized is 0V.
How is cell potential calculated?
V.cell = V (reduction at cathode) - V (reduction at anode)
A reaction is spontaneous if
Vcell > 0
Pros and cons of batteries:
Pros:
High Round-trip efficiency (i.e. Ratio between the energy you get out of a battery and the energy you put into it)
Easily scalable
Relatively high energy density
Cons:
Expensive
Energy and power density are intrinsically coupled
Self-discharge
Efficiency loss over time
Requirement of critical metals
What’s a half cell and full cell?
A half-cell is a single electrode in an electrochemical cell, while a full cell is a complete electrochemical cell that consists of two half-cells connected by a salt bridge.
The electrode potential of a half-cell is determined by the energy required to move ions from the half-cell to the solution, and vice versa.
Looking at a half cell…
Testing the electrode of interest against the metal (for example lithium)
Since Li/Li+ has a potential of 0, it allows you to look at only the potential of lithium insertion at the electrode of interest
You have an abundance of Li available, which means you are not limited by it and can look at limitations at the electrode of interest only.
Looking at full cell…
Testing the battery with the cathode and anode of interest
The voltage we measured (cell potential) is affected by both anode and cathode.
The effect of anode and cathode cannot be deconvoluted
It measures the performance of a real battery.
Useful to find out how different parts of battery perform.
Properties of coin cells:
Small area,
One cathode, one anode,
Single-sided electrodes,
Large void space requires more electrolyte,
Low currents.
Properties of pouch cells:
Larger area,
Multiple stacked electrodes,
Often double-sided electrodes,
Minimal void space requires less electrolyte,
Higher currents.
What is the difference between battery capacity (or charge), power, and energy?
Battery capacity (or charge): Total charge that can be stored in a battery (Ah)
Power: the power that can be delivered is the product of the current (measured in A) and the cell potential (measured in V)
Power is measured in W = V x A
Energy: the total energy stored in a battery is the integral of the supplied power over time
Energy if measured in Wh= V x Ah
1Wh=3600 J
What is DoD and SoD?
Depth of discharge (DoD) = the amount of charge (capacity) extracted compared to the total amount (at the same discharge rate) – expressed in fraction or percentage
State of charge (SoC) = the amount of charge (capacity) still available to extract compared to the total amount (at the same discharge rate)
SoC = 1-DoD
How is state of charge (SoC) found?
SoC = 1-DoD
Depth of discharge (DoD) = the amount of charge (capacity) extracted compared to the total amount (at the same discharge rate) – expressed in fraction or percentage
State of charge (SoC) = the amount of charge (capacity) still available to extract compared to the total amount (at the same discharge rate)
How is theoretical charge (in mAh/g) calculated?
Q = nF/3.6M
Where:
n - number of electrons
F - Faraday constant (96485 C/mol)
M - molecular mass
3.6 is the conversion factor, 1 C = 0.28 mAh
For example, if CoO2 is used as an electrode for Li –ion batteries, the reaction is
LiCoO2→Li+ +e− + CoO2
Each LiCoO2 (M=98g/mol) can store 1 electron (n=1) so the theoretical capacity is:
Q=1*96485/3.6/98= 274 mAh/g
By convention, when calculating the theoretical capacity of the cathode, we include the weight of litihium, when doing it with the anode we don’t.
How is power calculated?
P = IV
(Then energy (E) = capacity (Ah) * cell potential (V))
How is gravimetric energy density calculated?
Gravimetric energy density = cell potential (V) * gravimetric capacity (Ah/g)
The gravimetric capacity can be maximized by finding lighter materials, that can store a charge with a smaller weight.
The cell potential can be maximized by choosing cathode and anode materials with the biggest potential difference possible.
What is cell potential?
The cell potential is determined by the difference in potential between the anode and the cathode.
To maximize the cell potential, we should choose the anode with the lowest possible voltage and the cathode with the highest possible one.
How are batteries tested?
Electron flow is provided and the electric potential is measured.
Batteries are tested galvanostatically, i.e. at constant current (i.e. With a constant flow of electrons) and the potential is measured.
In an ideal battery:
- The cell potential is equal to the standard cell potential (4.1 in this case)
- The cell potential is constant over time
- The charge potential is equal to the discharge potential (4.1V in this case)
- What current we apply while measuring the potential (i.e. How fast we charge/discharge) doesn’t affect the total charge.
Once the battery has been fully charged or discharged, the potentiostat will keep changing the potential to maintain the current, this current will not be the effect of charging discharging the battery anymore, but will come from degradation of the battery. For this reason, we need to stop the experiment before this happens, using a CUT-OFF potential.
How does the charge-discharge curve behave for a real battery?
The cell potential is lower than the theoretical value during discharge.
You get less energy out of the battery.
The difference between theoretical and real is called overpotential.
The cell potential changes with the state of charge (or time)
What current we apply while measuring the potential (i.e. How fast we charge/discharge) has an impact on the total charge.
What is overpotential?
The difference between the theoretical cell potential and the experimental one.
Why are there differences between electrode potential / what causes overpotential?
Polarisation losses V=E-iR
(Polarization losses are proportional to the current we draw (i), and are caused by the resistance of the electrolyte to the flow of ions.
The proportionality constant is R, also known as ohmic resistance)
Electrode / Activation overpotential
(The activation overpotential is characteristic of an electrode and is due to kinetics limitation to the charge transfer process
(i.e. Kinetics limitation for Li+ to become LiC6))
Electrode overpotential - concentration overpotential
(The concentration overpotential is due to depletion of the reactant next to the electrode surface.
It is essentially a measure of the «extra driving force» needed to transport the reactant (Li+) to the surface))
What is the C-rate?
How fast we can charge/discharge a battery.
C-rate = 1 / time to charge or discharge
The higher the C-rate (i.e. the faster we discharge) the shorter the duration of discharge will be.
For an ideal battery, although the time is different, the capacity (i.e. the product of current and time) should be the same
In reality, as we will see, the capacity decreases the faster we charge/discharge.
How is coulombic efficiency found?
Q (charge) / Q (discharge) *100
What is coulombic efficiency?
A measure of the capacity that you can get out of a battery, compared to the capacity that you put in during charge
An important consideration when balancing electrode capacities, and for considering overall specific energy or capacity of the cell.
What is voltaic efficiency?
The ratio between the average discharge voltage to the average charge voltage (resistance of the cell, polarisation losses)
= E (discharge) / E (charge) * 100
How is battery efficiency found?
= QE (discharge) / QE (charge) *100
= voltaic efficiency * coulombic efficiency
It is the ratio of the energy retrieved from thebattery, to the energy provided to thebattery, when coming back to the same SOC state = Columbic efficiency X Voltaic Efficiency
How is it known if a reaction will be spontaneous?
A reaction is spontaneous if it results in an increase in free energy.
This is marked by a negative dG value in the Gibbs Free Energy Equation.
Since ΔG=-nFVcell…
A reaction is spontaneous if (cell potential) Vcell > 0
What does the reduction potential of a half reaction tell us?
The tendency for a material to be reduced.
The potential for Fe 3+ to Fe 2+ is more positive than Fe 2+ to Fe. This means that Fe 3+ has a greater tendency to gain electrons and be reduced to Fe 2+ compared to Fe 2+ to be reduced further to Fe.
Under standard conditions, the reduction of Fe 3+ is favourable.
Metal ions at the top of the series are good at picking up electrons. They are good oxidising agents. (for example Cu2+ is good at picking up electrons and becoming Cu) The oxidising ability of the metal ions increases as you go up the series.
Metals at the bottom of the series are good at giving away electrons. They are good reducing agents. (for example Fe is good at giving away electrons and becoming Fe2+)
The reducing ability of the metal increases as you go up the series.
Define:
Specific energy
Energy density (or volumetric energy density)
Specific power
Specific volume
Gravimetric Battery Capacity
Specific energy (or gravimetric energy density)= the stored energy per unit mass ( Wh/Kg)
Energy density (or volumetric energy density) = the stored energy per unit volume ( Wh/l)
Specific power = power per unit mass ( W/Kg)
Specific volume =power per unit volume ( W/L)
Gravimetric Battery Capacity = Ah/g or mAh/g
How can the gravimetric capacity and cell potential of a battery be maximised?
The gravimetric capacity can be maximized by finding lighter materials, that can store a charge with a smaller weight.
The cell potential can be maximized by choosing cathode and anode materials with the biggest potential difference possible.
What is open circuit potential?
The potential difference between the electrodes when not drawing any current, this should be equal to the theoretical cell potential.
In reality, the potential we measure is different, it has an overpotential.
Why do we use Li-ion batteries?
- Li is lightweight
- High power density
- Good energy density compared to other batteries
- Great cyclability
- More environmentally friendly than lead acid
All the elements on the first group have a single electron on the outer electron sphere, therefore:
- Removing the electron is “easy” and reversible
- They have an oxidation state of +1, meaning they can store one charge and being transported across a battery as +1 ion.
This means Li, Na, K are all good candidates
Mg and Ca even more so, as they can store 2 charges per atom
Out of all of them, Li is the lightest!
All other battery chemistry will intrinsically be heavier and therefore have a lower energy density.
What are the main components of a battery?
- Current collectors (conductive materials e.g. Cu or Al connected to the electrodes (anode and cathode) that allow the flow of electrons to the external circuit)
- Electrodes (anode often made of graphite and cathode made of a metal oxide)
- Electrolyte (medium allowing ion flow - can be solid, liquid, or a gel)
- Separator (permeable membrane that prevents direct contact between the anode and cathode while allowing the flow of ions)
- Container (holds all the components together and provides structural support and protection for the battery)
- Terminal (points of connection where the battery is connected to an external circuit to deliver or receive electrical energy)
Why do we need separators in batteries?
To separate the anode from the cathode to keep them electrically separated.
Must be porous to allow Li ions to pass back and forth between the anode and the cathode
Must be insulating to electrons.
Can be made from:
- Thin polymer films
- Ceramic
- Ceramic/polymer blends
What are current collectors typically made from?
Copper or carbon-coated Aluminium
Choice based on costs and compatibility.
What are binders in batteries?
Binders are materials that hold together the components within the battery cell, maintaining the structural integrity of the electrodes and ensuring proper electrical contact between the active materials and current collectors.
Binders are typically polymers that possess adhesive properties and chemical stability within the electrolyte environment of the battery. They help to immobilize the active materials (such as lithium cobalt oxide, graphite, etc.) onto the current collectors, preventing them from detaching or undergoing undesirable reactions during charge/discharge cycles.
Common binder materials used in lithium-ion batteries include polyvinylidene fluoride (PVDF) and its copolymers, such as PVDF-HFP (hexafluoropropylene).
What do we look for in an electrolyte?
The main requirement of an electrolyte is that it needs to be stable at the potential of the cathode and anode.
What does SEI stand for, regarding batteries?
Solid Electrolyte Interface
The SEI is the layer of electrolyte degradation products that is formed at the surface of the electrode
The SEI can be electrically conductive and/or ionically conductive.
The Solid Electrolyte Interface (SEI) is a protective layer that forms on the surface of electrodes in lithium-ion batteries, consisting of electrolyte decomposition products. It prevents further electrolyte decomposition and enables stable lithium-ion transport while allowing efficient battery operation.
What happens if the solid electrolyte interface (SEI) is electrically conductive?
Electrons will be transported to the new interface, where the electrolyte will keep degrading indefinitely.
What happens if the solid electrolyte interface (SEI) is not electrically or ionically conductive?
If a totally insulating layer is formed the degradation reaction stops, but so does the desired lithium reaction, so the battery is dead.
What happens if the solid electrolyte interface (SEI) is ionically conductive, but not electrically conductive?
This is the ideal scenario.
Since the electrons cannot be transport through the SEI, they can’t reach the electrolyte and further electrolyte degradation is not possible. At the same time, Li-ions can travel through the SEI to meet the electrons at the electrode surface and react with the electrode, so the battery is still working.
What is the ideal scenario for an battery SEI?
The solid electrolyte interface being ionically conductive but not electrically conductive is ideal.
Since the electrons cannot be transport through the SEI, they can’t reach the electrolyte and further electrolyte degradation is not possible.
At the same time, Li-ions can travel through the SEI to meet the electrons at the electrode surface and react with the electrode, so the battery is still working.
How is the SEI formed?
The Solid Electrolyte Interface (SEI) forms on the surface of lithium-ion battery electrodes through a series of electrochemical reactions between the electrolyte and the electrode materials during the initial charging and discharging cycles.
These reactions result in the deposition and rearrangement of electrolyte decomposition products, creating a thin, passivating layer that protects the electrode surface from further degradation and promotes stable battery performance.
The SEI is typically formed in the first cycle of the battery by decomposition of electrolyte at the electrode surface. The formation of the SEI prevents further degradation, but changes the energy levels.
It consists of many organic and inorganic compounds with thickness of around 20 nm.
Composition and structure depends on cathode, anode, electrolyte and cycling conditions used.
Low Coulombic efficiency due to irreversible Li consumption. Efficiently prevents further chemical reactions between electrolyte and anode.
What is LUMO and HOMO?
Lowest unoccupied molecular orbitals (LUMO) and highest occupied molecular orbitals (HOMO) of the electrolyte.
If μA of anode > LUMO of electrolyte
The electrolyte is reduced at the anode
If μC of cathode < HOMO of electrolyte
The electrolyte is oxidized at the cathode
Electrolytes have a stable operating voltage ‘window’ in which they can be cycled without degrading.
This ‘window’ is the energy gap between the lowest unoccupied molecular orbitals (LUMO) and highest occupied molecular orbitals (HOMO) of the electrolyte.
(μ is the Fermi level - A and C refer to anode and cathode)
Describe the ideal solid electrolyte interface (SEI):
- High ionic conductivity to reduce Li ion diffusion resistance.
- Appropriate thickness to allow easy diffusion of Li ions into the electrode, but prevent further electrolyte decomposition.
- Robust mechanical performance to accommodate non-uniform volume fluctuation, and withstand repeated Li deposition and plating processes.
- Excellent stability with respect to structure, shape, morphology and chemistry during long-term cycling performance.
Describe properties of the anode:
Graphite is the most common anode for Li-ion batteries
Lithium in stored via intercalation between the graphene sheets
It can store one lithium atom per 6 carbons: LiC6, with a theoretical capacity of Q=370 mAh g-1
What is the issue with having metallic Li anodes?
Metallic Li anode in the rechargeable battery is plated/stripped repeatedly upon cycling.
The initially present nucleation sites and positions contribute an imperative role in the following deposition nature/behaviour of Li.
Protrusions with large curvature possess a significantly higher electric field at their tip sites that are prone to attract more Li ions for deposition, creating more local inhomogeneity.
With repeated cycling, these finally grow into dendritic morphologies.
On repeated recharge, dendrites grew across the electrolyte from the anode to the cathode, leading to dangerous short-circuits in the cell in the presence of the flammable organic liquid electrolyte.
How can metallic Li anodes be protected?
The following approaches have been investigated to control the different reactions occurring on the lithium surface to suppress the formation of dendritic growths.
Electrolyte additives: salts, reactive organic compounds
Artificial SEI
Solid Electrolytes
Structuring the electrode architecture
Polymer coatings
Coatings with carbon materials
What does structuring the electrode architecture involve?
Providing a conductive 3D host structure which can stabilise Li metal deposition by:
- Creating a larger, favourable surface area for Li nucleation and growth,
- Providing porosity to accommodate Li metal growth,
- Regulating localised current density in the electrode.
It is done to protect the Li anode and prevent dendritic growths.
Carbon is often chosen as it is cheap, lightweight, safe, and conductive.
How are electrolyte additives (salts, reactive organic compounds) used to protect metallic Li anodes (from dendritic growths)?
Electrolyte additives can react with the metallic Li anode to form a more robust and passivating SEI film than that formed by Li salts in pure organic solvents, inhibiting further reaction between surface of Li and electrolyte. A more chemical and stable SEI can be formed.
Salt anions in nonaqueous electrolytes strongly affect the surface chemistry of metallic Li anodes.
The inner layer of SEI close to the surface of Li metal consists of inorganic salts. The composition is determined by the reduction of the anions present in solution.
LiPF6, LiSO3CF3, LiBF4 and LiTFSI salts are typically the more reactive salts with Li surface and consequently adversely influence the cycling efficiency of Li than LiClO4. The thicker interphase layers formed may lead to higher resistance, and decreased cell performance.
As the availability of salts/solvents is limited, additives that possess a higher reduction voltage compared to electrolyte salts and solvents can be employed, to contribute to stable SEI formation.
These additives are normally added in small amounts (ppm level) to the electrolyte.
Compare solid and liquid electrolytes:
Liquid:
- Poor chemical stability
- Leakage
- Flammable
- Dendrites form easily
- High ionic conductivity
Solid:
- Safe
- Chemically stable
- No leakage
- Prevent dendrite formation
- Poor ionic conductivity
Higher ionic conductivities, but brittle, and poor interfacial contact with electrodes.
What are the 2 main types of solid electrolyte?
Ceramic
Polymer
Can combine the two.
Can be true solid polymer, or gel polymer electrolytes.
PEO based.
Poly-ionic liquids.
Biopolymers.
Good interfacial adhesion with electrodes.
Poor thermal stability.
How does the formation of an artificial SEI help protect metallic Li anodes?
Essentially the formation of an artificial SEI:
By coating with a protective layer of e.g. carbon or CN.
Introducing a thin layer of SE on the electrode.
By inducing artificial SEI formation first before assembling the battery.
This prevents the formation of dendrites.
Why do Li-S systems have such high capacity?
What is the redox eq for this?
A single S atom can store 2 Li atoms, and sulphur is quite lightweight.
S + 2Li+ + 2e- ⇌ Li2S
(E° ≈ 2.15 V vs Li/Li+)
Overall conversion occurs via
formation of polysulfides Li2Sx, 8<x<1)
What are the advantages of Li-S batteries?
High theoretical capacity (1675 mAh g-1),
High theoretical specific energy (2500 Wh kg-1),
Current best is 500 Wh kg-1, compared to Li-ion 150-250 Wh kg-1,
Relatively lightweight,
Sulfur is cheap
(Likely to enter the market where mass is the critical factor above all else, e.g. unmanned aerial vehicles, space and automotive (buses and trucks, rather than consumer vehicles where volume is a constraint).
What are disadvantages of Li-S systems?
Many reaction steps needed to form Li2S
(S8 → Li2S8 → Li2S6 → Li2S4 → Li2S3 → Li2S2 → Li2S and many more)
All reaction intermediates are soluble, which means they can enter the electrolyte.
Polysulfide shuttle effect decreases capacity and rechargeability
Large volume expansion from S to Li2S,
Slow kinetics from Li2S2 to Li2S
Uncontrolled Li2S precipitation
Large amount of electrolyte needed
Not compatible with conventional organic carbonate electrolytes
Extremely low electrical conductivity of sulfur (5 × 10-30 S cm-1 at 25°C)
Formation of lithium dendrites
How can issues with Li-S systems be managed?
- Using separators
A functional separator interlayer can:
- Physically block or trap polysulfides to minimise the shuttle effect by tailoring nanostructure,
- Chemically trap polysulfides by introducing functional groups or dopants,
- Contain catalysts to accelerate polysulfide conversion to reduce shuttling.
- Using carbon-sulphur composite cathodes
Carbon provides:
- Conductivity,
- Structural scaffold,
- Trapping sites for S and polysulfides,
- Catalytic/functional surface.
- As cathode conversion reactions involve dissolution and precipitation of active material species, electrolyte plays a much more active role than just providing ionic transport between electrodes.
How is energy density (Wh/kg) of a Li-S system calculated?
E = Q.sVM.s / M.tot
How can specific energy in Li-S batteries be maximised?
Maximise sulfur loading:
Higher sulfur loading increases the areal capacity of the cathode (mA h cm2),
Increased fraction of active material offsets the ‘dead weight’ of inactive components,
However, the coating and drying processes are problematic for thick electrodes, and thicker electrodes result in increased ionic and electronic resistance, and therefore lower rate capability.
Reduce electrolyte loading:
Electrolyte contributes the highest weight and volume fraction of the cell components and has a huge impact on specific energy at cell level.
Reduce/eliminate weight of other inactive components (e.g. current collector, binder).
How is sulphur utilisation found?
Sulfur use = m (s used) )/ m (s total) =Q (practical) / Q (theoretical)
Sulfur utilisation can be affected by many factors including porosity, surface area, morphology, electrolyte loading.
Achieving high sulfur loadings is not necessarily always desirable, if full conversion to Li2S does not occur:
- Unutilised sulfur can cover and passivate the carbon surface, blocking charge transfer reactions,
- Unused sulfur adds mass to the cell without contributing capacity, decreasing energy density.
Why is water a bad electrolyte for Li batteries?
- Highly reactive with Li
- Water can corrode the electrodes and other components of the battery. Lithium reacts with water to form lithium hydroxide and hydrogen gas.
- Pure water has poor conductivity for ions compared to other electrolytes commonly used in Li-ion batteries, such as lithium salts dissolved in organic solvents like ethylene carbonate (EC) or dimethyl carbonate (DMC).
Why may electrolyte additives be used?
Flame retardant
SEI formation improvement and improved recyclability by suppressing anodic decomposition
Cathode protection
Improve thermal stability
Improve wettability
Improve corrosion resistance
How may carbon materials be used as supports for sulphur cathodes in rechargeable batteries?
Physical Confinement:
1. Hierarchical Porosity: Refers to the structure of the carbon material, which contains pores at different length scales (macro, meso, and micropores). This structure helps accommodate the volume changes that occur during the charge-discharge cycles of the battery.
- Yolk-Shell Structure/Encapsulation: This involves enclosing the sulfur within a carbon shell (yolk-shell structure), which helps to prevent the dissolution of sulfur into the electrolyte and improves the stability of the electrode.
- Capillary Absorption of Sulfur Species Through Porosity: The porous nature of the carbon material allows for the absorption and retention of sulfur species, which is beneficial for the battery’s performance.
- Polymeric Coating: Coating the carbon material with a polymer can further enhance the stability and performance of the electrode by providing additional protection and preventing the dissolution of sulfur.
Chemical Confinement:
1. Heteroatom Doping (N, O): Introducing heteroatoms such as nitrogen (N) and oxygen (O) into the carbon structure can modify its properties, such as increasing its conductivity and enhancing its interaction with sulfur species.
- Catalyst Decoration/Metal Additives: Adding catalysts or metal additives to the carbon material can improve the kinetics of the electrochemical reactions, leading to better battery performance.
- Directed Nucleation: Controlling the nucleation of sulfur species on the carbon surface can help prevent the formation of undesirable products and improve the stability of the electrode.
What are the 3 main points of the energy trilemma?
Sustainability
Energy equity
Energy security
The 2 main options to increase sustainability are battery recycling and different battery chemistry.
Why use Na ion batteries?
Na itself is cheaper and more abundant
We can use Al instead of Cu as current collector (more abundant, cheaper, and lighter, though less conductive)
[Potential to provide energy at 23/kWh/annum, less than half the cost of LIBs and a quarter that of lead-acid systems of the same size.]
The electrode materials can be cheaper and more sustainable
It is similar to Li-ion batteries (Same manufacturing and technology for development)
Not as good as lithium in terms of performance, but second lightest atom in the 1st group and Sodium’s standard redox potential is only 340 mV higher than Li+/Li.
Describe Na ion battery performance:
Sodium has:
Higher standard redox potential
Higher ionic radius
Is heavier than lithium?
Cell potential is lower to overall power will be lower.
Larger ionic radius makes it harder for diffusion.
Regarding insertion into electrode material, it will be harder as the ions are bigger and bulkier.
[all compared to Li]
Sodium’s higher standard redox potential (Na -2.71 V vs Li -3.04 V) and larger ionic radius (Na+ 1.02 Å vs Li+ 0.76 Å) generally mean that the capacity and voltage achieved will be lower, therefore projected energy density will be lower.
Pros and Cons of Na ion batteries (compared to Li):
Advantages of Na-ion:
Sodium is more abundant and cheaper than lithium
Can use hard carbon anions, instead of graphite used in Li-ion.
Do not require cobalt in the cathode
Can replace Cu with Al as current collector
Overall cheaper
Disadvantages of Na-ion:
Na-ion batteries have a shorter cycle life than Li-ion
Lower gravimetric energy density
Lower volumetric energy density
Graphite is a widely-used anode material for lithium-ion batteries. However, Na-ions do not intercalate into graphite due to the larger ion size.
NIB electrodes show slightly lower specific capacities than those for LIB, resulting in lower energy density. Therefore, the cost reduction is not significant in terms of the cost per energy.
What are Na ion batteries good for?
Large-scale stationary energy storage and low-speed electric vehicles, despite lower energy density (than Li).
This is due to the lower cost and greater abundance.
To be competitive with Li-ion, improvements must be made in terms of cycle life and they must be easy to manufacture at larger scale.
Anode materials with high specific capacities and appropriately low redox potentials to improve the energy density of NIBs could replace LIBs.
What may tin, Sn, be used for in batteries?
Metallic Sn is one of the most intensively investigated anode material for room-temperature NIBs, due to its ability to alloy up to 3.75 Na per Sn, corresponding to the high theoretical capacity of 847 mA h g−1.
Sodiation (replacement of metal ions (typically lithium) with those of sodium) of Sn is a multi-step alloying process.
However Sn prone to huge volumetric expansion (420%) which causes cracking and capacity fading.
How can tin anodes be protected to avoid damage from volume expansion (which leads to pulverisation and loss of electrical contact)?
Can coat Sn particles with various protective films, introduce additives into electrolyte e.g. FEC.
Particle size control - smaller particles can better accommodate volume expansions
Dispersion in carbon matrix -: for examples depositing tin on carbon nanofibers
Particle encapsulation - for example in a bigger carbon particle, so that if the Sn expands it still has space
Co-alloying to buffer volume changes - Other alloying materials: Sb, P, Ge, Bi, Si
Structured electrodes to accommodate volume change
Pros and cons of sodium titanates, used for anodes in Na batteries:
Pros:
Abundant and low cost,
Non-toxic,
Stable,
Low operation voltage,
Low strain,
Decent cyclability depending on the specific compound,
Cons:
Low specific capacity,
Low electrical conductivity,
Poor ion diffusivity.
How do Na ion battery cathodes store ions?
Most cathode materials store Na+ions by intercalation chemistry, which means that the number of storage sites is limited.
This suggests that it will be difficult to greatly increase the specific capacity of the cathode materials.
The use of cathode materials with high redox potentials is also limited because of electrolyte decomposition at high potentials.
Most commercialized electrolytes even for Li‐ion batteries are unstable and decompose at over 4.8 V versus Li/Li+.
What are the 3 main Na ion battery cathode families?
Oxides
Polyanions
Prussian Blue Analogue (PBA)
How do layered oxides compare to polyanions for Na ion battery cathodes?
Oxides were initially pursued because of their dominance in Li-ion batteries.
Na-based layered oxides show even richer crystal chemistry than Li-ion ones because Na ions can reside in more lattice sites.
However, they are more prone to structural phase transitions, reducing lifetime and limiting power density.
Meanwhile with polyanions, there is power switching from Li to Na for polyanion compounds due to open channels for ion diffusion.
However, it relies on the use of toxic vanadium.
How does the solid electrolyte interphase (SEI) compare for LIBs and NIBs?
Cycling performance of NIBs still doesn’t compare to LIBs, implying continual consumption of electrolyte and an unstable SEI:
- Less compact layer,
- More resistive,
- Mechanically less robust,
- More soluble?
Factors affecting the SEI:
Type of solvent,
Type of salt,
Charging rate,
Temperature of formation.
Comment on the use of K-ion batteries:
Similar redox potential to Li+ (-2.94 vs -3.04 V).
Larger ion size, lower energy density.
Fast ion diffusion – potentially faster charging batteries.
K+ can intercalate into graphite (unlike Na+) ~279 mAh g-1.
Combining graphite with soft carbon provides structural protection enhancing cycling behaviour.
Challenges:
Low capacity retention.
Need rigid cathode structures that can accommodate stable and repeatable K+ ion insertion.
High Lewis acidity of potassium results in fast electrolyte degradation.
Need electrolytes that can operate in the higher voltage window.
What are the main steps in battery recycling?
Disassembly and discharging (onto direct recycling involving delamination and regeneration)
Shredding
Mechanical separation (onto indirect recycling involving hydrothermals, drying, and relithation)
Hydrometallurgy (leaching, extraction, Li precipitation)
Pyrometallurgy (heating and slag separation)
Describe discharge in battery recycling and its pros and cons:
Discharge is the process of closing the battery circuit, allowing it to reach a stable open circuit voltage, to avoid short-circuiting later on.
Pros:
Takes electricity out of cells making them safe
Mature and safe
Electricity can be returned to the grid
Ni need for Li neutralization
Cons:
Only valid for large modules and packs
Li redeposition can occur if discharged too fast
Prone to thermal run away
Describe shredding in battery recycling and its pros and cons:
In the indirect route, the cells are shredded and mechanically separated to obtain a black mass, composed of cathode and anode material
Pros:
Easy and fast to do
Cons:
Purity of recovered material is intrinsically lower
Describe freezing in battery recycling and its pros and cons:
Another pre-treatment process is freezing, which consists of putting the cell in liquid nitrogen to freeze the electrolyte.
Pros:
Frozen in liquid N2 where the electrolyte becomes unreactive
Cons:
Only suitable for batch processes
Scale up difficult
Expensive reagents needed
Short processing time until the cells become active again
Describe pyrometallurgy in battery recycling and its pros and cons:
In the pyrometallurgy route, the black mass (which contains all the active cathode and anode material) is exposed to high temperature, to remove carbon, binders, solvents etc.
What is left is a lithium-rich slag and an alloy containing Ni, Co etc.
Pros:
Allows charged cells to be processed
Burns off the electrolyte taking away the biggest hazard
Mature and scalable
No post process neutralization
Makes the hydrometallurgical process easier
Cons:
Inert atmosphere required-costly
Large quantity of toxic gases and extensive scrubbing is needed to treat them
vaporized electrolyte forms explosive mixture
Low recovery efficiency and you can’t recover electrolyte and graphite, as they combust
Large input of energy required
CO2 emission via combustion processes
Al current collectors will melt at these temperatures
Describe hydrometallurgy in battery recycling and its pros and cons:
Hydrometallurgy is a leaching process, done with a variety of acid or alkaline solutions.
By adding other chemical precipitants or extractants, metals such as Co, Mn and NI can be separated via precipitation, extraction or adsorption.
Pros:
Higher recovery purity of active materials
Lower energy consumptions and lower emission of toxic gases compared to pyrolymetallurgy
Cons:
Highly corrosive solvents needed for the extraction
It requires longer pre-treatment compared to direct recycling
Describe direct recycling in battery recycling and its pros and cons:
In the direct route, the battery cells are disassembled down to the individual electrodes. The separated electrodes can be then subject to delaminiation process (for example soaking in organic solvent) to separate the active material from the current collector.
Pros:
Higher Purity of the materials recovery
Higher collection efficiency
Lower energy consumption
Fewer chemicals required
Cons:
Longer pre-treatment process
It needs cells to be designed for easier disassembling
What is the future of Li battery recycling:
Materials:
- Biodegradable binders
- No current collectors
- No critical materials
- Single crystal cathodes
Electrode/cell:
- Aqueous formulations
- Standardisation
- Digital materials labels
- Screw cap cells
Pack/module:
- No glues
- Design for disassembly
- Cell labels with components
- Easy lock release
What is grey, blue, and green hydrogen?
Grey: Hydrogen from reforming and gasification technology using natural gas and coal, with emission significant amount of CO2 in the atmosphere
Blue: Similar to grey but with incorporation of CCS. Advanced reforming technology
producing blue hydrogen from
natural gas and biomass, with most CO2 emissions captured by carbon capture and storage (CCS).
Green: Electrochemical or photochemical technology using electricity or solar power to produce green hydrogen, which is highly flexible and stores hydrogen by capturing excess generation.
Compare grey, blue, and green hydrogen:
Grey is from reforming and gasification of fossil fuels. Blue is similar but with CCS. Green is from electricity/solar power (e.g. electrolysis).
Grey hydrogen is the cheapest option (€1.50/kg), but CO2 emissions may make grey hydrogen more costly
Blue hydrogen can narrow the gap
Green hydrogen it the cleanest but it’s price depends on renewable electricity and electrolysis system
What are the main drivers for switching to electrochemical hydrogen production?
- Use renewable energy (wind, solar, etc)
- Fossil fuel free
- No CO2 emission during the process
- Low temperature, low pressure
- Decentralised, on-demand on-site chemical synthesis
- Fast start-up and shut-down
What are the issues with implementing a hydrogen economy at this stage?
High cost in H2 production
Challenges in Safe Storage
Transportation and distribution
Social awareness
Competition with other energy
Sources and storage systems
What are the 2 main hydrogen storage methods?
- REVERSIBLE ON-BOARD APPROACHES
Compressed gas
Liquefied hydrogen
Metal Hydrides
High surface area porous materials - CHEMICAL HYDROGEN STORAGE: REGENERABLE OFF-BOARD
Hydrolysis reactions
Hydrogenation/dehydrogenation reactions
Ammonia
Boron hydrides
What are the limitations with using compressed hydrogen gas for H2 storage?
Volumetric capacity (0.039 kg/L at 700 bar)
Limits of high pressure
Costs
Refueling or filling time
Compression energy penalty (15-20% less than atmospheric pressure hydrogen)
Heat management requirements