Next Generation Powering Solutions: Novel battery materials and functionalities

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Next Generation Powering Solutions:

Novel battery materials and functionalities

27.10.2021 Marja Vilkman

27/10/2021 VTT – beyond the obvious

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 Introduction & motivation

 Battery materials & their predicted demand

• The conventional Li-ion battery

• Battery generations

• Beyond lithium-ion batteries

 Batteries & sufficiency of materials

• Circular economy

• Longer lifetime

• Renewable materials

Contents

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The European Green Deal targets carbon neutrality in Europe by 2050.

Premature deaths

Extinction of species

Severe economic

losses Problems

with access to water

Flooding And if we do not act now, we see rising temperatures and…

https://ec.europa.eu/info/strategy/priorities-2019-2024/european-green-deal/actions-being-taken-eu_en

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VTT – beyond the obvious https://ec.europa.eu/eurostat/cache/infographs/energy/bloc-4a.html

Man-made GHG emissions are primarily a by-product of burning of fuels in power

plants, cars or homes.

25/8/2021

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Clean energy storage is needed!

VTT – beyond the obvious

CO₂ CO₂

CO₂

CO₂ CO₂

We have the

technologies – but how to take them widely in

use? And do we have enough materials?

25/8/2021

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 Batteries are needed for

• Electric vehicles

• Stationary energy storage, e.g. to store energy from solar and wind parks

• Portable & consumer electronics

Energy storage applications

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Battery materials

& their predicted demand

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The predicted battery demand

3 World Economic Forum, M. analysis. A Vision for a Sustainable Battery Value Chain in 2030 Unlocking the Full Potential to Power Sustainable Development and Climate Change Mitigation.

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Li-ion battery, the most used battery type

→ Which materials it contains and how much?

Separator

Cu current collector Al current collector

Copper

→ 17%

Binders (e.g. PVDF)

& conductive additive (carbon black) → 4%

Cathode active material, e.g. metal oxide → 31%

Aluminum

→ 8%

Usually porous plastic → 3%

Electrolyte solution → 15%

Anode active material, e.g. graphite → 22%

25/8/2021

Invented 50 years ago and the inventors, John B. Goodenough, M. Stanley Whittingham and Akira Yoshino, were awarded a Nobel price in chemistry in 2019.

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Battery

generations

Current and near future chemistries

Information taken from Batteries Europe –

Strategic Research Agenda for batteries 2020

https://ec.europa.eu/energy/sites/default/files/documents/batteries_europe_strategic_research_agenda_december_2020__1.pdf

LFP= Lithium iron phosphate

NCA = Lithium nickel cobalt aluminium oxide NMC = Lithium nickel manganese cobalt oxide

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Li-metal battery as an alternative for Li-ion battery

→ Higher energy density

Li metal as the anode instead of graphite

Thin Li metal Al current collector

Cu current collector Separator

Cu current collector Al current collector

Li metal battery Li-ion battery

Electrolyte as the separator

25/8/2021

Li metal batteries might replace some (or most?) of the Li-ion batteries in electric vehicles once the safety and lifetime issues have been solved. Research ongoing.

Note: For stationary energy storage, high energy density is not needed – price and long lifetime are more important.

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Na-ion battery as an alternative for Li-ion battery

→ Lower energy density but more abundant materials

Image from: https://renewablesnow.com/news/energy-innovator-introducing-altris-726974/

Very similar to Li-ion battery but uses Na ions instead of Li ions.

Suitable e.g. for stationary storage

applications where high energy density is not that important.

Several cathode materials for Na-ion batteries are studied.

One example is the Fennac® material by Altris from Sweden.

https://www.altris.se/

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Batteries &

sufficiency of materials

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 Annual energy storage demand is expected to increase from 200 GWh to 10 000 GWh in 20 years

 Energy storage solutions are needed to

fight against climate change, e.g. for electric vehicles and stationary energy storage

Motivation

We have the technologies - but do we have enough materials?!?

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Periodic table representing element scarcity

Important battery materials:

Cobalt Lithium Nickel Copper Aluminum Manganese

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The critical raw materials (CRMs)

CRMs combine raw materials of high importance to the EU economy and of high risk associated with their supply

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Is there enough natural resources?

→ What if we replace all cars with electric vehicles

Report by Simon Michaux, GTK:

https://tupa.gtk.fi/raportti/arkisto/42_2021.pdf

Limited resources!

Note: Assuming that all EV batteries would be Li-ion batteries

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How to enable sufficiency of materials?

Renewable materials

Longer

lifetime

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Circular chemistry to enable a

circular economy

Linear economy does not enable a

sustainable future. We do not have any other choice than to transfer to circular economy &

chemistry.

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Circular economy of battery materials

Value chain image from: https://www.eba250.com/about-eba250/value-chain/

Mining Renewable materials

Compostable materials

Other materials Waste streams

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Case example: How to increase the battery lifetime?

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Li metal battery would give the highest energy

density and would help to increase the amount of electric vehicles due to longer driving range

Li dendrites, which grow cycle by cycle… Leading to short circuit.

Li⁺ Li⁺ Li⁺ Li⁺

Li⁺ Li⁺

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 Some solutions, focusing e.g. on electrolytes, have been tested but so far Li metal batteries are not yet seen in electric vehicles

 Can functional materials help…? YES!

• → I’ll show you a few examples, which we are testing in an ongoing EU project, HIDDEN – Hindering dendrite growth in Li metal batteries

How to prevent the dendrite formation?

• High conductivity

• Safety issues, dendrite growth

Liquid electrolyte

• Safe-by-design & tunable mechanical properties

• Low conductivity

Gel & polymer electrolyte

• Safety & high conductivity

• Expensive processing & mechanically instable interfaces (cracks, voids…)

Solid state inorganic electrolyte

The optimal electrolyte for Li

metal batteries is yet to be developed.

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Utilizing liquid crystalline electrolytes to hinder dendrite growth

Potential for high ionic conductivity (due to nanoconfined Li+ transport within prescribed (1D/2D/3D) morphologies) and dendrite prevention.

Molecular structure and electrolyte composition to be optimized through modeling and artificial intelligence approaches.

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Utilizing piezoelectric separator to hinder dendrite growth

Processing, poling and optimal composition to be developed in HIDDEN.

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Biobased & renewable battery materials

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 All kinds of (waste) biomass may be carbonized and used in anodes of lithium- or sodium-ion batteries, cathodes in metal–sulfur or metal–oxygen batteries, or as conductive additives.

 A plethora of biomolecules, such as quinones, flavins, or carboxylates, contain redox-active groups that can be used as redox-active components in electrodes with very little chemical modification.

 Biomass-based binders can replace toxic

halogenated commercial binders to enable a truly sustainable future of energy storage devices.

 Besides the electrodes, electrolytes and separators may also be synthesized from biomass.

Bio-based batteries

First examples of biomass derived electrodes in year 2008

REVIEW: C. Liedel, “Sustainable Battery Materials from Biomass” ChemSusChem 13 (2020) 2110-2141

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 Synthetic graphite

• Produced as a side product in oil refineries → Environmental issues

• High purity

 Natural graphite

• Mined, mainly in China (>60%) → Environmental, ethical and supply chain issues

• Lower purity

• Listed as a critical raw material (CRM) in Europe

 Nowadays used ~50:50 in batteries, often also mixed together

 European mines e.g. in Finland & Sweden:

Currently used carbon types in batteries

https://beowulfmining.com/projects/fennoscandian-finland-graphite/

https://www.talgagroup.com/irm/content/graphite.aspx?RID=275

Used in the anode in a Li-ion battery

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 We will need so much carbon in batteries that we need to use all available options

Estimations on Li-ion battery production and graphite consumption

GRAPHITE CONSUMPTION FORECAST (2020 – 2030) Source: Roskill – Natural & Synthetic Graphite: Outlook to 2030

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Natural graphite markets

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Schematic representation of a softwood lignin structure

(Brunow et al., 1998)

Building blocks of lignin

p-Coumaryl alcohol (H)

Coniferyl alcohol (G)

Sinapyl alcohol (S)

Wood structure

Lignin accounts for 15–30% of the biomass

Phenolic lignin is valuable renewable raw material for the chemicals, fuels and materials to replace the present oil based products

Pulp mills and biorefineries fractionate biomass and produce lignin as a by-stream

We can make biocarbon to be used instead of graphite e.g.

from lignin from wood!

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 The carbon material, which is derived from biobased sources (e.g.

from lignin) is called hard carbon

 The “mainstream” carbon material in batteries is called graphite (natural or synthetic)

What kind of carbon material we will get from lignin?

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Comparison of properties between

natural/synthetic graphite and hard carbon (e.g. lignin-based carbon)

Xiao et al. 2018, ChemSusChem: https://doi.org/10.1002/cssc.201801879 Note: Hard carbon is optimal for Na-ion batteries! Na⁺is a bigger ion than Li⁺and needs more space to move between the graphene sheets.

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Hard carbon can be successfully produced from a wide range of biomass, making it especially interesting from a sustainability and circular economy viewpoint.

Alternative sources for hard carbon, in addition to lignin

Sustainable Potassium-Ion Battery Anodes Derived from Waste-Tire Rubber:

https://iopscience.iop.org/article/10.1149/2.1391706jes

Engineering Carbon Materials from the Hydrothermal Carbonization Process of Biomass:

https://onlinelibrary.wiley.com/doi/10.1002/adma.200902812

Peanut shell derived hard carbon as ultralong cycling anodes for lithium and sodium batteries:

https://www.sciencedirect.com/science/article/pii/S0013468615301262?via%3Dihub

Low-Cost and High-Performance Hard Carbon Anode Materials for Sodium-Ion Batteries (mangosteen shell): https://pubs.acs.org/doi/10.1021/acsomega.7b00259

High capacity hard carbon derived from lotus stem as anode for sodium ion batteries:

https://www.sciencedirect.com/science/article/pii/S0378775317316622?via%3Dihub

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 Li-based batteries will remain the mainstream chemistry especially for EVs. There are a lot of investments and LIB gigafactories are built.

• High Ni-content NMC cathode and Li-metal batteries for higher energy density and longer driving range

• LFP to cope with material availability, even though energy density is not high (e.g. Tesla!)

 Na-ion batteries will provide a near future option for LIBs, especially for stationary storage applications

 Other (emerging) options exist as well, e.g. organic radical batteries. Even though their energy density might not be extremely high, they have potential for fast

charging. In addition, they do not need mining to produce the materials.

Future outlook

Novel chemistries are needed to overcome the issues with the LIB materials.

Cathode materials, like cobalt, have the biggest problems with sustainability, availability, ethical production/mining, price volatility etc.

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 The Li-ion battery chemistries and their developers have enabled a greener future for us

• There are anyway issues with battery material

sufficiency, and societal and environmental concerns with mining

 A single battery chemistry won’t be enough for all applications

 Now it is our turn to lead the revolution to

• Develop long-lasting batteries

• Transfer from linear economy to circular economy

• Develop sustainable battery materials, which can be derived even from waste and biomass

Concluding words

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Marja Vilkman

[email protected] +358 50 3586644

@VTTFinland

@MarjaVilkman

www.vtt.fi