SMaRT MICROfactories adding value by creating circular … · 2020. 9. 23. · Maroufi, S., Nekouei, R. K., Hossain, R., Assefi, M., & Sahajwalla, V. (2018). Recovery of Rare Earth

SMaRT MICROfactories® adding value

by creating circular economies for

battery materials

Australian Research Council (ARC) Laureate Fellow

Director, ARC Microrecycling Hub

Director, Centre for Sustainable Materials Research & Technology

Director, NSW Circular

Scientia Professor Veena Sahajwalla

Centre for SMaRT@UNSW

Research Focus: Cutting edge sustainable materials & processes

Emphasis: Environmental, Social & Economic benefits

Recycling and

Materials

Transformations

New

Technologies

and Products

Sustainability of

materials

processes

Green

Manufacturing and

Translational

Research

Industry and Research partnerships

The SMaRT Vision

• Convert waste materials into

high-value materials

• Minimise the energy-intensive

transportation of waste

• Promote and support viable

local economies and jobs

• An embodiment of distributed

manufacturing

MICROfactorie®:

a SMaRT Solution

• Demonstrated safe

transformation of waste

• Market an Australian solution to

a rapidly growing international

problem

• Unlock the value embedded in

waste

• Establish how MICROfactories®

could work in the global value

chain

Handheld Battery Market in Australia

Battery End-of-Life

Arisings 2050 by chemistry

(Arisings: collected for recycling, disposal or stored)

Australian Battery Market Analysis (2020) Envisage

Works on behalf of the Battery Stewardship Council

Valuable metals in waste batteries

Valuable metals Nickel Cobalt Manganese Zinc Lithium Copper Aluminium

Amount present

in waste batteries

((Kg/ton)

~200 (Ni-MH)

~15 (Li-ion)

~30 (Ni-MH)

~200 (Li-ion)

~100 (Zn-C)

~200 (Alkaline)

~200 (Zn-C)

~120 (Alkaline)~30 (Li-ion) ~160 (Li-ion) ~50 (Li-ion)

Ref. www.reuters.com/article/us-southkorea-mining/urban-mining-in-south-korea-pulls-rare-

battery-materials-from-recycled-tech-idUSKBN1HJ14T

Handheld battery flow: Australia 2017-18

Australian Battery Market Analysis (2020) Envisage

Works on behalf of the Battery Stewardship Council

Selective thermal synthesis: Microrecycling &

MICROfactorie ® technology

MICROfactorie ® technology: Martials Microsurgery (MM)

Discovering selective thermal transformation for synthesis of materials from waste

Enabling multiple reactions and micromechanisms to harness the selective synthesis of

various value added materials

Selective thermal synthesis (STS) of Microrecycling pathways: Thermal “Nanosizing”,

“Isolation”, “Micronizing”; “Nanowiring”, “Disengagement”, etc.

Select Publications (STS):

Farzana R; Rajarao R; Hassan K; Behera PR; Sahajwalla V, 2018, 'Thermal nanosizing: Novel route to synthesize manganese oxide and zinc

oxide nanoparticles simultaneously from spent Zn–C battery', Journal of Cleaner Production, vol. 196, pp. 478 - 488,

http://dx.doi.org/10.1016/j.jclepro.2018.06.055

Farzana R; Rajarao R; Behera PR; Hassan K; Sahajwalla V, 2018, 'Zinc oxide nanoparticles from waste Zn-C battery via thermal route:

Characterization and properties', Nanomaterials, vol. 8, http://dx.doi.org/10.3390/nano8090717

Farzana R; Sayeed MA; Joseph J; Ostrikov K; O'Mullane AP; Sahajwalla V, 2020, 'Manganese Oxide Derived from a Spent Zn–C Battery as a

Catalyst for the Oxygen Evolution Reaction', ChemElectroChem, vol. 7, pp. 2073 - 2080, http://dx.doi.org/10.1002/celc.202000422

Maroufi S; Nekouei RK; Hossain R; Assefi M; Sahajwalla V, 2018, 'Recovery of Rare Earth (i.e., La, Ce, Nd, and Pr) Oxides from End-of-Life

Ni-MH Battery via Thermal Isolation', ACS Sustainable Chemistry and Engineering, vol. 6, pp. 11811 - 11818,

http://dx.doi.org/10.1021/acssuschemeng.8b02097

Maroufi S; Khayyam Nekouei R; Sahajwalla V, 2017, 'Thermal Isolation of Rare Earth Oxides from Nd-Fe-B Magnets Using Carbon from

Waste Tyres', ACS Sustainable Chemistry and Engineering, vol. 5, pp. 6201 - 6208, http://dx.doi.org/10.1021/acssuschemeng.7b01133

Behera PR; Farzana R; Sahajwalla V, 2020, 'Reduction of oxides obtained from waste Ni-MH battery's positive electrode using waste plastics

to produce nickel based alloy', Journal of Cleaner Production, http://dx.doi.org/10.1016/j.jclepro.2019.119407

Maroufi S; Assefi M; Khayyam Nekouei R; Sahajwalla V, 2020, 'Recovery of lithium and cobalt from waste lithium-ion batteries through a

selective isolation-suspension approach', Sustainable Materials and Technologies, vol. 23, http://dx.doi.org/10.1016/j.susmat.2019.e00139

Hossain R; Nekouei RK; Mansuri I; Sahajwalla V, 2019, 'Sustainable Recovery of Cu and Sn from Problematic Global Waste: Exploring Value

from Waste Printed Circuit Boards', ACS Sustainable Chemistry and Engineering, http://dx.doi.org/10.1021/acssuschemeng.8b04657

Al Mahmood A; Hossain R; Sahajwalla V, 2020, 'Investigation of the effect of laminated polymers in the metallic packaging materials on the

recycling of aluminum by thermal disengagement technology (TDT)', Journal of Cleaner Production, vol. 274, pp. 122541 - 122541,

http://dx.doi.org/10.1016/j.jclepro.2020.122541

Selective thermal synthesis: Microrecycling &

MICROfactorie ® technology

http://dx.doi.org/10.1016/j.jclepro.2018.06.055http://dx.doi.org/10.3390/nano8090717http://dx.doi.org/10.1002/celc.202000422http://dx.doi.org/10.1021/acssuschemeng.8b02097http://dx.doi.org/10.1021/acssuschemeng.7b01133http://dx.doi.org/10.1016/j.jclepro.2019.119407http://dx.doi.org/10.1016/j.susmat.2019.e00139http://dx.doi.org/10.1021/acssuschemeng.8b04657http://dx.doi.org/10.1016/j.jclepro.2020.122541

Selective thermal synthesis: Microrecycling &

MICROfactorie ® technology

Select Publications (MM):

Hossain R; Sahajwalla V, 2020, 'Material Microsurgery: Selective Synthesis of Materials via High-Temperature Chemistry for Microrecycling of

Electronic Waste', ACS Omega, http://dx.doi.org/10.1021/acsomega.0c00485

Hossain R; Pahlevani F; Cholake ST; Privat K; Sahajwalla V, 2019, 'Innovative Surface Engineering of High-Carbon Steel through Formation of Ceramic

Surface and Diffused Subsurface Hybrid Layering', ACS Sustainable Chemistry and Engineering, vol. 7, pp. 9228 - 9236,

http://dx.doi.org/10.1021/acssuschemeng.9b00051

Hassan K; Farzana R; Sahajwalla V, 2019, 'In-situ fabrication of ZnO thin film electrode using spent Zn-C battery and its electrochemical performance

for supercapacitance', SN APPLIED SCIENCES, vol. 1, http://dx.doi.org/10.1007/s42452-019-0302-1

Yin S; Rajarao R; Kong C; Wang Y; Gong B; Sahajwalla V, 2017, 'Sustainable fabrication of protective nanoscale TiN thin film on a metal substrate by

using automotive waste plastics', ACS Sustainable Chemistry and Engineering, vol. 5, pp. 1549 - 1556,

http://dx.doi.org/10.1021/acssuschemeng.6b02253

Pahlevani F; Kumar R; Gorjizadeh N; Hossain R; Cholake ST; Privat K; Sahajwalla V, 2016, 'Enhancing steel properties through in situ formation of

ultrahard ceramic surface', Scientific Reports, vol. 6, http://dx.doi.org/10.1038/srep38740

Kumar R; Nekouei RK; Sahajwalla V, 2020, 'In-situ carbon-coated tin oxide (ISCC-SnO2) for micro-supercapacitor applications', Carbon

Letters, http://dx.doi.org/10.1007/s42823-020-00142-0

Kumar, R., Soam, A., Hossain, R., Mansuri, I., & Sahajwalla, V. (2020). Carbon coated iron oxide (CC-IO) as high performance electrode material for

supercapacitor applications. Journal of Energy Storage, 32, 101737. https://doi.org/10.1016/j.est.2020.101737

Gaikwad V; Ghose A; Cholake S; Rawal A; Iwato M; Sahajwalla V, 2018, 'Transformation of E-Waste Plastics into Sustainable Filaments for 3D

Printing', ACS Sustainable Chemistry and Engineering, vol. 6, pp. 14432 - 14440, http://dx.doi.org/10.1021/acssuschemeng.8b03105

You Y; Mayyas M; Xu SONG; Gaikwad V; Munroe P; Sahajwalla V; Joshi RK, 2017, 'Growth of NiO Nanorods, SiC Nanowires and Monolayer Graphene

Via a CVD Method', Green Chemistry, vol. 19, pp. 5599 - 5607, http://dx.doi.org/10.1039/C7GC02523H

http://dx.doi.org/10.1021/acsomega.0c00485http://dx.doi.org/10.1021/acssuschemeng.9b00051http://dx.doi.org/10.1007/s42452-019-0302-1http://dx.doi.org/10.1021/acssuschemeng.6b02253http://dx.doi.org/10.1038/srep38740http://dx.doi.org/10.1007/s42823-020-00142-0https://doi.org/10.1016/j.est.2020.101737http://dx.doi.org/10.1021/acssuschemeng.8b03105http://dx.doi.org/10.1039/C7GC02523H

(a) Schematic representation of a typical Zn-C battery and (b) Different components

ANODE

CATHODE

Spent zinc carbon battery

Synthesis of manganese oxide & zinc oxide nanoparticles

from spent Zinc-Carbon battery

R. Farzana, R. Rajarao, PR. Behera, K. Hassan, V. Sahajwalla, Thermal nanosizing: Novel route to

synthesize manganese oxide and zinc oxide

nanoparticles simultaneously from spent Zn-C battery (2018), Journal of Cleaner Production, 196, 478-488.

Manganese oxide & Zinc oxide nanoparticles are recovered

from waste batteries using “thermal nanosizing”

Image of zinc oxide nanoparticles from a spent zinc carbon

battery in fabrication of a high-performance supercapacitor

Hassan, Kamrul, Rifat Farzana, and Veena Sahajwalla. "In-situ fabrication of ZnO thin film

electrode using spent Zn–C battery and its electrochemical performance for supercapacitance." SN

Applied Sciences 1.4 (2019): 302.

Feedstock: Electrolytic Zinc (Purified Zinc)

Melted and vaporized into Zinc vapor (950-1300˚C)

Oxygen is added to vapor in combustion zone (500-800 ˚C)

ZnO (High purity, Smaller particle size)

Feed material – Oxidized Zinc ore

concentrates

Reduction by carbonaceous agent

ZnO + C → Zn + CO ΔG1000C = -5.94 kj/molZnO + CO → Zn + CO2 (T>1317˚C, ΔG is negative)

Zinc metal and vaporization

Oxygen is added to vapor in the combustion

zone

ZnO (Less purity, Production cost is low)

Moezzi, A., McDonagh, A.M., Cortie, M.B., 2012. Zinc oxide particles: Synthesis, properties and

applications. Chemical Engineering Journal 185-186, 1-22.

▪ Hydrothermal route uses zinc containing

materials like Zn(NO3)2, ZnSO4 etc.

followed by solvent extraction,

precipitation processes.

▪ Small Scale

▪ Produce by products

Conventional ZnO Production

French Process (indirect process) American Process (direct process)

Lithium-ion battery

Ref. (a) & (b) X. Zhang, J. Li, N. Singh, Crit. Rev. Environ. Sci. Technology 44 (2014) 1129-1165.

(a) Classification of LiBs sections based on average weight, (b) Main section of LIBs

Chemical name Material Abbreviations Applications

Lithium cobalt oxide LiCoO2 LCO Cell phones, laptops, cameras

Lithium manganese oxide LiMnO2 LMO Power tools, Evs, medical,

hobbyist

Lithium iron phosphate LiFePO4 LFP Power tools, Evs, medical,

hobbyist

Lithium nickel manganese cobalt

oxide

LiNiMnCoO2 NMC Power tools, Evs, medical,

hobbyist

Lithium nickel cobalt aluminium

oxide

LiNiCoAlO2 NCA Evs, grid storage

Lithium titanate Li4Ti5O12 LTO Evs, grid storage

Lithium-ion battery technologies

Ref. Batteryuniversity.com

Selective thermal isolation of value added cobalt from spent

lithium-ion batteries

Rumana Hossain, Uttam Kumar, Irshad Mansuri, Veena Sahajwalla. ”Selective thermal

isolation of value added cobalt from spent lithium-ion batteries”. (under review)

Spent Ni-MH battery

A. Top positive terminal

B. External plastic casing

C. External steel casing

D. Metal grid current collector

E. Separator

F. Positive electrode

G. Negative electrode

ANODECATHODE

Families of intermetallic compounds used as

negative electrode in Ni-MH batteries Intermetallic

compounds

Examples A B Structure

AB5 LaNi5 , YCoH3 Group III (including rare earths and Th)

Group VIII Haucke phases,

hexagonal

AB2 ZrV2 , ZrMn2 Group III, rare earth or Group IV metal

Group VIII

(Group II,IV,VI or VII)

Laves phase,

hexagonal or cubic

AB TiFe, ZrNi Group IV or rare earth Group VIII Cubic, CsCl type

A2B7 Y2Ni7 , Th2Fe7 At least one rare earth, and also includes Mg

Include at Ni, the

atomic ratio of X to Y

is between 1:2 and

1:5 (AxBy)

Hexagonal,

Ce2Ni7 type

A2B Mg2Ni, Ti2Ni Group IV or Group IIA Group VIII Cubic, MoSi2 or Ti2Ni- type

Ref. P.J. Tsai and S. L. I. Chan, (2015) Nickel-based batteries: materials and chemistry, Advances in Batteries

for Medium- and Large-scale Energy Storage, Elsevier

Thermal isolation of Rare Earth Oxides from

Spent Ni-MH Battery

Maroufi, S., Nekouei, R. K., Hossain, R., Assefi, M., & Sahajwalla, V. (2018). Recovery of Rare Earth (ie, La, Ce, Nd, and Pr)

Oxides from End-of-Life Ni-MH Battery via Thermal Isolation. ACS Sustainable Chemistry & Engineering.

Rare Earth Oxides separated from an anode of a used

Nickel Metal Hydride battery using thermal isolation

The separated oxide phase contained

Lanthanum (La), cerium (Ce), Neodymium (Nd), and Praseodymium (Pr).

• Ni in Metal is > 92 wt%

• Co in Metal is ~ 7 wt%

Reduction by

waste plastic

Electrode from a

spent NiMH battery

Waste Plastic

Synthesis of Ni alloy from

a used NiMH Battery

Behera, Pravas Ranjan, Rifat Farzana, and Veena Sahajwalla. "Reduction of oxides obtained from waste

Ni-MH battery’s positive electrode using waste plastics to produce nickel based alloy." Journal of

Cleaner Production 249 (2020): 119407.

Microrecycling Mechanism for Materials Microsurgery

TEM EDS Elemental mapping of the Hybrid layer and the substrate

Rumana Hossain and Veena Sahajwalla. "Material Microsurgery: Selective Synthesis of Materials via High-

Temperature Chemistry for Microrecycling of Electronic Waste." ACS Omega (2020).

Materials microsurgery: use of zinc carbon battery

powder to fabricate supercapacitors

Hassan, Kamrul, Rifat Farzana, and Veena Sahajwalla. "In-situ fabrication of ZnO thin film

electrode using spent Zn–C battery and its electrochemical performance for supercapacitance."

SN Applied Sciences 1.4 (2019): 302.

Opens new

opportunity of Zinc

nanoparticle

electrodes

fabrication using

spent zinc carbon

battery powder

Room Temperature (T) 350oC 350oC - 800oC >800oC

Microrecycling and MICROfactorie technologies

“Microrecycling” has opened alternative pathways for harnessing the

potential value in waste and provide the scientific foundation for

MICROfactories

Based on Microrecycling:

We propose an innovative technique for materials synthesis:

“Materials Microsurgery”.

We are working towards new surfaces on materials to achieve properties not

possible by the parent materials

.

SMaRT MICROfactories®: A Global Solution

Value of MICROfactorie

http://www.smart.unsw.edu.au/

SMaRT MICROfactorie® technology promises to revolutionise recycling by

producing cost-effective green materials.

Relatively low entry costs for

establishing recyclingDecentralised solution

Increases safety by avoiding

transport of used batteriesLocal jobs and economic returns

Conclusions

MICROrecycling offers an important new

solution for a world looking for circular economy solutions

Micro-processing is disrupting the traditional recycling process enhancing sustainability and

producing value-added green materials