ORALS

SESSION: BatteryFriAM-R11	6th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Fri Oct, 25 2019 / Room: Coralino
Session Chairs: Katerina Aifantis; Rumen Tomov; Session Monitor: TBA

11:20: [BatteryFriAM01]
Future Thinking in Batteries
Vasant Kumar¹ ; ¹University of Cambridge, Cambridge, United Kingdom;
Paper Id: 336 [Abstract]

Given the massive shifts facing the future energy-environment paradigm, it is pertinent to evaluate the centrality of “New Thinking” within this energy-environment [1] nexus in the evolving scenario. This paper will look into aspects of energy storage, advanced materials [2] and environmental issues in electric grids, transportation, renewable energy, and resources. It is generally agreed that 2D-based materials have a bright future in electrochemical energy devices as they can combine good electrical conductivity & connectivity with a suitable porous structure that is able to facilitate rapid redox reactions. 2D materials are combined with other electroactive components for optimal synergy. A number of approaches for making the electrode structure will be presented. Recycling and recovery of upgraded materials from spent batteries are crucial considerations for the future use of batteries. A number of factors including future research trajectories and resources strategy issues will be considered.

References:
1. Leapfrogging to sustainable power, R.V. Kumar, Chapter in “Smart Villages: New Thinking for Off-Grid Communities Worldwide; Published by Banson (Lavenham Press, UK), 2015, pp. 35-41; ISBN 978-0-9932932-0-7(paperback); 978-0-9932932-1-4 (hardback)
2. “High Density Energy Lithium Batteries”; KE Aifantis, SA Hackney and RV Kumar (Editors), Wiley-VCH Verlag, 2010.

SESSION: BatteryFriAM-R11	6th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Fri Oct, 25 2019 / Room: Coralino
Session Chairs: Katerina Aifantis; Rumen Tomov; Session Monitor: TBA

12:35: [BatteryFriAM04]
Novel Carbon - Ultrafine Silicon Composite Anode for High-Performance Lithium-Ion Batteries
Dmitry Yarmolich¹ ; Dzianis Yarmolich² ; Yaroslav Odarchenko³ ; Carmen Murphy⁴ ; Enrico Petrucco⁴ ; Vasant Kumar⁵ ; Rumen Tomov⁵ ; ¹Plasma App Ltd, OX11 0QX, United Kingdom; ²Plasma App Ltd, Oxford , OX11 0QX, United Kingdom; ³Plasma App Ltd, Oxford OX11 0QX, United Kingdom; ⁴Johnson Matthey Battery Materials, Reading RG4 9NH, United Kingdom; ⁵University of Cambridge, Cambridge, United Kingdom;
Paper Id: 352 [Abstract]

Silicon (Si) has been widely considered as potential high capacity anode material in Li-ion batteries due to its desirable properties: (i) high theoretical specific capacity (1672 mA h g-1), (ii) nontoxicity and (iii) low cost and natural abundance [1]. Despite its favourable comparison to commercial graphite anodes (theoretical capacity of 372 mA h g-1), the implementation of bulk Si anode has been hindered by the large volume change during the charging and discharging cycle (~ 300%). Such structural instability results in loss of contact with the other electrode constituents and self-destruction [2]. Another adverse feature is the limited Li⁺ ion diffusivity and electronic conductivity of bulk Si at room temperature. A scalable method of producing carbon (ultrafine silicon composite electrode) was developed using the Virtual Cathode Deposition technique [3]. As-deposited coatings contained silicon nano-crystallites encapsulated in a novel polymorph of mesoporous disordered carbon matrix. The architecture of the electrode offers close-order integration of both materials ensuring fast Li⁺ ion diffusivity and mixed-(ionic/electronic) conductivity as well as alleviating Si volume change during cycling. The composite carbon polymorph-silicon anode tested versus Li displayed a first cycle specific capacity of more than 2000 mAh g^-1 retaining in the following cycles ~1200 mAh g^-1 at a 0.1C rate. The good cyclability (over 80 cycles) demonstrated the effectiveness of such Si - carbon encapsulation, addressing the instability issues of Si-based anodes.

References:
[1] P. G. Bruce, S. A. Freunberger, L. J. Hardwick and J. M. Tarascon, Nat. Mater., 2012, 11, 19–29.
[2] Li B, Xiao Q, Luo Y (2018) A modified synthesis process of three dimensional sulfur/graphene aerogel as binder-free cathode for lithium-sulfur batteries. Mater Des 153:9–14
[3] D. Yarmolich, D. Virtual cathode deposition (vcd) for thin film manufacturing WO2016042530A1. (2015).

SESSION: BatteryFriPM1-R11	6th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Fri Oct, 25 2019 / Room: Coralino
Session Chairs: Guoran Li; Claudio Capiglia; Session Monitor: TBA

14:00: [BatteryFriPM105]
Feasibility of a Physical Vapor Deposition technology for battery electrode manufacturing
Dmitry Yarmolich¹ ; Rumen Tomov² ; Vasant Kumar² ; Carmen Murphy³ ; Yaroslav Odarchenko⁴ ; Dzianis Yarmolich⁵ ; Enrico Petrucco³ ; ¹Plasma App Ltd, OX11 0QX, United Kingdom; ²University of Cambridge, Cambridge, United Kingdom; ³Johnson Matthey Battery Materials, Reading RG4 9NH, United Kingdom; ⁴Plasma App Ltd, Oxford OX11 0QX, United Kingdom; ⁵Plasma App Ltd, Oxford , OX11 0QX, United Kingdom;
Paper Id: 504 [Abstract]

The method of physical vapor deposition has been tested for the manufacture of electric vehicle lithium-ion battery anodes. The anode was fabricated using Virtual Cathode Deposition1 (VCD) which enables direct deposition of 20 μm thick carbon active material onto a 25 μm polypropylene separator, followed by deposition of a 2 μm copper current collector. Carbon polymorphism2 induced by the deposition process is responsible for active material high gravimetric and volumetric capacity allowing anode areal capacity up to 4.2 mAh/cm2 at the 0.1 C charge rate. The PVD process increases the purity of active materials and quality control compared to the state-of-the-art wet chemical3 method. Currently, the production of a 24 kWh Nissan Leaf’s battery pack requires about 25 MWh, more than 80% of which is spent on drying the electrodes and dry room conditioning. VCD eliminates use of solvents that saves the energy for electrode drying and increase the environmental safety of battery production.

References:
1. Yarmolich, D. Patent No. WO2016042530A1 (September 2014).
2. Zhao, C. X., Niu, Ch. Y., Qin, Z-J., Ren, X. Y., Wang, J-T., Cho J.H. and Jia, Y. H18Carbon: A New Metallic Phase with sp2-sp3 Hybridized Bonding Network. Sci. Rep. 6, 1–9 (2016).
3. A. Sakti , J. J. Michalek, E. R.H. Fuchs, Jay F. Whitacre., A techno-economic analysis and optimization of Li-ion batteries for light-duty passenger vehicle electrification. Journal of Power Sources 273 (2015)
4. C. Yuan, Ye. Deng, T. Li, F. Yang, Manufacturing energy analysis of lithium ion battery pack for electric vehicles, CIRP Annals - Manufacturing Technology 66 (2017)

SESSION: BatteryFriPM1-R11	6th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Fri Oct, 25 2019 / Room: Coralino
Session Chairs: Guoran Li; Claudio Capiglia; Session Monitor: TBA

14:25: [BatteryFriPM106] Keynote
NovoPb: A New, Complete and Sustainable Recycling Process for High-Purity Lead Oxide
Deise Menezes Santos¹ ; Francklin Jonas De Paula² ; Yandiara Larissa Barros³ ; Matheus Carvalho⁴ ; Wanderson Souza Da Silva⁵ ; Vasant Kumar⁶ ; ¹Universidade Federal do Espírito Santo, Vitoria, Brazil; ²Faculdade Pitagoras, Governador Valadares, Brazil; ³Instituto Federal do Espirito Santo, Vitoria, Brazil; ⁴Instituto Federal de Minas Gerais, Governador Valadares, Brazil; ⁵Universidade Federal do Espirito Santo, Vitoria, Brazil; ⁶University of Cambridge, Cambridge, United Kingdom;
Paper Id: 258 [Abstract]

Pyrometallurgical recycling of lead-acid battery (LAB) produces high-purity metallic lead (99.99% purity) through an energy-intensive and polluting process (1). The alternative hydrometallurgical method directly recovers lead oxide from spent lead paste, although many impurities may not be removed. We have experienced a breakthrough success in NovoPb, an ongoing project to implement a sustainable LAB recycling process in a 1 ton capacity pilot plant at Minas Gerais in Brazil(2). During NovoPb, a 3-step hydrometallurgical process was used for synthesis of high-purity leady oxide derived from spent LAB samples of industry pastes. Dessulfuration with NaOH, followed by acetic acid and H₂O₂ leaching of LAB paste removed the impurities and generated pure lead acetate solution (3), a blank canvas. A lead complex with citric acid(4) was formed to remove lead from the solution in order to produce a high-purity nanostructured leady oxide, by calcining it at a much lower temperature (350°C) than usual smelted lead (1200°C), saving energy and reducing hazardous gas emissions. The characterization of the 10 LAB pastes were performed by XRD, XRF, SEM/EDS and basic chemical analysis to successfully reproduce 20 recycling experiments at the laboratory. Factorial design was applied to determine optimal reaction conditions. 2.5 kg of lead citrate were synthesized and characterized by TGA, XRD, and SEM, then calcined to obtain leady oxide. Acid absorption, BET surface area, SEM/EDS, XRD and ICP-OES results show nanostructured leady oxide, 99,9% purity, with larger surface area and acid absorption than a lead oxide produced by traditional ball mill process. This research is part of the Embrapii project of the Vitoria Innovation Center of the Federal Institute of Espirito Santo, in partnership with the University of Cambridge, Innovate UK, Brazilian companies Tudor MG de Baterias, Antares Reciclagem LTDA, Embrapii and the British company, Aurelius Environmental.

References:
1. Ballantyne AD, Hallett JP, Jason D, Shah N, Payne DJ, Payne DJ. Lead acid battery recycling for the twenty-first century. Royal Society Open Science: 2018;
2. Ifes. Polo de Inovação firma convenio com empresas para implantar processo mais limpo na reciclagem de baterias [Internet]. 2018. Available from: https://www.ifes.edu.br/noticias/17758-polo-de-inovacao-firma-convenio-com-empresas-para-implantar-processo-mais-limpo-na-reciclagem-de-baterias
3. Yu W, Yang J, Li M, Hu Y, Hou H, Vasant R. A facile lead acetate conversion process for synthesis of high-purity alpha-lead oxide derived from spent lead-acid batteries. Society of Chemical Industry: 2018;(July).
4. Kumar RV. LEAD RECYCLING. UNITED KINGDOM; WO 2008/056125 A1, 2008. p. 35.

SESSION: BatteryFriPM1-R11	6th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Fri Oct, 25 2019 / Room: Coralino
Session Chairs: Guoran Li; Claudio Capiglia; Session Monitor: TBA

14:50: [BatteryFriPM107]
Adjustable Interlayer Spacing for Layered Titanate for Potassium Storage
Cheng-yen Lao¹ ; Vasant Kumar¹ ; Yingjun Liu¹ ; ¹University of Cambridge, Cambridge, United Kingdom;
Paper Id: 343 [Abstract]

Potassium-ion batteries (KIBs) are promising substitutes for lithium-ion batteries (LIBs) in grid-scale energy storage due to the Earth-abundancy of potassium [1]. Practical KIB applications, however, are hindered by slow diffusion kinetics and severe structural deterioration as the large cation is cycled in and out of the electrode, respectively leading to low specific capacity and short lifetime [2]. Herein we synthesize layered alkali titanates as electrode materials for KIBs by chemical reaction between nanoparticles and aqueous alkali hydroxides. By increasing the interlayer spacing of titanates, we show improvements in electrochemical performances in terms of specific capacity, charging rate and cycle life. Larger interlayer spacing allows quick and increased ion storage [3]. The adjustment of reaction temperature, concentration and types of hydroxides has direct effects on the interlayer spacing of these titanates. As a result, we have produced a range of alkali titanates with different interlayer spacing. Some as-prepared titanates with larger interlayer spacing deliver electrochemical performances for KIBs comparable to titanium-oxide based LIBs [4], [5]. Our work provides a method to design future energy storage electrode materials for large ions.

References:
[1] W. Zhang, Y. Liu, and Z. Guo, “Approaching high-performance potassium-ion batteries via advanced design strategies and engineering,” Sci. Adv., vol. 5, no. 5, p. eaav7412, May2019.
[2] T. A. Pham, K. E. Kweon, A. Samanta, V. Lordi, and J. E. Pask, “Solvation and dynamics of sodium and potassium in ethylene carbonate from ab Initio molecular dynamics simulations,” J. Phys. Chem. C, vol. 121, no. 40, pp. 21913–21920, Oct.2017.
[3] J. Yang et al., “Size-independent fast ion intercalation in two-dimensional titania nanosheets for alkali-metal-ion batteries,” Angew. Chemie Int. Ed., vol. 58, no. 26, pp. 8740–8745, Jun.2019.
[4] J. Liu, J. S. Chen, X. Wei, X. W. Lou, and X.-W. Liu, “Sandwich-like, stacked ultrathin titanate nanosheets for ultrafast lithium storage,” Adv. Mater., vol. 23, no. 8, pp. 998–1002, Dec.2010.
[5] J. Ma et al., “Layered lepidocrocite type structure isolated by revisiting the sol–gel chemistry of anatase TiO2: A new anode material for batteries,” Chem. Mater., vol. 29, no. 19, pp. 8313–8324, Oct.2017.

SESSION: BatteryFriPM1-R11	6th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Fri Oct, 25 2019 / Room: Coralino
Session Chairs: Guoran Li; Claudio Capiglia; Session Monitor: TBA

15:15: [BatteryFriPM108]
Inkjet Printing of PEDOT/PEO Semi-Interpenetrating Networks for Highly Scaleable Supercapacitor Electrodes
Paulina Librizzi¹ ; Vasant Kumar² ; ¹University of Cambridge - Department of Materials Science and Metallurgy, Cambridge, United Kingdom; ²University of Cambridge, Cambridge, United Kingdom;
Paper Id: 411 [Abstract]

A semi-interpenetrating network of PEDOT and PEO was used as a highly effective supercapacitor electrode. Wang and co-authors in 2017[1] detailed a process in which an semi-interpenetrating polyethylenedioxythiophene/polyethylene oxide (PEDOT/PEO) network with mixed ionic and electronic conductivity could be synthesized in a simultaneous fashion[1]. The ionically conducting PEO was phase separated with the electronically conductive PEDOT, leading to a larger triple phase boundary and thus a higher capacity[1,2]. The phase separation of PEDOT and PEO also allowed for mechanical robustness and increased cycling ability[1]. While these films represent a significant step forward for flexible electronics, solution casting, the current fabrication process, is not suitable for large scale production. In this work, films of this interpenetrating polymer network were made through inkjet printing[3]. The viscosity of the polymer precursor is 31 cP, at the upper limit of what a typical inkjet printhead can handle (~20 cP)[3,4]. The raw prepolymer also displays shear thinning behavior, dropping linearly to 21 cP between shear rates of 130 and 210 s-1. To make a more suitable precursor for inkjet printing, ethanol was added to decrease the viscosity of the precursor. Ethanol is a commonly used solvent for inkjet printing as is has an optimal viscosity (1.1 cP at STP), low vapor pressure, and good wetting properties. Additionally, ethanol is not known to polymerize via free-radical polymerization[5] and will not compromise the chemical integrity of the interpenetrating network [5]. Ethanol is a relatively safe organic solvent and is soluble in the precursor. It is also soluble in methanol, which is used in the initial polymer processing to clear away excess unpolymerized precursor. Cyclic voltammograms of both neat and inkjet printed films in an aqueous LiClO4 electrolyte with a platinum counter electrode and an Ag/AgCl reference electrode were taken. The results of the two cyclic voltammograms were comparable and showed a similar capacitance.

References:
1. Fong, K. D., Wang, T., Kim, H.-K., Kumar, R. V. & Smoukov, S. K. Semi-Interpenetrating Polymer Networks for Enhanced Supercapacitor Electrodes. ACS Energy Lett. 2014–2020 (2017). doi:10.1021/acsenergylett.7b00466.
2. Ghosh, S. & Inganäs, O. Networks of Electron-Conducting Polymer in Matrices of Ion-Conducting Polymers Applications to Fast Electrodes. Electrochem. Solid-State Lett. 3, 213 (1999).
3. Magdassi, S. et al. The Chemistry of Inkjet Inks. (World Scientific Publishing Co. Pte. Ltd., 2009). doi:10.1142/6869
4. Magdassi, S. Ink Requirements and Formulations Guidelines. in The Chemistry of Inkjet Inks 19–41 doi:10.1142/9789812818225_0002.
5. Hazrati, H. D., Whittle, J. D. & Vasilev, K. A Mechanistic Study of the Plasma Polymerization of Ethanol. doi:10.1002/ppap.201300110

SESSION: BatteryFriPM2-R11	6th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Fri Oct, 25 2019 / Room: Coralino
Session Chairs: Katsuya Teshima; Deise Menezes Santos; Session Monitor: TBA

15:55: [BatteryFriPM209]
Production of Ultra-Pure Lead Citrate from Spent Lead-Acid Battery Paste using a Cost-Effective, Eco-Friendly Process
Vimalnath Selvaraj¹ ; Marcel Yiao¹ ; Robert Liu² ; Rumen Tomov¹ ; Vasant Kumar¹ ; Peter Knight¹ ; Steve Andrew² ; Spencer Lowe² ; Athan Fox³ ; Miles Freeman² ; Johdie Harris² ; ¹University of Cambridge, Cambridge, United Kingdom; ²Aurelius Environmental, Dudley, United Kingdom; ³Aurelius Environmental, Tipton, United Kingdom;
Paper Id: 415 [Abstract]

Abstract The recovery of Pb from the spent lead-acid battery paste is achieved conventionally through pyrometallurgical processes. This process requires relatively high temperature (~1,100 °C) for the decomposition of PbSO4 which is a dominant compound in the paste along with PbO2, PbO, metallic Pb and other impurities. The high-temperature pyrometallurgical process releases SO2 gas and Pb particulates into the environment, raising serious environmental concerns. The hydro-electro metallurgical process, which has been developed as an alternative, also consumes high energy and uses toxic acids like HBF4 or H2SiF6. The need for an eco-friendly and cost-effective recycling process for the recovery of spent battery paste [1,2,3,4], is not only critical but also very timely. Indeed, the market size of secondary lead-acid batteries is forecasted to reach over $95 billion USD by 2026 [5]. Within this market, the recycling of lead-acid batteries is a revenue stream worth around $14-16 billion USD by 2025 [6]. In this paper, we present our work towards a fully hydrometallurgical, eco-friendly and cost-effective process. The recovery of Pb is achieved through the synthesis of ultrapure lead-citrate, which is obtained directly from spent lead-acid battery paste via desulphurisation and treatment with organic acids. Unlike previous iterations of this process, we have optimised the conditions to achieve production of ultra-pure lead-citrate, 99.99%, with minimum consumption of reagents. This paper shows how it is possible to minimise production costs for the recycled lead compounds to the extent that the process is as cost-effective, if not superior economically, when compared to the incumbent technology. The scalability and economic improvement of the latest iteration of this now-patented hydrometallurgical process greatly facilitate the globalisation of this innovative technology. Keywords Lead, battery, recycling, lead citrate, hydrometallurgy, organic acids

References:
References
[1] Sonmez, M. S., and R. V. Kumar, Hydrometallurgy 95.1-2 (2009) 53-60.
[2] Sonmez, M. S., and R. V. Kumar, Hydrometallurgy 95.1-2 (2009) 82-86.
[3] Yang, Jiakuan, Ramachandran Vasant Kumar, and Deepak P. Singh, Journal of Chemical Technology & Biotechnology 87.10 (2012) 1480-1488.
[4] Zhu, X., He, X., Yang, J., Gao, L., Liu, J., Yang, D., Sun, X., Zhang, W., Wang, Q. and Kumar, R.V, Journal of Hazardous Materials 250 (2013) 387-396.
[5] https://www.reportsanddata.com (report ID RND_00104)
[6] https://www.cambridgeindependent.co.uk/business/cambridge-battery-recycling-technology-set-to-disrupt-global-market-9052189/

SESSION: BatteryFriPM2-R11	6th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Fri Oct, 25 2019 / Room: Coralino
Session Chairs: Katsuya Teshima; Deise Menezes Santos; Session Monitor: TBA

17:10: [BatteryFriPM212]
Graphene-based lithium-sulfur batteries
Liam Bird¹ ; Kai Xi¹ ; Cheng-yen Lao¹ ; Vasant Kumar¹ ; Andrea Ferrari¹ ; Caterina Ducati¹ ; ¹University of Cambridge, Cambridge, United Kingdom;
Paper Id: 453 [Abstract]

Lithium-sulfur (Li-S) batteries have a theoretical capacity of 1675 mAhg^-1[1], five times that of conventional Li-ion batteries[2], facilitated by the sulfur cathode undergoing a series of redox reactions to form lithium polysulfides (PS)[3]. However, the continuous diffusion of PS through the electrolyte results in progressive loss of electrical contact to the active material and hence poor capacity retention with repeated cycling[4, 5]. A lightweight, electrically conductive host framework compatible with scalable manufacture is therefore required to exploit sulfur’s low cost and abundance[6] in batteries with sustained high capacity. Templated mesoporous carbons, including CMK-3, are electronically conductive and have a hierarchical porous structure suitable for constraining PS[7]. However, graphene and related materials (GRMs) are compatible with higher throughput manufacturing processes[8]. In addition to high conductivity[8], mechanical strength[8], and surface area, GRMs offer opportunities for tunable functionalisation to increase PS binding energy to the host framework[9]. Here, we investigate the use of graphene nanoplatelets synthesised by microfluidization[10] (GNPs) and graphene oxide (GO) with CMK-3 as composite sulfur hosts for Li-S batteries. We find that a composite of GNPs and CMK-3 improves the capacity of Li-S batteries, and that a composite of GO and CMK-3 improves the capacity retention of batteries for the first ~100 cycles, compared to CMK-3 alone in identical conditions. The incorporation of GNPs appears to enhance the contribution of long-chain PS (Li2Sx for 4≤x≤8) to the cell’s capacity, demonstrating improved constraint of this active material in contact with the conducting host. This improves the cycling capability of Li-S batteries, facilitating their application in electric vehicles and grid-scale renewable energy storage.

References:
1 J. R. Akridge, et al. Solid State Ion. 175, 243 (2004)
2 K. Mizushima, et al. Mater. Res. Bull. 15, 783 (1980)
3 E. Peled, J. Electrochem. Soc., 136, 1621 (1989)
4 Y. V. Mikhaylik et al., J Electrochem. Soc. 151, A1969 (2004)
5 S.-E. Cheon, et al., J. Electrochem. Soc. 150, A796 (2003)
6 A. Manthiram, et al., Chem. Rev. 114, 11751 (2014)
7 X. Ji, K. T. Lee, L. F. Nazar, Nat. Mater. 8, 500 (2009)
8 A. C. Ferrari, et al. Nanoscale, 11, 4598 (2015)
9 X. Zhou at al. J. Power Sources 243, 993 (2013)
10 P. G. Karagiannidis et al. ACS Nano 11, 2742 (2017)