In this paper we report synthesis, conductivity and structural data for the novel tetragonal garn... more In this paper we report synthesis, conductivity and structural data for the novel tetragonal garnet-related system, Li7La3Sn2O12. Neutron diffraction data shows that the tetragonal distortion is related to ordering of Li in three sites within the structure to ensure no short Li-Li interactions. Consistent with the ordered nature of the Li ions, the conductivity is low, with a high activation energy. The results are relevant to related highly conducting cubic garnets, Li5+xLn3-xAxM2O12 (Ln=rare earth, A=alkaline earth; M=Nb, Ta, Sb), showing how a high Li content can be accommodated by Li ordering within the garnet structure, supporting previous suggestions by Cussen for the cubic garnets, who proposed the presence of local ordering/clustering of Li in tetrahedral and "octahedral" sites to limit unfavourable short Li-Li interactions.
In this paper we examine the effect of Ga doping on the structure and conductivity of the high Li... more In this paper we examine the effect of Ga doping on the structure and conductivity of the high Li ion content garnet-related system, La(3)Zr(2)Li(7)O(12). Without Ga doping, La(3)Zr(2)Li(7)O(12) is tetragonal and has low Li ion conductivity. The introduction of Ga leads to a change to a cubic unit cell, and a large enhancement in the conductivity. Prior structural studies of La(3)Zr(2)Li(7)O(12) have shown the presence of both tetrahedral and distorted octahedral sites for Li, and the low conductivity can be explained by the ordered nature of the Li distribution. The present structural study of La(3)Zr(2)Ga(0.5)Li(5.5)O(12) shows that Ga substitutes onto the tetrahedral site. Despite the presence of non-mobile Ga(3+) on the Li sites, the conductivity is enhanced as a result of the introduction of vacancies in the Li sites, and consequent disorder on the Li sublattice. Further work has suggested that over time in air, there is some H(+)/Li(+) exchange, and consequently some variation in the conductivity.
The rheology of electrode slurries dictates the final coating microstructure. High slurry viscosi... more The rheology of electrode slurries dictates the final coating microstructure. High slurry viscosity creates excess pressure and limits coating speed, elasticity causes instabilities leading to coating defects and high flow causes slumping leading to thin, poorly structured coatings. However, due to differing solvent systems and components, and the complex nature of the many competing interactions, finding the source of these detrimental rheological properties can be difficult. Herein, a systematic rheological characterization of all components of an industrially relevant anode and cathode slurry is presented. Through a combinatory approach, the additive nature of the interactions is explored, using steady shear, small and large amplitude oscillatory shear to give insight into the underlying structure, which is vital to develop novel, more sustainable formulations. For water‐based anodes, the polymeric binder dictates the rheology, thickening the slurry, allowing efficient suspension...
As electric vehicles become more widely used, there is a higher demand for lithium‐ion batteries ... more As electric vehicles become more widely used, there is a higher demand for lithium‐ion batteries (LIBs) and hence a greater incentive to find better ways to recycle these at their end‐of‐life (EOL). This work focuses on the process of reclamation and re‐use of cathode material from LIBs. Black mass containing mixed LiMn2O4 and Ni0.8Co0.15Al0.05O2 from a Nissan Leaf pouch cell are recovered via two different recycling routes, shredding or disassembly. The waste material stream purity is compared for both processes, less aluminium and copper impurities are present in the disassembled waste stream. The reclaimed black mass is further treated to reclaim the transition metals in a salt solution, Ni, Mn, Co ratios are adjusted in order to synthesize an upcycled cathode, LiNi0.6Mn0.2Co0.2O2 via a co‐precipitation method. The two reclamation processes (disassembly and shredding) are evaluated based on the purity of the reclaimed material, the performance of the remanufactured cell, and the ...
This study has looked at 44 commercial recyclers and assessed their recycling and reclamation pro... more This study has looked at 44 commercial recyclers and assessed their recycling and reclamation processes. A novel qualitative measure termed "Strategic materials Weighting And Value Evaluation" (SWAVE) is proposed and used to compare the strategic importance and value of various materials in EoL LIBs. The sustainability and quality of recycled material is assessed by comparing the final form or composition after the recycling processes, the industrial processes and the industry type (primary material producer or recycler). SWAVE is applied to each company, producing a score out of 20, with a higher number indicating that more materials are recycled.
An increase in the demand for clean energy generation has brought about a need for improved energ... more An increase in the demand for clean energy generation has brought about a need for improved energy storage devices to distribute the power generated by renewable sources. Sodium-ion batteries have been proposed as a lower cost and more sustainable solution. In order to commercialise this emerging technology, new materials and characterisation techniques are required. Magnetic resonance imaging (MRI) is able to characterise both the electrode and electrolyte materials non-invasively, providing a more holistic view of battery chemistry. Furthermore, MRI can spatially resolve electrochemical processes, in real-time, within cells.(1-4) In this study, 23Na and 1H nuclear magnetic resonance (NMR) spectroscopy and MRI experiments have been performed, in operando, on sodium metal cells. At high cycle rates, the growth of dendrites is observed during galvanostatic plating. Operando 23Na NMR experiments on sodium full cells have also been performed, which provide unprecedented insight into th...
Commercial lithium ion cells are now optimised for either high energy density or high power densi... more Commercial lithium ion cells are now optimised for either high energy density or high power density. There is a trade off in cell design between the power and energy requirements. A tear down protocol has been developed, to investigate the internal components and cell engineering of nine cylindrical cells, with different power–energy ratios. The cells designed for high power applications used smaller particles of the active material in both the anodes and the cathodes. The cathodes for high power cells had higher porosities, but a similar trend was not observed for the anodes. In terms of cell design, the coat weights and areal capacities were lower for high power cells. The tag arrangements were the same in eight out of nine cells, with tags at each end of the anode, and one tag on the cathode. The thicknesses of the current collectors and separators were based on the best (thinnest) materials available when the cells were designed, rather than materials optimised for power or ener...
Direct reuse of current collectors can not only effectively tackle LIB waste issues but also skip... more Direct reuse of current collectors can not only effectively tackle LIB waste issues but also skip long conventional recycling processes, bringing environmental and economic benefits.
In this paper we report synthesis, conductivity and structural data for the novel tetragonal garn... more In this paper we report synthesis, conductivity and structural data for the novel tetragonal garnet-related system, Li7La3Sn2O12. Neutron diffraction data shows that the tetragonal distortion is related to ordering of Li in three sites within the structure to ensure no short Li-Li interactions. Consistent with the ordered nature of the Li ions, the conductivity is low, with a high activation energy. The results are relevant to related highly conducting cubic garnets, Li5+xLn3-xAxM2O12 (Ln=rare earth, A=alkaline earth; M=Nb, Ta, Sb), showing how a high Li content can be accommodated by Li ordering within the garnet structure, supporting previous suggestions by Cussen for the cubic garnets, who proposed the presence of local ordering/clustering of Li in tetrahedral and "octahedral" sites to limit unfavourable short Li-Li interactions.
In this paper we examine the effect of Ga doping on the structure and conductivity of the high Li... more In this paper we examine the effect of Ga doping on the structure and conductivity of the high Li ion content garnet-related system, La(3)Zr(2)Li(7)O(12). Without Ga doping, La(3)Zr(2)Li(7)O(12) is tetragonal and has low Li ion conductivity. The introduction of Ga leads to a change to a cubic unit cell, and a large enhancement in the conductivity. Prior structural studies of La(3)Zr(2)Li(7)O(12) have shown the presence of both tetrahedral and distorted octahedral sites for Li, and the low conductivity can be explained by the ordered nature of the Li distribution. The present structural study of La(3)Zr(2)Ga(0.5)Li(5.5)O(12) shows that Ga substitutes onto the tetrahedral site. Despite the presence of non-mobile Ga(3+) on the Li sites, the conductivity is enhanced as a result of the introduction of vacancies in the Li sites, and consequent disorder on the Li sublattice. Further work has suggested that over time in air, there is some H(+)/Li(+) exchange, and consequently some variation in the conductivity.
The rheology of electrode slurries dictates the final coating microstructure. High slurry viscosi... more The rheology of electrode slurries dictates the final coating microstructure. High slurry viscosity creates excess pressure and limits coating speed, elasticity causes instabilities leading to coating defects and high flow causes slumping leading to thin, poorly structured coatings. However, due to differing solvent systems and components, and the complex nature of the many competing interactions, finding the source of these detrimental rheological properties can be difficult. Herein, a systematic rheological characterization of all components of an industrially relevant anode and cathode slurry is presented. Through a combinatory approach, the additive nature of the interactions is explored, using steady shear, small and large amplitude oscillatory shear to give insight into the underlying structure, which is vital to develop novel, more sustainable formulations. For water‐based anodes, the polymeric binder dictates the rheology, thickening the slurry, allowing efficient suspension...
As electric vehicles become more widely used, there is a higher demand for lithium‐ion batteries ... more As electric vehicles become more widely used, there is a higher demand for lithium‐ion batteries (LIBs) and hence a greater incentive to find better ways to recycle these at their end‐of‐life (EOL). This work focuses on the process of reclamation and re‐use of cathode material from LIBs. Black mass containing mixed LiMn2O4 and Ni0.8Co0.15Al0.05O2 from a Nissan Leaf pouch cell are recovered via two different recycling routes, shredding or disassembly. The waste material stream purity is compared for both processes, less aluminium and copper impurities are present in the disassembled waste stream. The reclaimed black mass is further treated to reclaim the transition metals in a salt solution, Ni, Mn, Co ratios are adjusted in order to synthesize an upcycled cathode, LiNi0.6Mn0.2Co0.2O2 via a co‐precipitation method. The two reclamation processes (disassembly and shredding) are evaluated based on the purity of the reclaimed material, the performance of the remanufactured cell, and the ...
This study has looked at 44 commercial recyclers and assessed their recycling and reclamation pro... more This study has looked at 44 commercial recyclers and assessed their recycling and reclamation processes. A novel qualitative measure termed "Strategic materials Weighting And Value Evaluation" (SWAVE) is proposed and used to compare the strategic importance and value of various materials in EoL LIBs. The sustainability and quality of recycled material is assessed by comparing the final form or composition after the recycling processes, the industrial processes and the industry type (primary material producer or recycler). SWAVE is applied to each company, producing a score out of 20, with a higher number indicating that more materials are recycled.
An increase in the demand for clean energy generation has brought about a need for improved energ... more An increase in the demand for clean energy generation has brought about a need for improved energy storage devices to distribute the power generated by renewable sources. Sodium-ion batteries have been proposed as a lower cost and more sustainable solution. In order to commercialise this emerging technology, new materials and characterisation techniques are required. Magnetic resonance imaging (MRI) is able to characterise both the electrode and electrolyte materials non-invasively, providing a more holistic view of battery chemistry. Furthermore, MRI can spatially resolve electrochemical processes, in real-time, within cells.(1-4) In this study, 23Na and 1H nuclear magnetic resonance (NMR) spectroscopy and MRI experiments have been performed, in operando, on sodium metal cells. At high cycle rates, the growth of dendrites is observed during galvanostatic plating. Operando 23Na NMR experiments on sodium full cells have also been performed, which provide unprecedented insight into th...
Commercial lithium ion cells are now optimised for either high energy density or high power densi... more Commercial lithium ion cells are now optimised for either high energy density or high power density. There is a trade off in cell design between the power and energy requirements. A tear down protocol has been developed, to investigate the internal components and cell engineering of nine cylindrical cells, with different power–energy ratios. The cells designed for high power applications used smaller particles of the active material in both the anodes and the cathodes. The cathodes for high power cells had higher porosities, but a similar trend was not observed for the anodes. In terms of cell design, the coat weights and areal capacities were lower for high power cells. The tag arrangements were the same in eight out of nine cells, with tags at each end of the anode, and one tag on the cathode. The thicknesses of the current collectors and separators were based on the best (thinnest) materials available when the cells were designed, rather than materials optimised for power or ener...
Direct reuse of current collectors can not only effectively tackle LIB waste issues but also skip... more Direct reuse of current collectors can not only effectively tackle LIB waste issues but also skip long conventional recycling processes, bringing environmental and economic benefits.
Uploads
Papers by Emma Kendrick