Hydrides as High Capacity Anodes in Lithium Cells: An Italian “Futuro in Ricerca di Base FIRB-2010” Project
Abstract
:1. Introduction
2. The Futuro in Ricerca di Base FIRB-2010 Futuro in Ricerca Project
2.1. Basic Ideas
- The lack of experimental evidence of the electrochemical activity and HCR reversibility of almost all metallic and complex hydrides in lithium cells;
- The weak demonstration of an extended cycling ability of these materials in lithium cells;
- The almost negligible analysis of the chemical and electrochemical stability of the electrolyte/electrode interface in lithium cells.
2.2. Hydride Selection
- Cost and environmental compatibility: Candidate hydrides are required to be constituted by atomic elements that are naturally abundant and thus not expensive. They must be environmentally friendly, non-toxic non-explosive, non-pyrophoric and possibly inert to water and oxygen. Among the light elements, the latter constraint necessarily implies discarding Be-based hydrides and to strongly limit V and Co.
- Estimated theoretical performances: Candidate hydrides must show theoretical capacities as high as possible, at least higher than that of graphite (370 mAh·g−1 or 550 mAh·cc−1). Furthermore, in order to assure both the safety and high energy in the final application, the estimated Nernst working potential in the corresponding HCR must range between 1 and 0.1 V vs. Li, far from the Li deposition potential.
- Safety constraint: Selected hydrides must be stable from room temperature up to 200–250 °C with a negligible H2 desorption pressure at room temperature; quantitatively, this parameter is given by the so-called hydride decomposition temperature, which accordingly, is required to be >200 °C.
2.3. Methodological Approach
3. Project Results and Achievements
3.1. Materials Screening
3.1.1. Simple Metal Hydrides
3.1.2. Borohydrides
3.1.3. Alanates
3.1.4. Other Complex Hydrides
3.2. Mechanism Comprehension
3.3. Materials Optimization Trials
3.4. Electrochemical Cell Formulation Assessment
3.5. Li-Ion-Hydride Proof of Concept
4. Conclusions
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Hydride | Symmetry Space Group | Formula Weight (g·mol−1) | Theoretical Capacity (mAh·g−1) |
---|---|---|---|
MgH2 | Pbcn | 26.3 | 2037 |
NaH | Fm-3m | 24.0 | 1117 |
TiH2 | I4/mmm | 49.9 | 1075 |
CaH2 | Pnma | 42.1 | 1273 |
LiBH4 | Pnma | 21.8 | 4992 |
NaBH4 | P-421c | 37.8 | 2834 |
KBH4 | P421c | 53.9 | 1987 |
Mg(BH4)2 | P6122 | 54.0 | 3971 |
Ca(BH4)2 | α Fddd | 69.8 | 3074 |
β P42/m | |||
LiAlH4 | P21/c | 37.9 | 2119 |
Li3AlH6 | R-3 | 53.8 | 1493 |
NaAlH4 | I41/a | 54.0 | 1985 |
Na2LiAlH6 | Fm-3m | 85.9 | 1559 |
Na3AlH6 | P21/n | 102.0 | 1578 |
Mg2NiH4 | C2/c | 111.4 | 963 |
Mg2FeH6 | Fm-3m | 110.5 | 1455 |
Reaction | Theoretical Emf (V) |
---|---|
MgH2 + 2 Li = Mg + 2 LiH | 0.53 |
NaH + Li = Na + LiH | 0.43 |
TiH2 + 2 Li = Ti + 2 LiH | 0.15 |
CaH2 + 2 Li = Ca + 2 LiH | −0.02 |
Hydride | Theoretical Capacity (mAh·g−1) | Ball Milling Time (hours) | Ball Milling Time with Carbon (5:3 Ratio between Borohydride and Carbon) (hours) | First Discharge Capacity (mAh·g−1) | Li Equivalents Incorporated in PCGA Tests (First Discharge) |
---|---|---|---|---|---|
LiBH4 | 4992 | 15 | 5 | 52 | 0.04 |
NaBH4 | 2834 | 1 | ½ | 74 | 0.10 |
15 | 5 | 211 | 0.30 | ||
KBH4 | 1987 | 15 | 5 | 66 | 0.13 |
Mg(BH4)2 | 3971 | 1 | ½ | 539 | 1.09 |
15 | 5 | 205 | 0.41 | ||
Ca(BH4)2 | 3074 | 15 | 5 | 9 | 0.003 |
Reaction | Theoretical Emf (V) |
---|---|
2 NaAlH4 + 3 Li = LiNa2AlH6 + 2 LiH + Al | 0.73 |
3/2 LiNa2AlH6 + 3/2 Li = 3 LiH + 1/2 Al + Na3AlH6 | 0.66 |
Na3AlH6 + 3 Li = 3 NaH + Al + 3 LiH | 0.61 |
NaH + Li = Na + LiH | 0.43 |
3LiAlH4 + 6e + 6Li+ ⇄ Li3AlH6 + 2Al+6LiH | 0.86 |
Li3AlH6 + 3e+3Li+ ⇄ 6LiH + Al | 0.74 |
Al + Li ⇄ AlLi | 0.29 |
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Brutti, S.; Panero, S.; Paolone, A.; Gatto, S.; Meggiolaro, D.; Vitucci, F.M.; Manzi, J.; Munaò, D.; Silvestri, L.; Farina, L.; et al. Hydrides as High Capacity Anodes in Lithium Cells: An Italian “Futuro in Ricerca di Base FIRB-2010” Project. Challenges 2017, 8, 8. https://doi.org/10.3390/challe8010008
Brutti S, Panero S, Paolone A, Gatto S, Meggiolaro D, Vitucci FM, Manzi J, Munaò D, Silvestri L, Farina L, et al. Hydrides as High Capacity Anodes in Lithium Cells: An Italian “Futuro in Ricerca di Base FIRB-2010” Project. Challenges. 2017; 8(1):8. https://doi.org/10.3390/challe8010008
Chicago/Turabian StyleBrutti, Sergio, Stefania Panero, Annalisa Paolone, Sara Gatto, Daniele Meggiolaro, Francesco M. Vitucci, Jessica Manzi, David Munaò, Laura Silvestri, Luca Farina, and et al. 2017. "Hydrides as High Capacity Anodes in Lithium Cells: An Italian “Futuro in Ricerca di Base FIRB-2010” Project" Challenges 8, no. 1: 8. https://doi.org/10.3390/challe8010008