On the Comparative Stability of Li and Na Metal Anode Interfaces in Conventional Alkyl Carbonate Electrolytes

1,557

1,474

The Solid-Electrolyte-Interphase (SEI) model for non-aqueous alkali-metal batteries constitutes a paradigm change in the understanding of lithium batteries and has thus enabled the development of safer, durable, higher-power and lower-cost lithium batteries for portable and EV applications. Prior to the publication of the SEI model (1979), researchers used the Butler-Volmer equation, in which a direct electron transfer from the electrode to lithium cations in the solution is assumed. The SEI model proved that this is a mistaken concept and that, in practice, the transfer of electrons from the electrode to the solution in a lithium battery, must be prevented, since it will result in fast self-discharge of the active materials and poor battery performance. This model provides [E. Peled, in "Lithium Batteries," J.P. Gabano (ed), Academic Press, (1983), E. Peled, J. Electrochem. Soc., 126, 2047Soc., 126, (1979.] new equations for: electrode kinetics (i o and b), anode corrosion, SEI resistivity and growth rate and irreversible capacity loss of lithium-ion batteries. This model became a cornerstone in the science and technology of lithium batteries. This paper reviews the past, present and the future of SEI batteries. The PastPrior to the publication of the SEI model (1979), 1,4 researchers used the Butler-Volmer equation, in which direct electron transfer from the electrode to lithium cations in the solution is assumed. It was generally assumed that the rate-determining step (RDS) is the transfer of electrons from the metal to the cations in the solution. Researchers found that the lithium anode is covered by a passivating layer which interferes with the deposition/dissolution process of the anode. Brummer and Newman 2,3 concluded that a passivating anode can offer only a limited cycle life and in order to obtain a deep-discharge high-cycle-life secondary battery, the lithium anode must be free of a passivating layer and kinetically stable with respect to the electrolyte. The SEI model proved that this is a mistaken concept and that, in practice, the transfer of electrons from the electrode to the solution in a lithium battery, except when forming a SEI, must be prevented. The Present, Lithium-Metal and Lithium-Ion BatteriesIntroduction.-It is now generally accepted that the solidelectrolyte interphase (SEI) is essentially for the existence and successful operation of lithium-and sodium-battery systems, as primary and secondary power sources. 4 In 1979, it was proposed by Peled,

Section: Future Systemsmentioning

confidence: 99%

Section: Future Systemsmentioning

confidence: 99%

Section: Future Systemsmentioning

confidence: 99%

See 1 more Smart Citation

Review—SEI: Past, Present and Future

Peled

Menkin

2017

1,557

1,474

“…Although these conditions are, at least satisfactorily, met in Li half-cells, 20 recent studies point to several issues associated with the use of Na metal CEs and REs. [21][22][23][24] No extensive studies have been made in order to evaluate the reliability of Mg and Ca half-cell configurations. Undeniably, the poor divalent cation mobility within the electrolyte is an important limiting factor in Ca based cells, as reported in Ref.…”

mentioning

confidence: 99%

On the Reliability of Half-Cell Tests for Monovalent (Li⁺, Na⁺) and Divalent (Mg²⁺, Ca²⁺) Cation Based Batteries

Tchitchekova

Monti

Johansson

et al. 2017

Self Cite

113

141

A comprehensive study is reported entailing a comparison of Li, Na, K, Mg, and Ca based electrolytes and an investigation of the reliability of electrochemical tests using half-cells. Ionic conductivity, viscosity, and Raman spectroscopy results point to the cationsolvent interaction to follow the polarizing power of the cations, i.e. Mg 2+ > Ca 2+ > Li + > Na + > K + and to divalent cation based electrolytes having stronger tendency to form ion pairs -lowering the cation accessibility and mobility. Both increased temperature and the use of anions with delocalized negative charge, such as TFSI, are effective in mitigating this issue. Another factor impeding the divalent cations mobility is the larger solvation shells, as compared to those of monovalent cations, that in conjunction with stronger solvent -cation interactions contribute to slower charge transfer and ultimately a large impedance of Mg and Ca electrodes. An important consequence is the non-reliability of the pseudo-reference electrodes as these present both significant potential shifts as well as unstable behaviors. Finally, experimental protocols in order to achieve consistent results when using half-cell set-ups are Although the lithium-ion battery is currently being considered as the most promising technology for electric vehicle propulsion, the development of alternative and complementary battery chemistries and technologies is of great importance, especially aiming at large-scale applications, i.e. the grid for which the cost in $/kWh and sustainability are crucial indicators. Indeed, the implementation of lithium based technology at large scale faces a significant challenge, since the controversial debates on lithium availability and cost cannot be overlooked. Amongst several chemistries possible the most appealing alternatives involve the use of sodium (Na), magnesium (Mg) or calcium (Ca) for mainly two reasons. The prime is the abundance of the raw materials, i.e. Na, Mg, and Ca being the 6 th , 8 th , and 5 th most abundant elements in the Earth's crust, vs. 25 th for Li, making them 20 to 50 times cheaper than Li, e.g. $5000/ton, $135-165/ton, $265/ton, and $100/ton for Li 2 CO 3 , Na 2 CO 3 , MgO 2 , and CaCO 3 , 1 respectively. Performance wise, the low cost alternatives of Na, Mg, and Ca technologies would also benefit from high standard reduction potentials, ca. −2.71, −2.37, and −2.87 V vs. SHE for Na, Mg, and Ca, respectively, as compared to −3.04 V for Li, and large theoretical electrochemical capacities, both gravimetric and volumetric, for the metal electrodes (Fig. 1).Sodium metal anodes are already used in the liquid state (m.p. ∼97• C) in the Na/S technology 2 and room-temperature Na-ion technology is currently intensively investigated with hundreds of papers appearing per year, with progress being summarized in several review papers amongst which 3-5 are the most recent. For Mg and Ca metal anodes, the situation is radically different. For the Mg battery technology, proof-of-concept was achieved as late as in 2000, 6 although i...

“…As shown in Figure 4c, the crystal structure of the Na( As already shown by several groups, Na metal involves an unstable SEI layer and can be easily oxidized than Li metal during cycling, which can affect the electrochemical performances of the cathode materials. 36,37 To measure the exact electrochemical characteristics of Na[Cu 0.2 (Fe 1/3 Mn 2/3 ) 0.8 ]O 2 , therefore, we assembled a full cell with the P-TiP 2 -C alloy-type anode material that was developed by our group. 34 This material has nano-size particles and the SEM and XRD data of the samples are shown in Figure S2 (see supplementary material).…”

Section: Resultsmentioning

confidence: 99%

A High-Performance Sodium-Ion Full Cell with a Layered Oxide Cathode and a Phosphorous-Based Composite Anode

Kim

et al. 2016

A low-cost sodium-ion full cell with a O3-type layered Na[Cu 0.2 (Fe 1/3 Mn 2/3 ) 0.8 ]O 2 cathode and an alloy-type P-TiP 2 -C anode is presented. The cathode is synthesized by an oxalate coprecipitation method and optimized cathodes shows a high specific capacity of 135 mAh g −1 at 0.1C rate with a high rate capability of 90 mAh g −1 at 1C rate and 70 mAh g −1 at 2C rate with good cyclability. The full cell exhibits better capacity retention than the half cell with the cathode due to the elimination of the degradation caused by sodium-metal anode. The dramatically enhanced electrochemical performance of the Na[Cu 0.2 (Fe 1/3 Mn 2/3 ) 0.8 ]O 2 / P-TiP 2 -C full cell compared to that of the sample with no Cu is attributed to the structural stabilization imparted by Cu by suppressing the phase change from the O3 structure to the P3 structure during cycling. As the demand for rechargeable batteries is increasing, the research activities in the Li-ion battery area had grown exponentially during the past 25 years.1,2 However, due to the relatively low abundance of lithium resources and the high cost, there is immense interest to develop battery chemistries based on low-cost working ions, particularly for large-scale applications. In this regard, Na-ion batteries are emerging as an alternative due to the high abundance and low cost of Na. In addition, the larger size of Na + compared to Li + helps to minimize the cation disorder between Na + and the transition-metal ions. Therefore, various kinds of Na-based cathode materials have been investigated with the O3-type layered, 3-19 P2-type layered, [21][22][23][24][25][26][27][28][29] and polyanion-type structures. [30][31][32] Among them, the O3-type cathode materials are the most promising due to their similarity to the well-known LiCoO 2 cathode used in lithium-ion industry. Also, as has been reported in the literature, the O3-type cathodes have much more stable crystal structure and capacity retention than the P2-type cathode materials. 7,18,19 With the above perspective, several O3 type cathode compositions have been introduced, but they are generally based on expensive transition metal ions such as Ni and Co. 7,8,[10][11][12][13][14][15]17 To take the low-cost advantage of sodium-ion batteries, it is critical to replace these expansive transition-metal ions by low-cost transition-metal ions such as Fe, Mn and Cu. In this regard, several research groups have focused on the Fe-based O3-type cathode NaFeO 2 .4-6 However, the high-spin Fe 3+ :t 2g 3 e g 2 ions tend to migrate readily from the octahedral sites in the transition-metal layer to the octahedral sites in the sodium layer via a neighboring tetrahedral site as the Fe 3+ ion has no particular preference for octahedral sites.4 Therefore, to overcome this difficulty, it is necessary to mix Fe with other transition-metal ions such as