Theoretical Analysis of Interactions between Potassium Ions and Organic Electrolyte Solvents: A Comparison with Lithium, Sodium, and Magnesium Ions

Okoshi, Masaki; Yamada, Yuki; Komaba, Shinichi; Yamada, Atsuo; Nakai, Hiromi

doi:10.1149/2.0211702jes

Cited by 323 publications

(243 citation statements)

References 29 publications

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“…In addition, another possible reason for the slow electrochemical ion-exchange reaction could be attributed to the relatively lower solvation energy of the Na ion than that of the K ion in the organic electrolyte solution. 20 After 300 cycles, the multiple voltage steps obviously disappeared from the voltage profiles (Fig. 1b).…”

mentioning

confidence: 97%

Development of P3-K_0.69CrO₂ as an ultra-high-performance cathode material for K-ion batteries

Hwang

Kim

et al. 2018

Energy Environ. Sci.

175

131

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and exhibited the best cycling performance for a KIB cathode material to date. A combination of electrochemical profiles, ex situ X-ray diffraction, and first-principles calculations was used to understand the overall potassium storage mechanism of P3-K 0.69 CrO 2 . Based on a reversible phase transition, P3-K 0.69 CrO 2 delivers a high discharge capacity of 100 mA h g À1 and exhibits extremely high cycling stability with B65% retention over 1000 cycles at a 1C rate. Moreover, the K-ion hopping into the P3-K 0.69 CrO 2 structure was extremely rapid, resulting in great power capability of up to a 10C rate with a capacity retention of B65% (vs. the capacity at 0.1C).

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mentioning

confidence: 97%

Development of P3-K_0.69CrO₂ as an ultra-high-performance cathode material for K-ion batteries

Hwang

Kim

et al. 2018

Energy Environ. Sci.

175

131

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“…Each step is associated with an activation energy barrier and for Ca and Mg plating/stripping, the electrodeposition kinetics are expected to be hampered due to more energy consuming mass transport and desolvation than for monovalent cations, as outlined in recent computational studies. [45][46][47] For sake of comparison, in a Li system the desolvation was identified as the limiting step for the cation transport across the graphite anode/electrolyte interface. 48 From this, we foresee that the electrolyte formulation will play a major role in the development of divalent cation based batteries able to operate at low temperature and/or high power and should target the cation mobility and desolvation.…”

Section: Resultsmentioning

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

J. Electrochem. Soc.

114

141

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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...

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“…However, the authors did not provide specific evidence for these arguments, and the statement is at odds with the density functional theory prediction of faster mobility of K ion over Li and Na ions in nonaqueous electrolytes by Okoshi et al, and the experimental demonstration of this by Zhao et al using electrochemical impedance spectroscopy. [27,90] Overall, the specific energy achievable in K x Mn[Fe(CN) 6 ] 1−z -nH 2 O with the two-electron redox reaction rivals that of LiFePO 4 , though its volumetric energy density is unsatisfactory. [83,88] The full cell performance against the graphite anode shown in Figure 8b reveals excellent discharge rate capability, with delivery of 62 mA h g cathode −1 at a 2 A g cathode −1 rate.…”

Section: Hexacyanometallate Groups (Prussian Blue Analogues)mentioning

confidence: 99%

Recent Progress and Perspective in Electrode Materials for K‐Ion Batteries

Kim

Bianchini

et al. 2017

Advanced Energy Materials

615

465

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and demand in terms of time and space. Thus, grid-level stationary energy storage systems (ESSs) play a key role in making renewable energies both effective and efficient and thereby shaping a more sustainable and environmental friendly society.Although different energy storage technologies including mechanical, electrical, chemical, and electrochemical systems have been proposed, [2,3] mechanical energy storage through pumped hydroelectricity currently dominates the market (≈95% of the installed capacity, ≈183 GW). [4] Electrochemical energy storage is also being considered as a promising option for ESSs based on its flexibility of deployment with little restriction on size and geographical location, low maintenance costs, large energy density, high round-trip efficiency, and long cycle life. [3,5,6] The market for Li-ion batteries (LIBs), originally commercialized for portable electronic devices (i.e., cell phones and laptops), is now expanding to electric vehicles (EVs) and gridlevel ESSs. However, it remains debatable whether the global Li reserves, ≈14 million tons, can meet the increasing demand for such large-scale applications. [7][8][9] The price of lithium carbonate, which is a primary precursor for LIBs, has been continuously increasing since 2000, [10] and this trend is likely to accelerate once the EV and ESS markets take off. Moreover, Li is geographically limited to specific regions: ≈86% of the Li reserves are located in Bolivia, Chile, China, Argentina, and Australia; [9] therefore, geopolitical issues may arise. A more pressing issue for Li-ion markets is the use of Co in all high-energy-density systems. With more than 50% of all mined Co destined for use in Li-ion technology, and a substantial fraction of that coming from the Democratic Republic of the Congo, Li-ion growth may be hampered by the availability of Co. [11] As a less expensive alternative to LIBs, Na-ion batteries (NIBs) have been extensively studied. [6,[12][13][14] The relatively high standard redox potential of Na/Na + leads to a lower working voltage and thereby lower energy density than Li-ion. In addition, hard carbon, which is associated with a high production cost and low material's density, must be used as an anode in NIBs, as graphite, which is the standard anode for LIBs, cannot store Na ions. [15][16][17] Recently, K-ion batteries (KIBs) have emerged as another possible energy storage system. [18][19][20] It is notable that the abundance of K resources in the Earth's crust and oceans is similar to that of Na (Figure 1a). [21,22] The cost of potassium carbonate The development of rechargeable batteries using K ions as charge carriers has recently attracted considerable attention in the search for cost-effective and large-scale energy storage systems. In light of this trend, various materials for positive and negative electrodes are proposed and evaluated for application in K-ion batteries. Here, a comprehensive review of ongoing materials research on nonaqueous K-ion batteries is offered. Information on the status of ...

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Theoretical Analysis of Interactions between Potassium Ions and Organic Electrolyte Solvents: A Comparison with Lithium, Sodium, and Magnesium Ions

Cited by 323 publications

References 29 publications

Development of P3-K_0.69CrO₂ as an ultra-high-performance cathode material for K-ion batteries

Development of P3-K_0.69CrO₂ as an ultra-high-performance cathode material for K-ion batteries

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

Recent Progress and Perspective in Electrode Materials for K‐Ion Batteries

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Theoretical Analysis of Interactions between Potassium Ions and Organic Electrolyte Solvents: A Comparison with Lithium, Sodium, and Magnesium Ions

Cited by 323 publications

References 29 publications

Development of P3-K0.69CrO2 as an ultra-high-performance cathode material for K-ion batteries

Development of P3-K0.69CrO2 as an ultra-high-performance cathode material for K-ion batteries

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

Recent Progress and Perspective in Electrode Materials for K‐Ion Batteries

Contact Info

Product

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Development of P3-K_0.69CrO₂ as an ultra-high-performance cathode material for K-ion batteries

Development of P3-K_0.69CrO₂ as an ultra-high-performance cathode material for K-ion batteries

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