Layered Transition Metal Oxides as Cathodes for Sodium Secondary Battery

Okada, Shigeto; Takahashi, Yusuke; Kiyabu, Toshiyasu; Doi, Takayuki; Yamaki, Jun‐ichi; Nishida, Tetsuaki

doi:10.1149/ma2006-02/4/201

Cited by 83 publications

(52 citation statements)

References 3 publications

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“…They reported an average deintercalation voltage of the order of 2.72 V vs Na/ Na + . This reported potential is comparable to the potential of inorganic compounds used in sodium batteries such as NaFeO 2 , showing flat voltage profile of 3.3 V vs Na/Na + related to the Fe 3+ /Fe 4+ oxidation couple 13 and reasonably higher than the reported values of organic cathode materials already studied for sodium battery application. 5,6,14−17 The excellent performance of the chloranil as a cathode has motivated us to point out the missing links in its electrochemical reaction pathway.…”

Section: Introductionsupporting

confidence: 71%

Divulging the Hidden Capacity and Sodiation Kinetics of Na_xC₆Cl₄O₂: A High Voltage Organic Cathode for Sodium Rechargeable Batteries

2017

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In the current emerging sustainable organic battery field, quinones are seen as one of the prime candidates for application in rechargeable battery electrodes. Recently, C6Cl4O2, a modified quinone, has been proposed as a high voltage organic cathode. However, the sodium insertion mechanism behind the cell reaction remained unclear due to the nescience of the right crystal structure. Here, the framework of the density functional theory (DFT) together with an evolutionary algorithm was employed to elucidate the crystal structures of the compounds Na x C6Cl4O2 (x = 0.5, 1.0, 1.5 and 2). Along with the usefulness of PBE functional to reflect the experimental potential, also the importance of the hybrid functional to divulge the hidden theoretical capacity is evaluated. We showed that the experimentally observed lower specific capacity is a result of the great stabilization of the intermediate phase Na1.5C6Cl4O2. The calculated activation barriers for the ionic hops are 0.68, 0.40, and 0.31 eV, respectively, for NaC6Cl4O2, Na1.5C6Cl4O2, and Na2C6Cl4O2. These results indicate that the kinetic process must not be a limiting factor upon Na insertion. Finally, the correct prediction of the specific capacity has confirmed that the theoretical strategy used, employing evolutionary simulations together with the hybrid functional framework, can rightly model the thermodynamic process in organic electrode compounds.

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Section: Introductionsupporting

confidence: 71%

Divulging the Hidden Capacity and Sodiation Kinetics of Na_xC₆Cl₄O₂: A High Voltage Organic Cathode for Sodium Rechargeable Batteries

2017

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“…Sodium-ion batteries (SIBs) have been drawing much attention as candidates to replace lithium-ion batteries (LIBs) because sodium is a much more abundant and affordable alkali metal than lithium. − Lately, various cathode materials for SIBs have been developed. In particular, layer-structured materials such as Na x CoO 2 and Na x MnO 2 have been attracting considerable attention. − NaMeO compounds with a layered structure can be classified as being either of the prismatic (P2) or octahedral (O3) type. , In these materials, the sodium ions are intercalated between the MeO 2 slabs. O3-type materials including NaFe 1/2 Co 1/2 O 2 , NaNi 1/3 Fe 1/3 Mn 1/3 O 2 , and NaFe 1/2 Mn 1/2 O 2 have lower reversible discharge capacities than P2-type materials because of their complicated phase transition and alignment of sodium ions.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Rate Capability and Cycle Performance of Titanium-Substituted P2-Type Na_0.67Fe_0.5Mn_0.5O₂ as a Cathode for Sodium-Ion Batteries

Park

Kwak

et al. 2018

ACS Omega

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In this study, we developed a doping technology capable of improving the electrochemical performance, including the rate capability and cycling stability, of P2-type Na 0.67 Fe 0.5 Mn 0.5 O 2 as a cathode material for sodium-ion batteries. Our approach involved using titanium as a doping element to partly substitute either Fe or Mn in Na 0.67 Fe 0.5 Mn 0.5 O 2 . The Ti-substituted Na 0.67 Fe 0.5 Mn 0.5 O 2 shows superior electrochemical properties compared to the pristine sample. We investigated the changes in the crystal structure, surface chemistry, and particle morphology caused by Ti doping and correlated these changes to the improved performance. The enhanced rate capability and cycling stability were attributed to the enlargement of the NaO 2 slab in the crystal structure because of Ti doping. This promoted Na-ion diffusion and prevented the phase transition from the P2 to the OP4/″Z″ structure.

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“…However, it exhibited a cycle retention of only 79% over the course of 30 cycles. Okada et al demonstrated intercalation of Na + ions into an O3-type NaFeO 2 layer structure accompanied by Fe 3+/4+ redox reactions in the Na electrolyte. Komaba’s group pointed out the intrinsic problem of structural instability caused by Fe-ion migration during cycling in the O3-type NaFeO 2 layer structure .…”

Section: Introductionmentioning

confidence: 99%

Quaternary Transition Metal Oxide Layered Framework: O3-Type Na[Ni_0.32Fe_0.13Co_0.15Mn_0.40]O₂ Cathode Material for High-Performance Sodium-Ion Batteries

2018

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Analogous compounds in lithium-ion batteries (LIBs), various ternary chemical compositions in O3-type layered oxides, have been introduced in sodium-ion batteries (SIBs). However, O3-type ternary transition metal oxide cathodes, including the NaNi x Co y Mn z O 2 and NaNi x Fe y Mn z O 2 (x + y + z = 1) compounds, continue to face several challenges with respect to their low reversible capacity and poor cycle retention owing to their structural instability. Herein, we propose the wellbalanced quaternary transition metal oxide structure of O3-type Na[Ni 0.32 Fe 0.13 Co 0.15 Mn 0.40 ]O 2 as cathode materials that have an average composition of both Na[Ni 0.25 Fe 0.25 Mn 0.5 ]O 2 and Na[Ni 0.4 Co 0.3 Mn 0.3 ]O 2 compounds. Compared to its respective ternary members, the Na-[Ni 0.32 Fe 0.13 Co 0.15 Mn 0.40 ]O 2 cathode exhibits a higher specific capacity as well as improved cycling stability and rate capability. The post-mortem exsitu X-ray diffraction (XRD) studies of a cycled electrode clearly show that coexistence of quaternary transition metals in a Na[Ni 0.32 Fe 0.13 Co 0.15 Mn 0.40 ]O 2 cathode could improve the structural stability. Moreover, quaternary transition metal oxide frameworks effectively prevent the dissolution of transition metals during cycling, thus improving the battery performances. The appealing physical properties and electrochemical performance of this material demonstrate its great promise for a highperformance O3-type cathode in sodium-ion batteries.

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Layered Transition Metal Oxides as Cathodes for Sodium Secondary Battery

Abstract: not Available.

Cited by 83 publications

References 3 publications

Divulging the Hidden Capacity and Sodiation Kinetics of Na_xC₆Cl₄O₂: A High Voltage Organic Cathode for Sodium Rechargeable Batteries

Divulging the Hidden Capacity and Sodiation Kinetics of Na_xC₆Cl₄O₂: A High Voltage Organic Cathode for Sodium Rechargeable Batteries

Enhanced Rate Capability and Cycle Performance of Titanium-Substituted P2-Type Na_0.67Fe_0.5Mn_0.5O₂ as a Cathode for Sodium-Ion Batteries

Quaternary Transition Metal Oxide Layered Framework: O3-Type Na[Ni_0.32Fe_0.13Co_0.15Mn_0.40]O₂ Cathode Material for High-Performance Sodium-Ion Batteries

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Layered Transition Metal Oxides as Cathodes for Sodium Secondary Battery

Abstract: not Available.

Cited by 83 publications

References 3 publications

Divulging the Hidden Capacity and Sodiation Kinetics of NaxC6Cl4O2: A High Voltage Organic Cathode for Sodium Rechargeable Batteries

Divulging the Hidden Capacity and Sodiation Kinetics of NaxC6Cl4O2: A High Voltage Organic Cathode for Sodium Rechargeable Batteries

Enhanced Rate Capability and Cycle Performance of Titanium-Substituted P2-Type Na0.67Fe0.5Mn0.5O2 as a Cathode for Sodium-Ion Batteries

Quaternary Transition Metal Oxide Layered Framework: O3-Type Na[Ni0.32Fe0.13Co0.15Mn0.40]O2 Cathode Material for High-Performance Sodium-Ion Batteries

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Divulging the Hidden Capacity and Sodiation Kinetics of Na_xC₆Cl₄O₂: A High Voltage Organic Cathode for Sodium Rechargeable Batteries

Divulging the Hidden Capacity and Sodiation Kinetics of Na_xC₆Cl₄O₂: A High Voltage Organic Cathode for Sodium Rechargeable Batteries

Enhanced Rate Capability and Cycle Performance of Titanium-Substituted P2-Type Na_0.67Fe_0.5Mn_0.5O₂ as a Cathode for Sodium-Ion Batteries

Quaternary Transition Metal Oxide Layered Framework: O3-Type Na[Ni_0.32Fe_0.13Co_0.15Mn_0.40]O₂ Cathode Material for High-Performance Sodium-Ion Batteries