Sodium deficient nickel–manganese oxides as intercalation electrodes in lithium ion batteries

Kalapsazova, Mariya; Stoyanova, Р.; Zhecheva, E.; Tyuliev, G.; Nihtianova, D.

doi:10.1039/c4ta04094e

Cited by 55 publications

(73 citation statements)

References 59 publications

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“…The main peak with ab inding energy of 688 eV is assigned to PVDF (CH 2 -CF 2 ). [67] The smaller peak at lower binding energy ( % 684.8 eV;F igure 5b,g reen)i sm ainly presenta tt he outermost surface and can be assigned to traces of NaF.T he only source of fluorine in the pristine electrode is the PVDF binder;thus suggesting degradationo ft he binder during electrode preparation.T he presence of NaF resulting from ad ehydrofluorinationr eactioni n the PVDF binder wasa lso observedr ecently by MuÇoz-Mµrquez et al [21] The C1sa nd F1ss pectra are mainly dominated by the signalo ft he electrode components (binder and carbon additives).I nt his respect, ab etter look into the impurities and surface speciesp resent at the surface can be achieved through the analysis of the O1sa nd Na 1s core levels.…”

Section: Pristinee Lectrodementioning

confidence: 98%

Passivation Layer and Cathodic Redox Reactions in Sodium‐Ion Batteries Probed by HAXPES

et al. 2015

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The cathode material P2-Nax Co2/3 Mn2/9 Ni1/9 O2, which could be used in Na-ion batteries, was investigated through synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES). Nondestructive analysis was made through the electrode/electrolyte interface of the first electrochemical cycle to ensure access to information not only on the active material, but also on the passivation layer formed at the electrode surface and referred to as the solid permeable interface (SPI). This investigation clearly shows the role of the SPI and the complexity of the redox reactions. Cobalt, nickel, and manganese are all electrochemically active upon cycling between 4.5 and 2.0 V; all are in the 4+ state at the end of charging. Reduction to Co(3+), Ni(3+), and Mn(3+) occurs upon discharging and, at low potential, there is partial reversible reduction to Co(2+) and Ni(2+). A thin layer of Na2 CO3 and NaF covers the pristine electrode and reversible dissolution/reformation of these compounds is observed during the first cycle. The salt degradation products in the SPI show a dependence on potential. Phosphates mainly form at the end of the charging cycle (4.5 V), whereas fluorophosphates are produced at the end of discharging (2.0 V).

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Section: Pristinee Lectrodementioning

confidence: 98%

Passivation Layer and Cathodic Redox Reactions in Sodium‐Ion Batteries Probed by HAXPES

et al. 2015

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“…The unique property of P 3‐phases is their capability to intercalate not only Na + , but also Li + ions ,. Contrary to Na + insertion, the process of insertion of Li + into P3 ‐phase causes a structural transformation from the P3 ‐ to the O3 ‐type of structure ,,,,. The in‐situ generated O3 ‐phase gives rise to the further electrochemical response of P3 ‐phase in terms of voltage profile, cycling stability and rate capability .…”

Section: Structural Matrices Suitable For Li+ Na+ and Mg2+ Intercalamentioning

confidence: 99%

Lithium versus Mono/Polyvalent Ion Intercalation: Hybrid Metal Ion Systems for Energy Storage

Stoyanova

Koleva

2018

The Chemical Record

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The energy storage by redox intercalation reactions is, nowadays, the most effective rechargeable ion battery. When lithium is used as intercalating agents, the high energy density is achieved at an expense of non-sustainability. The replacement of Li with cheaper monovalent ions enables to make greener battery alternatives. The utilization of polyvalent ions instead of Li permits to multiplying the battery capacity. Contrary to Li , the realization of quick and reversible intercalation of bigger monovalent and of polyvalent ions is a scientific challenge due to kinetic constraints, polarizing ion effects and Coulomb interactions. Herein we provide a vision how to make the intercalation of these ions feasible. The idea is to perform dual intercalation of ions having different charges, radii, preferred coordination and diffusion pathway topology. All these features are demonstrated by the recent knowledge on selective and non-selective intercalation properties of oxides and polyanion compounds with layered and tunnel structures. Based on dual intercalation properties, the fabrication of hybrid metal ion batteries is presented and discussed.

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“…On the contrary, the transformation of P 2 into P 3 requires scission of Ni 0.5 Mn 0.5 −O bonds. Depending on the Na to (Ni+Mn) ratio, the sodium–nickel–manganese oxides can assume O 3‐, P 3 ‐, and P 2‐type structures . Although stoichiometric NaNi 0.5 Mn 0.5 O 2 adopts the O 3‐type structure, the P 2 and P 3 phases are established for sodium‐deficient oxides Na 1− x Ni 0.5 Mn 0.5 O 2 .…”

Section: Introductionmentioning

confidence: 99%

“…Depending on the Na to (Ni+Mn) ratio, the sodium–nickel–manganese oxides can assume O 3‐, P 3 ‐, and P 2‐type structures . Although stoichiometric NaNi 0.5 Mn 0.5 O 2 adopts the O 3‐type structure, the P 2 and P 3 phases are established for sodium‐deficient oxides Na 1− x Ni 0.5 Mn 0.5 O 2 . During desodiation of NaNi 0.5 Mn 0.5 O 2 to form Ni 0.5 Mn 0.5 O 2 , there is a reversible structural transformation from the hexagonal O 3‐type structure into the hexagonal P 3“‐type structure .…”

Section: Introductionmentioning

confidence: 99%

P3‐Type Layered Sodium‐Deficient Nickel–Manganese Oxides: A Flexible Structural Matrix for Reversible Sodium and Lithium Intercalation

et al. 2015

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Sodium‐deficient nickel–manganese oxides exhibit a layered structure, which is flexible enough to acquire different layer stacking. The effect of layer stacking on the intercalation properties of P3‐NaxNi0.5Mn0.5O2 (x=0.50, 0.67) and P2‐Na2/3Ni1/3Mn2/3O2, for use as cathodes in sodium‐ and lithium‐ion batteries, is examined. For P3‐Na0.67Ni0.5Mn0.5O2, a large trigonal superstructure with 2√3 a×2√3 a×2 c is observed, whereas for P2‐Na2/3Ni1/3Mn2/3O2 there is a superstructure with reduced lattice parameters. In sodium cells, P3 and P2 phases intercalate sodium reversibly at a well‐expressed voltage plateau. Preservation of the P3‐type structure during sodium intercalation determines improving cycling stability of the P3 phase within an extended potential range, in comparison with that for the P2 phase, for which a P2–O2 phase transformation has been found. Between 2.0 and 4.0 V, P3 and P2 phases display an excellent rate capability. In lithium cells, the P3 phase intercalates lithium, accompanied by a P3–O3 structural transformation. The in situ generated O3 phase, containing lithium and sodium simultaneously, determines the specific voltage profile of P3‐NaxNi0.5Mn0.5O2. The P2 phase does not display any reversible lithium intercalation. The P3 phase demonstrates a higher capacity at lower rates in lithium cells, whereas in sodium cells P3‐NaxNi0.5Mn0.5O2 operates better at higher rates. These findings reveal the unique ability of sodium‐deficient nickel–manganese oxides with a P3‐type structure for application as low‐cost electrode materials in both sodium‐ and lithium‐ion batteries.

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Sodium deficient nickel–manganese oxides as intercalation electrodes in lithium ion batteries

Abstract: The capability of sodium deficient nickel manganese oxides to participate in reactions of Li+intercalation and Na+/Li+exchange allows their use as low-cost electrode materials in lithium cells.

Cited by 55 publications

References 59 publications

Passivation Layer and Cathodic Redox Reactions in Sodium‐Ion Batteries Probed by HAXPES

Passivation Layer and Cathodic Redox Reactions in Sodium‐Ion Batteries Probed by HAXPES

Lithium versus Mono/Polyvalent Ion Intercalation: Hybrid Metal Ion Systems for Energy Storage

P3‐Type Layered Sodium‐Deficient Nickel–Manganese Oxides: A Flexible Structural Matrix for Reversible Sodium and Lithium Intercalation

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