P2-NaxMn1/2Fe1/2O2 Phase Used as Positive Electrode in Na Batteries: Structural Changes Induced by the Electrochemical (De)intercalation Process

Boisse, Benoit Mortemard de; Carlier, Dany; Guignard, Marie; Bourgeois, Lydie; Delmas, Claude

doi:10.1021/ic5017802

Cited by 225 publications

(280 citation statements)

References 31 publications

(23 reference statements)

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“…In many cases, the determination of the long-range order of layer stacking from X-ray diffraction patterns is particularly tricky. The diffraction pattern of the cathode in the high voltage region can either not be fully indexed due to extensive broadening of the diffraction peaks, or the goodness of fit is similar with different structural models (O2, O6, OP4), as was highlighted in a recent study of P2-Na x Mn 1/2 Fe 1/2 O 2 by Mortemard de Boisse et al 62 Lu and Dahn, in their study of the P2-Na x Ni 1/3 Mn 2/3 O 2 material, described two possible directions for oxygen layer shifts to form an octahedral close-packed oxygen framework, starting from the prismatic framework. 10 The authors explained that, because these two choices are selected at random (see Figure 5), the resulting structure necessarily develops stacking faults.…”

Section: The Different Crystal Chemistries Of Intercalated LImentioning

confidence: 98%

Review—Manganese-Based P2-Type Transition Metal Oxides as Sodium-Ion Battery Cathode Materials

Clément

Bruce

Grey

2015

J. Electrochem. Soc.

411

388

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Sodium transition metal oxides (NaMO 2 ) with a P2 structure exhibit good Na + ion conductivity and are promising sodium-ion battery cathode materials. Manganese-based compounds have a high working potential vs. Na + /Na, and high capacity. Yet, the layered nature of these materials means that they are prone to structural rearrangements at high voltage/low Na contents, the phase transformations and Na + ion/vacancy ordering transitions resulting in capacity fade and poor reversibility. This review discusses the latest advances in the field and focuses mainly on recent work on Na y Mn 1-x M x O 2 (x, y ≤ 1, M = Ni, Mg, Li) compounds. We compare the different lithium and sodium transition metal layered oxides (P2, O3, etc.) and describe the structures and mechanisms observed on alkali (de)intercalation. The strategies used to enhance the electrochemical properties and stabilize the structural framework of sodium transition metal oxides are reviewed. We show how X-ray diffraction and 7 Li/ 23 Na solid-state Nuclear Magnetic Resonance can be combined to provide a detailed insight into the structural and electronic processes occurring upon electrochemical cycling of these materials. Why Are We Interested in Na-Ion Battery Cathodes?Together, the increasing demand for energy and the threat from Global Warming make electrical energy storage (EES) a world wide strategic priority. EES is expected to play a key role in the decarbonization of electric power sources. The two billion people worldwide not currently served by a reliable electricity supply are likely to be connected via local grids, for which EES is essential. While Li-ion batteries (LIBs) will play a role, a key challenge is to develop lower cost batteries that deliver safe, reliable storage with high cycle and calendar life. In this regard, Na-ion batteries (NIBs) are potentially important. NIBs operate in a similar fashion to LIBs, offering both advantages and disadvantages. Concerning the former, the ability to use Al instead of Cu as a current collector at the anode could substantially reduce cost. Na is also far more abundant in the Earth's crust than Li, and more widely distributed geographically. Regarding the disadvantages, the standard operating potential of Na metal is 300 mV more positive than Li metal. This generally translates into lower operating potentials for Na-ion systems, although the potential of a full cell depends on the difference in the chemical potentials of Na in the anode and cathode materials. There are considerable opportunities for scientists to develop new combinations of anode, electrolyte and cathode that are optimized for a variety of applications with different criteria such as high energy density, high power, and high operating potential. This has encouraged a rapid growth of interest in research into NIB components. Hard carbons show some promise as anodes, [1][2][3] but more must be done to improve performance. The cathode remains a major challenge and it is to this that we direct the current review. A comparative plot sho...

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Section: The Different Crystal Chemistries Of Intercalated LImentioning

confidence: 98%

Review—Manganese-Based P2-Type Transition Metal Oxides as Sodium-Ion Battery Cathode Materials

Clément

Bruce

Grey

2015

J. Electrochem. Soc.

411

388

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“…Despite such harsh demands, there have been a few promising NIB electrode materials reported which meet most of the above requirements for grid-storage batteries. [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] Among them, there is a class of cathodes belonging to the Prussian Blue Analogue (PBA) family which is very appealing due to its reliance on Fe and/or Mn as the redox active centers and possession of high sodium storage capacities (theoretical capacity limit as high as 170.8 mAh g −1 assuming two mole sodium storage per mole of material) at relatively high voltages. 23 The general formula for PBAs relevant for NIBs is Na x M 1 [M 2 (CN) 6 ] 1-y y .nH 2 O with 0 ≤ x ≤ 2 and 0 ≤ y < 1.…”

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confidence: 99%

Monoclinic Sodium Iron Hexacyanoferrate Cathode and Non-Flammable Glyme-Based Electrolyte for Inexpensive Sodium-Ion Batteries

Rudola

Balaya

2017

J. Electrochem. Soc.

103

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One of the key requirements of large-scale grid-storage systems is development of inexpensive and safe batteries. Sodium-ion batteries using earth-abundant Fe or Ti based cathodes and anodes would be ideal candidates for such storage systems. Herein, a new phase of Na-rich and all Fe Prussian Blue Analogue, monoclinic Na2Fe2(CN)6.2H2O, is reported as a potential cathode for such grid-storage sodium-ion batteries. This water-insoluble and air-stable cathode can deliver 85 mAh g−1 at an average discharge voltage of 3 V vs Na/Na+ with excellent cycle life (3,000 cycles). Many facets about its sodium storage characteristics are discussed with particular emphasis on the role of interstitial water on the sodium storage performance and its conversion to the dehydrated rhombohedral phase. Its compatibility with a newly developed non-flammable glyme-based liquid electrolyte, 1M NaBF4 in tetraglyme, is also disclosed along with general electrochemical and thermal characterization of this electrolyte for sodium-ion battery application. Finally, three different types of full cells are revealed with either monoclinic or rhombohedral phase as cathode and graphite or the recently reported Na2Ti3O7 ⇋ Na3-xTi3O7 pathway of Na2Ti3O7 as anode. Full cell energy densities of 70–90 Wh kg−1 (using cumulative cathode and anode weights) could be obtained without any pre-cycling steps. This new cathode and safe electrolyte may hold great promise toward development of inexpensive, non-flammable and highly stable grid-storage sodium-ion batteries.

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“…(2) Interactions between black phosphorus and carbon are present in the sample as deduced from the XRD, Raman and XPS spectra. These interactions help to maintain electrical contact between BP and the carbon network and also preserve the structural integrity of the electrode during cycling.The improvement in cycling performance compared to ref.[21] will be the beneficial effects of several factors: (1), reduced size of carbon materials which enables better electrical conduction in the composite and more interactions with phosphorus; (2), higher energy applied in the ball milling procedure, which reduces the particle size allowing for faster kinetics and stronger interactions between phosphorus and carbon;(3), increased FEC concentration in the electrolyte which creates a more stable SEI layer and (4), limited voltage window for cycling resulting in ameliorated structural deformation along cycling [21,37,38] . In summary, we developed a cost-effective, highperformance anode for SIBs based on a facilely synthesized black phosphorus -carbon composite.…”

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confidence: 99%

High‐Performance and Low‐Cost Sodium‐Ion Anode Based on a Facile Black Phosphorus−Carbon Nanocomposite

Peng

Liu

et al. 2017

ChemElectroChem

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Black phosphorus (BP) has received increasing research attention as an anode material in sodium ion batteries (SIBs) due to its high capacity, electronic conductivity and chemical stability. However, it is still challenging for BP based SIB anodes to achieve a high electrochemical performance utilizing cost-effective materials and synthetic methods. This work presents a sodium ion anode based on a facile BP -carbon nanocomposite synthesized from commercial red phosphorus and low-cost super P carbon black. Intimate interactions between BP and carbon are present which help to maintain the electrical conduction during cycling and therefore a high cycling stability is achieved. It exhibits a high capacity retention of 1381 mAh g -1 for sodium ion storage after 100 cycles, maintaining 90.5 % of the initial reversible capacity. Such high performance / materials cost ratio may provide direction for future phosphorus based anodes in high energy density SIBs.Cost-effective and high energy density batteries and battery materials are required to meet the demand of electricity storage. Sodium ion batteries (SIBs) attract increasing research attention because of the high abundance of sodium compared to lithium, and significant progress has been made in recent years. [1][2][3] Among the high-capacity anode materials (Sb, Sn, etc.) for sodium ion storage, phosphorus exhibits the highest theoretical capacity of 2596 mAh g −1 (Na 3 P). Significant research interest has been triggered by the prospects of high energy density SIBs based on phosphorus anodes. [4,5] Phosphorus exists in several allotropes that exhibit strikingly different properties. White phosphorus is chemically unstable, volatile, toxic and non-conducting, and therefore not suitable for battery applications. The most common allotrope, red phosphorus, is widely available and chemically stable, and has been studied intensively for sodium ion batteries. [6][7][8][9][10][11][12][13] However, its low electrical conductivity appears to be a major drawback. To address this issue, these electrodes included a large amount of costly carbon nanomaterials (graphene, carbon nanotube (CNT), carbon nanofiber (CNF), etc.). For large scale applications the use of CNT's needs orders of magnitude reduced cost levels, [14] while also graphene and its processing are considered costly. [15] With respect to energy density and manufacturing cost these material factors [16] form a barrier for the commercial introduction of phosphorus as the anode materials for SIBs. Cost-effective super P carbon black are also investigated, [17] but the cycle life of the electrode (only 30 de-/sodiation cycles were reported) is still to be improved.The use of carbon should be noted because carbon and phosphorus do not form binary inorganic or molecular compounds; they can, however, form composites of phosphorus and carbon nanostructures held together by what will likely be weak van der Waals forces. The fact that no P-C compounds are stable implies that upon Na insertion and extraction there are...

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P2-Na_xMn_1/2Fe_1/2O₂ Phase Used as Positive Electrode in Na Batteries: Structural Changes Induced by the Electrochemical (De)intercalation Process

Cited by 225 publications

References 31 publications

Review—Manganese-Based P2-Type Transition Metal Oxides as Sodium-Ion Battery Cathode Materials

Review—Manganese-Based P2-Type Transition Metal Oxides as Sodium-Ion Battery Cathode Materials

Monoclinic Sodium Iron Hexacyanoferrate Cathode and Non-Flammable Glyme-Based Electrolyte for Inexpensive Sodium-Ion Batteries

High‐Performance and Low‐Cost Sodium‐Ion Anode Based on a Facile Black Phosphorus−Carbon Nanocomposite

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