Strain Accommodation during Phase Transformations in Olivine‐Based Cathodes as a Materials Selection Criterion for High‐Power Rechargeable Batteries

Meethong, Nonglak; Huang, Hsiao‐Ying Shadow; Speakman, Scott A.; Carter, W. C.; Chiang, Yet‐Ming

doi:10.1002/adfm.200600938

Cited by 420 publications

(456 citation statements)

References 33 publications

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“…In contrast, the overpotential is nearly constant and quite small at low current (C/2000−C/ 500), which is the energy needed for phase nucleation since this approaches the zero-current limit and thus thermodynamics dominates. 38 The inset in Figure 5B shows the low-current region. The overpotential approaches ∼20 mV at zero current.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

High-Capacity Micrometer-Sized Li₂S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries

Yang¹,

Zheng²,

et al. 2012

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Li 2 S is a high-capacity cathode material for lithium metal-free rechargeable batteries. It has a theoretical capacity of 1166 mAh/g, which is nearly 1 order of magnitude higher than traditional metal oxides/phosphates cathodes. However, Li 2 S is usually considered to be electrochemically inactive due to its high electronic resistivity and low lithiumion diffusivity. In this paper, we discover that a large potential barrier (∼1 V) exists at the beginning of charging for Li 2 S. By applying a higher voltage cutoff, this barrier can be overcome and Li 2 S becomes active. Moreover, this barrier does not appear again in the following cycling. Subsequent cycling shows that the material behaves similar to common sulfur cathodes with high energy efficiency. The initial discharge capacity is greater than 800 mAh/g for even 10 μm Li 2 S particles. Moreover, after 10 cycles, the capacity is stabilized around 500−550 mAh/g with a capacity decay rate of only ∼0.25% per cycle. The origin of the initial barrier is found to be the phase nucleation of polysulfides, but the amplitude of barrier is mainly due to two factors: (a) charge transfer directly between Li 2 S and electrolyte without polysulfide and (b) lithium-ion diffusion in Li 2 S. These results demonstrate a simple and scalable approach to utilizing Li 2 S as the cathode material for rechargeable lithium-ion batteries with high specific energy. ■ INTRODUCTIONRechargeable lithium-ion batteries have been widely used in portable electronics and are promising for applications in electric vehicles and smart grids. 1−4 However, due to limited capacity in both electrodes, the specific energy of Li-ion batteries needs to be improved significantly to fulfill the requirements in these applications. 5,6 Significant improvement has been achieved in the development of high-capacity materials to replace carbon-based anodes, such as silicon 7−12 and tin. 13 However, state-of-the-art cathode materials have a capacity less than one-half of the carbon anode. Accordingly, breakthroughs in cathodes are urgently needed to increase the specific energy of lithium-ion batteries. Current metal oxide and phosphate cathodes possess an intrinsic capacity limit of ∼300 mAh/g, with a potential of maximum 130% increase in the specific energy if all the capacity can be used. 14,15 In contrast, Li 2 S has a specific capacity of 1166 mAh/g, four times that of the limit in oxide/phosphate cathodes. 15,16 Considering pairing with Si anodes with 2000 mAh/g capacity, the specific energy of a Li 2 S-based lithium-ion battery could be 60% higher than the theoretical limit of metal oxide/phosphate counterparts ( Figure 1A, see Supporting Information for details) and three times that of the current LiCoO 2 /graphite system. Moreover, Li 2 S could be paired with a lithium-free anode, preventing safety concerns and low Coulomb efficiency of lithium metal in Li/S batteries. 17,18 The main hindrance for utilizing Li 2 S is that it is both electronically and ionically insulating. Therefore, Li 2 S was...

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Section: ■ Results and Discussionmentioning

confidence: 99%

High-Capacity Micrometer-Sized Li₂S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries

Yang¹,

Zheng²,

et al. 2012

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“…One good example of a collective variable for reorganizations in solids might be the lattice parameters that have also been often used to explain kinetics of cathode materials in the battery field (35). Because the cathode materials have a coherent or semicoherent interface between charged and discharged phases (36), the lattice parameters evolve gradually between those of the two phases, implying that the reaction pathway can be well defined along the changing lattice parameters.…”

Section: Significancementioning

confidence: 99%

Role of intermediate phase for stable cycling of Na ₇ V ₄ (P ₂ O ₇ ) ₄ PO ₄ in sodium ion battery

Lim

Kim

Chung

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

139

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Sodium ion batteries offer promising opportunities in emerging utility grid applications because of the low cost of raw materials, yet low energy density and limited cycle life remain critical drawbacks in their electrochemical operations. Herein, we report a vanadium-based ortho-diphosphate, Na 7 V 4 (P 2 O 7 ) 4 PO 4 , or VODP, that significantly reduces all these drawbacks. Indeed, VODP exhibits single-valued voltage plateaus at 3.88 V vs. Na/Na + while retaining substantial capacity (>78%) over 1,000 cycles. Electronic structure calculations reveal that the remarkable single plateau and cycle life originate from an intermediate phase (a very shallow voltage step) that is similar both in the energy level and lattice parameters to those of fully intercalated and deintercalated states. We propose a theoretical scheme in which the reaction barrier that arises from lattice mismatches can be evaluated by using a simple energetic consideration, suggesting that the presence of intermediate phases is beneficial for cell kinetics by buffering the differences in lattice parameters between initial and final phases. We expect these insights into the role of intermediate phases found for VODP hold in general and thus provide a helpful guideline in the further understanding and design of battery materials.cathode | single voltage | atomic reorganization | ab initio calculation S odium ion batteries (SIBs) provide advantages of unlimited resource, low material cost, and easy worldwide accessibility that could make them the material of choice for grid-scale energy storage systems (1, 2). Unfortunately, the electrochemical performance of current SIBs remains inferior to that of lithium ion batteries (LIBs). In particular, we require SIB cathode materials that give a long cycle life with large capacities and high voltages under fast operating conditions, comparable to the Li counterparts.Numerous layered Na x MO 2 [M = Co, Mn, Fe, Ni, Cr, and multicomponent transition metals (TMs)] have been intensively studied as candidate SIB cathodes because such layer-structured materials typically exhibit higher capacities than other classes of materials (3-10). However, they suffer from a substantial capacity decay with cycling, owing to crystal structure collapse and/or unstable electrode-electrolyte interfaces (10). For more stable host frameworks, various polyanion structures have also been studied as SIB cathodes as a natural extension of the success shown in the LIB materials of the same classes, including TM fluorophosphates (11-15), pyrophosphates (16-18) and phosphates (19)(20)(21)(22). However, most of these materials still exhibited insufficient cycle lifetimes and large voltage steps that limit their practical capacity. The Prussian blue family has also been extensively investigated for both organic (23, 24) and aqueous electrolytes (25) owing to its unique advantages related to low material cost, low temperature synthesis, and decent electrochemical performance from well-developed ionic channel structures. However, the as-syn...

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“…The effect of the elastic strain energy on battery reactions has been discussed in some negative electrodes such as Sn-Li and Al-Li alloys, [6][7][8] and in a positive electrode, especially LiFePO 4 . [9][10][11] Cogswell et al 12 mentioned in the phase-field simulation that the large coherent strain energy in the LiFePO 4 /FePO 4 electrode suppresses the phase change during charge/discharge processes. In our recent papers, it has been demonstrated with the phase-field micromechanical simulation that the coherent strain suppresses nucleation process inside the material and significantly retards even in spinodal decomposition, 13 and also shown that the coherent strain strongly affects the spinodal decomposition of nanometer-sized particles.…”

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confidence: 99%

Research Update: Retardation and acceleration of phase separation evaluated from observation of imbalance between structure and valence in LiFePO4/FePO4 electrode

et al. 2014

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LiFePO4 is a potential positive electrode material for lithium ion batteries. We have experimentally observed an imbalance between the valence change of Fe ions and the structure change from the LiFePO4 phase to the FePO4 phase during delithiation by simultaneous in situ XRD and XANES measurements in an LiFePO4/FePO4 electrode. The ratio of structure change to valence change clearly indicates that the phase separation from LiFePO4 to FePO4 is suppressed at the beginning of delithiation, while it is accelerated at the latter stage, which is due to the coherent strain caused by the lattice misfit between the two phases.

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Strain Accommodation during Phase Transformations in Olivine‐Based Cathodes as a Materials Selection Criterion for High‐Power Rechargeable Batteries

Cited by 420 publications

References 33 publications

High-Capacity Micrometer-Sized Li₂S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries

High-Capacity Micrometer-Sized Li₂S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries

Role of intermediate phase for stable cycling of Na ₇ V ₄ (P ₂ O ₇ ) ₄ PO ₄ in sodium ion battery

Research Update: Retardation and acceleration of phase separation evaluated from observation of imbalance between structure and valence in LiFePO4/FePO4 electrode

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Strain Accommodation during Phase Transformations in Olivine‐Based Cathodes as a Materials Selection Criterion for High‐Power Rechargeable Batteries

Cited by 420 publications

References 33 publications

High-Capacity Micrometer-Sized Li2S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries

High-Capacity Micrometer-Sized Li2S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries

Role of intermediate phase for stable cycling of Na 7 V 4 (P 2 O 7 ) 4 PO 4 in sodium ion battery

Research Update: Retardation and acceleration of phase separation evaluated from observation of imbalance between structure and valence in LiFePO4/FePO4 electrode

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High-Capacity Micrometer-Sized Li₂S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries

High-Capacity Micrometer-Sized Li₂S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries

Role of intermediate phase for stable cycling of Na ₇ V ₄ (P ₂ O ₇ ) ₄ PO ₄ in sodium ion battery