Thermodynamics of Electrochemical Lithium Storage

Maier, Joachim

doi:10.1002/anie.201205569

Cited by 203 publications

(193 citation statements)

References 100 publications

(184 reference statements)

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“…[ 11 ] Also, the equilibrium potential depends on the particle size, which is predicted to be the consequence of the surface energy which has more impact in smaller particles. [ 7,[12][13][14] In LiFePO 4 this results in a larger equilibrium voltage in smaller LiFePO 4 particles [ 12,15 ] which explains the spontaneous, without an externally applied potential, Li-ion transport from small to large LiFePO 4 particles. [ 16 ] (b) First-order phase transitions are generally thought to result in poor kinetics as compared to solid solution reactions.…”

mentioning

confidence: 93%

Direct Observation of Li‐Ion Transport in Electrodes under Nonequilibrium Conditions Using Neutron Depth Profiling

Zhang

Verhallen

Labohm

et al. 2015

Advanced Energy Materials

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connecting the active electrode material and the electrolyte, (3) the charge transfer reaction between the liquid electrolyte and the active electrode material, and (4) the solid state transport and phase nucleation/ transformation kinetics within the active electrode material.Many processes have been reported to improve Li-ion battery (dis)charge kinetics each improving one or more of the described aspects 1-4 illustrating the complexity and the lack of agreement concerning the rate-limiting step. This is best illustrated by LiFePO 4 , an important electrode material proposed by Padhi et al. [ 3 ] in 1997, and an intensively studied, well-established model system up to date. (a) For LiFePO 4 the initial hurdle of poor intrinsic electronic and solid-state ionic conduction were overcome by reducing the particle size in combination with carbon or metallic conducting coatings. [4][5][6] In addition to the trivial decrease in the solid-state diffusion distance, particle size reduction toward the nano range has also shown to impact the kinetic and thermodynamic properties of electrode materials. [7][8][9][10] For instance, the nucleation barrier for the fi rst-order phase transition in LiFePO 4 is predicted to be smaller for smaller particles. [ 11 ] Also, the equilibrium potential depends on the particle size, which is predicted to be the consequence of the surface energy which has more impact in smaller particles. [ 7,[12][13][14] In LiFePO 4 this results in a larger equilibrium voltage in smaller LiFePO 4 particles [ 12,15 ] which explains the spontaneous, without an externally applied potential, Li-ion transport from small to large LiFePO 4 particles. [ 16 ] (b) First-order phase transitions are generally thought to result in poor kinetics as compared to solid solution reactions. The observation that the fi rst-order phase transition can be bypassed in LiFePO 4 at high (dis)charge rates [ 17,18 ] driven by the overpotential, [19][20][21] is also considered to be responsible for the high (dis)charge rates that can be achieved. [17][18][19][20][21] (c) Surface diffusion on the LiFePO 4 particles appears to play a role as very fast (dis)charge rates were achieved by the addition of an ionic-conducting phase at the LiFePO 4 surface.[ 22 ] (d) In many studies it has been recognized that for higher rates the ionic transport through the porous electrode structure is rate limiting. [23][24][25][26][27][28][29] This is consistent with the direct observation that the electrode capacity decreases with increasing thickness at the same rate and loading density. [ 23,30 ] Over the years, various modelling approaches have been describing the complex phenomena that play a role, mainly focussing on the with the ion transport and charge transfer through the porous electrode matrix, [ 1,31 ] solid solutions and distributed ohmic drop in the One of the key challenges of Li-ion electrodes is enhancement of (dis)charge rates. This is severely hindered by the absence of a technique that allows direct and nondestructive observation of li...

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mentioning

confidence: 93%

Direct Observation of Li‐Ion Transport in Electrodes under Nonequilibrium Conditions Using Neutron Depth Profiling

Zhang

Verhallen

Labohm

et al. 2015

Advanced Energy Materials

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“…[1][2][3] LIBs with the characteristics of great safety performance, high energy density, long cycle life, capability of rapid charge/discharge and less pollution. [4][5][6] The conventional anode, graphite, with a theoretical capacity of 372 mAh·g -1 and low rate performance, cannot meet the constantly increasing demand for next generation anode.…”

Section: Introductionmentioning

confidence: 99%

Three-dimensional VS4/graphene hierarchical architecture as high-capacity anode for lithium-ion batteries

Chen

et al. 2016

Journal of Alloys and Compounds

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“…The interfacials toragec ould be realizedt hrough the absorption of Li + + ions onto the accessible interstitial sites of the NCs, for example, surfaceo rn earsurfacea toms, whereas the electrons are stored in another phase, for example, the carbon matrix or the polymeric surface layer. [47,48] In this regard, the pseudocapacitive process accounts for the facile electrode kinetics of Composite-650-30a t high rates.…”

Section: Resultsmentioning

confidence: 98%

Recycled Poly(vinyl alcohol) Sponge for Carbon Encapsulation of Size‐Tunable Tin Dioxide Nanocrystalline Composites

Tai

Gustafsson

et al. 2015

ChemSusChem

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The recycling of industrial materials could reduce their environmental impact and waste haulage fees and result in sustainable manufacturing. In this work, commercial poly(vinyl alcohol) (PVA) sponges are recycled into a macroporous carbon matrix to encapsulate size-tunable SnO2 nanocrystals as anode materials for lithium-ion batteries (LIBs) through a scalable, flash-combustion method. The hydroxyl groups present copiously in the recycled PVA sponges guarantee a uniform chemical coupling with a tin(IV) citrate complex through intermolecular hydrogen bonds. Then, a scalable, ultrafast combustion process (30 s) carbonizes the PVA sponge into a 3D carbon matrix. This PVA-sponge-derived carbon could not only buffer the volume fluctuations upon the Li-Sn alloying and dealloying processes but also afford a mixed conductive network, that is, a continuous carbon framework for electrical transport and macropores for facile electrolyte percolation. The best-performing electrode based on this composite delivers a rate performance up to 9.72 C (4 A g(-1) ) and long-term cyclability (500 cycles) for Li(+) ion storage. Moreover, cyclic voltammograms demonstrate the coexistence of alloying and dealloying processes and non-diffusion-controlled pseudocapacitive behavior, which collectively contribute to the high-rate Li(+) ion storage.

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Thermodynamics of Electrochemical Lithium Storage

Cited by 203 publications

References 100 publications

Direct Observation of Li‐Ion Transport in Electrodes under Nonequilibrium Conditions Using Neutron Depth Profiling

Direct Observation of Li‐Ion Transport in Electrodes under Nonequilibrium Conditions Using Neutron Depth Profiling

Three-dimensional VS4/graphene hierarchical architecture as high-capacity anode for lithium-ion batteries

Recycled Poly(vinyl alcohol) Sponge for Carbon Encapsulation of Size‐Tunable Tin Dioxide Nanocrystalline Composites

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