Ultimate Limits to Intercalation Reactions for Lithium Batteries

Whittingham, M. Stanley

doi:10.1021/cr5003003

Cited by 998 publications

(735 citation statements)

References 215 publications

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“…The different destabilization mechanisms which affect the performance of Li x MO 2 and Na x MO 2 cathodes upon electrochemical (de)intercalation of the alkali ion are discussed in the next sections. Destabilizing mechanisms for Li x MO 2 structures.-The similar ionic sizes of the Li + and M n+ species, as shown in Figure 3, leads to the destabilization of layered Li x MO 2 compounds via two related mechanisms: (i) antisite disorder (when a transition metal ion in the transition metal layer, M, exchanges with Li + in the alkali metal layer) and (ii) the formation of a spinel phase (see Figure 4) by migration of 25% of the M ions into the alkali metal layers, with Li + occupying the tetrahedral sites, 47 a phenomenon that occurs in partially delithiated materials when the spinel is the thermodynamic ground state structure for x = 0.5.…”

Section: The Different Crystal Chemistries Of Intercalated LImentioning

confidence: 99%

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

Clément

Bruce

Grey

2015

J. Electrochem. Soc.

438

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: 99%

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

Clément

Bruce

Grey

2015

J. Electrochem. Soc.

438

388

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“…The method is applied to the investigation of the 7 Li and 31 P NMR shifts of olivine-type LiTMPO 4 (TM=Mn, Fe, Co and Ni). These materials, and in particular LiFePO 4 [31] and its Mn-substituted derivatives [32], are commercially relevant lithium-ion battery positive electrode (cathode) materials. Computational results from solid-state Density Functional Theory (DFT) are compared to the experimental shifts obtained for the corresponding powder samples [33,34] and a method to extract individual g-tensors in solids containing high concentration of paramagnetic centres from DFT calculations is demonstrated.…”

Section: Introductionmentioning

confidence: 99%

DFT investigation of the effect of spin-orbit coupling on the NMR shifts in paramagnetic solids

et al. 2017

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Nuclear Magnetic Resonance (NMR) spectroscopy is a powerful tool for studying the structural and electronic properties of paramagnetic solids. However, the interpretation of paramagnetic NMR spectra is often challenging as a result of the interactions of unpaired electrons with the nuclear spins of interest. In this work, we extend the formalism of the paramagnetic NMR shielding in the presence of spin-orbit coupling towards solid systems with multiple paramagnetic centres. We demonstrate how the single-ion Electron Paramagnetic Resonance (EPR) g-tensor is defined and calculated in periodic paramagnetic solids. We then calculate the hyperfine tensor and the g-tensor with density functional theory (DFT) to show the validity of the presented model and we further demonstrate how these interactions can be combined to give the overall paramagnetic shielding tensor, σ s . The method is applied to a series of olivine-type LiTMPO4 materials (with TM=Mn, Fe, Co and Ni) and the corresponding 7 Li and 31 P NMR spectra are simulated. We analyse the effects of spin-orbit coupling and of the electron-nuclear magnetic interactions on the calculated NMR parameters. A detailed comparison is presented between contact and dipolar interactions across the LiTMPO4 series, in which the magnitudes and signs of the non-relativistic and relativistic components of the overall isotropic shift and shift anisotropy are computed and rationalized.

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“…4,5 With the demand for batteries with even higher capacities, lithium sulfur (Li-S) batteries, 6,7 with a theoretical capacity of 1672 mAh.g −1 based on cathode solid sulfur mass 8 and a potential gravimetric energy density of about 600 Wh.kg −1 , 9 has (re-)gained attention in recent years.…”

mentioning

confidence: 99%

A Microstructurally Resolved Model for Li-S Batteries Assessing the Impact of the Cathode Design on the Discharge Performance

Thangavel

Xue

Mammeri

et al. 2016

J. Electrochem. Soc.

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This paper reports a discharge model for lithium sulfur (Li-S) battery cells, supported by a multi-scale description of the composite C/S cathode microstructure. The cathode is assumed to be composed of mesoporous carbon particles with inter-particular pores in-between and the sulfur impregnated into both types of pores. The electrolyte solutes such as sulfur, polysulfides and lithium ions, produced during the discharge, are allowed to exchange between the pores. Furthermore, the model describes the Li 2 S (solid) precipitation and its effects on transport and reduction reaction kinetics. Hereby it provides fundamental insights on the impact on the Li-S discharge curve of practically modifiable manufacturing parameters and operation designs, such as current density, carbon porosity, C/S ratio and sizes of carbon particles and pores. Lithium-ion battery technologies based on dual intercalation electrodes have come to totally dominate the consumer electronics market for mobile devices.1,2 However their capacities still limit the driving ranges and user modes for both electric and hybrid electric vehicles, 3 despite approaching the intrinsic maximum for intercalation reactions. 4,5 With the demand for batteries with even higher capacities, lithium sulfur (Li-S) batteries, 6,7 with a theoretical capacity of 1672 mAh.g −1 based on cathode solid sulfur mass 8 and a potential gravimetric energy density of about 600 Wh.kg −1 , 9 has (re-)gained attention in recent years.10-23 Li-S batteries usually have a lithium metal anode, a porous separator, and a porous C/S composite cathode where the carbon acts as a host and provides electronic wiring for the insulating sulfur, existing as S 8(solid) and Li 2 S (solid) . The pores in both the cathode and the separator are filled with an aprotic electrolyte, e.g. 1 M LiTFSI dissolved in dimethoxyethane (DME): 1,3-dioxolane (DOL) (1:1 volume ratio). 24 There is a general consensus that the reasons behind the theoretical capacity of Li-S batteries not being achieved are short-comings: low sulfur utilization due to poor wiring and soluble polysulfide intermediates giving rise to a parasitic shuttle effect. 25,26 One breakthrough in the last decade was the finding that a host of mesoporous carbon greatly enhanced the active material utilization as compared to a ground C/S mixture. 5 The mesoporous architecture of the cathode primarily assisted in retaining polysulfide intermediates in the cathode. 27Theory and mathematical modeling are powerful tools to assist the optimization of electrochemical devices, by providing insight in operating principles and identifying limitations. [28][29][30] Continuum models applied to Li-S batteries have been successful in simulating various battery operation phenomena. [31][32][33][34][35][36][37] However, most of the continuum models reported so far model the cathode as a homogenous porous medium, described by an effective porosity, not accounting for the * Electrochemical Society Member.h Present address: Institut Charles Gerhardt, CNRS and Univers...

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Ultimate Limits to Intercalation Reactions for Lithium Batteries

Cited by 998 publications

References 215 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

DFT investigation of the effect of spin-orbit coupling on the NMR shifts in paramagnetic solids

A Microstructurally Resolved Model for Li-S Batteries Assessing the Impact of the Cathode Design on the Discharge Performance

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