Space-Charge Layers in All-Solid-State Batteries; Important or Negligible?

Klerk, Niek J. J. de; Wagemaker, Marnix

doi:10.1021/acsaem.8b01141

Cited by 100 publications

(133 citation statements)

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“…Therefore, in order to exploit the superionic transport properties of thiophosphates, the implementation of protective coatings to overcome the intrinsic electrochemical instabilities is most certainly a necessity. [31] Though the The last decade has seen considerable advancements in the development of solid electrolytes for solid-state battery applications, with particular attention being paid to sulfide superionic conductors. [2,[26][27][28] Several years ago, Takada summarized the early work on SSBs and described the need for coatings against the formation of space charge layers at the interface between high-voltage cathodes and thiophosphate SEs.…”

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confidence: 99%

“…[29] Haruyama et al concluded from density functional theory calculations that space charge layers between LiCoO 2 (LCO) and thiophosphate-based SEs are responsible for high impedances and that the addition of a buffer layer reduces such effects. [31] Though the The last decade has seen considerable advancements in the development of solid electrolytes for solid-state battery applications, with particular attention being paid to sulfide superionic conductors. While these considerations are certainly valuable, from a current perspective, effects arising from the space charge layer are likely overstated and the role of oxidative degradation of the SE is understated.…”

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On the Functionality of Coatings for Cathode Active Materials in Thiophosphate‐Based All‐Solid‐State Batteries

Culver

Koerver

Zeier

et al. 2019

Advanced Energy Materials

269

309

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achievable by SSBs. Meanwhile, polymer-, oxide-, and sulfide-based ionic conductors are being heavily investigated as the solid electrolyte (SE) separator. [9][10][11][12][13][14][15] Nevertheless, recent estimates [16,17] show that only batteries possessing sulfide-based SEs will be leading contenders for room-temperature applications.The sulfides, which are better denoted as thiophosphates, provide the highest lithium-ion conductivity, a relatively low E modulus, and can be processed at low temperatures. [2,3,18] Currently, only thiophosphates allow for the preparation of thick cathode composites with sufficient rate capability. [19,20] Unfortunately, thiophosphates also have a rather narrow electrochemical stability window, i.e., the onset of oxidative decomposition begins even before 3 V versus Li + /Li due to S(0)/S(−2) redox reactions, while reductive decomposition is theoretically expected at potentials of about 1.7 V versus Li + /Li due to P(+5)/P(−3) redox reactions. [21,22] Importantly, the perfect SE does not actually exist. The perfect SE would combine the ionic transport properties of thiophosphates, the mechanical properties of polymers, and the oxidation stability of oxides. Therefore, in order to exploit the superionic transport properties of thiophosphates, the implementation of protective coatings to overcome the intrinsic electrochemical instabilities is most certainly a necessity. The thermodynamic prerequisites for coatings (Figure 1) have already been treated in a number of theoretical papers, [18,21,[23][24][25] which provide the initial design guidelines.Beyond the thermodynamic considerations, it is well known that within SSBs, thiophosphate SEs are oxidized and decomposed in direct contact with cathode active materials (CAMs), in particular at high potentials during charging. [2,[26][27][28] Several years ago, Takada summarized the early work on SSBs and described the need for coatings against the formation of space charge layers at the interface between high-voltage cathodes and thiophosphate SEs. [29] Haruyama et al. concluded from density functional theory calculations that space charge layers between LiCoO 2 (LCO) and thiophosphate-based SEs are responsible for high impedances and that the addition of a buffer layer reduces such effects. [30] However, experimental evidence for such claims has not yet been reported. While these considerations are certainly valuable, from a current perspective, effects arising from the space charge layer are likely overstated and the role of oxidative degradation of the SE is understated. [31] Though the The last decade has seen considerable advancements in the development of solid electrolytes for solid-state battery applications, with particular attention being paid to sulfide superionic conductors. Importantly, the intrinsic electrochemical instability of these high-performance separators highlights the notion that further progress in the field of solid-state batteries is contingent on the optimization of component material interfaces in order to se...

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confidence: 99%

On the Functionality of Coatings for Cathode Active Materials in Thiophosphate‐Based All‐Solid‐State Batteries

Culver

Koerver

Zeier

et al. 2019

Advanced Energy Materials

269

309

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“…A comprehensive first-principles model is noticeably absent. Prediction of space-charge layers in solid electrolytes with heterogeneous interfaces has been attempted by lattice models [18], atomistic models [19,20], thermodynamic models [21,22], and DFT-informed thermodynamic models [23]. However, predicting spacecharge-layer formation at the solid-electrolyte/electrode interface is even more challenging, as ion insertion and/or reaction with the electrode alters the material and thus band alignments at the interfaces [24].…”

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First-Principles Prediction of Potentials and Space-Charge Layers in All-Solid-State Batteries

Swift

2019

Phys. Rev. Lett.

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As all-solid-state batteries (SSBs) develop as an alternative to traditional cells, a thorough theoretical understanding of driving forces behind battery operation is needed. We present a fully first-principles-informed model of potential profiles in SSBs and apply the model to the Li/LiPON/LixCoO2 system. The model predicts interfacial potential drops driven by both electron transfer and Li + space-charge layers that vary with the SSB's state of charge. The results suggest lower electronic ionization potential in the solid electrolyte favors Li + transport, leading to higher discharge power.

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“…In addition, Li atoms adsorbing to the cathode interface may also clog diffusing paths of Li + ions in the sulfide SSEs, also increasing the charge-transfer impedance. [258] Contrary to sulfide SSEs, the rigid oxide SSEs should be cosintered with cathode materials to achieve a close contact. The space-charge layer-driven interfacial impedance was as high as 1 × 10 4 Ω for the Li 1−x Mn 2 O 4 /Li 3.25 Ge 0.25 P 0.75 S 4 interface, [251] as has also been reported for the Li 1−x CoO 2 /Li 3.25 Ge 0.25 P 0.75 S 4 system.…”

Section: Origin Of the Interfacial Resistancementioning

confidence: 99%

Interfacial Incompatibility and Internal Stresses in All‐Solid‐State Lithium Ion Batteries

Liu

et al. 2019

Advanced Energy Materials

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The continuous depletion of fossil fuels, the increase of oil prices, and the need to decrease CO 2 emissions have stimulated intensive research on developing alternative renewable and clean energy sources. [1] Among these alternative energy sources, rechargeable Li-ion batteries (LIBs) are one of the promising candidates. To date, the LIBs basically consisting of a positive electrode (cathode), an electrolyte, and a negative electrode (anode) have widespread applications, such as portable electronic devices, pure electric vehicles (PEVs), and hybrid electric vehicles (HEVs). [2] The state-of-the-art electrolytes are usually the lithium salts (LiPF 6 , LiBF 4 , and LiCF 3 SO 3 ) dissolved in organic solvents, i.e., ethylene carbonate, propylene carbonate, polyethylene oxide, and dimethyl carbonate, [3] which exhibit excellent wetting of the electrodes and produce a fast transfer of Li + ions upon charging and discharging. However, they suffer from flammability, poor electrochemical stability, limited temperature range of operation, and low power density. [4] There is an ever-increasing demand for batteries with a higher energy and power density, although current LIBs offer volumetric and gravimetric energy densities up to 770 Wh L −1 and 260 Wh kg −1 , respectively. [5] To improve the energy/power density of LIBs, one way is to adopt high-potential cathode materials such as LiNi 0.5 Mn 1.5 O 4 (LNMO). The high-voltage plateau of LNMO (≈4.7 V vs Li/Li + ) makes its energy density 20-30% higher than the energy density of commercial LiCoO 2 and LiFePO 4 . [6] However, successful commercialization of the LNMO is restricted in high-energy LIBs due to electrolyte decomposition and side reaction of the cathodes and liquid electrolytes when operating at high voltages. [7,8] The other way to improve the energy/power density is to replace the conventional graphite anode with Li metal. The Li metal, with a low anode potential (−3.04 V vs standard hydrogen electrode) and high specific capacity (3862 mAh g −1 for the Li anode versus 372 mAh g −1 for the graphite anode), [9][10][11] has been considered as the "Holy Grail" of battery technologies. When paired with sulfur and oxygen, the theoretical energy density of Li-S (≈2567 Wh kg −1 ) and Li-O 2 (≈3505 Wh kg −1 ) batteries is far higher than the theoretical energy density of conventional LIBs (≈387 Wh kg −1 ). [12][13][14][15] When Li metal approaches the liquid electrolytes, however, unstable Li/electrolyte interface Rechargeable Li-ion batteries (LIBs) are electrochemical storage device widely applied in electric vehicles, mobile electronic devices, etc. However, traditional LIBs containing liquid electrolytes suffer from flammability, poor electrochemical stability, and limited operational temperature range. Replacement of the liquid electrolytes with inorganic solid-state electrolytes (SSEs) would solve this problem. However, several critical issues, such as poor interfacial compatibility, low ionic conductivity at ambient temperatures, etc., need to be surmounted befor...

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Space-Charge Layers in All-Solid-State Batteries; Important or Negligible?

Cited by 100 publications

References 70 publications

On the Functionality of Coatings for Cathode Active Materials in Thiophosphate‐Based All‐Solid‐State Batteries

On the Functionality of Coatings for Cathode Active Materials in Thiophosphate‐Based All‐Solid‐State Batteries

First-Principles Prediction of Potentials and Space-Charge Layers in All-Solid-State Batteries

Interfacial Incompatibility and Internal Stresses in All‐Solid‐State Lithium Ion Batteries

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