Sulfide solid electrolytes for all-solid-state lithium batteries: Structure, conductivity, stability and application

Chen, Shaojie; Xie, D. Z.; Liu, Gaozhan; Mwizerwa, Jean Pierre; Zhang, Qiang; Zhao, Yanran; Xu, Xin; Yao, Xiayin

doi:10.1016/j.ensm.2018.02.020

Cited by 441 publications

(287 citation statements)

References 140 publications

Supporting

Mentioning

285

Contrasting

Order By: Relevance

“…Such battery systems are attractive due to the inherently higher battery safety they provide. 8−10 An important family of the sulfide-based solid electrolytes is the Li-argyrodite Li 6 PS 5 X (X = Cl, Br, and I) providing Li-ion conductivities of up to 10 –3 S cm –1 at room temperature. 11,12 The high conductivity and the low-cost of the starting materials make the Li-argyrodite a viable candidate for application in all-solid-state batteries.…”

Section: Introductionmentioning

confidence: 99%

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte

Ganapathy

Hageman

et al. 2018

ACS Appl. Mater. Interfaces

161

167

View full text Add to dashboard Cite

The high Li-ion conductivity of the argyrodite Li6PS5Cl makes it a promising solid electrolyte candidate for all-solid-state Li-ion batteries. For future application, it is essential to identify facile synthesis procedures and to relate the synthesis conditions to the solid electrolyte material performance. Here, a simple optimized synthesis route is investigated that avoids intensive ball milling by direct annealing of the mixed precursors at 550 °C for 10 h, resulting in argyrodite Li6PS5Cl with a high Li-ion conductivity of up to 4.96 × 10–3 S cm–1 at 26.2 °C. Both the temperature-dependent alternating current impedance conductivities and solid-state NMR spin–lattice relaxation rates demonstrate that the Li6PS5Cl prepared under these conditions results in a higher conductivity and Li-ion mobility compared to materials prepared by the traditional mechanical milling route. The origin of the improved conductivity appears to be a combination of the optimal local Cl structure and its homogeneous distribution in the material. All-solid-state cells consisting of an 80Li2S–20LiI cathode, the optimized Li6PS5Cl electrolyte, and an In anode showed a relatively good electrochemical performance with an initial discharge capacity of 662.6 mAh g–1 when a current density of 0.13 mA cm–2 was used, corresponding to a C-rate of approximately C/20. On direct comparison with a solid-state battery using a solid electrolyte prepared by the mechanical milling route, the battery made with the new material exhibits a higher initial discharge capacity and Coulombic efficiency at a higher current density with better cycling stability. Nevertheless, the cycling stability is limited by the electrolyte stability, which is a major concern for these types of solid-state batteries.

show abstract

Section: Introductionmentioning

confidence: 99%

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte

Ganapathy

Hageman

et al. 2018

ACS Appl. Mater. Interfaces

161

167

View full text Add to dashboard Cite

show abstract

“…[2,3,18] Currently, only thiophosphates allow for the preparation of thick cathode composites with sufficient rate capability. [21,22] Importantly, the perfect SE does not actually exist. [21,22] Importantly, the perfect SE does not actually exist.…”

mentioning

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

240

309

View full text Add to dashboard Cite

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...

show abstract

“…For all-solid-state batteries, solide lectrolytes bring several advantages, [1][2][3][4][5][6] such as enhanced safety,i ncreased energy density,s olid device integration, and packaging;t hese expand the operation temperature range and potentially improve cycling stabilitya nd lifetime. For all-solid-state batteries, solide lectrolytes bring several advantages, [1][2][3][4][5][6] such as enhanced safety,i ncreased energy density,s olid device integration, and packaging;t hese expand the operation temperature range and potentially improve cycling stabilitya nd lifetime.…”

mentioning

confidence: 99%

Synthesis and Properties of NaSICON‐type LATP and LAGP Solid Electrolytes

2019

View full text Add to dashboard Cite

Inorganic solid electrolytes, in comparison with their liquid counterparts, have more potential in varioust ypes of batteries due to their dual roles of ion transportation and separation. For all-solid-state batteries, solide lectrolytes bring several advantages, [1][2][3][4][5][6] such as enhanced safety,i ncreased energy density,s olid device integration, and packaging;t hese expand the operation temperature range and potentially improve cycling stabilitya nd lifetime. Moreover,i norganic solid electrolytes are also beneficial for lithium-ion batteries and lithium-air batteries, in which they functiona se ither surface modification layers or lithium-ion conductors. [7,8] In principle, ideal solid electrolytes are expected to have several features: [9][10][11][12][13][14] 1) fast ion dynamics and negligible electronic conductivity (minimum ionic conductivity of 10 À4 Scm À1 at room temperature for practical consideration);2 )a wide electrochemical potential window for battery cycling;3 )ane xceptional mechanical strength to suppress lithium dendrite growth;4 )excellent thermal stability during the cycling processes;and 5) asimple and low cost synthetic process for large-scale applications.Generally,i norganic lithium superionic conductors are divided into three categories:o xides, sulfides, and phosphates. Suc-cessfule xamples in oxidesi nclude garnet oxides, [15,16] perovskite-type oxides, [17,18] and antiperovskite oxides. [19][20][21] Sulfide solid electrolytes include Li 2 SÀP 2 S 5 , [22,23] Li 3 PS 4 , [24][25][26] Li 7 P 3 S 11 , [27,28] Li 7 PS 6 ,a nd Li 6 PS 5 X( X = Cl, Br). [29][30][31] Popular phosphate solid electrolytes include sodium superionic conductor (NaSICON)structured lithium-ion conductors, [32][33][34][35][36] such as LiTi 2 (PO 4 ) 3 (LTP), Li 1 + x Al x Ti 2Àx (PO 4 ) 3 (LATP), and Li 1 + x Al x Ge 2Àx (PO 4 ) 3 (LAGP). Many exciting discoveries of these materials have been summarized in important review papers. [2,6,[37][38][39][40] NaSICON-type solid electrolytes, such as LATP and LAGP, have marked advantages compared with sulfides and oxides: they display chemicals tabilityi na ir and/or water,a re low cost and low toxicity,a nd have great electrochemical stability with the added benefito fe asy preparation. [2,36,38] They also exhibit attractive ionic conductivities of 10 À4 -10 À3 Scm À1 at room temperature. Such features have recently caused renewed interest in these NaSICON-structured materials and much effort has been devoted to the investigation of this type of solid electrolyte, especiallyL ATPa nd LAGP.T his manuscript reviewsr ecent progress in LATP and LAGP solid electrolytes, with as pecific focus on synthetic approaches and their effects on the crystal structures, conductive properties, and applications. Herein, general synthetic methods for LATP and LAGP solid electrolytes are first introduced, followed by ac omparison of the crystal structures, phase purities, and ionic conductivities that result from different approaches. Later,t he applications of LATP and LAGP in ful...

show abstract

Sulfide solid electrolytes for all-solid-state lithium batteries: Structure, conductivity, stability and application

Cited by 441 publications

References 140 publications

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte

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

Synthesis and Properties of NaSICON‐type LATP and LAGP Solid Electrolytes

Contact Info

Product

Resources

About

Sulfide solid electrolytes for all-solid-state lithium batteries: Structure, conductivity, stability and application

Cited by 441 publications

References 140 publications

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li6PS5Cl Solid-State Electrolyte

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li6PS5Cl Solid-State Electrolyte

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

Synthesis and Properties of NaSICON‐type LATP and LAGP Solid Electrolytes

Contact Info

Product

Resources

About

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte