Solid-State Electrolytes for Lithium-Ion Batteries: Fundamentals, Challenges and Perspectives

Zhao, Wenjia; Yi, Jin; He, Ping; Zhou, Haoshen

doi:10.1007/s41918-019-00048-0

Cited by 312 publications

(221 citation statements)

References 217 publications

(269 reference statements)

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“…Oxide‐based SSEs, [ 2 ] sulfide‐based SSEs, [ 3 ] halide‐based SSEs, [ 4 ] polymer‐based SSEs, [ 5 ] and hybrid electrolytes [ 6 ] are regarded as the most encouraging candidates for applications in SSBs. [ 7 ] Among them, polyethylene oxide (PEO) based solid polymer electrolytes (SPEs) show great promising due to its high ionic conductivity at elevated temperature, low interfacial resistance toward electrodes, and simple fabrication process. [ 8 ] More importantly, all‐solid‐state polymer batteries (ASSPBs) with lithium metal anode, SPE and LiFePO 4 cathode have been commercialized and used in the Bolloré Bluecar, [ 5 ] which clearly demonstrates the great capability of SPE for SSBs for EV application.…”

Section: Introductionmentioning

confidence: 99%

Insight into Prolonged Cycling Life of 4 V All‐Solid‐State Polymer Batteries by a High‐Voltage Stable Binder

Liang

Chen

Adair

et al. 2020

Advanced Energy Materials

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components of high-performance SSBs is the solid-state electrolyte (SSE). Oxidebased SSEs, [2] sulfide-based SSEs, [3] halidebased SSEs, [4] polymer-based SSEs, [5] and hybrid electrolytes [6] are regarded as the most encouraging candidates for applications in SSBs. [7] Among them, polyethylene oxide (PEO) based solid polymer electrolytes (SPEs) show great promising due to its high ionic conductivity at elevated temperature, low interfacial resistance toward electrodes, and simple fabrication process. [8] More importantly, all-solid-state polymer batteries (ASSPBs) with lithium metal anode, SPE and LiFePO 4 cathode have been commercialized and used in the Bolloré Bluecar, [5] which clearly demonstrates the great capability of SPE for SSBs for EV application.However, it has been found that the state-of-the-art PEO-based SPEs developed so far delivered poor electrochemical performance when coupling with high energy density cathodes, such as lithium cobalt oxide (LiCoO 2 ), layer structure lithium nickel manganese cobalt oxide (NMC), and lithium nickel cobalt aluminum oxide (NCA). [9] This is because PEO-based SPEs have a relatively low electrochemical oxidation potential-less than 3.8 V versus Li/Li + . [10] However, these high energy density cathodes typically require charging voltages up to 4.2 V or higher to achieve a high specific capacity. At these voltages range, PEO-based SPEs will undergo electrochemical oxidation decomposition. [10,11] In order to address this serious limitation, significant research efforts Polyethylene oxide (PEO) based solid polymer electrolytes (SPEs) are incompatible with the 4 V class cathodes such as LiCoO 2 due to the limited electrochemical oxidation window of PEO. Herein, a number of binders including commonly used binders PEO, polyvinylidene fluoride (PVDF), and carboxylrich polymer (CRP) binders such as sodium alginate (Na-alginate) and sodium carboxymethyl cellulose, are studied for application in the 4 V class all-solid-state polymer batteries (ASSPBs). The results show ASSPBs with CRP binders exhibit superior cycling performance up to 1000 cycles (60% capacity retention, almost 10 times higher than those with PEO and PVDF binders). Synchrotron-based X-ray absorption spectroscopy (XAS), morphology studies and density functional theory studies indicate that, with their carboxyl groups, CRPs can strongly bind the electrode materials together, and work as coating materials to protect the cathode/SPE interface. Cyclic voltammetry studies indicate that CRP binders are more stable at high voltage compared to PEO and PVDF. The stability under high voltage and the coating property of CRP binders contribute to stable cathode/SPE interfaces as disclosed by the X-ray photoelectron spectroscopy and Co L-edge XAS results, enabling long cycling life, high performance 4 V class ASSPBs.

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Section: Introductionmentioning

confidence: 99%

Insight into Prolonged Cycling Life of 4 V All‐Solid‐State Polymer Batteries by a High‐Voltage Stable Binder

Liang

Chen

Adair

et al. 2020

Advanced Energy Materials

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“…Compared to the related sulfide‐based lithium ion conductors, the anionic substructure of phosphido‐based conductors carry one additional charge (formal “P 3− ” versus a formal “S 2− ”), and thus the Li content that is required for charge balance is higher. Recently, we expanded this concept of highly charged tetrahedra to lithium phosphidoaluminates by replacing the central group 14 metal by aluminium …”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂

Restle

Dums

Raudaschl‐Sieber

et al. 2020

Chemistry A European J

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Thel ithium phosphidoaluminate Li 9 AlP 4 represents apromising new compound with ahigh lithium ion mobility. This triggered the searchf or new members in the familyo f lithium phosphidotrielates, and the novel compounds Li 3 AlP 2 and Li 3 GaP 2 ,o btained directly from the elements via ball milling ands ubsequenta nnealing, are reported here. It was unexpectedly found through band structure calculations that Li 3 AlP 2 and Li 3 GaP 2 are directb and gap semiconductors with band gaps of 3.1 and 2.8 eV,r espectively.R ietveld anal-yses revealt hat both compounds crystallize isotypically in the orthorhombic space group Cmce (no. 64) with lattice parameters of a = 11.5138(2), b = 11.7634(2)a nd c = 5.8202(1) for Li 3 AlP 2 ,a nd a = 11.5839(2), b = 11.7809(2) and c = 5.8129(2) for Li 3 GaP 2 .T he crystal structures feature TrP 4 (Tr = Al, Ga) corner-and edge-sharing tetrahedra, forming two-dimensional 1 2 TrP 2 3À ½ layers. The lithium atoms are located between and inside these layers. The crystal structures were confirmed by MAS-NMR spectroscopy.Li 2 SiP 2 . [8,11] Interestingly,t he phases Li 8 SiP 4 ,L i 5 SiP 3 (= Li 10 Si 2 P 6 ), Li 2 SiP 2 ,a nd LiSi 2 P 3 are connected by af ormal reduction of the formula by units of Li 3 P. [11] Al ower Li 3 Pc ontent leads to a higherc onnectivity of the tetrahedra.Compared to the related sulfide-basedl ithium ion conductors, [3,6,7,12] the anionic substructure of phosphido-based conductorsc arry one additional charge( formal "P 3À "v ersus a formal "S 2À "), and thus the Li content that is required for chargeb alance is higher.R ecently,w ee xpanded this concept of highly charged tetrahedra to lithium phosphidoaluminates by replacing the centralg roup 14 metal by aluminium. [13] Li 9 AlP 4 contains highly charged[TrP 4 ] 9À tetrahedra andreaches high ionic conductivities of % 3.0 mS cm at room temperature. Besides this first report of astructurally characterized lithium phosphidoaluminate, another compound of the composition Li 3 AlP 2 was mentioned already in 1952 and described with an orthorhombic distorted CaF 2 -type structure, in which the phosphorus atoms form ad istorted cubic close packing, althoughw ithoutr eliable crystallographic data. [14] Twoy ears later,t he corresponding gallium compound Li 3 GaP 2 was also postulated. [15] Despite the poorly characterized structure model, quantum-chemical calculations of Li 3 AlP 2 and Li 3 GaP 2 were performed, anticipating the model of vertex-sharing AlP 4 tetrahedra. [16][17][18] As forl ithium phosphidotetrelates, lithium phosphidoaluminates can also be connected on al ine in a Gibbs composition triangle (Finetti diagram). Li 3 AlP 2 is located on the line in the phase system Li-Al-P connecting Li 3 Pa nd AlP ( Figure S7, Supporting Information) by reducing Li 9 AlP 4 by two units of Li 3 P( Li 3 AlP 2 = Li 9 AlP 4 À2 Li 3 P). Assuming ac harge balanced valence compound, the degree of connectivity of the AlP 4 tetrahedra in Li 3 AlP 2 mustb eh igher, and isolated tetrahedra as observed in Li 9 AlP 4 cannot occur.Here...

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“…Due to the rapid development of portable devices and electric vehicles, current lithium-ion batteries cannot meet future requirements for energy density, cycle life, and safety 1 . Solid-state batteries (SSBs) have received much attention for their potential as next-generation batteries 2 . Solid-state electrolytes (SSEs) paired with a Li metal anode and a high-voltage cathode not only enhance energy density but also improve safety through the elimination of ammable liquid electrolytes.…”

Section: Introductionmentioning

confidence: 99%

A Flexible Electron-blocking Interfacial Shield for Dendrite-free Solid Lithium Metal Batteries

Huo

Gao

Zhao

et al. 2020

Preprint

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Solid-state batteries (SSBs) are considered to be the next-generation lithium-ion battery technology due to their enhanced energy density and safety. However, the high electronic conductivity of solid-state electrolytes (SSEs) leads to Li dendrite nucleation and proliferation. Uneven electric-field distribution resulting from poor interfacial contact can further promote dendritic deposition and lead to rapid short circuiting of SSBs. Herein, a flexible electron-blocking interfacial shield (EBS) is proposed to protect garnet electrolytes from the electronic degradation. The EBS formed by an in-situ substitution reaction can not only increase lithiophilicity but also stabilize the Li volume change, maintaining the integrity of the interface during repeated cycling. Density functional theory calculations show a high electron-tunneling energy barrier from Li metal to the EBS, indicating an excellent capacity for electron-blocking. EBS protected cells exhibit an improved critical current density of 1.2 mA cm-2 and stable cycling for over 400 h at 1 mA cm-2 (1 mAh cm-2) at room temperature. These results demonstrate an effective strategy for the suppression of Li dendrites and present fresh insight into the rational design of the SSE and Li metal interface.

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Solid-State Electrolytes for Lithium-Ion Batteries: Fundamentals, Challenges and Perspectives

Cited by 312 publications

References 217 publications

Insight into Prolonged Cycling Life of 4 V All‐Solid‐State Polymer Batteries by a High‐Voltage Stable Binder

Insight into Prolonged Cycling Life of 4 V All‐Solid‐State Polymer Batteries by a High‐Voltage Stable Binder

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂

A Flexible Electron-blocking Interfacial Shield for Dendrite-free Solid Lithium Metal Batteries

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Solid-State Electrolytes for Lithium-Ion Batteries: Fundamentals, Challenges and Perspectives

Cited by 312 publications

References 217 publications

Insight into Prolonged Cycling Life of 4 V All‐Solid‐State Polymer Batteries by a High‐Voltage Stable Binder

Insight into Prolonged Cycling Life of 4 V All‐Solid‐State Polymer Batteries by a High‐Voltage Stable Binder

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li3AlP2 and Li3GaP2

A Flexible Electron-blocking Interfacial Shield for Dendrite-free Solid Lithium Metal Batteries

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Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂