High temperature electrode‐electrolyte interface formation between LiMn1.5Ni0.5O4 and Li1.4Al0.4Ge1.6(<scp>PO</scp>4)3

Robinson, J. Pierce; Kichambare, Padmakar; Deiner, Jay; Miller, Ryan M.; Rottmayer, Michael; Koenig, Gary M.

doi:10.1111/jace.15294

Cited by 37 publications

(19 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The LATP NPs dispersed within the cathode had ahigh lithium-ion conductivity,w hichp layed ac rucial role in operating the all-solid-state lithium-ion battery. [111] Thick interfacial phases resulted in high electrochemical resistance and poor cycling performance. [95] The LCO/LATPi nterface remained stable during cycling, in comparison with the interface of the LCO cathode and sulfide or perovskite-type solid electrolytes.…”

Section: Composite Cathodementioning

confidence: 99%

See 1 more Smart Citation

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

Section: Composite Cathodementioning

confidence: 99%

“…Koenig et al also tried to deposit LiMn 1.5 Ni 0.5 O 4 (LMNO) on LAGP pelletst of orm ac omposite cathode and assembled ab attery with the structure of Li/LAGP/LMNOo n LAGP. [111] Thick interfacial phases resulted in high electrochemical resistance and poor cycling performance.…”

Section: Composite Cathodementioning

confidence: 99%

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

2019

View full text Add to dashboard Cite

show abstract

“…In a related study of co‐sintered LMNO and lithium aluminum titanium phosphate (LATP), similar species are identified in the XRD postsintering: LiMnPO 4 and AlPO 4 . The formation of resistive phases like AlPO 4 may explain the poor battery performance (<2% of theoretical capacity) recently observed for an Li/LAGP/LMNO cell formed by co‐sintering . In addition to suggesting the formation of Li(Ge 0.5 M 0.5 )PO 4 and AlPO 4 , the XRD pattern of the co‐sintered LAGP/LMNO indicates the emergence of a new spinel structure.…”

Section: Resultsmentioning

confidence: 80%

“…We limit our sintering study to the temperature region in which oxygen nonstoichiometry in LMNO is created and tuned (600°C‐800°C), but before which significant rock salt phases appear (900°C). In a previous study of the temperature dependence of the structure and morphology of co‐sintered LAGP/LMNO material, XRD indicated that structural changes commenced at 600°C and were fully realized by 800°C, while scanning electron microscopy indicated that morphological changes became visible at 750°C . We document oxidation state changes in the co‐sintered materials as sintering gas is varied from oxygen‐containing (air) to oxygen‐free (N 2 ).…”

Section: Introductionmentioning

confidence: 61%

Interfacial reaction during co‐sintering of lithium manganese nickel oxide and lithium aluminum germanium phosphate

Deiner

Howell

Koenig

et al. 2019

Int J Applied Ceramic Tech

Self Cite

View full text Add to dashboard Cite

Understanding interface evolution during co-sintering of solid Li-ion conducting electrolytes and Li-metal oxide cathodes is crucial to development of solid state batteries. In this work, X-ray photoelectron spectroscopy, X-ray diffraction (XRD), and thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC) document changes at the lithium manganese nickel oxide (LMNO)/lithium aluminum germanium phosphate interface during sintering. Measurements are performed as a function of sintering gas environment (air vs N 2 ). Upon sintering, manganese is reduced from +4 to a mixture of +4, +3, and +2, while nickel is oxidized from +2 to a mixture of +2 and +3. The Mn 2+ species does not arise when LMNO is sintered alone. XRD identifies formation of new chemical phases, LiGe 0.5 M 0.5 PO 4 (where M = Mn 3+ or Ni 3+ ), AlPO 4 , and NiMn 2 O 4 , also not observed when LMNO is sintered alone. The emergence of resistive interfacial phases may offset the increase in conductivity expected when Mn 3+ is formed. |DEINER Et al.

show abstract

“…The decomposition products, i.e., GeO 2 and LiMnPO 4 in the LiMn 1.5 Ni 0.5 O 4 /LAGP reaction system, [238] were electrochemically inactive and ionically blocking phases. However, different LATP(LAGP)/cathode material systems behave diversely.…”

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

View full text Add to dashboard Cite

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...

show abstract

High temperature electrode‐electrolyte interface formation between LiMn_1.5Ni_0.5O₄ and Li_1.4Al_0.4Ge_1.6(PO₄)₃

Cited by 37 publications

References 42 publications

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

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

Interfacial reaction during co‐sintering of lithium manganese nickel oxide and lithium aluminum germanium phosphate

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

Contact Info

Product

Resources

About

High temperature electrode‐electrolyte interface formation between LiMn1.5Ni0.5O4 and Li1.4Al0.4Ge1.6(PO4)3

Cited by 37 publications

References 42 publications

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

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

Interfacial reaction during co‐sintering of lithium manganese nickel oxide and lithium aluminum germanium phosphate

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

Contact Info

Product

Resources

About

High temperature electrode‐electrolyte interface formation between LiMn_1.5Ni_0.5O₄ and Li_1.4Al_0.4Ge_1.6(PO₄)₃