Garnet-type solid-state electrolytes have attracted extensive attention due to their high ionic conductivity, approaching 1 mS cm−1, excellent environmental stability, and wide electrochemical stability window, from lithium metal to ~6 V. However, to date, there has been little success in the development of high-performance solid-state batteries using these exceptional materials, the major challenge being the high solid–solid interfacial impedance between the garnet electrolyte and electrode materials. In this work, we effectively address the large interfacial impedance between a lithium metal anode and the garnet electrolyte using ultrathin aluminium oxide (Al2O3) by atomic layer deposition. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) is the garnet composition of choice in this work due to its reduced sintering temperature and increased lithium ion conductivity. A significant decrease of interfacial impedance, from 1,710 Ω cm2 to 1 Ω cm2, was observed at room temperature, effectively negating the lithium metal/garnet interfacial impedance. Experimental and computational results reveal that the oxide coating enables wetting of metallic lithium in contact with the garnet electrolyte surface and the lithiated-alumina interface allows effective lithium ion transport between the lithium metal anode and garnet electrolyte. We also demonstrate a working cell with a lithium metal anode, garnet electrolyte and a high-voltage cathode by applying the newly developed interface chemistry.
At a glance
- Self-organized core–shell structure for high-power electrode in solid-state lithium batteries. Chem. Mater. 23, 3798–3804 (2011). et al.
- All solid-state sheet battery using lithium inorganic solid electrolyte, thio-LISICON. J. Power Sources 194, 1085–1088 (2009). et al.
- All solid state lithium ion rechargeable batteries using NASICON structured electrolyte. Mater. Technol. 28, 276–279 (2013). , , , &
- Fabrication and performances of all solid-state symmetric sodium battery based on NASICON-related compounds. Electrochim. Acta 101, 59–65 (2013). , , , &
- Fast lithium-ion conducting thin-film electrolytes integrated directly on flexible substrates for high-power solid-state batteries. Adv. Mater. 23, 5663–5667 (2011). et al.
- Antiperovskite Li3OCl superionic conductor films for solid-state Li-ion batteries. Adv. Sci. 3, 1500359 (2016). et al.
- All-solid-state lithium battery with LiBH4 solid electrolyte. J. Power Sources 226, 61–64 (2013). et al.
- High lithium ion conducting Li2S–GeS2–P2S5 glass–ceramic solid electrolyte with sulfur additive for all solid-state lithium secondary batteries. Electrochim. Acta 56, 4243–4247 (2011). , &
- An all-solid-state Li-ion battery with a pre-lithiated Si–Ti–Ni alloy anode. J. Electrochem. Soc. 160, A1497–A1501 (2013). et al.
- Structure and dynamics of the fast lithium ion conductor “Li7La3Zr2O12”. Phys. Chem. Chem. Phys. 13, 19378–19392 (2011). et al.
- Nebulized spray pyrolysis of Al-doped Li7La3Zr2O12 solid electrolyte for battery applications. Solid State Ion. 263, 49–56 (2014). et al.
- Fast lithium ion conduction in garnet-type Li7La3Zr2O12. Angew. Chem. Int. Ed. 46, 7778–7781 (2007). , &
- Effects of Li source on microstructure and ionic conductivity of Al-contained Li6.75La3Zr1.75Ta0.25O12 ceramics. J. Eur. Ceram. Soc. 35, 561–572 (2015). et al.
- Tailoring ceramics for specific applications: a case study of the development of all-solid-state lithium batteries. Ionics 11, 11–23 (2005). , &
- A lithium superionic conductor. Nat. Mater. 10, 682–686 (2011). et al.
- Dielectric modification of 5 V-class cathodes for high-voltage all-solid-state lithium batteries. Adv. Energy Mater. 4, 1301416 (2014). et al.
- Interfacial phenomena in solid-state lithium battery with sulfide solid electrolyte. Solid State Ion. 225, 594–597 (2012). et al.
- All-solid-state lithium secondary batteries with metal-sulfide-coated LiCoO2 prepared by thermal decomposition of dithiocarbamato complexes. J. Mater. Chem. 22, 15247–15254 (2012). et al.
- All-solid-state lithium secondary batteries using Li2S-P2S5 solid electrolytes and LiFePO4 electrode particles with amorphous surface layer. Chem. Lett. 41, 260–261 (2012). et al.
- High rate capabilities of all-solid-state lithium secondary batteries using Li4Ti5O12-coated LiNi0.8Co0.15Al0.05O2 and a sulfide-based solid electrolyte. J. Power Sources 196, 6488–6492 (2011). , &
- LiNbO3-coated LiCoO2 as cathode material for all solid-state lithium secondary batteries. Electrochem. Commun. 9, 1486–1490 (2007). et al.
- In-situ Li7La3Zr2O12/LiCoO2 interface modification for advanced all-solid-state battery. J. Power Sources 260, 292–298 (2014). et al.
- All-solid-state lithium ion battery using garnet-type oxide and Li3BO3 solid electrolytes fabricated by screen-printing. J. Power Sources 238, 53–56 (2013). et al.
- Interface-engineered all-solid-state Li-ion batteries based on garnet-type fast Li + conductors. Adv. Energy Mater. 6, 1600736 (2016). , &
- Fast solid-state Li ion conducting garnet-type structure metal oxides for energy storage. J. Phys. Chem. Lett. 6, 292–299 (2015). , , &
- Interface behavior between garnet-type lithium-conducting solid electrolyte and lithium metal. Solid State Ion. 262, 151–154 (2014). et al.
- Co-sinterable lithium garnet-type oxide electrolyte with cathode for all-solid-state lithium ion battery. J. Power Sources 265, 40–44 (2014). et al.
- Bulk solid state rechargeable lithium ion battery fabrication with Al-doped Li7La3Zr2O12 electrolyte and Cu0.1V2O5 cathode. Electrochim. Acta 89, 407–412 (2013). &
- Novel fast lithium ion conduction in garnet-type Li5La3M2O12 (M = Nb, Ta). J. Am. Ceram. Soc. 86, 437–440 (2003). , &
- Switching on fast lithium ion conductivity in garnets: the structure and transport properties of Li3+xNd3Te2−xSbxO12. Chem. Mater. 20, 2360–2369 (2008). , , , &
- Concerted migration mechanism in the Li ion dynamics of garnet-type Li7La3Zr2O12. Chem. Mater. 25, 425–430 (2013). et al.
- A tale of two sites: on defining the carrier concentration in garnet-based ionic conductors for advanced Li batteries. Adv. Energy Mater. 5, 150096 (2015). et al.
- The origin of high electrolyte-electrode interfacial resistances in lithium cells containing garnet type solid electrolytes. Phys. Chem. Chem. Phys. 16, 18294–18300 (2014). et al.
- Effect of simultaneous substitution of alkali earth metals and Nb in Li7La3Zr2O12 on lithium-ion conductivity. ECS Electrochem. Lett. 2, A56–A59 (2013). , , &
- Chemical stability of cubic Li7La3Zr2O12 with molten lithium at elevated temperature. J. Mater. Sci. 48, 5846–5851 (2013). , , &
- How do Li atoms pass through the Al2O3 coating layer during lithiation in Li-ion batteries? J. Phys. Chem. Lett. 4, 2681–2685 (2013). &
- Sodium ion diffusion in Al2O3: a distinct perspective compared with lithium ion diffusion. Nano Lett. 14, 6559–6563 (2014). , , &
- Atomic-layer-deposition oxide nanoglue for sodium ion batteries. Nano Lett. 14, 139–147 (2013). et al.
- Atomic layer deposited coatings to significantly stabilize anodes for Li ion batteries: effects of coating thickness and the size of anode particles. J. Mater. Chem. A 2, 2306–2312 (2014). et al.
- Si nanotubes ALD coated with TiO2, TiN or Al2O3 as high performance lithium ion battery anodes. J. Mater. Chem. A 2, 2504–2516 (2014). et al.
- Silicon nanowire lithium-ion battery anodes with ALD deposited TiN coatings demonstrate a major improvement in cycling performance. J. Mater. Chem. A 1, 12850–12861 (2013). et al.
- Tuning electrochemical performance of Si-based anodes for lithium-ion batteries by employing atomic layer deposition alumina coating. J. Mater. Chem. A 2, 11417–11425 (2014). et al.
- Achieving high capacity in bulk-type solid-state lithium ion battery based on Li6.75La3Zr1.75Ta0.25O12 electrolyte: interfacial resistance. J. Power Sources 324, 349–357 (2016). et al.
- Characterizing the Li–Li7La3Zr2O12 interface stability and kinetics as a function of temperature and current density. J. Power Sources 302, 135–139 (2016). , , , &
- Li7La3Zr2O12 interface modification for Li dendrite prevention. ACS Appl. Mater. Interfaces 8, 10617–10626 (2016). et al.
- First principles study of the Li10GeP2S12 lithium super ionic conductor material. Chem. Mater. 24, 15–17 (2012). , &
- Fluorinated electrolytes for 5 V lithium-ion battery chemistry. Energy Environ. Sci. 6, 1806–1810 (2013). et al.
- Novel 5 V spinel cathode Li2FeMn3O8 for lithium ion batteries. Chem. Mater. 10, 3266–3268 (1998). , , , &
- Commentary: the Materials Project: a materials genome approach to accelerating materials innovation. APL Mater. 1, 011002 (2013). et al.
- Supplementary Information (932 KB)