Li3N-Modified Garnet Electrolyte for All-Solid-State Lithium Metal

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Li3N-Modified Garnet Electrolyte for All-solidstate Li-metal Batteries Operated at 40 ºC Henghui Xu, Yutao Li, Aijun Zhou, Nan Wu, Sen Xin, Zongyao Li, and John B. Goodenough Nano Lett., Just Accepted Manuscript • DOI: 10.1021/acs.nanolett.8b03902 • Publication Date (Web): 23 Oct 2018 Downloaded from http://pubs.acs.org on October 24, 2018

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Li3N-Modified Garnet Electrolyte for All-solid-state Li-metal Batteries Operated at 40 ºC Henghui Xu, Yutao Li,* Aijun Zhou, Nan Wu, Sen Xin, Zongyao Li, and John B. Goodenough* Materials Science and Engineering Program and Texas Materials Institute, The University of Texas at Austin, Austin, TX 78712, USA

ABSTRACT: Lithium carbonate on the surface of garnet blocks Li+ conduction and causes a huge interfacial resistance between the garnet and electrode. To solve this problem, this study presents an effective strategy to reduce significantly the interfacial resistance by replacing Li2CO3 with Li-ion conducting Li3N. Compared to the surface Li2CO3 on garnet, Li3N is not only a good Li+ conductor, but also offers a good wettability with both the garnet surface and a lithium-metal anode. In addition, the introduction of a Li3N layer not only enables a stable contact between the Li anode and garnet electrolyte, but also prevents the direct reduction of garnet by Li metal over a long cycle life. As a result, a symmetric lithium cell with this Li3Nmodified garnet exhibits an ultralow overpotential and stable plating/stripping cyclability without lithium dendrite growth at room temperature. Moreover, an all-solid-state Li/LiFePO4 battery with a Li3N-modified garnet also displays high cycling efficiency and stability over 300 cycles even at a temperature of 40 ºC.

KEYWORDS: Interfacial resistance, garnet, solid-state batteries, lithium nitride

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Compared to today’s commercially available lithium-ion batteries, all-solid-state Li-metal batteries are emerging as an attractive electric power because of their high safety, reliability, and high energy density.1-4 The garnets Li7-xLa3Zr2-xMxO12 (M = Nb or Ta) (LLZO) hold great promise of meeting the requirements of commercial all-solid-state Li-metal batteries because of their high lithium-ion conductivity close to 1 mS cm−1 at room temperature and their good chemical and electrochemical stability against a lithium-metal anode over many charge/discharge cycles.5-6 However, the performance of an all-solid-state lithium-metal battery with the garnet electrolyte is far from practical owing to the large interfacial resistance between the garnet electrolyte and the anode. Both the poor wettability with metallic lithium and rigid property of a garnet ceramic lead to a huge impedance at a garnet/lithium interface and an inhomogeneous current distribution across it.7-8 The high resistance of a garnet/lithium interface and anode dendrite formation and growth into the garnet grain boundaries has been attributed to a Liinsulating Li2CO3 on the garnet surface that is not removed by heating alone.9 Garnet LLZO reacts with moist air to form Li2CO3 due to a high tetrahedral site cation preference energy in the interstitial space of the cubic framework and a strong repulsion between the tetrahedral Li+ and Li+ in the face-sharing octahedral sites.10-12 Endeavors to reduce the interfacial resistance by removing the surface Li2CO3 by several methods were unsuccessful.13-15 Applying a high external pressure for improving physical contact between a garnet electrolyte and a lithium anode also proved to be impractical because of the brittleness of the garnet ceramic. Recently, strategies of coating a Li-alloy layer on a garnet pellet were also unsuccessful.16 Coating the garnet surface with a thin layer of ZnO has allowed wetting of the garnet electrolyte by a metallic lithium anode, and we speculate that the Zn reacts with the Li2CO3 layer to create Li+ vacancies in the carbonate to make it a Li+ conductor. In this


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paper, we presented an alternative strategy to create the needed Li+-conductive interphase between lithium anode and a garnet electrolyte. Previous results by Kyusung Park have shown that Li3N has a strong wetting interaction with lithium and thus effectively prevents lithium-dendrite growth.17-18 Besides, Li3N has several other appealing advantages: a) it possesses a high Li+ conductivity close to 10−3 S cm−1 at roomtemperature;19-20 b) it improves the physical contact between a garnet electrolyte and Li metal; c) it protects the garnet electrolyte from being reduced by Li metal; and d) it is more stable than a Li-alloy layer that may disappear after hundreds of cycles.21 Inspired by Luo’s strategy to achieve a close physical contact by coating lithiophilic materials,22 we remove the original Li2CO3 by a carbon anneal and then introduced a thin Li3N layer on the garnet surface. With the Li3N layer, the total impedance of the symmetric cells was remarkably decreased and the cell cycled stably at room temperature without dendrite growth. Moreover, an all-solid-state battery was demonstrated with a LiFePO4 cathode, a Li-metal anode, and a Li3N-modified garnet electrolyte; the cell displayed a high cycling efficiency and capacity retention even at a relatively low temperature of 40 ºC. As far as we know, there is no report about the garnet-based all-solid-state battery with complete solid-state components that is capable of being operated at 40 ºC. The original garnet Li6.5La3Zr1.5Ta0.5O12 (LLZT) pellet was fabricated through a traditional solid-state reaction according to previous studies.23 The X-ray diffraction (XRD) pattern of the original garnet pellet (Figure S1) shows a pure phase of cubic garnet (PDF-80-0457). No Li2CO3 was detected by XRD, but the yellowy color signals a surface Li2CO3 on the garnet pellet layer. This Li2CO3-covered garnet (LC-LLZT) pellet had a room-temperature Li-ion conductivity of 4 × 10−4 S cm−1.


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Figure 1. (a) Schematic of the preparation of Li3N coated LLZT pellet from original Li2CO3 coated LLZT. SEM images of (b) original LLZT with Li2CO3 surface layer, and (c) Li3N coated LLZT; inset shows the digital image of corresponding pellets. (d) SEM image of the LN-LLZT surface showing the boundary of Li3N and bare LLZT. The corresponding (e) N, and (f) Zr elemental distribution maps, and (g) their overlayer distribution. (h) XRD pattern of the Li3N deposited on a glass substrate; inset shows the Li3N crystal structure. High-resolution XPS spectra of (i) C 1s, (j) Li 1s, and (k) N 1s for the samples of LC-LLZT and LN-LLZT. Figure 1a demonstrates the preparation of a Li3N-modified garnet (LN-LLZT) pellet by removing the Li-insulating Li2CO3 and then coating an ultrathin layer of Li-conducting Li3N on the as-formed Li2CO3-free garnet pellet. Figures 1b and c show the scanning-electron-


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microscope (SEM) images of the corresponding LC-LLZT and LN-LLZT pellets. As shown in Figure 1b, the LC-LLZT crystalline particles had diameters in the range of several micrometers; the surface of LC-LLZT particles was very rough and covered by a layer of Li2CO3, which matches well with a previous report.22 To improve the physical contact at the Li/garnet interface, a layer of Li-conductive Li3N was coated on the treated LLZT surface through plasma enhanced chemical vapor deposition (PECVD). An SEM image of the brown area (Figure 1c) shows that the LLZT particles are covered by lots of dense plates of smaller size, which can be assigned to the Li3N deposition. Energy-dispersive X-ray (EDX) spectroscopy mapping images collected on the boundary of the brown area further prove the uniform coating of Li3N on the garnet LLZT pellet. As shown in Figure 1d-g, elemental N distributes uniformly on the designated area by evaporation while Zr has a homogeneous distribution in the LLZT pellet. To investigate the crystallinity and phase of the brown deposit, XRD was conducted on a sample with the deposit of Li3N on a glass holder instead of on LLZT to avoid the interference of the main phase of LLZT. As shown in Figure 1h, all the diffraction peaks can be readily indexed to a pure phase of alpha-Li3N (Space group: P6/mmm, (JCPDS no.: 30-0759), and the strong intensity of the peaks indicates a high crystallinity of the as-prepared Li3N. The X-ray photoelectron spectroscopy (XPS) spectra of the LC-LLZT and LN-LLZT pellets are collected to screen the surface chemical species of these pellets. As shown in Figure 1i, two peaks at binding energies of 284.8 eV and 289.9 eV were detected in the C 1s spectra for LC-LLZT pellet, which can be assigned to adventitious carbon and lithium carbonate, respectively. There was no obvious Li2CO3 peak observed from the LN-LLZT sample, indicating a successful removal of Li2CO3 on the LC-LLZT sample. Li 1s XPS spectra further validate this result. As shown in Figure 1j, the lower binding energy of 54.5 eV can be assigned to the Li-O bond in LLZT while


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the higher binding energy of 55.2 eV is attributed to Li2CO3 or Li3N.24 Compared to LC-LLZT, the higher ratio of the peak located at 55.2 eV for LN-LLZT sample can be assigned to the main Li3N phase. The N 1s XPS spectrum further proves that the brown product is Li3N (Figure 1k). The Zr 3d peaks for LN-LLZT become very weak due to the layer of Li3N covering the LLZT surface (Figure S2).


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Figure 2. (a) Normalized TOF-SIMS in-depth profiles of Li−, LiN−, LaO−, and ZrO2−secondary ion fragments taken at the surface of the LN-LLZT pellet in a negative mode, depicting the dense layer of Li3N deposited on LLZT pellet. (b) TOF-SIMS chemical maps of LiN−/LaO−/ZrO2− as a function of sputtering depth. (c) A 3D view of the overlap and individual element distribution of N, Zr, and La in the TOF-SIMS sputtered volumes of LN-LLZT, visualizing the Li3N coated on the surface of LLZT. Figure 2 presents the Time-of-flight secondary-ion mass spectroscopy (TOF-SIMS) depth profiling of deposited Li3N on the surface of LLZT, which reveals the evolution of several fragments as the sputtering proceeds in a negative mode. We selected a region of the thin layer of Li3N to carry out the TOF-SIMS measurement. Here, LiN− represents Li3N, while ZrO2− and LaO− represent LLZT underneath the Li3N. Note that the Li− signal comes from both Li from the top Li3N and underneath LLZT pellet. As shown in Figure 2a, the LiN− signal intensity is high initially, but then vanishes as the sputtering proceeds. This evidence proves the existence of Li3N on the surface of LLZT, which matches well with the XPS results. In contrast, the ZrO2− and LaO− fragments appear as weak signals, but then increase almost in parallel over the entire later sputter time, indicating a layer was covered on the LLZT pellet with a homogeneous element distribution. Several TOF-SIMS maps including combined signal counts of LiN−, LaO−, and ZrO2− further visualize the surface Li3N layer on the LLZT pallet as sputtering proceeds. As shown in Figure 2b, the LiN− signal becomes undetectable while the ZrO2− and LaO− signals grow stronger as the sputtering proceeds from the surface to the bulk of the garnet pellet. Figure 2c shows three-dimensional views of the sputtered volume of LN-LLZT from the depth profile that directly visualize the deposited Li3N on the surface of the bulk LLZT.


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The electrochemical impedance spectroscopy (EIS) spectra of the Li symmetric cells with LCLLZT and LN-LLZT pellets clearly show the changes of the interfacial resistance at the garnet/Li interface. As shown in Figures S3a and b, the total EIS resistance, including the garnet and the interfacial impedance, has a drastic decrease from 2512 Ω cm2 for LC-LLZT to 180 Ω cm2 for LN-LLZT at 60 °C; this obvious improvement can be attributed to both better wettability of Li3N by lithium and much higher conductivity of coated Li3N than Li2CO3. In accordance with the much reduced total impedance, a Li/LN-LLZT/Li symmetric cell exhibits a stable plating-stripping process with a very low overpotential of 23 mV at a current density of 100 μA cm−2 and a temperature of 60 °C (Figure S3c). When the current density was set as 200 μA cm−2, the voltage hysteresis shows a slight increase with cycling; but the voltage plateaus are still flat during plating/striping, delivering a small voltage hysteresis of ≈ 44 mV. In contrast, the Li/LCLLZT/Li cell showed a large overpotential of 130 mV due to the Li-blocking Li2CO3 layer, and then died in 30 h because of lithium-dendrite growth across the garnet pellet to give a short circuit (Figure S4).


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Figure 3. (a) The electrochemical impedance spectra of Li symmetric cells with LC-LLZT and LN-LLZT electrolytes tested at 25 °C. (b) Charge-discharge voltage profiles of Li/LN-LLZT/Li cell at 25 °C and at a current density of 100 μA cm−2, inset showing the magnified curve of Li/LN-LLZT/Li. (c) SEM image showing the surface morphology of the cycled Li metal disassembled from the Li/LN-LLZT/Li symmetric cell. When tested at 25 °C, a Li/LN-LLZT/Li cell also exhibited a substantial decrease of ohmic resistance (350 Ω cm2) compared to that for the Li/LC-LLZT/Li cell (4785 Ω cm2) as shown in Figure 3a. This symmetric Li/LN-LLZT/Li cell displayed a larger voltage overpotential of 60 mV at 25 °C and at 100 μA cm−2 because of the more sluggish Li+ diffusion at a lower temperature (Figure 3b). However, the voltage plateaus are flat and long-term cycling stability


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over 200 h was still delivered. The overpotential remained small even at 150 μA cm−2. In comparison, the Li/LC-LLZT/Li cell tested at 25 °C exhibited a large polarization with a fluctuating potential growth before dying in several hours because of an uneven lithium deposition and dissolution (Figure S5). After cycling, the Li/LN-LLZT/Li cell was disassembled and the cycled lithium was collected for SEM observation. The cycled Li surface shows no obvious lithium dendrites from Figure 3c, and the electrodeposited lithium only grows uniformly on the particles. These micro-scale particles possess a limited surface area, which can avoid unwanted side reactions. In contrast, the cycled Li surface with LC-LLZT shows obvious lithium dendrites (Figure S6), causing a quick short-circuit of the Li/LC-LLZT/Li cell. Overall, the Li3Nmodified LLZT exhibited a much-reduced resistance and stable plating/stripping process when tested at temperatures of both 25°C and 60°C, proving the effectiveness of Li+-conductive Li3N in optimizing the Li-metal/garnet interface. A stable electrolyte-electrode interface is proved to be of great importance in realizing a safe and long-life solid-state battery.25-27 Compared with our previously symmetric Li/Li cell with a Li2CO3-free garnet, the cycling of Li/Li cell with LNLLZT is more stable, which originates from the good wettability of Li3N by the Li-metal anode.


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Figure 4. Electrochemical impedance plots (a) and the electrochemical performance of the allsolid-state Li/LN-LLZT/LFP battery tested at (b, c) 60 °C and (d, e) 40 °C: (b, d) charge/discharge voltage profiles at various current densities and (c, e) cycling performance and corresponding Coulombic efficiency at different current densities. To demonstrate the feasibility of this Li3N-modified garnet electrolyte for practical application, all-solid-state Li/LN-LLZT/LiFePO4 batteries were assembled by sandwiching LN-LLZT between a Li-metal anode and an LFP cathode. Figure 4a shows that the as-prepared all-solidstate Li/LN-LLZT/LFP battery has a low total resistance of 142 Ω cm2 at 60 ºC. Figure 4b displays the voltage profiles of the Li/LN-LLZT/LFP at different current densities and at 60 ºC. All the charge-discharge curves show well-defined plateaus with small polarizations at current densities from 25 to 200 µA cm−2. The ﬂat plateau at 25 µA cm−2 shows a small voltage gap of only 0.04 V that expands to 0.42 V even at a current density of 200 µA cm−2, matching well with the small resistance shown in Figure 4a. The discharge capacities are 147, 143, 133, and 118 mAh g−1 at, respectively, 25, 50, 100, and 200 µA cm−2 (Figure 4c). Furthermore, the capacity


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recovers to 144 mAh g−1 when the current goes back to 50 µA cm−2, which is comparable to or higher than those hybrid cells with liquid electrolytes reported previously.28-29 The Coulombic efficiency is close to 100% during the entire cycling, which implies a stable component in the all-solid-state system. This all-solid-state Li-metal battery is also able to run at a lower temperature of 40 °C. As shown in Figure 4a, the total resistance at 40 °C is 380 Ω cm2, lower than those with antiperovskite Li2(OH)0.9F0.1Cl electrolyte and LiF-doped LLZT tested at 60 °C.11,

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profiles in Figure 4d present a higher voltage gap than that tested at 60 °C because both LFP cathode and LN-LLZT deliver a much slower Li+ transport at the lower temperature of 40 °C. Even though, the cell still exhibits clear voltage plateaus and maintains reasonable voltage polarizations, the discharge capacities at 50 and 100 µA cm−2 are 136.6 and 100.5 mAh g−1, respectively, slightly lower than results tested at 60 °C. In addition, this all-solid-state battery enables a long-term cycling life over 300 cycles with Coulombic efficiency maintaining almost 100% (Figure 4e), which indicates that both lower operating temperature and all-solid-state components contribute to a stable electrochemical reaction throughout the whole device. The low initial Coulombic efficiency is attributed to the formation of a stable electrolyte/cathode interface in the first several cycles. The onset of a slow capacity fade after 300 cycles reflects a loosening of the electrolyte/cathode interface. The coated Li3N does not introduce obvious additional resistance to the cell which is comparable to the all-solid-state battery with the LLZT-C electrolyte as reported in our previous work31, but the all-solid-state Li-metal battery with LNLLZT shows a more stable and much longer cycling life. In summary, through replacing Li-blocking Li2CO3 with Li-conductive Li3N on the surface of the garnet pellet, we successfully convert the garnet interface from lithium-insulating to lithium-


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conducting for all-solid-state Li-metal batteries. Compared to Li2CO3, Li3N is not only a good Li+ conductor, but it also bridges the energy gap between lithium and the LLZT pellet. As a result, a close and stable contact between lithium metal and garnet is achieved, enabling a great decrease of the interfacial resistance. Symmetric Li/Li cells with Li3N-modified garnet exhibit a small overpotential and stable Li stripping/plating behavior at 60 °C and room temperature, implying a fast charge transfer and a stabilized interface between the garnet electrolyte and Limetal. When paired with an LFP cathode, an all-solid-state LFP/LN-LLZT/Li battery showed good electrochemical performance with long-term life and high Coulombic efficiency at 40 °C, bringing the garnet electrolytes one step closer to practical application.

ASSOCIATED CONTENT Supporting Information. Detailed experimental procedures; XRD and EIS results of the original LLZT pellet; additional XPS of the LLZT before and after coating Li3N; The electrochemical performances of the symmetric cell with LN-LLZT pellet tested at 60 °C; Charge-discharge voltage profiles of Li/LC-LLZT/Li cell tested at 60 °C and 25 °C. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] *E-mail: [email protected] Notes The authors declare no competing financial interest.


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ACKNOWLEDGMENT This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy through the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium) award number DEEE0007762. Yutao Li also acknowledges the funding support from Enpower Greentech LLC UTA17-001111. REFERENCES 1.

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Nano Letters

Replacing lithium carbonate with a layer of lithium-conductive lithium nitride on the surface of garnet pellet (Li3N-LLZT) significantly reduces the interfacial resistance with a lithium metal anode. An all-solid-state Li/Li3N-LLZT/LiFePO4 battery exhibits a high cycling efficiency close to 100% and long-life stability of 300 cycles even at a low temperature of 40 ºC.


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Li3N-Modified Garnet Electrolyte for All-Solid-State Lithium Metal

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