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Fast cycling of lithium metal in solid-state batteries by constriction-susceptible anode materials

Nature Materials volume 23, pages 244–251 (2024)Cite this article

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Abstract

Interface reaction between lithium (Li) and materials at the anode is not well understood in an all-solid environment. This paper unveils a new phenomenon of constriction susceptibility for materials at such an interface, the utilization of which helps facilitate the design of an active three-dimensional scaffold to host rapid plating and stripping of a significant amount of a thick Li metal layer. Here we focus on the well-known anode material silicon (Si) to demonstrate that, rather than strong Li–Si alloying at the conventional solid–liquid interface, the lithiation reaction of micrometre-sized Si can be significantly constricted at the solid–solid interface so that it occurs only at thin surface sites of Si particles due to a reaction-induced, diffusion-limiting process. The dynamic interaction between surface lithiation and Li plating of a family of anode materials, as predicted by our constrained ensemble computational approach and represented by Si, silver (Ag) and alloys of magnesium (Mg), can thus more homogeneously distribute current densities for the rapid cycling of Li metal at high areal capacity, which is important in regard to solid-state battery application.

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Fig. 1: Significant Li plating capacity from Si anode.
Fig. 2: Thin lithiation shell of Si particles and forced plating of Li metal.
Fig. 3: Constriction susceptibility of anode materials and diffusion-limiting process for Li plating.
Fig. 4: Coin cell cycling data utilizing constriction-susceptible anode design.
Fig. 5: Pouch cell cycling data utilizing constriction-susceptible anode design.

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The data that support the findings of this study are available from the corresponding author on reasonable request.

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Acknowledgements

We thank J. Vlassak and F. Spaepen for helpful discussions. This work was supported by the Department of Energy Vehicle Technology Office, Harvard Climate Change Solutions Fund and Harvard Data Science Initiative Fund. SEM and TEM experiments were conducted at the Center for Nanoscale Systems at Harvard University, supported by the National Science Foundation. This work was also supported by computational resources from the Extreme Science and Engineering Discovery Environment Stampede and Frontera supercomputers.

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Author notes

  1. These authors contributed equally: Luhan Ye, Yang Lu.

Authors and Affiliations

  1. John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA

    Luhan Ye, Yang Lu, Yichao Wang, Jianyuan Li & Xin Li

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Contributions

X.L. conceived the project and supervised all aspects of the research. L.Y., Y.L. and J.L. performed experiments. Y.W. performed computations. J.L performed TEM. L.Y. and Y.L. made the coin cell and pouch cell. L.Y. and X.L. analysed results and wrote the paper, with contributions from all co-authors.

Corresponding author

Correspondence to Xin Li.

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Competing interests

X.L., L.Y., Y.L. and Y.W. report a US provisional patent application: Fast cycling of lithium metal solid-state battery at high loading (filed 29 November 2022; application serial no. 63/428,634). The other authors declare no competing interests.

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Extended data

Extended Data Fig. 1 The FIB-SEM and EDS mapping of Silicon/Graphite (SiG) layer with and without interfacing with Li metal foil.

To further confirm that the oxygen EDS signal is mainly contributed by lithium metal, the cross-sections SEM and EDS analysis of pristine SiG composites with and without a lithium metal anode foil being directly added beneath the SiG layer are compared, where major oxygen and nitrogen signals are only observed from the added lithium metal foil. (a) SiG film without lithium metal foil and does not undergo formation pressure. (b) SiG film (c) Si film without lithium metal foil and undergoes formation pressure. (d) SiG film with lithium metal foil and undergoes formation pressure. F is from PTFE binder and Ga is from FIB ion source.

Extended Data Fig. 2 SEM of cycled SiG in liquid- and solid-state batteries.

When LiNi0.83Mn0.06Co0.11O2 (NMC83) cathode is paired with SiG anode in a liquid electrolyte battery, pulverization of Si particles can be observed after just 5 cycles, accompanied by the poor cycling performance. In contrast, Si stays in an intact state in solid state batteries, with no cracks, pulverization, or irregular edges being found in the FIB-SEM images of Si particles after 500 cycles. (a-b) FIB-SEM image of SiG anode after the battery of SiG-liquid electrolyte-NMC83 (cathode loading = 25 mg/cm2) running for 5 cycles. (c) Charge and discharge curve for the battery of SiG-EC/DMC/1 M LiPF6-NMC83, where Si is micron-sized. (d-e) The FIB-SEM image of SiG anode after 500th cycling. The battery is with the structure of Li(25 um)/SiG-LPSCl-LGPS-LPSCl-NMC83 (cathode loading = 25 mg/cm2) with a nominal NP ratio of 1.5. (f) Charge and discharge profile of the solid-state battery at 55 oC at 2 C, which is also the battery used for STEM-EELS in Fig. 2a. Note that the NP of 1.5 was hypothetically calculated based on the Si practical capacity of 3000 mAh/g and NMC83 capacity of 200 mAh/g.

Extended Data Fig. 3 Li plating between Si particles observed from SEM images of cycled SiG at different cycling stages in solid-state batteries.

The FIB-SEM images and EDS mapping of SiG anode after the 1st (a, b, c) and the 5th (d, e, f) discharge. The batteries are with the structure of SiG-LPSCl-LGPS-LPSCl-NMC83 (loading = 25 mg/cm2) with a nominal NP ratio of 1.5. The batteries were cycled at room temperature at 0.5 C.

Extended Data Fig. 4 Li plating between Si particles observed from SEM images and EDS mapping of Si and SiG at large scales.

(a) FIB-SEM image of pure Si after charge from current collector side to separator side. (b-d) SEM and EDX on the separator side. (e-l) SEM and EDX on the current collector side. The battery is with the structure of Si-LPSCl-LGPS-LPSCl-NMC83 (loading = 25 mg/cm2) with a nominal NP ratio of 1.5 and charged at 3.8 V at 0.5 C-rate at room temperature. (m) FIB-SEM image of pure SiG after charge from current collector side (top) to separator side (bottom). (n-o) SEM and EDX on the current collector side. (p-q) SEM and EDX on the separator side. The battery is with the structure of SiG-LPSCl-LGPS-LPSCl-NMC83 (loading = 25 mg/cm2) with a nominal NP ratio of 1.5 and charged at 3.8 V at 0.5 C-rate at temperature.

Extended Data Fig. 5 Li plating and significant amount of unreacted Si observed from XPS, XRD, and XPS depth profile of SiG anode after lithiation process.

(a) XPS measurement of Li 1 s signal from SiG in an NMC-SEs-SiG solid state battery with nominal NP ratio = 1.5 after the 1st charge at 0.5 C-rate at room temperature, showing the existence of Li metal. Since no Li layer was assembled on the anode side initially, this further confirms the plating of Li metal to the current collector side of the SiG layer from charging the cathode. (b) XRD of SiG from the above charged battery, clearly showing the Si phase rather than the lithiated alloying phase. (c) XPS depth profile of SiG anode after the 1st charge at higher milling energy for longer duration to investigate across the entire SiG electrode. The majority of Si peak throughout the SiG layer indicates that the lithiation of Si across the entire anode is significantly constricted. The sputtered thickness is estimated based on the 0.7 nm/s sputtering rate for Si, giving the number (µm) on the right side that is the thickness sputtered away from the current collector side. Note that the total thickness of the original SiG layer is ~10 µm. The battery is with the structure of SiG-LPSCl-LGPS-LPSCl-NMC83 (loading = 25 mg/cm2) with a nominal NP ratio of 1 and charged at 4.1 V at 0.5 C-rate at room temperature.

Extended Data Fig. 6 Behaviors regarding constriction susceptibility for Si, Mg2Si, and Cu in experiment, and computational prediction of such behaviors for more materials.

(a) Change of XRD FWHM of Si powder in a solid layer pressed with Li metal solid layer at 400 MPa and held at 50 MPa for 40 hours (solid press), compared with that of such solid-pressed Si-Li interface after dropping liquid electrolyte (LE) and holding for 20 hours without external pressure. (b) Time evolution of XRD FWHM change for solid-pressed Si with Li metal after 10 min, 1 h, 20 h, and 40 h. (c) XRD peaks of Si after solid-pressing with Li metal and holding for 0 min, 10 min, and 40 hours. (d) XRD peaks of solid-pressed Si after dropping LE for 10 min, 20 min, and 30 hours. (e1-e3) Illustration of the time evolution of different XRD peaks in (c), which were used to plot ΔFWHM in (b). (e4) The time evolution of a XRD peak in (d) at 10 min and 20 h. The peak almost disappears after 30 hours. (f) Voltage v.s. lithiation composition per atom for materials with voltage between 0-1 V, and with capacity between 0-10000 mAh/g. (g) Two elements coappearance between the dashed lines in Fig. 3f. Only compounds with bandgap less than 1.5 eV are counted. (h) Electrochemical profiles for discharging Li toward Mg2Si in liquid-state and solid-state battery systems at 0.2 mA cm–2 at room temperature. Mg2Si is on the boundary but to the far right of Si in Fig. 3f. The lithiation capacity originally located above 0 V in the liquid electrolyte battery is largely suppressed in the solid-state battery, which is replaced by the lithium plating capacity below 0 V. This suggests that due to the much lower lithiation voltage and much higher constriction-susceptibility, Mg2Si intrinsically prefers Li plating, or with a much less active alloying preference than Si. Thus, lithium plating from Mg2Si will benefit less from the homogeneous current density distribution from the surface lithiation sites than Si. (i) Cyclig performance at 1 C-rate at 55 °C of battery with a structure of (Cu particle and graphite mixture)-SEs-NMC83 (cathode loading = 15 mg/cm2).

Extended Data Fig. 7 Cycle performance of solid-state batteries toward high C-rate, high loading, and lower temperature.

(a) Charge and discharge curves of solid state batteries at 5-10 C-rates and a NMC83 cathode loading of 22 mg/cm2 at 55 oC, where 1 C = 3.2 mA/cm2. The battery can deliver over 157 mAh/g at 5 C charge and 1 C normal discharge. (b) Low temperature voltage profiles of solid-state batteries with Li/SiG as anode and cathode loading of 22 mg/cm2. The discharge capacity of the battery at 0 oC is 154 mAh/g. (c) Capacity retention and coulombic efficiency of battery running at 10 C (charge) -2C (discharge) at 55 oC. At 10 C charge and 2 C discharge a 75% retention after 1200 cycles was obtained. (d-e) Charge and discharge curves for Li/SiG-SEs-NMC83 (22 mg/cm2 loading) battery running at 6C-6C (corresponding to Fig. 4c) and 10C-2C (corresponding to Extended Data Fig. 7c). It is worth emphasizing that the current densities for 6 C and 10 C here are extremely high at 19.5 and 32.7 mA/cm2, respectively. (f) Capacity and coulombic efficiency of battery (NMC83 cathode loading = 15 mg/cm2) running at 5C-5C at a lowered temperature of 35 oC (80% after 1400 cycles). (g) Charge and discharge curves of multilayer batteries with different cathode mass loading up to 60 mg/cm2 and areal capacity up to 7 mAh/cm2 at 0.5 C. The nominal NP ratio is kept at 1.5 for all batteries.

Extended Data Fig. 8 Morphology and chemistry of SiG anode after discharging at low operational pressure.

The FIB-SEM (a,b) and EDS mapping (c) of SiG anode after discharging at 5 MPa. The battery is with the structure of SiG-LPSCl-LGPS-LPSCl-NMC83 (loading = 25 mg/cm2) with a nominal NP ratio of 1.5 and was cycled at room temperature at 0.5 C. (d) Pouch cell with the structure of Li-SiG-SEs-NMC83 (loading = 15 mg/cm2) cycled at 5C charge and discharged at 5 MPa and 55 ℃, with initial areal capacity = 1.36 mAh/cm2.

Extended Data Fig. 9 Cycle performance of batteries with SiO2, Al2O3, and Ag coated SiO2 at anode, and the morphology analysis.

(a) Cyclig performance at 1 C of a solid-state battery with Al2O3 particles at anode. The battery structure is Al2O3&Graphite mixture-SEs-NMC83 (loading = 15 mg/cm2). A short circuit was observed after a few cycles, as lithium plates at the unwanted interface to the electrolyte layer due to a lack of ionic and electronic conductivity in Al2O3. Note that this is different from the diffusion limit to further lithiation discussed for Si, where both Li diffusion and electron conduction can still happen at the surface of Si particles. (b) FIB-SEM image of the Al2O3 layer after the 1st charge of a solid-state battery. (c) The first charge and discharge profiles at 0.5 C and (d) cylicng performance at 1 C of solid-state batteries with Ag coated SiO2 at anode, in comparision that with bare SiO2. The battery structure is SiO2&Graphite mixture-SEs-NMC83 (loading = 15 mg/cm2). A short circuit was observed at the initial charge for uncoated SiO2, similar to bare Al2O3. In contrast, coating Ag to SiO2 particles can make the battery run without a short circuit, but the migration of the coating layer with cycling could be an engineering challenge to solve in the future.

Extended Data Table 1 Energy density of the solid-state pouch cell
Full size table

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Ye, L., Lu, Y., Wang, Y. et al. Fast cycling of lithium metal in solid-state batteries by constriction-susceptible anode materials. Nat. Mater. 23, 244–251 (2024). https://doi.org/10.1038/s41563-023-01722-x

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