Breakthrough in 3D Printing: Enabling Large-Scale Production of High-Performance, Ultra-Low-Stacking-Pressure Sulfide-Based All-Solid-State Lithium Metal Pouch Batteries

All-solid-state lithium metal batteries (ASSLMBs) have garnered significant attention as a promising candidate in the energy storage sector due to their high energy density and enhanced safety features. However, critical challenges such as rapid lithium dendrite growth, low Coulombic efficiency, poor rate performance, and inadequate cycling stability have posed formidable obstacles to their commercialization.  

Innovative Multifunctional Composite Sulfide Electrolyte (M-CSE)  

A team led by Researcher Wu Fan from the Institute of Physics, Chinese Academy of Sciences, in collaboration with High Energy Digital Manufacturing, has achieved a groundbreaking advancement in sulfide-based all-solid-state batteries. Utilizing their newly developed multifunctional composite sulfide electrolyte (M-CSE) and High Energy Digital Manufacturing’s 3D battery printing technology, the researchers have demonstrated remarkable performance in ASSLMBs. These batteries exhibit an areal capacity of 10 mAh cm⁻², an energy density of 219 Wh kg⁻¹, and a current density of 3.76 mA cm⁻². Even after 500 cycles at a 0.5C rate, they maintain an impressive 95.04% capacity retention.  

Moreover, leveraging the integrated manufacturing process of High Energy Digital Manufacturing’s 3D printing technology, the team successfully facilitated the batch production of ultra-low-pressure sulfide-based all-solid-state batteries. In this process, Swagelok-type batteries require a stacking pressure of approximately 30 MPa, whereas pouch cells operate at just 2 MPa. These batteries deliver a specific capacity of 128.92 mAh g⁻¹ and maintain an energy density of 219 Wh kg⁻¹ during their first discharge cycle. Notably, the M-CSE interfacial layer consists of cost-effective composite materials, featuring a simple, scalable fabrication process, laying a robust foundation for large-scale production.  

Key Insights from Wu Fan’s Research  

The M-CSE layer inherits high chemical stability and excellent interfacial compatibility, effectively shielding electrode materials from corrosive side reactions and facilitating smooth lithium-ion conduction. Additionally, the localized interfacial passivation mitigates stress induced by volume changes, preserving interfacial integrity and stability. This mechanism also inhibits solid electrolyte decomposition and significantly suppresses lithium dendrite growth. Furthermore, the M-CSE layer ensures a uniform electric field distribution, guiding the stable and even deposition of lithium. Through a dual mechanism of physical isolation and chemical equilibrium, the M-CSE layer effectively prevents dendrite penetration through the solid electrolyte layer, enhancing overall battery longevity.  

Wu Fan’s study explores the high adaptability of sulfide-based solid electrolytes, integrating the unique advantages of different electrolyte types. By combining advanced electrolyte design with 3D printing technology, this research paves the way for the development of next-generation solid electrolytes tailored for the commercialization of all-solid-state batteries. The simplicity and efficiency of this 3D printing-based fabrication approach establish a solid groundwork for the mass production and real-world application of all-solid-state batteries, providing a valuable reference for future battery innovations.  

- Figure 1:  

  a) Battery with an unstable interface, where continuous interfacial layer growth leads to significant overpotential.  

  b) Battery with an SEI interface, showing lithium dendrite penetration.  

  c) Battery incorporating M-CSE.  

- Figure 2:  

  a-d) Cross-sectional scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) images of M-CSE at different magnifications.  

  e, f) SEM images of Li|LiSiSnPSBrO|Li and Li|LPSCILi symmetrical cells after 40 hours of rest.  

  g, h) SEM images of Li|M-CSE-LPSCI-M-CSE|Li symmetrical cells at different magnifications.  

- Figure 3:  

  a-e) Critical current density (CCD) of symmetrical lithium metal batteries with various electrolyte structures.  

  f) Cycling stability at a current density of 1.5 mA cm⁻².  

- Figure 4:  

  Rate performance (0.1–5C) of different ASSLMB configurations and corresponding charge/discharge curves:  

  a) Single electrolyte, b) Different M-CSE ratios, c) Cells incorporating M-CSE, d-g) Charge/discharge curves of M-CSE-enhanced cells.  

- Figure 5:  

  a-c) Discharge capacity and Coulombic efficiency at a 0.5C rate (areal capacity: 1 mAh cm⁻²).  

  d-f) Corresponding charge/discharge curves at various cycle numbers.  

- Figure 6:  

  a) Charge/discharge curves of LCO|LPSCI-M-CSE|Li all-solid-state batteries at different areal capacities.  

  b) Charge/discharge curves of a 2 cm × 2 cm square pouch cell (LCO|LPSCI-M-CSE|Li).  

  c-e) Charge/discharge curves, rate performance, and cycling stability of LCO|LPSCI-M-CSE|Li all-solid-state batteries with an areal capacity of 5 mAh cm⁻².  

  f) Nyquist plots of LCO|LPSCI-M-CSE|Li all-solid-state batteries after various cycling durations.  

High Energy Digital Manufacturing: A Leader in Solid-State Battery Manufacturing Technology  

As a pioneering force in all-solid-state battery intelligent manufacturing, High Energy Digital Manufacturing (Xi’an) Technology Co., Ltd. focuses on two core areas: solid-state battery production lines and dry electrode manufacturing lines. The company provides end-to-end intelligent solutions for new energy enterprises, covering everything from research and development to mass production.  

Currently, High Energy Digital Manufacturing offers customized production line designs and integrated equipment solutions for solid-state batteries and dry electrodes. These include pilot-scale solid-state battery production lines, standardized dry electrode manufacturing lines, and process optimization solutions for solid-state battery fabrication. Furthermore, through proprietary customized process designs and AI-driven robotic systems, the company enables comprehensive lifecycle services, from laboratory research to large-scale industrial production, empowering clients in the intelligent manufacturing of solid-state batteries and dry electrodes.  

Source: High Energy Digital Manufacturing