Advancements in lithium solid polymer batteries: surface modification, in-situ/operando characterization, and simulation methodologies
0 Abstract
The interest in lithium solid-state batteries (LSSBs) is rapidly escalating, driven by their impressive energy density and safety features. However, they face crucial challenges, including limited ionic conductivity, high interfacial resistance, and unwanted side reactions. Intensive research has been conducted on polymer solid-state electrolytes positioned between the anode and cathode, aiming to replace traditional liquid electrolytes. To alleviate interfacial resistance and mitigate adverse reactions between electrodes and polymer electrolytes, the interfacial modification strategy has been proven to enhance the energy density of LSSBs. This design process is grounded in precise and elaborate theories, with in-situ/operando techniques and simulation methods facilitating the interpretation and validation of structure-property relationships by simplifying them. This review first outlines the recent advancements in surface modification strategies specifically tailored for solid polymer electrolytes. Furthermore, it also provides an overview of innovative in-situ/operando characterizations and simulation methods featured in recent publications, which can gain a more accurate understanding of processes that occur within materials, devices, or chemical reactions as they are happening. Lastly, the review discusses the existing challenges and presents a forward-looking perspective on the future of the next-generation LSSBs.
Keywords
INTRODUCTION
The groundbreaking rechargeable lithium-ion battery (LIB), conceived by Goodenough et al. and
Although SPEs show better interfacial contact than inorganic solid-state electrolytes, polymer-based electrolytes continue to grapple with challenges pertaining to effective penetration and wettability within cathodes, particularly when paired with high-mass-loading cathodes[16,17]. Polymer electrolytes in lithium batteries suffer from suboptimal electrochemical performance due to issues such as interfacial side reactions, limited Li+ interfacial transport, and the formation of a detrimental space-charge layer at the electrode/electrolyte interface[18-20]. Addressing these interfacial issues can increase battery energy density and extend its lifespan. This concise review summarizes advanced strategies aimed at modifying and optimizing electrode/electrolyte surfaces. However, while post-disassembly characterization offers valuable insights into interfacial morphology and microstructure, it lacks the capability to provide real-time feedback on the complex dynamics occurring at electrodes, electrolytes, and their interfaces during battery operation. Recently, Ning et al. have visualized crack propagation in Li6PS5Cl solid electrolyte (SE) using in situ X-ray computed tomography (XRCT) and spatially resolved X-ray diffraction techniques[21].
The development of in-situ characterization techniques has significantly facilitated the resolution of crucial scientific issues in the field of lithium batteries, but monitoring the complex physical and chemical processes is expensive and time-consuming. Theoretical calculations and simulations can provide information without consuming any physical resources, saving both manpower and material resources. Some experiments are difficult or impossible to conduct under realistic conditions, such as those in extremely high temperatures, high pressures, or toxic environments, while theoretical analysis and simulation calculations are not constrained by these limitations. Advancements in theoretical concepts and methodologies across related disciplines such as solid-state physics, quantum chemistry, statistical mechanics, and computational mathematics have provided a solid theoretical foundation for the design of materials’ microstructures[25-27]. The maturity of computational methods such as Molecular Orbital (MO) methods and Density Functional Theory (DFT) has significantly enhanced computational accuracy and efficiency, enabling more precise predictions of material properties.
In this comprehensive review, we will present and discuss the recent advancements in the development of lithium batteries based on polymer electrolytes. Given the plethora of review articles focusing on lithium SPEs[28-30], in this review, we will organize our exploration of the topic in the following manner to ensure it is comprehensive and systematic: the surface modification strategies between polymer electrolytes and electrodes; in-situ characterization techniques; and the advanced modeling methods. Ultimately, this review will also elaborate on the bottlenecks hindering the development of polymer-based lithium batteries, propose corresponding solutions, and simultaneously provide insights into the future direction of development for this type of battery.
SURFACE MODIFICATION STRATEGY FOR LITHIUM SOLID-STATE BATTERY BASED ON POLYMER ELECTROLYTES
Compared with other inorganic SEs, SPEs possess numerous advantages, including flexibility, lightweightness, electrode compatibility, and ease of processing. These qualities make SPEs a powerful strategy for developing high-energy-density lithium batteries. However, despite their promising attributes, the lithium-ion conductivity of SPEs still urgently needs improvement. To address this issue, a significant amount of effort and technical innovations have been dedicated to enhancing their conductivity[31,32]. Considering the overall performance of the battery, the lithium-ion conductivity of SPEs is an important parameter that determines the performance of SSBs. However, low charge transport kinetics and side reactions occurring between electrodes and SPEs also have a serious impact on the battery’s output performance[33-35]. Despite significant improvements in their surface contacts, there remains significant potential for further enhancement when compared to liquid electrolytes. Generally, the poor interfacial contacts initiate an increase in overpotential, which deteriorates the SSB performance and makes them not comparable to liquid batteries. Thus, many researchers have been committed to improving the insufficient surface contacts through various surface modification strategies [Figure 1], such as liquid lithium additives, a quasi-solid layer, multi-layered SE, and direct coating methods. We will provide a comprehensive review of the aforementioned four surface modification strategies based on previous research. These surface modification strategies enhance ion transport efficiency, stabilize the surface, prevent dendrite growth, and improve battery safety and durability.
Figure 1. Schematic diagram of the surface modification strategies in solid lithium polymer battery.
Liquid lithium additives between SPE and electrodes
By adding liquid electrolytes between the electrode and the SPE, this type of SSB becomes a promising candidate to replace the current lithium battery, owing to its advantages of benign interfacial contact and the ability to create huge barriers against unwanted redox shuttles[36-38]. Kim et al. developed a hybrid electrolyte that integrated a solid polyethylene terephthalate (PET) electrolyte with an organic liquid electrolyte [LiPF6 in ethylene carbonate (EC), diethylcarbonate (DC) and dimethyl carbonate (DMC)], which was sandwiched between the anode and the PET electrolyte [Figure 2A][38]. The active cathode materials composed of In2O3-SnO2 (ITO) were coated on another surface of PET by vacuum sputtering deposition. Because lithium-ions migrated much faster in the small amount of organic liquid electrolytes, the solid-state cell exhibited a Coulombic efficiency of over 100% [Figure 2B]. During subsequent cycles, the battery’s capacity stabilizes, as evidenced by the long-term cycling results which indicate an average coulombic efficiency of approximately 110% over 1,278 cycles. The gravimetric capacity remained stable even at a higher charge rate (400 mA g-1), four times the initial rate, suggesting good electrode interphase consistency. Since the increase in SE interphase (SEI) resistance (RSEI) during severe cycling
Figure 2. (A) An illustration depicting the standard lithium-ion battery electrode alongside the newly devised PITO. (B) Performance evaluation, including coulombic efficiency and cycling stability. (C) Nyquist plot for an uncycled reference cell (PITO REF), a cell subjected to rate capability testing (PITO RT), a cell cycled 100 times (PITO × 100), and a cell cycled 500 times (PITO × 500). Reproduced with permission from Ref.[38] Copyright 2021, IOPscience. (D) Schematic illustrations depicting the intricate synthesis process of CSEs and the assembly procedure for SSBs. (E) The initial voltage profiles of the NCM622|B, F-CSE|Li cell with voltage limits at 4.4 and 4.5 V, respectively. Reproduced with permission from Ref.[39] Copyright 2021, Wiley-VCH.
Quasi-solid layer between SPE and electrodes
Researchers typically modify the SPE surface by introducing functional polymers with low molecular weights, as the superior contact compatibility between these polymers enhances lithium-ion interfacial kinetics[40,41]. Yang et al. prepared a polymeric buffer layer [adaptive buffer layer (ABL)] using polyacrylcarbonate, poly (ethylene oxide) (PEO) and LiTFSI, which was sandwiched between the SPE and the Li anode, thereby improving the surface contact among the cell [Figure 3A][42]. According to the reported results, after cell cycling, the Rt increased without the polymeric layer while there were no significant changes in the Rt with polymeric layer [Figure 3B]. The cross-sectional scanning electron microscopy (SEM) images [Figure 3C and D] revealed that, in the absence of a polymeric layer, the surface between the SPE and the Li anode was separated; in contrast, when a polymeric layer was present, the SPE and the Li anode were closely contacted with the polymeric layer. The Li/ABL/SPE/lithium iron phosphate (LFP) battery exhibited nearly double the initial specific discharge capacity (110 mAh/g) compared to the battery without ABL (60 mAh/g), due to improved interfacial contact between Li and SPE. Additionally, the battery with ABL demonstrated greater stability in Coulombic efficiency during cycling. Based on previous research works, quasi-solid layers can be tailored to specific battery chemistries and operating conditions. By adjusting the composition and structure of the layer, researchers can optimize battery performance for different applications.
Figure 3. (A) Configuration of a full cell setup intended for cycling tests and EIS measurements. (B) Nyquist plots at a temperature of
Multi-layered solid electrolytes
All solid-state electrolytes, whether SPEs or inorganic SE, exhibit larger interfacial resistances between electrodes and electrolytes, primarily arising from poor surface adhesion[43,44]. Liu et al. resolved the above issues by adopting a 3-dimension Li anode with high surface area connected to the bulk SE via a flowable polymer electrolyte interphase[45]. A molten SPE was thermally infiltrated into 3D Li-reduced graphene oxide (Li-rGO) [Figure 3E]. This work adopted various SEs for the comparative research, including a composite polymer electrolyte combining PEO and silica, a cross-linked poly (ethylene glycol) diacrylate (PEGDA) electrolyte, and cubic garnet-type LLZTO ceramic. After flowable poly (ethylene glycol)
Direct coating on SPE or electrodes
The atomic layer deposition (ALD) technology can build up condensed layers at atomic level through multiple steps[46-48]. Additionally, it addresses the “surface-wetting” issues by plasma exposure[49]. To solve the “shuttle effects” of lithium polysulfide intermediates in the SPEs and the poor interfacial compatibility between the anode and the SPE, Fan et al. successfully deposited a 5 nm Al2O3 layer on the two surfaces of poly(ethylene oxide)-LiTFSI SPE via ALD[50]. The FIB-SEM images exhibited that lithium existed in the form of dense particle-like deposits in the all-solid-state cell, indicating the nano-thin layer efficiently suppressed the growth of lithium dendrite. The weakened lithium shuttle effect made the Coulombic efficiency of the cell high, over 95%, during the charge/discharge cycling. In addition, the cell using an Al2O3 coating on SPEs demonstrated excellent cycling stability over 200 cycles and significantly reduced the self-discharge rate. Garbayo et al. also used alumina nano-coatings with a thickness of about 10 nm in the cathode-SPE surface to inhibit the polysulfide shuttle effects[51]. By enhancing interfacial stability and inhibiting the growth of lithium dendrites, nano-coating can alleviate fade and performance degradation during the battery cycling process.
ADVANCED IN-SITU/OPERANDO CHARACTERIZATION TECHNIQUES
As we all know, sophisticated electrochemical and chemical reactions usually occur at the interfaces between electrodes and electrolytes, and thus, it is difficult for conventional characterization systems to conduct a thorough investigation of the interfacial physical contact, interfacial ion transport, and interfacial reactions[52-54]. Advanced characterization techniques, including spectroscopy techniques, microscopy techniques, X-ray, mass spectrometry, and neutron techniques, have been actively explored to understand the interface compatibility and ion transport mechanism at atomic, micro, meso, and macroscopic scales[55-59]. Tracking the dynamic interface evolution in operating conditions can promote a deep and precise understanding of the electrochemical properties and stability of interfaces within batteries, providing theoretical guidance for the development of polymer-based batteries. This chapter will focus on the research efforts that employ in-situ/operando spectroscopy, in-situ/operando X-ray techniques, and
Figure 4. Schematic diagram of the in-situ/operando techniques in solid lithium polymer battery.
In-situ/operando spectroscopy technique
Fourier transform infrared spectroscopy
Fourier transform infrared spectroscopy (FTIR) technique uses a broadband infrared beam to measure the amount of light absorbed by a sample. The technique reveals the diverse absorption frequencies by analyzing the attenuated beam, and processes the detected absorption patterns to generate an infrared spectrogram. So far, the in-situ FTIR technology has achieved remarkable results in real-time representation of the microdynamic behavior and structural evolution of materials under various working conditions[60-62].
Figure 5. (A) A detailed description of the experimental arrangement used for in situ near-field infrared imaging and nanospectroscopy. (B) AFM images and IR white light images, and (C) local nano-FTIR spectra obtained at room temperature. Reproduced with permission from Ref.[63] Copyright 2022, Nature. (D and E) A series of time-resolved, stacked FTIR plots focused on a 1,727 cm-1 peak at the interface. Reproduced with permission from Ref.[64] Copyright 2021, Wiley-VCH.
Raman spectroscopy
Raman spectroscopy technology, utilizing the Raman scattering effect, is a powerful method for analyzing scattering spectra to extract valuable information on molecular vibration, rotation, and various other molecular properties[65-67]. Raman spectroscopy is sensitive to Li+-solvent interactions and/or anion concentration, allowing it to track the Li-ion transport mechanism and dendrite growth[68,69]. Given the limitations of conventional Raman spectroscopy, including weak signal and poor temporal resolution, Cheng et al. exploited stimulated Raman scattering (SRS) microscopy[57]. This microscopy utilizes two spatially and temporally synchronized picosecond laser pulse trains[70-72] to in-operando illustrate the Li-ion migration path in a SSB electrolyte [Figure 6A]. They prepared a cell model using a gel polymer electrolyte consisting of LiBOB, tetraethylene glycol dimethyl ether (TEGDME), and poly(vinylidene fluoride-cohexafluoropropylene) (PVDF-HFP), as shown in Figure 6B. The SRS signal obtained directly correlates with the ion concentration, as depicted in Figure 6C. Notably, this method exhibits minimal disruptive background noise. The detection threshold, based on a signal-to-noise ratio of 1, is remarkably low at
Figure 6. (A) A diagram of a Li-Li symmetric cell under SRS imaging. (B) A picture of a Li-Li symmetric cell (top) and a magnified microscope view (bottom) scale: 100 μm. (C) The SRS spectrum displays the characteristics of 0.5 M LiBOB in a TEGDME/PVDF-HFP gel electrolyte. The inset shows that as the LiBOB concentration increases from 0 to 0.5 M, the Raman intensity at 1,830 cm-1 (dashed circle) increases linearly with concentration. (D) 3D images reveal ion depletion near the lithium surface at 4.2 mA cm-2 current density. (E) The average Li+ concentration 5 μm from the Li surface along with a.c voltage profile of a Li/Li symmetric cell at
In-situ/operando X-ray technique
Small angle X-ray scattering technique
Small-angle X-ray scattering (SAXS) can quantify nanoscale electron density differences in a sample, enabling detailed structural analysis through the scattering electron contrast between blocks of polymer electrolytes[73-75]. SAXS typically provides structural information for sizes between 1 and 100 nm (up to
Figure 7. (A) The schematic diagram illustrates the in operando SAXS setup. Radial SAXS profiles were obtained for both (B) lithium metal and (C) graphite anode cells. Reproduced with permission from Ref.[56] copyright 2018, American Chemical Society. (D) The schematic diagram illustrates the experimental setup for an in-situ cell. (E) The current collector has an array of high-precision laser-drilled holes. (F) A picture showing the specialized setup using soft X-rays to study LIBs in real-time. Reproduced with permission from Ref.[76] Copyright 2013 Nature.
Soft X-ray absorption technique
Soft X-ray spectroscopy is an element-specific technique that exhibits high sensitivity to the local chemical environment and structural order of materials. It can provide detailed information about the electronic structure and chemical bonds of materials, which is crucial for understanding the complex electrochemical reactions and interfacial phenomena in polymer-based batteries. Employing the intricate elemental, chemical, and surface probing capabilities of soft X-rays, Liu et al. unveiled unique lithium-ion and electron behavior patterns within the Li(Co1/3Ni1/3Mn1/3)O2 and LiFePO4 cathodes embedded in polymer electrolyte matrices[76]. The fabricated battery cell was affixed to a plate equipped with electrical contacts, facilitating electrochemical cycling and temperature regulation [Figure 7D-F]. To mitigate potential radiation-induced damage to the polymer electrolyte, rigorous testing and precise control of both the X-ray flux and beam dimensions were executed utilizing a specialized refocusing mirror system. While the primary motivation behind utilizing polymer electrolytes was to streamline technical design, their findings reveal intriguing charge transport characteristics associated with these electrolytes, suggesting that this cell configuration holds promise for exploring solid-state electrolyte research avenues as well.
In-situ/operando neutron technique
Neutron depth profiling technique
In neutron depth profiling (NDP), a cold or thermal neutron beam interacts with the isotopes through a sample, which emit a proton and a recoil nucleus. As a near-surface analysis technique, NDP is often used to track the concentration profiles of light elements as a function of depth, since it is directly related to the residue energy of recoil nuclei after they penetrate the sample[77-79]. Upon interaction with a cold neutron beam (within the energy spectrum of 0.1-10 meV), specific nuclides within the material emit charged particles, including 3He, 6Li, 10B, 14N, 17O, 33S, 35Cl, and 40K. Leveraging its exceptional sensitivity towards 6Li detection, NDP is ideally suited for non-invasive quantification of the lithium concentration gradient throughout the electrode’s depth[80-82]. Liu et al. leveraged the unique features of NDP-selectivity, sensitivity, and non-destructive testing to monitor the lithium plating and stripping processes in LiNO3-gel polymer electrolytes within a SSB [Figure 8A][83]. Firstly, they established the in-operando NDP setup. Subsequently, the detection data were collected as the assembled pouch cell underwent ten plating and stripping cycles at a current density of 1 mA cm-2 [Figure 8B]. When compared with the control pouch cells assembled with either a single unit of LiNO3 or gel polymer electrolyte, the pouch cell combining both LiNO3 and gel polymer electrolyte showed a limited generation of inactive Li-species. Additionally, a thin and homogeneous SEI was formed, and Li3N was observed within the SEI, which promoted conductivity.
Figure 8. (A) Diagram of operando NDP for Li-metal plating and stripping. (B) Li distribution and mass in Cu/GPE-LNO/Li battery. Depth starts at ~11 μm (copper current collector thickness). Color scale shows Li density relative to Li-metal. Reproduced with permission from Ref.[83] Copyright 2019, American Chemical Society. (C) Diagram of operando SANS experiments. (D) Scatter plots along with LSV measurements of cells with WiSE and with WiSE-P5 during low-potential scanning. (E) Porod scattering amplitudes of cells with WiSE and WiSE-P5 at various potentials. Reproduced with permission from Ref.[90] Copyright 2021, Wiley-VCH.
Small angle neutron scattering technique
The small angle neutron scattering (SANS) technique is highly sensitive to light elements, enabling the acquisition of real-space structural information on various microstructural elements within materials[84-86]. In the field of SSBs, in-situ SANS technology has the capability to monitor interfacial reactions between SE and electrode materials in real-time, thereby unveiling the microscopic mechanisms underlying ion transport and charge transfer within SSBs[87-89]. Aqueous LIBs are popular for their safety, low cost, and environmental friendliness. Inevitably, lithium batteries based on aqueous electrolytes face many tough challenges, especially including low practical voltage and limited electrode materials. Extensive efforts have been made to construct a SEI to improve the electrochemical stability window. To form a more stable SEI,
SIMULATION METHODS FOR INTERFACE BETWEEN SPES AND ELECTRODE
Advancements in simulation methodologies for SSBs span a wide range of technical approaches, offering vital support for the design, optimization, and commercialization of these batteries. Molecular dynamics (MD) simulations are employed to investigate the dynamic behaviors of ions and molecules within SSBs, encompassing diffusion, migration, and reaction processes. By simulating the system’s response under varying temperatures and pressures, insights into the performance variations of SSBs under operational conditions can be unveiled. Quantum mechanical electronic structure methods, particularly DFT, serve as crucial tools for predicting material properties[91,92]. By solving the Schrödinger equation for electronic systems, DFT provides information on materials’ electronic structure, predicting their physical and chemical properties. In this chapter, we will provide an overview of the research advancements in the field of solid-state polymer batteries utilizing first-principles calculations, MD simulation, and Laplace-Fourier transform solution modeling methods [Figure 9]. First-principles calculations, MD simulations, and Laplace-Fourier transform solution modeling methods have made significant contributions to the research and development of solid-state polymer batteries. By providing insights into the fundamental properties of materials, the dynamic behavior of materials, and the transport processes within the battery, these methods have facilitated the design of new materials and battery systems with improved performance and reliability.
Figure 9. Schematic diagram of the simulation and modeling methods in solid lithium polymer battery.
First-principles calculations
Density functional theory
As we know, polymer electrolytes are complex in terms of their chemical structure; fortunately, computational methods have been developed to elucidate the Li+ binding property and its migration pathway, and to partially study the complex degradation pathways and reactions at electrode surfaces[93,94]. DFT is primarily utilized to investigate the electronic structure and chemical properties of SSB materials at the microscopic scale. By calculating parameters such as the energy band structure and the density of states, one can gain a profound understanding of the electrochemical performance and ion transport mechanisms of the materials. Wu et al. developed a computational method that combines DFT and Ab initio MD (AIMD) calculations, which was used to investigate the Li-nucleation process at the interface between electrolytes and metal electrodes, where Li atoms were introduced on the electrode surface[25]. Figure 10A depicts the flowchart illustrating the simulation process for the PEO-lithium anode system. The comprehensive computational analysis was conducted in a sequential manner, encompassing four distinct stages. Figure 10B and C illustrates the distribution of atomic charges among oxygen and carbon atoms within the PEO system and the PEO-Li anode system, respectively, at various stages of Li-nucleation. This study found that highly reactive Li atoms induced PEO decomposition during the simulated nucleation process, and the resulting SEI films contained lithium alkoxide, ethylene, and lithium ethylene complexes.
Figure 10. (A) The overall process to predict potential SEI components. The atomic charge distribution of (B) oxygen and (C) carbon in pure PEO and on the surface of a Li (100) anode at various stages of Li nucleation. Reproduced with permission from Ref.[25] Copyright 2023, Nature. Lithium dendrite growth model in SPEs with different Young’s modulus: (D) Morphology of lithium dendrite growth. (E) Stress distribution along the X-axis of the dendrite. (F) Electric field and voltage distribution within the dendrite. Reproduced with permission from Ref.[98] Copyright 2023, Chinese Physical SOC.
Phase-field simulation
Multi-physics simulations comprehensively consider the interactions among various physical fields, such as electrochemistry, thermodynamics, and mechanics, within SSBs. By establishing coupled multi-physics models, these simulations facilitate a comprehensive understanding of the complex behaviors exhibited by SSBs during operation. A phase-field model, as a mathematical tool, is utilized to address interfacial problems, making it suitable for exploring interfacial issues in lithium batteries[95-97]. Currently, phase-field simulations of lithium dendrites are predominantly based on a single physical field, which limits the ability to comprehensively study the interactions between various influencing factors. Geng et al. developed a mechanical stress-thermodynamic phase-field theory to investigate the growth mechanisms of lithium dendrites in solid-state polymer lithium batteries [Figure 10D-F][98]; in other words, their lithium dendrite growth model incorporates both mechanical stress and the thermal field. The research showed that high temperature, high electrolyte modulus, and external stress slow lithium dendrite growth and reduce long dendrites. Furthermore, they discovered that altering the Young’s modulus of SPE is 19% more effective in inhibiting lithium dendrite growth than changing the ambient temperature.
Molecular dynamics simulation
MD simulation addresses complex systems at the atomic and molecular levels, and visualizes the dynamic evolution of these systems over time through the corresponding equations[99-101]. As for LIBs, the cyclic high-rate charging and discharging processes often generate massive heat, leading to performance degradation and even thermal runaway, which poses challenges for thermal management. There is an urgent need to explore the internal heat transfer mechanism of lithium batteries, particularly at the interfaces.
Figure 11. (A) A structural model for NEMD simulations of the lithium/Xene (Xene = C, Si, Ge)/SPE interface. Temperature profiles of SPE at the interface, pristine sample (B) and with (C) graphene and (D) silicene. Reproduced with permission from Ref.[102] Copyright 2023, Elsevier. (E) Model of a symmetric solid-state lithium battery with two Li-metal electrodes, SSE, and current collectors. (F) Contact area ratio of electrodes with polymer electrolyte under varying pressures. Reproduced with permission from Ref.[103] Copyright 2022, Elsevier.
Laplace-Fourier transform solution
Many researchers have fully utilized electrochemical and contact mechanics theories to uncover the complex interface behaviors in solid-state lithium batteries. The Laplace-Fourier transform solution has been successfully applied in the simulation of solid-state lithium batteries[103,104]. Through this algorithm, researchers can develop more precise and reliable models that capture the complex interactions between the internal components of the battery. Additionally, this domain solution can be utilized to predict the battery’s performance under various conditions. Zhao et al. proposed a 3D cell model Figure 11E based on the Nernst-Planck equation and electroneutrality, using Talbot’s Laplace and Fourier transforms[103]. It links interface conformity, pressure, modulus, and ionic conductivity to solid-state lithium cell performance. Imperfections in contacts often emerge at the interface between solid-state electrolytes and electrodes during the charging and discharging cycles, arising from interactions between the Li-metal anode surface and solid-state electrolytes. Two types of electrolytes - a ceramic electrolyte system and a polymer electrolyte system - were selected to demonstrate the field distributions. Figure 11F shows how different volume fractions of external pressure affect the SSE-Li interface contact area ratio during 2-h plating at
CONCLUSION AND OUTLOOK
Significant advancements have been made in surface modification, in-situ characterization, and theoretical simulation methods for enhancing the performance and safety of polymer-based lithium batteries. Rational surface modification designs can significantly improve the stability and adhesion of the SEI, thereby reducing the growth of lithium dendrites. In-situ characterization techniques provide robust support for real-time monitoring of battery performance, facilitating a deeper understanding of battery operating and performance degradation mechanisms. Theoretical simulation methods offer new tools for battery design and optimization, aiding in the prediction of battery performance and optimization of material selection. However, there are still challenges pertaining to the aforementioned three advanced approaches, and the following is a specific analysis of these challenges:
In terms of polymer-based lithium battery surface treatment, advanced nanotechnology, surface coating technology, chemical modification techniques, and other means need to be employed to optimize interface performance. The application of these technologies not only increases production costs but also raises the difficulty of production. Furthermore, while current surface modification methods can suppress the growth of lithium dendrites to a certain extent, their effectiveness is limited, and it is difficult to maintain stability over long-term cycling.
In-situ characterization techniques need to simultaneously meet the requirements of real-time performance and high accuracy, which poses significant technical challenges. Moreover, in-situ characterization equipment is often complex and costly, limiting its widespread application. Importantly, the volume of data generated by in-situ characterization techniques is immense and complex, encompassing various types of information such as images, spectra, signals, and more. Effectively integrating this information and extracting the critical factors that impact battery performance poses a significant challenge.
The interface issues in polymer-based solid-state lithium batteries, such as surface contact and interface reactions between the polymer electrolyte and electrodes, are critical factors affecting battery performance. However, the complexity of these interface problems poses significant challenges for theoretical modeling and computation. The physicochemical properties at the interface are difficult to accurately describe, and the kinetic processes of interface reactions are challenging to precisely simulate, leading to notable discrepancies between theoretical simulation results and experimental observations. Currently, the computational models employed for theoretical simulations and calculations of polymer-based solid-state lithium batteries are mostly based on simplified assumptions and approximations, making it difficult to fully capture the intricate physical and chemical processes within the battery. For instance, some models may overlook crucial factors such as the ion transport mechanisms within the polymer chains and charge transfer processes at the interfaces, resulting in less accurate simulation outcomes.
In summary, polymer-based lithium batteries demonstrate immense potential in the field of energy storage, yet their development still faces numerous challenges. Further research should be conducted to delve into the chemical composition and structure of interface modification, aiming to enhance the adhesion and stability of the SEI. More advanced in-situ characterization technologies should be developed to improve the accuracy and real-time performance of data acquisition. Additionally, the integration of theoretical simulations with experimental verifications should be strengthened to enhance the accuracy and reliability of simulation results. Through continuous technological innovations, material improvements, and optimization of production processes, it is anticipated that those challenges can be overcome, propelling polymer-based lithium batteries towards higher energy densities, longer lifespans, enhanced safety and reliability, as well as more environmentally friendly and sustainable development.
DECLARATIONS
Authors’ contributions
Conceived the review and wrote the manuscript: Gu, Y.; Guo, S.; Zhang, Z.; Zhao, C.
Reviewed the manuscript and acquired funding: Li, X.; Gu, Y.; Xu, X.; Wang, H.
Contributed to the discussion of the manuscript: Guo, S.; Li, X.
Availability of data and materials
Not applicable.
Financial support and sponsorship
The work is financially supported by the Shandong Provincial Natural Science Foundation (Grant Nos. ZR2023QB149 and ZR2021QE218), Scientific Startup Foundation for Doctors of Weifang University (Grant No. 2023BS40), “Take on challenges and assume leadership” project from Shangrao city of Jiangxi Province (Grant No. 2022A006) and National Natural Science Foundation of China (Grant No. 52107231).
Conflicts of interest
All authors declared that there are no conflicts of interest.
Ethical approval and consent to participate
Not applicable.
Consent for publication
Not applicable.
Copyright
© The Author(s) 2025.
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Guo, S.; Li, X.; Zhang, Z.; Xu, X.; Wang, H.; Zhao, C.; Gu, Y. Advancements in lithium solid polymer batteries: surface modification, in-situ/operando characterization, and simulation methodologies. Energy Mater. 2025, 5, 500041. http://dx.doi.org/10.20517/energymater.2024.214
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