Key challenges and advancements toward fast-charging all-solid-state lithium batteries

Niaz Ahmad† ^a, Cailing Fan† ^a, Muhammad Faheem ^c, Xiaoxiao Liang ^a, Yirong Xiao^b, Xinting Cao^b, Chaoyuan Zeng *^a, Qinxi Dong^a and Wen Yang *^b
aSchool of Chemistry and Chemical Engineering, Key Laboratory of Ministry of Education for Advanced Materials in Tropical Island Resources, Collaborative Innovation Center of Ecological Civilization, Hainan University, No 58, Renmin Avenue, Haikou 570228, China. E-mail: zengchaoyuan@hainanu.edu.cn
^bKey Laboratory of Cluster Science of Ministry of Education Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, 5# Zhongguancun Road, Haidian District, Beijing 100081, P. R. China. E-mail: yw2323@qq.com; wenyang@bit.edu.cn
^cInterdisciplinary Research Center for Hydrogen Technologies and Carbon Management, King Fahd University of Petroleum and Minerals, KFUPM Box 5040, 31261 Dhahran, Saudi Arabia

First published on 11th July 2024

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Niaz Ahmad

Niaz Ahmad received his Master's degree in Chemistry in 2010 from Bahauddin Zakariya University, Multan (Pakistan), and then received his PhD in Chemistry at the Beijing Institute of Technology in 2021. Since 2021, he has been working as a postdoctoral fellow at Hainan University (Haikou). His core area of research belongs to the development of air-stable and lithium-metal compatible sulfide solid-state electrolytes and their application in next-generation high-energy all-solid-state lithium-metal batteries.

Cailing Fan

Cailing Fan received her BS degree from Yunnan Minzu University in 2010 and her MS degree from the Yunnan Minzu University in 2013. Currently, she is a PhD candidate at Hainan University (Haikou). Her main research is the development of air-stable and lithium metal-compatible sulfide solid-state electrolytes for next-generation high-energy all-solid-state lithium batteries.

Muhammad Faheem

Muhammad Faheem received his M.Sc. in Chemistry in 2010 from Bahauddin Zakariya University, Multan, Pakistan. In 2016, he earned his Master of Philosophy in Chemistry from Government College University Faisalabad, Pakistan, and received his Ph.D. in Chemistry in 2021 from Beijing Institute of Technology, Beijing, China. Muhammad Faheem is a postdoctoral researcher at the Interdisciplinary Research Center for Hydrogen and Energy Storage (IRC-HES), King Fahd University of Petroleum & Minerals, Saudi Arabia. His main research interests are energy storage devices like metal batteries and supercapacitors, especially lithium-ion batteries, lithium–sulfur batteries, aluminum–sulfur batteries, and aluminum-ion batteries.

Xiaoxiao Liang

Xiaoxiao Liang received her BS degree from Liaocheng University in 2018 and her MS degree from the Changchun University of Technology in 2021. Currently, she is a PhD candidate at Hainan University. Her main research interest includes designing and fabricating functional polymers as binders for Si-based electrodes in next-generation solid-state batteries with sulfide-based solid-state electrolytes.

Chaoyuan Zeng

Chaoyuan Zeng obtained his PhD at the Beijing Institute of Technology in 2019. Since 2019, he has been working as an associate professor at Hainan University. His research interests include new environmental/energy materials, including functional energy storage materials and sensors.

Wen Yang

Wen Yang received his BS degree in 2003 from Shaanxi Normal University, Xi'an, China, and his PhD in 2009 from the Changchun Institute of Applied Chemistry, Chinese Academy of Science. He joined the Max Planck Institute of Colloids and Interfaces (2009–2010) as a postdoctoral fellow. In 2011, he joined the School of Chemistry and Chemical Engineering at Beijing Institute of Technology. Since 2012, he has worked as an associate professor at the Beijing Institute of Technology. He was promoted to Associate Professor Tenure Track in 2016 and received tenure in 2021. Currently, he is working as Senior Engineer at A power Electronics Co., Ltd, Guangzhou. His main interests are lithium-ion and all-solid-state lithium batteries (Li-ion and Li–S batteries).

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1. Introduction

Rechargeable lithium-ion batteries (LIBs) have emerged as the predominant energy provider for electric and plugin hybrid vehicles (EVs and PHEVs), which are experiencing a rapid rise in market adoption, partly due to growing apprehensions about climate change.^1,2 Over the last 35 years, LIBs have revolutionized the energy storage sector, e.g., portable electronics, EVs, and PHEVs.³ Despite the incontestable advancements in LIB technology, the current state-of-the-art LIBs cannot yet compete with internal combustion engine (ICE) vehicles due to their longer charging time. Thus, the market penetration process encounters a setback due to the comparatively lengthy charging times of LIBs, whereas ICE vehicles can be refueled within a time of 8 to 10 minutes.^4–6 In this regard, the US Advanced Battery Consortium (USABC) set a goal to realize >80% state of charge (SOC) in 10–15 minutes (≥4C), which is comparable to refueling the internal combustion engine vehicles.^7–9 Until now, it has remained a challenge to achieve this goal even for the most advanced state-of-the-art LIBs.^10,11 The current high-energy LIBs with graphite anodes, metal oxide cathodes, and liquid electrolytes are unable to achieve the fast-charging goal without adversely impacting the battery performance and safety. When batteries are charged at high rates, a variety of internal polarizations (ohmic, concentration, and electrochemical) inside the battery will cause the limited utilization of active materials, enhanced propensity for Li plating, excessive heat generation, etc. More importantly, the non-unity Li⁺ transference number (t_Li⁺) of liquid electrolytes (∼0.3 to 0.45)¹² will inevitably establish a concentration gradient during battery operation, which becomes more pronounced at higher currents. The replacement of liquid electrolytes by solid-state electrolytes (SSEs) (t_Li⁺ ∼1), not only eliminates life-threatening safety issues (e.g., fire and explosion) but also facilitates fast-charging in LIBs.^13,14 Thus, solid-state batteries (SSBs) provide various potential advantages over conventional LIBs and could enable higher energy densities (>500–700 W h kg⁻¹) using Li–metal anodes.

Since the research interest in fast-charging electrochemical performances is increasing exponentially, this review aims to provide an overview of the state-of-the-art research achievements on the fast charging of ASSBs as well as practical engineering strategies for materials (cathode, anode, and solid-state electrolytes (SSEs)) and their interfaces toward effective design. This review primarily focuses on investigating research methodologies for active materials, interfaces, and electrodes utilizing predominantly sulfide-based solid electrolytes (SEs) in all-solid-state batteries (ASSBs).

2. Challenges faced in fast charging in ASSLBs

Inorganic solid-state electrolytes (ISSEs) are either glasses, glass-ceramics, or ceramics/crystalline with high stability at higher temperatures and have great potential to sweep over the unstable Li-deposition and concentration gradients that commonly occur in Li–metal batteries with liquid electrolytes thanks to their intrinsic mechanical stiffness and high lithium transference number (t_Li⁺ ∼1). However, designing practical ASSLBs with reliable fast-charging phenomenon while maintaining durability over a longer lifespan urgently needs to address several technical obstacles (Fig. 1) including the following: (i) electrode/SSE interfaces give rise to various electro-chemo-mechanical issues; (ii) nucleation and penetration of Li-dendrites inside SSE; (iii) void formation; (iv) solid–solid contact loss; (v) chemical/electrochemical decomposition;^15–19 (vi) limited charge (Li-ion and electrons) transportation within composite cathodes (cathode active material + SSE + conductive agent) during fast charging.^20,21 In this perspective, we commence by contrasting and comparing the fundamental electrochemical, transport, mechanical, and thermal aspects associated with the swift charging of SSBs. To meet the goal of fast charging in SSBs in <10 minutes, it is essential to address the significant electro-chemo-mechanical and transport issues.

3. Advantages of ASSLBs toward the fast-charging phenomenon

Inorganic solid-state electrolytes (ISSEs), the essential component of ASSLBs, hold distinct conductive, thermal, and mechanical properties that can potentially address the fast-charging blockades, e.g., safety concerns, low energy density, electrode degradation, and poor electrochemical performance, which originate from liquid electrolytes in conventional LIBs. Apart, from using lithium–metal anodes (LMA) instead of graphite, ASSLBs can potentially deliver gravimetric and volumetric energy densities about ∼40–70% higher in contrast to conventional LIBs.² Therefore, the theoretical benefits that make ASSLBs attractive candidates for the fast-charging phenomenon are covered in this section.

4. Advantages of ISSEs toward the fast-charging phenomenon

Inorganic solid-state electrolytes (ISSEs), e.g., halogen-based, oxide-based, and sulfide-based, can support battery operation at low and high temperatures (for example, −50 to 200 °C or higher), in which conventional liquid electrolytes would freeze, boil or decompose. The low activation energies associated with fast ionic conduction contribute to minimizing the impact of temperature fluctuations on ionic conductivity, thereby ensuring consistent performance. Additionally, the absence of bulk polarization in solid-state electrolytes, attributed to the immobility of the anionic framework, may result in increased power capabilities.

4.1. High Li-ion conductivity of solid-state electrolytes

Ion transport capability is the most important indicator for evaluating the quality of solid-state electrolytes, directly affecting the charging and discharging speed and power density of ASSLBs. In this context, sulfide-based solid-state electrolytes exhibit relatively high σ_Li⁺, ranging from 10⁻⁴ to 10⁻² S cm⁻¹ at RT.^22–32 The high σ_Li⁺ basically originated from polar P–S–Li bonds in conductive crystal units (tetrahedral: PS₄³⁻ and ditetrahedral: P₂S₇⁴⁻) in sulfide-solid-state electrolytes. However, the larger radius of S²⁻ (R_S²⁻: 1.84 Å) leads to an increase in the bottleneck of the Li⁺ conducting tunnel, which therefore facilitates faster Li⁺ migration. Moreover, the lithium transference number t_Li⁺ of ∼1.0 eliminates concentration gradient, largely prevents local ion depletion, and enables compact deposition morphologies, which is beneficial for fast-charging capability.

Based on the structural characteristics, sulfide-based solid-state electrolytes can be categorized into three types: glass, glass-ceramics, and crystalline. Typical glassy sulfides are the binary systems (100−x)Li₂S–xP₂S₅ (LPS), where Li₂S and P₂S₅ serve as the network modifiers and formers, respectively, exhibiting σ_Li⁺ of the order of ∼10⁻⁴ S cm⁻¹. Owing to a lack of grain boundary resistance, the σ_Li⁺ of sulfide glasses are generally 1–2 orders of magnitude higher than that of their crystalline counterparts. However, the σ_Li⁺ of (100−x)Li₂S–xP₂S₅ can be further improved via doping (substitution doping, interstitial doping, or dual-doping, etc.). It is reported that doping with oxides, such as Li₂O,³³ Li₂ZrO₃,³⁴ Li₃PO₄,³⁵ P₂O₅,³⁶ Nb₂O₅,³⁷ Sb₂O₅,³⁸ and GeO₂,²² into (100−x)Li₂S–xP₂S₅ can improve their chemical stabilities and σ_Li⁺ up to 4.77 mS cm⁻¹ RT. In addition, theoretical calculations revealed that the O dopant could create a portal around itself, which not only lowers the local vacancy hopping barriers but also creates a new path for vacancies at the b sites and Li ions at the d sites and thus develops a three-dimensional (3D) conduction channel in the β-Li₃PS₄ solid electrolyte.³⁹

In addition, sulfide-based dopants, e.g., P₂S₃, Ni₃S₂, In₂S₃, and MoS₂, also increased the σ_Li⁺ of the (100−x)Li₂S–xP₂S₅ system. Tu et al. incorporated MoS₂ into Li₇P₃S₁₁, enhancing the σ_Li⁺ to 4.8 mS cm⁻¹ at RT. Furthermore, dual-dopants, e.g., MnS and LiI, developed Li₇P_2.9Mn_0.1S_10.7I_0.3 glass-ceramic exhibited σ_Li⁺ of 5.6 mS cm⁻¹ at RT.

To increase the conductivities of the (100−x)Li₂S–xP₂S₅ system, Li₂S–M_xS_y–P₂S₅ with higher conductivities were achieved by incorporating small amounts of the third component such as GeS₂, SiS₂, SnS₂, or Al₂S₃ into the binary sulfide solid electrolytes to substitute for the P₂S₅.⁴⁰ Consequently, the ionic conductivities of the pure ionic conductors of the Li₂S–M_xS_y–P₂S₅ system are increased due to the introduction of a lithium vacancy by partial aliovalent substitution.⁴¹ In 2011, Li₁₀GeP₂S₁₂ was discovered by Kanno et al., which exhibited a high σ_Li⁺ of 1.2 × 10⁻² S cm⁻¹ at RT.⁴² The Li₁₀GeP₂S₁₂ superionic conductor has a 3D framework structure and a one-dimensional (1D) lithium conduction pathway along the c-axis, consisting of a (Ge_0.5P_0.5)S₄/PS₄ tetrahedra, LiS₄ tetrahedra and LiS₆ octahedra. With increasing temperature, the 1D pathway evolves into a 3D diffusion network.⁴³ Therefore, Li₂S–SiS₂–P₂S₅ solid electrolytes are considered a promising candidate for the development of a new generation of solid electrolytes. Recently, Sun et al. developed Li_10.35[Sn_0.27Si_1.08]P_1.65S₁₂, which offered σ_Li⁺ of 1.1 × 10⁻² S cm⁻¹ at RT, which is close to the value of the Li₁₀GeP₂S₁₂ superionic conductor.⁴⁴ Besides, Kato et al. developed a novel lithium superionic conductor Li_9.54Si_1.74P_1.44S_11.7Cl_0.3 through dual substitution with aliovalent-ion doping, which exhibits the highest conductivity, 2.5 × 10⁻² S cm⁻¹, twice that of the original Li₁₀GeP₂S₁₂.⁴⁵ The high ionic conductivity could be ascribed to the widely distributed 3D conduction pathways at room temperature.

Lithium argyrodites (Li₆PS₅X: X = Cl, Br, I) have also emerged as an important class of lithium-conducting materials. Lithium argyrodites achieved σ_Li⁺ beyond 10 mS cm⁻¹ at RT.^46–48 This increase in σ_Li⁺ is usually a result of an altered Li sublattice (presence of additional Li sites, shortened Li⁺–Li⁺ jump distances, etc.) and an increased S²⁻/X⁻ site disorder, both of which lead to facile lithium diffusion. Another approach to boost the ionic conductivity in lithium argyrodites is the substitution of sulfur with a halogen (Cl⁻ or Br⁻), leading to an increase in the Li vacancies and more pronounced S²⁻/X⁻ site disorder. Recently, Adeli et al. developed halogen-rich, lithium-deficient argyrodites, for e.g., Li_5.5PS_4.5Cl_1.5 not only possesses a high σ_Li⁺ of 9.4 mS cm⁻¹ but also shows a better (electro)chemical stability than the parent Li₆PS₅Cl.⁶⁰ Very recently, S. Li et al. developed halogen-rich lithium argyrodite Li_5.5PS_4.5Cl_0.8Br_0.7, which exhibits a σ_Li⁺ of 22.7 mS cm⁻¹ (determined by ⁷Li pulsed field gradient NMR spectroscopy) and 9.6 mS cm⁻¹ (by the EIS method) in the cold-pressed state.⁶¹ Furthermore, the Li-conductivities of different sulfide-based SSEs are summarized in Table 1.

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4.2. Moderate mechanical properties of sulfide-based SSEs

Along with conductive assets, the mechanical properties of SSEs are also very important for the high and long-term electrochemical performance of ASSLBs. Recent studies have reported that Li-dendrites can be easily produced inside SSEs, e.g., 70Li₂S–30P₂S₅ glass, 75Li₂S–25P₂S₅ glass, Li₇P₃S₁₁ glass-ceramic, polycrystalline β-Li₃PS₄, Li₁₀GeP₂S₁₂ and Li₆PS₅X (X: F, Cl, Br and I). The formation of Li-dendrites leads to the short-circuiting of the Li//Li symmetric cells at large currents. Hence, the favorable mechanical properties of sulfide-SSEs (with the Young's modulus ranging from 18 to 25 GPa) play a crucial role in inhibiting the penetration of Li-dendrites, thereby enhancing the overall performance of ASSLBs.

5. Challenges of solid-state electrolytes

Despite the incontestable uniqueness, e.g., high Li-ion conductivity (1–25 mS cm⁻¹), unity lithium transference number (t_Li⁺), moderate mechanical properties (Young's moduli from 18 to 25 GPa) and cold pressed applicability, sulfide-based SSEs suffer from the following key issues, which impede their application in fast charging ASSLBs: (i) brutal nature of the thick SSE pellet, (ii) narrow electrochemical stability window from 1.7 to 2.31 V;^64,65 (iii) low Li-dendrites suppression capability, e.g., low critical current density (CCD);^66–68 (iv) chemical/electrochemical instability against the electrodes (anodes and cathodes); and (v) cell volume changes during Li-plating/stripping give rise to mechanical stresses on the SSE, inducing deformations, e.g., voids, cracking and contact loss.^69,70

5.1. Poor physical contact at LMA–SSEs interface

Unlike the perfect contact between LEs and the LMA, SEs and the LMA exhibit point-to-point contact at the interface, resulting in the formation of numerous voids and gaps at the interface. Such defects can extend the Li⁺ transport path and reduce the Li⁺ transfer rate, eventually increasing battery impedance and reducing battery performance. An intimate physical contact between the SSEs and LMA is essential to carry out perfect electrochemical reactions in all-solid-state batteries. Inadequate physical contact promotes uneven Li-ion deposition, which in turn facilitates the nucleation and growth of Li-dendrites, leading to poor electrochemical performance ASSLMBs as well as early rapid failure. Furthermore, LMA experiences a volume change of ∼10% to 15% during the charge–discharge operation, even exceeding 20% after multiple cycles.^71,72 Thus, the longevity and electrochemical performance of ASSLMBs can be negatively impacted by the volume of LMA and insufficient physical contact. Recently, B. J. Hwang et al. achieved a robust artificial interphase SEI between LMA and SSE via the incorporation of a composite electrolyte composed of Li₆PS₅Cl (LPSC), polyethylene glycol (PEG) and lithium bis(fluorosulfonyl)imide (LiFSI), resulting in the in situ creation of an LiF-rich interfacial layer.⁷³ This interphase effectively mitigates electrolyte reduction, promotes lithium-ion diffusion and improves physical contact between the 3% LPSC SE and the LMA (Fig. 2b). Besides, Chen et al. reported an interesting work to construct a stable SEI between Li₆PS₅Cl and lithium metal anodes by a sustained release-driven method. Here, poly(propylene carbonate) (PPC) and LiTFSI steadily interacted with a lithium anode by the catalytic de-polymerization reaction and constantly decreased the interfacial resistance. Apart from intimate contact, the ultrastable LiF-enriched solid electrolyte interphase (SEI) is in situ formed via a sustained release effect, which suppresses the Li dendrite effectively. Su et al. introduced a thin amorphous and Li-ion conducting lithium phosphorus oxynitride (LiPON) interlayer between Li₆PS₅Cl SSE and LMA.⁷⁴ It is studied that the interlayer enhanced the wetting behavior of the Li₆PS₅Cl SSE and ensured an effective conformal interfacial contact between the Li₆PS₅Cl SSE and LMA, as depicted in Fig. 2c and d.

5.2. Voids formation

Lewis et al. recently utilized operando X-ray tomography to directly visualize the formation and evolution of voids during lithium stripping, meanwhile quantifying the loss of contact that drives current constriction at the Li₁₀SnP₂S₁₂/Li interfaces. The loss and reconfiguration of interfacial contact play a determinant role in inducing cell failure. Severe anodic failures in ASSLBs occur at fast charging under high-current densities, e.g., >3 mA cm⁻².⁷⁵ A functional battery's failures are caused by anodic inefficient Li kinetic (including Li-ion transport, interfacial charge transfer, the Li adatom, and vacancy diffusion) at solid–solid interfaces.^18,76 The Li vacancies resulting from Li stripping cannot be fully replenished due to their extremely low diffusion coefficient (<10⁻¹¹ cm² s⁻¹), which causes them to accumulate as Li voids near interfaces. Li void accumulation will gradually degrade the interfacial contacts that lead to the increased local current density and accelerate the subsequent Li-plating at solid–solid interfaces until dendrite failure.^77,78 Li void accumulation can (1) hinder Li-ion diffusion and charge transfer; (2) enhance interface resistance; and (3) increase the cell volume, which decreases the volumetric energy density of ASSLBs. Y. Lu et al.⁷⁹ recently, through in situ visualized morphological evolutions, revealed the microscopic features of void defects under different stripping circumstances (Fig. 3a). Moreover, the relationship of current densities from and EIS corresponding to the void formation is demonstrated in Fig. 3b–e.

5.3. Low critical current densities of SSEs

The evaluation of the rate capability of ASSLBs often relies on the critical current density (CCD) of solid-state electrolytes (e.g., Li₇La₃Zr₂O₁₂: 0.05–0.9 mA cm⁻², Li₂S–P₂S₅: 0.54–1.0 mA cm⁻² and LiPON >10 mA cm⁻²).^76,80–82 This parameter signifies the highest sustainable current density that can be endured during cycling without causing a short circuit. Recently, both experimental and computational studies have explored the significant role of the SE/LMA interface in the development of CCD, in addition to its impact on the intrinsic electronic conductivity.^83,84 The following section delves into the strategies employed to promote the advancement of CCDs.

6. Influence of anode/SSEs interface on fast charging

In ASSLBs, the direct interaction of SSEs with anode can result in a variety of interfacial reactions^110–114 not only in the charge–discharge operation but also at the open circuit voltage. Experimental and theoretical studies have identified these (chemical and electrochemical) reactions as potential roadblocks for fast-charging ASSLBs.^115–119

6.1. Chemical reaction at anode SSEs interface

Spontaneous interfacial chemical reactions can in principle happen when an electrode, such as an electropositive Li–metal anode (LMA), and SSEs have different chemical potentials.^15,114 Consequently, solid electrolyte interphase (SEI) is in situ developed at the anode side interface (Fig. 5a–c).¹²⁰ The chemical, mechanical, and electronic properties of SEI are critical for determining the long-term electrochemical performance and practicability of ASSBs.¹²¹ An SEI with non-passivating species, e.g., Li₂S (insulator), Li₃P (ionic conductor), and Li–Ge alloys (electronic conductors), collectively produced MIEC, as confirmed by in situ XPS. Herein, Li–Ge (electronic conductors) continued the decomposition of LGPS, which gradually increases the anode interfacial impedance and eventually contributes to cell failure. Likewise, the alloys of Si, Sb, and Sn are electronically conductive for continuously increasing the impedance of the LMA/SSE interface. However, phosphorus-based sulfide SSEs, e.g., Li₃PS₄, Li₇P₃S₁₁, and Li₆PS₅Cl, are known to be relatively stable with LMA since the expected decomposition products of these electrolytes, Li₂S, Li₃P, and LiX (X = Cl, Br, I), are thermodynamically stable with LMA. These binary lithiated conductors can prevent the further decomposition of ISEs, their anions are in the fully reduced state (S²⁻, N³⁻, P³⁻, O²⁻ and X⁻) and hence, so no further reduction occurs. The interface stability is attributed to the absence of any electronically conducting species, allowing the interphase to self-passivate.

6.2. Electrochemical reaction at the anode SSEs interface

SSEs intrinsically with a narrow electrochemical stability window (ESW) cannot operate in the full voltage range of cathode and anode materials.⁶⁵ Therefore, almost all state-of-the-art SSEs suffered from redox reactions beyond their actual ESW and thus decomposed to produce SEI/CEI and hence increase the charge transfer resistance.¹⁵ The ESW of Li₆PS₅Cl, Li₁₀GeP₂S₁₂, and Li₇La₃Zr₂O₁₂ are in the range of 1.7–2.31 and 0.5–2.91 V, respectively.⁶⁵ Recent experimental and computational research has revealed that for Li₆PS₅Cl SSE, the oxidation products contain S and P₂S₅, and the reduction products, such as Li₃P, Li₂S, and LiCl, have been identified at the phase equilibrium. Phase equilibrium showed that several lithiated products are stable LMA at 0 V, including Li₃P, Li₂S, Li₃N, LiF, LiCl, and LiI. Furthermore, phase equilibria of LPS and LGPS SSEs are enriched with Li₃P, Li₂S, Li₃P, Li₂S, and Li₁₅Ge₄ at 0 V, as confirmed by XPS technology.^102,122 The SEs undergo oxidative/reductive decomposition once the operating voltage of the ASSBs exceeds the electrochemical stability window of SEs. Sulfide-based solid-state electrolytes (SSE) undergo a transformation where the PS₄³⁻ tetrahedra can be oxidized, resulting in the formation of sulfur-bridging (–S–) elemental S. Conversely, when the voltage reaches 0 V, the initial reduction of PS₄³⁻ leads to the creation of –P–P– bonds, which are then further reduced to Li₃P and Li₂S. When sulfide-based SEs are coupled with high-voltage oxide-based cathodes LCO, NCM, or NCA, oxidative decomposition becomes more severe at higher voltages, resulting in a thicker CEI and a lower coulombic efficiency (CE). The extent of electrochemical decomposition is reflected by the CE of the first cycle.

6.3. Challenges of thick SSE layers

To realize fast-charging ASSBs, it is imperative to employ a thin and compact SE layer, which in turn can minimize the conduction path and the corresponding time for charge transportation. Furthermore, a thin SSE layer (<25 μm, comparable to the thickness of commercial separators (Celgard 2325)) ensures faster ionic conduction and lowers the internal resistance, which is beneficial for fast-charging SSLMBs.¹²³ Besides, a thin SSE layer can significantly increase the ratio of cathode active materials, which contributes to higher energy density (Fig. 6a). Meanwhile, the mechanical properties of the SSE layer, e.g., elastic modulus, fracture toughness, and relative density, are of great significance in hindering Li-dendrites and maintaining their stability while running the cell. However, most of the SSE layer is >100 mm thick with relatively high porosity.^124,125 The presence of such porosity in the SSE pellet serves as a pathway for Li-dendrites to penetrate through the SSEs and shorten the ASSBs. However, too thick an SSE layer will inevitably increase the internal resistance of SSLBs. Hence, the thickness of the SSE layer is a critical parameter that influences the internal resistance and energy density of SSLBs.^126–128 The internal resistance depends on the ionic conductance of the SSE and the charge transfer resistance of the electrodes. The ionic conductance, (G = σA/l, where G, σ, A, and l denote the ionic conductance, ionic conductivity, surface area, and thickness of the SSE, respectively) by definition, is inversely proportional to the thickness of the ISE layer.¹²³ Thus, the thickness of the SSE layer plays a key role in determining the cell-level energy densities. The thin SSE layer not only increases the energy density (gravimetric and volumetric energy) but also facilitates the fast-charging capability of SSLBs.

7. Effect of cathode/SSE interface on fast charging

Due to the inadequate solid–solid contact between the SSE and solid-state cathode in ASSLBs, the transfer resistance of Li⁺ at the interface can be several times larger than that in liquid systems. Accordingly, the high interfacial resistance in the cathode/SSE interface mainly comes from several parts: (1) poor physical contact in the composite cathode may incur inferior Li⁺ accessibility for the active materials; (2) space-charge layer; (3) cathode–electrolyte interface; and (4) undesirable side reaction.

7.1. Poor physical contact

The inflexible characteristic of the solid-state electrolyte (SSEs) restricts intimate contact (bridging for Li⁺/e⁻ transport) between the solid-state cathode active materials and the ion-conducting SSEs.¹⁴⁵ This unfavorable situation negatively impacts the transfer of charge carriers. The contact problem can be categorized as follows. (1) The pores/cracks in the cathode, which, however, can block the charge transfer in the cathode and limit the power density of the system. Additionally, inactive pores take up a specific amount of space, limiting the energy density of the system.¹⁴⁶ (2) Inadequate contact between the cathode and the SSEs results in interface separation, which hinders the diffusion of Li⁺ ions and may ultimately cause an open circuit.¹⁴⁷ Besides, under certain operating conditions, certain cathodes may experience phase transitions that lead to volume variations and troublesome contact. Choi et al. conducted a 3D reconstructed analysis on the composite cathode and visualized the distribution of the active material, electrolyte, conductive carbon, and their connectivity. After the addition of 29% SSE, a remarkable number of micropores with a volume ratio of nearly 15% were detected in the electrode. Additionally, a quantitative analysis was conducted to determine the area of the effective two-phase boundary, revealing that the effective interface accounted for only approximately 23% of the total interface.¹⁴³ In the given context, Zhang et al. carried out an optimization analysis on the LiCoO₂ cathode and Li₁₀GeP₂S₁₂ SSE ratio. Their study resulted in a conclusive finding that the mass fraction of the solid electrolyte needs to be higher than 20% to adequately support the ionic path.

7.2. Space-charge layer

The subpar performance of ASSLBs may also be attributed to a space charge effect at the cathode–SE interface. AIMD simulations and DFT calculations provide evidence that the contact between an oxide-based cathode and a sulfide SSE leads to the formation of a space charge layer (Fig. 7a).¹⁴⁸ The oxidation tendency of sulfides, in contrast to oxides, enables electrons to efficiently transfer from the sulfide SEs to the charged cathode. Li-ions will, in principle, diffuse out of this area to balance the charge, either toward the anode in the presence of an applied charging voltage or toward the charged cathode by self-diffusion. The conductivity of a material is greatly influenced by the concentration of mobile ions. Consequently, the presence of a space-charge layer can impede the diffusion of these ions, leading to a decrease in the rate performance. Takada and Ohta, along with their colleagues, attributed the restricted rate capability of ASSBs to the development of a space charge layer, which is intricately linked to vacancy creation and defect chemistry at the boundary.^149–151 Applying a Li-ion conductive and electronically insulative coating layer (with suitable intrinsic characteristics, e.g., phase stability, chemical/electrochemical stability, Li-ion conductivity, and mechanical property) has proven to be effective in overcoming the space charge layer effect and lowering the interfacial resistance.^152,153 Next, the electrical potential distribution around the LiCoO₂/Li_1+x+yAl_yTi_2−ySi_xP_3−xO₁₂ interface during the CV experiment obtained by electron holography is demonstrated in Fig. 7b.¹⁴⁴

7.3. Electro-chemo-mechanical breakdown

In SSLBs, the rigid nature of the composite electrode aggravates the difficulty in relieving electrochemical stress and leads toward contact loss between cathode active materials (CMA), conductive agents, and SSE. Lithiation/de-lithiation will alter the electrostatic repulsion in the host crystal structure of CMA, which, however, undergoes lattice changes during electrochemical charge/discharge operation. The intercalation-type cathode materials can be divided into olivine, spinel, and layered structures. Olivine structured materials, e.g., LiFeO₄, experienced 6.81% volumetric variation during the lithiation and de-lithiation (LiFePO₄ ↔ FePO₄) process. Spinel LiMn₂O₄ undergoes two cubic phase transitions at the 3.96 and 4.07 V plateau and turns into λ-Mn₂O₄, showing a volume change of 6.8%. Likewise, the layered materials, e.g., LiCoO₂, experience hexagonal phase H1, hexagonal phase H2, and monoclinic phase M. The composition changes from LiCoO₂ to Li_0.5CoO₂, which, first believed as the structural stable range, will cause a volumetric expansion of ∼2%. However, the substitution of Co in the layered structure with Ni, Mn, and Al results in higher reversible lithium utilization and therefore LiNi_xCo_yMn_1−x−yO₂ (NCM) and LiNi_xCo_yAl_1−x−yO₂ (NCA). Thus, the volume change of cathode materials will lead to mechanical breakdown inside the cathode and contact region between the cathode and electrolyte.

8. Strategies to overcome the cathodic issues

The preceding discourse highlights the fact that the implementation of ASSLBs continues to encounter various obstacles in the realms of physical, mechanical, and chemical/electrochemical domains that need to be surmounted. Substantial progress has been made in solid-state electrolytes (SSEs) and lithium–metal anodes. Extensive research efforts have focused on addressing cathodic challenges such as interfacial issues, volume changes, and degradation to enhance the electrochemical performance of solid-state lithium batteries (SSLBs) at elevated current densities or C-rates. The succeeding portion presents a compact review of the strategies targeted at minimizing cathodic concerns.

8.1. Reducing the tortuosity of cathodes

Reducing the tortuosity of electrodes is a widely established strategy for altering their structure as this results in superior charge transfer kinetics and excellent specific capacity at high current densities. The development of vertical channels is a straightforward strategy to reduce the tortuosity of electrodes. Y. Wang et al.¹⁵⁴ proposed a combination of screen printing and battery electrode manufacturing to produce low-tortuosity electrodes for fast-charging LIBs industrialization. The relationship between the electrochemical properties and architecture of the channels, including the pattern, channel diameter, and edge distance between channels, is revealed. The optimized screen-printed electrode exhibited a seven-fold higher charge capacity (72 mA h g⁻¹) at a current rate of 6C and superior stability compared with that of the conventional bar-coated electrode (10 mA h g⁻¹, 6C) at a mass loading of 10 mg cm⁻².

8.2. Improvement of kinetics within cathodes

Fast charging in ASSLBs faces a significant obstacle due to the kinetics involved in the solid-state cathodes’ active material and composite cathodes. This includes challenges related to ion transport and chemical/electrochemical reactions at interfaces. Designing cathode microstructures that offer ample electrochemically active area and pathways for ionic/electronic percolation is crucial in achieving fast-charge performance in ASSLBs. Owing to the low σ_Li⁺ of cathode active materials (CAM), such as LiCo_xNi_yMn_zO₂, the CAMs need to be combined with an SSE to create an ionic conduction pathway with the lowest impedance across the electrode. To achieve an ideal ion percolation, a significant portion (∼30–50 weight percent) of SSE is frequently used within the cathode. When the CAM loading is increased to approximately ∼80 wt%,^155–157 which in principle increases the energy density, the limitations of ion percolation within the cathode architecture become even more crucial. Additionally, inadequate interfacial area can restrict the charge-transfer reactions.¹⁵⁸ However, the existence of voids and the introduction of secondary phases, e.g., conductive additive and polymer binder, can further reduce the active interfacial area and impede ion percolation pathways. The microstructure of the composite cathode, e.g., particle size, porosity, and tortuosity, also plays an important role in the electrochemical performance along with ionic conductivity and active area.

At the high current charging process, chemo-mechanical challenges including interfacial degradation and particle cracking due to severe volume fluctuations of the CAM need to be understood and addressed.^159–161 The mechanical damage can be alleviated using single-crystal cathode particles. Besides, sufficient ionic and electronic percolation pathways in thick cathodes are also essential to realize fast-charging ASSLBs. Accordingly, thick and dense cathodes with higher electronic and ionic conductivity, have recently been reported using thick electrodeposited LiCoO₂ without conductive diluents.¹⁶² The electrodeposited cathodes, which were grown with preferred crystallographic facets, revealed optimized ionic conduction paths and transport and thus enabled fast charge. Moreover, 3D templates can deliver bi-continuous electronic and ionic pathways to minimize tortuosity and simultaneously enable high active material loading. The incorporation of liquid/gel electrolytes in the cathode can also enhance the rate performance of ASSLBs.^163,164

8.3. Nanoscale coating of cathode

Applying a nanoscale protective coating on the CAM surface is an effective strategy to improve the interfacial stability by avoiding direct physical contact with the SSEs.^{121,165–167} An ideal coating should not only be thin and uniform but also feature desirable properties, such as low electronic conductivity and high ionic conductivity and reduce the contact resistance caused by decomposition reactions, thereby enhancing the cycling performance.^165,166 Accordingly, Y. Ma et al.¹⁶⁸ reported a nanoscale coating of non-agglomerated nanoparticles (≤5 nm, exemplified for ZrO₂) to a layered Ni-rich oxide CAM, LiNi_0.85Co_0.10Mn_0.05O₂ (NCM85), producing a uniform surface layer with a unique structure (Fig. 8a). The coated NCM85 with Li₆PS₅Cl SSE exhibits superior lithium-storage properties (q_dis ≈ 204 mA h g_NCM85⁻¹ at 0.1C rate and 45 °C) and good rate capability. J. Liang with coworkers¹⁶⁹ developed a gradient Li₃P_1+xO₄S_4x artificial SSE interface on the surface and grain boundary of NMC811 primary particles by ALD of Li₃PO₄ and subsequent sulfurization using a P₄S₁₆-assisted solid–liquid process (Fig. 8b and c). The presence of a gradient artificial coating with Li⁺ conductivity but electronic insulation successfully hindered the side reactions between sulfide SSE and NMC811. The presence of the gradient Li₃P_1+xO₄S_4x coating on both the surface and grain boundary of primary NMC811 particles allows for the seamless migration of Li⁺ ions across the NMC811/Li₃P_1+xO₄S_4x/sulfide SSE interface. This migration ultimately helps in preventing the structural transformation of NMC811 from the desired layered LiNi_0.8Co_0.1Mn_0.1O₂ phase to the less favorable rock-salt LiNi_0.8Co_0.1Mn_0.1O₂ phase. W. He et al.¹⁷⁰ designed a nanometer Li_1.175Nb_0.645Ti_0.4O₃ (LNTO)-coated LCO cathode. Here, microscopic Ti and Nb segregation at the interface during cycling potentially stabilizes the cathode lattice and minimizes side reactions. Differential phase contrast scanning transmission electron microscopy (DPC-STEM) visualized that the nano-interlayer LNTO boosts Li⁺ migration at the cathode interface, effectively reducing the interfacial resistance. Resultantly, sulfide-based ASSLBs at 4.5 V offered long-cycle stability (0.5C for 1000 cycles, capacity retention: 88.6%), better specific capacity, and rate performance (179.8 mA h g⁻¹ at 0.1C, 97 mA h g⁻¹ at 2C) (Fig. 8e and f).

8.4. Cathode and anode interface engineering

The Li-dendrite suppression capability (CCD: 1.4 mA cm⁻²/1.4 mA h cm⁻²) of Li₆PS₅Cl was significantly improved by H. Wan et al.¹⁷¹ through the introduction of a small proportion (0.32 wt%) of electronic insulative CuF₂–LiNO₃. This resulted in the formation of a mixed conductive lithophilic LiF–Li₃N–Cu interface layer at the interface between Li₆PS₅Cl and Li. Additionally, AlF₃ was incorporated into the Li₆PS₅Cl–CuF₂–LiNO₃ electrolyte in the single-crystalline NMC811 (S-NMC811) cathode, while Cl⁻ was introduced onto the surface of S-NMC811 to inhibit the undesired side reaction with Li₆PS₅Cl–CuF₂–LiNO₃–AlF, which resulted in superior electrochemical performance, e.g., high-capacity retention of 69.4% after 100 cycles at 2.55 mA cm⁻²/2.55 mA h cm⁻² at RT. Recently, an investigation revealed the impressive performance of a Cl@NMC811/Li₆PS₅Cl–Mg₁₆Bi₈₄/Li cell with a high cathode loading of 5.1 mA h cm⁻². This cell achieved a capacity of 4.3 mA h cm⁻² at 2.55 mA cm⁻² (0.5C; 1C = 200 mA h g⁻¹) and 1.5 mA h cm⁻² at 10.2 mA cm⁻² (2.0C). Additionally, the Cl@NMC811/Li₆PS₅Cl–Mg₁₆Bi₈₄/Li cell at 80 °C demonstrates a reversible capacity of 1.5 mA h cm⁻² for 300 cycles at 3C (15.3 mA cm⁻²), highlighting the exceptional fast charging ability of the cell when equipped with an Mg₁₆Bi₈₄ interlayer. Additionally, it has been demonstrated that the F@NMC811/Li₆PS₅Cl–Mg₁₆Bi₈₄/Li cell, when charged at a higher voltage of 4.3 V, improves the structural stability of the NMC811. This is because F diffuses from the NMC811 surface to the bulk, resulting in a cell with a cathode loading of 0.51 mA h g⁻¹ after 444 cycles at 80 °C and 86.1 mA h g⁻¹ after 681 cycles at 60 °C and a rate of 5C (2.55 mA cm⁻²). Moreover, when the F@NMC811/Li₆PS₅Cl–Mg₁₆Bi₈₄/Li cell is charged at a higher voltage of 4.3 V, F diffused from the NMC811 surface to the bulk and enhanced the structural stability of the NMC811. The F@NMC811/Li₆PS₅Cl–Mg₁₆Bi₈₄/Li cell with a cathode loading of 0.51 mA h cm⁻² can provide a capacity of 157.8 mA h g⁻¹ after 444 cycles at 80 °C and 86.1 mA h g⁻¹ after 681 cycles at 60 °C at a rate of 5C (2.55 mA cm⁻²). The results confirmed that the fast-charging capabilities of ASSLMBs were greatly enhanced by the F-rich cathode interlayer and Mg₁₆Bi₈₄ anode interlayer strategies. Very recently, Y. Wang et al.¹⁷² achieved fast kinetics in full cells with high cathode loading and areal capacity. The kinetic improvement is achieved by designing a hierarchical structure of electrode composites (Fig. 9a–d). In the cathode, the large electrolyte particle is a highway for Li-ion conduction through the thick cathode layer plus the small electrolyte particle to ensure the nano-to-submicron scale interface contact between the NMC particle and the catholyte matrix. In the anode, adding solid electrolytes to the Si layer significantly improves the overall anode kinetics, which increases the critical C-rate and discharge voltage. Hereafter, the cell uses the best cell design with a mixed catholyte cathode layer paired with the Si–Cl|G|Li anode. Three batteries with different cathode loading from 18 to 27 mg cm⁻² could stably cycle with 2.5 to 4.6 mA h cm⁻² at a charge rate ranging from 5 to 3C for more than 2400 to 4200 cycles (Fig. 9e).

9. Conclusions

The limitations hindering the achievement of rapid charging in ASSLBs have been thoroughly examined in terms of sulfide-based SSEs, oxide-based cathodes, and lithium–metal anode materials. Subsequently, a comprehensive account is provided of the progress made in addressing the obstacles associated with materials. Furthermore, the specifications for electrodes, sulfide-based solid-state electrolytes (SSEs), and the interfaces between electrodes and SEs are elucidated to fulfill the prerequisites for efficient utilization in rapid charging scenarios.

The current state of fast-charging lithium battery technology is not yet fully developed. Various challenges persist in this sector. More efforts are required to enhance the practical applications of lithium-ion batteries for rapid charging.

10. Future prospects

10.1. Solid-state electrolytes

Almost all the highly conductive solid-state electrolytes (SSEs), e.g., halides, sulfides, oxides, and nitrides, have a limited electrochemical stability window (ESW), leading to the formation of a cathode electrolyte interphase (CEI) and solid-electrolyte interphase (SEI) by redox reactions of SSEs. It has been investigated that the charge transfer resistance across CEI and SEI is the bottleneck for high-power ASSLBs. Therefore, CEI and SEI affect the electrochemical performance and life span of ASSLBs. Thus, to enable fast-charging ASSLBs, it is imperative to design new SSEs with better intrinsic properties, e.g., wider ESW, higher Li-ion conductivity, and lower electronic conductivity.

The thickness of the SSE layer is also a key factor in realizing fast-charging ASSLBs. A thin and dense SSE layer can reduce the conduction path, ensure faster ionic conduction, and lower the internal resistance, which is beneficial for fast-charging SSLMBs. Meanwhile, the mechanical properties of the SSE layer, e.g., elastic modulus, fracture toughness, and relative density, are of great significance in hindering Li-dendrites and maintaining their stability while running the cell. Thus, new strategies to develop a free-standing thin SSE layer with appropriate mechanical strength need to be considered.

The mechanical incompatibility at the electrode/SSE interface is another crucial problem in ASSBs. Continuous volume change of the cathode and anode (during charging/discharging) induces stress at the interface results in the delamination of either the electrode materials or the protective coating layer. This is accompanied by the formation of cracks/voids at the interface, which leads to cycling deterioration. Thus, a gradient lithophilic–lithophobic layer strategy could improve the electrode/SSE physical contact and can realize fast-charging ASSLBs.

10.2. Cathode

Towards high-rate performances of LIBs, fast e⁻ and Li⁺ kinetics and their balanced percolation within electrodes are necessary. In terms of cathode active materials (CAMs), controlled crystallography is required for fast Li⁺ transport and cyclability with mitigated crack generation. Therefore, the overall charge transport pathways should be considered, including Li⁺ transport within the active materials, charge transfer at the interface between active materials and SEs, and Li⁺ percolation pathways within the entire electrode.

Chemical/electrochemical reactions at the cathode/SSE interface degrade the cathode and SSE, resulting in the formation of an unwanted resistive interfacial layer (CEI), causing huge interfacial resistance for Li⁺ transport and lowering the capacity and electrochemical performance of ASSLBs. The space charge layer is another factor affecting Li⁺ transport across the CEI and hence compromises the performance of ASSLBs. Therefore, new materials and strategies for a protective coating layer on CAMs to alleviate the interfacial reaction as well as SCL should be considered.

Electrochemical reactions between SSEs and CAMs within the composite cathode layer produce unwanted byproducts, which can significantly retard the charge transformation in the composite cathode layer and deteriorate the performance of ASSLBs. Therefore, the composite cathode layer needs to be prepared with the minimum amount of SSEs, which covers the effective surface of CAMs without side reactions in the fabrication process.

Li-conductive binders should be developed for the slurry mixing and coating method, which can provide continuous perculation networks for charge transportation and could be beneficial to the development of fast-charging ASSLBs.

10.3. Anode

The reactivity of the lithium–metal anode (LMA) is significant, leading to an immediate reduction in solid-state electrolytes (SSEs) upon contact and the formation of a solid electrolyte interphase (SEI). The SEI can increase the interfacial resistance and negatively impact the performance of advanced solid-state lithium batteries (ASSLBs). Therefore, it is crucial to regulate the reactivity of LMA to avoid detrimental side reactions during fast-charging operations.

To achieve rapid-charging capabilities in advanced solid-state lithium batteries (ASSLBs), it is crucial to establish a functional artificial solid electrolyte interface (SEI) that bridges lithium metal anodes (LMA) and solid-state electrolytes (SSEs), ensuring the prevention of side reactions and promoting fast Li⁺ kinetics across the SEI.

In order to achieve efficient fast-charging capabilities in ASSLBs, it is crucial to focus on the development of advanced Li–M alloy anode materials.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work is supported by the National Natural Science Foundation of China (No. 21203008, 21975025, 12274025, and 22372008). Additionally, funding was provided by the Hainan Province Science and Technology Special Fund (ZDYF2023GXJS022, ZDYF2024XDNY200, ZDYF2023SHFZ122 and ZDYF2024SHFZ076), the Innovational Fund for Scientific and Technological Personnel of Hainan Province (No. KJRC2023C02), and the Hainan Province Postdoctoral Science Foundation (No. 300333).

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Footnote

† These authors contributed equally to all aspects of this work.

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