Interface Design Enabling Stable Polymer/Thiophosphate Electrolyte Separators for Dendrite-Free Lithium Metal Batteries

Organic/inorganic interfaces greatly affect Li⁺ transport in composite solid electrolytes (SEs), while SE/electrode interfacial stability plays a critical role in the cycling performance of solid-state batteries (SSBs). However, incomplete understanding of interfacial (in)stability hinders the practical application of composite SEs in SSBs. Herein, chemical degradation between Li₆PS₅Cl (LPSCl) and poly(ethylene glycol) (PEG) is revealed. The high polarity of PEG changes the electronic state and structural bonding of the PS₄³⁻ tetrahedra, thus triggering a series of side reactions. A substituted terminal group of PEG not only stabilizes the inner interfaces but also extends the electrochemical window of the composite SE. Moreover, a LiF-rich layer can effectively prevent side reactions at the Li/SE interface. The results provide insights into the chemical stability of polymer/sulfide composites and demonstrate an interface design to achieve dendrite-free lithium metal batteries.     

In Situ Polymerized 1,3-Dioxolane Electrolyte for Integrated Solid-State Lithium Batteries

Solid-state lithium batteries are promising and safe energy storage devices for mobile electronics and electric vehicles. In this work, we report a facile in situ polymerization of 1,3-dioxolane electrolytes to fabricate integrated solid-state lithium batteries. The in situ polymerization and formation of solid-state dioxolane electrolytes on interconnected carbon nanotubes (CNTs) and active materials is the key to realizing a high-performance battery with excellent interfacial contact among CNTs, active materials and electrolytes. Therefore, the electrodes could be tightly integrated into batteries through the CNTs and electrolyte. Electrons/ions enable full access to active materials in the whole electrode. Electrodes with a low resistance of 4.5 Ω □⁻¹ and high lithium-ion diffusion efficiency of 2.5×10⁻¹¹ cm² s⁻¹ can significantly improve the electrochemical kinetics. Subsequently, the batteries demonstrated high energy density, amazing charge/discharge rate and long cycle life.     

Reactive Polymer as Artificial Solid Electrolyte Interface for Stable Lithium Metal Batteries

Lithium (Li) metal anodes have the highest theoretical capacity and lowest electrochemical potential making them ideal for Li metal batteries (LMBs). However, Li dendrite formation on the anode impedes the proper discharge capacity and practical cycle life of LMBs, particularly in carbonate electrolytes. Herein, we developed a reactive alternative polymer named P(St-MaI) containing carboxylic acid and cyclic ether moieties which would in situ form artificial polymeric solid electrolyte interface (SEI) with Li. This SEI can accommodate volume changes and maintain good interfacial contact. The presence of carboxylic acid and cyclic ether pendant groups greatly contribute to the induction of uniform Li ion deposition. In addition, the presence of benzyl rings makes the polymer have a certain mechanical strength and plays a key role in inhibiting the growth of Li dendrites. As a result, the symmetric Li||Li cell with P(St-MaI)@Li layer can stably cycle for over 900 h under 1 mA cm⁻² without polarization voltage increasing, while their Li||LiFePO₄ full batteries maintain high capacity retention of 96 % after 930 cycles at 1C in carbonate electrolytes. The innovative strategy of artificial SEI is broadly applicable in designing new materials to inhibit Li dendrite growth on Li metal anodes.     

Build a High-Performance All-Solid-State Lithium Battery through Introducing Competitive Coordination Induction Effect in Polymer-Based Electrolyte

Polymer-inorganic composite electrolytes (PICE) have attracted tremendous attention in all-solid-state lithium batteries (ASSLBs) due to facile processability. However, the poor Li⁺ conductivity at room temperature (RT) and interfacial instability severely hamper the practical application. Herein, we propose a concept of competitive coordination induction effects (CCIE) and reveal the essential correlation between the local coordination structure and the interfacial chemistry in PEO-based PICE. CCIE introduction greatly enhances the ionic conductivity and electrochemical performances of ASSLBs at 30 °C. Owing to the competitive coordination (Cs^{+ …} TFSI^{− …} Li⁺, Cs^{+ …} C−O−C ^… Li⁺ and 2,4,6-TFA ^… Li ^… TFSI⁻) from the competitive cation (Cs⁺ from CsPF₆) and molecule (2,4,6-TFA: 2,4,6-trifluoroaniline), a multimodal weak coordination environment of Li⁺ is constructed enabling a high efficient Li⁺ migration at 30 °C (Li⁺ conductivity: 6.25×10⁻⁴ S cm⁻¹; t_Li ⁺ =0.61). Since Cs⁺ tends to be enriched at the interface, TFSI⁻ and PF₆⁻ in situ form LiF-Li₃N-Li₂O-Li₂S enriched solid electrolyte interface with electrostatic shielding effects. The assembled ASSLBs without adding interfacial wetting agent exhibit outstanding rate capability (LiFePO_4: 147.44 mAh g⁻¹@1 C and 107.41mAhg⁻¹@2 C) and cycling stability at 30 °C (LiFePO₄:94.65 %@200cycles@0.5 C; LiNi_0.5Co_0.2Mn_0.3O₂: 94.31 %@200 cycles@0.3 C). This work proposes a concept of CCIE and reveals its mechanism in designing PICE with high ionic conductivity as well as high interfacial compatibility at near RT for high-performance ASSLBs.     

Reduction-Tolerance Electrolyte Design for High-Energy Lithium Batteries

Lithium batteries employing Li or silicon (Si) anodes hold promise for the next-generation energy storage systems. However, their cycling behavior encounters rapid capacity degradation due to the vulnerability of solid electrolyte interphases (SEIs). Though anion-derived SEIs mitigate this degradation, the unavoidable reduction of solvents introduces heterogeneity to SEIs, leading to fractures during cycling. Here, we elucidate how the reductive stability of solvents, dominated by the electrophilicity (EPT) and coordination ability (CDA), delineates the SEI formed on Li or Si anodes. Solvents exhibiting lower EPT and CDA demonstrate enhanced tolerance to reduction, resulting in inorganic-rich SEIs with homogeneity. Guided by these criteria, we synthesized three promising solvents tailored for Li or Si anodes. The decomposition of these solvents is dictated by their EPTs under similar solvation structures, imparting distinct characteristics to SEIs and impacting battery performance. The optimized electrolyte, 1 M lithium bis(fluorosulfonyl)imide (LiFSI) in N-Pyrrolidine-trifluoromethanesulfonamide (TFSPY), achieves 600 cycles of Si anodes with a capacity retention of 81 % (1910 mAh g⁻¹). In anode-free Cu||LiNi_0.5Co_0.2Mn_0.3O₂ (NCM523) pouch cells, this electrolyte sustains over 100 cycles with an 82 % capacity retention. These findings illustrate that reducing solvent decomposition benefits SEI formation, offering valuable insights for the designing electrolytes in high-energy lithium batteries.     

Simultaneous Stabilization of Lithium Anode and Cathode using Hyperconjugative Electrolytes for High-voltage Lithium Metal Batteries

Although great progress has been made in new electrolytes for lithium metal batteries (LMBs), the intrinsic relationship between electrolyte composition and cell performance remains unclear due to the lack of valid quantization method. Here, we proposed the concept of negative center of electrostatic potential (NCESP) and Mayer bond order (MBO) to describe solvent capability, which highly relate to solvation structure and oxidation potential, respectively. Based on established principles, the selected electrolyte with 1.7 M LiFSI in methoxytrimethylsilane (MOTMS)/ (trifluoromethyl)trimethylsilane (TFMTMS) shows unique hyperconjugation nature to stabilize both Li anode and high-voltage cathode. The 4.6 V 30 μm Li||4.5 mAh cm⁻² lithium cobalt oxide (LCO) (low N/P ratio of 1.3) cell with our electrolyte shows stable cycling with 91 % capacity retention over 200 cycles. The bottom-up design concept of electrolyte opens up a general strategy for advancing high-voltage LMBs.     

基于表界面反应及优化的锂金属电池研究进展

金属锂具有高理论比容量和低还原电位, 是锂电池阳极的理想材料之一. 但在长期循环充放电过程中, 金属锂因锂枝晶生长会导致出现界面恶化及能量损失严重等问题, 对锂金属电极与电解质表界面反应的优化是一个重要研究方向. 本文介绍了锂枝晶产生的危害, 从分析及抑制锂枝晶沉积两方面综合评述了为解决这一问题所采取的方法, 包括固态电解质界面形成机制和保护机理、 表面改性、 三维锂阳极和液态/固态电解质等方法, 总结了各种方法的优劣势, 并展望锂金属电池在能源领域的研究前景.     

Polymers with Intrinsic Microporosity as Solid Ion Conductors for Solid-State Lithium Batteries

Solid-state electrolytes (SSEs) with high ionic conductivity and superior stability are considered to be a key technology for the safe operation of solid-state lithium batteries. However, current SSEs are incapable of meeting the requirements for practical solid-state lithium batteries. Here we report a general strategy for achieving high-performance SSEs by engineering polymers of intrinsic microporosity (PIMs). Taking advantage of the interconnected ion pathways generated from the ionizable groups, high ionic conductivity (1.06×10⁻³ S cm⁻¹ at 25 °C) is achieved for the PIMs-based SSEs. The mechanically strong (50.0 MPa) and non-flammable SSEs combine the two superiorities of outstanding Li⁺ conductivity and electrochemical stability, which can restrain the dendrite growth and prevent Li symmetric batteries from short-circuiting even after more than 2200 h cycling. Benefiting from the rational design of SSEs, PIMs-based SSEs Li-metal batteries can achieve good cycling performance and superior feasibility in a series of withstand abuse tests including bending, cutting, and penetration. Moreover, the PIMs-based SSEs endow high specific capacity (11307 mAh g⁻¹) and long-term discharge/charge stability (247 cycles) for solid-state Li−O₂ batteries. The PIMs-based SSEs present a powerful strategy for enabling safe operation of high-energy solid-state batteries.     

Influencing Factors on Li-ion Conductivity and Interfacial Stability of Solid Polymer Electrolytes,Exampled by Polycarbonates,Polyoxalates and Polymalonates

The application of solid polymer electrolytes (SPEs) in all-solid-state(ASS) batteries is hindered by lower Li⁺-conductivity and narrower electrochemical window. Here, three families of ester-based F-modified SPEs of poly-carbonate (PCE), poly-oxalate (POE) and poly-malonate (PME) were investigated. The Li⁺-conductivity of these SPEs prepared from pentanediol are all higher than the counterparts made of butanediol, owing to the enhanced asymmetry and flexibility. Because of stronger chelating coordination with Li⁺, the Li⁺-conductivity of PME and POE is around 10 and 5 times of PCE. The trifluoroacetyl-units are observed more effective than −O−CH₂−CF₂−CF₂−CH₂−O− during the in situ passivation of Li-metal. Using trifluoroacetyl terminated POE and PCE as SPE, the interfaces with Li-metal and high-voltage-cathode are stabilized simultaneously, endowing stable cycling of ASS Li/LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) cells. Owing to an enol isomerization of malonate, the cycling stability of Li/PME/NCM622 is deteriorated, which is recovered with the introduce of dimethyl-group in malonate and the suppression of enol isomerization. The coordinating capability with Li⁺, molecular asymmetry and existing modes of elemental F, are all critical for the molecular design of SPEs.     

Eutectic-Based Polymer Electrolyte with the Enhanced Lithium Salt Dissociation for High-Performance Lithium Metal Batteries

The deployment of lithium metal anode in solid-state batteries with polymer electrolytes has been recognized as a promising approach to achieving high-energy-density technologies. However, the practical application of the polymer electrolytes is currently constrained by various challenges, including low ionic conductivity, inadequate electrochemical window, and poor interface stability. To address these issues, a novel eutectic-based polymer electrolyte consisting of succinonitrile (SN) and poly (ethylene glycol) methyl ether acrylate (PEGMEA) is developed. The research results demonstrate that the interactions between SN and PEGMEA promote the dissociation of the lithium difluoro(oxalato) borate (LiDFOB) salt and increase the concentration of free Li⁺. The well-designed eutectic-based PAN_1.2-SPE (PEGMEA: SN=1: 1.2 mass ratio) exhibits high ionic conductivity of 1.30 mS cm⁻¹ at 30 °C and superior interface stability with Li anode. The Li/Li symmetric cell based on PAN_1.2-SPE enables long-term plating/stripping at 0.3 and 0.5 mA cm⁻², and the Li/LiFePO₄ cell achieves superior long-term cycling stability (capacity retention of 80.3 % after 1500 cycles). Moreover, Li/LiFePO₄ and Li/LiNi_0.6Co_0.2Mn_0.2O₂ pouch cells employing PAN_1.2-SPE demonstrate excellent cycling and safety characteristics. This study presents a new pathway for designing high-performance polymer electrolytes and promotes the practical application of high-stable lithium metal batteries.     

Multiple Dynamic Bonds-Driven Integrated Cathode/Polymer Electrolyte for Stable All-Solid-State Lithium Metal Batteries

All-solid-state lithium metal batteries (LMBs) are considered as the promising higher-energy and improved-safety energy-storage systems. Nevertheless, the electrolyte-electrodes interfacial issues due to the limited solid physical contact lead to discontinuous interfacial charge transport and large interfacial resistance, thereby suffering from unsatisfactory electrochemical performance. Herein, we construct an integrated cathode/polymer electrolyte for all-solid-state LMBs under the action of polymer chains exchange and recombination originating from multiple dynamic bonds in our well-designed dynamic supramolecular ionic conductive elastomers (DSICE) molecular structure. The DSICE acts as polymer electrolytes with excellent electrochemical performance and mechanical properties, achieving the ultrathin pure polymer electrolyte thickness (12 μm). Notably, the DSICE also functions as lithium iron phosphate (LiFePO₄, LFP) cathode binders with enhanced adhesive capability. Such well-constructed Li|DSICE|LFP-DSICE cells generate delicate electrolyte-electrodes interfacial contact at the molecular level, providing continuous Li⁺ transport pathways and promoting uniform Li⁺ deposition, further delivering superior long-term charge/discharge stability (>600 cycles, Coulombic efficiency, >99.8 %) and high capacity retention (80 % after 400 cycles). More practically, the Li|DSICE|LFP-DSICE pouch cells show stable electrochemical performance, excellent flexibility and safety under abusive tests.     

Studies on the Anode/Electrolyte Interfacein Lithium Ion Batteries

Summary.  Rechargeable lithium ion cells operate at voltages of 3.5–4.5 V, which is far beyond the thermodynamic stability window of the battery electrolyte. Strong electrolyte reduction and anode corrosion has to be anticipated, leading to irreversible loss of electroactive material and electrolyte and thus strongly deteriorating cell performance. To minimize these reactions, anode and electrolyte components have to be combined that induce the electrolyte reduction products to form an effectively protecting film at the anode/electrolyte interface, which hinders further electrolyte decomposition reactions, but acts as membrane for the lithium cations, i.e. behaving as a solid electrolyte interphase (SEI). This paper focuses on important aspects of the SEI. By using key examples, the effects of film forming electrolyte additives and the change of the active anode material from carbons to lithium storage alloys are highlighted. Received May 30, 2000. Accepted June 14, 2000     

Achieving the High Capacity and High Stability of Li-Rich Oxide Cathode in Garnet-Based Solid-State Battery

Solid-state batteries (SSBs) based on Li-rich Mn-based oxide (LRMO) cathodes attract much attention because of their high energy density as well as high safety. But their development was seriously hindered by the interfacial instability and inferior electrochemical performance. Herein, we design a three-dimensional foam-structured GaN−Li composite anode and successfully construct a high-performance SSB based on Co-free Li_1.2Ni_0.2Mn_0.6O₂ cathode and Li_6.5La₃Zr_1.5Ta_0.5O₁₂ (LLZTO) solid electrolyte. The interfacial resistance is considerably reduced to only 1.53 Ω cm² and the assembled Li symmetric cell is stably cycled more than 10,000 h at 0.1–0.2 mA cm⁻². The full battery shows a high initial capacity of 245 mAh g⁻¹ at 0.1 C and does not show any capacity degradation after 200 cycles at 0.2 C (≈100 %). The voltage decay is well suppressed and it is significantly decreased from 2.96 mV/cycle to only 0.66 mV/cycle. The SSB also shows a very high rate capability (≈170 mAh g⁻¹ at 1 C) comparable to a liquid electrolyte-based battery. Moreover, the oxygen anion redox (OAR) reversibility of LRMO in SSB is much higher than that in liquid electrolyte-based cells. This study offers a distinct strategy for constructing high-performance LRMO-based SSBs and sheds light on the development and application of high-energy density SSBs.     

A Chemically Bonded Ultraconformal Layer between the Elastic Solid Electrolyte and Lithium Anode for High-performance Lithium Metal Batteries

Although high ionic conductivities have been achieved in most solid-state electrolytes used in lithium metal batteries (LMBs), rapid and stable lithium-ion transport between solid-state electrolytes and lithium anodes remains a great challenge due to the high interfacial impedances and infinite volume changes of metallic lithium. In this work, a chemical vapor-phase fluorination approach is developed to establish a lithiophilic surface on rubber-derived electrolytes, which results in the formation of a resilient, ultrathin, and mechanically integral LiF-rich layer after electrochemical cycling. The resulting ultraconformal layer chemically connects the electrolyte and lithium anode and maintains dynamic contact during operation, thus facilitating rapid and stable lithium-ion transport across interfaces, as well as promoting uniform lithium deposition and inhibiting side reactions between electrolyte components and metallic lithium. LMBs containing the novel electrolyte have an ultralong cycling life of 2500 h and deliver a high critical current density of 1.1 mA cm⁻² in lithium symmetric cells as well as showing good stability over 300 cycles in a full cell.     

亚磷酸三甲酯作为锂离子电池电解液溶剂的研究

为了提高锂离子电池电解液的热稳定性,使用亚磷酸三甲酯TMP作为溶剂来配置锂离子电池电解液,研究该电解液燃烧性能、电化学性能和热稳定性,并与商业用电解液作了比较.循环性能测试结果表明,亚磷酸三甲酯基电解液与正极材料LiNg0.8Co0.2O2有很好的相容性,有良好的电化学稳定性,而且与PC组成电解液时可一定程度地抑制PC对负极石墨材料的剥离.燃烧试验和微量量热实验表明,TMP的加入能显著地提高电解液的热稳定性与安全性能.     

Armor-like Inorganic-rich Cathode Electrolyte Interphase Enabled by the Pentafluorophenylboronic Acid Additive for High-voltage Li||NCM622 Batteries

Lithium metal batteries (LMBs) comprising Li metal anode and high-voltage nickel-rich cathode could potentially realize high capacity and power density. However, suitable electrolytes to tolerate the oxidation on the cathode at high cut-off voltage are urgently needed. Herein, we present an armor-like inorganic-rich cathode electrolyte interphase (CEI) strategy for exploring oxidation-resistant electrolytes for sustaining 4.8 V Li||LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) batteries with pentafluorophenylboronic acid (PFPBA) as the additive. In such CEI, the armored lithium borate surrounded by CEI up-layer represses the dissolution of inner CEI moieties and also improves the Li⁺ conductivity of CEI while abundant LiF is distributed over whole CEI to enhance the mechanical stability and Li⁺ conductivity compared with polymer moieties. With such robust Li⁺ conductive CEI, the Li||NCM622 battery delivered excellent stability at 4.6 V cut-off voltage with 91.2 % capacity retention after 400 cycles. The excellent cycling performance was also obtained even at 4.8 V cut-off voltage.     

Anion-modulated Ion Conductor with Chain Conformational Transformation for stabilizing Interfacial Phase of High-Voltage Lithium Metal Batteries

In solid-state lithium metal batteries (SSLMBs), the inhomogeneous electrolyte-electrode interphase layer aggravates the interfacial stability, leading to discontinuous interfacial ion/charge transport and continuous degradation of the electrolyte. Herein, we constructed an anion-modulated ionic conductor (AMIC) that enables in situ construction of electrolyte/electrode interphases for high-voltage SSLMBs by exploiting conformational transitions under multiple interactions between polymer and lithium salt anions. Anions modulate the decomposition behavior of supramolecular poly (vinylene carbonate) (PVC) at the electrode interface by changing the spatial conformation of the polymer chains, which further enhances ion transport and stabilizes the interfacial morphology. In addition, the AMIC weakens the “Li⁺-solvation” and increases Li⁺ vehicle sites, thereby enhancing the lithium-ion transport number (t_Li⁺=~0.67). Consequently, Li || LiNi_0.8Co_0.1Mn_0.1O₂ cell maintains about 85 % capacity retention and Coulombic efficiency >99.8 % in 200 cycles at a charge cut-off voltage of 4.5 V. This study provides a new understanding of lithium salt anions regulating polymer chain segment behavior in the solid-state polymer electrolyte (SPE) and highlights the importance of the ion environment in the construction of interfacial phases and ionic conduction.     

新型成膜电解液添加剂亚硫酸丁烯酯的电化学行为

合成制备了一种新的环状亚硫酸酯类有机溶剂——亚硫酸丁烯酯(BS). 量子化学计算结果表明, 亚硫酸丁烯酯有机溶剂分子的总能、LUMO值比碳酸丙烯酯有机溶剂的低, 具有较强的得电子能力, 不易被氧化. 其作为添加剂与碳酸丙烯酯(PC)混合应用于锂离子电池中, 可有效地抑制PC在石墨电极中的共插入, 能显著改善循环性能.     

Reforming the Uniformity of Solid Electrolyte Interphase by Nanoscale Structure Regulation for Stable Lithium Metal Batteries

The stability of high-energy-density lithium metal batteries depends on the uniformity of solid electrolyte interphase (SEI) on lithium metal anodes. Rationally improving SEI uniformity is hindered by poorly understanding the effect of structure and components of SEI on its uniformity. Herein, a bilayer structure of SEI formed by isosorbide dinitrate (ISDN) additives in localized high-concentration electrolytes was demonstrated to improve SEI uniformity. In the bilayer SEI, LiN_xO_y generated by ISDN occupies top layer and LiF dominates bottom layer next to anode. The uniformity of lithium deposition is remarkably improved with the bilayer SEI, mitigating the consumption rate of active lithium and electrolytes. The cycle life of lithium metal batteries with bilayer SEI is three times as that with common anion-derived SEI under practical conditions. A prototype lithium metal pouch cell of 430 Wh kg⁻¹ undergoes 173 cycles. This work demonstrates the effect of a reasonable structure of SEI on reforming SEI uniformity.     

1,3-二氧戊环基LiCF3SO3电解液对锂硫电池正极材料单质硫的电化学性能影响

测试了二元和多元溶剂组分的1,3-二氧戊环基LiCF3SO3电解液的粘度、离子电导率和单质硫的溶解度. 研究结果表明, 由较强的给电子能力溶剂组成的低粘度电解液较容易提高单质硫的氧化还原反应活性和可逆性能, 有利于提高单质硫在2.10 V附近的低放电平台电位和放电比容量. DOL-DME LiCF3SO3电解液能够较好地改善单质硫电极的表面钝化层结构, 促进电活性物质离子扩散和降低界面电荷传递阻抗, 从而表现出很好的放电倍率特性. 在室温下充放电流密度分别为0.1和0.2 mA/cm2时, 单质硫的首次放电比容量为792 mA·h/g, 第29次放电比容量达到412 mA·h/g.