全固态锂离子电池正极与石榴石型固体电解质界面的研究进展

全固态锂离子电池具有高安全性、高能量密度、宽使用温度范围以及长使用寿命等优势, 在动力电池汽车和大规模储能电网领域具有广阔的应用前景。作为全固态电池的重要组成部分, 无机固体电解质尤其是石榴石型固态电解质在室温下锂离子电导率可达10 ^-3 S·cm ^-1, 且对金属锂相对稳定, 在全固态电池的应用中具有明显的优势。然而正极与石榴石型固体电解质间接触性能以及界面的稳定性差, 使得电池表现出高的界面阻抗、低的库伦效率和差的循环性能。本文以全固态锂离子电池正极与石榴石型固体电解质界面为研究对象, 分析了正极/固体电解质的界面特性以及界面研究中存在的问题, 综述了正极复合、界面处理工艺、界面层引入等界面调控和改性的方法, 阐述了优化正极与石榴石型固体电解质界面结构, 改善界面润湿性的解决思路, 提出了未来全固态锂离子电池发展中有待进一步改进的关键问题, 为探索全固态锂离子电池的实际应用提供了借鉴。     

Composition Modulation and Structure Design of Inorganic‐in‐Polymer Composite Solid Electrolytes for Advanced Lithium Batteries

Owing to their safety, high energy density, and long cycling life, all‐solid‐state lithium batteries (ASSLBs) have been identified as promising systems to power portable electronic devices and electric vehicles. Developing high‐performance solid‐state electrolytes is vital for the successful commercialization of ASSLBs. In particular, polymer‐based composite solid electrolytes (PCSEs), derived from the incorporation of inorganic fillers into polymer solid electrolytes, have emerged as one of the most promising electrolyte candidates for ASSLBs because they can synergistically integrate many merits from their components. The development of PCSEs is summarized. Their major components, including typical polymer matrices and diverse inorganic fillers, are reviewed in detail. The effects of fillers on their ionic conductivity, mechanical strength, thermal/interfacial stability and possible Li⁺‐conductive mechanisms are discussed. Recent progress in a number of rationally constructed PCSEs by compositional and structural modulation based on different design concepts is introduced. Successful applications of PCSEs in various lithium‐battery systems including lithium–sulfur and lithium–gas batteries are evaluated. Finally, the challenges and future perspectives for developing high‐performance PCSEs are proposed.     

锂离子电池陶瓷复合全固态电解质的制备和性能研究

以负载Al₂O₃的无纺布为支撑膜, 浸涂PEO-LAGP-SN-LiTFSI的乙腈共混液干燥后制得新型复合固态电解质膜(CLASP)。该膜的热稳定性好, 即使在170℃的高温下依然不发生形变。当浸涂共混液中PEO: LAGP: SN: LiTFSI为3: 1: 1: 1, 固含量为10wt%时, 室温电导率可以达到3.66×10^-5 S/cm, 100℃时电导率可达2.52×10^-4 S/cm. CLASP膜的电化学窗口宽, 以该膜代替液态电解质装配的全固态LiFePO₄/CLASP/Li电池, 在55℃循环时表现出良好的循环稳定性, 高的库伦效率, 有望成为电化学性能优越的全固态电解质。     

Hydrothermal synthesis, structure and characterization of new NASICON related potassium iron (III) pyrophosphate

A new potassium iron (III) pyrophosphate was synthesized by hydrothermal technique and characterized by X-ray studies. The compound crystallizes in a monoclinic space group,P2 ₁/c, with cell parameters,a = 7 365(2) Å,b = 10017(2) Å,c = 8.214(1) Å,β = 106.50(1)° andZ = 4. The structure has tunnel-type cavities and are congenial for ion transportation through them. The compound exhibits moderate thermal stability.     

一种新型碱性多孔聚合物电解质的制备与性能研究

用萃取活化法制备了PVA基碱性多孔聚合物电解质,其制备过程包括3步:(1)PVA/PEG共混膜的制备;(2)通过萃取制备PVA基多孔膜;(3)用KOH溶液浸泡多孔膜.并采用交流阻抗、扫描电镜和X射线衍射法对该膜进行了分析,结果表明,制得的多孔膜具有不对称的孔状结构,当m(PVA)∶m(PEG)=7 ∶ 3时,样品经过萃取活化后吸液率与离子电导率最大,分别为94.4%和9.71×10-3S/cm;循环伏安测试表明,体系的电化学稳定窗口达到2.2V,经过50个循环后电化学稳定窗口仍保持在2.2V.这种新型碱性多孔聚合物电解质有望应用在镍氢电池中.     

Thiol-Branched Solid Polymer Electrolyte Featuring High Strength,Toughness, and Lithium Ionic Conductivity for Lithium-Metal Batteries

Lithium-metal batteries (LMBs) with high energy densities are highly desirable for energy storage, but generally suffer from dendrite growth and side reactions in liquid electrolytes; thus the need for solid electrolytes with high mechanical strength, ionic conductivity, and compatible interface arises. Herein, a thiol-branched solid polymer electrolyte (SPE) is introduced featuring high Li⁺ conductivity (2.26 × 10⁻⁴ S cm⁻¹ at room temperature) and good mechanical strength (9.4 MPa)/toughness (≈500%), thus unblocking the tradeoff between ionic conductivity and mechanical robustness in polymer electrolytes. The SPE (denoted as M-S-PEGDA) is fabricated by covalently cross-linking metal–organic frameworks (MOFs), tetrakis (3-mercaptopropionic acid) pentaerythritol (PETMP), and poly(ethylene glycol) diacrylate (PEGDA) via multiple C S C bonds. The SPE also exhibits a high electrochemical window (>5.4 V), low interfacial impedance (<550 Ω), and impressive Li⁺ transference number (t_Li+ = 0.44). As a result, Li||Li symmetrical cells with the thiol-branched SPE displayed a high stability in a >1300 h cycling test. Moreover, a Li|M-S-PEGDA|LiFePO₄ full cell demonstrates discharge capacity of 143.7 mAh g⁻¹ and maintains 85.6% after 500 cycles at 0.5 C, displaying one of the most outstanding performances for SPEs to date.     

Li2O烧结助剂对固体氧化物燃料电池LSGM电解质烧结特性及离子电导率的影响

本工作研究了Li₂O作为烧结助剂对固体氧化物燃料电池La_0.8Sr_0.2Ga_0.8Mg_0.2O_3-δ (LSGM)电解质烧结行为的影响规律, 系统表征了烧结助剂含量和烧结温度对LSGM烧结体的致密度、微观组织结构、相组成以及离子电导率的影响。研究结果表明, Li₂O烧结助剂不仅可显著降低LSGM电解质的完全致密化烧结温度, 还可以消除电解质粉体中原有的LaSrGa₃O₇杂相, 并且抑制常规烧结过程中易于产生的MgO杂相, 从而获得较高离子电导率的LSGM块体。当Li元素添加量为摩尔分数1%时, 在1400 ℃烧结4 h 获得的LSGM烧结体, 其体密度达到理论密度的99% 且为单一的钙钛矿结构。烧结体的离子电导率在800 ℃测试温度下达到最大值0.17 S/cm, 相比未添加烧结助剂的试样提升20%以上。上述结果表明, 通过添加适量的Li₂O作为烧结助剂对制备用于中温固体氧化物燃料电池(IT-SOFCs)高离子电导率的电解质具有重要意义。     

Optimized Solid Electrolyte Interphase and Solvation Structure of Potassium Ions in Carbonate Electrolytes for High-Performance Potassium Metal Batteries

The introduction of electrolyte additives is one of the most potential strategies to improve the performance of potassium metal batteries (PMBs). However, designing an additive that can alter the K⁺ solvation shell and essentially inhibit K dendrite remains a challenge. Herein, the amyl-triphenyl-phosphonium bromide was introduced as an additive to build a stable solid electrolyte interphase layer. The amyl-TPP cations can form a cation shielding layer on the metal surface during the nucleation stage, preventing K⁺ from gathering at the tip to form K dendrites. Besides, the cations can be preferentially reduced to form K_xP_y with fast K⁺ transport kinetics. The Br⁻ anions, as Lewis bases with strong electronegativity, can not only coordinate the Lewis acid pentafluoride to inhibit the formation of HF, but also change the K⁺ solvation structure to reduce solvent molecules in the first solvation structure. Therefore, the symmetrical battery exhibits a low deposition overpotential of 123 mV at 0.1 mA cm⁻² over 4200 h cycle life. The full battery, paried with a perylene-tetracarboxylic dianhydride (PTCDA) cathode, possesses a cycle life of 250 cycles at 2 C and 81.9% capacity retention. This work offers a reasonable electrolyte design to obtain PMBs with long-term stablity and safety.     

锂离子电池用聚合物固体电解质的研究及展望

聚合物固体电解质是制备高功率密度,高能量密度,长循环寿命的锂离子电池的关键材料之一。本文介绍了聚合物固体电解质的制备及基本性能,论述了不同品种聚合物固体电解质的制备方法,并根据存在的问题,提出发展方向。     

Structure and Interface Engineering of Ultrahigh-Rate 3D Bismuth Anodes for Sodium-Ion Batteries

Sodium-ion batteries (SIBs) have attracted tremendous attention as promising low-cost energy storage devices in future grid-scale energy management applications. Bismuth is a promising anode for SIBs due to its high theoretical capacity (386 mAh g⁻¹). Nevertheless, the huge volume variation of Bi anode during (de)sodiation processes can cause the pulverization of Bi particulates and rupture of solid electrolyte interphase (SEI), resulting in quick capacity decay. It is demonstrated that rigid carbon framework and robust SEI are two essentials for stable Bi anodes. A lignin-derived carbonlayer wrapped tightly around the bismuth nanospheres provides a stable conductive pathway, while the delicate selection of linear and cyclic ether-based electrolytes enable robust and stable SEI films. These two merits enable the long-term cycling process of the LC-Bi anode. The LC-Bi composite delivers outstanding sodium-ion storage performance with an ultra-long cycle life of 10 000 cycles at a high current density of 5 A g⁻¹ and an excellent rate capability of 94% capacity retention at an ultrahigh current density of 100 A g⁻¹. Herein, the underlying origins of performance improvement of Bi anode are elucidated, which provides a rational design strategy for Bi anodes in practical SIBs.     

锂离子电池正极材料LiMn2O4的合成及其电化学性能研究

以Li2CO3为Li源,化学MnO2(CMD)和电化学MnO2(EMD)为Mn源,以乙醇水混合物为分散介质,采用固相反应法合成了可充电锂离子电池正极材料LiMn2O4尖晶石,并采用XRD,BET,TEM和电化学测试对材料进行了表征。结果表明,750℃制备的样品呈良好的尖晶石结构,比表面积分别为4.8m^2/g和2.8m^2/g,产物的分布均匀,平均粒径为200nm。在0．4mA/cm^2(0.2-0.5C)和3．0－4．35V条件下恒流充放电,其首次放电容量大于110mAh/g ,效率大于90％,并具有较好的循环可逆性。考察 反应温度对材料比表面积的影响。     

Manipulating the Solvation Structure of Nonflammable Electrolyte and Interface to Enable Unprecedented Stability of Graphite Anodes beyond 2 Years for Safe Potassium‐Ion Batteries

Potassium‐ion batteries (PIBs) are attractive for low‐cost and large‐scale energy storage applications, in which graphite is one of the most promising anodes. However, the large size and the high activity of K⁺ ions and the highly catalytic surface of graphite largely prevent the development of safe and compatible electrolytes. Here, a nonflammable, moderate‐concentration electrolyte is reported that is highly compatible with graphite anodes and that consists of fire‐retardant trimethyl phosphate (TMP) and potassium bis(fluorosulfonyl)imide (KFSI) in a salt/solvent molar ratio of 3:8. It shows unprecedented stability, as evidenced by its 74% capacity retention over 24 months of cycling (over 2000 cycles) at the 0.2 C current rate. Electrolyte structure and surface analyses show that this excellent cycling stability is due to the nearly 100% solvation of TMP molecules with K⁺ cations and the formation of FSI^?‐derived F‐rich solid electrolyte interphase (SEI), which effectively suppresses the decomposition of the solvent molecules toward the graphite anode. Furthermore, excellent performance on high‐mass loaded graphite electrodes and in a full cell with perylenetetracarboxylic dianhydride cathode is demonstrated. This study highlights the importance of the compatibility of both electrolyte and the interface, and offers new opportunities to design the electrolyte–SEI nexus for safe and practical PIBs.     

Facile Formation of a Solid Electrolyte Interface as a Smart Blocking Layer for High‐Stability Sulfur Cathode

The practical application of lithium–sulfur batteries (LSBs) is hindered by their poor cycle life, which stems mainly from the “redox shuttle reactions” of dissolved polysulfides. To develop a high‐performance cathode for LSBs, encapsulation of polysulfides with a blocking layer is potentially straightforward. Herein, a novel strategy is reported encapsulate sulfur and the electrolyte together in porous carbon spheres by using a solid electrolyte interface (SEI) that can selectively sieve Li⁺ ions while efficiently avoiding polysulfide accumulation and suppressing undesired polysulfide migration. This strategy is simple, straightforward, and effective. The carbon/sulfur cathode only needs to be cycled a few times within a voltage window of 0.3–1.0 V to form such a smart SEI, allowing the resulting cathode to exhibit superior stability extending 600 cycles. This strategy can be combined with other existing advanced sulfur cathode designs to improve the overall performance of LSBs.     

Fe2BP3O12的合成及晶体结构

采用固态反应方法合成了有序的铁基硼磷酸盐Fe2BP3O12,用X射线粉末衍射方法精修了其晶体结构,属三方晶系,空间群为P3,a=8.02703(6)A,c=7.40168(9)A,V=413.02(1)A3,Dx=3.2758(1)(g/cm3),Z=2,对于55个参数,用188条衍射线及18001个衍射强度全谱数据点精修到R(I)=6.35%,R(p)=15.36%,所对应的R(dbw)=10.12%.B原子具有三角形氧配位,P和Fe的氧配位分别是四面体和八面体.Fe的两配位八面体共面形成新结构单元,BO3三角形联接磷氧和铁氧多面体形成三维结构.对比同构的铬硼磷酸盐,此化合物期望具有类似的非线性光学及其它非线性物理性质.     

钠离子电池Na3Zr2Si2PO12陶瓷电解质的喷雾干燥法制备及性能优化

目前钠离子电池采用的有机电解液存在易燃易爆等安全隐患,迫切需要开发高性能的固体电解质材料.其中NASICON型Na3Zr2Si2PO12电解质具有宽电化学窗口、高机械强度、对空气稳定、高离子电导率等优点,应用前景广阔.但已有研究的陶瓷生坯由于黏结剂包覆不均匀导致生坯内部气孔较多,难以烧成高致密、高离子电导的陶瓷电解质....     

结构凝聚动刚度的有效简化方案

本文提出一种基于模态展开和幂级数展开的混合方案,用于简化结构凝聚动刚度的计算.本方案的收敛性较好,并且它的误差易于估计,因此较实用方便.     

Potato extract as reducing agent and stabiliser in a facile green one-step synthesis of ZnO nanoparticles

A facile green recipe was developed to synthesise highly pure, safe and durable zinc oxide nanoparticles (ZnO Nps) using homemade starch-rich potato extract. The ZnO Nps were synthesised using zinc nitrate and potato extract, and the whole reaction is carried out for 30 min at 80 °C. In the synthesis, starch-rich potato extract acted as the reducing agent and as a stabilising layer on freshly formed ZnO Nps. Hexagonal (wurtzite) shaped ZnO Nps with size about 20 ± 1.2 nm were synthesised and characterised using X-ray diffraction, transition electron microscope and scanning microscopy analyses. Fourier transform infrared spectral analysis indicated that highly pure ZnO nanopowders were obtained at higher temperatures. The use of environmentally benign and renewable material as the respective reducing and protecting agents, starch-rich potato extract, as well as a gentle solvent medium (H₂O), offered a simple and quite efficient procedure for the synthesis of ZnO Nps in neutral medium with promising potential for biological and biomedical applications.     

无机固体电解质Li7La3Zr2O12的制备及掺杂改性研究进展

无机固体电解质由于其安全性能高、能量密度大等特点备受研究者的青睐。其中Garnet型锂离子无机固体电解质Li_7La_3Zr_2O_(12)具有较高的离子导电率,较低的界面电阻,优良的稳定性能和电化学性能,在未来的全固态锂离子电池、锂空气电池等领域有着广阔的应用前景。主要从Li_7La_3Zr_2O_(12)的晶体结构、制备工艺和掺杂改性等方面详细阐述无机固态电解质Li_7La_3Zr_2O_(12)的研究进展。