Failure analysis with a focus on thermal aspect towards developing safer Na-ion batteries

Safety requirements stimulate Na-based batteries to evolve from high-temperature Na–S batteries to room-temperature Na-ion batteries(NIBs).Even so,NIBs may still cause thermal runaway due to the external unexpected accidents and internal high activity of electrodes or electrolytes,which has not been comprehensively summarized yet.In this review,we summarize the significant advances about the failure mechanisms and related strategies to build safer NIBs from the selection of electrodes,electrolytes and the construction of electrode/electrolyte interfaces.Considering the safety risk,the thermal behaviors are emphasized which will deepen the understanding of thermal stability of different NIBs and accelerate the exploitation of safe NIBs.     

Tuning hybrid liquid/solid electrolytes by lowering Li salt concentration for lithium batteries

Hybrid liquid/solid electrolytes(HLSEs) consisting of conventional organic liquid electrolyte(LE), polyacrylonitrile(PAN), and ceramic lithium ion conductor Li_(1.5)Al_(0.5)Ge_(1.5)(PO_4)_3(LAGP) are proposed and investigated. The HLSE has a high ionic conductivity of over 2.25 × 10~(-3) S/cm at 25?C, and an extended electrochemical window of up to 4.8 V versus Li/Li+. The Li|HLSE|Li symmetric cells and Li|HLSE|Li FePO_4 cells exhibit small interfacial area specific resistances(ASRs) comparable to that of LE while much smaller than that of ceramic LAGP electrolyte, and excellent performance at room temperature. Bis(trifluoromethane sulfonimide) salt in HLSE significantly affects the properties and electrochemical behaviors. Side reactions can be effectively suppressed by lowering the concentration of Li salt. It is a feasible strategy for pursuing the high energy density batteries with higher safety.     

锂离子电池正极材料的结构设计与改性

正极材料是目前锂离子电池中锂离子的唯一或主要提供者,也是锂离子电池能量密度提高和价格降低的瓶颈.本文在简要介绍几类典型的正极材料结构、性能特点及存在的主要问题后,重点介绍本实验室近年来在正极材料的表面改性和结构设计方面的研究进展.     

Ni掺杂对纳米结构牡丹花状CeO2材料催化特性的影响（英文）

制备了一种新型Ni掺杂多层纳米结构牡丹花状CeO2材料,研究了其催化性能,同时与Ni负载牡丹花状CeO2样品进行了比较.结果表明,Ni掺杂CeO2样品具有纳米晶粒和开放的介孔结构,特殊的形貌使其在CO氧化和甲烷部分氧化反应中具有独特的催化特性.Ni掺杂后,CeO2中产生了多余氧空位,同时其氧化还原活性也增强,其在CO氧化反应中的催化活性明显高于纯CeO2和Ni负载CeO2样品;在甲烷部分氧化反应中,牡丹花状CeO2负载3atm%Ni催化剂样品上甲烷转化率高于所有Ni掺杂的催化剂样品.但是在Ni负载型催化剂和花状CeO2催化剂上,甲烷的起始转化温度为400oC,而5.7atm%Ni的掺杂使其降至340oC.     

Spinel lithium titanate (Li4Ti5O12) as novel anode material for room-temperature sodium-ion battery

This is the first time that a novel anode material, spinel Li₄Ti₅O₁₂ which is well known as a “zero-strain” anode material for lithium storage, has been introduced for sodium-ion battery. The Li₄Ti₅O₁₂ shows an average Na storage voltage of about 1.0 V and a reversible capacity of about 145 mAh/g, thereby making it a promising anode for sodium-ion battery. E_x-situ X-ray diffraction (XRD) is used to investigate the structure change in the Na insertion/deinsertion process. Based on this, a possible Na storage mechanism is proposed.     

Mg-doped layered oxide cathode for Na-ion batteries

Na-ion batteries (NIBs) are regarding as the optimum complement for Li-ion batteries along with the rapid development of stationary energy storage systems. In order to meet the commercial demands of cathodes for NIBs, O3-type Cu containing layered oxide Na_0.90Cu_0.22Fe_0.30Mn_0.48O₂ with good comprehensive performance and low-cost element components is very promising for the practical use. However, only part of the Cu³⁺/Cu²⁺ redox couple participated in the redox reaction, thus impairing the specific capacity of the cathode materials. Herein, Mg²⁺-doped O3-Na_0.90Mg_0.08Cu_0.22Fe_0.30Mn_0.40O₂ layered oxide without Mn³⁺ was synthesized successfully, which exhibited improved reversible specific capacity of 118 mAh/g in the voltage range of 2.4-4.0 V at 0.2 C, corresponding to the intercalation/deintercalation of 0.47 Na⁺ (0.1 more than that of Na_0.90Cu_0.22Fe_0.30Mn_0.48O₂). This work demonstrates an important strategy to obtain advanced layered oxide cathodes for NIBs.     

Temperature-Dependent Dynamic Properties of LixMn2O4 in Monte Carlo Simulations

Monte Carlo (MC) simulations are used to simulate the voltage profile and the ionic conductivity s of Li ions in LixMn2O4 and its dependence on the lithium concentration x. The open circuit potential shows clearly the two plateaus in the charge/discharge curve, which agrees well with the experimental results. The two plateaus become more and more steep when the temperature is increased. The simulated ionic conductivity shows an M-shaped curve in the plot of ionic conductivity cr versus x when the simulation temperature is low. Interestingly,the minimum valley, which lies at the middle single-phase area near x=0.5, disappears gradually when the temperature increases to 453K.     

树脂填充EVAL纤维吸附剂的制备及其吸附性能表征

采用具有亲水性的乙烯-乙烯醇共聚物(EVAL)作为纤维吸附剂基质材料,粉末型Lewatit阳离子交换树脂CNP80ws为功能材料,采用可控相分离方法,制备了不同表面形态结构的树脂填充EVAL吸附剂.当使用外部液体调控相分离过程时,在纤维的表面形成了粗糙的开孔结构,并且随树脂的填充量提高纤维表面的粗糙度与开孔度有所提高.研究结果表明:树脂填充EVAL纤维吸附剂具有较大的吸附容量与较高的脱附率,其吸附容量不低于53.9mg BSA/g吸附剂(树脂填充量50%).     

Conductivity and applications of Li-biphenyl-1,2-dimethoxyethane solution for lithium ion batteries

The total conductivity of Li-biphenyl-1,2-dimethoxyethane solution(Li_xBp(DME)_(9.65), Bp = biphenyl, DME = 1,2-dimethoxyethane, x = 0.25, 0.50, 1.00, 1.50, 2.00) is measured by impedance spectroscopy at a temperature range from 0℃ to 40℃. The Li_(1.50)Bp(DME)_(9.65) has the highest total conductivity 10.7 m S/cm. The conductivity obeys Arrhenius law with the activation energy(E_(a(x=0.50))= 0.014 eV, E_(a(x=1.00))= 0.046 eV). The ionic conductivity and electronic conductivity of Li_xBp(DME)_(9.65) solutions are investigated at 20℃ using the isothermal transient ionic current(ITIC) technique with an ion-blocking stainless steal electrode. The ionic conductivity and electronic conductivity of Li_(1.00)Bp(DME)_(9.65) are measured as 4.5 mS/cm and 6.6 mS/cm, respectively. The Li_(1.00)Bp(DME)_(9.65) solution is tested as an anode material of half liquid lithium ion battery due to the coexistence of electronic conductivity and ionic conductivity. The lithium iron phosphate(LFP) and Li_(1.5)Al_(0.5)Ti_(1.5)(PO_4)_3(LATP) are chosen to be the counter electrode and electrolyte, respectively. The assembled cell is cycled in the voltage range of 2.2 V-3.75 V at a current density of 50 mA/g. The potential of Li_(1.00)Bp(DME)_(9.65) solution is about 0.3 V vs. Li~+/Li, which indicates the solution has a strong reducibility. The Li_(1.00)Bp(DME)_(9.65) solution is also used to prelithiate the anode material with low first efficiency, such as hard carbon, soft carbon and silicon.     

Enhanced ionic conductivity in LAGP/LATP composite electrolyte

Nasicon materials(sodium superionic conductors) such as Li_(1.5)Al_(0.5)Ge_(1.5)(PO_4)_3(LAGP) and Li_(1.4)Al_(0.4)Ti_(1.6)(PO_4)_3(LATP) have been considered as important solid electrolytes due to their high ionic conductivity and chemical stability.Compared to LAGP, LATP has higher bulk conductivity around 10~(-3) S/cm at room temperature; however, the apparent grain boundary conductivity is almost two orders of magnitude lower than the bulk, while LAGP has similar bulk and grain boundary conductivity around the order of 10~(-4) S/cm. To make full use of the advantages of the two electrolytes, pure phase Li_(1.5)Al_(0.5)Ge_(1.5)(PO_4)_3 and Li_(1.4)Al_(0.4)Ti_(1.6)(PO_4)_3 were synthesized through solid state reaction, a series of composite electrolytes consisting of LAGP and LATP with different weight ratios were designed. XRD and variable temperature AC impedance spectra were carried out to clarify the crystal structure and the ion transport properties of the composite electrolytes. The results indicate that the composite electrolyte with the LATP/LAGP weight ratio of 80:20 achieved the highest bulk conductivity which shall be due to the formation of solid solution phase Li1.42 Al0.42 Ge0.3 Ti1.28(PO4)3, while the highest grain boundary conductivity appeared at the LATP/LAGP weight ratio of 20:80 which may be due to the excellent interfacial phase between Li_(1+x)Al_xGe_yTi_(2-x-y)(PO_4)_3/LATP. All the composite electrolytes demonstrated higher total conductivity than the pure LAGP and LATP, which highlights the importance of heterogeneous interface on regulating the ion transport properties.