Chloride ion battery:A new emerged electrochemical system for next-generation energy storage

In the scope of developing new electrochemical concepts to build batteries with high energy density,chloride ion batteries(CIBs)have emerged as a candidate for the next generation of novel electrochemical energy storage technologies,which show the potential in matching or even surpassing the current lithium metal batteries in terms of energy density,dendrite-free safety,and elimination of the dependence on the strained lithium and cobalt resources.However,the development of CIBs is still at the initial stage with unsatisfactory performance and several challenges have hindered them from reaching commercialization.In this review,we examine the current advances of CIBs by considering the electrode material design to the electrolyte,thus outlining the new opportunities of aqueous CIBs especially combined with desalination,chloride redox battery,etc.With respect to the developing road of lithium ion and fluoride ion batteries,the possibility of using solid-state chloride ion conductors to replace liquid electrolytes is tentatively discussed.Going beyond,perspectives and clear suggestions are concluded by highlighting the major obstacles and by prescribing specific research topics to inspire more efforts for CIBs in large-scale energy storage applications.

Overcoming the Na-ion conductivity bottleneck for the cost-competitive chloride solid electrolytes

Chloride solid electrolytes possess multiple advantages for the construction of safe,energy-dense allsolid-state sodium batteries,but presently the chlorides with sufficiently high cost-competitiveness for commercialization almost all exhibit low Na-ion conductivities of around 10^(-5)S cm^(-1)or lower.Here,we report a chloride solid electrolyte,Na_(2.7)ZFCl_(5.3)O_(0.7),which reaches a Na-ion conductivity of 2.29×10^(-4)S cm^(-1)at 25℃without involving overly expensive raw materials such as rare-earth chlorides or Na_(2)S.In addition to the efficient ion transport,Na_(2.7)ZrCl_(5.3)O_(0.7)also shows an excellent deformability surpassing that of the widely studied Na_(3)PS_(4),Na_(3)SbS_(4),and Na_(2)ZrCl_(6)solid electrolytes.The combination of these advantages allows the all-solid-state cell based on Na_(2.7)ZrCl_(5.3)O_(0.7)and NaCrO_(2)to realize stable room-temperature cycling at a much higher specific current than those based on other non-viscoelastic chloride solid electrolytes in literature(120 mA g^(-1)vs.12-55 mA g^(-1));after 100 cycles at such a high rate,the Na_(2.7)ZFCl_(5.3)O_(0.7)-based cell can still deliver a discharge capacity of 80 mAh g^(-1)at25℃.

Hydrometallurgical recycling of valuable metals from spent lithium-ion batteries by reductive leaching with stannous chloride

The reductant is a critical factor in the hydrometallurgical recycling of valuable metals from spent lithium-ion batteries(LIBs).There is limited information regarding the use of SnCl_(2) as a reductant with organic acid(maleic acid)for recovering valuable metals from spent Li-CoO_(2) material.In this study,the leaching efficiencies of Li and Co with 1 mol·L^(−1) of maleic acid and 0.3 mol·L^(−1) of SnCl_(2) were found to be 98.67%and 97.5%,respectively,at 60°C and a reaction time of 40 min.We investigated the kinetics and thermodynamics of the leaching process in this study to better understand the mechanism of the leaching process.Based on a comparison with H_(2)O_(2) with respect to leaching efficiency,the optimal leaching parameters,and the activation energy,we determined that it is feasible to replace H_(2)O_(2) with SnCl_(2) as a leaching reductant in the leaching process.In addition,when SnCl_(2) is used in the acid-leaching process,Sn residue in the leachate may have a positive effect on the re-synthesis of nickel-rich cathode materials.Therefore,the results of this study provide a potential direction for the selection of reductants in the hydrometallurgical recovery of valuable metals from spent LIBs.

Cooperative Chloride Hydrogel Electrolytes Enabling Ultralow-Temperature Aqueous Zinc Ion Batteries by the Hofmeister Effect

Aqueous zinc ion batteries have high potential applicability for energy storage due to their reliable safety,environmental friendliness,and low cost.However,the freezing of aqueous electrolytes limits the normal operation of batteries at low temperatures.Herein,a series of high-performance and low-cost chloride hydrogel electrolytes with high concentrations and low freezing points are developed.The electrochemical windows of the chloride hydrogel electrolytes are enlarged by>1 V under cryogenic conditions due to the obvious evolution of hydrogen bonds,which highly facilitates the operation of electrolytes at ultralow temperatures,as evidenced by the low-temperature Raman spectroscopy and linear scanning voltammetry.Based on the Hofmeister effect,the hydrogen-bond network of the cooperative chloride hydrogel electrolyte comprising 3 M ZnCl_(2)and 6 M LiCl can be strongly interrupted,thus exhibiting a sufficient ionic conductivity of 1.14 mS cm;and a low activation energy of 0.21 e V at-50℃.This superior electrolyte endows a polyaniline/Zn battery with a remarkable discharge specific capacity of 96.5 mAh g;at-50℃,while the capacity retention remains~100%after 2000 cycles.These results will broaden the basic understanding of chloride hydrogel electrolytes and provide new insights into the development of ultralow-temperature aqueous batteries.

Synthesis of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2 cathode material by chloride co-precipitation method

LiNi0.8Co0.1Mn0.1O2 was prepared by a chloride co-precipitation method and characterized by thermogravimetric analysis, X-ray diffractometry with Rietveld refinement,electron scanning microscopy and electrochemical measurements.Effects of lithium ion content and sintering temperature on physical and electrochemical performance of LiNi0.8Co0.1Mn0.1O2 were also investigated. The results show that the sample synthesized at 750℃with 105%lithium content has fine particle sizes around 200 nm and homogenous sizes distribution.The initial discharge capacity for the powder is 184 mA·h/g between 2.7 and 4.3 V at 0.1C and room temperature.

氯化镁-氯化铝-EMImBF_(4)/有机醚可充镁电池电解液

可充镁电池(RMBs)是下一代最具潜力的储能体系之一,电解液对RMBs的性能具有重要影响.本文通过将1-乙基-3-甲基咪唑鎓四氟硼酸盐(EMImBF_(4))添加到MgCl_(2)+AlCl_(3)电解液(MACC)中,构建了一种MACC-EMImBF_(4)/有机醚(MACCE)可充镁电池电解液体系;采用循环伏安(CV)、线性扫描伏安(LSV)、电化学交流阻抗谱(EIS)和恒流充放电曲线(GCD)等方法测试了MACCE电解液的电化学性能及全电池性能;并通过场发射扫描电子显微镜(FESEM)、X射线衍射仪(XRD)和X射线光电子能谱仪(XPS)对循环后的电极表面进行了分析.结果表明,EMImBF_(4)的添加有效改善了电解液的性能,MgCl_(2)-AlCl_(3)与EMImBF_(4)的最佳摩尔比为5∶1.MACCE电解液的离子电导率为3.94 mS/cm,Mg^(2+)沉积-溶出过电位为59 mV,库仑效率达97.5%以上,氧化稳定电位可达2.8 V(vs.Mg/Mg^(2+))且循环时间超过500 h.MACCE电解液在循环过程中可在Mg负极表面形成一层纳米颗粒层,有助于改善循环稳定性.MACCE电解液与正极材料Mo6S8的兼容性好,Mo6S8|MACCE|Mg全电池的放电平均比容量可达64.4mA∙h/g(12.88mA/g,0.1C),100次循环后比容量保持率可达73.2%.

某油冷却器换热管泄漏原因

某公司生产的油冷却器换热管在投入使用9~12个月后发生腐蚀泄漏现象。采用宏观观察、化学成分分析、金相检验、扫描电镜和能谱分析、原子吸收光谱分析等方法分析了管道腐蚀泄漏的原因。结果表明:油冷却器换热管介质中的氯离子和硫离子在管内壁积垢中沉积并富集在管壁基体前沿,导致内壁产生大量点腐蚀,点腐蚀位置与未腐蚀位置形成大阴极小阳极腐蚀电池,增大了腐蚀速率,在管内介质的冲刷作用下,点腐蚀坑进一步扩大,最终导致管道泄漏。

磺酰氯促进金属氯化物插层石墨以实现高效钠存储

金属氯化物-石墨插层化合物具有导电性优异,石墨层间距大等特点,可用作钠离子电池负极材料。然而,在传统金属氯化物插层石墨过程中,不可避免地用到氯气,既增加了实验操作的风险,也对实验设备提出更高要求。基于上述原因,本文创新性地使用SO_(2)Cl_(2)作为氯源来促进BiCl_(3)插层石墨。该方法不仅有效提高了BiCl_(3)插层效率,也避免了直接使用氯气带来的安全性风险。采用该方法所合成的三氯化铋-石墨插层化合物(BiCl_(3)-GICs)的层间距为1.26 nm,BiCl_(3)插层含量高达42%。以其为负极材料,组装的钠离子电池具有高的比容量(213 mAh g^(-1)at 1 A g^(-1))和优异的倍率性能(170 mAh g^(-1)at 5 A g^(-1))。此外,原位拉曼光谱测试结果表明,首圈放电后石墨与插层的BiCl_(3)相互作用减弱,该过程有效促进了钠离子在石墨层内的存储。采用该方法可成功制备多种类型金属氯化物-石墨插层化合物,为开发高性能储能材料提供了可行思路。

高纯4,5-二氰基-2-三氟甲基咪唑锂的制备与性能研究

以4,5-二氰基-2-三氟甲基咪唑(TDI)和无水氯化锂为原料,制备高纯4,5-二氰基-2-三氟甲基咪唑锂(LiTDI)。考察了原料物质的量比、反应温度和反应时间对粗品收率的影响,以及重结晶溶剂、溶剂用量、降温速率、重结晶时间对产品纯度和收率的影响。实验结果表明:在m(DMC)/m(TDI)=2、n(LiCl)/n(TDI)=1、反应温度为45℃、反应时间为5 h条件下,反应液经过滤-浓缩-降温结晶后,粗品收率可达78%;在重结晶溶剂为乙二醇二甲醚、m(乙二醇二甲醚)/m(LiTDI粗品)=2、降温速率为3℃/h、结晶时间为10 h条件下,制得的LiTDI纯度≥99.95%、收率可达88%。此外,LiTDI作为锂离子电池添加剂,可以显著提升锂电池的常温和高温循环性能。

热电池用氯化镍正极材料研究

采用升华氯化镍为原材料,通过不同碳材料掺杂工艺制备氯化镍正极材料,装配成电池,采用石墨烯包覆正极材料制备工艺氯化镍正极材料电性能最优;利用该正极材料与不同配比隔膜材料的匹配性实验中,三元全锂隔膜和高电导率隔膜与氯化镍的匹配性最好,与三元全锂隔膜匹配,石墨烯包覆氯化镍正极的功率特性比硫化物正极更为优异。与硫化物正极材料相比,氯化镍正极材料具有更高的电压平台。在1000 mA/cm^(2)脉冲电流下,氯化镍正极的电池功率比硫化物正极的电池可提升20%左右,氯化镍正极更适用于短时间高功率型热电池。

热电池用高电位NiCl_(2)正极材料的制备及改性研究

采用两步法除水工艺制备了无水NiCl_(2),通过物理掺杂改性方式制备了NiCl_(2)-FeS_(2)复合正极材料,并对其理化特性和电化学性能进行了研究。研究结果表明:低温翻松脱水工艺叠加高温升华工艺可以批量制备出无氧化杂质、低吸水率和高结晶度的无水NiCl_(2);在NiCl_(2)中添加FeS_(2)可以提高热电池的峰值电压和前期大电流负载能力,并大幅延长工作时间;当FeS_(2)添加量为10%时,电池整体性能优异,脉冲比功率高达20 kW/kg,对高电压、高比功率热电池的研发具有重要价值。

金属氯化物固态电解质及其全固态电池研究现状与展望

基于无机固态电解质体系的全固态电池,具有高能量密度、长循环寿命和高安全性等特点,被认为是下一代电化学储能电池中备受期待的候选体系。实现高性能全固态电池的关键在于设计和制备具有高离子电导率、界面稳定且易形变的固态电解质材料。金属氯化物型固态电解质作为一种新兴的材料体系,同时具备氧化物固态电解质的抗氧化性以及硫化物固态电解质的高离子传导率和机械延展性,且制备过程简单,无须严苛的环境和极高的烧结温度,可规模化生产潜力大,正逐渐成为实现全固态电池商业化的技术路线竞争者之一。本文通过对近五年来相关电解质材料研究进展的深入分析,对金属氯化物固态电解质体系的研究现状进行了系统评述,涵盖了其合成方法学、晶体结构学、离子传导机制、性能优化策略、电极-电解质界面兼容性以及实用化可行性分析等多个方面。同时,展望了金属氯化物固态电解质未来可能的发展方向,为基于金属氯化物的高性能全固态电池的研究提供了理论和实验参考。

热电池正极材料的研究进展

本文综述了正极材料的最新研究进展,包括正极材料的制备、表征及其在热电池上的性能应用,并对比了不同材料的优劣势,最后对热电池正极材料未来的发展方向进行了展望。该进展对发展高性能、低成本的转换型电池及其在工业上的大规模生产具有重要意义。

Ultrafine Sn_(4)P_(3)nanocrystals from chloride reduction on mechanically activated Na surface for sodium/lithium ion batteries

Nanostructured metal phosphides are very attractive materials in energy storage and conversion,but their applications are severely limited by complicated preparation steps,harsh conditions and large excess of highly toxic phosphorus source.Here we develop a highly efficient one-step method to synthesize Sn_(4)P_(3)nanostructure based on simultaneous reduction of SnCl_(4)and PCl_(3)on mechanically activated Na surface and in situ phosphorization.The low-toxic PCl3 displays a very high phosphorizing efficiency(100%).Furthermore,this simple method is powerful to control phosphide size.Ultrafine Sn_(4)P_(3)nanocrystals(<5 nm)supported on carbon sheets(Sn_(4)P_(3)/C)are obtained,which is due to the unique bottom-up surface-limited reaction.As the anode material for sodium/lithium ion batteries(SIBs/LIBs),the Sn_(4)P_(3)/C shows profound sodiation/lithiation extents,good phase-conversion reversibility,excellent rate performance and long cycling stability,retaining high capacities of 420 mAh/g for SIBs and 760 mAh/g for LIBs even after 400 cycles at 1.0 A/g.Combining simple and efficient preparation,low-toxic and high-efficiency phosphorus source and good control of nanosize,this method is very promising for low-cost and scalable preparation of high-performance Sn_(4)P_(3)anode.

Bismuth chloride@mesocellular carbon foam nanocomposite cathode materials for rechargeable chloride ion batteries

Chloride ion batteries(CIB) are considered to be one of the most promising energy storage devices. As cathode materials for CIBs, metal chlorides have many advantages, such as high theoretical energy density, abundant elemental resources and ideal discharge voltage plateau. However, the dissolution and huge volume change of metal chlorides during cycling lead to considerable short lifespan, which limits their potential application for CIBs. Herein, the bismuth chloride nanocrystal is confined in mesocellular carbon foam matrix by a new vacuum impregnation approach. The mesocellular carbon foam with large interconnected pores(15.7 or 23.2 nm) may buffer the large volume variation of bismuth chloride during charge and discharge, giving rise to significantly enhanced electrochemical performance. The as-prepared bismuth chloride@mesocellular carbon foam cathode delivered an initial discharge capacity of 298 m Ah/g and a reversible capacity of 91 m Ah/g after 60 cycles. In contrast, the pure bismuth chloride cathode almost cannot discharge after 30 cycles. This is the first report that the metal chloride cathode can achieve a prolonged cycling in CIBs.

Using highly concentrated chloride solutions to leach valuable metals from cathode-active materials in spent lithium-ion batteries

This study focused on the extraction of valuable metals from the cathode-active materials in spent lithiumion batteries using a high-concentration chloride solution.The effects of the concentrations of ammonium chloride(NH4 Cl),hydrochloric acid(HCl),and reductants such as hydrogen peroxide(H_(2)O_(2))and urea(CO(NH_(2))_(2))on metal extraction and chlorine production were studied experimentally.The leaching mechanism was analyzed,and a leaching model was established.It was found that the addition of solid NH4 Cl to an HCl solution significantly improved the metal extraction capability of the latter and reduced the formation of chlorine gas by 96.0%compared to that only using HCl.The activation energies for leaching Li,Ni,Co,and Mn were determined to be 30.4,38.5,30.6,and 38.2 kJ·mol^(-1),respectively.This study demonstrates an environmentally friendly method for recycling metal resources from cathode-active materials and furthers understanding of how NH4 Cl inhibits chlorine production when leaching with mixed solutions of HCl and NH4 Cl.

亚铜离子掺杂增强氯化镍高温放电性能研究

氯化镍(NiCl_(2))作为一种高电位热电池正极材料,自身不佳的导电性限制了其在热电池中的应用。在本研究中,利用液相混合-低温煅烧工艺制备了亚铜离子掺杂的氯化镍(NiCl_(2)-Cu_(x))。其中NiCl_(2)-Cu5具备最佳的电化学性能,与NiCl_(2)相比,NiCl_(2)-Cu5展现出高电压、高比能量优势,尤其是在500 mA cm-2电流密度下,NiCl_(2)-Cu5展现出724 Wh kg-1的高比能量,相比于NiCl_(2)约提升了82%。脉冲测试证明,NiCl_(2)-Cu5正极材料具备更低的内阻,能够缓解放电过程中的欧姆极化,实现高比能量输出。这项工作为高性能热电池正极材料的开发提供了一种新的思路。

米粒型氯插层NiFe层状双金属氢氧化物作为新概念氯离子电池正极材料

以卤素氯离子为载荷离子的新概念氯离子电池(CIBs)被认为是“下一代”大规模、高安全电化学储能设备的有力竞争者。层状双金属氢氧化物(LDHs)因具有高的储氯容量与稳定的层状拓扑结构,被视为一类极具发展前景的CIBs正极材料。本工作以MOFs材料MIL-88A为模板前驱体,采用先水解后离子交换的两步法,制备了具有米粒形貌的氯离子插层NiFe LDH纳米多面体(g-NiFe-Cl LDH),其具有高于常规NiFe LDH纳米片两倍的比表面积。这种纳米多面体g-NiFe-Cl LDH材料能够克服一般LDHs纳米片层板间易堆积的本征缺陷,增大材料电化学活性位点暴露率,提高其与电解液的有效接触面积,促进氯离子扩散动力学,最终实现其储氯性能的强化。将g-NiFe-Cl LDH作为CIB正极材料时,电池表现出286.1 mAh/g的最大放电比容量,且在经过200次充放电循环后仍可保持155.3 mAh/g的稳定放电比容量,为常规NiFe-Cl LDH纳米片的两倍。同时,g-NiFe-Cl LDH基CIB的储能机理也被揭示:充电过程中,g-NiFe-Cl LDH正极中的氯离子从层间脱出,其主体层板中的双金属Ni^(3+)/Fe^(3+)被还原成Ni^(2+)/Fe^(2+)。考虑到LDHs材料简单的制备过程和高度可调的化学组分,本工作为设计具有高容量输出和长循环寿命的CIBs正极材料提供了新的思路。

固态电池研究及发展现状

固态电池是指采用固态电解质代替有机液态电解液的锂离子电池,针对电动汽车在续航、安全性等方面的短板,固态电池的高安全性和更高能量密度,使其成为了各个国家新能源技术研究的重点。各大机构和企业也将固态电池作为下一代锂电池的主要发展方向。就固态电池的发展、固态电解质的解析、固态电池优势与挑战、国内外发展现状等方面进行了介绍。

锂-亚硫酰氯电池的试验与性能分析

能源供给是海洋能源与资源开发需重点突破的核心共性关键技术。文章介绍了锂-亚硫酰氯电池的特性及优势,设计出一种电池舱来保证电池组在海底低温情况下也不会降低放电效率;同时根据哈尔伯格—佩克公式,评估出电池在高温高湿的环境下功能和使用寿命也不会受到影响;最后利用微热量仪测试电池的自放电率,测得在常温条件下电池的年容量损失<1%。电池舱的设计保证了海洋装备供电系统的高效性与安全性,锂-亚硫酰氯电池的使用保障了海底观测的长期续航。