Suppress oxygen evolution of lithium-rich manganese-based cathode materials via an integrated strategy

Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.

Stabilized cobalt-free lithium-rich cathode materials with an artificial lithium fluoride coating

Iron-substituted cobalt-free lithium-rich manganese-based materials,with advantages of high specific capacity,high safety,and low cost,have been considered as the potential cathodes for lithium ion batteries.However,challenges,such as poor cycle stability and fast voltage fade during cycling under high potential,hinder these materials from commercialization.Here,we developed a method to directly coat LiF on the particle surface of Li_(1.2)Ni_(0.15)Fe_(0.1)Mn_(0.55O2).A uniform and flat film was successfully formed with a thickness about 3 nm,which can effect-ively protect the cathode material from irreversible phase transition during the deintercalation of Li^(+).After surface coating with 0.5wt%LiF,the cycling stability of Li_(1.2)Ni_(0.15)Fe_(0.1)Mn_(0.55O2) cycled at high potential was significantly improved and the voltage fade was largely suppressed.

Oxygen redox chemistry in lithium-rich cathode materials for Li-ion batteries:Understanding from atomic structure to nano-engineering

Lithium-rich oxide compounds have been recognized as promising cathode materials for high performance Li-ion batteries,owing to their high specific capacity.However,it remains a great challenge to achieve the fully reversible anionic redox reactions to realize high capacity,high stability,and low voltage hysteresis for lithiumrich cathode materials.Therefore,it is critically important to comprehensively understand and control the anionic redox chemistry of lithium-rich cathode materials,including atomic structure design,and nano-scale materials engineering technologies.Herein,we summarize the recent research progress of lithium-rich cathode materials with a focus on redox chemistry.Particularly,we highlight the oxygen-based redox reactions in lithium-rich metal oxides,with critical views of designing next generation oxygen redox lithium cathode materials.Furthermore,we purposed the most promising strategies for improving the performances of lithium-rich cathode materials with a technology-spectrum from the atomic scale to nano-scale.

Phase Transformation of Lithium-rich Oxide Cathode in Full Cell and its Suppression by Solid Electrolyte Interphase on Graphite Anode

Lithium-rich oxide is one of the most promising cathodes that meet high energy density requirement for batteries of the future, but its phase transformation from layer to spinel structure caused by the lattice instability presents severe challenge to cycling stability and the actually accessible capacity. The currently available approaches to suppress this undesired irreversible process often resort to limit the high voltages that lithium-rich oxide is exposed to. However, cycling stability thus improved is at the expense of the eventual energy output. In this work, we identified a new mechanism that is directly responsible for the lithium-rich oxide phase transformation and established a clear correlation between the successive consumption of Li+on anode due to incessant interphase repairing and the over-delithiation of lithium-rich oxide cathode. This new mechanism enables a simple but effective solution to the cathode degradation, in which an electrolyte additive is used to build a dense and protective interphase on anode with the intention to minimize Li depletion at cathode. The application of this new interphase effectively suppresses both electrolyte decomposition at anode and the phase transformation of lithium-rich oxide cathode, leading to high capacity and cycling stability.

Optimize two-phase distribution of lithium-rich materials to stabilize structure and suppress voltage attenuation

Lithium-rich materials possess the ultra-high specific capacity,but the redox of oxygen is not completely reversible,resulting in voltage attenuation and structural instability.A stepwise co-precipitation method is used for the first time in this paper to achieve the control of the two-phase distribution through controlling the distribution of transition metal elements and realize the modification of particle surface structure without the aid of heterologous ions.The results of characterization tests show that the content of LiMO_(2) phase inside the particles and the content of Li_(2)MnO_(3) phase on the surface of the particles are successfully increased,and the surface induced formation of Li_(4)Mn_(5)O_(12) spinel phase or some disorderly ternary.The electrochemical performance of the modified sample is as follows:LR(pristine)shows specific discharge capacity of 72.7 mA·h·g^(−1)after 500 cycles at 1 C,while GR(modified sample)shows specific discharge capacity of 137.5 mA·h·g^(−1) at 1 C,and the discharge mid-voltage of GR still remains above 3 V when cycling to 220 cycles at 1 C(mid-voltage of LR remains above 3 V when cycling to 160 cycles at 1 C).Therefore,deliberately regulating the local state of the two phases is a successful way to reinforced the material structure and inhibition the voltage attenuation.

Geochronology and geochemistry of lithium-rich tuffs in the Sichuan basin,western Yangtze:Implication for the magmatic origin and final closure of eastern Paleo-Tethys

The felsic volcanogenic tuffs named"green-bean rocks"(GBRs),characterized by a green or yellowish green color,are widely distributed in the western Yangtze platform and have a high lithium content(286-957 ppm).This paper studies the ages,origin and tectonic setting of the GBRs in the Sichuan basin on the western margin of the Yangtze platform through the whole-rock geochemistry and zircon trace elements by using U-Pb dating and Hf-O isotopes.The GBR samples from the Quxian and Beibei sections yielded zircon U-Pb ages of 245.5±1.8 Ma and 244.8±2.2 Ma.These samples can be used as the isochronous stratigraphic marker of the Early-Middle Triassic boundary(EMTB)for regional correlation.The whole-rock and zircon geochemistry,and zircon Hf-O isotopes exhibited S-type geochemical affinities with high positiveδ^(18)0 values(9.28‰-11.98‰),low negativeε_(Hf)(t)values(-13.87 to-6.79),and T_(DM)^(2)ages of 2150-1703 Ma,indicating that the lithium-rich GBRs were generated by the remelting of the pre-existing ancient Paleoproterozoic layer without mantle source contamination in the arcrelated/orogenic tectonic setting.The results of this study demonstrate that the lithium-rich GBRs in the western Yangtze platform were derived from arc volcanic eruptions along the Sanjiang orogen,triggered by the closure of the eastern Paleo-Tethys Ocean and the syn-collision between the continental Indochina and Yangtze blocks at ca.247 Ma.This was marked by a major shift from I-type magmas with intermediateε_(Hf)(t)values to S-type magmas with low negativeε_(Hf)(t)values.Collectively,our results provide new insights into the origin of the GBRs and decodes the closure of the eastern Paleo-Tethys.

Challenges and strategies of lithium-rich layered oxides for Li-ion batteries

Lithium-ion batteries are considered a promising energy storage technology in portable electronics and electric vehicles due to their high energy density,competitive cost,and environmental friendliness.Improving cathode materials is an effective way to meet the demand for better batteries,of which the utilization of high-voltage cathode materials is an important development trend.In recent years,lithium-rich layered oxides have gained great attention due to their desirable energy density.This review presents the relationships between lattice structure and electrochemical properties,the underlying degradation mechanisms,and corresponding modification strategies.The recent progress and strategies are then highlighted,including element doping,surface coating,morphology design,size control,etc.Finally,a concise perspective for future developments and practical applications of lithium-rich layered oxides has been provided.

川西巴塘地区富锂温泉的同位素特征及其成因探讨

川西巴塘地区处于青藏高原东南缘,是地壳新构造运动活跃、地震活动强烈而密集的地区,其中茶洛—德达地段是温泉聚集区,富锂沸泉与温泉密集发育。为进一步认识该区富锂温泉的成因以及温泉与地震活动的关系,开展了温泉水氢、氧、碳和锂同位素的综合研究,阐明了地热流体、锂和热量的来源,探讨了富锂温泉的成因及其与地震活动的关系,为该区富锂温泉的研究和勘查提供支撑。研究结果显示:1)茶洛—德达地段发育章柯、茶洛富锂沸泉和查青卡富锂温泉,锂含量高达1353.00~3592.00µg·L^(-1),其锂同位素组成δ7Li介于-0.53‰~1.74‰之间;2)该区富锂温泉水主要来源于周边4800~5200 m的高山区域大气降水,温泉流体循环深度可达6900~8500 m,与该区部分地震的震源深度相当;3)富锂温泉的深部发生较强的高温(温度236~289℃)水-岩反应,碳酸盐岩、富锂花岗岩等释放出碳和锂等元素,形成查青卡富锂温泉(1353~1392µg·L^(-1));章柯、茶洛沸泉除上述锂来源外,还有深部高温富锂流体混入,从而形成更高温(240~289℃)、更富锂(2736~3592µg·L^(-1))的地热流体;4)该区章柯、茶洛富锂沸泉的热源除以深部(地壳、地幔)热流为主要热源外,还有地震断层摩擦热、深部流体热为补充热源,频发的地震活动持续地、脉动式地为章柯、茶洛地热系统补充热量,形成富锂沸泉。查青卡富锂温泉热源主要为深部(地壳、地幔)热流,无断层摩擦热和深部流体热补充。

基于第一性原理高价元素Mo稳定层状富锂锰基材料的氧框架机制

采用基于密度泛函理论的第一性原理计算探究了高价元素Mo取代Mn稳定层状富锂锰基材料氧离子框架机制.Mo掺杂将体积变化率从‒2.95%降至‒0.53%,改善了锂化前后的晶格畸变.空位形成能及巴德电荷分析结果表明,7种氧空位形成能均明显提升,且第一配位氧平均巴德电荷从1.13 e升至1.18 e,抑制了不稳定氧析出;锂化前后氧原子巴德电荷改变量从0.51 e降至0.11 e,表明循环前后的体系均具有良好的氧框架稳定性.通过差分电荷密度计算,发现Mo能够在Li去除后提供电荷补偿,而且Mo掺杂后锂离子迁移速率得到了提升,最低势垒从0.55 eV降至0.42 eV.为高价元素掺杂锂离子电池正极材料奠定了坚实的理论依据.

层状富锂锰基正极材料包覆改性的最新进展

首先综述了富锂锰基材料的结构和循环过程中存在的问题,然后介绍了富锂锰基正极材料包覆改性研究的最新进展,系统描述了电化学活性材料、非电化学活性材料和导电聚合物等不同种类包覆物质及单层包覆、双层复合包覆和原位包覆等包覆方法在该材料改性领域中的应用,进一步从材料结构、失效机制等角度深入分析了各种包覆改性方法及包覆物质改善富锂锰基材料循环性能的作用机制.最后,对Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_(2) (LMNC)材料及改性方法等未来发展方向进行了展望.

富锂正极材料Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_(2)的制备及性能

为满足当前新能源发电技术对高比容量电化学储能材料的需求,采用聚合物热解法,通过优化前体聚合过程中金属离子与丙烯酸配比制备高比容量层状富锂锰基氧化物Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_(2)。依据丙烯酸聚合反应实现金属离子均匀分散,通过二次升温煅烧制备出富锂锰基正极材料Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_(2)。改变煅烧温度,制备不同煅烧温度下的正极材料样品,研究煅烧温度对其微观形貌及电化学性能的影响。利用X射线衍射(XRD)、扫描电镜(SEM)测试技术观测不同材料样品微观形貌和晶体结构的差异,利用能谱分析技术(EDS)观察材料中的元素分布情况,使用新威电池测试系统和电化学工作站对所制备正极材料的电化学性能进行研究。结果表明,在925℃下制备的Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_(2)正极材料结晶度高,层状结构明显,阳离子混排程度低,各元素分散均匀。在2.0~4.8 V范围循环充放电测试,0.1C倍率下首周放电比容量达到290.3 mAh/g,0.5C倍率下循环充放电100周放电容量保持在204.8 mAh/g,容量保持率为81.9%,具有较好的循环稳定性。本实验制备出的富锂锰基正极材料Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_(2)具有良好的电化学性能,有助于推动富锂锰基正极材料的应用,为高比容量正极材料的发展提供实验依据。

前驱体预处理对富锂锰基氧化物电化学的影响

实验通过小规模共沉淀和固相反应成功合成了无钴富锂锰基前驱体Ni_(0.3)Mn_(0.7)(OH)_(2),将前驱体不进行和进行机械粉碎,分别得到2种不同粒径的Ni_(0.3)Mn_(0.7)(OH)_(2)(D_(50)=1.626μm和0.710μm)前驱体。不同粒径大小的前驱体与LiOH以1∶1.55的摩尔比混合,经过高温烧结,合成2种颗粒大小的富锂锰基正极材料Li_(1.2)Ni_(0.24)Mn_(0.56)O_(2)(D_(50)=1.667μm和1.148μm)。实验结果表明,颗粒尺寸影响其物理化学性质和电化学性能。Li_(1.2)Ni_(0.24)Mn_(0.56)O_(2)(D_(50)=1.148μm)正极材料具有较小颗粒尺寸,显示出优异的电化学性能(在0.5 C下循环100次后,容量为190.7 mAh/g,循环保持率高达91.2%)。研究揭示了一种简易方法改变颗粒大小,并证明了粒径对电化学的重要性。

富锂锰基材料低首次库仑效率原因及改性策略

富锂锰基正极材料〔xLi_(2)MnO_(3)•(1–x)LiTMO_(2),0<x<1,TM=Mn、Co、Ni等〕(LROs)具有高容量、高工作电压、高安全、低成本等诸多优点,是下一代新型锂离子电池材料中最具有应用前景的正极材料之一。然而,LROs的低首次库仑效率严重地阻碍了其商业化,亟需深入研究其低首次库仑效率原因。从LROs的晶体结构及充放电行为出发,全面剖析了氧的不可逆流失、Li^(+)不可逆脱/嵌、Li^(+)与H^(+)离子交换等造成LROs低首次库仑效率原因的具体机理;针对性地总结了离子掺杂、表面工程、单晶化等提升首次库仑效率的相关改性策略;展望了提升LROs未来商业化的研究方向。

纳米富锂锰基正极材料的合成及性能研究

富锂层状氧化物材料具有较高的比容量,被认为是下一代先进锂离子电池正极材料。采用丙烯酸热聚合法和柠檬酸溶胶-凝胶法分别合成了纳米富锂锰基正极材料Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_(2),并进行Mg^(^(2+))掺杂改性。通过扫描电子显微镜、X射线粉末衍射仪对制备的正极材料进行形貌和结构表征,并组装成纽扣电池进行充放电性能测试和电化学阻抗谱分析。结果表明,丙烯酸热聚合法合成的正极材料粒径均匀,结晶度更高;与未掺杂样品相比,掺杂Mg^(2+)的正极材料首次库伦效率从67.66%提高到73.34%,循环性能显著改善。

普光地区下三叠统富锂钾卤水成因与分布规律

通过对普光地区钻孔卤水和油田水水化学分析测试,开展离子比例研究,明确嘉陵江组和飞仙关组各亚段卤水的成因机制和分布规律。研究结果表明:嘉陵江组卤水K^(+)质量浓度在4060.00~20160.00 mg/L,Li^(+)质量浓度在26.00~271.00 mg/L,整体为海水浓缩特征。嘉四段—嘉五段卤水K^(+)质量浓度在4110.00~20160.00 mg/L,Li^(+)质量浓度在76.15~271.00 mg/L,Li^(+),K^(+)富集受海水蒸发浓缩、“绿豆岩”风化作用和淋滤作用主控;嘉二段卤水K^(+)质量浓度在4060.00~4140.00 mg/L,Li^(+)质量浓度在26.00~27.80 mg/L,受海水蒸发浓缩及膏盐溶解主控。飞仙关组卤水K^(+)质量浓度在6.13~650.00 mg/L,Li^(+)质量浓度在0.02~50.60 mg/L,整体为地下溶滤特征。飞三段—飞四段卤水K^(+)质量浓度在588.00~650.00 mg/L,Li^(+)质量浓度在40.40~50.60 mg/L,Li^(+),K^(+)富集受膏岩等围岩溶滤和嘉陵江组卤水运移主控;飞一段—飞二段卤水K^(+)质量浓度在6.13~478.00 mg/L,Li^(+)质量浓度在0.02~17.90 mg/L,由地层水对碳酸盐岩溶解主控。富锂钾卤水平面上主要分布在大湾-土主构造及其构造作用中等的翼部。

High-capacity lithium-rich cathode oxides with multivalent cationic and anionic redox reactions for lithium ion batteries

Lithium-rich cathode oxides with capability to realize multivalent cationic and anionic redox reactions have attracted much attention as promising candidate electrode materials for high energy density lithium ion batteries because of their ultrahigh specific capacity. However, redox reaction mechanisms, especially for the anionic redox reaction of these materials, are still not very clear. Meanwhile, several pivotal challenges associated with the redox reactions mechanisms, such as structural instability and limited cycle life, hinder the practical applications of these high-capacity lithium-rich cathode oxides. Herein, we review the lithium-rich oxides with various crystal structures. The multivalent cationic/anionic redox reaction mechanisms of several representative high capacity lithium-rich cathode oxides are discussed, attempting to understand the origins of the high lithium storage capacities of these materials. In addition, we provide perspectives for the further development of these lithium-rich cathode oxides based on multivalent cationic and anionic redox reactions, focusing on addressing the fundamental problems and promoting their practical applications.

通过CTAB辅助TEOS水解制备LMO@SiO_(2)调控氧活性提高循环稳定性

采用共沉淀法制备了富锂锰基正极材料,并利用CTAB辅助TEOS水解对富锂锰基正极材料进行SiO_(2)表面包覆改性进行调控氧活性。通过恒电流充放电、循环伏安及电化学交流阻抗等电化学测试方法对富锂锰基正极材料进行表征,研究了SiO_(2)包覆改性对富锂锰基材料电化学性能的影响。研究结果表明,SiO_(2)包覆层能有效调控氧活性,这对材料循环稳定性能的提升具有积极作用。

Electrospinning synthesis of novel lithium-rich 0.4Li2MnO3.0.6LiNi1/3CO1/3Mn1/3O2 nanotube and its electrochemical performance as cathode of lithium-ion battery

In this study, a lithium-rich 0.4Li2MnO3.0.6LiNi1/3Co1/3Mn1/3O2 nanotube layered cathode synthesized by novel electrospinning is reported, and the effects of temperature on the electrochemical performance and morphologies are investigated. The crystal structure is characterized by X-ray diffraction patterns, and refined by two sets of diffraction data （R-3m and C2/m）. Refined crystal structure is 0.4Li2MnO3.0.6LiNi1/3COl/3Mn13O2 compos- ite. The inductively coupled plasma optical emission spec- trometer and thermogravimetric and differential scanning calorimetry analysis measurement supply reference to opti- mize the calcination temperature and heat-treatment time. The morphology is characterized by scanning and high- resolution transmission electron microscope techniques, and the micro-nanostructured hollow tubes of Li-rich 0.4Li2MnO3-0.6LiNil/3COl/3Mn1/3O2 composite with outer diameter of 200-400 nm and the wall thickness of 50-80 nm are synthesized successfully. The electrochemical evaluation shows that 0.4Li2MnO3.0.6LiNi1/3Cov3Mn1/3O2 sintered at 800 ℃ for 8 h delivers the highest capacity of the first dis- charge capacity of 267.7 mAh/g between 2.5 V and 4.8 V at 0.1C and remains 183.3 mAh/g after 50 cycles. The electro- spinning method with heat-treatment to get micro-nanos- tructured lithium-rich cathode shows promising application inlithium-ion batteries with stable electrochemical performance and higher C-rate performance for its shorter Li ions transfer channels and stable designed structure.

无钴富锂锰基正极材料Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2)的表面改性及电化学性能研究

无钴富锂锰基正极材料Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2)因高比容量、低成本等优点备受关注,是极具潜力的下一代锂离子电池正极材料。然而,Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2)材料存在首次库伦效率低、倍率性能差及容量衰减等问题,限制了其进一步发展。为解决此问题,采用柠檬酸溶液表面处理结合再重新煅烧方法,通过在其表面包覆一层尖晶石相,对Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2)开展了表面改性研究,并对改性前后样品进行物理表征和电化学测试分析。结果表明,改性前后的Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2)正极材料,形貌基本一致,均为尺寸100—400 nm的不规则颗粒,改性后的粉末颗粒边缘略有不平整。使用柠檬酸溶液表面处理后,Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2)材料形成了内部为层状相、表面为尖晶石相的结构。尖晶石相的存在不仅为锂离子扩散提供了三维离子扩散通道、提高倍率性能,还可充当正极材料表面与电解液间的保护层,提高首次库伦效率,改善循环性能。改性后的Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2)的首次库伦效率为92.4%,可逆比容量为292 mAh·g^(-1),与改性前相比分别提高了13.8%和22 mAh·g^(-1),并且在不同倍率下的可逆比容量和长循环容量保持率均有明显提升,表明其具有更好的倍率性能和更优的循环稳定性能。本研究提出了一种无钴富锂锰基正极材料表面改性方法,该改性方法操作简单、效果明显,可应用于不同组分的富锂正极材料,为富锂锰基正极材料的进一步发展提供了新的思路。

Suppression of voltage decay through adjusting tap density of lithium-rich layered oxides for lithium ion battery

The voltage decay of lithium-rich layered oxides(LLOs)is still one of the key challenges for their application in commercial battery although these materials possess the advantages of high specific capacity and low cost.In this work,the relationship between voltage decay and tap density of LLOs has been focused.The voltage decay can be significantly suppressed with the increasing tap density as well as the homogenization of the primary or secondary particle size of agglomerated spherical LLOs.Experimental results have shown that an extreme small voltage decay of 0.98 m V cycle^(-1)can be obtained through adjusting the tap density of agglomerated spherical LLOs to 1.99 g cm^(-3),in which the size of primary and secondary particles are uniform.Our work offers a new insight towards the voltage decay and capacity fading of LLOs through precursor preparation process,promoting their application in the real battery in the future.