低冰镍衍生的具有高结构稳定性和快速扩散动力学的钠离子掺杂层状LiNi1/3Co1/3Mn1/3O2正极(英文)

通过共沉淀法合成钠离子(Na⁺)掺杂的高稳定性Li_1-xNa_xNi_1/3Co_1/3Mn_1/3O₂(NCM-Na)正极材料。首先论证采用低冰镍提取镍作为合成材料镍源的可行性。其次,在化学试剂合成的NCM(Ni,Co,Mn)材料中预先引入最优含量的Na⁺,占据部分Li⁺位点,实现具有更低Li⁺/Ni²⁺阳离子混排的稳定结构,从而提高其电化学性能。结果表明,当Na⁺掺杂量为1%(质量分数)(x=0.01)时,获得的NCM-Na正极材料在1C电流密度下,循环100次后容量保持率从76.84%提高至89.21%。特别是在5C大电流密度下,循环200次后,可逆放电比容量依然维持在110 mA·h·g^-1。这为杂原子掺杂耦合材料化冶金开发低成本、高性能锂离子电池三元LiNi_1/3Co_1/...     

富镍三元层状正极材料表面残碱去除工艺：研究进展、挑战及展望

富镍LiNi_1-x-yCo_xMn_yO₂(NCM)/LiNi_1-x-yCo_xAl_yO₂(NCA)三元层状正极材料因其比容量高、成本低等优势，被认为是最具前景的锂电池正极材料之一。但由于其对空气中H₂O和CO₂的敏感效应，表面易生成残碱化合物LiOH/Li₂CO₃(RLCs)，而RLCs的存在会急剧恶化富镍三元材料热稳定性能和电化学性能，致使其大规模商业化应用面临严峻挑战。本文首先综述了RLCs的组成和形成机理，并系统概括RLCs引起的微裂纹扩展、Li⁺/Ni²⁺混排、界面副反应和晶格相变等材料失效机制以及常用RLCs去除策略；重点阐述去离子水洗涤、无水乙醇洗涤、溶液洗涤及后续一体化处理等三种RLCs去除工艺的研究进展及对材料结构、形貌及电化学性能的影响机理。最后，归纳总结上述溶液洗涤去...     

原位掺杂的高镍正极材料LiNi0.92Co0.039Mn0.038Zr0.003O2的烧结工艺与性能

采用共沉淀-固相烧结法成功制备了锆离子原位掺杂的高镍正极LiNi_0.92Co_0.039Mn_0.038Zr_0.003O₂,通过X射线衍射(XRD)、扫描电镜(SEM)、电化学阻抗(EIS)、循环伏安(CV)和恒流充放电测试等探究了不同烧结温度、烧结时间以及锂配比对高镍正极材料的结构及电化学性能的影响。结果表明：当烧结温度为720℃、烧结时间为18 h、锂配比为1∶1.02时，烧结得到的材料具有最佳的电化学性能。在30℃、0.1 C的测试条件下，其首次放电比容量为234.5 mAh·g^-1,首次库伦效率为89.9%;其在1 C倍率下循环100次后容量保持率为98.6%。     

Ni-Cu掺杂诱导制备两类截角八面体LiMn2O4材料及其电化学性能

结合元素掺杂和晶面调控策略制备了同时包含(111)、(110)和(100)三个晶面和包含(111)和(100)两个晶面的两类截角八面体形貌的LiNi_0.03Cu_0.06Mn_1.91O₄正极材料，并研究了其电化学性能。结果表明：Ni-Cu共掺杂有效抑制了尖晶石LiMn₂O₄的Jahn-Teller效应，促进了其晶体发育和晶面的择优生长，但部分晶面发育较不完善，与一般情况不同的是Ni-Cu共掺后LiNi_0.03Cu_0.06Mn_1.91O₄正极材料的颗粒粒径显著增大；形成的截角八面体形貌中高暴露(111)面降低了Mn的溶解，少部分(110)和(100)晶面增加了Li⁺的扩散通道。恒电流充放电测试结果表明：在5 C和10 C倍率下，LiNi_0.03Cu_0.06Mn_1.91O₄     

Al2O3包覆改善P2型Na2/3Fe1/2Mn1/2O2正极材料的存储性能

采用超声喷雾热解与高温固相烧结相结合的方法合成P2型Na_2/3Fe_1/2Mn_1/2O₂材料。通过X射线衍射仪、扫描电子显微镜和电化学充放电设备对材料的结构、形貌和电化学性能进行全面的表征。此外,在Na_2/3Fe_1/2Mn_1/2O₂表面包覆Al₂O₃薄层,该包覆层可以抑制Na₂CO₃·H₂O的形成,提高Na_2/3Fe_1/2Mn_1/2O₂材料的存储性能,从而改善其电化学性能。这种简单的表面改性方法为合成高性能钠离子电池正极材料提供了新思路。     

磷酸铁锂/石墨烯复合材料的低温微波水热法制备及性能

采用喷雾干燥结合低温微波水热法制备了石墨烯/LiFePO₄复合正极材料,利用SEM、XRD、DLS等对其微观形貌、结构、粒度分布进行了表征,并利用恒流充放电、CV、EIS等测试研究了复合正极材料的电化学性能和电极动力学过程。结果表明,与未包覆的样品相比,石墨烯包覆的LiFePO₄具有优异的倍率性能(5C放电比容量为125.4 mAh?g_-1)和循环稳定性(1C条件下100次充放电后容量保持率在95%左右)。包覆石墨烯后LiFePO₄正极材料的电荷迁移电阻减小,电化学可逆性增强,从而提高了材料的倍率性能。本文提供了一条提高磷酸铁锂正极材料电化学性能的简便途径,具有良好的应用前景。     

废旧磷酸铁锂电池高值回收制备磷酸铁锂材料

针对传统湿法冶金回收废旧磷酸铁锂电池存在含磷废水排放量大、产品附加值低等问题，提出一种还原酸浸-沉淀-固相再生回收废旧磷酸铁锂正极材料的新方法。区别于传统氧化酸浸，本研究在浸出过程中加入有机还原剂，将铁元素以Fe²⁺的形式浸出到溶液中；然后，通过控制pH值制备Fe₃(PO₄)₂·8H₂O，以此作为再生LiFePO₄正极材料的前驱体，避免了后续混锂烧结过程中Fe³⁺还原不彻底、再生磷酸铁锂纯度低等问题。结果表明：通过控制浸出条件，Li⁺和Fe²⁺的浸出率分别达到98.15%和98.10%。利用氨水调控浸出液pH值，沉淀出形貌为一次片状簇拥成团状结构的Fe₃(PO₄)₂·8H₂O前驱体；最后，将Fe₃(PO₄)₂·8H₂O...     

锂离子电池富镍正极基础科学问题：关键元素掺杂及其作用机理

富镍层状氧化物因其相对较高的比容量成为高能量密度锂离子电池的首选正极,进一步提高Ni含量,材料特性趋向于LiNiO₂,电化学和结构稳定性恶化。晶格元素掺杂是提升LiNiO₂稳定性的有效策略。厘清LiNiO₂正极材料结构并明晰掺杂元素对其影响及规律,对开发Ni含量大于90%的富镍正极材料具有重要意义。本文首先介绍了LiNiO₂材料结构及面临的稳定性问题。然后综述了Co、Mn、Al、Mg、Ti、Zr、W等典型掺杂元素对LiNiO₂的影响及规律,并讨论了阴离子和多元素掺杂以及有潜力的掺杂元素。本文旨在对LiNiO₂掺杂提供一个新的视角,以期使用更有效的掺杂方案开发可用于动力电池的高容量稳定的富镍正极材料。     

LiFePO4包覆LiCoO2的结构及性能

采用固相法在锂离子电池正极材料LiCoO2表面包覆一层LiFePO4;研究了LiFePO4包覆量对材料性能的影响;采用X射线衍射仪和扫描电镜分析样品的晶体结构和表面形貌.研究结果表明:样品具备LiCoO2的α-NaFeO2型层状结构,但随着包覆量的增加,XRD衍射谱显示样品存在多种杂相;合成的样品电化学性能良好,当LiFePO4的包覆量为1%时,在室温下以0.1C倍率充放电,首次放电比容量达145.9 mA·h/g,纯相LiCoO2放电比容量为146.2 mA·h/g.样品采用1C倍率放电时,首次放电比容量达138.9 mA·h/g,循环性能较好,经过20次循环放电比容量仅衰减4.97%.     

Nb5+掺杂LiFePO4/C的反应挤出合成

以LiOH.H2O、FeC2O4.2H2O和P2O5为原料,以草酸铌为添加剂,采用反应挤出法合成Li1 5xNbxFePO4/C材料;采用X射线衍射(XRD)、扫描电镜(SEM)、循环伏安(CV)和充放电测试研究不同Nb5+掺杂量对Li1 5xNbxFePO4/C材料结构、形貌以及电化学性能的影响。结果表明,适量的Nb5+掺杂不会改变材料的结构和形貌;Nb5+掺杂可以有效减小电极的极化,其中Li0.97Nb0.006FePO4/C表现出最佳的电化学性能,在0.2C、0.5C、1C和2C倍率下的首次放电比容量分别为162.9、148.9、141.7和137.1 mA.h/g;材料循环性能良好,经10次循环后,材料的放电比容量都保持在99%以上。     

Porous Li4Ti5O12 anode material synthesized by one-step solid state method for electrochemical properties enhancement

A porous Li₄Ti₅O₁₂ anode material was successfully synthesized from mixture of LiCl and TiCl₄ with 70 wt% oxalic acid by a modified one-step solid state method. The anode material Li₄Ti₅O₁₂ exhibited a cubic spinel structure and only one voltage plateau occurred around 1.5 V. The initial capacity of porous Li₄Ti₅O₁₂ was 167 and 133 mAh g⁻¹ at 0.5 and 1C charge/discharge rate, respectively, and the capacity retention maintained above 98% after 200 cycles. The porous Li₄Ti₅O₁₂ structure showed promising rate performance with a capacity of 70 mAh g⁻¹ at charge/discharge 10C rate after 200 cycles. It was demonstrated that the porous structure could withstand 50C charge/discharge rate and exhibited excellent cycling stability.     

Effects of Na+ doping on crystalline structure and electrochemical performances of LiNi0.5Mn1.5O4 cathode material

Pristine LiNi_0.5Mn_1.5O₄ and Na-doped Li_0.95Na_0.05Ni_0.5Mn_1.5O₄ cathode materials were synthesized by a simple solid-state method. The effects of Na⁺ doping on the crystalline structure and electrochemical performance of LiNi_0.5Mn_1.5O₄ cathode material were systematically investigated. The samples were characterized by XRD, SEM, FT-IR, CV, EIS and galvanostatic charge/discharge tests. It is found that both pristine and Na-doped samples exhibit secondary agglomerates composed of well-defined octahedral primary particle, but Na⁺ doping decreases the primary particle size to certain extent. Na⁺ doping can effectively inhibit the formation of Li_xNi_1–xO impurity phase, enhance the Ni/Mn disordering degree, decrease the charge-transfer resistance and accelerate the lithium ion diffusion, which are conductive to the rate capability. However, the doped Na⁺ ions tend to occupy 8a Li sites, which forces equal amounts of Li⁺ ions to occupy 16d octahedral sites, making the spinel framework less stable, therefore the cycling stability is not improved obviously after Na⁺ doping.     

掺F锂离子电池正极材料Li1.03Co0.10Mn1.90FzO4-z的制备及电化学性能

以Li2CO3、Mn2O3、Co2O3及LiF为原料,采用高温固相法合成了掺F的Li1.03Co0.10Mn1.90FzO4?z锂电池正极材料。通过离子发射光谱(ICP)和电位分析法确定了材料的化学组成,用X-射线衍射(XRD)、扫描电子显微镜(SEM)和电化学测试仪分析了 F 掺杂量对材料结构、形貌和电池性能的影响。结果表明,掺 F 的Li1.03Co0.10Mn1.90FzO4?z正极材料为尖晶石结构,在F掺入量z≤0.10时,随着掺杂量的增加晶胞参数逐渐增加,当F掺杂量继续增加时,晶胞参数的增幅有所减小。适量的F?与金属离子Li+、Co+的复合掺杂提高了材料的放电比容量,同时增强了材料结构的稳定性。电化学性能测试表明,Li1.03Co0.10Mn1.90F0.15O3.85的首次放电比容量达到111.0 mA·h/g,0.2C倍率下30次循环后容量保持率为97.0%。     

Synthesis of porous nano/micro structured LiFePO4/C cathode materials for lithium-ion batteries by spray-drying method

In order to enhance electrochemical properties of LiFePO₄ (LFP) cathode materials, spherical porous nano/micro structured LFP/C cathode materials were synthesized by spray drying, followed by calcination. The results show that the spherical precursors with the sizes of 0.5–5 μm can be completely converted to LFP/C when the calcination temperature is higher than 500 °C. The LFP/C microspheres obtained at calcination temperature of 700 °C are composed of numerous particles with sizes of ～20 nm, and have well-developed interconnected pore structure and large specific surface area of 28.77 m²/g. The specific discharge capacities of the LFP/C obtained at 700 °C are 162.43, 154.35 and 144.03 mA·h/g at 0.5C, 1C and 2C, respectively. Meanwhile, the capacity retentions can reach up to 100% after 50 cycles. The improved electrochemical properties of the materials are ascribed to a small Li⁺ diffusion resistance and special structure of LFP/C microspheres.     

para-Sexiphenylene as a model compound of poly(para-phenylene) during the electrochemical intercalation of lithium and sodium ions in ethylene carbonate-based electrolyte

The electrochemical intercalation of alkaline ions (Na⁺, Li⁺) into para-sexiphenylene (PSP) has been carried out in ethylene carbonate (EC) using MClO₄ as the alkaline salt (M-Na or Li). Cyclic voltammetry and galvanostatic experiments reveal different behaviour for lithium and sodium. Intercalation of Na⁺ into PSP occurs with formation of successive stages of Na_0.33(C₆H₄) and Na_0.5(C₆H₄). After the first cycle, where the irreversible side reactions (such as the decomposition of the electrolyte, the reduction of the binder, etc.) occurred giving important capacity loss, the system exhibits a good reversibility. On the other hand, intercalation of Li⁺ into PSP is partially reversible whatever the cycle. A reversible capacity of 0.2 is reported in this case. The galvanostatic curves do not show any well-defined plateaux as in the case of the intercalation of Na⁺.     

模拟废旧锂离子电池湿法冶金浸出液再生铝掺杂LiNi0.5Co0.2Mn0.3O2正极材料

采用共沉淀法制备均相Al掺杂的LiNi0.5Co0.2Mn0.3O2正极材料,以利用Al对再生镍钴锰(NCM)正极材料的正面改性作用,并改善锂离子电池回收过程中繁琐和高成本的除杂过程.当浸出液中的Al3+含量为过渡金属(Ni、Co和Mn)总量的1％(摩尔分数)时,制备的Al掺杂NCM正极材料中晶格氧和Ni2+的浓度增加...     

Investigation on temperature dependence of photoluminescence in Sr1.7Eu0.3MxCeO4.15+x/2 (M = Li, Na, K, x = 0, 0.3) red phosphors

The temperature-dependent luminescence of Sr_1.7Eu_0.3M_xCeO_4.15+x/2 (M = Li⁺, Na⁺, K⁺, x = 0, 0.3) samples was investigated and discussed in the temperature range from 303 to 573 K. It is found that the thermal quenching temperature of samples decreases with Li⁺-/Na⁺-doping but increases with the incorporation of K⁺. We suggest that these observations are resulted from two factors. One is that the incorporation of Li⁺/Na⁺/K⁺ ions reduces the strength of potential field at the O²⁻ sites, and then results in a red-shift of the Eu-O charge transfer band. The other is that Δr expands with Li⁺-/Na⁺-doping but shrinks with K⁺-doping. We consider that it is a feasible way to adjust the temperature-dependent luminescence properties of materials by introducing appropriate impurities.     

Electrogeneration and electrochemical properties of hybrid materials: polypyrrole doped with polyoxometalates PW12−xMoxO403− (x=0,3,6,12)

Hybrid materials such as polypyrrole doped with polyoxometalates PW_12−xMo_xO₄₀³⁻ (x=0,3,6,12) were electrogenerated from organic solution. The effects of the Mo-substitution on the electrogeneration and electrochemical properties of the hybrid materials were studied by potential step and cyclic voltammetry. It was found that Mo-substituted polyoxometalates could stimulate the oxidation–polymerization of pyrrole. The oxidation–polymerization potential of pyrrole decreases as the Mo content increases, correlating the redox properties of the polyoxometalates. During the initial cathodic sweep, a great cathodic peak (altogether a blue cloud of material release) with a shoulder is shown by all the studied materials. A substantial loss of weight was always observed during this reduction process. Polyoxometalates and polypyrrole oligomers determined by FT-IR [J. Chem. Phys. B 104 (2000) 10528] and UV–VIS contributed to the weight loss giving rise to a partial electrochemically stimulated dissolution of the material. After this initial cycle, the consecutive voltammograms present two redox processes. Charges and current densities involved in those two cathodic processes show a linear variation, in opposite directions, at almost the same rate upon cycling. Those shifts of the cathodic processes are related to a continuous change of the counter-ion involved in the redox process from Li⁺ to ClO₄⁻, altogether the subsequent release of polyoxometalate (that required the Li⁺ counter-ion) from the hybrid.     

Sn_(0.35-0.5x)Co_(0.35-0.5x)Zn_xC_(0.30)复合材料的制备及电化学性能

采用固相烧结和球磨相结合的方法制备了锂离子电池负极复合材料Sn_0.35-0.5xCo_0.35-0.5xZn_xC_0.30 (摩尔分数x分别为0, 0.05, 0.10, 0.15和0.20), 考察了Zn添加量对材料结构和电化学性能的影响. 烧结粉末样品的XRD分析表明, 随着Zn含量的增多, 在CoSn主相基础上, 先形成少量CoSn₂相, 随后形成少量Co₃Sn₂, Zn和Sn相. 大部分 Zn原子固溶于CoSn相. 电性能分析表明, 随着Zn含量的增加, 首次放电容量和充放电效率都呈现先增加而后趋于稳定的趋势, 当x=0.15时, 首次放电容量和充放电效率都接近最大值, 分别为343 mA-h/g和73.8%; 经过 25 cyc充放电后放电容量保持了首次放电容量的87.6%. 这表明Zn原子固溶引起的晶格畸变和多种相生成导致相界数量的增多, 加快了Li⁺动力学扩散速度, 从而显著改善了电化学性能. 选择烧结粉末样品Sn_0.275Co_0.275Zn_0.15C_0.30进行球磨, 晶粒和颗粒的细化使样品的放电容量显著提升, 但对首次放电效率和循环性能改善不明显.     

Electrochemical behavior of Li+, Mg2+, Na+ and K+ in LiFePO4/ FePO4 structures

Besides Li⁺ and Mg²⁺, the electrochemical behavior of Na⁺ and K⁺ in LiFePO₄/ FePO₄ structures was studied since they naturally coexist with Li⁺ and Mg²⁺ in brine. The cyclic voltammogram (CV) results indicated that Na⁺ exhibits some reversibility in LiFePO₄/FePO₄ structures. Its reduction peak appears at ?0.511 V, more negative than that of Li⁺ (?0.197 V), meaning that a relatively positive potential is beneficial for decreasing Na⁺ insertion. The reduction peak of K⁺ could not be found clearly, indicating that K⁺ is difficult to insert into the FePO₄ structure. Furthermore, technical experiments using real brine with a super high Mg/Li ratio (493) at a cell voltage of 0.7V showed that the final extracted capacity of Li⁺, Mg²⁺ and Na⁺ that can be attained in 1 g LiFePO₄ is 24.1 mg, 7.32 mg and 4.61 mg, respectively. The Mg/Li ratio can be reduced to 0.30 from 493, and the Na/Li ratio to 0.19 from 16.7, which proves that, even in super high Mg/Li ratio brine, if a cell voltage is appropriately controlled, it is possible to separate Li⁺ and other impurities effectively.