Adsorption equilibrium, kinetics, and dynamic separation of Ca2+ and Mg2+ ions from phosphoric acid–nitric acid aqueous solution by strong acid cation resin

The separation of Ca2+and Mg2+ions from phosphoric acid-nitric acid aqueous solution is very significant for the neutralization process of nitrophosphate fertilizer.This paper studied the adsorption equilibrium,kinetics,and dynamic separation of Ca2+and Mg2+ions by strong acid cation resin,and the effects of phosphoric acid and nitric acid on the adsorption process were investigated.The results reveal that the adsorption process of Ca2+and Mg2+ions in pure water on resin is in good agreement with the Langmuir isotherm model and their maximal adsorption capacities are 1.86 mmol·g-1 and 1.83 mmol·g-1,respectively.The adsorption kinetics of Ca2+and Mg2+ions on resin fits better with the pseudo-first-order model,and the adsorption equilibrium in pure water is reached within 10 min contact time,while at the present of phosphoric acid,the adsorption rate of Ca2+and Mg2+ions on resin will go down.The dynamic separation experiments demonstrate that the designed column adsorption is able to undertake the separation of metal ions from the mix acids aqueous solution,but the dynamic operation should control the flow rate of mix acid solution.Besides nitric acid solution was proved to be effective to completely regenerate the spent resin and achieve the recyclable operation of separation process.

变形处理对Mg-Li合金显微组织演变和力学性能的影响

镁锂合金具有较高的比强度和比刚度、优秀的电磁屏蔽效应和阻尼性能等优点,是目前最轻的金属结构材料,在自动化、航空、交通运输、医疗等领域有广泛的应用前景。但是,和其他金属结构材料相比,镁锂合金的强度仍然偏低,需要对镁锂合金进行合金化或者变形处理来提高力学性能。总结了各类变形处理镁锂合金的研究现状,讨论了常规变形加工和剧烈塑性变形加工对镁锂合金显微组织和力学性能的影响,并总结了变形加工过程中形变量和温度对显微组织和力学性能的影响,以及镁锂合金的几种晶粒细化机制,阐述了镁锂合金在工业应用中遇到的问题。晶粒细化和加工硬化目前仍然是提高镁锂合金性能的主要手段。强调了几种变形和结构设计(异质材料),这将有助于镁锂合金的创新工作,从而得到高强度镁锂合金。

Al−Cu−Li−Mg合金纳米相之间溶质配分行为的第一性原理研究

采用一性原理计算考察25种合金化元素在大多数商业牌号Al−Cu−Li−Mg合金中主要纳米相(δʹ-Al3Li、θʹ-Al2Cu、T1-Al6Cu4Li3和S-Al2CuMg)之间的溶质配分能和配分行为。计算结果表明,主合金化元素Li不能直接影响θʹ和S相,Cu不能直接影响δʹ相,Mg不能直接影响θʹ和δʹ相,但可以较弱地固溶于T1相。对于微合金化元素,Si是唯一一种可以固溶于4种纳米相的元素。Au能固溶于δʹ、θʹ和S相,Cd能固溶于δʹ、T1和S相,Zr能固溶于δʹ和T1相,Ni仅有微弱的趋势固溶于θʹ和S相。Ti、V、Zn、Ag和Mo只能固溶于δʹ相,而Cr、Mn、Fe和Co对这4种纳米相均没有直接影响。几乎所有的稀土元素均能强烈固溶于T1、δʹ和S相,但无法固溶于θʹ相。仅Sc略显特殊,对S相没有明显的固溶趋势。计算预测的溶质配分能构成了一个原型数据库,有利于指导和加速Al−Li合金及其他相关Al合金的设计。

不同Mg/Li比对粉末冶金Al-Mg-Li合金显微组织及力学性能的影响

采用粉末冶金工艺和热挤压方法制备了Al-Mg-Li合金,并通过金相显微镜、扫描电子显微镜、透射电子显微镜和拉伸试验机对合金的微观组织、断口形貌和力学性能进行了分析。研究了不同Mg/Li比(1.3、1.8、2.5)对合金在烧结态、挤压态和T6热处理态下的微观组织和力学性能的影响。结果显示,随着Mg/Li比的增加,烧结态合金的相对密度增加,表明Mg元素对烧结过程具有促进作用。对于挤压态Al-Mg-Li合金,随着Mg/Li比的增加,合金中含Mg的析出相逐渐增多,并聚集在晶界附近,力学性能得到了很大提高,抗拉强度由285 MPa增加至407 MPa。经T6热处理后,Al-Mg-Li合金的第二相主要由δ′相和T相组成,其中δ′相是主要的强化相,均匀分布在铝基体中,而T相在晶界处呈链状分布。研究表明,提高Mg/Li比可以提高Al-Mg-Li合金的抗拉强度和屈服强度,但延伸率可能会有所下降。T6热处理后Al-5Mg-2Li合金可达到抗拉强度532 MPa、屈服强度473 MPa、延伸率4.5%。

微弧氧化后Mg-8Li合金表面MgLiAlY-LDHs@GO膜层的生长及耐蚀性能

目的提高Mg-8Li合金的耐蚀性能。方法首先在Mg-8Li合金表面制备微弧氧化膜(MAO),然后使用原位水热法在微弧氧化膜表面原位生长掺杂氧化石墨烯(GO)的四元(MgLiAlY)层状双羟基金属氧化物(LDHs)智能自修复膜层。采用SEM、XRD、FT-IR、EDS、ICP等手段研究MgLiAlY-LDHs@GO膜层的形貌、结构以及成分。通过EIS、Tafel以及浸泡试验等研究膜层的耐蚀性能,分析膜层的腐蚀行为,阐释其耐蚀机理。结果GO的掺杂可以促使LDHs纳米片生长得更加致密,主体层板中具有缓蚀作用的Y3+可以提高涂层的耐蚀性,四元LDHs的生长所需要的Mg^(2+)、Li^(+)、Al^(3+)等离子来源于镁锂合金基体以及微弧氧化膜的溶解,其中Li+也可以促进LDHs纳米片生长得更为均匀细密。膜层的腐蚀电流密度为6.03×10^(–7)A/cm^(2),比MAO膜层降低了1个数量级,提高了镁锂合金的耐蚀性能。结论GO的负载使LDHs的耐蚀性能和膜层稳定性均有一定程度的提升,引入稀土元素Y会改变LDHs的骨架,造成晶格畸变,使得LDHs微观形貌呈现褶皱状,剩下部分以Y(OH)3形式存在于涂层表面,可进一步提高膜层的耐蚀性能和稳定性。

Zn和Gd元素含量和比例对铸态和挤压态Mg-8Li合金显微组织和力学性能的影响

研究Zn和Gd元素含量及其质量比对铸态和挤压态Mg-8Li合金显微组织和力学性能的影响。挤压后,析出相破碎。β-Li中分散着粒径约100 nm的球形微粒。形成了由长条状α-Mg粗晶和再结晶β-Li细晶组成的双峰结构。挤压后合金的强度和塑性显著提高,且屈服强度和极限抗拉强度随Zn和Gd含量的增加而增加。Mg-8Li-8Zn-2Gd合金表现出最优的综合性能,其屈服强度、极限抗拉强度和伸长率分别为274 MPa、283 MPa和39.9%。挤压态合金主要强化机制为由β-Li的细晶强化和α-Mg的织构强化组成的双模态结构强化和析出相的弥散强化。

高强耐蚀1420Al-Li/Mg-9Li/1420Al-Li复合板制备及力学性能

采用高强耐蚀超轻1420 Al-Li合金作为覆板,通过一道次热轧制备了1420Al-Li/Mg-9Li/1420Al-Li复合板,研究了不同压下量、450℃热轧复合板界面的微观组织和力学性能。结果表明:当轧制压下量为35%时,复合板仅为部分结合—机械结合+冶金结合,界面无化合物生成,复合板的抗拉强度为236 MPa,伸长率为26%;当轧制压下量为50%时,复合板实现完全冶金结合,无界面化合物生成,复合板的抗拉强度高达272 MPa,伸长率为14%,在提高抗腐蚀性的同时,大幅提高了Mg-9Li合金的强度。

A multifunctional separator with Mg(OH)2 nanoflake coatings for safe lithium-metal batteries

Dendrite growth and thermal runaway induce serious safety hazards,impeding the practical applications of lithium metal batteries(LMBs).Although extensive advances have been attained in terms of LMB safety,most work only focus on a single aspect at a time.This paper reports a multifunctional separator coated by Mg(OH)2 nanoflakes with various excellent properties including electrolyte wettability,ionic conductivity,Li+ transference number,puncture strength,thermal stability and flame retardance.When used in LMBs,the Mg(OH)2 nanoflake coatings enable uniform Li+ distributing,which makes it homogeneous to deposit lithium,realizing effective dendrite suppression and less volume expansion.Meanwhile,Mg(OH)2 coatings can ensure LMBs are in normal conditions without thermal runaway until 140 ℃.A part of lithium can be converted into Li+ ions by Mg(OH)2 during repeated charge/discharge cycles,not only reducing the risk of separator damage and consequent short circuit,but also replenishing the capacity loss of LMBs.The Mg(OH)2 nanoflakes can coat on all kinds of commercial separators to improve their performances,which offers a facile but effective strategy for fabricating multifunctional separators and a comprehensive insight into enhancing LMB safety.

Mg^(2+)掺杂对富锂层状氧化物材料Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_(2)的影响

Mg^(2+)作为一种电化学惰性的阳离子,由于其离子半径(0.072 nm)与Li^(+)的离子半径(0.076 nm)相近,因此被广泛应用于取代富锂层状氧化物(LLOs)材料中Li^(+)的位置。然而,Mg^(2+)对LLOs材料晶体结构的影响还存在争议。利用溶胶凝胶法成功制备了一系列Mg^(2+)掺杂富锂正极材料Li_(1.2-x)Mg_(x)Mn_(0.54)Ni_(0.13)Co_(0.13)O_(2),通过X射线衍射仪和X射线光电子能谱等对其晶体结构和元素价态进行了系统的研究。结果表明,Mg^(2+)掺杂导致LLOs材料晶胞参数的增加。通过与Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_(2)材料的电化学性能对比发现,Mg^(2+)掺杂有效地提高了LLOs材料的电化学性能。经过优化后,Mg-0.03样品展现出最优异的电化学性能,在0.1 C倍率下的初始放电比容量为291.9 mA•h/g,首圈库伦效率为78.40%。

Improvement of microstructure and mechanical properties of Al−Cu−Li−Mg−Zn alloys through water-cooling centrifugal casting technique

The microstructure and mechanical properties of as-cast Al−Cu−Li−Mg−Zn alloys fabricated by conventional gravity casting and centrifugal casting techniques combined with rapid solidification were investigated.Experimental results demonstrated that compared with the gravity casting technique,the water-cooling centrifugal casting technique significantly reduces porosity,refinesα(Al)grains and secondary phases,modifies the morphology of secondary phases,and mitigates both macro-and micro-segregation.These improvements arise from the synergistic effects of the vigorous backflow,centrifugal field,vibration and rapid solidification.Porosity and coarse plate-like Al13Fe4/Al7Cu2Fe phase result in the fracture before the gravity-cast alloy reaches the yield point.The centrifugal-cast alloy,however,exhibits an ultra-high yield strength of 292.0 MPa and a moderate elongation of 6.1%.This high yield strength is attributed to solid solution strengthening(SSS)of 225.3 MPa,and grain boundary strengthening(GBS)of 35.7 MPa.Li contributes the most to SSS with a scaling factor of 7.9 MPa·wt.%^(-1).The elongation of the centrifugal-cast alloy can be effectively enhanced by reducing the porosity and segregation behavior,refining the microstructure and changing the morphology of secondary phases.

A Single-Layer Piezoelectric Composite Separator for Durable Operation of Li Metal Anode at High Rates

Piezoelectric ceramic and polymeric separators have been proposed to effectively regulate Li deposition and suppress dendrite growth,but such separators still fail to satisfactorily support durable operation of lithium metal batteries owing to the fragile ceramic layer or low-piezoelectricity polymer as employed.Herein,by combining PVDF-HFP and ferroelectric BaTiO_(3),we develop a homogeneous,single-layer composite separator with strong piezoelectric effects to inhibit dendrite growth while maintaining high mechanical strength.As squeezed by local protrusion,the polarized PVDF-HFP/BaTiO_(3)composite separator generates a local voltage to suppress the local-intensified electric field and further deconcentrate regional lithium-ion flux to retard lithium deposition on the protrusion,hence enabling a smoother and more compact lithium deposition morphology than the unpoled composite separator and the pure PVDF-HFP separator,especially at high rates.Remarkably,the homogeneous incorporation of BaTiO_(3)highly improves the piezoelectric performances of the separator with residual polarization of 0.086 pC cm^(-2)after polarization treatment,four times that of the pure PVDF-HFP separator,and simultaneously increases the transference number of lithium-ion from 0.45 to 0.57.Beneficial from the prominent piezoelectric mechanism,the polarized PVDF-HFP/BaTiO_(3)composite separator enables stable cyclic performances of Li||LiFePO_(4)cells for 400 cycles at 2 C(1 C=170 mA g^(-1))with a capacity retention above 99%,and for 600 cycles at 5 C with a capacity retention over 85%.

Electronic Phase Separation in Iron Selenide(Li,Fe)OHFeSe Superconductor System

The phenomenon of phase separation into antiferromagnetic（AFM） and superconducting（SC） or normal-state regions has great implication for the origin of high-temperature（high-T_c） superconductivity. However, the occurrence of an intrinsic antiferromagnetism above the T_c of（Li,Fe）OHFe Se superconductor is questioned. Here we report a systematic study on a series of（Li,Fe）OHFe Se single crystal samples with T_c up to ～41 K. We observe an evident drop in the static magnetization at T_（afm） ～ 125 K, in some of the SC（T_c 38 K, cell parameter c■9.27 ？） and non-SC samples. We verify that this AFM signal is intrinsic to（Li,Fe）OHFe Se. Thus, our observations indicate mesoscopic-to-macroscopic coexistence of an AFM state with the normal（below T_（afm）） or SC（below T_c） state in（Li,Fe）OHFe Se. We explain such coexistence by electronic phase separation, similar to that in high-T_c cuprates and iron arsenides. However, such an AFM signal can be absent in some other samples of（Li,Fe）OHFe Se, particularly it is never observed in the SC samples of T_c 38 K, owing to a spatial scale of the phase separation too small for the macroscopic magnetic probe. For this case, we propose a microscopic electronic phase separation. The occurrence of two-dimensional AFM spin fluctuations below nearly the same temperature as T_（afm）, reported previously for a（Li,Fe）OHFe Se（T_c ～ 42 K） single crystal, suggests that the microscopic static phase separation reaches vanishing point in high T_c（Li,Fe）OHFe Se. A complete phase diagram is thus established. Our study provides key information of the underlying physics for high-T_c superconductivity.

挤压比对双相Mg-8Li-6Zn-2Gd合金显微组织、织构和力学性能的影响

通过显微组织观察、织构分析和拉伸测试等手段研究挤压比对双相Mg-8Li-6Zn-2Gd合金显微组织、织构和力学性能的影响。结果表明:均匀化态Mg-8Li-6Zn-2Gd合金中含有α-Mg、β-Li、Mg Li Zn、I相和W相。经热挤压后,共晶I相被碾碎成细小颗粒状,而W相保持原有块状形状。合金中α-Mg基体和β-Li基体在热挤压过程中均发生了动态再结晶(DRX),且晶粒随着挤压比的增加逐渐细化。经热挤压后,α-Mg基体的基面织构弱化和柱面织构增强是由于非基面滑移的激活;β-Li基体中形成明显的α和γ纤维织构主要与动态回复与动态再结晶相关。热挤压同时提升Mg-8Li-6Zn-2Gd合金的抗拉强度和伸长率,并在挤压比为16:1时获得最佳的综合力学性能。

STUDIES ON SEPARATION AND DETERMIINATION OF THE LIGNANS IN DIPHYLLEIA SIENSIS LI BY RP-HPLC

A simple,sensitive and accurate RP-HPLC method for the separation and determination of eight lignans in Diphylleia sinensis was described.The method has been applied to the analysis of different samples.

Mg-Li-Al-Zn-RE合金铸态和退火态的组织与性能

制备了Mg-xLi-5Al-1Zn-0.8RE系合金。研究了不同Li含量和均匀化退火工艺对Mg-xLi-5Al-1Zn-0.8RE系合金组织及性能的影响。结果表明,随着Li含量增加,合金的强度下降,塑性变形能力提高;随均匀化退火温度的升高和时间的延长合金中α相发生了融合和长大,显微硬度增加。

微量Ag,Mg对Al-Cu-Li合金时效特性和显微组织的影响

研究了微量Ag,Mg对Al-Cu-Li合金显微组织和时效特性的影响。结果表明:单独加Ag对Al-Cu-Li系2197合金的固溶强化效果很小,但有较强的时效强化作用,Ag含量不同,时效强化效果也不同;Ag,Mg共同加入提高了T1相(Al2CuLi)的析出速率和析出密度,使合金具有较大的固溶强化效果及最强烈的时效响应和时效强化效果。Ag,Mg的添加对合金的不同影响可通过溶质原子与空位、溶质原子与溶质原子之间的相互作用来解释。

超轻Mg-Li-Al系变形镁合金冷轧及热处理后的组织和性能

研究了超轻变形镁合金Mg (5% ~ 22%)Li 2%Al冷轧性能,热处理特性以及机械性能。合金的密度为1.206~1.642g/cm3。在室温条件下β相合金(16%和22%(质量分数)Li)具有非常良好的延展性,压下极限可达到90%以上。研究了Mg Li Al 系变形镁合金铸锭经不同温度、时间均匀化退火后的组织性能。对均匀化后的合金锭进行了冷轧,轧后板材在不同温度下进行了退火,研究其再结晶行为及组织性能。结果表明, Mg 9Li 2Al 2Ca合金在573K温度均匀化退火12h后合金铸锭组织均匀,有利于冷轧开坯变形;而对于Mg 9Li 2Al 合金, 523K 温度均匀化退火24h后组织较好。冷轧合金板材在573K温度退火1h 可发生完全再结晶,生成细小均匀的等轴晶组织。

Ca对变形Mg-9Li-2Zn合金显微组织和机械性能的影响

实验熔制了Mg9％Li-2％Zn（质量分数）合金并研究了添加质量分数为0.1％～0．5％的巳对合金的影响．合金板材具有良好的冷加工性能，室温下可以轧成2mm厚的薄板．研究了微量元素巳对板材显微组织和机械性能的影响．室温下对板材进行拉伸测试，结果表明添加元素已能够提高合金的机械性能，当添加质量分数为0．1％的Ca时，板材的抗拉强度和延伸率分别提高了19％和6％，随着Ca含量的增加，强度略有提高而延伸率下降．通过显微观察可知，Ca对显微组织有细化作用，其中含Ca0．1％时效果最明显．通过分析结果可知Ca在晶界处的吸附致使显微组织细化，进而影响了板材的机械性能．

Mg-9Li-5Gd-1Zr合金的组织转变及力学性能

采用常规熔炼工艺制备Mg-9Li-5Gd-1Zr合金,考察了合金元素、均匀化热处理及ECAP挤压对Mg-9Li双相合金组织转变与力学性能的影响。结果表明,合金元素Gd和Zr能显著细化Mg-9Li双相合金中的α-Mg相,使其成为细小的条状,并均匀分布于基体中;与形成的具有取向分布的针状Mg3Gd对铸态合金起主要强化作用。均匀化热处理使β-Li基体晶粒明显长大;β-Li基体内的针状Mg3Gd相发生部分溶解、数量急剧减少;条状α-Mg相沿晶界偏聚长大,形成块状;合金强度较铸态略有下降,伸长率显著提高。ECAP一道次挤压在细化基体组织,改善组织均匀性的同时,导致均匀化处理合金中条状α-Mg相和针状Mg3Gd相破碎细化,诱导回溶的Mg3Gd相沿流变方向再次析出,合金较均匀化处理的强度、塑性均有所下降。

Al-Li-Mg(Ti)合金形成焓的EAM研究

采用普适分析型的嵌入原子模型,通过拟合纯元素的晶格常数、空位形成能、结合能和体积弹性模量等,确定了Al、Li、Mg和Ti4个元素的嵌入原子模型参数.不同元素之间的相互作用势的参数由拟合实验或第一原理计算结果确定.用确定的嵌入原子模型分别计算了由Al、Li、Mg和Ti元素构成的二元系以及三元系中的有序合金化合物的形成焓,计算结果与已有的实验结果和第一原理计算结果符合得比较好.