添加C10H10Cl2Ti对6LiBH4-CaH2-3MgH2体系储氢性能的影响

C_(10)H_(10)Cl_2Ti的添加可以有效改善6LiBH_4-CaH_2-3MgH_2样品吸放氢性能,添加的质量分数为5%时具有较好的催化效果。样品的起始和终止放氢温度比原始样品分别降低约30和25℃,可逆储氢量(质量分数)约为8.1%。添加C_(10)H_(10)Cl_2Ti催化剂的样品在360℃下等温放氢速率比原始样品提高了178%。两步放氢反应的表观活化能分别为131.4和138.8 kJ·mol~(-1),相比原始样品降低了约18.6%和15.8%。利用X射线光电子能谱(X-ray photoelectron spectroscopy,XPS)对样品进行分析发现,热分解过程中C_(10)H_(10)Cl_2Ti生成了多价态的Ti化合物,催化了LiBH_4与CaH_2的反应,从而改善了复合体系的储氢性能。     

Mg2 FeH6 纳米晶的制备及储氢性能

在室温和氩气气氛下, 以MgH2 和纳米Fe为原料, 采用机械合金化(球磨法)制备了Mg2FeH6纳米晶. 考察了球磨参数(时间、 转速)对产物的影响, 对所制备的Mg2FeH6 纳米晶的组成、 结构和形貌进行了表征, 并对其储氢性能进行了测试. 结果表明, 所制备的Mg2FeH6纳米晶为立方结构, 纯度较高(91.4%), 其晶粒尺寸较小, 约为10~30 nm, 但团聚现象较为严重. Mg2FeH6纳米晶具有较低的活化能和较好的吸放氢动力学性能, 其放氢的脱附焓和脱附熵分别为(-42.8±2) kJ/mol和(-72.0±3) J/(mol·K). 在503 K和6 kPa的氢气压力下, Mg2FeH6纳米晶在70 min内放氢量达到2.5%(质量分数); 在2 MPa的氢气压力下, 上述放氢产物具有较快的起始吸氢速率.     

MgH2+20%(w)MgTiO3复合材料的吸/放氢性能

为了降低MgH₂的吸放氢温度, 提高其吸放氢动力学性能, 本文通过球磨方法制备了MgH₂+20%(w)MgTiO₃复合储氢材料, 并研究了其储氢性能. X射线衍射(XRD)结果表明, MgTiO₃在与MgH₂球磨过程中生成Mg₂TiO₄和TiO₂, 并且Mg₂TiO₄和TiO₂在体系的吸放氢过程中保持稳定, 能够对MgH₂的吸放氢过程产生催化作用. 程序升温脱附和吸/放氢动力学测试结果表明, 添加MgTiO₃后MgH₂的初始放氢温度从389 ℃降至249 ℃.150 ℃下的吸氢量从0.977%(w)提高到2.902%(w), 350 ℃下的放氢量从2.319%(w)提高到3.653%(w). 同时, MgH₂放氢反应的活化能从116 kJ·mol^-1降至95.7 kJ·mol^-1. 与MgH₂相比, MgH₂+20%(w) MgTiO₃复合材料的热力学与动力学性能均有显著提高, 这主要是由于球磨和放氢过程中原位生成的TiO₂和Mg₂TiO₄具有良好的催化活性.     

添加叔丁醇钾对Mg(NH2)2-2LiH体系储氢性能的影响

叔丁醇钾(C_4H_9OK)的添加显著改善了Mg(NH_2)_2-2LiH体系的储氢性能。添加0.08 mol C_4H_9OK的Mg(NH_2)_2-2LiH-0.08C_4H_9OK样品表现出最佳储氢性能。该样品的起始放氢温度仅为70℃,较Mg(NH_2)_2-2LiH原始样品降低了60℃;130℃完全放氢后,该样品可在50℃开始吸氢,较原始样品降低了50℃。Mg(NH_2)_2-2LiH-0.08C_4H_9OK样品可在150℃的等温条件下50min内迅速放出质量分数3.82%的氢气,完全放氢后可在120℃的等温条件下50 min内快速吸收质量分数4.11%的氢气,表现出良好的吸放氢动力学性能。C_4H_9OK的添加降低了样品放氢反应的表观活化能和反应焓变,改善了放氢反应的动力学和热力学性能,从而降低了放氢反应温度。进一步的放氢反应机理研究发现,在180℃之前,C_4H_9OK对Mg(NH_2)_2-2LiH体系的放氢起催化改性作用;温度继续升高后,C_4H_9OK将会分解并参与放氢反应最终生成Li_3K(NH_2)_4。     

MgH_2+20%(w)MgTiO_3复合材料的吸/放氢性能(英文)

为了降低MgH2的吸放氢温度,提高其吸放氢动力学性能,本文通过球磨方法制备了MgH2+20%(w)MgTiO3复合储氢材料,并研究了其储氢性能.X射线衍射(XRD)结果表明,MgTiO3在与MgH2球磨过程中生成Mg2TiO4和TiO2,并且Mg2TiO4和TiO2在体系的吸放氢过程中保持稳定,能够对MgH2的吸放氢过程产生催化作用.程序升温脱附和吸/放氢动力学测试结果表明,添加MgTiO3后MgH2的初始放氢温度从389°C降至249°C.150°C下的吸氢量从0.977%(w)提高到2.902%(w),350°C下的放氢量从2.319%(w)提高到3.653%(w).同时,MgH2放氢反应的活化能从116kJ·mol-1降至95.7kJ·mol-1.与MgH2相比,MgH2+20%(w)MgTiO3复合材料的热力学与动力学性能均有显著提高,这主要是由于球磨和放氢过程中原位生成的TiO2和Mg2TiO4具有良好的催化活性.     

La-H化合物对LaMg2Ni合金中Mg2Ni相吸氢过程的影响

采用感应熔炼技术在Ar气氛保护下制备得到LaMg2Ni与Mg2Ni合金。X射线衍射(XRD)图表明LaMg2Ni合金在吸氢过程中分解为LaH3相和Mg2NiH4相,放氢过程中LaH3相转化为La3H7相。与Mg2Ni合金相比,LaMg2Ni合金显示出优良的吸氢动力学性能,这是由于镧氢化合物的存在及其在吸氢过程中所发生的相转变所造成的。LaMg2Ni合金280 s内吸氢即可达到最大储氢量的90%以上,而Mg2Ni合金则需要1200 s才能达到,且在相同温度下LaMg2Ni合金的吸氢反应速率常数大于Mg2Ni合金速率常数。镧氢化合物不仅有利于改善动力学性能,而且可以提高热力学性能。LaMg2Ni合金中的Mg2Ni相氢化反应焓与熵分别为-53.02 kJ.mol-1和84.96 J.K-1.mol-1(H2),这一数值小于单相Mg2Ni氢化反应焓与熵(-64.50 kJ.mol-1,-123.10 J.K-1.mol-1(H2))。压力-组成-温度(P-C-T)测试结果表明在603 K至523 K温度范围内,LaMg2Ni合金储氢容量保持稳定为1.95wt%左右,然而Mg2Ni合金的储氢容量则由4.09wt%衰减为3.13wt%,Mg2Ni合金的储氢容量在523K低温下仅为603 K时的76.5%,表明镧氢化合物能够改善Mg2Ni合金低温下的吸放氢性能。     

镨、钕氢化物催化剂对NaH/Al复合物吸放氢性能的影响

采用NaH和Al为合成原料,镨、钕氢化物为催化剂,通过机械球磨(NaH/Al+6%(摩尔分数)RE-H)(RE=Pr,Nd)复合物的方法并加氢合成NaAlH4络合氢化物,系统研究了催化剂对其吸放氢性能的影响。结果表明,加入PrH2.92和NdH2.27能明显改善NaH/Al复合物的吸放氢动力学性能,有效降低NaAlH4的脱氢温度。(NaH/Al+6%PrH2.92)和(NaH/Al+6%NdH2.27)复合物的120℃吸氢容量分别为3.57%和3.61%(质量分数),170℃放氢容量分别为2.57%和2.95%;且两者均具有较好的吸放氢循环稳定性,但吸(放)氢后样品中均存在少量Na3AlH6相,表明样品的吸(放)氢反应进行得并不彻底,使得其实际吸放氢容量低于理论可逆储氢容量。研究表明,PrH2.92和NdH2.27在球磨、吸/放氢过程中始终稳态存在,起着催化储氢作用;(NaH/Al+6%PrH2.92)复合物的放氢活化能稍低于(NaH/Al+6%NdH2.27)复合物。     

Ti-Zr催化剂对NaH/A1复合物可逆储氢特性的影响

采用机械球磨(NaH/A1 Ti)和(NaH/A1 Ti-Zr)复合物的方法加氢制备了NaAIH4配位氢化物,系统研究了Ti、Ti-Zr催化剂以及不同加氢条件对其可逆储氢行为的影响.结果表明,对于NaH/A1体系的吸放氢性能,共掺金属Ti粉/Zr粉的催化作用比单独掺金属Ti粉的催化作用要好.随着加氢温度从85 ℃上升到140 ℃,体系的吸氢容量先增后减,并在120 ℃时达到最大值;同时,发现共掺Ti-Zr催化剂的复合物具有最佳的储氢性能,在120和85℃时的吸氢量分别为4.61％和3.52％(w),比仅掺Ti催化剂的复合物分别高出0.40％和0.70％(w)的吸氢量.随着加氢压力的增大,(NaH/A1 Ti-Zr)复合物的吸氢性能随之提高.XRD和DSC分析结果表明,NaA1H4体系的放氢过程明显发生两步分解反应,共掺Ti-Zr催化剂的复合物储氢性能优于单独掺Ti催化剂的原因是,共掺催化剂能有效改善NaA1H4体系吸放氢反应的动力学性能,并降低体系的放氢温度.     

固溶体MAX相(Ti0.5V0.5)3AlC2的制备及其对MgH2储氢性能的催化影响

通过无压烧结法制备了固溶体MAX相(Ti_(0.5)V_(0.5))_3AlC_2,研究了其添加对MgH_2储氢性能的影响。结果发现,固溶体MAX相(Ti_(0.5)V_(0.5))_3AlC_2中的Ti和V元素通过协同作用,呈现出更高的催化活性。添加质量分数10%(Ti_(0.5)V_(0.5))_3AlC_2的MgH_2样品的起始放氢温度为230℃,较原始MgH_2降低了60℃。在275℃下等温放氢,(Ti_(0.5)V_(0.5))_3AlC_2添加样品的放氢速率可达0.35%·min~(-1),是原始MgH_2样品的4倍左右。此外,完全放氢后的MgH_2-10%(Ti_(0.5)V_(0.5))_3AlC_2样品在150℃、5 MPa氢压下,可在60 s内吸收4.7%的氢。计算显示,MgH_2-10%(Ti_(0.5)V_(0.5))_3AlC_2样品的表观活化能为79.6 kJ·mol~(-1),较原始MgH_2(153.8 kJ·mol~(-1))降低了48%,这是MgH_2放氢性能得到改善的主要原因。     

Fe2O3与TiF3添加剂对LiBH4-MgH2复合氢化物体系的协同催化作用

通过球磨方法制备出2LiBH4-MgH2,2LiBH4-MgH2-10%Fe2O3,2LiBH4-MgH2-10%TiF3,2LiBH4-MgH2-5%Fe2O3-5%TiF3和2LiBH4-MgH2-10%Fe2O3-10%TiF35个复合氢化物体系,用热重(TG)、差示扫描量热(DSC)、X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)和压力-组成-温度仪(PCT)等对所制备体系进行表征.结果表明,Fe2O3和TiF3的掺杂均能够有效地改善2LiBH4-MgH2复合体系的放氢性能,尤其是两者共掺杂的2LiBH4-MgH2-10%Fe2O3-10%TiF3体系,初始放氢温度为110℃,总放氢量达到约9.6%.对2LiBH4-MgH2-5%Fe2O3-5%TiF3体系的PCT表征结果表明,在400℃时,10 min内放氢量达到了8.6%,放氢热力学和放氢动力学均优于单一相的掺杂,体现了两相掺杂的协同催化作用.     

Hydrogen storage over alkali metal hydride and alkali metal hydroxide composites

Alkali metal hydroxide and hydride composite systems contain both protic(H bonded with O) and hydridic hydrogen. The interaction of these two types of hydrides produces hydrogen. The enthalpy of dehydrogenation increased with the increase of atomic number of alkali metals,i.e.,-23 kJ/molH2 for LiOH-LiH, 55.34 kJ/molH2 for NaOH-NaH and 222 kJ/molH2 for KOH-KH. These thermodynamic calculation results were consistent with our experimental results. H2 was released from LiOH-LiH system during ball milling. The dehydrogenation temperature of NaOH-NaH system was about 150℃; whereas KOH and KH did not interact with each other during the heating process. Instead, KH decomposed by itself. In these three systems, NaOH-NaH was the only reversible hydrogen storage system, the enthalpy of dehydrogenation was about 55.65 kJ/molH2, and the corresponding entropy was ca. 101.23 J/(molH2 K), so the temperature for releasing 1.0 bar H2 was as high as 518℃, showing unfavorable thermodynamic properties. The activation energy for hydrogen desorption of NaOH-NaH was found to be57.87 kJ/mol, showing good kinetic properties.     

Reversible storage of hydrogen in destabilized LiBH4

Destabilization of LiBH4 for reversible hydrogen storage has been studied using MgH2 as a destabilizing additive. Mechanically milled mixtures of LiBH4 + (1/2)MgH2 or LiH + (1/2)MgB2 including 2-3 mol % TiCl3 are shown to reversibly store 8-10 wt % hydrogen. Variation of the equilibrium pressure obtained from isotherms measured at 315-400 degrees C indicate that addition of MgH2 lowers the hydrogenation/dehydrogenation enthalpy by 25 kJ/(mol of H2) compared with pure LiBH4. Formation of MgB2 upon dehydrogenation stabilizes the dehydrogenated state and, thereby, destabilizes the LiBH4. Extrapolation of the isotherm data yields a predicted equilibrium pressure of 1 bar at approximately 225 degrees C. However, the kinetics were too slow for direct measurements at these temperatures.     

Body centered cubic magnesium niobium hydride with facile room temperature absorption and four weight percent reversible capacity

We have synthesized a new metastable metal hydride with promising hydrogen storage properties. Body centered cubic (bcc) magnesium niobium hydride (Mg(0.75)Nb(0.25))H(2) possesses 4.5 wt% hydrogen gravimetric density, with 4 wt% being reversible. Volumetric hydrogen absorption measurements yield an enthalpy of hydride formation of -53 kJ mol(-1) H(2), which indicates a significant thermodynamic destabilization relative to the baseline -77 kJ mol(-1) H(2) for rutile MgH(2). The hydrogenation cycling kinetics are remarkable. At room temperature and 1 bar hydrogen it takes 30 minutes to absorb a 1.5 μm thick film at sorption cycle 1, and 1 minute at cycle 5. Reversible desorption is achieved in about 60 minutes at 175 °C. Using ab initio calculations we have examined the thermodynamic stability of metallic alloys with hexagonal close packed (hcp) versus bcc crystal structure. Moreover we have analyzed the formation energies of the alloy hydrides that are bcc, rutile or fluorite.     

LiAlH4与LiNH2的相互作用机理及储氢特性

将LiAlH4和LiNH2按摩尔比1：2进行球磨复合,随后将复合物进行加热放氢特性研究,然后对其完全放氢后的产物进行再吸氢特性研究。通过X射线衍射分析(XRD)、热分析(DSC)和红外 (FTIR)分析等测试手段对其反应过程进行了系统分析研究。研究结果表明,LiAlH4/2LiNH2加热放氢分为3个反应阶段,放氢后生成Li3AlN2,总放氢量达到8.65wt%。放氢生成的Li3AlN2在10MPaH2压力和400℃条件下,可以可逆吸氢5.0wt%,吸氢后的产物为 LiNH2 、AlN和LiH,而不能再生成LiAlH4。本文对LiAlH4/2LiNH2复合物放氢/再氢化过程机理进行了分析。     

Hydrogen release from Mg(NH2)2-MgH2 through mechanochemical reaction

A total of 7.4 wt % of hydrogen was released from the mixture of magnesium amide and magnesium hydride at a molar ratio of 1:2 by mechanical ball milling. Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Diffraction (XRD) characterizations along with the amount of hydrogen released at different stages of ball milling reveal that magnesium imide was first formed in the reaction. The imide then reacted continuously with magnesium hydride and was converted to magnesium nitride and hydrogen. Thermodynamic calculation shows that the hydrogen desorption is a mild endothermic reaction with the standard enthalpy change of about 3.5 kJ/mol of H2.     

Hydrogen desorption exceeding ten weight percent from the new quaternary hydride Li3BN2H8

Mobile applications of hydrogen power have long demanded new solid hydride materials with large hydrogen storage capacities. We report synthesis of a new quaternary hydride having the approximate composition Li(3)BN(2)H(8) with 11.9 wt % theoretical hydrogen capacity. It forms by reacting LiNH(2) and LiBH(4) powders in a 2:1 molar ratio either by ball milling or by heating the mixed powders above 95 degrees C. This new quaternary hydride melts at approximately 190 degrees C and releases > or =10 wt % hydrogen above approximately 250 degrees C. A small amount of ammonia (2-3 mol % of the generated gas) is released simultaneously. Preliminary calorimetric measurements suggest that hydrogen release is exothermic and, hence, not easily reversible.     

机械球磨固相化学反应制备AlH3及其放氢性能

以LiAlH4和AlCl3为原料, 采用机械球磨固相化学反应方法制备了铝氢化合物, 通过X射线衍射(XRD)、热分析(TG-DSC)和质谱(MS)分析等方法对反应产物进行分析和表征, 研究了不同球磨时间(4、8、15和20 h)对LiAlH4+AlCl体系的固相反应转变规律﹑合成产物和放氢性能的影响. 研究结果表明, 随球磨时间的增加, 球磨固相反应按3LiAlH4+AlCl3→4AlH3+3LiCl方向进行, 形成了非晶态铝氢化合物AlH3, 球磨20 h时反应基本完全. 球磨产物的放氢动力学特性随球磨时间增加而改善, 其放氢起始温度均低于100 ℃, 最大放氢量达到2.6%-3.6%(H2)(w), 接近反应体系的理论储氢量4.85%(H2)(w). 球磨过程中反应产物形成LiCl·H2O以及少量AlH3发生分解是影响球磨产物最大放氢量的主要因素.     

Improved Hydrogen‐Storage Thermodynamics and Kinetics for an RbF‐Doped Mg(NH2)2–2 LiH System

The introduction of RbF into the Mg(NH₂)₂–2 LiH system significantly decreased its (de‐)hydrogenation temperatures and enhanced its hydrogen‐storage kinetics. The Mg(NH₂)₂–2 LiH–0.08 RbF composite exhibits the optimal hydrogen‐storage properties as it could reversibly store approximately 4.76 wt % hydrogen through a two‐stage reaction with the onset temperatures of 80 °C for dehydrogenation and 55 °C for hydrogenation. At 130 °C, approximately 70 % of hydrogen was rapidly released from the 0.08 RbF‐doped sample within 180 min, and the fully dehydrogenated sample could absorb approximately 4.8 wt % of hydrogen at 120 °C. Structural analyses revealed that RbF reacted readily with LiH to convert to RbH and LiF owing to the favorable thermodynamics during ball‐milling. The newly generated RbH participated in the following dehydrogenation reaction, consequently resulting in a decrease in the reaction enthalpy change and activation energy.     

Ti-Zr催化剂对NaH/Al复合物可逆储氢特性的影响

采用机械球磨(NaH/Al+Ti)和(NaH/Al+Ti-Zr)复合物的方法加氢制备了NaAlH4配位氢化物, 系统研究了Ti、Ti-Zr催化剂以及不同加氢条件对其可逆储氢行为的影响. 结果表明, 对于NaH/Al体系的吸放氢性能, 共掺金属Ti粉/Zr粉的催化作用比单独掺金属Ti粉的催化作用要好. 随着加氢温度从85 ℃上升到140 ℃, 体系的吸氢容量先增后减, 并在120 ℃时达到最大值; 同时, 发现共掺Ti-Zr催化剂的复合物具有最佳的储氢性能, 在120和85 ℃时的吸氢量分别为4.61%和3.52%(w), 比仅掺Ti 催化剂的复合物分别高出0.40%和0.70%(w)的吸氢量. 随着加氢压力的增大, (NaH/Al+Ti-Zr)复合物的吸氢性能随之提高. XRD和DSC分析结果表明, NaAlH4体系的放氢过程明显发生两步分解反应, 共掺Ti-Zr催化剂的复合物储氢性能优于单独掺Ti 催化剂的原因是, 共掺催化剂能有效改善NaAlH4体系吸放氢反应的动力学性能,并降低体系的放氢温度.     

机械合金化Mg/MmNi5-x(CoAlMn)x复合储氢合金的组织结构与吸氢特性

运用Ｘ射线衍射、扫描电及粒度分析等方法表征了机械合金化制备Ｍｇ／ＭｎＮｉ５－ｘ（ＣｏＡｌＭｎ）ｘ复合储氢合金的结构,通过ＰＣＴ曲线研究了基储氢性能。结果表明,在适当的球磨条件下能够获得纳米晶结构的Ｍｇ／ＭｎＮｉ５－ｘ（ＣｏＡｌＭｎ）ｘ复合储氢合金,ＭｍＮｉ５－ｘ（ＣｏＡｌＭｎ）ｘ合金相彘,复合储氢合金的活化性能及储氢量有明显提高。此外,还考察了Ｍｇ含量对复合储氢合金的组织结构及储氢性能的影响。