Enhancing the crystallinity and stability of perovskite solar cells with 4-tert-butylpyridine induction for efficiency exceeding 24%

Perovskite solar cells(PSCs)have emerged as a promising photovoltaic technology because of their high light absorption coefficient,long carrier diffusion distance,and tunable bandgap.However,PSCs face challenges such as hysteresis effects and stability issues.In this study,we introduced a novel approach to improve film crystallization by leveraging 4-tert-butylpyridine(TBP)molecules,thereby enhancing the performance and stability of PSCs.Our findings demonstrate the effective removal of PbI_(2)from the perovskite surface through strong coordination with TBP molecules.Additionally,by carefully adjusting the concentration of the TBP solution,we achieved enhanced film crystallinity without disrupting the perovskite structure.The TBP-treated perovskite films exhibit a low defect density,improved crystallinity,and improved carrier lifetime.As a result,the PSCs manufactured with TBP treatment achieve power conversion efficiency(PCE)exceeding 24%.Moreover,we obtained the PCE of 21.39%for the 12.25 cm^(2)module.

Mitigating kinetic hindrance of single-crystal Ni-rich cathodes through morphology modulation,nickel reduction,and lithium vacancy generation achieved by terbium doping

Single crystallization has proven to be effective in enhancing the capacity and stability of Ni-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(SNCM)cathode materials,particularly at high cut-off voltages.Nevertheless,the synthesis of high-quality single-crystal particles remains challenging because of severe particle agglomeration and irregular morphologies.Moreover,the limited kinetics of solid-phase Li^(+)diffusion pose a significant concern because of the extended diffusion path in large single-crystal particles.To address these challenges,we developed a Tb-doped single-crystal LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(SNCM-Tb)cathode material using a straightforward mixed molten salt sintering process.The Tb-doped Ni-rich single crystals presented a quasi-spherical morphology,which is markedly different from those reported in previous studies.Tb^(4+)oping significantly enhanced the dynamic transport of Li^(+)ions in the layered oxide phase by reducing the Ni valence state and creating Li vacancies.A SNCM-Tb material with 1 at%Tb doping shows a Li^(+)diffusion coefficient up to more than 9 times higher than pristine SNCM in the non-diluted state.In situ X-ray diffraction analysis demonstrated a significantly facilitated H1-H2-H3 phase transition in the SNCM-Tb materials,thereby enhancing their rate capacity and structural stability.SNCM-Tb exhibited a reversible capacity of 186.9 mA h g^(-1)at 5 C,retaining 94.6%capacity after 100 cycles at 0.5 C under a 4,5 V cut-off.Our study elucidates the Tb^(4+)doping mechanisms and proposes a scalable method for enhancing the performance of single-crystal Ni-rich NCM materials.

Surface deterioration dependent on the crystal facets of spinel LiNi_(0.5)Mn_(1.5)O_(4) cathode active material

The spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode active materials(CAMs)are considered a promising alternative to commercially available cathodes such as layered and polyanion oxide cathodes,primarily due to their notable safety and high energy density,particularly in their single-crystal type.Nevertheless,the industrial application of the LNMO CAMs is severely inhibited due to the interfacial deterioration and corrosion under proton-rich and high-voltage conditions.This study successfully designed and synthesized two typical types of crystal facets-exposed single-crystal LNMO CAMs.By tracking the electrochemical deterioration and chemical corrosion evolution,this study elucidates the surface degradation mechanisms and intrinsic instability of the LNMO,contingent upon their crystal facets.The(111)facet,due to its elevated surface energy,is found to be more susceptible to external attack compared to the(100)and(110)facets.Our study highlights the electrochemical corrosion stability of crystal plane engineering for spinel LNMO CAMs.

Analyses of Reaction Mechanisms among Different Sulfonation Reagents and m-Diphenylamine and Crystal Structures of the Formed Compounds

In the traditional process, m-phenylenediamine reacts with fuming sulfuric acid at high temperature to get intermediates, and then after dehydration occurs intramolecular rearrangement to get 2,4-diaminobenzenesulfonic acid. Traditional methods need to consume a lot of fuming sulfuric acid or concentrated sulfuric acid, resulting in high industrial large-scale production cost, more waste, and posing a serious environmental pollution risk. In this thesis, three different sulfonation reagents were used for the sulfonation reaction of m-phenylenediamine, and the reaction mechanisms and crystal structures of the three pathways were investigated. The three routes are: 1) one-step synthesis of monosulfonated compound 1 from raw material and sulfur trioxide (SO3);2) rapid reaction of raw material and chlorosulfonic acid to synthesize bisulfonated compound 2;3) direct eutectic crystallization of raw material and ordinary sulfuric acid to obtain compound 3. The crystal structure of the compounds synthesized by three paths was analyzed by X-ray single crystal diffraction, and compound 1 was characterized by NMR, Fourier infrared spectra, UV-visible spectrum and Mass spectrometry. The one-step synthesis of SO3 as a sulfonation reagent has the advantages of mild reaction conditions, simple operation and low cost.

Dy^(3+)-doped LiYF_4 crystals for UV-excited white light-emitting diodes

A Dy3＋-doped LiYF4 single crystal capable of generating white light by simultaneous blue and yellow light emission of phosphorescent centers is produced. Chromaticity coordinates and photoluminescence intensity vary with excitation wavelength. Under 350, 365, and 388 nm excitation, the crystal shows excellent white light emission. The most efficient wavelength for white light is 388 nm. The CIE coordina.tes are x=0.316 and y =0.321, and the color temperature （Tc） is 6 368 K. These results indicate that the studied crystal is a potential candidate for ultraviolet light-excited white light-emitting diodes.

Crystallization thermodynamics of 2,4(5)-dinitroimidazole in binary solvents

2,4(5)-Dinitroimidazole(2,4(5)-DNI)is an important organic intermediate,and itself can also be used for energetic material.In this work,the solubility of 2,4(5)-DNI in(methanol+water,acetonitrile+water,acetone+water)binary solvents were measured by using a dynamic test method from 278.15 K to 323.15 K under 101.1 k Pa.The Jouyban–Acree model,van't Hoff–Jouyban–Acree model,Apelblat–Jouyb an–Acree model,Ma model,and Sun model were used to correlate the experimental data.The values of relative average deviation(RAD)and root-mean-square deviation(RMSD)were very small,indicating that the error between the experimental value and the correlated value was very small.The thermodynamic parameters such as dissolution enthalpy,dissolution entropy and Gibbs energy were calculated based on solubility data.High-purity of 2,4(5)-DNI was efficiently obtained by using cooling and dilution crystallization method.

Refractive Index Change and Color Center Formation in LiYF_4 Crystal Induced by a Femtosecond Laser

The refractive index change and color centers formation in LiYF4 crystal at room temperature are induced by a femtosecond laser irradiation. A mechanism for refractive index change and color centers formation is proposed.

Optimum fluorescence emission around 1.8μm for LiYF_4 single crystals of various Tm^(3+)-doping concentrations

In this paper, optical spectra of LiYF4 single crystals doped with Tm3＋ ions of various concentrations are reported. The emission intensity at 1.8 ktm first increases with increasing Tm3＋ concentration, and reaches a maximum value when the concentration of Tm3＋ is about 1.28 mol%, then it decreases rapidly as the concentration of Tm3＋ further increases to 3.49 mol%. The emission lifetime at 1.8 p.m also shows a similar tendency to the emission intensity. The maximum lifetime of 1.8 μm is measured to be 17.68 ms for the sample doped with Tm3＋ of 1.28 mol%. The emission cross section of 3F4 level is calculated. The maximum reaches 3.76 × 10 -21 cm2 at 1909 nm. The cross relaxation （3H6, 3H4 →3 F4, 3F4） between Tm3＋ ions and the concentration quenching effect are mainly attributed to the change of emission with Tm3＋ concentration. The largest quantum efficiency between Tm3＋ ions is estimated to be ,-147% from the measured lifetime and calculated radiative lifetime. All the results suggest that the Tm3＋/LiYF4 single crystal may have potential applications in 2 μm mid-infrared lasers.

Optical Spectra and Gain Properties of Ho^(3+)/Pr^(3+)Co-doped LiYF_4 Crystal

The LiYF4 single crystals singly doped Ho3＋ and co-doped Ho3＋, Pr3＋ ions were grown by a modified Bridgman method. The Judd-Ofelt strength parameters （Ω2, Ω4, Ω6） of No3＋ were calculated according to the absorption spectra and the Judd-Ofelt theory, by which the radiative transition probabilities （A）, fluorescence branching ratios （β） and radiative lifetime （τ rad） were obtained. The radiative lifetimes of 5/6 and 5/7 levels in Ho3＋ （1 mol%）：LiYF4 are 10.89 and 20.19 ms, respectively, while 9.77 and 18.50 ms in Ho3＋/pr3＋ doped crystals. Hence, the τ rad of 5/7 level decreases significantly by introduction of Pr3＋ into Ho3＋：LiYF4 crystal which is beneficial to the emission of 2.9 μm. The maximum emission cross section of Ho3＋：LiYF4 crystal located at 2.05 μm calculated by McCumber theory is 0.51 ×10-20 cm2 which is compared with other crystals. The maximum emission cross section at 2948 nm in Ho3＋/pr3＋ co-doped LiYF4 crystal obtained by Fuchtbauer- Ladenburg theory is 0.68 × 10-20 cm2, and is larger than the value of 0.53 × 10-20 cm2 in Ho3＋ singly doped LiYF4 crystal. Based on the absorption and emission cross section spectra, the gain cross section spectra were calculated. In the Ho3- ions singly doped LiYF4 crystal, the gain cross sections for 2.05 μm infrared emission becomes positive once the population inversion level reaches 30%. It means that the pump threshold for obtaining 2.05 μm laser is probably lower which is an advantage for Ho3＋-doped LiYF4 2.05 μm infrared lasers. The calculated gain cross section for 2.9 μm mid-infrared emission does not become positive until the population inversion level reaches 40% in Ho3＋/pr3＋：LiYF4 crystal, but 50% in Ho3＋ singly doped LiYF4 crystal, indicating that a low pumping threshold is achieved for the H03＋：5/6 → 5/7 laser operation with the introduction of Pr3＋ ions. It was also demonstrated that Pr3＋ ion can deplete rapidly the lower laser Ho3＋：5/7 level and has influence on the Ho3＋：5/6 level. The Ho3＋/pr3＋：LiYF4 crystal may be a potential media for 2.9 μm mid-infrared laser.

2.0-μm emission and energy transfer of Ho^(3+)/Yb^(3+) co-doped LiYF_4 single crystal excited by 980 nm

Ho3＋/yb3＋ co-doped LiYF4 single crystals with various Yb3＋ concentrations and ,-~ 0.98 mol% Ho3＋ concentration are grown by the Bridgman method under the conditions of taking LiF and YF3 as raw materials and a temperature gradient （40 ~C/cm-50 ~C/cm） for the solid-liquid interface. The luminescent performances of the crystals are investigated through emission spectra, infrared transmittance spectrum, emission cross section, and decay curves under excitation by 980 nm. Compared with the Ho3＋ single-doped LiYF4 crystal, the Ho3＋/yb3＋ co-doped tiYf4 single crystal has an obviously enhanced emission band from 1850 nm to 2150 nm observed when excited by a 980-nm diode laser. The energy transfer from Yb3＋ to Ho3＋ and the optimum fluorescence emission around 2.0 p-m of Ho3＋ ions are investigated. The maximum emission cross section of the above sample at 2.0 p.m is calculated to be 1.08 × 10-20 cm2 for the LiYF4 single crystal of 1-mol% Ho3＋ and 6-mo1% Yb3＋ according to the measured absorption spectrum. The high energy transfer efficiency of 88.9% from Yb3＋ to Ho3＋ ion in the sample co-doped by Ho3＋ （1 mol%） and Yb3＋ （8 tool%） demonstrates that the Yb3＋ ions can efficiently sensitize the Ho3＋ ions.

Synthesis of energetic coordination polymers based on 4-nitropyrazole by solid-melt crystallization in non-ionization condition

Based on the theory of crystallization,a solvent-free solid-liquid phase crystallization method called solid-melt crystallization was designed to prepare energetic coordination polymers.Two target compounds[Cu(NPyz)_(4)NO_(3)]·NO_(3)(ECPs-1)and Cu(NPyz)_(4)(ClO_(4))_(2)(ECCs-2)were prepared through programmed heating and cooling by using 4-nitropyrazole(NPyz),(Cu(NO_(3))_(2)·5H_(2)O and Cu(ClO_(4))_(2)·5H_(2)O) as raw materials.In addition,crystallization pre-experiments and annealing experiments also verified the feasibility of the method.Their structures were confirmed by IR,elemental analysis,single-crystal X-ray diffraction and powder X-ray diffraction.The physicochemical properties and sensitivity test results showed that ECCs-2 has better thermal stability(T_(d)=221℃),while ECPs-1 is less sensitive to mechanical stimuli(IS=12 J,FS=240 N).Calculations based on EXPLO5 and the Kamlet-Jacobs equation showed that ECCs-2 has more considerable detonation performance(P=25.2 GPa,D=7.5 km/s).In comparison,the more intuitive results from the HN test,flame test,thermal resistance test and lead plate explosion test revealed that ECCs-2 has an“acceptable”detonation performance.The laser detonation test also showed that ECCs-2 is a promising excellent laser detonation material(E=408 mJ,P=24 W,τ=17 ms).

Na-Mn共掺对磷酸铁锂正极材料结构与性能的影响

利用碳热还原法成功制备了Li_(0.97)Na_(0.03)Fe_(7/8)Mn_(1/8)PO_(4)正极材料,运用XRD、SEM、EDS和电化学测试等手段对其晶体结构、形貌、元素分布和电化学性能进行研究,并结合第一性原理计算分析材料性能提升的机理。结果表明,Na-Mn掺杂一方面导致LiFePO_(4)晶格畸变,晶格体积增大,扩大了锂离子迁移通道,为锂离子嵌入/脱出提供更大的空间;另一方面使材料在电化学性能上表现出优异的高倍率性能和循环稳定性。Na-Mn掺杂有利于提高材料的锂离子扩散系数和电导率,从而提高其电化学性能。基于第一性原理计算结果表明,Na-Mn共掺杂使LiFePO_(4)晶格膨胀,晶格体积增大,并促使带隙宽度减小,增强了费米能级附近的电子态密度,提高了材料的电子电导率和锂离子迁移率。

Na_(2)O对锂铝硅微晶玻璃析晶及性能的影响

采用熔融法制备了不同Na_(2)O含量的透明锂铝硅微晶玻璃,通过DSC、XRD、FESEM等测试方法研究了不同Na_(2)O含量对玻璃析晶及性能的影响。结果表明:Na_(2)O的引入能显著降低玻璃的转变温度和析晶温度,抑制LiAlSi_(4)O_(10)晶相的析出。但Na_(2)O的引入促使微晶玻璃中析出Li_(2)Si_(2)O_(5)新相,并且随着Na_(2)O引入量的增加,Li_(2)Si_(2)O_(5)转变为主晶相。由于晶体尺寸均为纳米级,主晶相的转变对透过率影响较小,微晶玻璃的可见光透过率均高于85%。主晶相的转变有效增强了微晶玻璃的机械性能,其弯曲强度由300 MPa提升至331 MPa。Na_(2)O的引入有效增强了Na-K交换,Na_(2)O含量为4%(质量分数)的Li 2O-Al_(2)O_(3)-SiO_(2)微晶玻璃在410℃的KNO_(3)熔盐中交换6 h后,维氏硬度由7.108 GPa提升至7.403 GPa,弯曲强度由331 MPa提升至470 MPa。

Er^(3+)/Yb^(3+)/Pr^(3+):SrLaGaO_(4)晶体的光谱分析及中红外发射增强

采用非化学计量配比的提拉法成功生长出Er^(3+)/Yb^(3+)/Pr^(3+):SrLaGaO_(4)晶体、Er^(3+)/Yb^(3+):SrLaGaO_(4)和Er^(3+):SrLaGaO_(4)晶体并进行了详细的光谱分析,同时对纯的SrLaGaO_(4)晶体进行了热学性能分析。与Er^(3+):SrLaGaO_(4)晶体相比,Er^(3+)/Yb^(3+)/Pr^(3+):SrLaGaO_(4)晶体不仅展示了更好的吸收特性,而且还表现出较弱的近红外发射,以及优异的中红外发射;Er^(3+)/Yb^(3+)/Pr^(3+):SrLaGaO_(4)晶体中2.7μm铒激光下能级4I13/2的荧光寿命显著减少,而上能级4I11/2的寿命略微下降,成功抑制了自终止效应。此外,本工作还研究了Er^(3+)/Yb^(3+)/Pr^(3+):SrLaGaO_(4)晶体中Yb^(3+)的敏化作用和Pr^(3+)离子的去激活作用以及能量传递机制。总之,引入Yb^(3+)和Pr^(3+)有利于在Er^(3+)/Yb^(3+)/Pr^(3+):SrLaGaO_(4)晶体中实现增强的2.7μm发射,这使其成为中红外激光有前途的候选材料。

掺铈Cs_(2)BaBr_(4)晶体的生长和闪烁性能研究

以高纯度BaBr_(2)、CsBr、CeBr_(3)为原料,采用高温固相反应法合成了Cs_(2)BaBr_(4)∶1%Ce^(3+)多晶料,并通过坩埚下降法生长了Cs_(2)BaBr_(4)∶1%Ce^(3+)晶体。将晶体切割研磨抛光后得到不同厚度的Cs_(2)BaBr_(4)∶1%Ce^(3+)晶片。对晶体进行了物相分析,XRD图谱表明晶体为一致熔融物,且无相变。研究了晶体的闪烁性能,测试了光学透射率、光致发光、X射线激发发光、多通道gamma能谱、衰减时间。与LaBr_(3)晶体对比,分析了晶体的吸湿性。结果表明,晶体的光学透过率接近80%,在一定波段的紫外光及X射线的激发下,晶体在349与372 nm波长有发射峰。^(137)Cs源伽马射线的激发下,能量分辨率为11%,在紫外激发下,晶体衰减时间为21.9 ns。晶体的吸湿性比LaBr_(3)晶体有大幅改善。

基于实验参数的Dy^(3+),Na^(+):PbGa_(2)S_(4)中红外激光理论研究

基于加工出的Dy^(3+),Na^(+):PbGa_(2)S_(4)晶体元件的吸收光谱测试以及Judd-Ofelt理论计算数据,通过互易法计算出各发光能级间的荧光吸收与发射截面.通过测试与计算得到的数据,数值模拟了采用1.3μm和1.7μm泵浦源直接抽运Dy^(3+),Na^(+):PbGa_(2)S_(4)晶体产生4.3μm中红外激光的实验方案.计算分析了激光功率、增益和吸收系数在晶体内的空间分布,分析比较了泵浦光功率、元件长度和输出镜反射率对输出功率的影响.模型中在光路中引入2.9μm级联激光振荡,以此抽运因为4.3μm发光堆积在能级^(6)H_(13/2)上的粒子数,发现其可以有效降低能级^(6)H_(11/2)到^(6)H_(13/2)跃迁的自终止效应,提高激光输出功率.计算结果表明:采用1.3μm和1.7μm泵浦源,当功率都为4 W时,最大的输出功率分别为103 mW和315 mW,斜率效率可达到2.8%和8.0%.数值模拟的结果对下一步晶体元件的改良加工以及光路搭建参数的选取提供了一定的指导意义.

快速热压烧结制备高性能B_(4)C-LaB_(6)复合陶瓷

为了解决碳化硼(B_(4)C)难以烧结致密化和韧性差的问题,以B_(4)C和氧化镧(La_(2)O_(3))为原料,在2000℃和30 MPa下快速热压烧结制备B_(4)C-LaB_(6)复合陶瓷,研究La_(2)O_(3)含量对B_(4)C-LaB_(6)复合陶瓷微观结构和力学性能的影响,分析LaB_(6)的增韧机制。结果表明:w(La_(2)O_(3))=3%的B_(4)C-LaB_(6)复合陶瓷综合力学性能较好,其相对密度、维氏硬度、抗弯强度和断裂韧性分别为99.51%、36.56 GPa、547.43 MPa和4.18 MPa·m^(1/2)。LaB_(6)可细化B_(4)C-LaB_(6)复合陶瓷晶粒,同时提高其相对密度和断裂韧性。LaB_(6)的增韧机制与裂纹偏转和晶粒裂解有关。

在Ar与CF_4混合气氛中生长LiYF_4晶体

报道了在Ar与CF4 混合气氛中成功地生成出高质量的Nd∶LiYF4 晶体 ,并比较了在单一Ar气氛和Ar与CF4 混合气氛中生长的LiYF4 晶体的差别。X射线衍射表明 ,在单一Ar气氛中产生的不纯物质主要是氟氧化合物 ,Ar与CF4 混合气氛中 ,此种不纯物质能够被有效地消除。

{P_(4)Mo_(6)}基多金属氧酸盐构筑的镍配合物作为一种电化学传感器用于检测Cr^(Ⅵ)和Fe^(Ⅲ)离子

以钼酸钠、硫酸镍和3-氨甲基吡啶为原料,通过水热法合成了一个{P_(4)Mo_(6)}基多金属氧酸盐构筑的镍配合物,其化学式为[H_(2)(3-AP)]_(6){Ni[Mo_(6)O_(12)(OH)_(3)(PO_(4))_(2)(HPO_(4))_(2)]_(2)}(化合物1),3-AP为3-氨甲基吡啶.该化合物为三维超分子结构,其由{Ni[P_(4)Mo_(6)^(Ⅴ)O_(31)]_(2)}^(22-)记为{Ni(P_(4)Mo_(6))_(2)}和质子化的3-AP通过氢键相互作用连接而成.研究了该配合物修饰的碳糊电极(1-CPE)对Cr^(Ⅵ)和Fe^(Ⅲ)离子的电化学检测,检出限(LODs)分别为2.3和4.6μmol/L.同时1-CPE在各种金属离子的存在下对Cr^(Ⅵ)和Fe^(Ⅲ)表现出良好的选择性和较强的抗干扰能力.

基于2-(1H-咪唑-4-基)苯酚和Keggin型多酸构筑的杂化化合物的合成、结构及电化学性质研究

利用水热工艺,选用H_(3)PMo_(12)O_(40), 2-(1H-咪唑-4-基)苯酚和CuCl_(2)为主要原料,我们成功地合成了一个新的有机-无机杂化化合物[Cu_(2)(HX)4(H_(2)O)2](H_(3)PMo_(12)O_(40))(H_(2)X=2-(1H-咪唑-4-基)苯酚。X-射线单晶衍射分析结果表明该化合物属于单斜晶系,P2_(1)/c空间群。晶胞参数:a=1.102 8(5) nm,b=1.705 8(5) nm,c=1.6128(5) nm,β=92.424(5)~o,V=3.031 2(19) nm^(3),Z=4,R_(1)=0.066 6,wR_(2)=0.171 3。该化合物中的[Cu_(2)(HX)4(H_(2)O)2]络合物片段和H_(3)PMo_(12)O_(40)间通过氢键作用连接形成三维超分子结构。对该化合物的电化学性质进行了研究。