Structural/Compositional-Tailoring of Nickel Hexacyanoferrate Electrodes for Highly Efficient Capacitive Deionization

Prussian blue analogs (PBAs) represent a crucial class of intercalation electrode materials for electrochemical water desalination. It is shown here that structural/compositional tailoring of PBAs, the nickel hexacyanoferrate (NiHCF) electrodes in particular, can efficiently modulate their capacitive deionization (CDI) performance (e.g., desalination capacity, cyclability, selectivity, etc.). Both the desalination capacity and the cyclability of NiHCF electrodes are highly dependent on their structural/compositional features such as crystallinity, morphology, hierarchy, and coatings. It is demonstrated that the CDI cell with hierarchically structured NiHCF nanoframe (NiHCF-NF) electrode exhibits a superior desalination capacity of 121.38 mg g⁻¹, a high charge efficiency of up to 82%, and a large capacity retention of 88% after 40 cycles intercalation/deintercalation. In addition, it is discovered that coating of carbon (C) film over NiHCF can lower its desalination capacity owing to the partial blockage of diffusion openings by the coated C film. Moreover, the hierarchical NiHCF-NF electrode also demonstrates a superior selectivity toward monovalent sodium ions (Na⁺) over divalent calcium (Ca²⁺) and magnesim (Mg²⁺) ions, allowing it to be a promising platform for preferential capturing Na⁺ ions from brines. Overall, the structural/compositional tailoring strategies would offer a viable option for the rational design of other intercalation electrode materials applied in CDI techniques.     

Pt／n—n＋-Si电极上化学沉积铁氰化镍薄膜及其应用

在表面外延生长9μm的n型层的磷重掺杂的硅基底n—n＋一Si）结构上沉积约40nm铂（Pt）,经氩气保护673K热处理30min作为半导体电极（Pt／n—n＋-Si）。将半导体电极和铁氰化钾、硫酸镍以及硝酸钠的溶液接触,沉积出稳定的铁氰化镍（NiHCF）薄膜。复合电极与Pt电极组成光电化学电池,在零偏电压条件下,通过测量该电池的光电流可检测过氧化氢。通过循环伏安和X-光电子能谱对NiHCF薄膜进行了分析与表征。     

多金属普鲁士蓝类化合物亚铁氰化铜镍钴对铯离子的吸附

采用共沉淀法制备了一种多金属普鲁士蓝类化合物——亚铁氰化铜镍钴(CNC-PB),采用TEM、FTIR对其进行了表征,并利用XRF和穆斯堡尔谱对CNC-PB吸附交换铯离子的机理进行了初步分析。通过静态吸附实验,研究了吸附时间、pH值、Na~+浓度、初始Cs~+浓度、CNC-PB投加量等因素对吸附效果的影响,分析了吸附过程的反应动力学和吸附等温线。结果表明,随着溶液pH值的增大,CNC-PB对Cs~+的吸附量先增大后减少,吸附速度较快;在氯化钠溶液中,CNC-PB对Cs~+具有极高的选择性吸附能力;CNC-PB对Cs~+的吸附过程符合准二级动力学方程模型和Langmuir单分子吸附模型,最大吸附量为130.81mg/g。     

Activating C‐Coordinated Iron of Iron Hexacyanoferrate for Zn Hybrid‐Ion Batteries with 10 000‐Cycle Lifespan and Superior Rate Capability

Prussian blue analogue (PBA)‐type metal hexacyanoferrates are considered as significant cathodes for zinc batteries (ZBs). However, these PBA‐type cathodes, such as cyanogroup iron hexacyanoferrate (FeHCF), suffer from ephemeral lifespan (≤1000 cycles), and inferior rate capability (1 A g^?1). This is because the redox active sites of multivalent iron (Fe(III/II)) can only be very limited activated and thus utilized. This is attributed to the spatial resistance caused by the compact cooperation interaction between Fe and the surrounded cyanogroup, and the inferior conductivity. Here, it is found that high‐voltage scanning can effectively activate the C‐coordinated Fe in FeHCF cathode in ZBs. Thanks to this activation, the Zn–FeHCF hybrid‐ion battery achieves a record‐breaking cycling performance of 5000 (82% capacity retention) and 10 000 cycles (73% capacity retention), respectively, together with a superior rate capability of maintaining 53.2% capacity at superhigh current density of 8 A g^?1 (≈97 C). The reversible distortion and recovery of the crystalline structure caused by the (de)insertion of zinc and lithium ions is revealed. It is believed that this work represents a substantial advance on PBA electrode materials and may essentially promote application of PBA materials.     

Size‐, Water‐, and Defect‐Regulated Potassium Manganese Hexacyanoferrate with Superior Cycling Stability and Rate Capability for Low‐Cost Sodium‐Ion Batteries

Potassium manganese hexacyanoferrate (KMHCF) is a low‐cost Prussian blue analogue (PBA) having a rigid and open framework that can accommodate large alkali ions. Herein, the synthesis of KMHCF and its application as a high‐performance cathode in sodium‐ion batteries (NIBs) is reported. High‐quality KMHCF with low amounts of crystal water and defects and with homogeneous microstructure is obtained by controlling the nucleation and grain growth by using a high‐concentration citrate solution as a precipitation medium. The obtained KMHCF exhibits superior cycling and rate performance as a NIB cathode, showing 80% capacity retention after 1000 cycles at 1 C and a high capacity of 95 mA h g^?1 at 20 C. Unlike conventional single‐cation batteries, the hybrid NIB with KMHCF as cathode and Na as anode in Na‐ion electrolyte displays three reversible plateaus that involve stepwise insertion/extraction of both K⁺ and Na⁺ in the PBA framework. In later cycling, the K⁺–Na⁺ cointercalated phase is partially converted into a cubic sodium manganese hexacyanoferrate (NaMHCF) phase due to the increasing replacement of Na⁺ for K⁺.     

Removal of Radiocesium from Aqueous Media with Zinc–Aluminum Layered Double Hydroxide Intercalated with Copper(II) Hexacyanoferrate

Sorption of radiocesium from aqueous media with zinc–aluminum layered double hydroxide intercalated with copper(II) hexacyanoferrate (Zn/Al-CuFeCN) was studied. The highest ¹³⁷Cs distribution coefficients (790–850 cm³ g^–1) on this sorbent are reached at initial pH in the range 5.0–9.0 (pH after sorption 6.8–7.3). The limiting value of the Cs⁺ adsorption onto Zn/Al-CuFeCN, calculated from the Langmuir equation, is 64.1 mg g^–1. At a concentration of up to 100 mg dm^–3, Na⁺ ions do not noticeably affect the Cs⁺ sorption onto Zn/Al-CuFeCN, whereas the K⁺ and Ca²⁺ ions slightly (by 5–10%) decrease the degree of the Cs⁺ removal. The sorbent shows high selectivity (99.8%) in decontamination of natural water.     

电沉积NiHCF薄膜在碱土金属溶液中的电控离子分离性能

采用电沉积方法在铂基体上制备出电活性NiHCF(Nickel Hexacyanoferrate)薄膜,在碱土金属溶液中考察了薄膜电极对碱土金属离子的电控离子分离性能.通过循环伏安法在0.1mol·L-1Mg(NO3)2、Ca(NO3)2、Sr(NO3)2和Ba(NO3)2溶液中可逆置入和释放碱土金属离子,比较了不同溶液中NiHCF膜电极的电活性、电化学行为和离子的置入机制;在0.1mol·L-1[Mg(NO3)z Ba(NO3)2]混合溶液中结合电化学石英晶体微天平(EQCM)原位检测了不同浓度下膜电极氧化还原过程中的伏安特性曲线和频率响应,分析了薄膜对Mg/Ba离子的选择性;并通过XPS测定了氧化还原状态下NiHCF膜的化学组成及元素价态.结果表明,NiHCF膜在二价碱土金属溶液中具有可逆的离子交换行为,对Ba2 离子的选择性大于Mg2 离子,通过电控离子分离方法可以实现碱土金属离子的有效分离.     

Hexacyanoferrate(III) oxidation of arsenic and its subsequent removal from the spent reaction mixture

Inorganic arsenic is the most toxic form and has been classified in group 1 as carcinogenic to humans which induces lung, urinary bladder and primary skin cancer. Worldwide concern over its presence in water bodies have prompted much research and policy development focusing on the removal of this chronic human carcinogen. It has been observed that the ash of Unio (Lamellidens marginalis--the fresh water mussel) can be used successfully for the removal of arsenic(V) from the aqueous solutions at low pH (～9.0). Initially the kinetics of oxidation of arsenic(III) by alkaline hexacyanoferrate(III), both with and without adding iridium(III) chloride was studied. Subsequently after complete removal of ferrocyanide, the removal of arsenic(V) produced in the spent reaction mixture was taken up. Out of the five ashes obtained from different sources, the ash of Unio was found to be the best which results in decreasing arsenic(V) concentration from 1000 ppb to >10 ppb, TDS from 16.9 ppt to 8.5 ppt and conductivity from 33.8 mS to 17.1 mS. Kinetic results show the possibility of graphical separation of the reaction proceeding in the absence of iridium(III) from that proceeding in the presence of iridium(III) chloride.     

炭/炭-陶瓷/炭多元复合材料的原位热压制备与性能

以纤维素和凹凸棒石(PG)为原料,在220℃下水热24h制备凹凸棒石/炭(PG/C)复合材料。采用浸渍-炭化工艺在炭/炭(C/C)复合材料中引入PG/C作为添加剂,一步热压对材料最终成型,原位获得C/C-陶瓷/C复合材料。研究了添加PG/C对C/C力学性能和抗氧化性能的影响。结果表明:PG/C在热压过程中转变为顽辉石/C,顽辉石/C通过"填充"和"桥联"起增强作用,顽辉石陶瓷表面负载纳米炭层有效避免了陶瓷相与基体炭间弱结合的产生。随着PG/C中表面负载纳米炭含量的减少,C/C的强度逐渐增加。当炭含量为13%的PG/C作为添加剂时,C/C的抗弯强度为263MPa,弹性模量为47GPa,相对于没有添加剂的C/C抗弯强度提高了45%,弹性模量提高了42%;相对于以PG作为添加剂的C/C抗弯强度提高了16%,弹性模量提高了27%。添加PG/C使C/C抗氧化性得到了提高;1 000℃下C/C的质量损失降低了12%~18%。     

C/C-Cu复合材料等离子体烧蚀性能

为了研究渗铜对C/C复合材料烧蚀性能的影响,利用化学气相渗透(CVI)和液态压力浸渗工艺制备了C/C-Cu复合材料,并采用等离子体烧蚀装置对C/C-Cu复合材料进行烧蚀,研究其烧蚀性能。结果表明: Cu的加入有效缩短了材料的制备周期;Cu均匀分布在C/C坯体内,呈连续的网状结构;在烧蚀前30 s阶段,Cu通过熔化吸热降低了C/C-Cu试样的升温速度,C/C-Cu复合材料的线烧蚀率低于C/C复合材料,耐烧蚀性能优异;随着烧蚀时间的延长,C/C-Cu复合材料表层的Cu液被火焰带走,表层变为多孔低密度的C/C层,C/C-Cu复合材料的线烧蚀率迅速增加并超过C/C复合材料,耐烧蚀性能降低。     

高性能C/SiC刹车材料及其优化设计

对比分析了 C/ C和 C/ SiC刹车材料的力学性能和摩擦磨损性能。结果表明 , C/ SiC刹车材料的力学性能比 C/ C的高 , 而且 C/ SiC刹车材料克服了 C/ C静态摩擦系数低和湿态摩擦性能严重衰减的不足 , 说明 C/ SiC刹车材料是一种新型高性能刹车材料。以 C/ C复合材料为基础 , 在深入分析机轮刹车盘服役环境特点的基础上探讨了 C/ SiC刹车材料的力学性能、 热物理性能、 摩擦磨损性能、 复合材料结构和制造工艺等方面的优化设计途径和方法 , 为实现材料微结构2力学性能2摩擦磨损性能的协同设计与制造奠定基础。      

含钽(Ta)C/C复合材料烧蚀分析

根据TaC和C/C复合材料的物理化学性质及烧蚀环境推测C/TaC/C复合材料的烧蚀机理,并对其抗侵蚀机理及剥蚀进行了预测分析,在分析C/TaC/C复合材料烧蚀机理的基础上建立其烧蚀模型。根据Darcy定律确定TaC液体流动的速度,并在此基础上利用流体动力学和质量守恒定律等推导出C/TaC/C复合材料质量烧蚀率公式。     

C/C坯体密度对2D C_f/SiC复合材料结构和性能的影响

通过理论计算,探究C_f/SiC复合材料密度与C/C坯体密度的相关性;而后采用碳纤维布叠层制作2D C/C坯体,经先驱体浸渍裂解工艺增密,制得密度分别为0.98、1.06、1.12g/cm~3的C/C坯体,通过液相渗硅法反应合成2DC_f/SiC复合材料,探究C/C坯体密度对其结构和性能的影响。与理论计算结果来对比。研究结果表明:试验结果与理论数学计算结果基本一致。随着C/C坯体密度的增加,C_f/SiC复合材料的密度出现先上升后下降的趋势,当C/C坯体密度大于0.98g/cm~3后,复合材料的弯曲强度随着C/C坯体密度的增加而降低,C/C坯体密度为0.98g/cm~3时,2DC_f/SiC复合材料结构和性能较优。     

碳/碳复合材料密封性能分析

为使高性能碳/碳(C/C)复合材料在航天密封材料领域中得到进一步的应用,本文研究了碳布叠层以及碳毡结构的C/C复合材料在一定压力下气体的渗漏情况,对比试样为俄罗斯高强石墨密封环材料,采用扫描电镜观察分析气体通过C/C复合材料的途径.结果表明:C/C复合材料比高强石墨更适合用作航天动密封材料.碳毡C/C复合材料比碳布叠层C/C复合材料气密性更好.C/C复合材料中的穿刺纤维以及贯穿基体的孔隙和裂纹以及纤维与碳基体的结合情况对密封材料的密封性能会产生很大的影响.     

不同ZrC含量的(C/C)/SiC-ZrC复合材料的抗烧蚀性能

采用先驱体转化(PIP)法制备了不同ZrC含量的(C/C)/SiC-ZrC复合材料,考察了ZrC含量对复合材料微观结构和抗烧蚀性能的影响。结果表明,氧乙炔烧蚀600 s后,(C/C)/SiC复合材料表面疏松,出现了较大的烧蚀凹坑;而(C/C)/SiC-ZrC复合材料表面相对较致密,被白色氧化物质覆盖,烧蚀率均有所降低。在较低的ZrC含量下,(C/C)/SiC-ZrC复合材料表面形成ZrO₂-SiO₂二元共熔体系氧化膜,有效抑制氧化性气氛向复合材料内部渗透,同时氧化物不断熔化和挥发,降低了复合材料烧蚀表面的温度;而当ZrC体积分数为12.4vol%时,在烧蚀过程中(C/C)/SiC-ZrC复合材料表面能形成一个ZrO₂外层/SiO₂内层的双层结构保护膜,ZrO₂是一种优异的热障材料,且导热系数较低,使烧蚀过程中烧蚀区域热扩散降低,因此(C/C)/SiC-ZrC复合材料表现为较高的表面温度,但双层氧化膜阻挡有氧气氛进一步进入复合材料内部,使复合材料表现出优异的抗烧蚀性能。      

致密化工艺对厚壁针刺C/C复合材料性能的影响

采用化学气相渗透(CVI)+树脂浸渍碳化法(PIC)、CVI+沥青高压浸渍碳化法(HPIC)及HPIC工艺分别制备了IR-C/C、IP-C/C以及P-C/C三种厚壁针刺C/C复合材料,研究了三种材料的热力学性能及材料内部密度均匀性。结果表明,IP-C/C材料轴向拉伸强度为24.7 MPa,IR-C/C材料轴向压缩强度达到200 MPa,而P-C/C材料轴向拉伸强度仅为7.4 MPa,相比IR-C/C材料降低了53%,相比IP-C/C材料降低了70%。复合致密化工艺制备的材料具有较低的热膨胀系数,而P-C/C材料1000℃热膨胀系数达到了3.566×10-6℃-1,是IPC/C材料的2.5倍。IP-C/C材料和P-C/C材料采用高压碳化工艺增密,材料的致密度高,密度分布均匀,导热系数高。IR-C/C材料内部密度降为14.5%,密度分布为外高内低。以CVI+HPIC复合制备的材料综合性能优异,且内部密度分布均匀,适合于制备厚壁材料。     

Comparative study on tensile fracture behavior of monofilament and bundle C/C composites

Strength controlling factors in C/C composites were experimentally examined using monofilament fiber reinforced C/C composites and those reinforced by one carbon fiber bundle. Tensile strength of the monofilament C/C composites was almost the same level with that of the carbon fiber. This result indicated that carbon fibers in the C/C composites were intact even after the processing. On the other hand, remarkable reduction was observed in the bundle C/C composites. It was indicated that the fracture of the C/C composite is dominated by the brittle fracture of the sub-bundles, in which the fiber/matrix interface is bonded well.     

C／C—ZrC复合材料高温氧乙炔焰烧蚀性能及机理研究

采用基体改性技术将ZrC引入C／C复合材料中,制备了一种新型的C／C—ZrC复合材料。通过氧乙炔焰烧蚀实验,研究了ZrC含量及烧蚀时间对C／C—ZrC复合材料高温耐烧蚀性能的影响。用XRD和TEM对烧蚀后材料的相组成和微观结构进行了分析,结果表明,ZrC被氧化的主要生成物为ZrO2,伴有少量ZrC和C,含26．46％ZrC的C／C—ZrC复合材料,在氧乙炔焰烧蚀50s后,在材料表面生成致密的ZrO2膜,阻挡了氧对基体的扩散,并有隔热作用,有效保护复合材料被烧蚀和冲刷。实验表明,复合材料在高温氧乙炔焰烧蚀20s后,线烧蚀率和质量饶蚀率分别为0．012mm／s和0．0033g／s,比C／C复合材料分别降低7．6％和50％。