钼酸根阴离子在增强聚苯胺包覆的镍钴层状氢氧化物的电容和析氧行为中的关键作用

理论容量大且过电位低的层状氢氧化物(LDHs)是极有前景的超级电容电池和析氧反应的电极材料;然而,体相LDHs的低电导率和活性位点不足增加了电极的内阻,降低了电极容量和产氧效率.本文采用两步法制备了聚苯胺包覆的MoO42?插层的镍钴层状双金属氢氧化物复合电极(M-LDH@PANI).随着LDH中MoO42?含量的增加,针状的LDH微球逐渐演化为具有较高比表面积的片状M-LDH微球,这为整个电极提供了更多的电化学位点.此外,非晶态的聚苯胺包覆提高了复合电极的电导率.在引入适量MoO42?插层离子时,M-LDH@PANI表现出显著强化的储能和催化性能.所获得的M-LDH@PANI-0.5在析氧反应中表现出优越的电催化活性(10 mA cm?2时的过电位为266 mV),作为超级电容电池电极则具有864.8 C g?1的高容量.采用M-LDH@PANI-0.5作为正极及以活性炭作为负极组装的超级电容电池在功率密度为8,300.0 W kg?1时能量密度为44.6 Wh kg?1,且具有优异的循环稳定性(10000次循环后保留83.9％的初始容量).本文为LDH基材料的阴离子插层改性增强材料性能的机理提供了一个非传统的解释.在上述研究基础上,采用射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、高分辨透射电镜(HRTEM)和比表面积测试(BET)等手段对样品进行了深入表征.XRD结果表明,MoO42?插层的LDH材料的层间晶面(003)的峰随着MoO42?含量的增加而逐渐消失,这是由于晶面间距越大越容易受到晶粒细化的影响,间距大的晶格更容易受到破坏,导致晶格的展宽和弱化,从而间接证明MoO42?的成功插层.SEM、HRTEM和BET测试结果表明,MoO42?的含量对材料的形貌和比表面积具有重大影响.利用XPS对样品的价态进行了研究,发现随着MoO42?含量的增加,Co和Ni的价态没有明显变化.电化学测试结果表明,电极的储能和催化性能随MoO42?含量的增加而先增加后减小.利用理论计算分析了MoO42?在LDH中的插层行为,发现少量的MoO42?有利于扩大LDH的层间间距,而过量的MoO42?则会与LDH的H原子结合,从而与电解液中的OH?竞争,导致复合电极的电化学性能下降.此外,MoO42?插层的片状微球能有效调节材料的去质子化能,大大加速电极表面的氧化还原反应.因此,MoO42?插层能够显著强化LDH基材料的超级电容电池电极和OER催化剂电化学性能.     

钼酸根阴离子在增强聚苯胺包覆的镍钴层状氢氧化物的电容和析氧行为中的关键作用（英文）

理论容量大且过电位低的层状氢氧化物(LDHs)是极有前景的超级电容电池和析氧反应的电极材料;然而,体相LDHs的低电导率和活性位点不足增加了电极的内阻,降低了电极容量和产氧效率.本文采用两步法制备了聚苯胺包覆的MoO_4~(2-)插层的镍钴层状双金属氢氧化物复合电极(M-LDH@PANI).随着LDH中MoO_4~(2-)含量的增加,针状的LDH微球逐渐演化为具有较高比表面积的片状M-LDH微球,这为整个电极提供了更多的电化学位点.此外,非晶态的聚苯胺包覆提高了复合电极的电导率.在引入适量MoO_4~(2-)插层离子时,M-LDH@PANI表现出显著强化的储能和催化性能.所获得的M-LDH@PANI-0.5在析氧反应中表现出优越的电催化活性(10 mA cm~(-2)时的过电位为266 mV),作为超级电容电池电极则具有864.8 C g~(-1)的高容量.采用M-LDH@PANI-0.5作为正极及以活性炭作为负极组装的超级电容电池在功率密度为8,300.0 W kg~(-1)时能量密度为44.6 Wh kg~(-1),且具有优异的循环稳定性(10000次循环后保留83.9%的初始容量).本文为LDH基材料的阴离子插层改性增强材料性能的机理提供了一个非传统的解释.在上述研究基础上,采用射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、高分辨透射电镜(HRTEM)和比表面积测试(BET)等手段对样品进行了深入表征.XRD结果表明,MoO_4~(2-)插层的LDH材料的层间晶面(003)的峰随着MoO_4~(2-)含量的增加而逐渐消失,这是由于晶面间距越大越容易受到晶粒细化的影响,间距大的晶格更容易受到破坏，导致晶格的展宽和弱化,从而间接证明MoO_4~(2-)的成功插层.SEM、HRTEM和BET测试结果表明,MoO_4~(2-)的含量对材料的形貌和比表面积具有重大影响.利用XPS对样品的价态进行了研究,发现随着MoO_4~(2-)含量的增加,Co和Ni的价态没有明显变化.电化学测试结果表明,电极的储能和催化性能随MoO_4~(2-)含量的增加而先增加后减小.利用理论计算分析了MoO_4~(2-)在LDH中的插层行为,发现少量的MoO_4~(2-)有利于扩大LDH的层间间距,而过量的MoO_4~(2-)则会与LDH的H原子结合,从而与电解液中的OH~-竞争,导致复合电极的电化学性能下降.此外,MoO_4~(2-)插层的片状微球能有效调节材料的去质子化能,大大加速电极表面的氧化还原反应.因此,MoO_4~(2-)插层能够显著强化LDH基材料的超级电容电池电极和OER催化剂电化学性能.     

无机插层材料在电化学能量存储与转换领域的研究进展

由于全球能源和环境危机的不断加剧,清洁高效能源的研究和应用引起了人们的极大关注.层状双金属氢氧化物LDHs是一类典型的阴离子黏土材料,由于其电化学活性高、稳定、价廉,近年来被广泛用于电化学传感器、超级电容器、锂离子电池和燃料电池等领域.本文详细介绍了插层材料LDHs的材料设计、可控制备及其在电化学能量存储与转换领域的研究进展,并进一步讨论了LDHs材料在该领域面临的挑战和发展趋势.     

用于超级电容器电极材料的聚苯胺基碳(英文)

在不同温度下碳化硫酸掺杂的聚苯胺制备了含杂原子(氮和氧原子)的新型碳材料.分别通过扫描电镜、元素分析仪、X射线光电子能谱仪和比表面积测试仪对这些碳材料的形貌特征、元素组成、表面化学组成和比表面积进行了表征.用循环伏安法、恒电流充放电法和交流阻抗法对其进行了电化学性能的研究.研究结果表明,在温度为800℃下碳化聚苯胺得到的碳有很好的电化学性能,尽管它的比表面积很小(325m·2g-1),但在0.5A·g-1电流密度下其比电容高达153F·g-1.它的高比电容可能与其含有合适比例的杂原子(氮和氧原子)有关,因为合适比例的氮和氧杂原子能够产生最大的赝电容.这些结果表明这种碳材料是一种很有发展前景的超级电容器电极材料.     

提高电容性电化学储能装置能量容量的一些尝试

本文从作者所在的课题组在超级电容器和超级电容电池方向的研究内容为基础,在电极材料和装置层面综述了电容性电化学储能装置的发展. 导电聚合物和过渡金属氧化物分别与碳纳米管复合后的复合物能显著提高前两者作为电容性法拉第储能电极的电容性能. 活性炭和碳黑等一类碳材料则可作为非法拉第储能的电极材料. 通过对超级电容器正负极电容做相应的匹配调整可以提高超级电容器的最大充电电压,从而提高超级电容器的能量容量. 此外,为了与实际设备相匹配,超级电容可以以双极板的方式串联堆积,满足高电压的需求. 超级电容电池作为新一代的电容性电化学储能装置,分别由具有电容性和法拉第电荷储存原理的电极组成,具有高比功率和高比能量的特点,也是近年来的研究热点.     

大碳层间距的沥青基多级孔碳材料的制备及其在超级电容器中的应用

基于KOH活化法,以纳米级片层多孔MgO为模板剂,制备大碳层间距的沥青基超级电容器用多级孔碳材料。考察了模板剂添加量对多孔碳材料孔分布、碳层间距等理化性能及电化学性能的影响。结果表明模板剂添加量为沥青质量的25%时,多孔碳材料比表面积、孔体积分别为2 634 m~2·g~(-1)、1.12 cm~3·g~(-1),碳层间距高达0.374 nm,用于超级电容器电极材料时,1和20A·g~(-1)电流密度下的比电容分别为338和277 F·g~(-1),经过10 000次循环恒电流充放电,1 A·g~(-1)下容量保持率为93.5%,展现了优异的电化学性能。     

提高电容性电化学储能装置能量容量的一些尝试（英文）

本文从作者所在的课题组在超级电容器和超级电容电池方向的研究内容为基础,在电极材料和装置层面综述了电容性电化学储能装置的发展.导电聚合物和过渡金属氧化物分别与碳纳米管复合后的复合物能显著提高前两者作为电容性法拉第储能电极的电容性能.活性碳和碳黑等一类碳材料则可作为非法拉第储能的电极材料.通过对超级电容器正负极电容做相应的匹配调整可以提高超级电容器的最大充电电压,从而提高超级电容器的能量容量.此外,为了与实际设备相匹配,超级电容可以以双极板的方式串联堆积,满足高电压的需求.超级电容电池作为新一代的电容性电化学储能装置,分别由具有电容性和法拉第电荷储存原理的电极组成,具有高比功率和高比能量的特点,也是近年来的研究热点.     

高容量超级电容器电极材料的设计与制备

超级电容器寿命长,安全性高,并可以实现快速充放电,是化学电源研究的热点之一。然而,超级电容器的能量密度较低限制了其更多的应用。因此,超级电容器领域的研究关注点在如何提高超级电容器的能量密度。其中,提高比容量是提高能量密度的一种有效途径。本文通过对电极材料和电解液的优化来研究制备得到高容量超级电容器的方法。电极材料的比表面积、孔道结构和导电性对其电化学性能有着直接的影响。一方面,通过优化电极材料的孔道结构和比表面积可以增加活性位点并提高电解液离子传导率,从而得到高比电容。另一方面,电极材料导电性的提高有利于提升其电子传导率从而得到较高的比容量。本文分别对碳材料和金属氧化物/氢氧化物的优化达到了增加双电层电容和赝电容的目的。不仅如此,还可以通过在电解液中增加氧化还原电对从而得到高比电容。这一方法为高容量超级电容器的制备提供了新的思路。     

基于金属氧化物的赝电容器

电极是电化学超级电容器的重要组成部分,电极材料是决定超级电容器性能的最重要因素。金属氧化物电极材料兼有双电层电容和准电容性质,其比电容远远大于活性炭材料表面的双电层电容,基于金属氧化物电极材料的超级电容器具有使用寿命长、维护简单等优点,是一种新型、高效、实用的能量存储装置,引起研究者的广泛兴趣。本文综述了基于金属氧化物电极材料的赝电容器的储能原理、类型和性能的研究现状,并展望了其发展前景。     

水性聚苯胺纳米线超级电容器电极材料

使用"假高稀"方法,分别以过硫酸铵、硝酸铁和三氯化铁为氧化剂,含有1个乙氧基基团的酸性磷酸酯为质子酸,经过原位聚合制备了直径分别为78～90 nm、18～30 nm和16～25 nm水分散性聚苯胺纳米线.聚苯胺膜的电导率分别为18,32和35 S cm-1,比表面积为65,70和82 m2g-1.该聚苯胺纳米线能够很好地分散在水中,是一种环境友好型超级电容器电极材料.该电极材料在1 mol L-1四乙基氟硼酸/碳酸丙烯酯非水性电解液中,在-1～1 V扫描范围内,以0.4 A g-1的放电速率下,分别得到了110,140和152 F g-1的比容,比电容与材料的比表面积和电导率有关,随着比表面积以及电导率的增大而增大.聚苯胺纳米线电极材料有较高的充放电效率(大于98%),表明了它们有很好的电化学可逆性.     

Recent advances in layered double hydroxides-based electrochemical sensors: Insight in transition metal contribution

Among the nanomaterials reported in the literature, layered double hydroxides (LDHs) are considered promising for the electrochemical sensor technology. Transition metal-based layered double hydroxides (TM-LDHs) show excellent electrocatalytic properties that facilitate redox reactions with analytes, e. g. H₂O₂, glucose or glyphosate. Elaboration of porous nano-structures with TM-LDHs nanosheets on the electrode surface allows a rapid diffusion of the analytes and a good accessibility of the TM active sites. An association of TM-LDHs with conductive materials, e. g. graphene or metal nanoparticles (M-NPs), improves the electronic conductivity in the LDH-based composites and also the electrocatalytic activity. With a selection of recent publications, the present mini-review aims to discuss about the specific electrocatalytic role played by TMs (Ni, Co, Cu, Mn and Fe) present in the LDH layers on the performance (sensitivity and detection limit) of these TM-LDHs-based sensors.     

Layered Double Hydroxide Nanosheets with Multiple Vacancies Obtained by Dry Exfoliation as Highly Efficient Oxygen Evolution Electrocatalysts

Layered double hydroxides (LDHs) with two-dimensional lamellar structures show excellent electrocatalytic properties. However, the catalytic activity of LDHs needs to be further improved as the large lateral size and thickness of the bulk material limit the number of exposed active sites. However, the development of efficient strategies to exfoliate bulk LDHs into stable monolayer LDH nanosheets with more exposed active sites is very challenging. On the other hand, the intrinsic activity of monolayer LDH nanosheets can be tuned by surface engineering. Herein, we have exfoliated bulk CoFe LDHs into ultrathin LDH nanosheets through Ar plasma etching, which also resulted in the formation of multiple vacancies (including O, Co, and Fe vacancies) in the ultrathin 2D nanosheets. Owing to their ultrathin 2D structure, the LDH nanosheets expose a greater number of active sites, and the multiple vacancies significantly improve the intrinsic activity in the oxygen evolution reaction (OER).     

12-磷钨酸插层MgAl水滑石的合成、表征及催化酯化原油脱酸性能

采用离子交换法合成了不同Mg/Al物质的量比的12-磷钨酸(H_3PW_(12)O_(40),HPW)插层水滑石(LDHs),采用XRD、FT-IR、Raman、ICP-AES、TG-DSC等分析手段表征其物化性质,Hammett指示剂-正丁胺滴定法测定其酸强度和酸量分布。进一步将其用于原油催化酯化脱酸反应,并与NO_3型LDHs对比,探讨酯化活性与催化剂性质之间的关系。结果表明,催化剂的活性主要受酸性和比表面积的影响。HPW插层LDHs的酯化活性明显优于NO3型LDHs,归因于增强的酸性和增大的比表面积。对于弱酸性的NO_3型LDHs,酯化活性与比表面积呈正向关系,Mg/Al物质的量比为4时,具有最大的比表面积和脱酸活性。而对于较强酸性的HPW插层LDHs,酯化活性主要受到酸量的影响,Mg/Al物质的量比为2的催化剂具有最高的酸量和脱酸活性。     

多孔纳米立方FeSe2/石墨烯复合材料的可控构建及在钠离子电池中的应用

设计具有较高比容量和循环稳定性的负极材料对于钠离子电池的发展至关重要。过渡金属硒化物因其具有较高的理论容量而成为潜在的负极材料。但是,硒化物电导率低下且在钠离子嵌入/脱出的过程中会发生较大程度的体积膨胀,导致比容量快速下降。因此,结构调控显得尤为重要。通过常规水热法在二维还原氧化石墨烯（rGO）上原位生长多孔纳米立方体FeSe₂,制备了具有更多活性位点和结构更加稳定的FeSe₂/rGO复合材料。当用作钠离子电池的负极时,复合材料FeSe₂/rGO在0.2 A/g时比容量为694.6 mA?h/g,在2.0 A/g电流密度下,循环300圈后比容量为300 mA?h/g。     

Synthesis and adsorption properties of p-sulfonated calix[4 and 6]arene-intercalated layered double hydroxides

The intercalation of water-soluble p-sulfonated calix[4 and 6]arene (CS4 and CS6) in the interlayer of the Mg-Al and Zn-Al layered double hydroxide (LDH) by the coprecipitation method has been investigated, as well as the adsorption properties of the resulting CS/LDHs for benzyl alcohol (BA) and p-nitrophenol (NP) to prepare new microporous organic-inorganic hybrid adsorbents. The amount and arrangement of CS intercalated was different by the kind of the host metal ions. CS4 cavity axis was perpendicular for the Mg-Al LDH basal layer and parallel for the Zn-Al LDH basal layer, while CS6 cavity axis was perpendicular for both the LDH basal layers. In the BET surface area measurement, the surface area of the Zn-Al/CS4/LDH was four times than that of the Mg-Al/CS4/LDH, expecting that the former has higher adsorption capacity than the latter. In fact, the adsorption ability of the CS/LDHs for BA and NP in aqueous solution was found to be larger in the Zn-Al/CS4/LDH than in the Mg-Al/CS4/LDH. In addition, the adsorption ability of both the LDHs was larger in the CS6/LDHs than in the CS4/LDHs. These results were explained by the difference in the amount and arrangement of CS intercalated in the LDH interlayer space.     

Construction of CoS_2 nanoparticles embedded in well-structured carbon nanocubes for high-performance potassium-ion half/full batteries

Metal sulfides have been widely investigated as promising electrode materials for potassium-ion batteries(PIBs) due to their high theoretical capacities.However,the practical application of metal sulfides in PIBs is still hindered by their intrinsic shortcomings of low conductivity and severe volume changes during the potassiation/depotassiation process.Herein,a simple template-based two-step annealing strategy is proposed to impregnate CoS_2 nanoparticles in the well-structured carbon nanocubes(denoted CoS_2/CNCs) as an advanced anode material for PIBs.The ex-situ XRD measurements reveal the K storage mechanism in CoS_2/CNCs.Benefiting from the unique structures,including abundant active interfacial sites,high electronic conductivity,and significantly alleviated volume variation,CoS_2/CNCs present a high specific capacity(537.3 mAh g~(-1) at0.1 A g~(-1)),good cycling stability(322.4 mAh g~(-1) at 0.5 A g~(-1) after 300 cycles),and excellent rate capability(153.1 mAh g~(-1) at5 A g~(-1)).Moreover,the obtained nanocomposite shows superior potassium storage properties in K-ion full cells when it is coupled with a KVP04 F cathode.     

One Step Fabrication of Au Nanoparticles‐Ni‐Al Layered Double Hydroxide Composite Film for the Determination of L‐Cysteine

This paper reports the fabrication of Au nanoparticles (Au NPs)‐Ni‐Al layerd double hydroxide (LDH) composite film by one step electrochemical deposition on the surface of a glass carbon electrode from the mixture solution containing HAuCl₄ and nitrate salts of Ni²⁺ and Al³⁺. Improved conductivity was obtained by Au NPs codeposited on LDH film. The synergic effect of LDHs and Au NPs dramatically improves the performance of L ‐cysteine electro‐oxidation, displaying low oxidation peak potential (0.16 V) and high current response. Thus the electrode was used to sense L ‐cysteine, showing good sensitivity and selectivity.     

Enhanced conductivity of a glassy carbon electrode modified with a graphene-doped film of layered double hydroxides for selectively sensing of dopamine

A strategy is presented for doping graphene into layered double hydroxide films (LDHs) as a means of improving charge transport of the LDH film in a modified glassy carbon electrode. This result in an enhanced electrocatalytic current for dopamine (DA) and a good separation of the potentials of DA, uric acid and ascorbic acid. Under selected conditions, the square wave voltammetric response of the electrode to DA is linear in the concentration range from 1.0 to 199???M even in the presence of 0.1?mM ascorbic acid, and the detection limit is 0.3???M at a signal-to-noise ratio of 3. The method was applied to the determination of DA in pharmaceutical injections with satisfactory results.

Carbonyl-rich Poly(pyrene-4,5,9,10-tetraone Sulfide) as Anode Materials for High-Performance Li and Na-Ion Batteries

Organic carbonyl electrode materials are widely employed for alkali metal-ion secondary batteries in terms of their sustainability, structure designability and abundant resources. As a typical redox-active organic electrode materials, pyrene-4, 5, 9, 10-tetraone (PT) shows high theoretical capacity due to the rich carbonyl active sites. But its electrochemical behavior in secondary batteries still needs further exploration. Herein, PT-based linear polymers (PPTS) is synthesized with thioether bond as bridging group and then employed as an anode material for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). As expected, PPTS shows improved conductivity and insolubility in the non-aqueous electrolyte. When used as an anode material for LIBs, PPTS delivers a high reversible specific capacity of 697.1 mAh g⁻¹ at 0.1 A g⁻¹ and good rate performance (335.4 mAh g⁻¹ at 1 A g⁻¹). Moreover, a reversible specific capacity of 205.2 mAh g⁻¹ at 0.05 A g⁻¹ could be obtained as an anode material for SIBs.