高硫石油焦基活性炭的制备及其在二次电池负极材料中的应用

以我国产量较大的山东淄博高硫石油焦为原料,利用KOH活化法,于800℃下通过改变碱焦质量比(质量比为1∶1,2∶1,3∶1,4∶1)制备得到不同比表面积的高硫石油焦基活性炭(AC-PC-X),利用比表面积分析仪对其孔结构进行了分析,并进一步利用水热法担载Mn₃O₄制备得到AC-PC-X/Mn₃O₄复合材料,分别将AC-PC-X/Mn₃O₄和高硫石油焦基活性炭作为二次电池负极材料分别应用于锂离子电池和钾离子电池中,利用JSM-7001F型热场发射扫描电子显微镜和JEM-2100F型场发射透射电子显微镜观察了负极材料的微观形貌,以及利用LAND CT2001A型电池测试系统和CHI660D型电化学工作站考察了负极材料的性能。结果表明:不同碱焦质量比条件下制备得到的高硫石油焦基活性炭均以微孔结构为主,比表面积随碱焦质量比的增加而增大;碱焦质量比为3∶1时制备得到的高硫石油焦基活性炭(AC-PC-3,比表面积为996m²/g)表现出最佳的长期循环稳定性,比表面积过大或过小的高硫石油焦基活性炭的电化学稳定性均不如ACPC-3的电化学稳定性。在锂离子电池中,AC-PC-3/Mn₃O₄在初始循环中的比容量为907mAh/g,但其循环容量衰减较慢,120次充/放电循环后其稳定比容量为400mAh/g;在钾离子电池中,ACPC-3在500次循环后比容量几乎没有衰减,稳定在95mAh/g。     

锰的氧化物活化过硫酸盐处理有机废水

研究了一系列锰氧化物(MnO、MnO₂、Mn₂O₃、Mn₃O₄),并测试了锰的氧化物活化 PMS对苯酚降解的效果。结果表明：活性由高到低的顺序为 Mn₂O₃、MnO、Mn₃O₄、MnO₂。同时研究了不同因素下的处理效果,指出 PMS 投加量、催化剂投加量、温度与苯酚的降解效果均成正相关,且 Mn₂O₃重复使用效果较好,可多次循环利用,是高效环保的催化材料。     

Mn3O4微观结构对固相合成类单晶锰酸锂的影响

探究了Mn₃O₄的微观结构对高温固相法制备类单晶锰酸锂(LiMn₂O₄)的影响。结果表明,前驱体对LiMn₂O₄的结构和形貌有决定性的影响。粒度小、比表面积大的类球形Mn₃O₄更易制得类单晶锰酸锂,其颗粒团聚致密、表面光滑,且晶胞参数小、能量密度大、Li⁺浓度高。类单晶锰酸锂的综合电化学性能和热稳定性远高于非类单晶材料,在0.2 C倍率下首次放电比容量和库仑效率分别高达112.50 mA·h/g、96.5%,8 C倍率下放电比容量仍有102.11 mA·h/g,200次循环后容量保持率为90.1%。类单晶锰酸锂优异的性能归因于其具有稳定的晶体结构和外露表面、较高的Li⁺浓度,在电化学反应中结构稳定、锂离子迁移速率快、电极极化和电荷转移阻抗小。     

锂离子电池电极材料Li1+xV3O8研究进展

钒酸锂（Li_1+xV₃O₈）具有比容量大的优点,可用作传统锂离子电池正极材料及水溶液锂离子电池负极材料,是一种重要的锂离子电池活性材料。Li_1+xV₃O₈作为传统锂离子电池正极材料已被广泛研究,近年来Li_1+xV₃O₈作为水溶液锂离子电池负极材料的研究备受瞩目,成为了锂离子电池研究领域的热点与前沿。本文综述了Li_1+xV₃O₈作为传统锂离子电池正极材料的研究现状,从结构与充放电机理、合成方法及改性等方面进行了讨论,此外,综述了Li_1+xV₃O₈作为水溶液锂离子电池负极材料的研究现状并指出了其发展趋势。     

高温固相内氧式锰酸锂的试验合成研究

以Mn₃O₄和MnO₂为原料,采用高温固相内氧法制备LiMn₂O₄电池正极材料。通过对LiMn₂O₄的振实密度、粒度分布、比容量、循环性能、结构及形态等各项理化性能进行检测分析,结果表明：在烧结温度为750℃,Mn₃O₄和MnO₂的摩尔比为3∶1的条件下,所制备的锰酸锂电化学性能最佳,其振实密度为1.84 g/cm³,比表面积为0.698 cm²/g, D₅₀粒径为16.567μm, 1C放电容量为122.65 mAh/g, 50次循环容量保持率为94.02%。     

K+掺杂尖晶石型(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)3O4高熵氧化物负极材料制备与储锂性能研究

通过溶液燃烧法成功合成了一系列非活性K⁺掺杂的尖晶石型(K_xCoCrFeMnNi)₍3/(5+x))O₄(x=0,0.5,1,1.5)高熵氧化物锂离子电池负极材料,系统研究了K⁺掺杂对结构和储锂性能的影响。结果表明：随着K⁺掺杂量的增加,均可制备出具有单一尖晶石结构的纳米晶粉体材料,其中等摩尔K⁺掺杂的(K_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)₃O₄高熵氧化物负极材料具有最高的比容量、优异的循环稳定性和倍率性能。(K_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)₃O_4<...     

锂离子电池碳负极材料研究概述

摘锂离子电池由于具有高能量密度、长循环寿命等优点,被广泛应用于电动汽车、储能、便携式电子产品等领域。电极材料是制约锂离子电池发展的关键。碳材料因为容量高、放电平台低、来源广泛等优点成为目前商业化锂离子电池负极材料的主流,主要包括石墨、无定形碳。文章总结了锂离子电池碳负极材料的发展历史,重点对石墨、无定型碳的储锂机理进行了分析。     

废旧锂离子电池回收制备MnO2及其储锌性能

随着锂离子电池产业的快速发展,退役锂离子电池的回收利用问题已成为工业和学术界关注的热点。前人对废旧锂离子电池中有价值资源的回收做了大量研究,但将回收的锂离子电池材料直接转化为新型储能体系电极材料的研究鲜有报道。为实现退役电池的资源化再利用,可通过简单的H₂SO₄浸渍法,将废旧锂离子电池中锰酸锂(LiMn₂O₄)材料转化为MnO₂,并用做水系锌离子电池正极材料。通过XRD、XPS、BET、SEM、CV、TEM、EIS以及电化学性能测试等表征方法,探究酸浸渍条件如温度、时间等对所制备MnO₂形貌、结构和电化学性能的影响规律。结果表明：LiMn₂O₄材料经酸浸渍会发生歧化反应,使Li⁺和部分Mn²⁺从晶格中溶出,而浸渍温度对离子的溶出速度有显著影响。室温下,LiMn₂O₄晶格中离子的溶出速度较慢,可获得与其晶体结构相近的λ-MnO<...     

新型电池负极与隔膜材料

随着纯电动汽车(EV)、混合动力汽车(HEV)以及高端储能系统对锂离子电池的迫切需求,开发具有高比容量、高安全性以及循环寿命长的负极材料成为该领域的主流方向。目前商业化应用的负极材料仍以石墨类碳素材料为主,最大理论比容量只有372 mAh/g,难以满足新一代移动通讯、移动电器以及电动汽车对于锂离子电池容量     

超小尺寸碳载Mn3O4纳米催化剂制备及其催化性能

以MnCl₂为原料,聚乙烯醇(PVA)为稳定剂,利用PVA介导沉淀法制备Mn₃O₄纳米粒子(PVA/Mn₃O₄),进一步将冻干的PVA/Mn₃O₄复合物炭化制备了超小尺寸的Mn₃O₄-C催化剂。使用XRD、XPS、TEM、BET表征制备材料的结构和形貌,发现PVA能够有效减小Mn₃O₄在制备过程中的聚集和长大。无PVA介导沉淀法制备的Mn₃O₄-P平均粒径为(38.8±9.3)nm。加入PVA后,制备过程中PVA分子链间的Mn₃O₄纳米粒子平均粒径为(3.2±0.8)nm,经过Ar保护炭化处理后,平均粒径为(4.5±1.2)nm的Mn₃O₄纳米粒子被均匀固定在碳基底上。制备的Mn₃O_4<...     

The reduction and oxidation behaviour of manganese oxides

The reduction of manganese oxides with methane was studied to investigate the suitability of manganese as an oxygen storage compound. Manganese oxides are reduced by CH₄ to a lower-valent manganese oxide, producing CO₂ and water. Once the manganese oxide is reduced, it can be regenerated, i.e. reoxidised. By integrating this exothermic oxidation cycle with endothermic methane reforming, a new setup for exothermic, small scale syngas production is obtained. Manganese oxides can be reduced to manganese(II) oxide with methane at temperatures higher than 723 K. Reoxidation of MnO at 823 K leads to the formation of Mn₂O₃ at 823 K. At 1073 K reoxidation of MnO gives Mn₃O₄ , which corresponds to a lower Mn-valency than expected thermodynamically. Subsequent oxidation–reduction cycles lead to an increase in reduction temperature, probably due to a higher crystallinity.     

A spillover approach to oxidation catalysis over copper and manganese mixed oxides

The activity of a hopcalite-type catalyst for H₂ and CO oxidation is compared with that of single-phase oxides CuO, Mn₂O₃ and CuMn₂O₄ (spinel) and a mixture of 1:1 CuO and Mn₂O₃ in order to elucidate the effects that are responsible for the high catalytic activity of the former. The reaction rates over the hopcalite catalyst calcined at 550°C (a mixture of CuO, Mn₂O₃ and CuMn₂O₄) are very close to those of the physical mixture of CuO and Mn₂O₃, being much greater than the rates over the single-phase oxides. CuO, Mn₂O₃ and CuMn₂O₄ show a kinetic compensation behavior both in H₂ and CO oxidation. By taking into account the activation energies and the reducibility measured by TPR it was concluded that the oxidation reactions over CuO follow a redox mechanism using lattice oxygen, while over Mn₂O₃ the mechanism is associative involving adsorbed oxygen species. Based on the TPR and kinetic results, the synergy between copper and manganese oxides in hopcalite and in the CuO–Mn₂O₃ mixture is assigned to a spillover effect.     

Synthesis of CeO2–MnOx mixed oxides and catalytic performance under oxygen-rich condition

Ce_0.5Zr_0.5O₂, Ce_0.5Zr_0.2Mn_0.3O₂ and Ce_0.5Mn_0.5O₂ were prepared by citric acid sol–gel method. The effect of manganese on the structural and redox properties of ceria-based mixed oxides was investigated by means of powder X-ray diffraction, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller analyses, temperature-programmed reduction and catalytic activity evaluation in the presence of excess O₂. The results showed that some Mn cations could enter into the ceria lattice to form solid solutions. Mn₃O₄ appeared due to the instability of the mixed oxides with increment of the Mn doping ratio while another oxide Mn₂O₃ is detected in the physical mixture of ceria and manganese oxide. These Mn-doped mixed oxides, especially Ce_0.5Mn_0.5O₂, presented better catalytic activities than Ce_0.5Zr_0.5O₂ and even Pt-loaded catalyst for total oxidation of C₃H₈ and oxidative sorption of NO in the presence of excess oxygen. The oxidation ability of Mn and the strong interaction between Mn and Ce were suggested to promote the oxygen storage/transport capacity of the mixed oxides as well as reactive adsorption of nitric oxide and hydrocarbons.     

Catalyst screening for oxidative desulfurization using hydrogen peroxide

Oxidation of a mixture of thiophene, benzothiophene and dibenzothiophene with hydrogen peroxide using supported Pd, Cr₂O₃, unsupported manganese oxides and a commercial Co-Mo/Al₂O₃ as catalysts has been studied in a mixture of hexadecane and acetonitrile. Based solely on the conversion of each organic sulfur compound, the ranking of catalyst efficiency found was: supported Pd > Cr₂O₃ ≈ manganese oxides ≈ Co-Mo/Al₂O₃. The influence of the calcination temperature on synthesized manganese oxides was also investigated. Mn₃O₄, amorphous manganese compounds, Mn₂O₃ and MnO₂ showed a similar catalytic activity independent of the hydrogen peroxide concentration. According to these preliminary results, it seemed that the catalyzed decomposition of the hydrogen peroxide competes with the oxidative desulfurization, however, at short reaction time (10 min) conversions at around 60–70% of thiophene were reached.     

Physico-chemical characteristics and CO oxidation studies over Pd/(Mn2O3 + SnO2) catalyst

The mixed oxide catalyst (Mn₂O₃ + SnO₂) prepared by the coprecipitation method has been impregnated with Pd metal and it's catalytic behaviour for CO oxidation reaction has been investigated. In the coprecipitated material, Mn₂O₃ and SnO₂ were found to crystallise at 875 K and 1175 K, respectively, which are significantly higher than the crystallisation temperatures of individual oxides prepared under similar conditions. Results of catalytic oxidation of CO, carried out using the pulse method for the mixed oxide system and the individual oxides, suggest significant synergistic effects between these two oxides. The impregnation of palladium metal facilitated CO oxidation and the catalyst Pd/(Mn₂O₃ + SnO₂) was found to be quite effective for CO oxidation even at room temperature. Further, the CO disproportionation has been observed on palladium sites in the temperature range 350 to 400 K for the individual oxide systems.     

氧化锰基电催化材料的设计合成及其铝空气电池应用

电催化剂作为铝空气电池阴极的核心部分,其催化性能的优劣直接影响铝空气电池的产业化进程。本文采用尿素高温处理法将商业的Vulcan-72XC碳材料进行掺氮改性处理制备了N/VC₂。在此基础上,进一步负载不同的锰氧化物得到三种Mn₃O₄@N/VC₂、MnO@N/VC₂和MnO₂@N/VC₂复合材料。其中,MnO₂@N/VC₂具有最优的氧还原反应(ORR)催化性能,起始电位高达0.872 V。作为铝空气电池阴极催化剂,在大电流密度下放电功率密度可达到136 mW·cm^-2。本文通过对比分析不同氧化锰基复合材料的电催化性能,研究了碳载体和锰氧化物之间的交互作用。结果表明,多孔结构和丰富缺陷位点的协同作用是提高材料催化活性的主要原因。该工作为锰基氧化物催化剂的研发提供理论依据。     

Novel hierarchical yolk-shell α-Ni(OH)2/Mn2O3 microspheres as high specific capacitance electrode materials for supercapacitors

For high performance supercapacitors, novel hierarchical yolk-shell a-Ni(OH)₂/Mn₂O₃ microspheres were controllably synthesized using a facile two-step method based on the solvothermal treatment. The unique a-Ni(OH)₂ based yolk-shell microstructures decorated with numerous interconnected nanosheets and the hetero-composition features can synergistically enhance reactive site exposure and electron conduction within the microspheres, facilitate charge transfer between electrolyte and electrode materials, and release structural stress during OH⁻ chemisorption/desorption. Moreover, the Mn₂O₃ sediments distributed over the a-Ni(OH)₂ microspheres can serve as an effective protective layer for electrochemical reactions. Consequently, when tested in 1 mol·L⁻¹ KOH aqueous electrolyte for supercapacitors, the yolk-shell a-Ni(OH)₂/Mn₂O₃ microspheres exhibited a considerably high specific capacitance of 2228.6 F·g⁻¹ at 1 A·g⁻¹ and an impressive capacitance retention of 77.7% after 3000 cycles at 10 A·g⁻¹. The proposed a-Ni(OH)₂/Mn₂O₃ microspheres with hetero-composition and unique hierarchical yolk-shell microstructures are highly promising to be used as electrode materials in supercapacitors and other energy storage devices.     

Location and size regulation of manganese oxides within mesoporous silica for enhanced antibiotic degradation

Refractory antibiotics in domestic wastewater are hard to be completely eliminated by conventional methods, and then lead to severe environmental contamination and adverse effects on public health. In present work, advanced oxidation processes (AOPs) are adopted to remove the antibiotic of sulfachloropyridazine (SCP). Nanosized Mn₂O₃ was fabricated on the SBA-15 material to catalytically activate potassium peroxydisulfate (PDS) to generate reactive oxygen radicals of ?OH and SO₄^- for SCP degradation. The effects of location and size of Mn₂O₃ were explored through choosing either the as-made or template-free SBA-15 as the precursor of substrate. Great influences from the site and size of Mn₂O₃ on the oxidation activity were discovered. It was found that Mn₂O₃ with a large size at the exterior of SBA-15 (Mn-tfSBA) was slightly easier to degrade SCP at a low manganese loading of 1.0–2.0?mmol?g^?1; however, complete SCP removal could only be achieved on the catalyst of Mn₂O₃ with a refined size at the interior of SBA-15 (Mn-asSBA). Moreover, the SO₄^- species were revealed to be the decisive radicals in the SCP degradation processes. Exploring the as-made mesoporous silica as a support provides a new idea for the further development of environmentally friendly catalysts.     

Ga掺杂FeNb11O29材料的制备及其电化学性能

FeNb₁₁O₂₉由于其高的理论充电容量(400 mAh·g^-1),作为锂离子电池(LIBs)负极材料具有很大的应用前景。然而,目前报道的FeNb₁₁O₂₉实际容量仅有168~273 mAh·g^-1。因此,有必要进一步提高其电化学性能。本文介绍了一种制备Ga掺杂FeNb₁₁O₂₉材料的方法,成功合成了Ga_xFe_1-xNb₁₁O₂₉(x=0.1,0.2)。结果表明,Ga_0.2Fe_0.8Nb₁₁O₂₉的电导率比FeNb₁₁O₂₉提高了两个数量级。X射线衍射结果显示,Ga掺杂不会改变FeNb₁₁O₂₉的正交剪切ReO₃晶体结构。扫描电镜结果显示,材料的微观形貌没有发生明显改变。电化学实验表明,Ga_0.2Fe_0.8Nb₁₁O₂₉具有较好的电化学性能,在电流密度为0.1 C时,Ga_0.2Fe_0.8Nb₁₁O₂₉充电容量为290 mAh·g^-1,当电流密度达到5 C时容量仍能保持145 mAh·g^-1,此外,Ga_0.2Fe_0.8Nb₁₁O₂₉具有良好的循环稳定性,在电流密度为5 C时循环1 000圈之后,容量保持率为91.0%,而不掺杂的FeNb₁₁O₂₉的充电容量仅有107 mAh·g^-1,容量保持率仅为55.9%。利用Ga掺杂改善FeNb₁₁O₂₉负极材料的电化学性能在锂离子电池中具有广阔的应用前景。