Article(id=1320107557860000484, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320107530261479891, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20250437, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1749139200000, receivedDateStr=2025-06-06, revisedDate=1757433600000, revisedDateStr=2025-09-10, acceptedDate=null, acceptedDateStr=null, onlineDate=1792667768205, onlineDateStr=2026-10-22, pubDate=1782144000000, pubDateStr=2026-06-23, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792667768205, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792667768205, creator=13701087609, updateTime=1792667768205, updator=13701087609, issue=Issue{id=1320107530261479891, tenantId=1146029695717560320, journalId=1263187385517883426, year='2026', volume='54', issue='7', pageStart='2171', pageEnd='2576', issueExtLink='null', onlineDate='null', pubDate='1784476800000', pubDateStr='2026-07-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792667761625, creator='13701087609', updateTime=1792720444956, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1320328500238725499, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320107530261479891, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1320328500238725500, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320107530261479891, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=2408, endPage=2423, ext={EN=ArticleExt(id=1320107558036161253, articleId=1320107557860000484, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Construction of Hierarchically Porous Nitrogen-Doped Carbon Supported Mo
2C Materials and Its Performance in Catalyzing Conversion of Lithium Polysulfides, columnId=1263922769897599102, journalTitle=Journal of the Chinese Ceramic Society, columnName=Research Articles, runingTitle=null, highlight=null, articleAbstract=
Introduction Hierarchical porous nitrogen-doped carbon-supported Mo2C particle composite materials (Mo2C@PCN-X) were constructed by an anti-solvent method and a subsequent in-situ pyrolysis process with ammonium molybdate tetrahydrate and ammonium citrate as precursors, and sodium chloride as a template. The nitrogen-doped carbon pore structure and Mo2C loading in Mo2C@PCN-X were regulated via adjusting the addition ratio of ammonium molybdate tetrahydrate. The results show that the number of hollow cavities in Mo2C@PCN-X increases with the increase in the amount of ammonium molybdate tetrahydrate added, providing abundant storage space for lithium polysulfides (Li2Sn, n=4-8) and restricting the diffusion of LiPS through physical interactions. Furthermore, the Mo2C particles exhibit significant adsorption capacity and catalytic activity toward LiPS, accelerating the conversion of soluble Li2Sn to solid-state Li2S2/Li2S, thereby effectively suppressing the shuttle effect. The S@Mo2C@PCN-1.5 cathode delivers a high reversible discharge capacity of 1207 mA·h·g-1 at 0.1 C and maintains 517 mA·h·g-1 at 1.0 C. After 200 cycles, this cathode demonstrates a low per-cycle decay rate of merely 0.1%, exhibiting superior cycling stability compared to pristine S@PCN.
Methods 15 g of sodium chloride was dissolved in 50 mL of deionized water. Afterwards, 1.5 g of ammonium molybdate tetrahydrate [(NH4)6Mo7O24·4H2O] and 4.786 g of ammonium citrate (C6H17O7N3) were sequentially added to the solution, followed by continuous stirring until complete dissolution. The mixed solution above was rapidly poured into 400 mL of industrial ethanol and vigorously stirred for 5 min. After precipitation, the NaCl@C6H17O7N3-1.5 precursor was obtained by filtration and drying. Also, NaCl@C6H17O7N3-0, NaCl@C6H17O7N3-1.0, and NaCl@C6H17O7N3-2.0 precursors were prepared via varying the addition amount of ammonium molybdate tetrahydrate (0, 1 g, and 2 g), respectively, based on the above procedure. The NaCl@C6H17O7N3-X (X=0, 1.0, 1.5, and 2.0) precursors were heated in a tube furnace to 450 ℃ at a rate of 5 ℃·min-1 under an Ar-H2 (10%, in volume fraction) mixed atmosphere for 2 h, and then continuously heated to 800 ℃ at the same rate and held for another 2 h. After cooling to room temperature, NaCl-Mo2C@PCN-X powders were obtained. The powders were washed for three times with deionized water to remove the NaCl template (with template recovery), and dried at 70 ℃ to obtain Mo2C@PCN-X composites and PCN support materials. Mo2C@PCN-X was mixed with sulfur powder at a mass ratio of 3∶7, ground uniformly with a small amount of ethanol and dried. The mixture was heated in a tube furnace to 155 ℃ at a rate of 5 ℃·min-1, held for 12 h, and then further heated to 200 ℃ and held for 20 min to remove the excess sulfur on the surface of Mo2C@PCN-X. After natural cooling, the S@Mo2C@PCN-X composite cathode material was prepared. In addition, S@PCN composite cathode material was also prepared as a control sample using PCN as a substrate according to the procedure above.
Results and discussion The analysis of micro-morphologies of PCN and Mo2C@PCN-X composites shows that the number of elongated pore structures increases from Mo2C@PCN-1.0 to Mo2C@PCN-1.5, but decreases significantly from Mo2C@PCN-1.5 to Mo2C@PCN-2.0 as the addition amount of (NH4)6Mo7O24·4H2O increases, possibly due to the collapse of excessive pore structures. Abundant pore structures are beneficial for the storage and transport of electrolytes. Compared with other samples, Mo2C@PCN-1.5 exhibits a larger specific surface area and pore structure, which can provide more internal voids for sulfur loading and inhibit the dissolution of Li2Sn. Meanwhile, the smaller pore diameters can enhance the adsorption capacity of carbon materials for polysulfides. Compared with pure carbon materials, the specific surface area of composites with added ammonium molybdate tetrahydrate increases significantly. This is likely because during the precursor preparation process, ammonium molybdate tetrahydrate crystallizes on the sodium chloride template after adding ethanol. In the subsequent carbonization process, ammonium molybdate tetrahydrate crystals extract carbon from the carbon material to form molybdenum carbide. In this process, the vacancies of extracted carbon form micropores, and unreacted molybdate leaves some micropores after washing. These micropores provide a larger specific surface area for the carbon material. However, the specific surface area decreases with the increase in the addition amount of ammonium molybdate tetrahydrate, possibly because the excessive addition causes larger crystal grains to form on the sodium chloride template. The larger grains extract too much carbon during the reaction, leading to the collapse of generated micropores. The adsorption capacity of the support materials for polysulfides is intuitively determined by visual experiments and UV-VIS absorption spectroscopy. After adsorption by Mo2C@PCN-1.5, the solution color significantly fades, and the absorption peak intensities of Li2S6 and Li2S4 decrease significantly, indicating that the Mo2C@PCN-1.5 support material can strongly adsorb polysulfides. The results of symmetrical battery and deposition experiments demonstrate that Mo2C@PCN-1.5 with appropriate molybdenum carbide catalysis exhibits better polysulfide conversion kinetics. The electrochemical performance analysis of full batteries confirms that Mo2C@PCN-1.5 has superior cycling and rate performance, as well as high sulfur loading capacity. As a cathode substrate, Mo2C@PCN-1.5 is more conducive to promoting the retention of polysulfides and the utilization of active materials.
Conclusions In this work, a Mo2C@PCN-X composite material with a hierarchical pore structure was constructed by a green and facile anti-solvent strategy. The results showed that the introduction of the precursor (NH4)6Mo7O24·4H2O had a regulatory effect on the crystallization behavior of the NaCl template, inducing the carbon component in the Mo2C@PCN-X composite to form a hierarchical pore structure with additional cavities, and the cavity density was positively correlated to the molybdenum source concentration. When Mo2C@PCN-X was used as a host for LSB batteries, the three-dimensional interconnected pores of the PCN matrix could promote electrolyte infiltration and adsorb soluble Li2Sn (n=4-8) through physical action. Moreover, the Mo2C particles loaded on its surface could enhance the chemical adsorption of Li2Sn by the Mo2C@PCN-X host material through d-p orbital hybridization, while reducing the energy barrier for Li2S deposition/decomposition. However, Mo2C could agglomerate as the loading amount increased, reducing the specific surface area of the material. Therefore, under the same conditions, the S@Mo2C@PCN-1.5 positive electrode exhibited the optimum reversible discharge capacity and capacity retention rate during cycling. The crystallization regulation mechanism could provide an idea for the controllable preparation of porous carbon-based composites. Future research could focus on reducing the particle size of Mo2C through strategies such as surface functional modification, so as to provide a theoretical reference for the design of positive electrode materials for high-energy-density LSBs.
, authors=Bingshu GUO, Hengyu WANG, Miao FU, Junchen CHEN, Bo YU, Shouwen GAO, Bin SUN, Chunshuang WANG, Lin CHEN, Nanfeng XIANG, authorsList=Bingshu GUO, Hengyu WANG, Miao FU, Junchen CHEN, Bo YU, Shouwen GAO, Bin SUN, Chunshuang WANG, Lin CHEN, Nanfeng XIANG, authorCompany=null, correspAuthors=Bingshu GUO, Junchen CHEN, Bo YU, authorNote=
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2C复合材料的构筑及其催化多硫化锂转化性能, columnId=1263922770220560512, journalTitle=硅酸盐学报, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=
锂硫电池具有能量密度高、成本低廉且环境友好的优势，但其循环寿命受限于多硫化物穿梭效应。本工作以四水合钼酸铵和柠檬酸铵为前驱体，氯化钠为模板，利用反溶剂法和原位热解过程，构建分级多孔氮掺杂碳负载Mo2C复合材料（Mo2C@PCN-X），用以缓解上述难题。通过调整四水合钼酸铵的添加量，调节Mo2C@PCN-X中氮掺杂碳孔结构及Mo2C的负载量。分析结果显示，Mo2C@PCN-X中空腔数量随四水合钼酸铵的添加量增多而增加，为多硫化锂（Li2Sn，n=4～8）提供了丰富的存储空间，可以物理限制Li2Sn的扩散。此外，Mo2C颗粒对Li2Sn具有显著的吸附能力和催化作用，可以加速可溶性Li2Sn向固态Li2S2/Li2S的转化，从而有效抑制穿梭效应。得益于上述协同作用，S@Mo2C@PCN-1.5正极在0.1C时表现出1207 mA·h·g-1的高可逆放电容量，在1.0 C下容量依然保持517 mA·h·g-1，经过200次循环后，每圈衰减率仅为0.1%，循环稳定性优于S@PCN。
, authors=郭秉淑, 汪恒宇, 付淼, 陈俊臣, 于博, 高守文, 孙斌, 王春爽, 陈琳, 向南风, authorsList=郭秉淑, 汪恒宇, 付淼, 陈俊臣, 于博, 高守文, 孙斌, 王春爽, 陈琳, 向南风, authorCompany=null, correspAuthors=郭秉淑, 陈俊臣, 于博, authorNote=
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郭秉淑（1992—），女，博士，讲师；
陈俊臣（1988—），男，博士，讲师；
于博（1991—），男，博士，副研究员。
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