Article(id=1319969628344922383, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319969627665445134, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20230314, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1683648000000, receivedDateStr=2023-05-10, revisedDate=1686672000000, revisedDateStr=2023-06-14, acceptedDate=null, acceptedDateStr=null, onlineDate=1792634883247, onlineDateStr=2026-10-22, pubDate=1705680000000, pubDateStr=2024-01-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792634883247, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792634883247, creator=13701087609, updateTime=1792634883247, updator=13701087609, issue=Issue{id=1319969627665445134, tenantId=1146029695717560320, journalId=1263187385517883426, year='2024', volume='52', issue='1', pageStart='1', pageEnd='370', issueExtLink='null', onlineDate='null', pubDate='1705680000000', pubDateStr='2024-01-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792634883085, creator='13701087609', updateTime=1792641944622, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1319999245965443838, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319969627665445134, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1319999245965443839, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319969627665445134, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=46, endPage=55, ext={EN=ArticleExt(id=1319969630068781328, articleId=1319969628344922383, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Preparation of Na
2Ti
3O
7/C Anode Materials for Sodium Ion Battery by Biological Template Method and Its Sodium Storage Characteristics, columnId=1319726165087077079, journalTitle=Journal of the Chinese Ceramic Society, columnName=Research Article, runingTitle=null, highlight=null, articleAbstract=
Introduction Sodium batteries become a novel energy storage device due to their higher safety factor and superior comprehensive performance. The existing electrode materials such as NaxCoO2, NaxTiO2, NaTi2(PO4)3, etc. are investigated for sodium batteries. However, these electrodes have a disadvantage of poor ion/electronic conductivity, restricting their widespread application. Na2Ti3O7 is an ideal alternative titanium-based negative electrode material for sodium batteries due to its Ti3+/Ti4+ variability and suitable redox pairs, as well as its low voltage plateau. Embedding carbon in Na2Ti3O7 electrode for sodium ion batteries can improve their conductivity and electrochemical performance, especially for the large-scale energy storage applications with different energy density and volume requirements. In this paper, Na2Ti3O7/C composite anode material for sodium ion battery was prepared by a special template method, and its electrochemical characteristics were investigated.
Methods Na2Ti3O7/C composite anode material for sodium ion battery was synthesized with natural spirulina as a biological template. Spirulina was added into Na2Ti3O7 precursor solution, heated and stirred in a magnetic stirrer for 1 h, and then put them in a hydrothermal reactor (with a polytetrafluoroethylene inner tank capacity of 100 mL) at 180 ℃ for 18 h. In addition, Na2Ti3O7 precursor solution was also placed into a tank to hydrothermal reaction under the same condition for comparing with the template method. The final products were calcined in an air furnace (with a heating rate of 1 ℃/min from room temperature to 850 ℃) at 850 ℃ for 5 h to form the perfect crystals and remove the spirulina templates. A CR2032-typed buckle battery was assembled in a glove box (GRS-1200, Wuhan Grace New Energy Co., Ltd., China) filled in argon gas and with the synthesized Na2Ti3O7/C or Na2Ti3O7 electrodes as anodes, high purity sodium tablets as counter electrodes.
The microstructure of the product was characterized by a model Quanta 200 environmental scanning electron microscopy (ESEM) (FEI Ltd., Netherlands), and the components were analyzed by an EDAX spectrometer in the ESEM microscope. The crystal structure was determined by a model X'Pert PRO X-ray diffracto meter (XRD, PANalytical B.V. Ltd., Netherlands). The 2θ range of XRD is 5° to 70°. Their electrochemical properties were analyzed by a model CT2001A programmatical-controllable Land battery testing system (Hubei Lanbo New Energy Equipment Co., Ltd., China). The test parameters involved the charge-discharge capacities at a constant current (i.e., 0.5 C=125 mA/g), cycle stability and coulomb efficiency, and discharge capacities after 20 cycles at different rates (i.e., 0.1, 0.2, 0.3, 0.4 C, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 2.0 C, and 5.0 C). The alternating aurrent (AC) impedance was analyzed via a model CS350 electrochemical workstation (Wuhan Kesite Instrument Co., Ltd., China). The test parameters are the total impedance (R1) of electrode and electrolyte in series, electrode contact resistance (R2), sodium ion charge transfer resistance (R3) and semi-infinite diffusion Warburg impedance of Na+ in electrolyte (Ws).
Results and discussion The ESEM results show that Na2Ti3O7/C material prepared with the spirulina biological template has a good network strip structure, with a small amount of carbon residue (the mass fraction of carbon of 1.29%). The Na2Ti3O7 materials by a hydrothermal method are nano-particles with the diameters of approximately 10-30 nm. Their XRD patterns of both materials are consistent with the standard spectra of Na2Ti3O7 (JCPDS 31-1329), indicating a perfect crystal structure. The initial charge-discharge capacity of Na2Ti3O7/C electrode material prepared with spirulina template is 109.3 mA·h/g and 117.6 mA·h/g, respectively. The initial charge-discharge capacity is 89.3 mA·h/g and 86.3 mA·h/g of Na2Ti3O7 electrode material by the hydrothermal method, respectively. After 250 cycles, the average retention rate of the charge-discharge specific capacity of Na2Ti3O7/C material is 70%, which is better than that of Na2Ti3O7 material (i.e., 35%), showing a better cyclic stability and a higher Coulomb efficiency. Based on the results of the specific discharge capacities at different rates, the discharge attenuation of both the materials are faster at a lower current, while they are relatively stable at a higher current, which provides a good power support for high-power hybrid electric vehicles. At the same rate, the stability of Na2Ti3O7/C electrode material is better than that of Na2Ti3O7 electrode material. The electrochemical impedance spectra shows that R1, R2, R3 and Ws resistances of Na2Ti3O7/C material are smaller than those of Na2Ti3O7 material.
Conclusions The specific capacity decay rate of Na2Ti3O7/C electrode obtained by the spirulina template method was slower than that of Na2Ti3O7 electrode obtained by the hydrothermal method after charge-discharge cycles. This was due to the nano-network strip structure prepared by natural spirulina as a template. Na2Ti3O7/C electrode reduced the detachment resistance of sodium ions on the electrode surface and the diffusion resistance in the electrolyte, increased the contact area between the electrolyte and the electrode surface, thereby proved a good channel for the detachment of sodium ions, thus effectively improving the electrochemical performance of electrode materials. Moreover, the residual carbon in calcination improved its conductivity of Na2Ti3O7 electrode material, and enhanced its electrochemical performance, thus providing a basic support for the development and application of novel sodium batteries.
, authors=Li HUA, Jianhua ZENG, Yuhan ZHU, Fangqing WENG, authorsList=Li HUA, Jianhua ZENG, Yuhan ZHU, Fangqing WENG, authorCompany=null, correspAuthors=Jianhua ZENG, authorNote=
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2Ti
3O
7/C负极材料及其储钠性能, columnId=1263922770220560512, journalTitle=硅酸盐学报, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=
以天然螺旋藻为生物模板合成钠离子电池Na2Ti3O7/C负极材料，并与水热法合成Na2Ti3O7纳米材料进行对比。结果表明：该法制备的Na2Ti3O7/C负极材料呈良好的网络条状结构，其上有少量碳残留，首次充放电比容量分别是109.3 mA·h/g和117.6 mA·h/g。而水热法制备的Na2Ti3O7材料首次充放电比容量分别为89.3 mA·h/g和86.3 mAh/g。250次循环后其充放电比容量平均保持率在70%左右，明显优于水热法制备的Na2Ti3O7负极材料（平均为35%），且有更好的循环稳定性和更高的Coulomb效率。通过对合成的Na2Ti3O7/C和Na2Ti3O7在不同倍率下进行20次循环后分析其放电比容量，结果表明：两者在小电流条件下放电衰减比较快，大电流放电时电化学性能相对较稳定，且在相同倍率下Na2Ti3O7/C电极材料的稳定性较之水热法合成的Na2Ti3O7材料好，这为大功率混合动力电车提供了较好的动力支撑。交流阻抗对比分析显示：模板法获得的Na2Ti3O7/C在充放电过程中其电极和电解液总阻抗、电极接触电阻、钠离子电荷转移电阻、Na+在电解液中半无限扩散Wurburg阻抗均比水热法制备的Na2Ti3O7材料要小，进一步表明以天然螺旋藻为模板合成的纳米网络条状结构可以有效提高电极材料的电化学性能且锻烧中残留碳可提高其导电性，这为新型钠电池开发和应用的提供基础支持。
, authors=华丽, 曾建华, 朱玉涵, 翁方青, authorsList=华丽, 曾建华, 朱玉涵, 翁方青, authorCompany=null, correspAuthors=曾建华, authorNote=
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曾建华（1983—），男，博士，讲师。
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华丽（1974—），女，博士，教授。
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