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zhaocl铁杆木虫 (职业作家)
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关于赝电容电极材料和Battery-type electrode materials的争论已有8人参与
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最近做钴、镍等相关赝电容电极材料的的朋友在投稿时都会遇到审稿人提到Battery-type electrode materials，如下： （1）“The as-prepared Ni3(VO4)2 material in this manuscript is termed as a “supercapacitor” electrode material, however, the authors need to carefully check whether Ni3(VO4)2 is a supercapacitor electrode material. The sharp redox peaks in CVs and the flat voltage plateaus in the charge-discharge curves indicate that this material should be a typical battery-type electrode material instead of a pseudocapacitive electrode material. This means that all terms and the calculation of electrochemical performance based on the supercapacitor in this manuscript are unacceptable. More discussion about this issue could be found in literatures, e.g., DOI: 10.1149/2.0201505jes, 10.1021/nn503164x, 10.1126/science.1249625, 10.1126/science.1213003, and B. E. Conway’s book (Electrochemical supercapacitors: scientific fundamentals and technological applications). （2）However, to the best of my knowledge and according to the most recent studies, such system shoudn't be classified as pseudocapacitive material. It's because its electrochemical characteristics is different from a fundamental definition of capacitance (or pseudocapacitance). I'm aware that there is a growing number of reports describing "pseudocapacitive" nature of such oxides as cobalt or nickel but from the fundamental point of view such diffusion controlled faradaic processes charactersistics of aforementioned materials have nothing to do with simple capacitor (or pseudocapacitor)-type storage of electrical charge. Therefore, I suggest to change reported specific capacitances (in F/g) values into specific capacities (in C/g or mAh/g). Also, the energy densities should be calculated using recently suggested methods of evaluation reported in following papers: Thierry Brousse, Daniel Belanger, Jeffrey W. Long, Journal of The Electrochemical Society, 162 A5185-A5189 (2015) * Laheäär, A., Przygocki, P., Abbas, Q., Béguin, Electrochemistry Communications, 60 (2015), 21-25 Further, terms such as " pseudocapacitance", pseudocapacitive" should be used in the manuscript only to distinguish between real pseudocapacitance (such as observed and measured eg. for RuOx or MnOx) and battery-type behaviour such as those reported in the paper. To conclude: the material is of a great potential but as high power battery electrode, rather than capacitive (or pseudocapacitive) material. （3）Materials like Co3O4 should be called as Battery-type electrode, not the Pseudocapacitance according to Journal of the Electrochemical Society, 162 (2015) A5185-A5189. 最近有几篇文章是彻底妥协了，如： 1）Physicochemical identity and charge storage properties of battery-type nickel oxide material and its composites with activated carbon. ELECTROCHIMICA ACTA 卷: 194 页: 480-488 出版年: MAR 10 2016 2) Zhen Li*, et al. A facile enhancement in battery-type of capacitive performance of spinel NiCo2O4 nanostructure via directly tuning thermal decomposition temperature. ELECTROCHIMICA ACTA 卷: 191 页: 364-374 出版年: FEB 10 2016 3) Erqing Xie*, et al. Construction of hierarchical ZnCo2O4@NixCo2x(OH)6x core/shell nanowire arrays for high-performance supercapacitors. J. Mater. Chem. A, 2016,4, 173-182. 4) Zhongtai Zhang*, et al. Hydroxyl compensation effects on the cycle stability of Nickel-Cobalt layered double hydroxides synthesized via solvothermal method. ELECTROCHIMICA ACTA 卷: 182 页: 445-451 出版年: NOV 10 2015. 5) High-performance hybrid supercapacitor with 3D hierarchical porous flower-like layered double hydroxide grown on nickel foam as binder-free electrode. Journal of Power Sources, Volume 318, 30 June 2016, Pages 76–85. 关键是 Daniel Belanger, Jeffrey W. Long, Journal of The Electrochemical Society, 162 A5185-A5189 (2015)这篇文章很一般，但很多赝电容的文章审稿都要落到这个人手里，他顺便引用几篇Science上似是而非的文章，要求你必须按照他这篇文章的要求来修改。 但是Gogotsi et al (Science, 2011, 334, 917) suggesting to create a National or International testing facility for benchmarking electrodes and devices similar to the facilities that exist for benchmarking photovoltaics . “There should be clear rules for reporting the performance of new materials for EES devices. This would help scientists who are not experts in the field, as well as engineers, investors, and the general public, who rely on the data published by the scientists, to assess competing claims.” 不知道大家遇到这个问题该如何处理？ 非常感谢您的交流！ |
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7楼2016-05-09 10:17:24
wrt8089503
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2楼2016-04-28 01:48:27
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不错的整理。 个人觉得问题最大的根源，在于一开始是把redox/faradaic capacitance当成一种pseudocapacitance。 然后用一般计算electric double layer capacitance的计算法来操作，但并不符合capacitance的基本原理。 Daniel Belanger, Jeffrey W. Long, Journal of The Electrochemical Society, 162 A5185-A5189 (2015) 这篇文章看起来很一般，但作者们是领域先驱，也是真正的电化学专家（包括Gogotsi, P. Simon等），尝试拨乱反正。因为近年这领域火热，许多电化学基础不好的科研人员都涌着去做这块（包括我自己），节奏太快，很多机理没搞清楚就赶着发表，人云亦云，就把错误当正宗了。如果是对的，就不会近期文章“妥协”的情况，因为没有道理说服编辑和审稿人......目前也没有师姐所说的争论之说，因为大家原本一窝蜂的发表，之后大牛们出来指正，然后又一窝蜂的改正。如果师姐有很好的论述，可以尝试写篇correspondence去回应。 Gogotsi et al (Science, 2011, 334, 917) 提的是另外的问题，在PV领域，个别实验室的太阳能电池，测量出的Solar Cell Efficiency如果有特出数值，会把器件送到其他公共实验室（比如NREL, Fraunhofer, AIST）根据国际标准做审核（certify），得到的数据就有公信力。但是电化学电容器没有这种审核，个别实验室用个别的制备方法、实验、计算，得到的结果并不基于同样的测试标准，很容易夸大，难以被其他实验室复制、实用价值低。我个人曾在PV课题组工作过，也做过电化学电容，非常认可Gogotsi论点的必要。 |
3楼2016-04-28 17:02:42
dens314
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4楼2016-04-29 00:21:07