Supercapattery: Merit merge of capacitive and Nernstian charge storage mechanisms

Supercapattery is the generic name for hybrids of supercapacitor and rechargeable battery. Batteries store charge via Faradaic processes, involving reversible transfer of localised or zone-delocalised valence electrons. The former is governed by the Nernst equation. The latter leads to pseudocapacitance (or Faradaic capacitance) which may be differentiated from electric double layer capacitance with spectroscopic assistance such as electron spin resonance. Because capacitive storage is the basis of supercapacitors, the combination of capacitive and Nernstian mechanisms has dominated supercapattery research since 2018, covering nanostructured and compounded metal oxides and sulphides, water-in-salt and redox active electrolytes and bipolar stacks of multicells. The technical achievements so far, such as specific energy of 270 Wh/kg in aqueous electrolyte, and charging–discharging for more than 5000 cycles, benchmark a challenging but promising future of supercapattery.     

Development of Miniaturized Electrochemiluminescence Instrument using Multi‐pixel Photon Counter as the Optical Detector

We developed a miniaturized electrochemiluminescence (ECL) instrument coupled with a light‐emitting diode‐based bipolar electrochemical sensor (LED‐BPES). This instrument composes of a microcontroller circuit, a power supply circuit, a potentiostat, an optical detecting circuit, and a communication circuit. The multi‐pixel photon counter (MPPC), which is low‐cost, small‐size, and wide‐range in optical measurements, is chosen as the optical detector. The LED‐BPES composes of a disposable screen‐printed carbon electrode (SPCE) and a surface‐mount red LED. Depended on the closed bipolar electrode (C‐BPE) structure, the LED‐BPES not only avoids the employment of unstable and complex ECL reactions but also offers a cost‐effective alternative for the over‐priced ECL reagents by using a mini‐size commercial LED as the luminescent producer. The combination of MPPC and LED‐BPES helps to set up the simplified and downsized instrument system with low price and high efficiency. The presented instrument coupled with LED‐BPES works excellent in electroactive molecules detection and has great potential in the application of heavy metal ions detection.     

基于三苯胺/二苯砜的热激活延迟荧光材料

通过Suzuki反应合成了三种基于三苯胺/二苯砜的热激活延迟荧光(TADF)材料(1-3),采用紫外-可见(UV-Vis)吸收光谱、时间分辨荧光发射光谱、循环伏安(CV)测试、理论计算、热重分析和差示扫描量热法,系统地研究了三种材料的光物理、电化学、延迟荧光性能和热稳定性.材料1-3均为基于分子内电荷转移(ICT)的双极性分子.三种材料在薄膜中的单线态-三线态能级差分别为0.46、0.39和0.29 eV.荧光量子效率和荧光寿命的测试结果表明,三种材料均能发射延迟荧光,其中材料3具有最佳的延迟荧光性能.材料1-3的最高占有分子轨道(HOMO)能级分别为-4.91、-4.89和-4.89 eV.结合UV-Vis吸收光谱中得到的能隙(E_g)值,我们得到材料1-3的最低未占分子轨道(LUMO)能级,分别为-1.74、-1.89和-1.94 eV.热分析的结果表明,材料1-3具有其较高的热分解温度(T_d,失重5%时的温度),分别为436、387和310 ℃.     

Study on the deterioration process of bipolar coating using electrochemical impedance spectroscopy

A bipolar coating, which is composed of inner layer epoxy with nano SiO₂ modified by cetyltrimethylammonium bromide (CTAB) (containing positive fixed charge) and outer layer epoxy with nano SiO₂ modified by sodium dodecylbenzenesulfonate (SDBS) (containing negative charge), was prepared in this paper. Its deterioration process after exposure to 5% KCl solution was also studied by EIS measurement and SEM observation. The results indicate that the impedance module of the bipolar coating is about 1E+9 ohm after a longer time immersion period. The bipolar coating has a better anti-corrosion capacity than that of epoxy coating. The cation-selective outer layer in bipolar coating inhibits the aggressive anion, such as Cl⁻ ion, passing through the outer coating. Similarly, the anion-selective inner layer inhibits the metal cation passing through the inner coating. Thus the bipolar coating can protect the metal substrate from corrosion effectively. The p-n junction of bipolar coating, which has great charge storage ability, is the key factor in the anti-corrosion capacity of bipolar coating.     

Experiment and simulation of space charge suppression in LDPE/MgO nanocomposite under external DC electric field

In this paper, space charge dynamics under DC electric field of −100 kV/mm in low-density polyethylene (LDPE) and its nanocomposite containing a small amount of MgO nanoparticles were measured using an improved pulsed electro-acoustic (PEA) system. Unlike negative packet-like space charge accumulating in LDPE films, no remarkable space charge was observed in LDPE/MgO nanocomposite films, which indicated that the introduction of MgO nanoparticles played a key role on the space charge suppression. Different with current qualitative models, this paper describes space charge suppression on the basis of simulation using the bipolar charge transport model, which featured bipolar charges injection, transport, trapping, recombination, and extraction process. It was shown from the simulation that trap depth, trap concentration, local electric field and charge injection barrier height were all significant factors on the space charge suppression process. A deeper trap depth in LDPE/MgO nanocomposites made it easier for traps to capture mobile carriers. And a larger trap concentration effectively slowed down the whole carrier movement although there seemed a trap concentration threshold less than 30 Cm⁻³, above which this effect became slight. In addition, both the high permittivity of LDPE/MgO nanocomposites and low local electric field in the vicinity of cathode led to a larger injection barrier height based on the Schottky injection law, which would tremendously block the charge injection. At last, the suppression mechanism of space charge formation in the LDPE/MgO nanocomposites is presented.     

Role of oxygen vacancies formed between top electrodes and epitaxial NiO films in bipolar resistance switching

We investigated bipolar resistance switching (RS) behavior of a top electrode/epitaxial NiO using Al and Pt as the top electrodes (TEs) and epitaxial NiO deposited at 500 °C (NiO-500) and 700 °C (NiO-700). We found that the contact between Al and Pt TEs and NiO-500 was a high resistance insulating contact, while the contact between the two TEs and NiO-700 was a low-resistance metallic contact. We also found that only NiO-500 with the Pt TE exhibited bipolar RS after an electroforming process. This study suggests that during the formation of the Pt/NiO-500 interface, the amount and behavior of oxygen at the interface seem to play the most important role in bipolar RS behavior. In order to improve the device performance, better control of oxygen content and its movement at the interface seems necessary.     

双极界面聚合物膜燃料电池研究进展

双极界面聚合物膜燃料电池(BPFCs)作为一类新型的具有酸碱双极界面结构的聚合物膜燃料电池,其新颖的膜电极结构带来了突出的优势以及独特的界面问题。随着关键材料与界面工艺的发展,近年来双极界面聚合物膜燃料电池取得了显著的研究成果。本文将梳理膜电极工艺及结构、关键反应界面、水传输机制以及非铂催化剂应用等方面的研究进展。这些基础理论与关键技术的发展为双极界面聚合物膜燃料电池未来深入研究和开发奠定了良好的基础。     

改性316L不锈钢表面聚苯胺的制备及电化学性能

采用原位氧化技术调整316L不锈钢(SS316L)基体元素Cr和Ni在界面的浓度和分布, 形成了Ni和Cr富集改性界面. 应用计时电位技术, 通过Cr和Ni改性层催化草酸溶液中的苯胺单体在其表面吸附并聚合, 在SS316L表面沉积了附着力良好的聚苯胺(PANI)膜. 与SS316L相比, 表面富Ni-Cr的SS316L在涂覆PANI膜后, 在80 ℃ 0.5 mol/L H₂SO₄+5 mg/L F^-溶液中阳极和阴极的腐蚀电位分别提高470和500 mV, 维钝电流均下降2~3个数量级; 在模拟质子交换膜燃料电池运行环境中, 经36000 s恒电位极化, 其阳极和阴极的腐蚀电流分别下降约1和2个数量级, 腐蚀速度分别约为6~9 和< 5 μA/cm²; 在1.4 MPa压力下, 聚苯胺膜层与Toray 060碳纸间接触电阻下降约250 mΩ·cm². SS316L表面形成富Ni-Cr改性层并涂覆聚苯胺膜后, 其耐蚀性和导电性均明显优于原始SS316L, 这主要取决于富Ni-Cr改性层的结构、 组成和聚苯胺膜的厚度.     

Generalized MAGSTE with bipolar diffusion-weighting gradient pulses

The generalized magic asymmetric gradient stimulated echo (generalized MAGSTE) sequence compensates background gradient cross-terms and can be adjusted to asymmetric timing boundary conditions which for instance are present in echo-planar MR imaging. However, its efficiency is not optimal because one of the two diffusion-weighting gradients applied in each interval usually must have a reduced amplitude to ensure the desired cross-term compensation. In this work, a modification of generalized MAGSTE is investigated where this gradient pulse is replaced by two gradient pulses with full amplitude but opposite polarities. It is shown that with these bipolar gradients (i) the sequence retains the cross-term compensation capability for an appropriate choice of the gradient pulse durations and (ii) the diffusion-weighting efficiency is improved, i.e. higher k and b values can be achieved without prolonging the echo time. These results are confirmed in MR imaging experiments on phantoms and in vivo in the human brain at 3 T using spin-echo and echo-planar MR imaging. In the examples shown, the b value could be increased between about 30% and 200% when using the bipolar gradient pulses. Thus, bipolar gradients may help to improve the applicability of the generalized MAGSTE sequence.     

CoPc(COOH)8-SA/mCS双极膜的制备及表征

分别用Fe3+离子和戊二醛作为交联剂对海藻酸钠(SA)阳膜层和壳聚糖(CS)阴膜层进行改性, 制备了八羧基钴酞菁-海藻酸钠/改性壳聚糖(CoPc(COOH)8-SA/mCS)双极膜(BPM). 在海藻酸钠阳膜层中添加八羧基钴酞菁以提高阳膜的离子交换容量, 促进中间层水的解离. 用傅立叶红外(FT-IR)光谱、扫描电镜(SEM)等方法对制备的双极膜进行了表征. 实验结果表明, 经八羧基钴酞菁改性后, 阳离子交换膜层的离子交换容量、H+离子透过率均获得提高. 与Fe3+离子改性或二茂铁离子改性的mSA/mCS双极膜相比, CoPc(COOH)8-SA/mCS双极膜的交流阻抗、电阻压降(IR降)和溶胀度降低. 当电流密度高达105 mA·cm-2时, CoPc(COOH)8-SA/mCS双极膜的IR降仅为0.7 V.