Unveiling Organic Electrode Materials in Aqueous Zinc-Ion Batteries:From Structural Design to Electrochemical Performance

Aqueous zinc-ion batteries(AZIBs)are one of the most compelling alternatives of lithium-ion batteries due to their inherent safety and economics viability.In response to the growing demand for green and sustainable energy storage solutions,organic electrodes with the scalability from inexpensive starting materials and potential for biodegradation after use have become a prominent choice for AZIBs.Despite gratifying progresses of organic molecules with electrochemical performance in AZIBs,the research is still in infancy and hampered by certain issues due to the underlying complex electrochemistry.Strategies for designing organic electrode materials for AZIBs with high specific capacity and long cycling life are discussed in detail in this review.Specifically,we put emphasis on the unique electrochemistry of different redox-active structures to provide in-depth understanding of their working mechanisms.In addition,we highlight the importance of molecular size/dimension regarding their profound impact on electrochemical performances.Finally,challenges and perspectives are discussed from the developing point of view for future AZIBs.We hope to provide a valuable evaluation on organic electrode materials for AZIBs in our context and give inspiration for the rational design of high-performance AZIBs.

Experimental Study on the Electrochemical Performance of PEMFC under Different Assembly Forces

Proton exchange membrane fuel cell(PEMFC)is of paramount significance to the development of clean energy.The components of PEMFC are assembled using many pairs of nuts and bolts.The assembly champing bolt torque is critical to the electrochemical performance and mechanical stability of PEMFC.In this paper,a PEMFC with the threechannel serpentine flow field was used and studied.The different assembly clamping bolt torques were applied to the PEMFC in three uniform assembly bolt torque and six non-uniform assembly bolt torque conditions,respectively.And then,the electrochemical performance experiments were performed to study the effect of the assembly bolt torque on the electrochemical performance.The test results show that the assembly bolt torque significantly affected the electrochemical performance of the PEMFC.In uniform assembly bolt torque conditions,the maximal power density increased initially as the assembly bolt torque increased,and then decreased on further increasing the assembly torque.It existed the optimum assembly torque which was found to be 3.0 N·m in this work.In non-uniform assembly clamping bolt torque conditions,the optimum electrochemical performance appeared in the condition where the assembly torque of each bolt was closer to be 3.0 N·m.This could be due to the change of the contact resistance between the gas diffusion layer and bipolar plate and mass transport resistance for the hydrogen and oxygen towards the catalyst layers.This work could optimize the assembly force conditions and provide useful information for the practical PEMFC stack assembly.

Research on Preparation and Electrochemical Performance of the High Compacted Density Ni-Co-Mn Ternary Cathode Materials

The high compacted density LiNi0.5-xCo0.2Mn0.3MgxO2 cathode material for lithium-ion batteries was synthesized by high temperature solid-state method, taking the Mg element as a doping element and the spherical Ni0.5Co0.2Mn0.3 (OH)2, Li2CO3 as raw materials. The effects of calcination temperature on the structure and properties of the products were investigated. The structure and morphology of cathode materials powder were analyzed by X-ray diffraction spectroscopy (XRD) and scanning electronmicroscopy (SEM). The electrochemical properties of the cathode materials were studied by charge-discharge test and cyclic properties test. The results show that LiNi0.4985Co0.2Mn0.3 Mg0.0015O2 cathode material prepared at calcination temperature 930°C has a good layered structure, and the compacted density of the electrode sheet is above 3.68 g/cm3. The discharge capacity retention rate is more than 97.5% after 100 cycles at a charge-discharge rate of 1C, displaying a good cyclic performance.

Enhanced Electrochemical Performances of Ni Doped Cr_(8)O_(21)Cathode Materials for Lithium-ion Batteries

Cathode materials,nickel doped Cr_(8)O_(21),were synthesized by a solid-state method.The effects of Ni doping on the electrochemical performances of Cr_(8)O_(21) were investigated.The experimental results show that the discharge capacities of the samples depend on the nickel contents,which increases firstly and then decreases with increasing Ni contents.Optimized Ni_(0.5)Cr_(7.5)O_(21)delivers a first capacity up to 392.6 m Ah·g^(-1)at 0.1C.In addition,Ni doped sample also demonstrates enhanced cycling stability and rate capability compared with that of the bare Cr_(8)O_(21).At 1 C,an initial discharge capacity of 348.7 m Ah·g^(-1)was achieved for Ni_(0.5)Cr_(7.5)O_(21),much higher than 271.4 m Ah·g^(-1)of the un-doped sample,with an increase of more than 28%.Electrochemical impedance spectroscopy results confirm that Ni doping reduces the growth of interface resistance and charge transfer resistance,which is conducive to the electrochemical kinetic behaviors during charge-discharge.

Influence of Cathode Modification by Chitosan and Fe^(3+)on the Electrochemical Performance of Marine Sediment Microbial Fuel Cell

The electrochemical performances of cathode play a key role in the marine sediment microbial fuel cells(MSMFCs)as a long lasting power source to drive instruments,especially when the dissolved oxygen concentration is very low in seawater.A CTS-Fe^(3+)modified cathode is prepared here by grafting chitosan(CTS)on a carbon fiber surface and then chelating Fe^(3+)through the coordination process.The electrochemical performance in seawater and the output power of the assembled MSMFCs are both studied.The results show that the exchange current densities of CTS and the CTS-Fe^(3+)group are 5.5 and 6.2 times higher than that of the blank group,respectively.The potential of the CTS-Fe^(3+)modified cathode increases by 138 mV.The output power of the fuel cell(613.0 mW m^(-2))assembled with CTS-Fe^(3+)is 54 times larger than that of the blank group(11.4 mW m^(-2))and the current output corresponding with the maximum power output also increases by 56 times.Due to the valence conversion between Fe^(3+)and Fe^(2+)on the modified cathode,the kinetic activity of the dissolved oxygen reduction is accelerated and the depolarization capability of the cathode is enhanced,resulting higher cell power.On the basis of this study,the new cathode materials will be encouraged to design with the complex of iron ion in natural seawater as the catalysis for oxygen reduction to improve the cell power in deep sea.

Ce&F multifunctional modification improves the electrochemical performance of LiCoO_(2)at 4.60 V

Lithium cobalt oxide(LiCoO_(2))is proverbially employed as cathode materials of lithium-ion batteries attributed to the high theoretical capacity,and currently,it is developing towards higher cut-off voltages in the pursuit of higher energy density.However,it suffers from serious structural degradation and surface side reactions,in particular,at the voltage above 4.60 V,leading to rapid decay of the battery life.Taking into account the desirable oxygen buffering property and the fast ion mobility characteristic of cerium oxide fluoride,in this work,we prepared Ce&F co-modified LiCoO_(2)by using the precursors of Ce(NO_(3))_(3)·6H_(2)O and NH_(4)F,and evaluated the electrochemical performance under voltages exceeding 4.60 V.The results indicated that the modified samples have multiphase heterostructure of surface CeO_(2-x)and unique Ce-O-F solid solution phase.At 3.0–4.60 V and 25℃,the preferred sample LCO-0.5Ce-0.3F has a high initial discharge specific capacity of 221.9 mA h g^(-1)at 0.1 C,with the retention of 80.3%and 89.6%after 300 cycles at 1 and 5 C,comparing with the pristine LCO(56.4%and 22.6%).And at 3.0–4.65 V,its retention is 64.0%after 300 cycles at 1 C,versus 8.5%of the pristine LCO.Through structural characterizations and DFT calculations,it suggests that Ce^(4+)&F^(-)co-doping suppresses the H3 to H1/3 irreversible phase transition,stabilizes the lattice structure,and reduces the redox activity of the lattice oxygen by modulating the Co 3d–O 2p energy band,consequently improving the electrochemical performance of LiCoO_(2)at high voltages.

Influence of Ga and Bi on electrochemical performance of Al-Zn-Sn sacrificial anodes

The influence of Ga and Bi on the microstructure and electrochemical performance of Al-7Zn-0.1Sn （mass fraction,%） sacrificial anodes was investigated by means of optical microscopy （OM）,scanning electron microscopy/energy dispersive X-ray analysis （SEM/EDAX） and electrochemical measurements.It was found that the coarse dendrites structure transformed into the equiaxed grains as well as a small amount of dendrite grains after adding Ga and Bi into Al-Zn-Sn alloys.A high current efficiency of 97% and even corrosion morphology were obtained for Al-7Zn-0.1Sn-0.015Ga-0.1Bi alloy.The results indicate that the proper amount of Ga and Bi is effective on improving the microstructure and electrochemical performance of Al-Zn-Sn alloy.

Effects of stoichiometric ratio La/Mg on structures and electrochemical performances of as-cast and annealed La-Mg-Ni-based A_2B_7-type electrode alloys

In order to investigate the influences of the stoichiometric ratio of La/Mg （increasing La and decreasing Mg on the same mole ratio） on the structure and electrochemical performances of the La-Mg-Ni-based A2B7-type electrode alloy, the as-cast and the annealed ternary Lao.8＋xMgo.2_xNi3.5 （x=0-0.05） electrode alloys were prepared. The characterization of electrode alloys by X-ray diffraction （XRD） and scanning electron microscopy （SEM） shows that all the as-cast and the annealed alloys hold two major phases of （La,Mg）2Ni7 and LaNi5 as well as a residual phase of LaNi3. Moreover, the increase of La/Mg ratio brings on a decline of （La,Mg）2Ni7 phase and a rise of LaNi5 and LaNi3 phases. The variation of La/Mg ratio gives rise to an evident change of the electrochemical performances of the alloys. The discharge capacities of the as-cast and the annealed alloys evidently decrease with growing the La/Mg ratio, while the cycle stabilities of the alloys visibly augment under the same condition. Furthermore, the high rate discharge ability （HRD）, the electrochemical impedance spectrum （EIS）, the Tafel polarization curves, and the potential step measurements all indicate that the electrochemical kinetic properties of the alloy electrodes increase with the La/Mg ratio rising.

Grinding sol gel synthesis and electrochemical performance of mesoporous Li_3V_2(PO_4)_3 cathode materials

Li3V2（PO4）3 precursor was obtained with V2Os.nH2O , LiOH＇H2O, NH4H2PO4 and sucrose as starting materials by grinding-sol-gel method, and then the monoclinic-typed Li3Vz（PO4）3 cathode material was prepared by sintering the amorphous Li3V2（PO4）3. The as-sintered samples were investigated by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, N2 adsorption-desorption and electrochemical measurement. It is found that Li3Vz（PO4）3 sintered at 700 ℃ possesses good wormhole-like mesoporous structure with the largest specific surface area of 188 cmZ/g, and the smallest pore size of 9.3 nm. Electrochemical test reveals that the initial discharge capacity of the 700 ℃ sintered sample is 155.9 mA.h/g at the rate of 0.2C, and the capacity retains 154 mA.h/g after 50 cycles, exhibiting a stable discharge capacity at room temperature.

Effect of ultrasonic on structure and electrochemical performance of α-Ni(OH)_2 electrodes

Al/Co co-doped α-Ni（OH）2 samples were prepared by either ultrasonic co-precipitation method （Sample B） or co-precipitation method （Sample A）. The crystal structure and particle size distribution of the prepared samples were examined by X-ray diffraction （XRD） and laser particle size analyzer, respectively. The results show that Sample B has more crystalline defects and smaller average diameter than Sample A. The cyclic voltammetry and electrochemical impedance spectroscopy measurements indicate that Sample B has better electrochemical performance than Sample A, such as better reaction reversibility, lower charge-transfer resistance and better cyclic stability. Proton diffusion coefficient of Sample B is 1.96×10-10cm2/s, which is two times as large as that （9.78×10-11cm2/s） of Sample A. The charge-discharge tests show that the discharge capacity （308 mA·h/g） of Sample B is 25 mA·h/g higher than that of Sample A （283 mA·h/g）.

Preparation and electrochemical performance of nano-scale Ni(OH)_2 doped with zinc

Nano-scale Ni（OH）2 doped with Zn was prepared by precipitation transformation method and characterized by XRD and TEM. The electrochemical performance was investigated by cyclic voltammetry （CV） and constant current technology. The measurement results indicate that the lattice parameters of nano-scale Ni（OH）2 are changed and the agglomeration of particles becomes obvious with the increased Zn-doped content. Compared with un-doped one, the discharge specific capacities ofnano-scale Ni（OH）2 doped with 10% Zn are enhanced by 8% and 6%, respectively, at the discharge rate of 0.2C and 3C. After 110 cycles, the discharge specific capacity of the sample doped with 10% zinc is still above 85% of its initial capacity discharged at 0.2C. Therefore, a suitable Zn-doped content is beneficial to improving the discharge performance of nano-scale Ni（OH）2.

Effect of germanium on electrochemical performance of chain-like Co-P anode material for Ni/Co rechargeable batteries

Co-P （4.9% P） powders with a chain-like morphology were prepared by a novel chemical reduction method. The Co-P and germanium powders were mixed at various mass ratios to form Co-P composite electrodes. Charge and discharge test and electrochemical impedance spectroscopy （EIS） were carried out to investigate the electrochemical performance, which can be significantly improved by the addition of germanium. For instance, when the mass ratio of Co-P powders to germanium is 5：1, the sample electrode shows a reversible discharge capacity of 350.3 mA·h/g and a high capacity retention rate of 95.9% after 50 cycles. The results of cyclic voltammmetry （CV） show the reaction mechanism of Co/Co（OH）2 within Co-P composite electrodes and EIS indicates that this electrode shows a low charge-transfer resistance, facilitating the oxidation of Co to Co（OH）2.

Improving electrochemical performances of LiFePO_4 /C cathode material via a novel three-layer electrode

As an improvement on the conventional two-layer electrode （active material layerlcurrent collector）, a novel sandwich-like three-layer electrode （conductive layerlactive material layertcurrent collector） for cathode material LiFePO4/C was introduced in order to improve its electrochemical performance. LiFePO4/C in the three-layer electrode exhibited superior rate capability in comparison with that in the two-layer electrode in accordance with charge-discharge examination. Cyclic voltammetry and electrochemical impedance spectroscopy indicated that Fe3＋/Fe2＋ redox couple for LiFePO4 in the three-layer electrode displayed faster kinetics, better reversibility and much lower charge transfer resistance than that in the two-layer electrode in electrochemical process. For three-layer electrode, the holes in the surface of active material layer were filled by smaller acetylene black grains, which formed electrical connections and provided more pathways to electron transport to/from LiFePO4/C particles exposed to the bulk electrolyte.

Structure and electrochemical performance of Cu singly doped and Cu/Al co-doped nano-nickel hydroxide

Nanometer Cu singly doped and Cu/Al co-doped nickel hydroxides were synthesized by ultrasonic-assisted precipitation method. Their crystal structure, particle size, morphology, tap density and electrochemical performance were investigated. The results show that the samples have a-phase structure with narrow particle size distribution. Cu singly doped nano-Ni（OH）2 contains irregular particles, while Cu/Al co-doped nano-Ni（OH）2 displays a quasi-spherical shape and has a relatively higher tap density. Composite electrodes were prepared by mixing 8% （mass fraction） nanometer samples with commercial micro-size spherical nickel. The charge/discharge test and cyclic voltammetry results indicate that the electrochemical performance of Cu/Al co-doped nano-Ni（OH）2 is better than that of Cu singly doped nano-Ni（OH）2, the former＇s discharge capacity reaches 330 mA.h/g at 0.2C, 12 mA.h/g and 91 mA.h/g larger than that of Cu singly doped sample and pure spherical nickel electrode, respectively. Moreover, the proton diffusion coefficient of Cu/Al co-doped sample is 52.3% larger than that of Cu singly doped sample.

Electrochemical performances of AB_5-type hydrogen storage alloy modified with Co_3O_4

Anodic electrodes with the mixture of hydrogen storage alloys and different contents of Co3O4（2%,4%,6% and 8%,mass fraction） powders were made.The effects of Co3O4 on the electrochemical performance of the alloy electrodes were studied.The constant charge-discharge tests show that the discharge capacity of alloy electrodes with Co3O4 significantly increases,and the maximum discharge capacities of electrodes with 2%,4%,6% and 8% Co3O4 are higher than the electrode with no Co3O4 by 0.83%,4.86%,7.18% and 9.21%,accordingly.Linear polarization（LP） and electrochemical impedance spectroscopy（EIS） tests suggest that charge-transfer resistance decreases by the addition of Co3O4.Cyclic voltammogram（CV）,scanning electron microscopy（SEM） and energy dispersive spectrum（EDS） tests indicate that Co3O4 can partly dissolve and experience a reversible oxidation-reduction process of Co to Co（OH）2,leading to the improvement in the electrochemical performance of hydrogen storage alloy.

Electrochemical performances of Mg_(45)M_5Co_(50)(M=Pd, Zr) ternary hydrogen storage electrodes

In order to improve the discharge capacity and cyclic life of Mg-Co-based alloy, ternary Mg45M5Co50 （M=Pd, Zr） alloys were synthesized via mechanical alloying. TEM analysis demonstrates that these alloys all possess body-centered cubic （BCC） phase in nano-crystalline. Electrochemical experiments show that Mg45Zr5Co50 electrode exhibits the highest capacity （425 mA·h/g） among the Mg45M5Co50 （M=Mg, Pd, Zr） alloys. And Mg45Pd5Co50 electrode lifts not only the initial discharge capacity （379 mA·h/g）, but also the discharge kinetics, e.g., exchange current density and hydrogen diffusion ability from that of Mg50Co50. It could be concluded that the electrochemical performances were enhanced by substituting Zr and Pd for Mg in Mg-Co-based alloy.

Electrochemical performance of sulfur composite cathode materials for rechargeable lithium batteries

The structure and characteristic of carbon materials have a direct influence on the electrochemical performance of sulfur-carbon composite electrode materials for lithium-sulfur battery. In this paper, sulfur composite has been synthesized by heating a mixture of elemental sulfur and activated carbon, which is characterized as high specific surface area and microporous structure. The composite, contained 70% sulfur, as cathode in a lithium cell based on organic liquid electrolyte was tested at room temperature. It showed two reduction peaks at 2.05 V and 2.35 V, one oxidation peak at 2.4 V during cyclic voltammogram test. The initial discharge specific capacity was 1180.8 mAh g-1 and the utilization of electrochemically active sulfur was about 70.6% assuming a complete reaction to the product of Li2S. The specific capacity still kept as high as 720.4 mAh g^-1 after 60 cycles retaining 61% of the initial discharge capacity.

Influence of Mg and Ti on the microstructure and electrochemical performance of aluminum alloy sacrificial anodes

The experiments focused on the influence of magnesium and titanium as additional alloying elements on the microstructure and electro-chemical behavior of Al-Zn-In sacrificial anodes. The electrochemical behavior of the aluminum sacrificial anode with 3 wt.% sodium chloride solution was studied by electrochemical impedance spectroscopy (EIS) tests. It was found that a microstructure with few precipitates and refined grains could be achieved by adding 1 wt.% Mg and 0.05 wt.% Ti to the Al-Zn-In alloy,resulting...

Electrochemical performances of as-cast and annealed La_(0.8-x)Nd_xMg_(0.2)Ni_(3.35)Al_(0.1)Si_0.05(x=0-0.4) alloys applied to Ni/metal hydride (MH) battery

The La-Mg-Ni-based A2B7-type Lao.8_xNdx Mgo.2Ni3.35Alo.lSio.o5 （x = 0, 0.1, 0.2, 0.3, and 0.4） electrode alloys were prepared by casting and annealing. The influence of the partial substitution of Nd for La on the structure and electrochemical performances of the alloys was investigated. The structural analysis of X-ray diffraction and scanning electron microscopy reveals that the experimental alloys consist of two major phases： （La,Mg）2Ni7 with the hexagonal Ce2Ni7-type structure and LaNi5 with the hexagonal CaCus-type structure as well as some residual phases of LaNi3 and NdNis. The electrochemical measurements indicate that an evident change of the electrochemical performance of the alloys is associated with the substitution of Nd for La. The discharge capacity of the alloy first increases then decreases with the growing Nd content, whereas their cycle stability clearly grows all the time. Furthermore, the measurements of the high rate discharge ability, the limiting current density, and hydrogen diffusion coefficient all demonstrate that the electrochemical kinetic properties of the alloy electrodes first augment then decline with the rising amount of Nd substitution.

Enhanced Electrochemical Performances of LiFePO4/C via V and F Co-doping for Lithium-Ion Batteries

Based on the method of in situ polymerization synthesis combined with two-step sinter- ing process, LiFel-xVx（PO4）（3-y）/3Fy/C was prepared. The effects of V and F co-doping on the structure, morphology, and electrochemical performances of LiFePO4/C were in- vestigated by X-ray diffraction, Fourier transform infrared spectra, scanning electron mi- croscope, charge/discharge tests, and electrochemical impedance spectroscopy, respectively. The results indicated that the V and F co-doping did not destroy the olivine structure of LiFePO4/C, but it can stabilize the crystal structure, decrease charge transfer resistance, enhance Li ion diffusion velocity, further improve its cycling and high-rate capabilities of LiFePO4/C.