Calcium Cobalt Hexacyanoferrate Cathodes for Rechargeable Divalent Ion Batteries

2016 ◽  
Vol 19 (2) ◽  
pp. 057-064 ◽  
Author(s):  
Prasanna Padigi ◽  
Neal Kuperman ◽  
Joseph James Thiebes ◽  
Gary Goncher ◽  
David Evans ◽  
...  

Calcium cobalt hexacyanoferrate (CaCoHCF) was synthesized and tested as a cathode material for rechargeable batteries, using divalent cations (Mg2+, Ca2+, Ba2+). CaCoHCF demonstrated reversible specific capacity and coulombic efficiency (in parentheses) of 45.49 mAh/g (99.18%) for Mg2+, 55.04 mAh/g (99.2%) for Ca2+, and 44.09 mAh/g (99.42%) for Ba2+, at a current density of 25 mA/g. Of the three ions, Ca2+ resulted in the highest absolute specific capacity as well as high specific capacity utilization. The cathodes were also subjected to rate capability measurements using current densities of 50 mA/g (30 cycles) and 0.1 A/g (100 cycles). Upon addition of 2 mL water to the non-aqueous electrolyte, the fraction of theoretical specific capacity increased to 0.55 for Mg2+, 94.8% for Ca2+, and 95.53% forBa2+. This increase has been interpreted as the ability of the cathode material to intercalate and de-intercalate more ions due to the electrostatic shielding provided by water molecules between the host lattice and the guest cations. An empirical relationship between the cation size and specific capacity utilization is presented.Calcium cobalt hexacyanoferrate (CaCoHCF) was synthesized and tested as a cathode material for rechargeable batteries, using divalent cations (Mg2+, Ca2+, Ba2+). CaCoHCF demonstrated reversible specific capacity and coulombic efficiency (in parentheses) of 45.49 mAh/g (99.18%) for Mg2+, 55.04 mAh/g (99.2%) for Ca2+, and 44.09 mAh/g (99.42%) for Ba2+, at a current density of 25 mA/g. Of the three ions, Ca2+ resulted in highest absolute specific capacity as well as high specific capacity utilization. The cathodes were also subjected to rate capability measurements using current densities of 50 mA/g (30 cycles) and 0.1 A/g (100 cycles). Upon addition of 2 mL water to the non-aqueous electrolyte, the fraction of theoretical specific capacity increased to 0.55 for Mg2+, 94.8% for Ca2+, and 95.53% forBa2+. This increase has been interpreted as the ability of the cathode material to intercalate and de-intercalate more ions due to the electrostatic shielding provided by water molecules between the host lattice and the guest cations. An empirical relationship between the cation size and specific capacity utilization is presented.

MRS Advances ◽  
2019 ◽  
Vol 4 (14) ◽  
pp. 821-828 ◽  
Author(s):  
Gaind P. Pandey ◽  
Kobi Jones ◽  
Lamartine Meda

ABSTRACTHigh-energy lithium-sulfur (Li-S) batteries still suffer from poor rate capability and short cycle life caused by the polysulfides shuttle and insulating nature of S (and the discharge product, Li2S). Selenium disulfide (SeS2), with a theoretical specific capacity of 1342 mAh g−1, is a promising cathode material as it has better conductivity compared to sulfur. The electrochemical reaction kinetics of CNFs-S/SeS2 composites (denoted as CNFs/S1-xSex, where x ≤ 0.1) are expected to be remarkably improved because of the better conductivity of SeS2 compared to sulfur. Here, a high-performance composite cathode material of CNFs/S1-xSex for novel Li-S batteries is reported. The CNFs/S1-xSex composites combine the higher conductivity and higher density of SeS2 with high specific capacity of sulfur. The CNFs/S1-xSex electrode shows good initial discharge capacity of ∼1050 mAh g−1 at 0.05 C rate with high mass loading of materials (∼6-7 mg cm−2 of composites) and > 97% initial coulombic efficiency. The CNFs/S1-xSex electrode shows more than 600 mAh g-1 specific capacity after 50 charge-discharge cycles at 0.5C rate, much higher compared to the CNFs/S cathodes.


RSC Advances ◽  
2015 ◽  
Vol 5 (94) ◽  
pp. 77324-77331 ◽  
Author(s):  
Qingliang Xie ◽  
Chenhao Zhao ◽  
Zhibiao Hu ◽  
Qi Huang ◽  
Cheng Chen ◽  
...  

Layered Li[Li0.2Mn0.56Ni0.16Co0.08]O2 porous microspheres have been successfully synthesized by a urea combustion method, and then coated with appropriate amount of LaPO4via a facile chemical precipitation route.


2019 ◽  
Vol 10 ◽  
pp. 514-521 ◽  
Author(s):  
Yongguang Zhang ◽  
Jun Ren ◽  
Yan Zhao ◽  
Taizhe Tan ◽  
Fuxing Yin ◽  
...  

In this work, a unique three-dimensional (3D) structured carbon-based composite was synthesized. In the composite, multiwalled carbon nanotubes (MWCNT) form a lattice matrix in which porous spherical reduced graphene oxide (RGO) completes the 3D structure. When used in Li–S batteries, the 3D porous lattice matrix not only accommodates a high content of sulfur, but also induces a confinement effect towards polysulfide, and thereby reduces the “shuttle effect”. The as-prepared S-3D-RGO@MWCNT composite delivers an initial specific capacity of 1102 mAh·g−1. After 200 charging/discharge cycles, a capacity of 805 mAh·g−1 and a coulombic efficiency of 98% were maintained, implying the shuttle effect was greatly suppressed by the composite matrix. In addition, the S-3D-RGO@MWCNT composite also exhibits an excellent rate capability.


2018 ◽  
Vol 2018 ◽  
pp. 1-7
Author(s):  
He Wang ◽  
Mingning Chang ◽  
Yonglei Zheng ◽  
Ningning Li ◽  
Siheng Chen ◽  
...  

A lithium-rich manganese-based cathode material, Li1.25Ni0.2Co0.333Fe0.133Mn0.333O2, was prepared using a polyvinyl alcohol (PVA)-auxiliary sol-gel process using MnO2 as a template. The effect of the PVA content (0.0–15.0 wt%) on the electrochemical properties and morphology of Li1.25Ni0.2Co0.333Fe0.133Mn0.333O2 was investigated. Analysis of Li1.25Ni0.2Co0.333Fe0.133Mn0.333O2 X-ray diffraction patterns by RIETAN-FP program confirmed the layered α-NaFeO2 structure. The discharge capacity and coulombic efficiency of Li1.25Ni0.2Co0.333Fe0.133Mn0.333O2 in the first cycle were improved with increasing PVA content. In particular, the best material reached a first discharge capacity of 206.0 mAhg−1 and best rate capability (74.8 mAhg−1 at 5 C). Meanwhile, the highest capacity retention was 87.7% for 50 cycles. Finally, electrochemical impedance spectroscopy shows that as the PVA content increases, the charge-transfer resistance decreases.


2020 ◽  
Vol 12 (1) ◽  
Author(s):  
Jiangmin Jiang ◽  
Guangdi Nie ◽  
Ping Nie ◽  
Zhiwei Li ◽  
Zhenghui Pan ◽  
...  

AbstractAmong the various morphologies of carbon-based materials, hollow carbon nanostructures are of particular interest for energy storage. They have been widely investigated as electrode materials in different types of rechargeable batteries, owing to their high surface areas in association with the high surface-to-volume ratios, controllable pores and pore size distribution, high electrical conductivity, and excellent chemical and mechanical stability, which are beneficial for providing active sites, accelerating electrons/ions transfer, interacting with electrolytes, and giving rise to high specific capacity, rate capability, cycling ability, and overall electrochemical performance. In this overview, we look into the ongoing progresses that are being made with the nanohollow carbon materials, including nanospheres, nanopolyhedrons, and nanofibers, in relation to their applications in the main types of rechargeable batteries. The design and synthesis strategies for them and their electrochemical performance in rechargeable batteries, including lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, and lithium–sulfur batteries are comprehensively reviewed and discussed, together with the challenges being faced and perspectives for them.


2021 ◽  
Vol 13 (1) ◽  
Author(s):  
Qiulong Wei ◽  
Qidong Li ◽  
Yalong Jiang ◽  
Yunlong Zhao ◽  
Shuangshuang Tan ◽  
...  

AbstractHigh-performance and low-cost sodium-ion capacitors (SICs) show tremendous potential applications in public transport and grid energy storage. However, conventional SICs are limited by the low specific capacity, poor rate capability, and low initial coulombic efficiency (ICE) of anode materials. Herein, we report layered iron vanadate (Fe5V15O39 (OH)9·9H2O) ultrathin nanosheets with a thickness of ~ 2.2 nm (FeVO UNSs) as a novel anode for rapid and reversible sodium-ion storage. According to in situ synchrotron X-ray diffractions and electrochemical analysis, the storage mechanism of FeVO UNSs anode is Na+ intercalation pseudocapacitance under a safe potential window. The FeVO UNSs anode delivers high ICE (93.86%), high reversible capacity (292 mAh g−1), excellent cycling stability, and remarkable rate capability. Furthermore, a pseudocapacitor–battery hybrid SIC (PBH-SIC) consisting of pseudocapacitor-type FeVO UNSs anode and battery-type Na3(VO)2(PO4)2F cathode is assembled with the elimination of presodiation treatments. The PBH-SIC involves faradaic reaction on both cathode and anode materials, delivering a high energy density of 126 Wh kg−1 at 91 W kg−1, a high power density of 7.6 kW kg−1 with an energy density of 43 Wh kg−1, and 9000 stable cycles. The tunable vanadate materials with high-performance Na+ intercalation pseudocapacitance provide a direction for developing next-generation high-energy capacitors.


2021 ◽  
Vol 9 ◽  
Author(s):  
Chengwei Lu ◽  
Ruyi Fang ◽  
Kun Wang ◽  
Zhen Xiao ◽  
G. Gnana kumar ◽  
...  

Selenium-sulfur solid solutions (Se1-xSx) are considered to be a new class of promising cathodic materials for high-performance rechargeable lithium batteries owing to their superior electric conductivity than S and higher theoretical specific capacity than Se. In this work, high-performance Li-Se1-xSx batteries employed freestanding cathodes by encapsulating Se1-xSx in a N-doped carbon framework with three-dimensional (3D) interconnected porous structure (NC@SWCNTs) are proposed. Se1-xSx is uniformly dispersed in 3D porous carbon matrix with the assistance of supercritical CO2 (SC-CO2) technique. Impressively, NC@SWCNTs host not only provides spatial confinement for Se1-xSx and efficient physical/chemical adsorption of intermediates, but also offers a highly conductive framework to facilitate ion/electron transport. More importantly, the Se/S ratio of Se1-xSx plays an important role on the electrochemical performance of Li- Se1-xSx batteries. Benefiting from the rationally designed structure and chemical composition, NC@[email protected] cathode exhibits excellent cyclic stability (632 mA h g−1 at 200 cycle at 0.2 A g−1) and superior rate capability (415 mA h g−1 at 2.0 A g−1) in carbonate-based electrolyte. This novel NC@[email protected] cathode not only introduces a new strategy to design high-performance cathodes, but also provides a new approach to fabricate freestanding cathodes towards practical applications of high-energy-density rechargeable batteries.


NANO ◽  
2019 ◽  
Vol 14 (08) ◽  
pp. 1950103
Author(s):  
Wen-Zhe Shen ◽  
Yi Ma ◽  
Yao-Chun Yao ◽  
Feng Liang

Ni-rich Li(Ni[Formula: see text]Co[Formula: see text]Mn[Formula: see text]O2 cathode material is widely recognized as one of the most cathode materials for lithium-ion batteries due to its high specific capacity, high energy density and low cost. In this paper, the NCM cathode material precursor Ni[Formula: see text]Co[Formula: see text]Mn[Formula: see text](OH)2 was prepared by coprecipitation method and the optimum experimental conditions were investigated. The effects of water bath temperature on the electrochemical performances of the prepared materials were investigated by controlling the morphology. The results showed that 60∘C was the best bath temperature for the precursor which has a regular spheroidal morphology and uniform particles with the diameter of 10[Formula: see text][Formula: see text]m. After coprecipitation, the samples calcined under oxygen atmosphere displayed good electrochemical properties. The discharge specific capacity is up to 194[Formula: see text]mA[Formula: see text][Formula: see text][Formula: see text]h[Formula: see text][Formula: see text][Formula: see text]g[Formula: see text] and 134[Formula: see text]mA[Formula: see text][Formula: see text][Formula: see text]h[Formula: see text][Formula: see text][Formula: see text]g[Formula: see text] at 0.2∘C and 5∘C, respectively. The initial coulombic efficiency is 87.57% at 0.2∘C.


Materials ◽  
2021 ◽  
Vol 14 (5) ◽  
pp. 1071
Author(s):  
Xuli Ding ◽  
Daowei Liang ◽  
Hongda Zhao

Although the silicon oxide (SiO2) as an anode material shows potential and promise for lithium-ion batteries (LIBs), owing to its high capacity, low cost, abundance, and safety, severe capacity decay and sluggish charge transfer during the discharge–charge process has caused a serious challenge for available applications. Herein, a novel 3D porous silicon oxide@Pourous Carbon@Tin (SiO2@Pc@Sn) composite anode material was firstly designed and synthesized by freeze-drying and thermal-melting self-assembly, in which SiO2 microparticles were encapsulated in the porous carbon as well as Sn nanoballs being uniformly dispersed in the SiO2@Pc-like sesame seeds, effectively constructing a robust and conductive 3D porous Jujube cake-like architecture that is beneficial for fast ion transfer and high structural stability. Such a SiO2@Pc@Sn micro-nano hierarchical structure as a LIBs anode exhibits a large reversible specific capacity ~520 mAh·g−1, initial coulombic efficiency (ICE) ~52%, outstanding rate capability, and excellent cycling stability over 100 cycles. Furthermore, the phase evolution and underlying electrochemical mechanism during the charge–discharge process were further uncovered by cyclic voltammetry (CV) investigation.


Author(s):  
Bumjun Park ◽  
Christiana Oh ◽  
Sooyoun Yu ◽  
Bingxin Yang ◽  
Nosang Vincent Myung ◽  
...  

Abstract As the energy storage markets demand increased capacity of rechargeable batteries, Li metal anodes have regained major attention due to their high theoretical specific capacity. However, Li anodes tend to have dendritic growth and constant electrolyte consumption upon cycling, which lead to safety concerns, low Coulombic efficiency, and short cycle life of the battery. In this work, both conductive and non-conductive 3D porous hosts were coupled with a viscous (melt) polymer electrolyte. The cross-section of the hosts showed good contact between porous hosts and the melt polymer electrolyte before and after extensive cycling, indicating that the viscous electrolyte successfully refilled the space upon Li stripping. Upon deep Li deposition/stripping cycling (5 mAh cm-2), the non-conductive host with the viscous electrolyte successfully cycled, while conductive host allowed rapid short circuiting. Post-mortem cross-sectional imaging showed that the Li deposition was confined to the top layers of the host. COMSOL simulations indicated that current density was higher and more restricted to the top of the conductive host with the polymer electrolyte than the liquid electrolyte. This resulted in quicker short circuiting of the polymer electrolyte cell during deep cycling. Thus, the non-conductive 3D host is preferred for coupling with the melt polymer electrolyte.


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