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The present work is aimed at investigating the electrochemical properties of Li-ion cells, assembled using lithium substituted polyaniline and its composites with LiFePO4 and LiMn2O4 as the cathode active materials. Lithium substitution in PANI can be achieved by a variety of approaches and the present work introduces one of the cost effective meth...
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... Figure 6. In order to improve the charge storage capacity, Puthirath et al. mixed 15% lithium substituted polyaniline (LiPo) and LFP/LM in the ratio of 9:1 to synthesize the composite cathode material of LiPo-LFP/LM and compared its performance through the cyclic voltammetry curve and charge-discharge test of assembled batteries [22]. It was found that the theoretical capacity of polyaniline was 142mAh/g after 100% lithium substitution [23]. ...
The global climate change, which is intensifying yearly, makes more countries realize that mankind needs to take effective actions as soon as possible. Eliminating carbon emissions from diesel vehicles has become the research target under the spotlight in recent decades; that is to say, electric vehicles are expected to be accessible and popularized by more people shortly. Batteries are the key component of electric vehicles. However, they are also the major impediment to the development of electric vehicles for their high production costs, safety issues, durability, long charging time and low working efficiency, making them less attractive to consumers than traditional fossil fuel-powered cars. Enhancing the performance of electrodes is the most direct and effective way toward highly efficient lithium-ion batteries. This paper will introduce the mainstream electrode materials commonly used in the lithium-ion battery industry and the possible methods of improving the properties of electrode materials through compositing and nanotechnology.
... In a number of studies, LiFePO 4 -based cathodes were prepared using conventional additives (carbon black and PVDF) to the slurry containing lithium iron phosphate and ex situ polymerized EAECP (PEDOT:PSS [102,103], poly-o-methoxyaniline [104], PANI [105], or a redox active fluoflavin polymer [106]). Cíntora-Juárez et al. [102] reported the fabrication of two different LiFePO 4 /CB/PEDOT:PSS/PVDF electrodes (79:7:7:7 wt% and 84:8:1:7 wt%) from in-house synthesized lithium iron phosphate and a commercial PEDOT:PSS aqueous dispersion (1.1 wt%). ...
... At the same time, the composite electrode failed to demonstrate good high rate performance, likely because of the variable potential-dependent conductivity of the POMA. Another study reported the use of ex situ lithium-doped PANI as a conductive binder in LiFePO 4 /CB/Li-PANI/PVDF composites [105]. The lithiation accomplished by treating PANI with n-butyllithium yielded enhanced crystallinity/order in Li substituted samples compared to pure PANI. ...
As a cathode material for lithium-ion batteries, lithium iron phosphate (LiFePO4, LFP) successfully transitioned from laboratory bench to commercial product but was outshone by high capacity/high voltage lithium metal oxide chemistries. Recent changes in the global economy combined with advances in the battery pack design brought industry attention back to LFP. However, well-recognized intrinsic drawbacks of LiFePO4 such as relatively low specific capacity and poor electronic and ionic conductivity have not yet been fully mitigated. Integration of electrochemically active electron-conducting polymers (EAECPs) into the cathode structure to replace conventional auxiliary electrode components has been proposed as an effective strategy for further performance improvement of LFP batteries. In this review, we show how various combinations of polymer properties/functions have been utilized in composite LiFePO4 electrodes containing EAECP components. We present recent advances in the cathode design, materials, and methods and highlight the impact of synthetic strategies for the cathode preparation on its electrochemical performance in lithium-ion cells. We discuss advantages and limitations of the proposed approaches as well as challenges of their adoption by the battery manufactures. We conclude with perspectives on future development in this area.
... After 15 cycles, the cell capacity saturated around 50 mAh g À1 . Moreover, to improve the electrochemical properties of the battery cells, advanced hybrid cathode materials are explored combining PANI with inorganic and organic materials such as LiFePO 4 [291][292][293], LiMn 2 O 4 [293], MOS 2 [294,295], V 2 O 5 [296], polyoxometalate (POM) [232], graphene or reduced graphene [297]. Ajpi and co-workers [292] have reported that the hybrid PANI-LiFePO 4 shows much improved capacity of 145 mAh g À1 at a charge/discharge rate of 0.1C while compared with pristine PANI (which is 95 mAh g À1 ) or LiFePO 4 (120 mAh g À1 ) cathode system. ...
... After 15 cycles, the cell capacity saturated around 50 mAh g À1 . Moreover, to improve the electrochemical properties of the battery cells, advanced hybrid cathode materials are explored combining PANI with inorganic and organic materials such as LiFePO 4 [291][292][293], LiMn 2 O 4 [293], MOS 2 [294,295], V 2 O 5 [296], polyoxometalate (POM) [232], graphene or reduced graphene [297]. Ajpi and co-workers [292] have reported that the hybrid PANI-LiFePO 4 shows much improved capacity of 145 mAh g À1 at a charge/discharge rate of 0.1C while compared with pristine PANI (which is 95 mAh g À1 ) or LiFePO 4 (120 mAh g À1 ) cathode system. ...
Polymer material provides significant advantages over the conventional inorganic material-based electronics due to its attractive features including miniaturized dimension and feasible improvisations in physical properties through molecular design and chemical synthesis. In particular, conjugate polymers are of great interest because of their ability to control the energy gap and electronegativity through molecular design that has made possible the synthesis of conducting polymers with a range of ionization potentials and electron affinities. Polyaniline (PANI) is one of the most popular conjugated polymers that has been widely explored so far for its multifunctionality in diverse potential applications. This review is focusing on the recent advances of PANI for smart energy applications including supercapacitors, batteries, solar cells and nanogenerators and the development in its synthesis, design, and fabrication processes. A details investigation on the different types of chemical process has been discussed to fabricate PANI in nanostructures, film, and composites form. The paper includes several studies which are advantageous for understanding: the unique chemical and physical properties of this polymer; and the easily tunable electrical properties along with its redox behavior; and different processes to develop nanostructures, film, or bulk form of PANI that are useful to derive its applicability in smart objects or devices.
... The diameter of the semicircle is different, the highest resistance at the electrode/electrolyte interface belongs to the LMO/CNT-Gr, which can be explained by the hydrophobic properties of the carbon materials present and involved in the activation process which appears at the start of the electrochemical cycling. The corresponding impedance at high frequencies shows that the resistance for the LMO/CNT-Gr/PANI during the charge transfer from the electrode to the electrolyte exhibit the smallest value, thus it can be concluded that introducing PANI into the composite electrode causes an increase of Li+ insertion/extraction, which leads to improving the electrochemical performance [46]. The quasi-linear part at a low frequency is known as the Warburg element and appears during the Li-ion diffusion through the electrode material. ...
The electrochemical parameters of a novel binder-free self-standing biomimetic cathode based on lithium manganese oxide (LMO) and carbon nanotubes (CNT) for rechargeable Lithium-ion aqueous batteries (ReLIAB) are improved using polyaniline (PANI) core-shell in situ polymerization and graphene (Gr). The fabricated cathode material exhibits the so-called “tectonic plate island bridge” biomimetic structure. This constitution is created by combining three components as shown by a SEM and a TEM analysis: the Gr substrates support an entangled matrix of conductive CNT which connect island of non-conductive inorganic material composed of LMO. The typical spinel structure of the LMO remains unchanged after modifying the basic structure with Gr and PANI due to a simplified hydrothermal method used for synthesis. The Gr and PANI core-shell coating improves the electric conductivity from 0.0025 S/cm up to 1 S/cm. The electrochemical performances of the LMO/CNT-Gr/PANI composite electrode are optimized up to 136 mA h g−1 compared to 111 mA h g−1 of the LMO/CNT. Besides that, the new electrode shows good cycling stability after 200 galvanostatic charging/discharging cycles, making this structure a future candidate for cathode materials for ReLIAB.
... The maximum lithiation was calculated only 15 % in this report. The cell constructed by 5% doped PANI as cathode and lithium metal as anode exhibit capacity of 25.04 mAhg −1 [98]. ...
Electrical energy storage has become one of most interesting topics due to energy and environment crises. Exploration and development of high performance rechargeable batteries are the primary research goals where polymeric materials are key ingredients for these devices. The replacement of traditional redox active materials like metals, metal oxides by innovatively new polymeric materials based on the requirements of structure-property relationships and physical phenomenon that lead the way in sustainably developing high-energy density devices. Such type of energy storage devices ensures the enhanced cycling life, charging speed, flexible batteries fabrication as well as high power densities. In the present review, we discuss the fundamental aspects of polymer science that are employed to facilitate the progress of battery's material aspects. Precisely, designing of polymers is discussed for acquiring the desired chemical interactions, electrical and ionic conductivity and mechanical stability. The role of polymeric species as artificial interface builders and their future developments are also discussed for variety of battery chemistries.
... Li-doped polyaniline (LIPO) mixed with LiFePO 4 and LiMn 2 O 4 synthesized through a cost-effective method, which can act as flexible cathode materials inLIBs. Li substitution or lithiation in PANI has been employed by treating PANI with n-butyllithium (n-BuLi) in hexane, and the Li-doped PANI was later mixed with LFP and LiMnO 2 (LMO) (weight ratio of 9:1) [85]. In this work, the maximum lithiation was only 15%. ...
... In this work, the maximum lithiation was only 15%. In addition, a cell constructed with 5% Li-doped PANI as the cathode and Li metal as the anode 25.04 mAhg − 1 capacity at C/10 rate [85]. This method can be considered eco-friendly since n-BuLi was used as the precursor material for Li-doping instead of toxic compounds, such as LiPF 6 and LiBF 4 . ...
Recently, polymers, especially conducting (CPs) and non-conducting polymers (nCPs), have been emerged as the promising flexible electrode components for lithium-ion batteries due to their inherent high mechanical tolerance limit, excellent thermal and chemical stability, low density, ease of processing, low cost, and versatility. In addition, CPs provide good electrical conductivity. Polymeric structures remain almost the same even after hundreds to thousands of electrochemical cycles. However, some crucial factors, such as low conductivity, energy density, and rate performance, often limit the large-scale exploitation of these polymers. Although CPs, and nCPs can provide the desired flexibility, nCPs, in particular, increase the ‘dead volume’ of electrodes. In this context, it is necessary to resolve the issues existing with the polymers to make them effective confinement matrices for flexible electrodes. On the other hand, customizing the electrode architectures is vital for achieving multidirectional flexibility without compromising energy density and overall capacity. However, low active materials loading and deviation from the customized structures after several deformation cycles still affect the desired performance in terms of electrochemical and mechanical. Furthermore, the intricate and costly preparation processes of customized electrodes are the major bottlenecks toward practical applications. This review discusses the recent progress, merits, and demerits of the most widely studied polymer composites-based and architectural engineering induced flexible electrodes for lithium-ion batteries (LIBs). Both CPs and nCPs are discussed in the perspectives of current research status, major limitations, key factors associated with electrochemical performances and future outlook of the developments on polymer-based flexible electrodes.
... Extensive research efforts have been devoted for the development of novel types of electrode materials with excellent electrochemical performance [2]. Conducting polymer-based rechargeable Li-ion cells with high specific capacity, high energy density, excellent cycling characteristics and long life span [3,4] are being widely investigated as novel types of devices for developing flexible energy storage systems. ...
... Puthirath AB and co-workers have investigated the structural and electrochemical properties of Li-ion cells, assembled using Li-substituted polyaniline (PANI) as the cathode active material, and the cells are found to show a maximum discharge capacity of 25.04 mAh/g and cycling stability over 50 cycles [4]. Present authors have already reported the synthesis of polypyrrole by chemical oxidative polymerization using FeCl 3 as the oxidant, followed by detailed structural, morphological and electrochemical characterizations of the Li-enriched PPy [16]. ...
... The good oxidation/ reduction reversibility of the lithiated polypyrrole cathode is revealed by the symmetrical peaks in the CV curves corresponding to the four lithiated samples with relative increment in the narrow peak-to-peak separation of the anodic and the cathodic potential. Excellent electrochemical activity of Liions in lithium-substituted polypyrrole is revealed by the increase in the area under the anodic and cathodic peaks with increase in lithium substitution [4]. ...
Present study deals with the efforts undertaken to improve the electrochemical performance of lithium-substituted polypyrrole (PPy) as the cathode active material in Li-ion-based cells. Improvement in the electrochemical performance is achieved by synthesizing polypyrrole by chemical oxidative polymerization strategy using ammonium persulfate (APS) as the oxidant. Polypyrrole synthesized using the modified approach is subjected to lithiation by treating with n-butyllithium in hexanes (n-BuLi). Lithium-enriched PPy is used as the cathode active material to assemble Li-ion cells, and the assembled cells are subjected to detailed electrochemical characterization. The cells are found to show significant improvement in the electrochemical performance.
... Moreover, several coating properties may improve one aspect of performance while hindering another [24]. Several coating materials with variable characters and conventionality have been found to increase cathode performance as measured by both increasing the capacity and capacity retention [28]. LMO can be prepared by different methods, like conventional solid-state reaction [29], sol-gel [30], solid-state coordination reaction [31], microwave [32], and agitation [33]. ...
... The acquired impedance data are given in Table 1, which demonstrates that R CT increases in the order of LMO (1) [ PANI [ LMO@PANI. This indicates that introducing PANI into LMO (1) material causes an increase in Li-ion conductivity that resulted in enhanced cycling performance [28]. The spike observed on the Nyquist plot for each electrode at the low-frequency section points to the distinguishing character of supercapacitors and positions of Warburg impedance of the electrode, i.e., the resistance of the diffusion of Li ? and NO 3 ions into the electrode. ...
Polyaniline has received much concentration in both basic and applied studies because it has electrical and electrochemical properties comparable to those of both conventional semiconductors and metals. In this work, PANI was used as a conducting additive to formulate a nanocomposite as a high functioning cathode material for Li-ion batteries. PANI, spinel cathode materials of LiMn2O4, and LMO@PANI were synthesized and characterized via scanning electron microscopy (SEM), Fourier transforms infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). SEM of the composite illustrated the formation of long rods of LiMn2O4 covered by PANI layers. The electrical and electrochemical properties of the prepared materials were studied by electrochemical impedance spectroscopy as well as cyclic voltammetry. The composite sample showed higher electrical conductivity (5.5 × 10–2 S/cm) compared with that of PANI (9.1 × 10–4 S/cm) and also showed improving in its specific electrical capacity with a value of 75 mAh/g at a scan rate of 5 mV/s in 1 M LiNO3 electrolyte compared with that of PANI (33 mAh/g). The cycling stability of the composite electrode was significantly improved and showed cycling performance, with ~ 86.2% capacity retained over 1000 cycles. Results predict that the developed LMO@PANI nanocomposite could be used in an electrochemical energy storage device.
... As pointed out in a number of reports [21][22][23][24], they can be electrochemically active as well, raising the electrochemical capacity of composites. Previous reports described composites of lithium iron phosphate with polypyrrole [25], polyaniline [26], polythiophene [27], and PEDOT [28][29][30]. The use of the last material appears to be particularly attractive owing to its high electronic conductivity and the stability of composites containing it [29,30]. ...
... The observed switching behavior, specifically in the nanocomposite film samples is of high technological relevance, since it offers the possibility of direct application of these films as optical switches. Puthirath et al. (2015) have highlighted the suitability of using n-butyllithium, a cost-effective substitute for expensive counterparts for synthesizing lithium (Li) doped PANI to be used as the active cathode material in rechargeable Li-ion cells. They synthesized Li-doped PANI samples for three different concentrations of n-BuLi and had analyzed using various characterization tools. ...
