Li-storage performance of binder-free and flexible iron fluoride@graphene cathodes

Hu, Xuebo; Ma, Minhao; Mendes, Rafael G.; Zeng, Mengqi; Zhang, Qin; Xue, Yinghui; Zhang, Tao; Rümmeli, Mark H.; Fu, Lei

doi:10.1039/c5ta08014b

Cited by 31 publications

(18 citation statements)

References 41 publications

(47 reference statements)

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“…F00 exhibited better cyclability but low capacity is due to the inferior reaction kinetics of pure FeF 3 , Li + could not be transferred and diffused rapidly under the high current, so the Li + can only be inserted in certain depth. [4,12,27,79] Furthermore, an additional anodic peak at about 4.3 V was detected in FC0 might be associated with the solid electrolyte interphase (SEI) film formation on the electrodes. The reaction kinetics of FC0 and FCN were obviously enhanced, the electrochemical reaction was relatively complete.…”

Section: Electrochemical Performancementioning

confidence: 97%

“…[4][5][6] In this case, the conversion reaction involving multiple-electrons have received much attention because it can deliver high specific capacity. [10][11][12] However, the strong ionic character of FeÀ F bonds lead to poor electronic conductivity and inferior kinetics, which greatly limits the capacity for storing lithium. [5,8] Among them, iron fluoride (FeF 3 ) has been widely studied because the high theoretical capacity of 712 mAh g À 1 (delivering three electrons) and working potential (about 3.0 V for the redox reaction).…”

Section: Introductionmentioning

confidence: 99%

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Improved Electrochemical Performance of FeF₃ by Inlaying in a Nitrogen‐Doped Carbon Matrix

Zhu

et al. 2019

ChemElectroChem

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FeF 3 is favored by researchers because of its high theoretical specific capacity and high voltage. It is expected to be utilized as a cathode material for lithium-ion batteries in the future. However, the poor electronic conductivity, inferior reaction kinetics, and severe volume expansion seriously prevents its practical application. Herein, a FeF 3 @N-doped carbon nanocomposite was successfully produced by in situ fluorination and dehydration. In addition, the nanocomposite showed a reversible capacity of 84.9 mAh g À 1 for 200th cycle after cycling at a high current of 2 C, which is approximately 300 times higher than that of bare FeF 3 . Benefitting from the N-doped carbon matrix, the composite electrodes exhibited minor transfer resistance (117.4 Ω, only 44.0 % of that of bare FeF 3 ) and very low polarization voltage (ca. 0.19 V). Meanwhile, it provided a buffer for volume expansion during the insertion of Li + and maintained cycling stability. This work can supply a simple pathway for designing ultrahigh-rate and long-life FeF 3 cathode materials.

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Section: Electrochemical Performancementioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Improved Electrochemical Performance of FeF₃ by Inlaying in a Nitrogen‐Doped Carbon Matrix

Zhu

et al. 2019

ChemElectroChem

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“…the CEI should ideally be formed at the potentials below that of the Li extraction from the cathode at the first cycle. In this sense, a large first cycle overpotential commonly observed in conversion cathodes 11,13,[16][17][18]23,27,28,39,41,48,[60][61][62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77][78] is beneficial, as it provides more freedom to select electrolyte compositions with suitable oxidation/reduction potentials [ Fig. 4(a)].…”

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confidence: 99%

In situ surface protection for enhancing stability and performance of conversion-type cathodes

Borodin

Yushin

2017

MRS Energy & Sustainability

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Lithium and lithium-ion batteries (LBs and LIBs) are the most popular battery systems for electrochemical energy storage technologies. Commercial LIBs utilize intercalation-type cathode materials, mostly nickel (Ni)-based and cobalt (Co)-based cathodes, showing specific capacities of up to ∼200 mA h/g (theoretical capacity below 300 mA h/g), which limit the specific energy of batteries, and are additionally expensive and toxic. An EPA study showed that the Ni-and Co-containing batteries that use solvent-based electrode processing have the highest potential for negative environmental impacts. 1 These impacts include resource depletion, global warming, ecological toxicity, and human health impacts with the largest contributing processes include those associated with the production, processing, and use of cobalt and nickel metal compounds, which may cause adverse respiratory, pulmonary, and neurological effects in those exposed. 1 The study suggested cathode material substitution and solvent-less electrode processing to reduce these impacts. 1 The uneven distribution of Co in the earth crust 2 and the insufficient use of suitable personal protection equipment in many Co mining developing countries 3,4 created a major concern. For example, Amnesty International findings of major exploitations of children in Co mines and the related child sickness and deaths 3,4 demonstrate some of the most horrific examples of child labor, which international community should not tolerate and certainly should not encourage through growing market demands for Co. The growing Co contained-electronic waste ABSTRACTThe use of in situ formed protective layer on conversion cathodes was introduced as a cheap and simple strategy to shield these materials from undesirable interactions with liquid electrolytes.Conversion-type cathodes have been viewed as promising candidates to replace Ni-and Co-based intercalation-type cathodes for next-generation lithium (Li) and Li-ion batteries with higher specific energy, lower cost, and potentially longer cycle life. Typically, in conversion reactions two or three Li ions may be stored per just one atom of chalcogen (e.g., S or Se) or transition metal (e.g., Fe or Cu used in halides). Unfortunately, in conversion chemistries the active materials or intermediate charge/discharge products suffer from various unfavorable interactions and dissolution in organic electrolytes. In this mini-review article, we discuss the current interfacial challenges and focus on the protective layers in situ formed on the cathode surface to effectively shield conversion materials from undesirable interactions with liquid electrolytes. We further explore the mechanisms and current progress of forming such protective layers by using various salts, solvents, and additives together with the insight from molecular modeling. Finally, we discuss future opportunities and perspectives of in situ surface protection.Keywords: Li; S; F; coating; energy storage Review DiSCUSSiON POiNTS• Conversion-type cathodes have been viewed as promi...

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“…The presence of +2 oxidation state of iron in the nanocomposite can be attributed to the reduction of ionic liquid during the reaction . The binding energy of F 1s is centered at about 685 eV (Figure c), which well corresponds to the Fe−F bonding . The high resolution XPS spectrum of N 1s of 3D FFNPC is presented in Figure d, which can be deconvoluted into three peaks located at 398.5, 400.2 and 404.9 eV, representing pyridinic N (N‐6 at 398.6±0.3 eV), pyrrolic N (N‐5 at 400.5±0.3 eV) and oxidized N (N−X at 402–405 eV), respectively .…”

Section: Resultsmentioning

confidence: 93%

Three‐Dimensional Nanocomposite of Iron‐Based Fluoride Loaded in N‐Doped Porous Carbon as a High‐Performance Cathode for Rechargeable Li‐Ion Batteries

Zhang

Meng

et al. 2017

ChemElectroChem

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Iron-based fluorides are considered to be one of the most promising candidate cathode materials for high-performance Li-ion batteries due to their large capacities and high working potential. In this work, a three-dimensional (3D) hybrid nanocomposite of Fe2F5·H 2O (FF) loaded in N-doped porous carbon (NPC) is successfully synthesized by a facile and scalable ionic liquid based precipitation followed by a mild heat treatment strategy. The 3D Fe2F5·H 2O@NPC (FFNPC) nanocomposite with a hierarchical framework utilized as cathode delivers a high reversible capacity of 185 mAh g -1 at 0.25 C (1 C = 200 mA g -1) and 163 mAh g -1 at 0.5 C in the voltage range of 1.7-4.5 V (vs. Li/Li + ) at room temperature.Moreover, the 3D FFNPC cathode shows a robust long-term cycling stability, maintaining 118 mAh g -1 after 200 cycles even at 2 C. The rate performance is also displayed, showing specific capacity of 115 mAh g -1 at high current rate of 5 C. The improved electrochemical properties of 3D FFNPC cathode can be attributed to the combination of the small-sized iron fluoride nanoparticles and the NPC matrix, which not only provides a large surface area for the reaction, but also shortens the diffusion length for Li + and increases the electrical conductivity.

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Li-storage performance of binder-free and flexible iron fluoride@graphene cathodes

Abstract: As flexible devices have become increasingly popular in our daily life, flexible energy-supply devices, especially flexible lithium-ion batteries (LIBs), have attracted great attention.

Cited by 31 publications

References 41 publications

Improved Electrochemical Performance of FeF₃ by Inlaying in a Nitrogen‐Doped Carbon Matrix

Improved Electrochemical Performance of FeF₃ by Inlaying in a Nitrogen‐Doped Carbon Matrix

In situ surface protection for enhancing stability and performance of conversion-type cathodes

Three‐Dimensional Nanocomposite of Iron‐Based Fluoride Loaded in N‐Doped Porous Carbon as a High‐Performance Cathode for Rechargeable Li‐Ion Batteries

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Li-storage performance of binder-free and flexible iron fluoride@graphene cathodes

Abstract: As flexible devices have become increasingly popular in our daily life, flexible energy-supply devices, especially flexible lithium-ion batteries (LIBs), have attracted great attention.

Cited by 31 publications

References 41 publications

Improved Electrochemical Performance of FeF3 by Inlaying in a Nitrogen‐Doped Carbon Matrix

Improved Electrochemical Performance of FeF3 by Inlaying in a Nitrogen‐Doped Carbon Matrix

In situ surface protection for enhancing stability and performance of conversion-type cathodes

Three‐Dimensional Nanocomposite of Iron‐Based Fluoride Loaded in N‐Doped Porous Carbon as a High‐Performance Cathode for Rechargeable Li‐Ion Batteries

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Improved Electrochemical Performance of FeF₃ by Inlaying in a Nitrogen‐Doped Carbon Matrix

Improved Electrochemical Performance of FeF₃ by Inlaying in a Nitrogen‐Doped Carbon Matrix