No carbon added: Using the intrinsic oxidative power of LiFePO4/FePO4 combined with the reinsertion of lithium ions, the formation of the conducting polymer poly(3,4‐ethylenedioxythiophene) (PEDOT) at the solid surface is demonstrated (see picture). The resulting composites have very promising electrochemical properties in rechargeable lithium batteries; in particular, they allow for the elimination of carbon additives.
The resurgence of the lithium metal battery requires innovations in technology, including the use of non-conventional liquid electrolytes. The inherent electrochemical potential of lithium metal (-3.04 V vs. SHE) inevitably limits its use in many solvents, such as acetonitrile, which could provide electrolytes with increased conductivity. The aim of this work is to produce an artificial passivation layer at the lithium metal/electrolyte interface that is electrochemically stable in acetonitrile-based electrolytes. To produce such a stable interface, the lithium metal was immersed in fluoroethylene carbonate (FEC) to generate a passivation layer via the spontaneous decomposition of the solvent. With this passivation layer, the chemical stability of lithium metal is shown for the first time in 1 m LiPF in acetonitrile.
Summary
The effects of solvent absorption on the electrochemical and mechanical properties of polymer electrolytes for use in solid-state batteries have been measured by researchers since the 1980s. These studies have shown that small amounts of absorbed solvent may increase ion mobility and decrease crystallinity in these materials. Even though many polymers and lithium salts are hygroscopic, the solvent content of these materials is rarely reported. As ppm-level solvent content may have important consequences for the lithium conductivity and crystallinity of these electrolytes, more widespread reporting is recommended. Here we illustrate that ppm-level solvent content can significantly increase ion mobility, and therefore the reported performance, in solid polymer electrolytes. Additionally, the impact of absorbed solvents on other battery components has not been widely investigated in all-solid-state battery systems. Therefore, comparisons will be made with systems that use liquid electrolytes to better understand the consequences of absorbed solvents on electrode performance.
Gel
polymer electrolytes (GPEs) based on polyacrylonitrile elastomer
(HNBR) are investigated for lithium-ion batteries application. This
study examines the acrylonitrile content, as well as the solvent used
to make the GPE, to understand their impact on lithium solvation.
To do so, we propose a three-component system comprising HNBR:solvent:LiTFSI
to pinpoint the correct ratio to provide the GPE with competitive
conductivity. Infrared spectroscopy is used to shed light on the interactions
between nitriles and lithium ions. Spin–lattice relaxation
times (T
1) and diffusion coefficients
of 7Li and 19F for various HNBR-based GPEs are
obtained through PFG-NMR, enabling determination of the transport
number of lithium cations (t
+) and activation
energy (E
a). Among the GPEs tested, those
composed of propylene carbonate with 2 M LiTFSI and HNBR with an acrylonitrile
content of 50% are the most promising, with an ionic conductivity
of 2.1 × 10–3 S/cm, D
7Li of 12.0 × 10–8 cm/s,
and a t
+ of 0.42 at room temperature.
When this GPE was tested in Li5Ti4O12/LiFePO4 coin cells, a capacity of 135 mAh/g was obtained
at a discharge rate of D/5, showing promising results
for its use in Li-ion batteries. This study highlights the benefits
of high acrylonitrile content in the polymer and a solvent with a
moderate donor number to promote interactions between nitriles and
Li+.
h i g h l i g h t s < Free-standing PEDOTeLiFePO 4 composites for lithium ion batteries by dynamic three phase interline electropolymerization. < PEDOTeLiFePO 4 serves as current collector, binder and carbon filler free functional electrodes. < LiFePO 4 mass fraction of 33.5 wt.% in the composite film confirmed by TGA analysis. < The cathode discharge capacity of the PEDOTeLiFePO 4 composite film is 75 mAh g À1 at C/10.
a b s t r a c tFree-standing poly(3,4-ethylenedioxythiophene) (PEDOT)eLiFePO 4 composite films were successfully prepared by dynamic three phase interline electropolymerization (D3PIE). These films were used without further modification as the positive electrode in standard lithium ion batteries. As such, this new process eliminates all electrochemically inactive materials (carbon, polymer binder and current collector) used in conventional composite cathodes. The PEDOTeLiFePO 4 composite film offers a discharge capacity of 75 mAh g À1 at the C/10 rate and high capacity retention at the C/2 rate. When reporting this value to the relative amount of LiFePO 4 in the PEDOT-LiFePO 4 composite film, the discharge capacity reached 160 mAh g À1 , close to the theoretical maximum value (170 mAh g À1 ). As such, this approach yield highly functional hybrid free-standing conductive polymer/active material composite cathode with controllable size and structure.
With the ever-growing energy storage notably due to the electric vehicle market expansion and stationary applications, one of the challenges of lithium batteries lies in the cost and environmental impacts of their manufacture. The main process employed is the solvent-casting method, based on a slurry casted onto a current collector. The disadvantages of this technique include the use of toxic and costly solvents as well as significant quantity of energy required for solvent evaporation and recycling. A solvent-free manufacturing method would represent significant progress in the development of cost-effective and environmentally friendly lithium-ion and lithium metal batteries. This review provides an overview of solvent-free processes used to make solid polymer electrolytes and composite electrodes. Two methods can be described: heat-based (hot-pressing, melt processing, dissolution into melted polymer, the incorporation of melted polymer into particles) and spray-based (electrospray deposition or high-pressure deposition). Heat-based processes are used for solid electrolyte and electrode manufacturing, while spray-based processes are only used for electrode processing. Amongst these techniques, hot-pressing and melt processing were revealed to be the most used alternatives for both polymer-based electrolytes and electrodes. These two techniques are versatile and can be used in the processing of fillers with a wide range of morphologies and loadings.
Kein Kohlenstoff nötig: Mithilfe des intrinsischen Oxidationsvermögens von LiFePO4/FePO4 in Kombination mit der Reinsertion von Lithiumionen gelingt die Bildung des leitfähigen Polymers Poly(3,4‐ethylendioxythiophen) (PEDOT) an festen Oberflächen. Die resultierenden Komposite haben vielversprechende elektrochemische Eigenschaften in wiederaufladbaren Lithiumbatterien; insbesondere ermöglichen sie das Weglassen von Kohlenstoffadditiven.
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