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Related Concept Videos

Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

2.3K
The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

2.0K
The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
2.0K
Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

2.1K
The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
2.1K
α-Alkylation of Ketones via Enolate Ions01:10

α-Alkylation of Ketones via Enolate Ions

3.1K
Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the...
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Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

2.4K
Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
2.4K
Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

3.3K
Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications
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Radical Polymer-based Positive Electrodes for Dual-Ion Batteries: Enhancing Performance with γ-Butyrolactone-based

Katharina Rudolf1, Linus Voigt1, Simon Muench2,3

  • 1University of Münster, MEET Battery Research Center, Institute of Physical Chemistry, Corrensstraße 46, 48149, Münster, Germany.

Chemsuschem
|May 15, 2024
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Summary

Dual-ion batteries using poly(2,2,6,6-tetramethylpiperidinyl-N-oxyl methacrylate) (PTMA) show improved cycle life and rate performance with specific lithium salts in γ-butyrolactone (GBL) electrolytes.

Keywords:
Dual-ion batteriesFast chargeHigh powerPolymer-based cathodeslithium salts

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Synthesis of Ionic Liquid Based Electrolytes, Assembly of Li-ion Batteries, and Measurements of Performance at High Temperature
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Area of Science:

  • Electrochemistry
  • Materials Science
  • Energy Storage

Background:

  • Dual-ion batteries (DIBs) offer a promising alternative to lithium-ion batteries (LIBs) for specific applications.
  • Polymer-based active materials like poly(2,2,6,6-tetramethylpiperidinyl-N-oxyl methacrylate) (PTMA) are suitable for high-power DIBs.
  • Electrolyte formulation is critical for optimizing DIB performance, particularly anion mobility.

Purpose of the Study:

  • To investigate the impact of different lithium salts on the performance of PTMA-based DIBs.
  • To identify electrolytes that enhance cycle life and rate capability in PTMA||Li metal cells.
  • To understand the mechanisms behind improved battery performance with specific salt additives.

Main Methods:

  • Electrochemical testing of PTMA||Li metal cells with varying lithium salts (LiDFOB, LiBOB) in a γ-butyrolactone (GBL) solvent.
  • Comparison with a reference electrolyte (LiPF6 and carbonate-based).
  • Analysis of charge-transfer, mass transport, pseudo-capacitive contributions, and overpotentials.

Main Results:

  • Lithium difluoro(oxalate)borate (LiDFOB) and lithium bis(oxalate)borate (LiBOB) significantly improved cycle life compared to the reference electrolyte.
  • LiDFOB demonstrated superior rate performance, retaining ~90% capacity at 5.0 A g⁻¹ (≈50C).
  • Enhanced performance is linked to faster kinetics, increased pseudo-capacitance, and reduced Li metal electrode overpotentials.

Conclusions:

  • LiDFOB and LiBOB are effective electrolyte additives for enhancing PTMA-based DIBs.
  • The choice of lithium salt critically influences DIB performance, especially at high rates.
  • These findings pave the way for developing high-power DIBs with improved stability and energy delivery.