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Materials 2018, 11, x FOR PEER REVIEW Materials 2018, 11, 2567 Materials 2018, 11, x FOR PEER REVIEW 8 of 20 2.2.2. Charge Storage Mechanism in Schiff Base Polymers 2.2.2. Charge Storage Mechanism in Schiff Base Polymers Figure 5. Structure of Schiff base polymers. Figure 5. Structure of Schiff base polymers. Figure 5. Structure of Schiff base polymers. 8 of 18 8 of 20 2.2.2. Charge Storage Mechanism in Schiff Base Polymers Schiff base polymers are increasingly being explored as organic electrode materials for NIBs. The Schiff base polymers are increasingly being explored as organic electrode materials for NIBs. Schiff base polymers are increasingly being explored as organic electrode materials for NIBs. The active centre of Schiff base polymers for the sodium‐ion storage is the C=N of conjugated –N=CH–Ar– The active centre of Schiff base polymers for the sodium-ion storage is the C=N of conjugated active centre of Schiff base polymers for the sodium‐ion storage is the C=N of conjugated –N=CH–Ar– CH=N– (Ar = aromatic ring) (Scheme 3). Planarity and conjugation are the key properties required for –N=CH–Ar–CH=N– (Ar = aromatic ring) (Scheme 3). Planarity and conjugation are the key properties CH=N– (Ar = aromatic ring) (Scheme 3). Planarity and conjugation are the key properties required for electrochemical activity of Schiff base polymers [52]. The “reverse” configuration –C=NH–Ar–NH=C–, required for electrochemical activity of Schiff base polymers [52]. The “reverse” configuration electrochemical activity of Schiff base polymers [52]. The “reverse” configuration –C=NH–Ar–NH=C–, though isoelectronic, is not electrochemically active. –C=NH–Ar–NH=C–, though isoelectronic, is not electrochemically active. though isoelectronic, is not electrochemically active. Scheme 3. Schematic representation of sodium-ion storage in Schiff base polymers. Scheme 3. Schematic representation of sodium‐ion storage in Schiff base polymers. Scheme 3. Schematic representation of sodium‐ion storage in Schiff base polymers. 2.2.3. Recent Development of Schiff Base Polymer Electrode Materials for NIBs 2.2.3. Recent Development of Schiff Base Polymer Electrode Materials for NIBs 2.2.3. RTehceefinrtsDt estvuedloypomneSncthoiffSbcahsieffpBoalsyemPeorlsy(m19e–r2E4l)eacstraondoedMe amteartiearlisalfsorfoNr INBIsBs was reported by the The first study on Schiff base polymers (19–24) as anode materials for NIBs was reported by the group of Armand in 2014 [52]. It was found that the reduction reaction takes place at potentials below The first study on Schiff base polymers (19–24) as anode materials for NIBs was reported by the group of Armand+in 2014 [52]. It was found that the reduction reaction takes place at potentials below 1.5 V vs. Na/Na , indicating that Schiff base polymers are very promising anode materials for NIBs. group of Arman+ d in 2014 [52]. It was found that the reduction reaction takes place at potentials below 1.5 V vs. Na/Na , indicating that Schiff base polymers are very promising anode materials for NIBs. The The redox potential can be adjusted by addition of appropriate substituents without compromising 1.5 V vs. Na/Na+, indicating that Schiff base polymers are very promising anode materials for NIBs. The redox potential can be adjusted by addition of appropriate substituents without compromising the the polymer chain planarity and extent of conjugation. A maximum capacity of 350 mAh·g−1 was redox potential can be adjusted by addition of appropriate substituents without com−1promising the polymer chain planarity and extent of conjugation. A maximum capacity of 350 mAꞏhꞏg was achieved achieved on addition of 50 wt% of Ketjen Black, corresponding to 2.8 sodium ions per monomer unit. polymer chain planarity and extent of conjugation. A maximum capacity of 350 mAꞏhꞏg−1 was achieved on addition of 50 wt% of Ketjen Black, corresponding to 2.8 sodium ions per monomer unit. Recently, the Armand group reported a polySchiff-polyether terpolymer (25) with an on addition of 50 wt% of Ketjen Black, corresponding to 2.8 sodium ions per monomer unit. Recently, the Armand group reported a polySchiff‐polyether terpolymer (25) with an electrochemical activity at low redox potential vs. Na/Na+ and self-binding property, allowing R e c e n t l y , t h e A r m a n d g r o u p r e p o r t e d a p o l y S c h+ i f f ‐ p o l y e t h e r t e r p o l y m e r ( 2 5 ) w i t h a n electrochemical activity at low redox potential vs. Na/Na and self‐binding property, allowing the the preparation of laminated electrodes without binder [53]. At the same carbon content, the laminate electrochemical activity at low redox potential vs. Na/Na+ and self‐binding property, allowing the preparation of laminated electrodes without binder [53]. At the same carbon content, the laminate electrode delivered higher capacities than the powder counterpart due to superior cohesive preparation of laminated electrodes without binder [53]. At the same carbon content, the laminate electrode delivered higher capacities than the powder counterpart due to superior cohesive inter‐ inter-particle contact. A stable reversible capacity of ~185 mAh·g−1 could be obtained for the electrode delivered higher capacities than the powder coun‐1terpart due to superior cohesive inter‐ particle contact. A stable reversible capacity of ~185 mAhg could be obtained for the binder‐free binder-free laminated electrode. Due to its intriguing adhesive properties, this polySchiff-polyether particle contact. A stable reversible capacity of ~185 mAhg‐1 could be obtained for the binder‐free laminated electrode. Due to its intriguing adhesive properties, this polySchiff‐polyether terpolymer terpolymer was also tested as a binder for hard carbon, representing a proof-of-concept in the field of laminated electrode. Due to its intriguing adhesive properties, this polySchiff‐polyether terpolymer was also tested as a binder for hard carbon, representing a proof‐of‐concept in the field of redox‐active redox-active binders. was also tested as a binder for hard carbon, representing a proof‐of‐concept in the field of redox‐active binders. binders. 2.2.4. Challenges and Opportunities in Developing Schiff Base Polymer Electrode Materials 2.2.4. Challenges and Opportunities in Developing Schiff Base Polymer Electrode Materials The low solubility of Schiff base polymers in most organic solvents [54] is an advantage for 2.2.4. Challenges and Opportunities in Developing Schiff Base Polymer Electrode Materials The low solubility of Schiff base polymers in most organic solvents [54] is an advantage for electrode materials; however, this makes the materials difficult to process. The balance between the The low solubility of Schiff base polymers in most organic solvents [54] is an advantage for electrode materials; however, this makes the materials difficult to process. The balance between the solubility and processability can be manipulated by modifying the polymer chain using appropriate electrode materials; however, this makes the materials difficult to process. The balance between the solubility and processability can be manipulated by modifying the polymer chain using appropriate linkers between the azomethine units [52–54]. Furthermore, the electrical conductivity of Schiff base solubility and processability can be manipulated by modifying the polymer chain using appropriate linkers between the azomethine units [52–54]. Furthermore, the electrical conductivity of Schiff base polymers can be increased up to the level of semiconductors by doping with iodine [55]. This important linkers between the azomethine units [52–54]. Furthermore, the electrical conductivity of Schiff base polymers can be increased up to the level of semiconductors by doping with iodine [55]. This important property makes Schiff base polymers very promising electrode materials for NIBs. polymers can be increased up to the level of semiconductors by doping with iodine [55]. This important property makes Schiff base polymers very promising electrode materials for NIBs. property makes Schiff base polymers very promising electrode materials for NIBs.PDF Image | Polymer Electrode Materials for Sodium-ion Batteries
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