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Synthesis and Characterization of Redox-Responsive Disulfide Cross-Linked Polymer Particles for Energy Storage ApplicationsClick to copy article linkArticle link copied!
- Garrett L. GrockeGarrett L. GrockePritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United StatesJoint Center for Energy Storage Research, Argonne National Laboratory, Argonne, Illinois 60439, United StatesMore by Garrett L. Grocke
- Hongyi ZhangHongyi ZhangPritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United StatesJoint Center for Energy Storage Research, Argonne National Laboratory, Argonne, Illinois 60439, United StatesMore by Hongyi Zhang
- Samuel S. KopfingerSamuel S. KopfingerPritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United StatesMore by Samuel S. Kopfinger
- Shrayesh N. Patel*Shrayesh N. Patel*Email: [email protected]Pritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United StatesJoint Center for Energy Storage Research, Argonne National Laboratory, Argonne, Illinois 60439, United StatesChemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, United StatesMore by Shrayesh N. Patel
- Stuart J. Rowan*Stuart J. Rowan*Email: [email protected]Pritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United StatesJoint Center for Energy Storage Research, Argonne National Laboratory, Argonne, Illinois 60439, United StatesChemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, United StatesDepartment of Chemistry, University of Chicago, Chicago, Illinois 60637, United StatesMore by Stuart J. Rowan
ACS Macro Letters
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Abstract
Cross-linking poly(glycidyl methacrylate) microparticles with redox-responsive bis(5-amino-l,3,4-thiadiazol-2-yl) disulfide moieties yield redox-active particles (RAPs) capable of electrochemical energy storage via a reversible 2-electron reduction of the disulfide bond. The resulting RAPs show improved electrochemical reversibility compared to a small-molecule disulfide analogue in solution, attributed to spatial confinement of the polymer-grafted disulfides in the particle. Galvanostatic cycling was used to investigate the impact of electrolyte selection on stability and specific capacity. A dimethyl sulfoxide/magnesium triflate electrolyte was ultimately selected for its favorable electrochemical reversibility and specific capacity. Additionally, the specific capacity showed a strong dependence on particle size where smaller particles yielded higher specific capacity. Overall, these experiments offer a promising direction in designing synthetically facile and electrochemically stable materials for organosulfur-based multielectron energy storage coupled with beyond Li ion systems such as Mg.
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The development and use of organic materials that can be employed in the next generation of batteries has seen an increase in interest over the past decade or so. Such interest has been spurred by a number of factors, (1) such as the design/development of many redox-active organic molecules that offer competitive if not higher theoretical specific capacities than current inorganic electrode offerings. (2) Furthermore, the ability to systematically tune the structure of organic materials allows fine-tuning of their electrochemical behavior/stability, and the raw materials for organic systems are generally more abundant compared to many of the key metal oxides employed in inorganic systems, offering an advantage when considering renewable/sustainable technologies.
Disulfides are one class of redox-active organic compounds that have been explored as possible alternatives to metal oxide cathode materials for lithium-ion batteries. The disulfide bond undergoes a reversible 2-electron reduction process (Figure 1a), making it an attractive candidate for energy-dense cathode materials. (3) Furthermore, the electrochemical properties of disulfides can be tuned via the selection of neighboring electron-withdrawing or -donating groups. As such, a multitude of disulfide compounds have been investigated with an eye toward battery applications, including soluble dimers and oligomers, linear polymers, and networks. (4) Through such studies, 2,5-dimercapto-1,3,4-thiadiazole (DMcT) and its analogues have garnered particular interest as organosulfur compounds for cathode active materials. (5−9) Numerous studies over the years have demonstrated DMcT as an attractive candidate for lithium battery cathodes, switching between Li–S and disulfide states with high energy density and excellent cyclability. However, DMcT alone suffers from diffusion of the soluble active species away from the electrode, which degrades battery performance. (10−12)
Figure 1
Figure 1. (a) Reversible electrochemical reaction of thiadiazole-based disulfides. (b) Reaction scheme for the synthesis of 1-SS-1-functionalized PGMA particles (P2) from PGMA particles with a 1 wt % HMDA permanent cross-linker (P1).
Polymer-bound organosulfur compounds may offer a solution to this challenge. Covalently securing the organosulfur moiety to a scaffold material, such as a nonreactive polymer backbone, results in isolation of the electrode material to the cathode half cell. This approach has been investigated in films of DMcT-functionalized poly(3,4-ethylenedioxythiophene) (PEDOT). (9) However, it was found that the conductivity of PEDOT proved insufficient to adequately charge the entire thickness of the film. (13) A possible solution to this problem rests in the synthetic flexibility of polymer systems. The use of particulate morphologies for electrode-active materials results in dramatically increased surface area to volume ratios relative to films and other monolith morphologies and allows for simple blending with conductive additives, such as carbon black, to enhance electrical connectivity with the electrode substrate. This technique is utilized in current Li+-ion battery metal oxide electrodes and has been demonstrated with organic materials; for example, suspensions of polyaniline particles have been shown to charge more thoroughly than polyaniline films. (14) While inorganic electrode materials must be milled to reduce their size, an energetically intensive process, colloidal polymerization techniques allow for facile synthesis of polymer particles with controlled size. Using particulate morphologies for polymeric redox-active materials has been successfully demonstrated in solid electrode batteries as well as in the emerging field of organic flow batteries. (15−22) This particulate-based modality presents a potential route for simple, modular synthesis of effective electrodes with disulfide active chemistries.
Thus, the goal of this work is to explore the synthesis and redox behavior of disulfide-containing colloids with an eye toward their use in energy storage applications. Poly(glycidyl methacrylate) (PGMA) was selected as the matrix polymer for this study, as it is possible to access narrow dispersed colloidal particles using different polymerization techniques, (23) and the epoxide group provides a functional handle for modular epoxy-amine “click” chemistry, allowing for a wide range of functional modifications to the polymer scaffold. (24) Dispersion polymerization was used to produce particles with two targeted sizes (ca. 710 and 1670 nm in diameter, measured via scanning electron microscopy, SEM). (23) Hexamethylene diamine (HMDA) (1 wt %) was reacted with these particles to produce cross-linked polymer microspheres (P1). (25) Bis(5-amino-l,3,4-thiadiazol-2-yl) disulfide (1-SS-1) and bis(5-ethylamino-l,3,4-thiadiazol-2-yl) disulfide (2-SS-2) were selected as the disulfide-containing cross-linker and small-molecule analogue for this study and synthesized according to known procedures. (26) Functionalization of P1 with an excess of 1-SS-1 (5 equiv of 1-SS-1 per epoxy moiety) was carried out using a THF/DMSO cosolvent (tetrahydrofuran (THF) is a good solvent for PGMA, and dimethyl sulfoxide (DMSO) provides solubility for 1-SS-1) (27) to yield P2 (Figure 1b). Successful synthesis of P2 was determined by both Raman and FTIR. Raman of P2 confirmed the presence of disulfides in the system (Figure S1a), while FTIR monitored the ring opening of the epoxides (Figure S1b). (28) Based on this analysis, it was determined that roughly 88% of the available epoxide groups in P1 reacted with 1-SS-1 to produce P2 (Figure S2, Table S1).
Given the relatively low reactivity of the aromatic amine and the large excess of 1-SS-1 used in the reaction, it can be expected that a significant percentage of the reacted 1-SS-1 would only be monofunctionalized to the polymer (x-SS-1) and thus not act as a cross-linker (Figure 1b, in green). In fact, dynamic light scattering of P1 and P2 showed that there is little to no change in the hydrodynamic diameter of the particles upon reaction with 1-SS-1, consistent with this expectation (Table S3). Removal of these x-SS-1 “loose ends” is critical to accessing electrochemically reversible redox particles, as cleavage of these groups would result in diffusion of the unbound redox-active molecules out of the particle.
It is known that disulfide bonds can undergo dynamic exchange with UV light. (29,30) As such, it was hypothesized that removal of the x-SS-1 could be achieved by irradiation of the particles to induce disulfide exchange and result in the formation of additional disulfide cross-links x-SS-x and free 1-SS-1, which can diffuse into the solvent (Figure 2a). Exposing the particles to UV light (350 mW/cm2) in DMSO (which both swells the particles and is a good solvent for 1-SS-1) results in the liberation of 1-SS-1 into the solution. To monitor the removal of 1-SS-1, two UV annealing cycles were performed sequentially, and the supernatant was analyzed via UV–vis at 322 nm to determine the concentration of released 1-SS-1 (Figure S3). Following each UV irradiation cycle, the particle suspensions were centrifuged; the supernatant was poured off before being replaced by fresh DMSO; and the next irradiation cycle was performed. Results showed that no additional 1-SS-1 was detected in the solution during a second UV annealing process, consistent with the removal of x-SS-1 from P2 and the formation of the more densely cross-linked P2-SS containing only disulfide cross-linkers x-SS-x. This is further supported by dynamic light scattering (DLS) of P2-SS, which showed a decrease in diameter to 1731 ± 109 nm in acetonitrile (ACN), which is ca. 21% smaller compared to P2 (Figure 2b). In addition, the diameter of P2-SS was more consistent across different solvents (ACN, DMSO, and DMSO with salt) than P1 or P2, consistent with a more dense cross-linking and demonstrating the effectiveness of the UV annealing technique (Table S3).
Figure 2
Figure 2. (a) Scheme for UV annealing of P2 particles to remove dangling monofunctionalized x-SS-1. (b) Particle size reduction after UV annealing as measured by dynamic light scattering (DLS) in acetonitrile (ACN). (c) SEM image of DS-RAP.
Following functionalization with 1-SS-1, approximately 12% of the PGMA epoxy groups remain unreacted within P2-SS based on FTIR integration data (Figure S2). Epoxides are highly reactive electrophiles, and therefore it is desirable to passivate any residual groups. To this end, N-methylbutylamine was added to the particle and heated (Figure S4), where the removal of residual epoxides was confirmed by FTIR (Figure S1), (31) resulting in stabilized disulfide-functionalized redox-active particles (DS-RAP) as shown in Figure 2c. DLS data showed that DS-RAPs swelled more in the organic solvents tested, presumably resulting from the addition of the aliphatic side groups (Table S3).
Cyclic voltammetry (CV) and galvanostatic cycling (GC) techniques were used to investigate the electrochemical properties of DS-RAP and compared to the soluble small-molecule analogue, bis(5-ethylamino-l,3,4-thiadiazol-2-yl) disulfide (2-SS-2). Carbon paper (CP) was selected as the working electrode as it allowed for the best electrochemical reversibility in CV experiments (Figure S5a). Specifically, solution CV of 2-SS-2 in ACN shows a reduction peak potential (Ep,r) at −0.79 V vs Ag/Ag+ and an oxidation peak potential (Ep,o) at −0.39 V vs Ag/Ag+. Samples for the CV of DS-RAP were obtained by drop-casting from an ethanol suspension onto CP electrodes resulting in 0.2 mg/cm2 of active material. DS-RAP exhibited an Ep,r at −0.69 V vs Ag/Ag+ and an Ep,o at −0.41 V vs Ag/Ag+ (Figure 3a), demonstrating a marked drop in peak to peak spacing (DEp) of 0.28 V relative to the DEp of 0.40 V for 2-SS-2. While the onset of the reduction process for both systems occurs at approximately −0.5 V vs Ag/Ag+, the more positive Ep,r position and sharper peak profile quantitively indicate faster electrochemical kinetics for the DS-RAP particles at the electrode surface. These values total to an approximate 30% overall reduction in DEp, suggesting the immobilization of x-SS-x on a polymer backbone as reversible cross-links lead to a considerable increase in electrochemical reversibility. This conclusion is supported by the far greater difference between reduction peak current density (ip,r) and oxidation peak current density (ip,o) in the in 2-SS-2 small molecule when compared to DS-RAP. This can be rationalized by the fact that the reductively cleaved small molecules are free to diffuse away from the electrode surface, preventing oxidation back to the disulfide during the return sweep (Figure 3a, inset i). In contrast, the disulfide moieties bound to the polymer are held in a relatively fixed position, keeping them in closer proximity to its cleaved partner (or other thiolates) and the electrode surface (Figure 3a, inset ii).
Figure 3
Figure 3. CV data with inset schemes. 100 mM tetrabutylammonium hexafluorophosphate (TBAPF6)/ACN electrolyte, with 20 mV/s scan rate. Potentials are relative to Ag/Ag+ nonaqueous reference electrodes. (a) 2-SS-2 solution and drop-cast DS-RAP. (b) Enhanced electrochemical response of DS-RAP by 1:1 by weight blending of Super P carbon black (CB).
A second reductive process is observed in the particle system starting at approximately −0.8 V vs Ag/Ag+ and extending out to the maximum scan value of −1.2 V vs Ag/Ag+. To eliminate the possibility that the second reductive process is the result of irreversible reductive degradation, control CV experiments were performed on a series of differently functionalized particles. P1 particles lacking x-SS-x showed no appreciable signal along the reduction sweep (Figure S5b). Additionally, a batch of P1 was reacted with excess HMDA cross-linker to ring open the epoxide, resulting in densely cross-linked particles with redox-inert cross-linkers. These particles showed no electrochemical reactivity in the potential window of interest. As such, these control experiments suggest that both reductive processes in the DS-RAP particles are a consequence of the reductive cleavage of x-SS-x.
The DS-RAP particles investigated in this study are electronically insulating. Thus, to increase electronic access, the DS-RAPs were blended with Super P carbon black (CB) particles (1:1 by weight). For these blended samples, ip,r increased by an approximate factor of 2, while the reduction current density increased more than five times across the potential range of −0.8 to −1.2 V vs Ag/Ag+. The value of ip,o was shown to increase much more than ip,r, providing evidence that the reductive process at lower potentials is the result of continued disulfide reduction into the depth of the particle (Figure 3b). It is possible that the dynamic nature of the disulfide bond means the reductive process is not self-limiting at the surface. For example, thiolate–disulfide exchange reactions could result in disulfide bonds effectively moving from the core of the particle to the surface, thus promoting additional electrochemical reactions. Overall, these CV results show that the DS-RAP particles blended with CB particles in the electrode are more readily accessed electrochemically.
Galvanostatic cycling (GC) experiments were performed to test the feasibility of DS-RAPs as an energy storage material. Electrodes were prepared by casting 0.4 mg of 1:1 DS-RAP:CB from ethanol onto 1 cm2 of CP. All GC experiments were performed at a C-rate of 0.25 C (3.95 μA/cm2) with potential limits of −1.2 to 0 V vs Ag/Ag+ (ca. 2.4 to 3.6 V vs Li/Li+) using a 3-electrode electrochemical cell. Figure 4a shows a representative charge/discharge profile, while Figure 4b shows capacity and efficiency over multiple cycles. The DS-RAP synthesized in this study contains an estimated 39% x-SS-x by mass (compared to a theoretical maximum of 48%, assuming two epoxides per x-SS-x) (Figure S6), leading to a theoretical specific capacity of 79 mAh/gparticle, assuming a two-electron reduction process (eqs S1 and S2). DS-RAPs were initially tested using 1 M TBAPF6 in ACN as the electrolyte. The initial cycle yielded a specific discharge capacity (SDC) of 4.81 mAh/g and Coulombic efficiency (CE) of 88.4%. However, this system demonstrated a sharp initial decrease in capacity, along with a further decrease over progressive cycles, resulting in an SDC of 2.97 mAh/gparticle and CE of 83.7% at cycle 50 (Figure S7b).
Figure 4
Figure 4. Galvanostatic cycling (GC) of the smaller DS-RAP (ca. 1000 nm) at a C-rate of 0.10 and 0.25 C. (a) Charge/discharge curves (cycle 3 for 0.10 C and cycle 46 for 0.25 C). Potential (V) vs Li/Li+ is converted from Ag/Ag+. (b) Charge/discharge cycling stability and Coulombic efficiency (CE) data. The reported GC experiments were performed using DMSO with 0.5 M Mg(OTf)2. Additional GC results are shown in the Supporting Information (Figure S6).
Alternative solvents were explored for the electrolyte as a strategy to improve cycling stability. Of the multiple solvents investigated (Table S4), DMSO yielded stable cycling across the full 50 cycle range. The initial cycle yielded an SDC of 1.65 mAh/g and CE of 86.1%. At cycle 50, the SDC remained stable at 1.65 mAh/g along with an improvement in CE to 92.7% (Figure S7b). Comparison of the GC results between ACN and DMSO indicates that ACN is likely promoting an irreversible electrochemical reaction that leads to the capacity fade, while contributing to a portion of the specific charging capacity. While the cycling stability is improved in DMSO, the resulting SDC remains below that obtained in ACN. In order to address the low specific capacity of DS-RAP, the effect of particle size and supporting electrolyte salt selection was examined next.
As a route to further increase the specific capacity, DS-RAPs with a smaller diameter of ca. 711 nm (dry diameter via SEM) were synthesized (Figure S8) and cycled using TBAPF6/DMSO electrolyte. This particle size approaches the lower limit at which DS-RAP can be synthesized using the employed dispersion polymerization method. The new DS-RAP swelled to 1034 ± 57 nm in diameter in TBAPF6/DMSO, compared to 1867 ± 46 nm for the larger particle. Notably, the GC results indicate that the SDC and CE are 3.32 mAh/g and 89.5% at cycle 50, respectively. The 44.6% smaller DS-RAP exhibited double the SDC of the larger DS-RAP in the presence of TBAPF6/DMSO while maintaining similar CE at cycle 50 (Figure S7d). Moreover, the smaller DS-RAP maintains stable cycling across the full 50 cycles, similar to the larger DS-RAP along with the particle integrity maintained before and after cycling (Figure S9). The smaller particles reduce the characteristic diffusion length and have larger surface area to volume ratios, resulting in a larger portion of the particle being electrochemically accessible as indicated by the improved SDC.
The selection of salt cation for the electrolyte was also shown to impact the cycling capacity. While TBAPF6 is stable in electrochemical applications and highly soluble in many organic solvents, the bulky organic cation can limit diffusion into the particle. LiPF6 and KPF6 were investigated but found to exhibit reduced electrochemical reversibility due to the greater positive potential needed to reoxidize the thiolates (Figure S5c). Batteries based on divalent cations, such as Mg2+, continue to garner interest on account of their higher theoretical energy densities. Interestingly, unlike LiPF6, magnesium triflate (Mg(OTf)2) did not show substantially increased peak spacing relative to TBAPF6 (Figure S5d). Thus, Mg(OTf)2 was selected as an alternative to TBAPF6. A 0.5 M Mg(OTf)2 DMSO solution was used on account of its practical solubility limits. By using the Mg(OTf)2/DMSO electrolyte, the GC experiments showed a SDC and CE of 4.94 mAh/g and 89.0% at cycle 46, respectively (Figure S7f, Table S5). This SDC is a 49.7% increase compared to the SDC when using TBAPF6/DMSO, which could be explained, at least in part, by the divalent Mg2+ cation being able to neutralize two thiolate anions, reducing the amount of cations needed to diffuse into the polymer matrix.
Given the relatively slow charge-transfer kinetics of the disulfide redox couple, (5) the C-rate was lowered from 0.25 C used in the screening experiments to 0.10 C, resulting in an SDC of 15.21 mAh/g after 5 cycles, increasing the capacity by over three times to 19.25% of the theoretical. This result is in line with efficiencies from conceptually similar materials from recent works. (9,32)
In summary, this work demonstrates a simple synthetic approach for disulfide-containing redox-active particles. Through epoxy-amine click chemistry, PGMA particles, prepared using dispersion polymerization, were functionalized with bis(5-amino-1,3,4-thiadiazole-2-yl) disulfide, in which the disulfide behaves as a reversible cross-linker, resulting in densely cross-linked particles with a theoretical capacity of 79 mAh/g. Cyclic voltammetry revealed that the incorporation of the disulfide into the particle resulted in improved electrochemical reversibility of the redox couple compared it its small-molecule equivalent, reducing CV peak spacing by 30%. Moreover, galvanostatic cycling demonstrated potential use of this material as an energy storage material, using a Mg-based electrolyte to achieve high cycling stability, obtaining 15.21 mAh/g at 0.1 C, with high Coulombic efficiency. A specific discharge capacity reaching 19.25% that of the theoretical appears to be limited largely by particle size, offering a direction for future improvement. Overall, this work shows a successful demonstration of a modular RAC platform and provides a tool for the design of organic battery materials, where spatial confinement of the redox-active material is a key consideration.
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsmacrolett.1c00682.
Experimental procedures, FT-IR, Raman spectroscopy, and FT-IR fitting data for particle synthesis, supporting electrolyte viscosities, particle DLS, UV annealing data, reaction scheme for epoxy ring opening, CV data for substrate and electrolyte selection, particle UV–vis, GCPL data with a summary of results, small particle SEM, and qualitative observations (PDF)
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Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Author Information
- Shrayesh N. Patel - Pritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United States; Joint Center for Energy Storage Research, Argonne National Laboratory, Argonne, Illinois 60439, United States; Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, United States;
https://orcid.org/0000-0003-3657-827X;
- Stuart J. Rowan - Pritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United States; Joint Center for Energy Storage Research, Argonne National Laboratory, Argonne, Illinois 60439, United States; Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, United States; Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States;https://orcid.org/0000-0001-8176-0594;
- Garrett L. Grocke - Pritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United States; Joint Center for Energy Storage Research, Argonne National Laboratory, Argonne, Illinois 60439, United States;https://orcid.org/0000-0001-8661-5038
G.L.G. and H.Z. contributed equally to this work.
Acknowledgments
The authors gratefully acknowledge financial support from the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (BES). This work made use of the shared facilities at the University of Chicago Materials Research Science and Engineering Center, supported by the National Science Foundation under award number DMR-2011854. Parts of this work were carried out at the Soft Matter Characterization Facility of the University of Chicago. S.S.K. acknowledges support from the National Science Foundation (NSF) Graduate Research Fellowship under Grant No. (DGE-1746045).
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- 2Lu, Y.; Chen, J. Prospects of Organic Electrode Materials for Practical Lithium Batteries. Nat. Rev. Chem. 2020, 4 (3), 127– 142, DOI: 10.1038/s41570-020-0160-9Google Scholar2https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXjtFWisro%253D&md5=60556a33988c364d1a47128eed4a280aProspects of organic electrode materials for practical lithium batteriesLu, Yong; Chen, JunNature Reviews Chemistry (2020), 4 (3), 127-142CODEN: NRCAF7; ISSN:2397-3358. (Nature Research)A review. Abstr.: Org. materials have attracted much attention for their utility as lithium-battery electrodes because their tunable structures can be sustainably prepd. from abundant precursors in an environmentally friendly manner. Most research into org. electrodes has focused on the material level instead of evaluating performance in practical batteries. This Review addresses this by first providing an overview of the history and redox of org. electrode materials and then evaluating the prospects and remaining challenges of org. electrode materials for practical lithium batteries. Our evaluations are made according to energy d., power d., cycle life, gravimetric d., electronic cond. and other relevant parameters, such as energy efficiency, cost and resource availability. We posit that research in this field must focus more on the intrinsic electronic cond. and d. of org. electrode materials, after which a comprehensive optimization of full batteries should be performed under practically relevant conditions. We hope to stimulate high-quality applied research that might see the future commercialization of org. electrode materials.
- 3Liu, M.; Visco, S. J.; De Jonghe, L. C. Novel Solid Redox Polymerization Electrodes: Electrochemical Properties. J. Electrochem. Soc. 1991, 138 (7), 1896– 1901, DOI: 10.1149/1.2085896Google Scholar3https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3MXlt1agsrk%253D&md5=7c8df4c875e000782da85b542f118f6eNovel solid redox polymerization electrodes. Electrochemical propertiesLiu, Meilin; Visco, Steven J.; De Jonghe, Lutgard C.Journal of the Electrochemical Society (1991), 138 (7), 1896-901CODEN: JESOAN; ISSN:0013-4651.The generic redox reaction of a class of linear sulfur-contg. redox polymn. electrodes can be described as: (-SRS-)n + n(2e-)↹n(-SRS-), i.e., the polymer electrode can be progressively depolymd., leading ultimately to monomeric anions, as the sulfur-sulfur bridges between the org. R groups are cleaved during discharge and then the monomer anions can be subsequently reoxidized back to the original polymer during charge. This is the first time the process of electrodepolymn.-electropolymn. has been exploited for energy storage, establishing a broad class of chem. flexible, low equiv. wt., and inexpensive electrodes for advanced batteries. Electrochem. investigation of a diverse group of novel solid redox polymn. electrodes indicates that these materials are excellent candidates for all-solid-state, thin-film, energy-storage systems. Some of the advantages offered by the batteries based on these materials include high energy d. and rate capability, extensive utilization of pos. electrode capacity, ease of fabrication, low cost, and superior reliability, and safety. In addn., these materials are reversible to lithium and sodium (as well as many alk. earth and transition metals), allowing for a much greater choice of neg. electrode materials, in stark contrast to cells based on analogous intercalation compds. Further, and in particular, a great advantage of redox polymn. electrodes is the ability to alter the phys., chem., and electrochem. properties of these materials in a very predictable manner through manipulation of various functional groups, electron-withdrawing heteroatoms, and the mol. architecture.
- 4Baloch, M.; BenYoucef, H.; Li, C.; Garcia -Calvo, O.; Rodriguez, L. M.; Shanmukaraj, D.; Rojo, T.; Armand, M. New Redox Polymers That Exhibit Reversible Cleavage of Sulfur Bonds as Cathode Materials. ChemSusChem 2016, 9 (22), 3206– 3212, DOI: 10.1002/cssc.201601032Google Scholar4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhslKntLzM&md5=d96603c39a49601383d0b0ae81e5ef8dNew Redox Polymers that Exhibit Reversible Cleavage of Sulfur Bonds as Cathode MaterialsBaloch, Marya; Ben Youcef, Hicham; Li, Chunmei; Garcia-Calvo, Oihane; Rodriguez, Lide M.; Shanmukaraj, Devaraj; Rojo, Teofilo; Armand, MichelChemSusChem (2016), 9 (22), 3206-3212CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)Two new cathode materials based on redox organosulfur polymers were synthesized and investigated for rechargeable lithium batteries as a proof-of-concept study. These cathodes offered good cycling performance owing to the absence of polysulfide soly., which plagues Li/S systems. Herein, an aliph. polyamine or a conjugated polyazomethine was used as the base to tether the redox-active species. The activity comes from the cleavage and formation of S-S or N-S bonds, which is made possible by the rigid conjugated backbone. The synthesized polymers were characterized through FTIR spectroscopy and thermogravimetric anal. (TGA). Galvanostatic measurements were performed to evaluate the discharge/charge cycles and characterize the performance of the lithium-based cells, which displayed initial discharge capacities of approx. 300 mA h g-1 at C/5 over 100 cycles with approx. 98 % Coulombic efficiency.
- 5Oyama, N.; Tatsuma, T.; Sato, T.; Sotomura, T. Dimercaptan–Polyaniline Composite Electrodes for Lithium Batteries with High Energy Density. Nature 1995, 373 (6515), 598– 600, DOI: 10.1038/373598a0Google Scholar5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2MXjsl2msbw%253D&md5=fa1ecd81d158db8ca1f79c6c85242cf0Dimercaptan-polyaniline composite electrodes for lithium batteries with high energy densityOyama, N.; Tatsuma, T.; Sato, T.; Sotomura, T.Nature (London) (1995), 373 (6515), 598-600CODEN: NATUAS; ISSN:0028-0836. (Macmillan Magazines)We report the development of a rechargeable lithium battery with a composite org. cathode based on a mixt. of a dimercaptan and polyaniline. The redox behavior of the dimercaptan, which is normally too slow for practical applications, is accelerated when coupled to that of the polyaniline (which itself functions as an active cathode material). Intimate mixing of the two materials is achieved by casting them jointly from soln. The resulting electrode can be repeatedly charged to near its theor. limit and discharged. The gravimetric energy d. of our materials exceeds that of the oxide electrodes in com. available lithium-ion batteries, a feature that is likely to prove advantageous in applications where wt., rather than vol., is a crit. factor.
- 6Pope, J. M.; Oyama, N. Organosulfur/Conducting Polymer Composite Cathodes: I. Voltammetric Study of the Polymerization and Depolymerization of 2,5-Dimercapto-1,3,4-thiadiazole in Acetonitrile. J. Electrochem. Soc. 1998, 145 (6), 1893– 1901, DOI: 10.1149/1.1838573Google Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1cXjsFSlsLw%253D&md5=67de02e0ef103d1fd386d79c351c8e3fOrganosulfur/conducting polymer composite cathodes. Voltammetric study of the polymerization and depolymerization of 2,5,-dimercapto-1,3,4-thiadiazole in acetonitrilePope, John M.; Oyama, NoboruJournal of the Electrochemical Society (1998), 145 (6), 1893-1901CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)This paper describes general trends in the redox potential and soly. of a dimercaptan, 2,5,-dimercapto-1,3,4-thiadiazole (DMcT), and its various derivs. in acetonitrile, and illustrates how these trends manifest in the cyclic voltammetry obsd. at glassy carbon electrodes. Attention is focused on the polymn./depolymn. processes which are the origins of the excellent charge-storage capabilities of electrodes based on the DMcT family of compds. The extent of oligomerization/polymn. of DMcT at glassy carbon increases with increasing overpotential and/or oxidn. time, as judged from its subsequently obsd. quasi-stable depolymn. wave. Oxidn. of dimer DMcT results in extensive pptn. onto the electrode, relative to that obsd. for oxidn. of monomer DMcT, as expected in light of solubilities obsd. for those compds. in acetonitrile. The protonation state of the compds. has a considerable effect on both their soly. and, as reported previously in part, redox potential. Similarly, chem. coupling of the redox processes of these compds. to their protonation state and, for DMcT, to a disproportionation reaction known to occur for its oxidn. product(s) complicates anal. of the system as a whole. However, from consideration of all of the obsd. trends, a general picture emerges illustrating the redox character of DMcT during polymn. and depolymn. Most importantly, the electrochem. irreversibility typical of those processes can be avoided by careful control of the protonation state and soly. of the electroactive species, allowing the measurement of quasi-reversible redox couples. That and other results are discussed in the context of the use of DMcT in secondary battery electrodes.
- 7Oyama, N.; Kiya, Y.; Hatozaki, O.; Morioka, S.; Abruña, H. D. Dramatic Acceleration of Organosulfur Redox Behavior by Poly(3,4-Ethylenedioxythiophene). Electrochem. Solid-State Lett. 2003, 6 (12), A286, DOI: 10.1149/1.1621753Google Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXosF2lu7c%253D&md5=bb0954092f66f4276877705722070610Dramatic Acceleration of Organosulfur Redox Behavior by Poly(3,4-ethylenedioxythiophene)Oyama, Noboru; Kiya, Yasuyuki; Hatozaki, Osamu; Morioka, Satoru; Abruna, Hector D.Electrochemical and Solid-State Letters (2003), 6 (12), A286-A289CODEN: ESLEF6; ISSN:1099-0062. (Electrochemical Society)High electrocatalytic activity of electropolymd. films of poly(3,4-ethylenedioxythiophene) (PEDOT) toward the redox reactions of 2,5-dimercapto-1,3,4-thiadiazole (DMcT), a promising cathode material for high-energy Li-ion batteries, is discussed. The irreversible redox reaction of DMcT monomer at an unmodified glassy C electrode was accelerated at a PEDOT film-coated electrode to give a reversible response. PEDOT also showed high electrocatalytic activity toward the redox reactions of DMcT dimers and oligomers. Such an acceleration of the DMcT redox reaction, which is essential to practical application of organosulfur compds. in batteries, was ascribed to the electronic properties of PEDOT. Chronopotentiometric results indicated that at PEDOT film-coated electrodes, the redox reactions of DMcT proceed fast enough to produce an electrolysis current of 1.0 mA/cm2.
- 8Kiya, Y.; Henderson, J. C.; Hutchison, G. R.; Abruña, H. D. Synthesis, Computational and Electrochemical Characterization of a Family of Functionalized Dimercaptothiophenes for Potential Use as High-Energy Cathode Materials for Lithium/Lithium-Ion Batteries. J. Mater. Chem. 2007, 17 (41), 4366– 4376, DOI: 10.1039/b707235jGoogle Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXhtFKrsrfI&md5=2e184cda92bba9731aae12e009c30d94Synthesis, computational and electrochemical characterization of a family of functionalized dimercaptothiophenes for potential use as high-energy cathode materials for lithium/lithium-ion batteriesKiya, Yasuyuki; Henderson, Jay C.; Hutchison, Geoffrey R.; Abruna, Hector D.Journal of Materials Chemistry (2007), 17 (41), 4366-4376CODEN: JMACEP; ISSN:0959-9428. (Royal Society of Chemistry)We present a family of a novel class of organosulfur compds. based on dimercaptothiophene and its derivs., with a variety of functional groups (electron-donating or electron-withdrawing groups) and regiochemistries, designed as potential high-energy cathode materials with sufficient charge/discharge cyclability for lithium/lithium-ion rechargeable batteries. This study uses as a point of departure the electrochem. and computational understanding of the electrocatalytic effect of poly(3,4-ethylenedioxythiophene) (PEDOT) towards the redox reactions of 2,5-dimercapto-1,3,4-thiadiazole (DMcT). The effective redox potentials of these materials exhibited good correlation with the highest-occupied MO (HOMO) levels predicted via computational modeling. Furthermore, the redox reactions of all the compds. studied were electrocatalytically accelerated at PEDOT film-coated glassy carbon electrodes (GCEs), although some materials exhibited higher energy output than others. By using this approach we have identified several compds. that exhibit clear promise as potential cathode materials and have characterized the mol. interactions between the organosulfur compds. and PEDOT film surfaces involved in the electrocatalytic reactions.
- 9Rodríguez-Calero, G. G.; Conte, S.; Lowe, M. A.; Gao, J.; Kiya, Y.; Henderson, J. C.; Abruña, H. D. Synthesis and Characterization of Poly-3,4-Ethylenedioxythiophene/2,5-Dimercapto-1,3,4-Thiadiazole (PEDOT-DMcT) Hybrids. Electrochim. Acta 2015, 167, 55– 60, DOI: 10.1016/j.electacta.2015.02.159Google Scholar9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXjtFersbY%253D&md5=b4db7dc000fa002c770e99b95bc5b57fSynthesis and Characterization of Poly-3,4-ethylenedioxythiophene/2,5-Dimercapto-1,3,4-thiadiazole (PEDOT-DMcT) HybridsRodriguez-Calero, Gabriel G.; Conte, Sean; Lowe, Michael A.; Gao, Jie; Kiya, Yasuyuki; Henderson, Jay C.; Abruna, Hector D.Electrochimica Acta (2015), 167 (), 55-60CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)Organosulfur Compds. (OSCs) represent an attractive alternative as org. cathode materials for electrochem. energy storage (EES) applications. They intrinsically have high gravimetric capacity (although low volumetric) and are typically inexpensive, since they are composed of abundant elements (i.e. C, N, O, and S). However, OSCs, specifically thiolate-contg. OSCs generally suffer from slow charge transfer kinetics. To mitigate the charge transfer limitations, conducting polymers (CPs) such as poly-3,4-ethylenedioxythiophene (PEDOT) were employed as electrocatalysts. In this manuscript, the authors have covalently modified a PEDOT film with an OSC (i.e. 2,5-dimercapto-1,3,4-thiadiazole di-Li salt (Li2DMcT)). The authors have developed a synthetic strategy that employs, for the 1st time, a post-polymn. modification reaction as a tractable and viable technique to modify org. materials for EES electrodes. Electrochem. characterization, via cyclic voltammetry showed the expected pseudocapacitive response of PEDOT with the superimposed faradaic processes of the covalently bound DMcT. Also, spectroscopic characterization using Raman spectroscopy provided mechanistic insights into the electrochem. reactions. Also, the authors electropolymd. films onto coin-cell electrodes and tested them in half-cell configurations and found that the capacity retention of the films was significantly enhanced, when compared with the PEDOT/DMcT composites (mixed but not covalently bound).
- 10Kiya, Y.; Hutchison, G. R.; Henderson, J. C.; Sarukawa, T.; Hatozaki, O.; Oyama, N.; Abruña, H. D. Elucidation of the Redox Behavior of 2,5-Dimercapto-1,3,4-Thiadiazole (DMcT) at Poly(3,4-Ethylenedioxythiophene) (PEDOT)-Modified Electrodes and Application of the DMcT - PEDOT Composite Cathodes to Lithium/Lithium Ion Batteries. Langmuir 2006, 22 (25), 10554– 10563, DOI: 10.1021/la061213qGoogle Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtVajt7jL&md5=0664fa33d49e5085e3cc10458009ca84Elucidation of the Redox Behavior of 2,5-Dimercapto-1,3,4-thiadiazole (DMcT) at Poly(3,4-ethylenedioxythiophene) (PEDOT)-Modified Electrodes and Application of the DMcT-PEDOT Composite Cathodes to Lithium/Lithium Ion BatteriesKiya, Yasuyuki; Hutchison, Geoffrey R.; Henderson, Jay C.; Sarukawa, Tomoo; Hatozaki, Osamu; Oyama, Noboru; Abruna, Hector D.Langmuir (2006), 22 (25), 10554-10563CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)The redox reactions of DMcT at PEDOT-modified glassy carbon electrodes (GCEs) in acetonitrile (AN) have been investigated via cyclic voltammetry (CV) and the electrochem. quartz crystal microbalance (EQCM) in order to elucidate the redox reaction mechanism. A redox couple at -0.29 V vs. Ag/Ag+ was assigned to the dimerization process of singly protonated DMcT (DMcT-1H), and a second couple obsd. at +0.42 V was assigned to the polymn. process of the protonated DMcT dimer. Our investigations revealed further that the anodic current response at +0.55 V (polymn. process) has a shoulder at +0.38 V ascribed to the dimerization process of doubly protonated DMcT (DMcT-2H), indicating that the redox couple at +0.42 V is the overlapping response of the polymn. of the protonated DMcT dimer and the dimerization of the DMcT-2H monomer. It was also confirmed that the dimerization process of DMcT-1H at -0.29 V proceeded not only at the surface of a PEDOT film but also inside the film as previously suggested. Moreover, the thermodn. of these redox reactions at PEDOT-modified GCEs are dependent on the basicity (or acidity) of the soln., as anticipated and previously shown at unmodified GCEs. The oxidn. of DMcT occurs at less pos. potentials and the redn. occurs at more neg. potentials in the presence of base. On the basis of the results obtained, the full redox reaction scheme for DMcT at a PEDOT-modified GCE is proposed.
- 11Mistry, A. N.; Mukherjee, P. P. Shuttle” in Polysulfide Shuttle: Friend or Foe?. J. Phys. Chem. C 2018, 122 (42), 23845– 23851, DOI: 10.1021/acs.jpcc.8b06077Google Scholar11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvVKltLzJ&md5=fd0b18a9354865e817d5543360fd3a9d"Shuttle" in Polysulfide Shuttle: Friend or Foe?Mistry, Aashutosh N.; Mukherjee, Partha P.Journal of Physical Chemistry C (2018), 122 (42), 23845-23851CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)The polysulfide shuttle effect, where S species reach the neg. electrode surface and undergo chem. redn., is believed to be a major bottleneck in Li-S chem. The importance of this phenomenon is often judged based on phenomenol. arguments, which do not account for meso-scale complexations. This work presents a comprehensive study of the coupled interactions arising from speciation, concd. electrolyte soln., and reaction time scales. Polysulfide transport consists of diffusion and migration, which dets. the net flux. The polysulfide shuttle effect can be bounded between reaction-limited and shuttle-limited regimes, depending on the operational extremes. At high S to electrolyte ratio (i.e. lean electrolyte condition), the polysulfide shuttle effect may not necessarily attribute to the cell performance limitation, believed contrarily otherwise.
- 12Li, J.; Zhan, H.; Zhou, Y. Synthesis and Electrochemical Properties of Polypyrrole-Coated Poly(2,5-Dimercapto-1,3,4-Thiadiazole). Electrochem. Commun. 2003, 5 (7), 555– 560, DOI: 10.1016/S1388-2481(03)00121-8Google Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXkvFKltLY%253D&md5=eced0df26aa8f3e560b17974125f42aeSynthesis and electrochemical properties of polypyrrole-coated poly(2,5-dimercapto-1,3,4-thiadiazole)Li, Jinxia; Zhan, Hui; Zhou, YunhongElectrochemistry Communications (2003), 5 (7), 555-560CODEN: ECCMF9; ISSN:1388-2481. (Elsevier Science B.V.)A new composite cathode active material, conductive polypyrrole (PPy)-coated poly(2,5-dimercapto-1,3,4-thiadiazole) (PDMcT) was prepd. as a thin film via the surfactant template technique. Formation of the uniform and well-attached film on the surface of PDMcT particles was confirmed by FTIR spectroscopy and TEM. Cyclic voltammetry and galvanostatic charge-discharge tests indicated that the coated composite showed a better electrochem. performance than PDMcT alone as evidenced by enhanced redox processes and improved coulombic efficiency. The elec. cond. of the material was 10-3 S/cm and an initial discharge capacity of 250 mA-h/g was obtained. It had less fading of discharge capacity than PDMcT when used as cathode material in secondary Li batteries with liq. electrolytes.
- 13Shi, T.; Tu, Q.; Tian, Y.; Xiao, Y.; Miara, L. J.; Kononova, O.; Ceder, G. High Active Material Loading in All-Solid-State Battery Electrode via Particle Size Optimization. Adv. Energy Mater. 2020, 10 (1), 1902881, DOI: 10.1002/aenm.201902881Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXit1KqtLvI&md5=8c486a7f9f5760c8b6e8102e394827f6High Active Material Loading in All-Solid-State Battery Electrode via Particle Size OptimizationShi, Tan; Tu, Qingsong; Tian, Yaosen; Xiao, Yihan; Miara, Lincoln J.; Kononova, Olga; Ceder, GerbrandAdvanced Energy Materials (2020), 10 (1), 1902881CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)Low active material loading in the composite electrode of all-solid-state batteries (SSBs) is one of the main reasons for the low energy d. in current SSBs. In this work, it is demonstrated with both modeling and expts. that in the regime of high cathode loading, the utilization of cathode material in the solid-state composite is highly dependent on the particle size ratio of the cathode to the solid-state conductor. The modeling, confirmed by exptl. data, shows that higher cathode loading and therefore an increased energy d. can be achieved by increasing the ratio of the cathode to conductor particle size. These results are consistent with ionic percolation being the limiting factor in cold-pressed solid-state cathode materials and provide specific guidelines on how to improve the energy d. of composite cathodes for solid-state batteries. By reducing solid electrolyte particle size and increasing the cathode active material particle size, over 50 vol% cathode active material loading with high cathode utilization is able to be exptl. achieved, demonstrating that a com.-relevant, energy-dense cathode composite is achievable through simple mixing and pressing method.
- 14Zhao, Y.; Si, S.; Liao, C. A Single Flow Zinc//Polyaniline Suspension Rechargeable Battery. J. Power Sources 2013, 241, 449– 453, DOI: 10.1016/j.jpowsour.2013.04.095Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhtV2lt7jE&md5=e993a49fe29d3ff07d68d1a7d4659f73A single flow zinc//polyaniline suspension rechargeable batteryZhao, Yongfu; Si, Shihui; Liao, CuiJournal of Power Sources (2013), 241 (), 449-453CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)Both the electrochem. activity and the energy d. of polyaniline (PANI) microparticles suspensions are enhanced by using the compact PANI powder, which is synthesized galvanostatically with 4,4'-diaminobiphenyl as additive. A Zn//PANI suspension rechargeable flow battery system is proposed, in which the flowable PANI suspension is used as cathode electroactive material, zinc plate as anode. A microporous membrane is used as separator to prevent PANI particles from getting into the anode compartment. Results obtained from the small lab. battery show that the discharge capacity d. gradually decreases with no. of cycles and the av. of discharge capacity loss during 32 cycles is about 0.07% per cycle. However, an av. coulombic efficiency of 97% has been achieved at the c.d. of 20 mA/cm2 and the value of coulombic efficiency shows no significant change during 32 charge/discharge cycles. The flow-through mode for PANI cathode material enables the PANI-based battery to operate at a higher c.d. in comparison with the conventional Zn-PANI film batteries, and the present findings can mark a new route to improve the performance of conductive polymer-based energy storage devices.
- 15Karami, H.; Mousavi, M. F.; Shamsipur, M. A New Design for Dry Polyaniline Rechargeable Batteries. J. Power Sources 2003, 117 (1–2), 255– 259, DOI: 10.1016/S0378-7753(03)00168-XGoogle Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXjsVSjurc%253D&md5=3b198a8d9afd3bc67bc48688e28db297A new design for dry polyaniline rechargeable batteriesKarami, Hassan; Mousavi, Mir Fazlollah; Shamsipur, MojtabaJournal of Power Sources (2003), 117 (1-2), 255-259CODEN: JPSODZ; ISSN:0378-7753. (Elsevier Science B.V.)Polyaniline powder of high cond. is prepd. by chem. polymn. of aniline in a soln. of 0.10M aniline, 2 M perchloric acid and 0.15M ammonium persulfate at 5°. The powder is mixed with graphite and acetylene black to obtain the required cond. and porosity. The mixed powder is compressed into a ring shape at a pressure of 2 t cm-2 for use as pos. electrodes (cathodes) in batteries. Zinc powder is mixed with magnesium oxide, zinc oxide and sodium CM-cellulose (CMC), and then compressed into a cylindrical shape at a pressure of 7 t cm-2 for use as neg. electrodes (anodes) in batteries. The battery electrolyte comprises 2 M Zn(ClO4)2, 1 M NH4ClO4, and 1.0 × 10-4 M Triton-X100 at pH 3. A 1% Optalloy powder is added to the neg.-electrode composite to prevent the release of hydrogen gas. The assembled battery has an open-circuit voltage (OCV) of 1.64 V, a charge storage capacity of 125.43 m Ah g-1, and a Coulombic efficiency >95% during the 1st 100 charge-discharge cycles. Due to the low amt. of electrolyte used, the battery is considered as a dry battery.
- 16Hauffman, G.; Maguin, Q.; Bourgeois, J.-P.; Vlad, A.; Gohy, J.-F. Micellar Cathodes from Self-Assembled Nitroxide-Containing Block Copolymers in Battery Electrolytes. Macromol. Rapid Commun. 2014, 35 (2), 228– 233, DOI: 10.1002/marc.201300532Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhs1WisbvI&md5=b50410815c08c4a171cb239a06bed535Micellar Cathodes from Self-Assembled Nitroxide-Containing Block Copolymers in Battery ElectrolytesHauffman, Guillaume; Maguin, Quentin; Bourgeois, Jean-Pierre; Vlad, Alexandru; Gohy, Jean-FrancoisMacromolecular Rapid Communications (2014), 35 (2), 228-233CODEN: MRCOE3; ISSN:1022-1336. (Wiley-VCH Verlag GmbH & Co. KGaA)This contribution describes the synthesis of block copolymers contg. electrochem. active blocks, their micellization, and finally their use as micellar cathodes in a lithium battery. The self-assembly of the synthesized poly(styrene)-block-poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PS-b-PTMA) diblock copolymers is realized in a typical battery electrolyte made of 1 M lithium trifluoromethanesulfonate dissolved in a mixt. of ethylene carbonate/diethyl carbonate/dimethyl carbonate (1:1:1, in vol.). Dynamic light scattering and at. force microscopy indicate the formation of well-defined spherical micelles with a PS core and a PTMA corona. The electrochem. properties of those micelles are further investigated. Cyclic voltammograms show a reversible redox reaction at 3.6 V (vs. Li+/Li). The charge/discharge profiles indicate a flat and reversible plateau around 3.6 V (vs. Li+/Li). Finally, the cycling performances of the micellar cathodes are demonstrated. Such self-assembled block copolymers open new opportunities for nanostructured org. radical batteries.
- 17Oh, S. H.; Lee, C. W.; Chun, D. H.; Jeon, J. D.; Shim, J.; Shin, K. H.; Yang, J. H. A Metal-Free and All-Organic Redox Flow Battery with Polythiophene as the Electroactive Species. J. Mater. Chem. A 2014, 2 (47), 19994– 19998, DOI: 10.1039/C4TA04730CGoogle Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhslOjtb7I&md5=760c254a308828bdf4c2e6368d6f36d8A metal-free and all-organic redox flow battery with polythiophene as the electroactive speciesOh, S. H.; Lee, C.-W.; Chun, D. H.; Jeon, J.-D.; Shim, J.; Shin, K. H.; Yang, J. H.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2014), 2 (47), 19994-19998CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)A metal-free and all-org. redox flow battery is proposed and investigated. It employs polythiophene microparticles dispersed in electrolyte solns. as the redox couple and does not depend on limited metal resources. It shows a high cell potential and stable charge/discharge performance with a high energy efficiency of 60.9%.
- 18Wu, S.; Zhao, Y.; Li, D.; Xia, Y.; Si, S. An Asymmetric Zn//Ag Doped Polyaniline Microparticle Suspension Flow Battery with High Discharge Capacity. J. Power Sources 2015, 275, 305– 311, DOI: 10.1016/j.jpowsour.2014.11.012Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvVKltbvK&md5=eab5a769c2e18014388ebcdae8ff5a67An asymmetric Zn//Ag doped polyaniline microparticle suspension flow battery with high discharge capacityWu, Sen; Zhao, Yongfu; Li, Degeng; Xia, Yang; Si, ShihuiJournal of Power Sources (2015), 275 (), 305-311CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)In this study, the effect of oxygen on the potential of reduced polyaniline (PANI) was investigated. In order to enhance the air oxidn. of reduced PANI, several composites of PANI doped with co-catalysts were prepd., and a reasonable flow Zn//PANI suspension cell system was designed to investigate the discharge capacity of obtained PANI composite microparticle suspension cathodes. Compared with PANI doped with Cu2+, La+, Mn2+ and zinc protoporphyrin, Ag doped PANI composite at 0.90 wt. percent doping of Ag gave the highest value of discharge capacity for the half-cell potential from the initial value to -0.20 V (vs. SCE). A comparison study on the electrochem. properties of both PANI and Ag doped PANI microparticle suspension was done by using cyclic voltammetry, AC Impedance. Due to partial utilization of Zn//air fuel cell, the discharge capacity for Ag doped PANI reached 470 mA h g-1 at the c.d. of 20 mA cm-2. At 15 mA cm-2, the discharge capacity even reached up to 1650 mA h g-1 after 220 h const. current discharge at the final discharge voltage of 0.65 V. This work demonstrates an effective and feasible approach toward obtaining high energy and power densities by a Zn//Ag-doped PANI suspension flow battery system combined with Zn//air fuel cell.
- 19Montoto, E. C.; Nagarjuna, G.; Hui, J.; Burgess, M.; Sekerak, N. M.; Hernández-Burgos, K.; Wei, T.-S. S.; Kneer, M.; Grolman, J.; Cheng, K. J.; Lewis, J. A.; Moore, J. S.; Rodríguez-López, J. Redox Active Colloids as Discrete Energy Storage Carriers. J. Am. Chem. Soc. 2016, 138 (40), 13230– 13237, DOI: 10.1021/jacs.6b06365Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsFWnt73L&md5=eb1f512eef10705346a80e0241f4d34dRedox Active Colloids as Discrete Energy Storage CarriersMontoto, Elena C.; Nagarjuna, Gavvalapalli; Hui, Jingshu; Burgess, Mark; Sekerak, Nina M.; Hernandez-Burgos, Kenneth; Wei, Teng-Sing; Kneer, Marissa; Grolman, Joshua; Cheng, Kevin J.; Lewis, Jennifer A.; Moore, Jeffrey S.; Rodriguez-Lopez, JoaquinJournal of the American Chemical Society (2016), 138 (40), 13230-13237CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Versatile and readily available battery materials compatible with a range of electrode configurations and cell designs are desirable for renewable energy storage. Here we report a promising class of materials based on redox active colloids (RACs) that are inherently modular in their design and overcome challenges faced by small-mol. org. materials for battery applications, such as crossover and chem./morphol. stability. RACs are cross-linked polymer spheres, synthesized with uniform diams. between 80 and 800 nm, and exhibit reversible redox activity as single particles, as monolayer films, and in the form of flowable dispersions. Viologen-based RACs display reversible cycling, accessing up to 99% of their capacity and 99 ± 1% Coulombic efficiency over 50 cycles by bulk electrolysis owing to efficient, long-distance intraparticle charge transfer. Ferrocene-based RACs paired with viologen-based RACs cycled efficiently in a nonaq. redox flow battery employing a simple size-selective separator, thus demonstrating a possible application that benefits from their colloidal dimensions. The unprecedented versatility in RAC synthetic and electrochem. design opens new avenues for energy storage.
- 20Zhuo, S.; Tang, M.; Wu, Y.; Chen, Y.; Zhu, S.; Wang, Q.; Xia, C.; Wang, C. Size Control of Zwitterionic Polymer Micro/Nanospheres and Its Dependence on Sodium Storage. Nanoscale Horizons 2019, 4 (5), 1092– 1098, DOI: 10.1039/C9NH00154AGoogle Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXntVSnsbw%253D&md5=14ae7487b1e63765710f468a8b6d6929Size control of zwitterionic polymer micro/nanospheres and its dependence on sodium storageZhuo, Shuming; Tang, Mi; Wu, Yanchao; Chen, Yuan; Zhu, Shaolong; Wang, Qian; Xia, Cong; Wang, ChengliangNanoscale Horizons (2019), 4 (5), 1092-1098CODEN: NHAOAW; ISSN:2055-6764. (Royal Society of Chemistry)In this study, the size control of org. materials and its dependence on sodium storage are investigated. Poly(pyrrole-squaraine) (PPS), a polymer contg. zwitterionic repeating units, was selected as a proof for demonstration. The growth control of PPS micro/nanospheres could facilely be achieved via an in situ one-step polymn. We found that the smallest-sized PPS showed the best rate performance and cycling performance, and the shortest activation process. Moreover, the Na-ion diffusion coeff. did not strictly correlate to the particle size. These results prove that the smaller size and the shorter ionic diffusion length rather than the ionic diffusion coeff. of the material dominated the charge transfer and ionic diffusion, thereby enhancing the rate performance.
- 21Wei, Z.; Wang, D.; Liu, Y.; Guo, X.; Zhu, Y.; Meng, Z.; Yu, Z.-Q.; Wong, W.-Y. Ferrocene-Based Hyperbranched Polymers: A Synthetic Strategy for Shape Control and Applications as Electroactive Materials and Precursor-Derived Magnetic Ceramics. J. Mater. Chem. C 2020, 8 (31), 10774– 10780, DOI: 10.1039/D0TC01380CGoogle Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXms12jt7s%253D&md5=bdd200019af8b5dbcc73fb12df65c43cFerrocene-based hyperbranched polymers: a synthetic strategy for shape control and applications as electroactive materials and precursor-derived magnetic ceramicsWei, Zhuoxun; Wang, Dong; Liu, Yurong; Guo, Xuyun; Zhu, Ye; Meng, Zhengong; Yu, Zhen-Qiang; Wong, Wai-YeungJournal of Materials Chemistry C: Materials for Optical and Electronic Devices (2020), 8 (31), 10774-10780CODEN: JMCCCX; ISSN:2050-7534. (Royal Society of Chemistry)The stable sandwich structure and the excellent redox activity of ferrocene make it a ubiquitous component in organometallic systems. The introduction of a ferrocenyl unit into a polymer skeleton provides a good avenue towards novel materials for various applications in redox batteries, enantioselective catalysis, optical and magnetic switches, etc. Herein, we report a strategic design and synthesis of new ferrocene-based hyperbranched polymers, and demonstrate promising methods for their morphol. control as spheres by direct coupling reactions and hollow polyhedra by a templating approach. Furthermore, task-specific applications targeted for their resp. architectures are investigated in lithium ion batteries (LIBs) and water treatment, resp. The spherical polymer used as an electroactive anode in LIBs has a high capacity of 755.2 mA h g-1, stable chargeable performance of over 200 cycles and superior rate capability. For comparison, the hollow counterpart shows a sharp increase of the sp. surface area in the precursor-derived magnetic ceramics from 417 to 1195 m2 g-1, and the as-made material exhibits great potential for the rapid removal of trace amts. of pollutants in water with magnetic reusability.
- 22Lai, Y. Y.; Li, X.; Zhu, Y. Polymeric Active Materials for Redox Flow Battery Application. ACS Appl. Polym. Mater. 2020, 2 (2), 113– 128, DOI: 10.1021/acsapm.9b00864Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXksVygtQ%253D%253D&md5=cbeed3e68304b179e43d2fe5549ea968Polymeric Active Materials for Redox Flow Battery ApplicationLai, Yun Yu; Li, Xiang; Zhu, YuACS Applied Polymer Materials (2020), 2 (2), 113-128CODEN: AAPMCD; ISSN:2637-6105. (American Chemical Society)A review. The redox flow battery (RFB) is one of the most promising systems for large scale electrochem. energy storage applications. The development of redox-active materials is an essential part of RFB research. Com. RFBs use redox-active inorg. ions, which have several issues such as expensive and toxic active materials, crossover of redox species, and high cost of the ion exchange membrane. The incorporation of redox-active polymeric materials is an intriguing soln. because low-cost polymeric redox-active materials and size-exclusion porous membranes formed by commodity polymers could be applied to replace expensive inorg. redox-active materials and ion exchange membranes, resp. The development of polymer-based redox-active materials in RFB application (PRFB) has advanced rapidly in the past few years. In this review, the recent progress of PRFB is summarized. Three major categories based on materials are discussed: the aq. redox-active polymers, the nonaq. redox-active polymers and oligomers, and polymer suspension systems. This review not only provides comprehensive information on synthetic strategy of polymeric redox-active materials and their properties such as redox potential and soly. in electrolyte but also reports the performance of recent PRFB cells, including cycling stability, cell voltage, and implementation of size-exclusion porous membranes. Finally, a short future perspective of PRFB development is provided.
- 23Horák, D.; Shapoval, P. Reactive Poly(Glycidyl Methacrylate) Microspheres Prepared by Dispersion Polymerization. J. Polym. Sci., Part A: Polym. Chem. 2000, 38 (21), 3855– 3863, DOI: 10.1002/1099-0518(20001101)38:21<3855::AID-POLA20>3.0.CO;2-2Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXnsFaru7g%253D&md5=dc0a388033f8b5384bbae3fa0b6369bcReactive poly(glycidyl methacrylate) microspheres prepared by dispersion polymerizationHorak, Daniel; Shapoval, PavloJournal of Polymer Science, Part A: Polymer Chemistry (2000), 38 (21), 3855-3863CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)Poly(glycidyl methacrylate) (PGMA) microspheres of narrow size distribution were prepd. in a simple one-step procedure by dispersion radical polymn. Depending on the solvent used, PGMA particle size could be controlled at 0.5-4 μm by changing the soly. parameter of the reaction mixt. In DMF/MeOH, the particle size increased and the size distribution broadened with decreasing initial soly. parameter. In the DMF/MeOH solvent system, hydroxypropyl cellulose or cellulose acetate butyrate were used as steric stabilizers in the dispersion polymn., poly(N-vinyl-2-pyrrolidone) (PVP) was used in alc. media. Contrary to the DMF/methanol system, narrow particle size distributions were obtained with PVP-stabilized polymns. in EtOH, MeOH, PrOH or BuOH. Both the particle size and polydispersity were reduced with increasing stabilizer concn. PGMA samples prepd. in neat alc. medium virtually quant. retained oxirane group content after the polymn. The reactivity of the PGMA microspheres was confirmed by their hydrolysis and aminolysis.
- 24Muzammil, E. M.; Khan, A.; Stuparu, M. C. Post-Polymerization Modification Reactions of Poly(Glycidyl Methacrylate)S. RSC Adv. 2017, 7 (88), 55874– 55884, DOI: 10.1039/C7RA11093FGoogle Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhvFersbnM&md5=c521aa3f87a6afe97f7483455c6ffbcfPost-polymerization modification reactions of poly(glycidyl methacrylate)sMuzammil, Ezzah M.; Khan, Anzar; Stuparu, Mihaiela C.RSC Advances (2017), 7 (88), 55874-55884CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)A review. Post-polymn. modification of poly(glycidyl methacrylate) (PGMA) through the nucleophilic ring opening reactions of the pendent epoxide groups allows for the installation of a variety of functionalities onto the reactive scaffold. The primary modification processes involve amine-epoxy, thiol-epoxy, azide-epoxy, acid-epoxy, and hydrolysis reactions. In all cases, sequential post-synthesis modification reactions can also be carried out if multiply-functionalised polymers are required. This, in particular, includes reactions of the hydroxyl group(s) that come into being through the initial oxirane ring-opening reaction. The overall flexibility of these functionalisations, coupled with the com. availability of glycidyl methacrylate monomer, its controlled polymn. behavior through free radical polymn. methods and high shelf life of the resulting polymers makes PGMA one of the most adaptable reactive scaffolds in polymer chem. In this review article, our aim is to discuss the fundamental aspects of the epoxy ring-opening reactions and highlight the utilitarian nature of PGMA by addressing the range of chem. that has been used to transform this simple structure into a plethora of customised functional polymers.
- 25Kocak, G.; Solmaz, G.; Dikmen, Z.; Bütün, V. Preparation of Cross-Linked Micelles from Glycidyl Methacrylate Based Block Copolymers and Their Usages as Nanoreactors in the Preparation of Gold Nanoparticles. J. Polym. Sci., Part A: Polym. Chem. 2018, 56 (5), 514– 526, DOI: 10.1002/pola.28922Google Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhvFajsb3K&md5=5fd301dc7bc1b1b8ec70165f67129f4ePreparation of Cross-Linked Micelles from Glycidyl Methacrylate Based Block Copolymers and Their Usages as Nanoreactors in the Preparation of Gold NanoparticlesKocak, Goekhan; Solmaz, Goekhan; Dikmen, Zeynep; Buetuen, VuralJournal of Polymer Science, Part A: Polymer Chemistry (2018), 56 (5), 514-526CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)This study reports the synthesis of poly(ethylene glycol)methyl ether-block-poly(glycidyl methacrylate) (MPEG-b-PGMA) diblock, and poly(ethylene glycol)methyl ether-block-poly(glycidyl methacrylate)-block-poly(Me methacrylate) (MPEG-b-PGMA-b-PMMA) triblock copolymers via atom transfer radical polymn. and their self-assembly behaviors in aq. media by using acetone as cosolvent. These block copolymers formed near monodisperse core-shell micelles having crosslinkable cores. Two types of crosslinked micelles, namely spherical MPEG-b-PGMA core crosslinked (CCL) micelles and MPEG-b-PGMA-b-PMMA interlayer crosslinked (ILCL) micelles, were also successfully prepd. from these block copolymers by using various bifunctional crosslinkers such as hexamethylenediamine (HMDA), ethylenediamine (EDA), and 2-aminoethanethiol (AET). Crosslinking was successfully carried out via ring-opening reactions of epoxy residues of hydrophobic-cores with primary amine or thiol groups of bifunctional crosslinkers. Finally, these crosslinked micelles were successfully used as nanoreactors in the synthesis of gold nanoparticles (AuNPs) in aq. media. Both CCL and ILCL micelles were found to be good stabilizers for AuNPs in aq. media. Both CCL- and ILCL-stabilized AuNP dispersions were stable for a long time without any size changes and flocculation at room temp. These crosslinked stabilized AuNPs exhibited good catalytic activities in the redn. of p-nitrophenol. © 2017 Wiley Periodicals, Inc.J. Polym. Sci., Part A: Polym. Chem. 2017.
- 26Bartels-Keith, J. R.; Burgess, M. T.; Stevenson, J. M. Carbon-13 Nuclear Magnetic Resonance Studies of Heterocycles Bearing Carbon-Sulfur and Carbon-Selenium Bonds: 1,3,4-Thiadiazole, 1,3,4-Selenadiazole, and Tetrazole Derivatives. J. Org. Chem. 1977, 42 (23), 3725– 3731, DOI: 10.1021/jo00443a020Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaE1cXjslKquw%253D%253D&md5=789eec4d12468480bf1895f43362a48cCarbon-13 nuclear magnetic resonance studies of heterocycles bearing carbon-sulfur and carbon-selenium bonds: 1,3,4-thiadiazole, 1,3,4-selenadiazole, and tetrazole derivativesBartels-Keith, J. R.; Burgess, M. T.; Stevenson, J. M.Journal of Organic Chemistry (1977), 42 (23), 3725-31CODEN: JOCEAH; ISSN:0022-3263.A number of 1,3,4-thiadiazole- and selenadiazolethiols and -selenols I (X, X = S, Se; R = Me NH, p-MeC6H4NH, 2-thienyl) were synthesized. Thus, H2NNHCSeNHMe was treated with CSe2 to give I (X = Z = Se). 13C NMR offers a reliable method for distinguishing thiones and selones from the corresponding thiol and selenol derivs. All the products were obtained in the thione or selenone form. Substitution of Se for exocyclic S (at C-2) leads to a shielding effect at the C of attachment and (for selones) a deshielding effect at C-5, suggestive of transmission of inductive effects across the ring chalcogen. Substitution of Se for ring S results in deshielding at both C-2 and C-5; comparison with models shows this effect to be essentially independent of the number of ring N. The possible origin of this deshielding effect is discussed. These correlations have been extended to the tetrazole series, where they were used to establish the structure of the tetrazolium salt II (obtained by alkylation of the tetrazole) and its mesoionic solvolysis products. Some 13C-77Se coupling data are presented.
- 27McEwan, K. A.; Slavin, S.; Tunnah, E.; Haddleton, D. M. Dual-Functional Materials via CCTP and Selective Orthogonal Thiol-Michael Addition/Epoxide Ring Opening Reactions. Polym. Chem. 2013, 4 (8), 2608– 2614, DOI: 10.1039/c3py21104eGoogle Scholar27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXksVKrtL0%253D&md5=9322a989f11c62efe97d75e92f5d866dDual-functional materials via CCTP and selective orthogonal thiol-Michael addition/epoxide ring opening reactionsMcEwan, Kayleigh A.; Slavin, Stacy; Tunnah, Edward; Haddleton, David M.Polymer Chemistry (2013), 4 (8), 2608-2614CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)Poly(glycidyl methacrylate) (PGMA) was synthesized by cobalt catalyzed chain transfer polymn. (CCTP) yielding, in one step, polymers with two points for post polymn. functionalization: the activated terminal vinyl bond and in chain epoxide groups. Epoxide ring-opening and a combination of thiol-Michael addn. and epoxide ring-opening was used for post-functionalization with amines and thiols to prep. a range of functional materials.
- 28Jang, J.; Bae, J.; Ko, S. Synthesis and Curing of Poly(Glycidyl Methacrylate) Nanoparticles. J. Polym. Sci., Part A: Polym. Chem. 2005, 43 (11), 2258– 2265, DOI: 10.1002/pola.20706Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXksVagtb0%253D&md5=fb9c96259a4faa208e96954c2f1731b6Synthesis and curing of poly(glycidyl methacrylate) nanoparticlesJang, Jyongsik; Bae, Joonwon; Ko, SungrokJournal of Polymer Science, Part A: Polymer Chemistry (2005), 43 (11), 2258-2265CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)Glycidyl-functional polymer nanoparticles [poly(glycidyl methacrylate) (PGMA)] were fabricated with microemulsion polymn. The successful fabrication of PGMA nanoparticles was confirmed by Fourier transform IR spectroscopy and transmission electron microscopy (TEM). A TEM image showed that the av. diam. of the PGMA nanoparticles was approx. 10-28 nm and was fairly monodisperse. As the surfactant concn. increased, the av. size of the nanoparticles decreased and approached an asymptotic value. A significant redn. of the nanoparticle size to the nanometer scale led to an enhanced no. of surface functionalities, which played an important role in the curing reaction. The PGMA nanoparticles were cured with a low-temp. curing agent, diethylene triamine, to produce ultrafine thermoset nanoparticles. The low-temp. curing process was performed below the glass-transition temp. of PGMA to prevent the coagulation and deformation of the nanoparticles. A TEM image indicated that the cured PGMA nanoparticles did not exhibit interparticle aggregation and morphol. transformation during curing. The av. size of the cured PGMA nanoparticles was consistent with that of the pristine PGMA nanoparticles.
- 29Patai, S. The Chemistry of the Thiol Group. Chem. Thiol Gr. 2010, 1– 479, DOI: 10.1002/9780470771310Google ScholarThere is no corresponding record for this reference.
- 30Helmkamp, G. K. Organic Chemistry of Sulfur; Oae, S., Ed.; Plenum Press, 1978; Vol. 55. DOI: 10.1021/ed055pa390.3 .Google ScholarThere is no corresponding record for this reference.
- 31Gao, H.; Elsabahy, M.; Giger, E. V.; Li, D.; Prud’homme, R. E.; Leroux, J.-C. Aminated Linear and Star-Shape Poly(Glycerol Methacrylate)s: Synthesis and Self-Assembling Properties. Biomacromolecules 2010, 11 (4), 889– 895, DOI: 10.1021/bm901241kGoogle Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXislWltbw%253D&md5=c6d327ebfd3d125abaa3c6eec3721f3fAminated Linear and Star-Shape Poly(glycerol methacrylate)s: Synthesis and Self-Assembling PropertiesGao, Hui; Elsabahy, Mahmoud; Giger, Elisabeth V.; Li, Dekun; Prud'homme, Robert E.; Leroux, Jean-ChristopheBiomacromolecules (2010), 11 (4), 889-895CODEN: BOMAF6; ISSN:1525-7797. (American Chemical Society)Over the past 10 years, polyglycerols and their structurally related analogs have received considerable attention in the biomedical field. Poly(glycidyl methacrylate) (PGMA) is a versatile polymer because its pendant epoxide groups can be opened with different functional groups to generate poly(glycerol methacrylate)s (PGOHMA) derivs. In this work, linear and star-shape PGMAs were synthesized by atom transfer radical polymn. and then functionalized with four different amines by ring-opening addn. This resulted in the formation of polyglycerol-like polymers having both hydroxyl and amine moieties and different water-soly. The water-insol. polymers could form pH-sensitive nanoassemblies, while the sol. derivs. efficiently complexed a short strand polynucleotide. The aminated polyglycerol interacted more avidly with the oligonucleotide than the control poly(ethyleneimine), and high transfection efficacy could be obtained with the linear deriv. Such polymers could find practical applications for the delivery of drugs and nucleic acids.
- 32Kozhunova, E. Y.; Gvozdik, N. A.; Motyakin, M. V.; Vyshivannaya, O. V.; Stevenson, K. J.; Itkis, D. M.; Chertovich, A. V. Redox-Active Aqueous Microgels for Energy Storage Applications. J. Phys. Chem. Lett. 2020, 11 (24), 10561– 10565, DOI: 10.1021/acs.jpclett.0c03164Google ScholarThere is no corresponding record for this reference.
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https://doi.org/10.1002/ange.202215329
- Bang‐Sen Wang, Qi Zhang, Zhi‐Qiang Wang, Chen‐Yu Shi, Xue‐Qing Gong, He Tian, Da‐Hui Qu. Acid‐catalyzed Disulfide‐mediated Reversible Polymerization for Recyclable Dynamic Covalent Materials. Angewandte Chemie International Edition 2023, 62
(11)
https://doi.org/10.1002/anie.202215329
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Abstract
Figure 1
Figure 1. (a) Reversible electrochemical reaction of thiadiazole-based disulfides. (b) Reaction scheme for the synthesis of 1-SS-1-functionalized PGMA particles (P2) from PGMA particles with a 1 wt % HMDA permanent cross-linker (P1).
Figure 2
Figure 2. (a) Scheme for UV annealing of P2 particles to remove dangling monofunctionalized x-SS-1. (b) Particle size reduction after UV annealing as measured by dynamic light scattering (DLS) in acetonitrile (ACN). (c) SEM image of DS-RAP.
Figure 3
Figure 3. CV data with inset schemes. 100 mM tetrabutylammonium hexafluorophosphate (TBAPF6)/ACN electrolyte, with 20 mV/s scan rate. Potentials are relative to Ag/Ag+ nonaqueous reference electrodes. (a) 2-SS-2 solution and drop-cast DS-RAP. (b) Enhanced electrochemical response of DS-RAP by 1:1 by weight blending of Super P carbon black (CB).
Figure 4
Figure 4. Galvanostatic cycling (GC) of the smaller DS-RAP (ca. 1000 nm) at a C-rate of 0.10 and 0.25 C. (a) Charge/discharge curves (cycle 3 for 0.10 C and cycle 46 for 0.25 C). Potential (V) vs Li/Li+ is converted from Ag/Ag+. (b) Charge/discharge cycling stability and Coulombic efficiency (CE) data. The reported GC experiments were performed using DMSO with 0.5 M Mg(OTf)2. Additional GC results are shown in the Supporting Information (Figure S6).
References
This article references 32 other publications.
- 1Winsberg, J.; Hagemann, T.; Janoschka, T.; Hager, M. D.; Schubert, U. S. Redox-Flow Batteries: From Metals to Organic Redox-Active Materials. Angew. Chem., Int. Ed. 2017, 56 (3), 686– 711, DOI: 10.1002/anie.2016049251https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xhsl2hsLrF&md5=ff596c450ef64fd500ffb2832d096756Redox-Flow Batteries: From Metals to Organic Redox-Active MaterialsWinsberg, Jan; Hagemann, Tino; Janoschka, Tobias; Hager, Martin D.; Schubert, Ulrich S.Angewandte Chemie, International Edition (2017), 56 (3), 686-711CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Research on redox-flow batteries (RFBs) is currently experiencing a significant upturn, stimulated by the growing need to store increasing quantities of sustainably generated elec. energy. RFBs are promising candidates for the creation of smart grids, particularly when combined with photovoltaics and wind farms. To achieve the goal of "green", safe, and cost-efficient energy storage, research has shifted from metal-based materials to org. active materials in recent years. This Review presents an overview of various flow-battery systems. Relevant studies concerning their history are discussed as well as their development over the last few years from the classical inorg., to org./inorg., to RFBs with org. redox-active cathode and anode materials. Available technologies are analyzed in terms of their tech., economic, and environmental aspects; the advantages and limitations of these systems are also discussed. Further technol. challenges and prospective research possibilities are highlighted.
- 2Lu, Y.; Chen, J. Prospects of Organic Electrode Materials for Practical Lithium Batteries. Nat. Rev. Chem. 2020, 4 (3), 127– 142, DOI: 10.1038/s41570-020-0160-92https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXjtFWisro%253D&md5=60556a33988c364d1a47128eed4a280aProspects of organic electrode materials for practical lithium batteriesLu, Yong; Chen, JunNature Reviews Chemistry (2020), 4 (3), 127-142CODEN: NRCAF7; ISSN:2397-3358. (Nature Research)A review. Abstr.: Org. materials have attracted much attention for their utility as lithium-battery electrodes because their tunable structures can be sustainably prepd. from abundant precursors in an environmentally friendly manner. Most research into org. electrodes has focused on the material level instead of evaluating performance in practical batteries. This Review addresses this by first providing an overview of the history and redox of org. electrode materials and then evaluating the prospects and remaining challenges of org. electrode materials for practical lithium batteries. Our evaluations are made according to energy d., power d., cycle life, gravimetric d., electronic cond. and other relevant parameters, such as energy efficiency, cost and resource availability. We posit that research in this field must focus more on the intrinsic electronic cond. and d. of org. electrode materials, after which a comprehensive optimization of full batteries should be performed under practically relevant conditions. We hope to stimulate high-quality applied research that might see the future commercialization of org. electrode materials.
- 3Liu, M.; Visco, S. J.; De Jonghe, L. C. Novel Solid Redox Polymerization Electrodes: Electrochemical Properties. J. Electrochem. Soc. 1991, 138 (7), 1896– 1901, DOI: 10.1149/1.20858963https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3MXlt1agsrk%253D&md5=7c8df4c875e000782da85b542f118f6eNovel solid redox polymerization electrodes. Electrochemical propertiesLiu, Meilin; Visco, Steven J.; De Jonghe, Lutgard C.Journal of the Electrochemical Society (1991), 138 (7), 1896-901CODEN: JESOAN; ISSN:0013-4651.The generic redox reaction of a class of linear sulfur-contg. redox polymn. electrodes can be described as: (-SRS-)n + n(2e-)↹n(-SRS-), i.e., the polymer electrode can be progressively depolymd., leading ultimately to monomeric anions, as the sulfur-sulfur bridges between the org. R groups are cleaved during discharge and then the monomer anions can be subsequently reoxidized back to the original polymer during charge. This is the first time the process of electrodepolymn.-electropolymn. has been exploited for energy storage, establishing a broad class of chem. flexible, low equiv. wt., and inexpensive electrodes for advanced batteries. Electrochem. investigation of a diverse group of novel solid redox polymn. electrodes indicates that these materials are excellent candidates for all-solid-state, thin-film, energy-storage systems. Some of the advantages offered by the batteries based on these materials include high energy d. and rate capability, extensive utilization of pos. electrode capacity, ease of fabrication, low cost, and superior reliability, and safety. In addn., these materials are reversible to lithium and sodium (as well as many alk. earth and transition metals), allowing for a much greater choice of neg. electrode materials, in stark contrast to cells based on analogous intercalation compds. Further, and in particular, a great advantage of redox polymn. electrodes is the ability to alter the phys., chem., and electrochem. properties of these materials in a very predictable manner through manipulation of various functional groups, electron-withdrawing heteroatoms, and the mol. architecture.
- 4Baloch, M.; BenYoucef, H.; Li, C.; Garcia -Calvo, O.; Rodriguez, L. M.; Shanmukaraj, D.; Rojo, T.; Armand, M. New Redox Polymers That Exhibit Reversible Cleavage of Sulfur Bonds as Cathode Materials. ChemSusChem 2016, 9 (22), 3206– 3212, DOI: 10.1002/cssc.2016010324https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhslKntLzM&md5=d96603c39a49601383d0b0ae81e5ef8dNew Redox Polymers that Exhibit Reversible Cleavage of Sulfur Bonds as Cathode MaterialsBaloch, Marya; Ben Youcef, Hicham; Li, Chunmei; Garcia-Calvo, Oihane; Rodriguez, Lide M.; Shanmukaraj, Devaraj; Rojo, Teofilo; Armand, MichelChemSusChem (2016), 9 (22), 3206-3212CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)Two new cathode materials based on redox organosulfur polymers were synthesized and investigated for rechargeable lithium batteries as a proof-of-concept study. These cathodes offered good cycling performance owing to the absence of polysulfide soly., which plagues Li/S systems. Herein, an aliph. polyamine or a conjugated polyazomethine was used as the base to tether the redox-active species. The activity comes from the cleavage and formation of S-S or N-S bonds, which is made possible by the rigid conjugated backbone. The synthesized polymers were characterized through FTIR spectroscopy and thermogravimetric anal. (TGA). Galvanostatic measurements were performed to evaluate the discharge/charge cycles and characterize the performance of the lithium-based cells, which displayed initial discharge capacities of approx. 300 mA h g-1 at C/5 over 100 cycles with approx. 98 % Coulombic efficiency.
- 5Oyama, N.; Tatsuma, T.; Sato, T.; Sotomura, T. Dimercaptan–Polyaniline Composite Electrodes for Lithium Batteries with High Energy Density. Nature 1995, 373 (6515), 598– 600, DOI: 10.1038/373598a05https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2MXjsl2msbw%253D&md5=fa1ecd81d158db8ca1f79c6c85242cf0Dimercaptan-polyaniline composite electrodes for lithium batteries with high energy densityOyama, N.; Tatsuma, T.; Sato, T.; Sotomura, T.Nature (London) (1995), 373 (6515), 598-600CODEN: NATUAS; ISSN:0028-0836. (Macmillan Magazines)We report the development of a rechargeable lithium battery with a composite org. cathode based on a mixt. of a dimercaptan and polyaniline. The redox behavior of the dimercaptan, which is normally too slow for practical applications, is accelerated when coupled to that of the polyaniline (which itself functions as an active cathode material). Intimate mixing of the two materials is achieved by casting them jointly from soln. The resulting electrode can be repeatedly charged to near its theor. limit and discharged. The gravimetric energy d. of our materials exceeds that of the oxide electrodes in com. available lithium-ion batteries, a feature that is likely to prove advantageous in applications where wt., rather than vol., is a crit. factor.
- 6Pope, J. M.; Oyama, N. Organosulfur/Conducting Polymer Composite Cathodes: I. Voltammetric Study of the Polymerization and Depolymerization of 2,5-Dimercapto-1,3,4-thiadiazole in Acetonitrile. J. Electrochem. Soc. 1998, 145 (6), 1893– 1901, DOI: 10.1149/1.18385736https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1cXjsFSlsLw%253D&md5=67de02e0ef103d1fd386d79c351c8e3fOrganosulfur/conducting polymer composite cathodes. Voltammetric study of the polymerization and depolymerization of 2,5,-dimercapto-1,3,4-thiadiazole in acetonitrilePope, John M.; Oyama, NoboruJournal of the Electrochemical Society (1998), 145 (6), 1893-1901CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)This paper describes general trends in the redox potential and soly. of a dimercaptan, 2,5,-dimercapto-1,3,4-thiadiazole (DMcT), and its various derivs. in acetonitrile, and illustrates how these trends manifest in the cyclic voltammetry obsd. at glassy carbon electrodes. Attention is focused on the polymn./depolymn. processes which are the origins of the excellent charge-storage capabilities of electrodes based on the DMcT family of compds. The extent of oligomerization/polymn. of DMcT at glassy carbon increases with increasing overpotential and/or oxidn. time, as judged from its subsequently obsd. quasi-stable depolymn. wave. Oxidn. of dimer DMcT results in extensive pptn. onto the electrode, relative to that obsd. for oxidn. of monomer DMcT, as expected in light of solubilities obsd. for those compds. in acetonitrile. The protonation state of the compds. has a considerable effect on both their soly. and, as reported previously in part, redox potential. Similarly, chem. coupling of the redox processes of these compds. to their protonation state and, for DMcT, to a disproportionation reaction known to occur for its oxidn. product(s) complicates anal. of the system as a whole. However, from consideration of all of the obsd. trends, a general picture emerges illustrating the redox character of DMcT during polymn. and depolymn. Most importantly, the electrochem. irreversibility typical of those processes can be avoided by careful control of the protonation state and soly. of the electroactive species, allowing the measurement of quasi-reversible redox couples. That and other results are discussed in the context of the use of DMcT in secondary battery electrodes.
- 7Oyama, N.; Kiya, Y.; Hatozaki, O.; Morioka, S.; Abruña, H. D. Dramatic Acceleration of Organosulfur Redox Behavior by Poly(3,4-Ethylenedioxythiophene). Electrochem. Solid-State Lett. 2003, 6 (12), A286, DOI: 10.1149/1.16217537https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXosF2lu7c%253D&md5=bb0954092f66f4276877705722070610Dramatic Acceleration of Organosulfur Redox Behavior by Poly(3,4-ethylenedioxythiophene)Oyama, Noboru; Kiya, Yasuyuki; Hatozaki, Osamu; Morioka, Satoru; Abruna, Hector D.Electrochemical and Solid-State Letters (2003), 6 (12), A286-A289CODEN: ESLEF6; ISSN:1099-0062. (Electrochemical Society)High electrocatalytic activity of electropolymd. films of poly(3,4-ethylenedioxythiophene) (PEDOT) toward the redox reactions of 2,5-dimercapto-1,3,4-thiadiazole (DMcT), a promising cathode material for high-energy Li-ion batteries, is discussed. The irreversible redox reaction of DMcT monomer at an unmodified glassy C electrode was accelerated at a PEDOT film-coated electrode to give a reversible response. PEDOT also showed high electrocatalytic activity toward the redox reactions of DMcT dimers and oligomers. Such an acceleration of the DMcT redox reaction, which is essential to practical application of organosulfur compds. in batteries, was ascribed to the electronic properties of PEDOT. Chronopotentiometric results indicated that at PEDOT film-coated electrodes, the redox reactions of DMcT proceed fast enough to produce an electrolysis current of 1.0 mA/cm2.
- 8Kiya, Y.; Henderson, J. C.; Hutchison, G. R.; Abruña, H. D. Synthesis, Computational and Electrochemical Characterization of a Family of Functionalized Dimercaptothiophenes for Potential Use as High-Energy Cathode Materials for Lithium/Lithium-Ion Batteries. J. Mater. Chem. 2007, 17 (41), 4366– 4376, DOI: 10.1039/b707235j8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXhtFKrsrfI&md5=2e184cda92bba9731aae12e009c30d94Synthesis, computational and electrochemical characterization of a family of functionalized dimercaptothiophenes for potential use as high-energy cathode materials for lithium/lithium-ion batteriesKiya, Yasuyuki; Henderson, Jay C.; Hutchison, Geoffrey R.; Abruna, Hector D.Journal of Materials Chemistry (2007), 17 (41), 4366-4376CODEN: JMACEP; ISSN:0959-9428. (Royal Society of Chemistry)We present a family of a novel class of organosulfur compds. based on dimercaptothiophene and its derivs., with a variety of functional groups (electron-donating or electron-withdrawing groups) and regiochemistries, designed as potential high-energy cathode materials with sufficient charge/discharge cyclability for lithium/lithium-ion rechargeable batteries. This study uses as a point of departure the electrochem. and computational understanding of the electrocatalytic effect of poly(3,4-ethylenedioxythiophene) (PEDOT) towards the redox reactions of 2,5-dimercapto-1,3,4-thiadiazole (DMcT). The effective redox potentials of these materials exhibited good correlation with the highest-occupied MO (HOMO) levels predicted via computational modeling. Furthermore, the redox reactions of all the compds. studied were electrocatalytically accelerated at PEDOT film-coated glassy carbon electrodes (GCEs), although some materials exhibited higher energy output than others. By using this approach we have identified several compds. that exhibit clear promise as potential cathode materials and have characterized the mol. interactions between the organosulfur compds. and PEDOT film surfaces involved in the electrocatalytic reactions.
- 9Rodríguez-Calero, G. G.; Conte, S.; Lowe, M. A.; Gao, J.; Kiya, Y.; Henderson, J. C.; Abruña, H. D. Synthesis and Characterization of Poly-3,4-Ethylenedioxythiophene/2,5-Dimercapto-1,3,4-Thiadiazole (PEDOT-DMcT) Hybrids. Electrochim. Acta 2015, 167, 55– 60, DOI: 10.1016/j.electacta.2015.02.1599https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXjtFersbY%253D&md5=b4db7dc000fa002c770e99b95bc5b57fSynthesis and Characterization of Poly-3,4-ethylenedioxythiophene/2,5-Dimercapto-1,3,4-thiadiazole (PEDOT-DMcT) HybridsRodriguez-Calero, Gabriel G.; Conte, Sean; Lowe, Michael A.; Gao, Jie; Kiya, Yasuyuki; Henderson, Jay C.; Abruna, Hector D.Electrochimica Acta (2015), 167 (), 55-60CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)Organosulfur Compds. (OSCs) represent an attractive alternative as org. cathode materials for electrochem. energy storage (EES) applications. They intrinsically have high gravimetric capacity (although low volumetric) and are typically inexpensive, since they are composed of abundant elements (i.e. C, N, O, and S). However, OSCs, specifically thiolate-contg. OSCs generally suffer from slow charge transfer kinetics. To mitigate the charge transfer limitations, conducting polymers (CPs) such as poly-3,4-ethylenedioxythiophene (PEDOT) were employed as electrocatalysts. In this manuscript, the authors have covalently modified a PEDOT film with an OSC (i.e. 2,5-dimercapto-1,3,4-thiadiazole di-Li salt (Li2DMcT)). The authors have developed a synthetic strategy that employs, for the 1st time, a post-polymn. modification reaction as a tractable and viable technique to modify org. materials for EES electrodes. Electrochem. characterization, via cyclic voltammetry showed the expected pseudocapacitive response of PEDOT with the superimposed faradaic processes of the covalently bound DMcT. Also, spectroscopic characterization using Raman spectroscopy provided mechanistic insights into the electrochem. reactions. Also, the authors electropolymd. films onto coin-cell electrodes and tested them in half-cell configurations and found that the capacity retention of the films was significantly enhanced, when compared with the PEDOT/DMcT composites (mixed but not covalently bound).
- 10Kiya, Y.; Hutchison, G. R.; Henderson, J. C.; Sarukawa, T.; Hatozaki, O.; Oyama, N.; Abruña, H. D. Elucidation of the Redox Behavior of 2,5-Dimercapto-1,3,4-Thiadiazole (DMcT) at Poly(3,4-Ethylenedioxythiophene) (PEDOT)-Modified Electrodes and Application of the DMcT - PEDOT Composite Cathodes to Lithium/Lithium Ion Batteries. Langmuir 2006, 22 (25), 10554– 10563, DOI: 10.1021/la061213q10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtVajt7jL&md5=0664fa33d49e5085e3cc10458009ca84Elucidation of the Redox Behavior of 2,5-Dimercapto-1,3,4-thiadiazole (DMcT) at Poly(3,4-ethylenedioxythiophene) (PEDOT)-Modified Electrodes and Application of the DMcT-PEDOT Composite Cathodes to Lithium/Lithium Ion BatteriesKiya, Yasuyuki; Hutchison, Geoffrey R.; Henderson, Jay C.; Sarukawa, Tomoo; Hatozaki, Osamu; Oyama, Noboru; Abruna, Hector D.Langmuir (2006), 22 (25), 10554-10563CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)The redox reactions of DMcT at PEDOT-modified glassy carbon electrodes (GCEs) in acetonitrile (AN) have been investigated via cyclic voltammetry (CV) and the electrochem. quartz crystal microbalance (EQCM) in order to elucidate the redox reaction mechanism. A redox couple at -0.29 V vs. Ag/Ag+ was assigned to the dimerization process of singly protonated DMcT (DMcT-1H), and a second couple obsd. at +0.42 V was assigned to the polymn. process of the protonated DMcT dimer. Our investigations revealed further that the anodic current response at +0.55 V (polymn. process) has a shoulder at +0.38 V ascribed to the dimerization process of doubly protonated DMcT (DMcT-2H), indicating that the redox couple at +0.42 V is the overlapping response of the polymn. of the protonated DMcT dimer and the dimerization of the DMcT-2H monomer. It was also confirmed that the dimerization process of DMcT-1H at -0.29 V proceeded not only at the surface of a PEDOT film but also inside the film as previously suggested. Moreover, the thermodn. of these redox reactions at PEDOT-modified GCEs are dependent on the basicity (or acidity) of the soln., as anticipated and previously shown at unmodified GCEs. The oxidn. of DMcT occurs at less pos. potentials and the redn. occurs at more neg. potentials in the presence of base. On the basis of the results obtained, the full redox reaction scheme for DMcT at a PEDOT-modified GCE is proposed.
- 11Mistry, A. N.; Mukherjee, P. P. Shuttle” in Polysulfide Shuttle: Friend or Foe?. J. Phys. Chem. C 2018, 122 (42), 23845– 23851, DOI: 10.1021/acs.jpcc.8b0607711https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvVKltLzJ&md5=fd0b18a9354865e817d5543360fd3a9d"Shuttle" in Polysulfide Shuttle: Friend or Foe?Mistry, Aashutosh N.; Mukherjee, Partha P.Journal of Physical Chemistry C (2018), 122 (42), 23845-23851CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)The polysulfide shuttle effect, where S species reach the neg. electrode surface and undergo chem. redn., is believed to be a major bottleneck in Li-S chem. The importance of this phenomenon is often judged based on phenomenol. arguments, which do not account for meso-scale complexations. This work presents a comprehensive study of the coupled interactions arising from speciation, concd. electrolyte soln., and reaction time scales. Polysulfide transport consists of diffusion and migration, which dets. the net flux. The polysulfide shuttle effect can be bounded between reaction-limited and shuttle-limited regimes, depending on the operational extremes. At high S to electrolyte ratio (i.e. lean electrolyte condition), the polysulfide shuttle effect may not necessarily attribute to the cell performance limitation, believed contrarily otherwise.
- 12Li, J.; Zhan, H.; Zhou, Y. Synthesis and Electrochemical Properties of Polypyrrole-Coated Poly(2,5-Dimercapto-1,3,4-Thiadiazole). Electrochem. Commun. 2003, 5 (7), 555– 560, DOI: 10.1016/S1388-2481(03)00121-812https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXkvFKltLY%253D&md5=eced0df26aa8f3e560b17974125f42aeSynthesis and electrochemical properties of polypyrrole-coated poly(2,5-dimercapto-1,3,4-thiadiazole)Li, Jinxia; Zhan, Hui; Zhou, YunhongElectrochemistry Communications (2003), 5 (7), 555-560CODEN: ECCMF9; ISSN:1388-2481. (Elsevier Science B.V.)A new composite cathode active material, conductive polypyrrole (PPy)-coated poly(2,5-dimercapto-1,3,4-thiadiazole) (PDMcT) was prepd. as a thin film via the surfactant template technique. Formation of the uniform and well-attached film on the surface of PDMcT particles was confirmed by FTIR spectroscopy and TEM. Cyclic voltammetry and galvanostatic charge-discharge tests indicated that the coated composite showed a better electrochem. performance than PDMcT alone as evidenced by enhanced redox processes and improved coulombic efficiency. The elec. cond. of the material was 10-3 S/cm and an initial discharge capacity of 250 mA-h/g was obtained. It had less fading of discharge capacity than PDMcT when used as cathode material in secondary Li batteries with liq. electrolytes.
- 13Shi, T.; Tu, Q.; Tian, Y.; Xiao, Y.; Miara, L. J.; Kononova, O.; Ceder, G. High Active Material Loading in All-Solid-State Battery Electrode via Particle Size Optimization. Adv. Energy Mater. 2020, 10 (1), 1902881, DOI: 10.1002/aenm.20190288113https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXit1KqtLvI&md5=8c486a7f9f5760c8b6e8102e394827f6High Active Material Loading in All-Solid-State Battery Electrode via Particle Size OptimizationShi, Tan; Tu, Qingsong; Tian, Yaosen; Xiao, Yihan; Miara, Lincoln J.; Kononova, Olga; Ceder, GerbrandAdvanced Energy Materials (2020), 10 (1), 1902881CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)Low active material loading in the composite electrode of all-solid-state batteries (SSBs) is one of the main reasons for the low energy d. in current SSBs. In this work, it is demonstrated with both modeling and expts. that in the regime of high cathode loading, the utilization of cathode material in the solid-state composite is highly dependent on the particle size ratio of the cathode to the solid-state conductor. The modeling, confirmed by exptl. data, shows that higher cathode loading and therefore an increased energy d. can be achieved by increasing the ratio of the cathode to conductor particle size. These results are consistent with ionic percolation being the limiting factor in cold-pressed solid-state cathode materials and provide specific guidelines on how to improve the energy d. of composite cathodes for solid-state batteries. By reducing solid electrolyte particle size and increasing the cathode active material particle size, over 50 vol% cathode active material loading with high cathode utilization is able to be exptl. achieved, demonstrating that a com.-relevant, energy-dense cathode composite is achievable through simple mixing and pressing method.
- 14Zhao, Y.; Si, S.; Liao, C. A Single Flow Zinc//Polyaniline Suspension Rechargeable Battery. J. Power Sources 2013, 241, 449– 453, DOI: 10.1016/j.jpowsour.2013.04.09514https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhtV2lt7jE&md5=e993a49fe29d3ff07d68d1a7d4659f73A single flow zinc//polyaniline suspension rechargeable batteryZhao, Yongfu; Si, Shihui; Liao, CuiJournal of Power Sources (2013), 241 (), 449-453CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)Both the electrochem. activity and the energy d. of polyaniline (PANI) microparticles suspensions are enhanced by using the compact PANI powder, which is synthesized galvanostatically with 4,4'-diaminobiphenyl as additive. A Zn//PANI suspension rechargeable flow battery system is proposed, in which the flowable PANI suspension is used as cathode electroactive material, zinc plate as anode. A microporous membrane is used as separator to prevent PANI particles from getting into the anode compartment. Results obtained from the small lab. battery show that the discharge capacity d. gradually decreases with no. of cycles and the av. of discharge capacity loss during 32 cycles is about 0.07% per cycle. However, an av. coulombic efficiency of 97% has been achieved at the c.d. of 20 mA/cm2 and the value of coulombic efficiency shows no significant change during 32 charge/discharge cycles. The flow-through mode for PANI cathode material enables the PANI-based battery to operate at a higher c.d. in comparison with the conventional Zn-PANI film batteries, and the present findings can mark a new route to improve the performance of conductive polymer-based energy storage devices.
- 15Karami, H.; Mousavi, M. F.; Shamsipur, M. A New Design for Dry Polyaniline Rechargeable Batteries. J. Power Sources 2003, 117 (1–2), 255– 259, DOI: 10.1016/S0378-7753(03)00168-X15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXjsVSjurc%253D&md5=3b198a8d9afd3bc67bc48688e28db297A new design for dry polyaniline rechargeable batteriesKarami, Hassan; Mousavi, Mir Fazlollah; Shamsipur, MojtabaJournal of Power Sources (2003), 117 (1-2), 255-259CODEN: JPSODZ; ISSN:0378-7753. (Elsevier Science B.V.)Polyaniline powder of high cond. is prepd. by chem. polymn. of aniline in a soln. of 0.10M aniline, 2 M perchloric acid and 0.15M ammonium persulfate at 5°. The powder is mixed with graphite and acetylene black to obtain the required cond. and porosity. The mixed powder is compressed into a ring shape at a pressure of 2 t cm-2 for use as pos. electrodes (cathodes) in batteries. Zinc powder is mixed with magnesium oxide, zinc oxide and sodium CM-cellulose (CMC), and then compressed into a cylindrical shape at a pressure of 7 t cm-2 for use as neg. electrodes (anodes) in batteries. The battery electrolyte comprises 2 M Zn(ClO4)2, 1 M NH4ClO4, and 1.0 × 10-4 M Triton-X100 at pH 3. A 1% Optalloy powder is added to the neg.-electrode composite to prevent the release of hydrogen gas. The assembled battery has an open-circuit voltage (OCV) of 1.64 V, a charge storage capacity of 125.43 m Ah g-1, and a Coulombic efficiency >95% during the 1st 100 charge-discharge cycles. Due to the low amt. of electrolyte used, the battery is considered as a dry battery.
- 16Hauffman, G.; Maguin, Q.; Bourgeois, J.-P.; Vlad, A.; Gohy, J.-F. Micellar Cathodes from Self-Assembled Nitroxide-Containing Block Copolymers in Battery Electrolytes. Macromol. Rapid Commun. 2014, 35 (2), 228– 233, DOI: 10.1002/marc.20130053216https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhs1WisbvI&md5=b50410815c08c4a171cb239a06bed535Micellar Cathodes from Self-Assembled Nitroxide-Containing Block Copolymers in Battery ElectrolytesHauffman, Guillaume; Maguin, Quentin; Bourgeois, Jean-Pierre; Vlad, Alexandru; Gohy, Jean-FrancoisMacromolecular Rapid Communications (2014), 35 (2), 228-233CODEN: MRCOE3; ISSN:1022-1336. (Wiley-VCH Verlag GmbH & Co. KGaA)This contribution describes the synthesis of block copolymers contg. electrochem. active blocks, their micellization, and finally their use as micellar cathodes in a lithium battery. The self-assembly of the synthesized poly(styrene)-block-poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PS-b-PTMA) diblock copolymers is realized in a typical battery electrolyte made of 1 M lithium trifluoromethanesulfonate dissolved in a mixt. of ethylene carbonate/diethyl carbonate/dimethyl carbonate (1:1:1, in vol.). Dynamic light scattering and at. force microscopy indicate the formation of well-defined spherical micelles with a PS core and a PTMA corona. The electrochem. properties of those micelles are further investigated. Cyclic voltammograms show a reversible redox reaction at 3.6 V (vs. Li+/Li). The charge/discharge profiles indicate a flat and reversible plateau around 3.6 V (vs. Li+/Li). Finally, the cycling performances of the micellar cathodes are demonstrated. Such self-assembled block copolymers open new opportunities for nanostructured org. radical batteries.
- 17Oh, S. H.; Lee, C. W.; Chun, D. H.; Jeon, J. D.; Shim, J.; Shin, K. H.; Yang, J. H. A Metal-Free and All-Organic Redox Flow Battery with Polythiophene as the Electroactive Species. J. Mater. Chem. A 2014, 2 (47), 19994– 19998, DOI: 10.1039/C4TA04730C17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhslOjtb7I&md5=760c254a308828bdf4c2e6368d6f36d8A metal-free and all-organic redox flow battery with polythiophene as the electroactive speciesOh, S. H.; Lee, C.-W.; Chun, D. H.; Jeon, J.-D.; Shim, J.; Shin, K. H.; Yang, J. H.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2014), 2 (47), 19994-19998CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)A metal-free and all-org. redox flow battery is proposed and investigated. It employs polythiophene microparticles dispersed in electrolyte solns. as the redox couple and does not depend on limited metal resources. It shows a high cell potential and stable charge/discharge performance with a high energy efficiency of 60.9%.
- 18Wu, S.; Zhao, Y.; Li, D.; Xia, Y.; Si, S. An Asymmetric Zn//Ag Doped Polyaniline Microparticle Suspension Flow Battery with High Discharge Capacity. J. Power Sources 2015, 275, 305– 311, DOI: 10.1016/j.jpowsour.2014.11.01218https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvVKltbvK&md5=eab5a769c2e18014388ebcdae8ff5a67An asymmetric Zn//Ag doped polyaniline microparticle suspension flow battery with high discharge capacityWu, Sen; Zhao, Yongfu; Li, Degeng; Xia, Yang; Si, ShihuiJournal of Power Sources (2015), 275 (), 305-311CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)In this study, the effect of oxygen on the potential of reduced polyaniline (PANI) was investigated. In order to enhance the air oxidn. of reduced PANI, several composites of PANI doped with co-catalysts were prepd., and a reasonable flow Zn//PANI suspension cell system was designed to investigate the discharge capacity of obtained PANI composite microparticle suspension cathodes. Compared with PANI doped with Cu2+, La+, Mn2+ and zinc protoporphyrin, Ag doped PANI composite at 0.90 wt. percent doping of Ag gave the highest value of discharge capacity for the half-cell potential from the initial value to -0.20 V (vs. SCE). A comparison study on the electrochem. properties of both PANI and Ag doped PANI microparticle suspension was done by using cyclic voltammetry, AC Impedance. Due to partial utilization of Zn//air fuel cell, the discharge capacity for Ag doped PANI reached 470 mA h g-1 at the c.d. of 20 mA cm-2. At 15 mA cm-2, the discharge capacity even reached up to 1650 mA h g-1 after 220 h const. current discharge at the final discharge voltage of 0.65 V. This work demonstrates an effective and feasible approach toward obtaining high energy and power densities by a Zn//Ag-doped PANI suspension flow battery system combined with Zn//air fuel cell.
- 19Montoto, E. C.; Nagarjuna, G.; Hui, J.; Burgess, M.; Sekerak, N. M.; Hernández-Burgos, K.; Wei, T.-S. S.; Kneer, M.; Grolman, J.; Cheng, K. J.; Lewis, J. A.; Moore, J. S.; Rodríguez-López, J. Redox Active Colloids as Discrete Energy Storage Carriers. J. Am. Chem. Soc. 2016, 138 (40), 13230– 13237, DOI: 10.1021/jacs.6b0636519https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsFWnt73L&md5=eb1f512eef10705346a80e0241f4d34dRedox Active Colloids as Discrete Energy Storage CarriersMontoto, Elena C.; Nagarjuna, Gavvalapalli; Hui, Jingshu; Burgess, Mark; Sekerak, Nina M.; Hernandez-Burgos, Kenneth; Wei, Teng-Sing; Kneer, Marissa; Grolman, Joshua; Cheng, Kevin J.; Lewis, Jennifer A.; Moore, Jeffrey S.; Rodriguez-Lopez, JoaquinJournal of the American Chemical Society (2016), 138 (40), 13230-13237CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Versatile and readily available battery materials compatible with a range of electrode configurations and cell designs are desirable for renewable energy storage. Here we report a promising class of materials based on redox active colloids (RACs) that are inherently modular in their design and overcome challenges faced by small-mol. org. materials for battery applications, such as crossover and chem./morphol. stability. RACs are cross-linked polymer spheres, synthesized with uniform diams. between 80 and 800 nm, and exhibit reversible redox activity as single particles, as monolayer films, and in the form of flowable dispersions. Viologen-based RACs display reversible cycling, accessing up to 99% of their capacity and 99 ± 1% Coulombic efficiency over 50 cycles by bulk electrolysis owing to efficient, long-distance intraparticle charge transfer. Ferrocene-based RACs paired with viologen-based RACs cycled efficiently in a nonaq. redox flow battery employing a simple size-selective separator, thus demonstrating a possible application that benefits from their colloidal dimensions. The unprecedented versatility in RAC synthetic and electrochem. design opens new avenues for energy storage.
- 20Zhuo, S.; Tang, M.; Wu, Y.; Chen, Y.; Zhu, S.; Wang, Q.; Xia, C.; Wang, C. Size Control of Zwitterionic Polymer Micro/Nanospheres and Its Dependence on Sodium Storage. Nanoscale Horizons 2019, 4 (5), 1092– 1098, DOI: 10.1039/C9NH00154A20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXntVSnsbw%253D&md5=14ae7487b1e63765710f468a8b6d6929Size control of zwitterionic polymer micro/nanospheres and its dependence on sodium storageZhuo, Shuming; Tang, Mi; Wu, Yanchao; Chen, Yuan; Zhu, Shaolong; Wang, Qian; Xia, Cong; Wang, ChengliangNanoscale Horizons (2019), 4 (5), 1092-1098CODEN: NHAOAW; ISSN:2055-6764. (Royal Society of Chemistry)In this study, the size control of org. materials and its dependence on sodium storage are investigated. Poly(pyrrole-squaraine) (PPS), a polymer contg. zwitterionic repeating units, was selected as a proof for demonstration. The growth control of PPS micro/nanospheres could facilely be achieved via an in situ one-step polymn. We found that the smallest-sized PPS showed the best rate performance and cycling performance, and the shortest activation process. Moreover, the Na-ion diffusion coeff. did not strictly correlate to the particle size. These results prove that the smaller size and the shorter ionic diffusion length rather than the ionic diffusion coeff. of the material dominated the charge transfer and ionic diffusion, thereby enhancing the rate performance.
- 21Wei, Z.; Wang, D.; Liu, Y.; Guo, X.; Zhu, Y.; Meng, Z.; Yu, Z.-Q.; Wong, W.-Y. Ferrocene-Based Hyperbranched Polymers: A Synthetic Strategy for Shape Control and Applications as Electroactive Materials and Precursor-Derived Magnetic Ceramics. J. Mater. Chem. C 2020, 8 (31), 10774– 10780, DOI: 10.1039/D0TC01380C21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXms12jt7s%253D&md5=bdd200019af8b5dbcc73fb12df65c43cFerrocene-based hyperbranched polymers: a synthetic strategy for shape control and applications as electroactive materials and precursor-derived magnetic ceramicsWei, Zhuoxun; Wang, Dong; Liu, Yurong; Guo, Xuyun; Zhu, Ye; Meng, Zhengong; Yu, Zhen-Qiang; Wong, Wai-YeungJournal of Materials Chemistry C: Materials for Optical and Electronic Devices (2020), 8 (31), 10774-10780CODEN: JMCCCX; ISSN:2050-7534. (Royal Society of Chemistry)The stable sandwich structure and the excellent redox activity of ferrocene make it a ubiquitous component in organometallic systems. The introduction of a ferrocenyl unit into a polymer skeleton provides a good avenue towards novel materials for various applications in redox batteries, enantioselective catalysis, optical and magnetic switches, etc. Herein, we report a strategic design and synthesis of new ferrocene-based hyperbranched polymers, and demonstrate promising methods for their morphol. control as spheres by direct coupling reactions and hollow polyhedra by a templating approach. Furthermore, task-specific applications targeted for their resp. architectures are investigated in lithium ion batteries (LIBs) and water treatment, resp. The spherical polymer used as an electroactive anode in LIBs has a high capacity of 755.2 mA h g-1, stable chargeable performance of over 200 cycles and superior rate capability. For comparison, the hollow counterpart shows a sharp increase of the sp. surface area in the precursor-derived magnetic ceramics from 417 to 1195 m2 g-1, and the as-made material exhibits great potential for the rapid removal of trace amts. of pollutants in water with magnetic reusability.
- 22Lai, Y. Y.; Li, X.; Zhu, Y. Polymeric Active Materials for Redox Flow Battery Application. ACS Appl. Polym. Mater. 2020, 2 (2), 113– 128, DOI: 10.1021/acsapm.9b0086422https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXksVygtQ%253D%253D&md5=cbeed3e68304b179e43d2fe5549ea968Polymeric Active Materials for Redox Flow Battery ApplicationLai, Yun Yu; Li, Xiang; Zhu, YuACS Applied Polymer Materials (2020), 2 (2), 113-128CODEN: AAPMCD; ISSN:2637-6105. (American Chemical Society)A review. The redox flow battery (RFB) is one of the most promising systems for large scale electrochem. energy storage applications. The development of redox-active materials is an essential part of RFB research. Com. RFBs use redox-active inorg. ions, which have several issues such as expensive and toxic active materials, crossover of redox species, and high cost of the ion exchange membrane. The incorporation of redox-active polymeric materials is an intriguing soln. because low-cost polymeric redox-active materials and size-exclusion porous membranes formed by commodity polymers could be applied to replace expensive inorg. redox-active materials and ion exchange membranes, resp. The development of polymer-based redox-active materials in RFB application (PRFB) has advanced rapidly in the past few years. In this review, the recent progress of PRFB is summarized. Three major categories based on materials are discussed: the aq. redox-active polymers, the nonaq. redox-active polymers and oligomers, and polymer suspension systems. This review not only provides comprehensive information on synthetic strategy of polymeric redox-active materials and their properties such as redox potential and soly. in electrolyte but also reports the performance of recent PRFB cells, including cycling stability, cell voltage, and implementation of size-exclusion porous membranes. Finally, a short future perspective of PRFB development is provided.
- 23Horák, D.; Shapoval, P. Reactive Poly(Glycidyl Methacrylate) Microspheres Prepared by Dispersion Polymerization. J. Polym. Sci., Part A: Polym. Chem. 2000, 38 (21), 3855– 3863, DOI: 10.1002/1099-0518(20001101)38:21<3855::AID-POLA20>3.0.CO;2-223https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXnsFaru7g%253D&md5=dc0a388033f8b5384bbae3fa0b6369bcReactive poly(glycidyl methacrylate) microspheres prepared by dispersion polymerizationHorak, Daniel; Shapoval, PavloJournal of Polymer Science, Part A: Polymer Chemistry (2000), 38 (21), 3855-3863CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)Poly(glycidyl methacrylate) (PGMA) microspheres of narrow size distribution were prepd. in a simple one-step procedure by dispersion radical polymn. Depending on the solvent used, PGMA particle size could be controlled at 0.5-4 μm by changing the soly. parameter of the reaction mixt. In DMF/MeOH, the particle size increased and the size distribution broadened with decreasing initial soly. parameter. In the DMF/MeOH solvent system, hydroxypropyl cellulose or cellulose acetate butyrate were used as steric stabilizers in the dispersion polymn., poly(N-vinyl-2-pyrrolidone) (PVP) was used in alc. media. Contrary to the DMF/methanol system, narrow particle size distributions were obtained with PVP-stabilized polymns. in EtOH, MeOH, PrOH or BuOH. Both the particle size and polydispersity were reduced with increasing stabilizer concn. PGMA samples prepd. in neat alc. medium virtually quant. retained oxirane group content after the polymn. The reactivity of the PGMA microspheres was confirmed by their hydrolysis and aminolysis.
- 24Muzammil, E. M.; Khan, A.; Stuparu, M. C. Post-Polymerization Modification Reactions of Poly(Glycidyl Methacrylate)S. RSC Adv. 2017, 7 (88), 55874– 55884, DOI: 10.1039/C7RA11093F24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhvFersbnM&md5=c521aa3f87a6afe97f7483455c6ffbcfPost-polymerization modification reactions of poly(glycidyl methacrylate)sMuzammil, Ezzah M.; Khan, Anzar; Stuparu, Mihaiela C.RSC Advances (2017), 7 (88), 55874-55884CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)A review. Post-polymn. modification of poly(glycidyl methacrylate) (PGMA) through the nucleophilic ring opening reactions of the pendent epoxide groups allows for the installation of a variety of functionalities onto the reactive scaffold. The primary modification processes involve amine-epoxy, thiol-epoxy, azide-epoxy, acid-epoxy, and hydrolysis reactions. In all cases, sequential post-synthesis modification reactions can also be carried out if multiply-functionalised polymers are required. This, in particular, includes reactions of the hydroxyl group(s) that come into being through the initial oxirane ring-opening reaction. The overall flexibility of these functionalisations, coupled with the com. availability of glycidyl methacrylate monomer, its controlled polymn. behavior through free radical polymn. methods and high shelf life of the resulting polymers makes PGMA one of the most adaptable reactive scaffolds in polymer chem. In this review article, our aim is to discuss the fundamental aspects of the epoxy ring-opening reactions and highlight the utilitarian nature of PGMA by addressing the range of chem. that has been used to transform this simple structure into a plethora of customised functional polymers.
- 25Kocak, G.; Solmaz, G.; Dikmen, Z.; Bütün, V. Preparation of Cross-Linked Micelles from Glycidyl Methacrylate Based Block Copolymers and Their Usages as Nanoreactors in the Preparation of Gold Nanoparticles. J. Polym. Sci., Part A: Polym. Chem. 2018, 56 (5), 514– 526, DOI: 10.1002/pola.2892225https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhvFajsb3K&md5=5fd301dc7bc1b1b8ec70165f67129f4ePreparation of Cross-Linked Micelles from Glycidyl Methacrylate Based Block Copolymers and Their Usages as Nanoreactors in the Preparation of Gold NanoparticlesKocak, Goekhan; Solmaz, Goekhan; Dikmen, Zeynep; Buetuen, VuralJournal of Polymer Science, Part A: Polymer Chemistry (2018), 56 (5), 514-526CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)This study reports the synthesis of poly(ethylene glycol)methyl ether-block-poly(glycidyl methacrylate) (MPEG-b-PGMA) diblock, and poly(ethylene glycol)methyl ether-block-poly(glycidyl methacrylate)-block-poly(Me methacrylate) (MPEG-b-PGMA-b-PMMA) triblock copolymers via atom transfer radical polymn. and their self-assembly behaviors in aq. media by using acetone as cosolvent. These block copolymers formed near monodisperse core-shell micelles having crosslinkable cores. Two types of crosslinked micelles, namely spherical MPEG-b-PGMA core crosslinked (CCL) micelles and MPEG-b-PGMA-b-PMMA interlayer crosslinked (ILCL) micelles, were also successfully prepd. from these block copolymers by using various bifunctional crosslinkers such as hexamethylenediamine (HMDA), ethylenediamine (EDA), and 2-aminoethanethiol (AET). Crosslinking was successfully carried out via ring-opening reactions of epoxy residues of hydrophobic-cores with primary amine or thiol groups of bifunctional crosslinkers. Finally, these crosslinked micelles were successfully used as nanoreactors in the synthesis of gold nanoparticles (AuNPs) in aq. media. Both CCL and ILCL micelles were found to be good stabilizers for AuNPs in aq. media. Both CCL- and ILCL-stabilized AuNP dispersions were stable for a long time without any size changes and flocculation at room temp. These crosslinked stabilized AuNPs exhibited good catalytic activities in the redn. of p-nitrophenol. © 2017 Wiley Periodicals, Inc.J. Polym. Sci., Part A: Polym. Chem. 2017.
- 26Bartels-Keith, J. R.; Burgess, M. T.; Stevenson, J. M. Carbon-13 Nuclear Magnetic Resonance Studies of Heterocycles Bearing Carbon-Sulfur and Carbon-Selenium Bonds: 1,3,4-Thiadiazole, 1,3,4-Selenadiazole, and Tetrazole Derivatives. J. Org. Chem. 1977, 42 (23), 3725– 3731, DOI: 10.1021/jo00443a02026https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaE1cXjslKquw%253D%253D&md5=789eec4d12468480bf1895f43362a48cCarbon-13 nuclear magnetic resonance studies of heterocycles bearing carbon-sulfur and carbon-selenium bonds: 1,3,4-thiadiazole, 1,3,4-selenadiazole, and tetrazole derivativesBartels-Keith, J. R.; Burgess, M. T.; Stevenson, J. M.Journal of Organic Chemistry (1977), 42 (23), 3725-31CODEN: JOCEAH; ISSN:0022-3263.A number of 1,3,4-thiadiazole- and selenadiazolethiols and -selenols I (X, X = S, Se; R = Me NH, p-MeC6H4NH, 2-thienyl) were synthesized. Thus, H2NNHCSeNHMe was treated with CSe2 to give I (X = Z = Se). 13C NMR offers a reliable method for distinguishing thiones and selones from the corresponding thiol and selenol derivs. All the products were obtained in the thione or selenone form. Substitution of Se for exocyclic S (at C-2) leads to a shielding effect at the C of attachment and (for selones) a deshielding effect at C-5, suggestive of transmission of inductive effects across the ring chalcogen. Substitution of Se for ring S results in deshielding at both C-2 and C-5; comparison with models shows this effect to be essentially independent of the number of ring N. The possible origin of this deshielding effect is discussed. These correlations have been extended to the tetrazole series, where they were used to establish the structure of the tetrazolium salt II (obtained by alkylation of the tetrazole) and its mesoionic solvolysis products. Some 13C-77Se coupling data are presented.
- 27McEwan, K. A.; Slavin, S.; Tunnah, E.; Haddleton, D. M. Dual-Functional Materials via CCTP and Selective Orthogonal Thiol-Michael Addition/Epoxide Ring Opening Reactions. Polym. Chem. 2013, 4 (8), 2608– 2614, DOI: 10.1039/c3py21104e27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXksVKrtL0%253D&md5=9322a989f11c62efe97d75e92f5d866dDual-functional materials via CCTP and selective orthogonal thiol-Michael addition/epoxide ring opening reactionsMcEwan, Kayleigh A.; Slavin, Stacy; Tunnah, Edward; Haddleton, David M.Polymer Chemistry (2013), 4 (8), 2608-2614CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)Poly(glycidyl methacrylate) (PGMA) was synthesized by cobalt catalyzed chain transfer polymn. (CCTP) yielding, in one step, polymers with two points for post polymn. functionalization: the activated terminal vinyl bond and in chain epoxide groups. Epoxide ring-opening and a combination of thiol-Michael addn. and epoxide ring-opening was used for post-functionalization with amines and thiols to prep. a range of functional materials.
- 28Jang, J.; Bae, J.; Ko, S. Synthesis and Curing of Poly(Glycidyl Methacrylate) Nanoparticles. J. Polym. Sci., Part A: Polym. Chem. 2005, 43 (11), 2258– 2265, DOI: 10.1002/pola.2070628https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXksVagtb0%253D&md5=fb9c96259a4faa208e96954c2f1731b6Synthesis and curing of poly(glycidyl methacrylate) nanoparticlesJang, Jyongsik; Bae, Joonwon; Ko, SungrokJournal of Polymer Science, Part A: Polymer Chemistry (2005), 43 (11), 2258-2265CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)Glycidyl-functional polymer nanoparticles [poly(glycidyl methacrylate) (PGMA)] were fabricated with microemulsion polymn. The successful fabrication of PGMA nanoparticles was confirmed by Fourier transform IR spectroscopy and transmission electron microscopy (TEM). A TEM image showed that the av. diam. of the PGMA nanoparticles was approx. 10-28 nm and was fairly monodisperse. As the surfactant concn. increased, the av. size of the nanoparticles decreased and approached an asymptotic value. A significant redn. of the nanoparticle size to the nanometer scale led to an enhanced no. of surface functionalities, which played an important role in the curing reaction. The PGMA nanoparticles were cured with a low-temp. curing agent, diethylene triamine, to produce ultrafine thermoset nanoparticles. The low-temp. curing process was performed below the glass-transition temp. of PGMA to prevent the coagulation and deformation of the nanoparticles. A TEM image indicated that the cured PGMA nanoparticles did not exhibit interparticle aggregation and morphol. transformation during curing. The av. size of the cured PGMA nanoparticles was consistent with that of the pristine PGMA nanoparticles.
- 29Patai, S. The Chemistry of the Thiol Group. Chem. Thiol Gr. 2010, 1– 479, DOI: 10.1002/9780470771310There is no corresponding record for this reference.
- 30Helmkamp, G. K. Organic Chemistry of Sulfur; Oae, S., Ed.; Plenum Press, 1978; Vol. 55. DOI: 10.1021/ed055pa390.3 .There is no corresponding record for this reference.
- 31Gao, H.; Elsabahy, M.; Giger, E. V.; Li, D.; Prud’homme, R. E.; Leroux, J.-C. Aminated Linear and Star-Shape Poly(Glycerol Methacrylate)s: Synthesis and Self-Assembling Properties. Biomacromolecules 2010, 11 (4), 889– 895, DOI: 10.1021/bm901241k31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXislWltbw%253D&md5=c6d327ebfd3d125abaa3c6eec3721f3fAminated Linear and Star-Shape Poly(glycerol methacrylate)s: Synthesis and Self-Assembling PropertiesGao, Hui; Elsabahy, Mahmoud; Giger, Elisabeth V.; Li, Dekun; Prud'homme, Robert E.; Leroux, Jean-ChristopheBiomacromolecules (2010), 11 (4), 889-895CODEN: BOMAF6; ISSN:1525-7797. (American Chemical Society)Over the past 10 years, polyglycerols and their structurally related analogs have received considerable attention in the biomedical field. Poly(glycidyl methacrylate) (PGMA) is a versatile polymer because its pendant epoxide groups can be opened with different functional groups to generate poly(glycerol methacrylate)s (PGOHMA) derivs. In this work, linear and star-shape PGMAs were synthesized by atom transfer radical polymn. and then functionalized with four different amines by ring-opening addn. This resulted in the formation of polyglycerol-like polymers having both hydroxyl and amine moieties and different water-soly. The water-insol. polymers could form pH-sensitive nanoassemblies, while the sol. derivs. efficiently complexed a short strand polynucleotide. The aminated polyglycerol interacted more avidly with the oligonucleotide than the control poly(ethyleneimine), and high transfection efficacy could be obtained with the linear deriv. Such polymers could find practical applications for the delivery of drugs and nucleic acids.
- 32Kozhunova, E. Y.; Gvozdik, N. A.; Motyakin, M. V.; Vyshivannaya, O. V.; Stevenson, K. J.; Itkis, D. M.; Chertovich, A. V. Redox-Active Aqueous Microgels for Energy Storage Applications. J. Phys. Chem. Lett. 2020, 11 (24), 10561– 10565, DOI: 10.1021/acs.jpclett.0c03164There is no corresponding record for this reference.
Supporting Information
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsmacrolett.1c00682.
Experimental procedures, FT-IR, Raman spectroscopy, and FT-IR fitting data for particle synthesis, supporting electrolyte viscosities, particle DLS, UV annealing data, reaction scheme for epoxy ring opening, CV data for substrate and electrolyte selection, particle UV–vis, GCPL data with a summary of results, small particle SEM, and qualitative observations (PDF)
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