Patent Application
20240014441
The present invention relates to a polymer-based electrolyte and a network formed by crosslinking of this electrolyte through its amine groups. The network is designed as a multifunctional energy storage system that is capable of transferring mobile cations through the passageways present in its structure. The present invention also relates to a method for obtaining such network and electrolyte.
The invention of new energy storage materials has contributed significantly to the advancement of technologies used for applications such as aviation, portable electronic products and electric vehicles. Performance improvements of energy storage systems have been made over the years at the expense of increasing the weight of structural components. The emergence of multifunctional energy storage materials has provided a massive and significant opportunity for the manufacturing of low weight and high performance structures. “Multifunctional energy storage materials” refer to materials offering energy storage and load-bearing properties simultaneously, thereby achieving weight reductions in weight-sensitive energy storage applications. The successful commercialization of multifunctional energy storage devices has not been achieved yet mainly due to the trade-off relationship between energy storage capabilities and mechanical properties such as load-bearing and structural integrity. The technology readiness levels (TRLs) of multifunctional energy storage devices are at TRL 4 to TRL 5. Most research groups in the relevant technical field have focused on the development of different types of electrode materials and the improvement of specific capacitance and surface area values to overcome this trade-off problem. Although improvements have been observed in this respect, the poor performance of devices underlines the urgent need to improve performances of other components such as electrolyte, separator and their interface. The most pressing need in applications concerning energy storage materials is the enhancement of power density, which is directly related to the improvement of ionic conductivity of the employed electrolyte. In structural applications where mostly epoxy systems are used, the design of a multifunctional resin that functions as both an electrolyte and a high performance matrix is difficult due to the trade-off between mechanical performance and ionic conductivity. The former requires an acceptable degree of mechanical stiffness of polymer chain segments and an undamaged microstructure, while the latter requires soft chain segments and interconnected passageways throughout the epoxy network. The two most commonly used epoxy resins for the production of multifunctional electrolytes are poly (ethylene glycol) diglycidyl ether (PEGDGE) and diglycidyl ether of bisphenol-A (DGEBA). In solvent-free polymer electrolytes, long-range ion conduction is enabled by local polymer motion. A polymer matrix with a low degree of stiffness (robustness) typically provides a higher conductivity. Incorporation of an ionic liquid (IL) to the matrix along with the addition of some amount of lithium salts has been found to be an effective way to facilitate ion transportation (Shirshova et al., J. Mater. Chem. A. 1 (2013) 15300-15309, DOI:10.1039/c3ta13163g; Jang et al., Macromol. Chem. Phys. 219 (2018), DOI:10.1002/macp.201700514; Baskoro and Yen, ACS Appl. Energy Mater. 2 (2019) 3937-3971, DOI:10.1021/acsaem.9b00295). ILs are widely used in polymer-based electrolytes because of their unique properties such as excellent thermal and chemical stability, low vapor pressure, nonflammability, low melting temperature and high ionic conductivity.
As described by Shirshova et al. (J. Mater. Chem. A. 1 (2013) 15300-15309, DOI:10.1039/c3ta13163g), the presence of ILs as molten salts in an epoxy network forms a bicontinuous phase, which facilitates ion transfer. However, the matrix becomes soft and cannot provide sufficient structural properties (i.e. mechanical performance) as a result of the increase in the amount of IL. In this regard, IL and epoxy form a heterogeneous microstructure that suffers from insufficient ion transport due to the lack of interconnected network (Shirshova et al. J. Phys. Chem. C. 118 (2014) 28377-28387. doi:10.1021/jp507952b).
Another approach to provide the ionic conductivity and load-bearing simultaneously is the copolymerization of certain kinds of non-structural monomers with structural ones (Feng et al., Mater. Sci. Eng. B Solid-State Mater. Adv. Technol. 219 (2017) 37-44. doi:10.1016/j.mseb.2017.03.001; DOI:10.1016/j.mseb.2017.03.001). Among various non-structural polymer electrolytes, polyethylene oxide (PEO) has been considered as the most promising polymeric electrolyte due to the suitable distance between etheric oxygen groups (Westover et al., J. Mater. Chem. A. 3 (2015) 20097-20102. DOI:10.1039/c5ta05922d). Since the movement of ions in the amorphous regions of polymers is easier, some research studies have focused on reducing the crystallinity of PEO-based electrolytes by crosslinking, copolymerization, and adding an inorganic filler (Kwon et al., ACS Appl. Mater. Interfaces. 10 (2018) 35108-35117, DOI:10.1021/acsami.8b11016; Ji et al., Electrochim. Acta. 55 (2010) 9075-9082, DOI:10.1016/j.electacta.2010.08.036). However, it should be mentioned that crosslinking leads to the binding of both ends of the PEO chains, thereby significantly reducing the mobility of PEO (Snyder et al., Polymer. 50(20), 4906-4916). Multifunctionality plots are effective in interpretting the trade-off between ionic conductivity and Young's modulus of structural electrolytes. The goal is to achieve ionic conductivity and Young's modulus values higher than 0.1 mS/cm and 200 MPa, respectively, which are considered as the threshold values. A reasonable goal for a structural electrolyte is to achieve both mechanical stiffness and ion conductivity within one order of magnitude of conventional materials.
The primary object of the present invention is to overcome the shortcomings in the prior art.
Another object of the present invention is to provide a polymer-based electrolyte with increased multifunctionality degree.
A further object of the present invention is to obtain a network using this polymer-based electrolyte.
An even further object of the present invention is to propose a low-cost method which enables the generation or constitution of such a network and polymer-based electrolyte.
The present invention proposes a network which comprises a polyoxazoline (POZ) backbone cross-linked through amine groups thereof. The network formed by employing the polymer-based electrolyte according to the present invention enables a high extent of multifunctionality. The present invention further proposes a method to obtain such a network and polymer-based electrolyte.
The figures, briefly explained here, are intended solely to provide a better understanding of the present invention and not to define the scope of protection or the context in which said scope is to be interpreted in the absence of the description.
”: epoxy-PEO/IL 60:40; “●”: PEGDGE/IL 60:40; “▾”: BADGE/Tetrafunctional epoxy/IL/hardener; “★”: commercial epoxy-1/IL/salt; “□”: commercial epoxy-2/IL/salt; “○”: commercial epoxy-3/IL/salt; “▪”: BADGE/IL/plasticizer/salt/hardener/organoclay.
The present invention is described in detail below, with reference to the respective figures described above.
The present invention relates to a network formed by crosslinking of a polyoxazoline (POZ)-based electrolyte. The secondary amine groups present on the polymer backbone are allowed to react with an epoxy resin to obtain the network structure. Said secondary amine groups eliminate the need to use a separate curing agent for the constitution of the network structure.
The epoxy resin can be selected from the class having at least two epoxide groups, which will allow the formation of a crosslinked network structure. Various epoxy resins can be utilized for this purpose. For instance, diglycidyl ethers with different structures can be reacted with secondary amine groups of two adjacent POZ polymers to form a network structure. The size and structure of the epoxy resin selected determine the distance between two POZ polymers and the flexibility of the network structure. This will in turn determine both the distance between ionic groups present on different POZ polymers that will form the passageways for the migration of cations therethrough and thus the ionic conductivity. The general structure of the network illustrating the passageways thoroughout the network is provided in
The present invention further proposes a polymer-based electrolyte that helps encapsulate anions (Y−) and cations (X+) in the network defined above. Said anions (Y−) and cations (X+) are introduced by use of an ionic component (e.g. one or more ionic solvents). The presence of such ionic component would help the migration of Li+ ions through the passageways in the network. POZ-based polymer has secondary and tertiary amine groups that can be used in protonated or non-protonated forms. These groups are preferably protonated to a certain extent to obtain quaternary ammonium and secondary amine groups along the polymer backbone, thereby obtaining a polymer-based electrolyte that carries cationic groups and can also react to form a crosslinked network structure. After crosslinking the polymer-based electrolyte with epoxy resins, a network with dispersed quaternary ammonium groups that form the main structure of the passageways is obtained. The migration of Li+ ions is accelerated by both the formation of passageways between the quaternary ammonium groups of the polymer in the network and the repulsive forces between said cations and quaternary ammonium groups.
Anions and cations can preferably be provided using one or more ionic solvents (abbreviated as XY) in said electrolyte. Since the positive charge in a quaternary ammonium cation is higher than the secondary or tertiary amine, the migration of lithium ions (Li+) is accelerated in the presence of quaternary ammonium groups throughout the network.
The present invention further proposes a method to obtain the network discussed above. The method includes the following consecutive steps.:
In step (ii), hydrolysis can be performed using any method known in the art, such as those involving the use of a strong acid or a strong base.
Preferably, the method includes the following step (x1) between the step (ii) and step (iii):
Preferably, prior to the step (iii), the step (x1) is followed by the step (x2) as defined below:
The “R1” group of the oxazoline monomer represents a linear, branched or cyclic aliphatic group or an aromatic group. The type of R1 has an effect on the solubility of the monomer and mechanical properties of the formed network. A monomer with an aromatic R1 group (such as 2-phenyl-2-oxazoline) results in a network with a higher rigidity and Tg (glass transition temperature) and a lower ionic conductivity compared to a network created using a monomer with an aliphatic R1 group (such as 2-ethyl-2-oxazoline). On the other hand, the use of an oxazoline monomer with a short alkyl chain, which is highly compatible with a wide variety of crosslinkers, leads to a flexible network structure with sufficient mechanical strength and high ionic conductivity.
Considering the R1 group of the monomer, the aliphatic groups are more preferred among all groups listed above due to their commercial availability and ease and feasiblity of their synthesis. Linear aliphatic groups can be selected from alkyl chains with a carbon number between 1 and 22, more preferably between 1 and 8, and even more preferably between 1 and 3, which are methyl-, ethyl-, and propyl- groups. Accordingly, the 2-R1-2-oxazoline corresponds to a 2-alkyl-2-oxazoline selectable from 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, or mixtures thereof. These monomers are highly preferable, since they are easy to synthesize and have low prices and high commercial availability. The extent of hydrophobicity of the monomers increases as the alkyl chain length increases. The compatibility of 2-ethyl-2-oxazoline is very good with both polar solvents (e.g. water) and non-polar solvents. Accordingly, 2-ethyl-2-oxazoline is particularly the most preferred monomer in the present invention.
In step (ii), the extent of hydrolysis can be preferably exercised such that the ratio of the number of amide groups (n) to the number of secondary amines (k) is arranged to be within the range between 100:1 and 1:100, more preferably 9:1 and 1:9. This measure can be applied without undue burden by a person skilled in polymer synthesis. Increasing the (n)/(k) ratio corresponds to:
In step (ii), a portion of amide groups on the polymer chains are hydrolyzed to form secondary amine groups. The molar ratio of amide groups to secondary amines (i.e. the n/k ratio as discussed above) can be arranged via controlling the extent of hydrolysis, by a person skilled in organic chemistry, without undue burden. A pre-determined portion of secondary amines in the resulting polymer can be methylated. This can be followed by quaternization in step (x1) with the use of ionic solvent (XY) to obtain quaternary ammonium groups on the POZ backbone that will act as polymer-bound ionic components. These ionic components will provide a medium for lithium salts to dissolve. The presence of the ionic components on the polymer will also make it possible not to include additional ionic liquids and/or other solvents in the network or include them at lower quantities in case they are included. The negative effect of the inclusion of such molecules (ionic liquids and/or other solvents) in the network on the mechanical properties will therefore be limited by this way. These ionic components will also create an ionic passageway for lithium ions to move throughout the network, which is shown in
The ionic conductivity of electrolyte can be improved by proper selection of ionic components (XY). The anions (Y−) with highly delocalized negative charges would promote the solvation of Li+ ions in the network by faciliating the movement of the Li+ ions through passageways along the network, thereby increasing the conductivity of the respective polymer-based electrolyte. Selection of lithium salts can be made taking dissociation constants (Kd) and/or volumetric bulkiness degrees of respective anions. Since Y− anions are not bonded covalently to the network, they will move inside the network as well. However, by selecting a relatively bigger anion, the movement of anions would be rather limited. Although the relatively bigger anions also contribute to the ionic conductivity, the movement of such anions will also lead to the polarization, which decreases the life time of the electrolyte. If Li+ cations are the only components which contribute to ionic conduction, it can be considered as a single-ion conducting solid electrolyte.
Increasing Kd values (well delocalized electrical charges along with low basicity) inherently corresponds to increasing differences between volumetric bulkiness degrees of respective anions (Y−) and Li+ cations in a respective lithium salt structure and are therefore preferable. When comparing various lithium salts (i.e. LiPF6, LiClO4, LiBF4, LiTFSI, LiTf, LiFSI), larger bulkiness of anions promotes the dissociation of Li+ ions and facilitates the travel thereof through passageways along the network, thereby increasing the conductivity of a respective polymer-based electrolyte.
Considering the above-discussed main effects of the (n)/(k) ratio, said ratio being within the range between 9:1 and 1:9 ensures a high extent of rigidity along with a sufficient extent of ionic conductivity. More preferably, said ratio of (n)/(k) is within the range between 3:1 and 1:3. This range corresponds to a sweet spot that simultaneously enables acceptable degrees of rigidity and conductivity.
In step (iii), the cross-linking of POZ chains takes place via the reaction of secondary amine groups of the polymers with epoxy resins to form a mechanically and ionic conductively high-performing interconnected polymeric network. The presence of secondary amines on the POZ backbone eliminates the necessity to use any additional curing agents. Chemical structures of R1 and R4 groups determine the final mechanical properties, viscosity, crystallinity and cation mobility.
Polyoxazoline (POZ) as backbone attains a mechanically strong and ionically conductive polymer. POZ is considered as a suitable and even advantageous alternative to poly(ethylene oxide) (PEO/PEG) polymers, which are widely used as solid electrolytes for energy storage devices. The multifunctional network of POZ makes it possible to link several chemical groups to a single polymer backbone, which improves the multifunctionality of the structure. For the first time in the literature, ionically conductive POZ-based polymer will be utilized as a “multifunctional electrolyte” through integration of the ionic component(s) to the backbone of POZ polymer. The confinement of ionic component(s) to the POZ backbone enables us to 1) control the pathway of ions in molecular scales and increase the lithium ion transference number and 2) eliminate the two-phase problem in structural electrolytes. The multifunctional nature of POZ along with other features used in formation of the polymer-based electrolyte, provides a highly ion conductive network with adequate mechanical performance, i. e. both conductivity and Young's modulus values fall within the targeted multifunctionality region shown in
An inorganic nanofiller e.g. silica (SiO2), titanium dioxide (TiO2), or halloysite nanotube (HNT) can be employed to increase the extent of amorphousness of the network, to even further improve ionic transportation ability inside the polymer-based electrolyte.
As a way to determine a geometric shape/contour of the network, prior to cross-linking, POZ can be casted using thin separators made of robust (e.g. self-supporting) polymeric films and veils to prepare an ionically conductive prepreg. This exemplary way is applicable in preparation of various types of multifunctional energy storage devices such as wearable/flexible supercapacitors, structural supercapacitors and lithium-ion batteries, with the network according to the present application.
Hence, the present invention renders at least the following advantages available:
As mentioned in the Background section, currently used electrolyte systems deteriorate the mechanical performance of the final composite product since there is a trade-off between ionic conductivity and mechanical performance. The present invention proposes a polymeric network by precise engineering of functional groups, molecular weight, and morphology of synthesized polymer, which leads to enhanced electrolyte properties without drastically degrading mechanical performance of final composite product in comparison to neat resin system.
Polyoxazoline (POZ) is used as an advantageous alternative to known polymeric electrolytes. The multifunctional network of POZ provides ease in the design and formulation of polymer-based electrolytes with desired characteristics. The ability to attach a great variety of cross-linkers (e.g. various diglycidyl ethers such as ethylene glycol diglycidyl ether, resorcinol diglycidyl ether, bisphenol A diglycidyl ether) enables an easy tailoring of stiffness and ionic conductivity.
Secondary amine groups in the POZ acts as curing agent, eliminating the need to include additional curing agents during the formation of the network.
In background art, since the combination of IL with PEG accelerates the curing time of polymer, it leads to a reduced processability. In contrast to PEG, POZ has lower viscosity, which helps the processibility, while the lack or minimal use of ILs and solvents during the network formation process lowers the possibility of having any problems related to the processability such as the accelaration of curing.
Multifunctional network of POZ enables an enhanced control on various parameters such as molecular weight, chain length, distance between consecutive functional groups, and crosslinking density; resulting in the formation of a homogeneous and interconnected network with improved ion transport and mechanical performance.
The proposed POZ-based electrolyte can be integrated to various structural energy storage systems such as structural supercapacitors, structural lithium-ion batteries, flexible electronics, wearable electronics, etc.
The present invention is expected to open up new opportunities specially in the field of multifunctional polymeric composites and makes it possible to expand technology readiness level (TRL) of structural energy storage devices.
The following example is based on a proof-of-concept experiment within the context of the present application. Depicted or mentioned specific features such as chain lengths and functional groups are to be considered as mere examples to possible variations thereof, within the scope of the independent claims.
An experimental work is performed to prove that the proposed technology establishes an alternative to conventional multifunctional electrolyte systems. An exemplary route in obtainment of a polymer-based electrolyte is shown in
In the present exemplary experiment, POZ is synthesized via ring opening polymerization of 2-ethyl-2-oxazoline as monomer and triflic acid as initiator (
For the ring-opening polymerization (step (i)), first, a mixture including a monomer and initiator is prepared. The molecular weight (MW) of the resulting polymeric chain can be easily pre-determined by adjusting the ratio of the molar amounts of the monomer (M0) and initiator (I0) in the initial mixture. A broad range of molecular weights can be synthesized by varying the process parameters, as deducible to a person skilled in organic synthesis, using prior art knowledge. The mixture is heated in a reactor, e.g. to a temperature within the range between 60° C. and 90° C., depending on desired MW. To terminate the polymerization, contents of the reactor is cooled down and mixed with a terminating agent containing a group terminus, e.g. hydroxyl or carboxylic acid.
The quaternary ammonium groups can be considered as sites to provide an ionic liquid character to the electrolyte according to the present invention.
This application is the national phase entry of International Application No. PCT/TR2020/050662, filed on Jul. 27, 2020, the entire contents of which are incorporated herein by reference.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/TR2020/050662 | 7/27/2020 | WO |
