CN115010109B - Preparation method of phenolic epoxy resin-based hard carbon material, hard carbon material and sodium ion battery - Google Patents
Preparation method of phenolic epoxy resin-based hard carbon material, hard carbon material and sodium ion battery Download PDFInfo
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- CN115010109B CN115010109B CN202210473748.8A CN202210473748A CN115010109B CN 115010109 B CN115010109 B CN 115010109B CN 202210473748 A CN202210473748 A CN 202210473748A CN 115010109 B CN115010109 B CN 115010109B
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- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application provides a preparation method of a phenolic epoxy resin-based hard carbon anode material, which comprises the following steps: a. taking phenolic epoxy resin as a precursor, mixing the phenolic epoxy resin and maleic anhydride according to the mass ratio of 5:1-1:1, and uniformly stirring; b. transferring the mixture of the phenolic epoxy resin and the maleic anhydride into a heater, and heating at 120-180 ℃ for 8-12 h for curing; c. taking out the cured phenolic epoxy resin, and grinding the phenolic epoxy resin into powder; d. placing the powder into a reactor, heating to 400-800 ℃ under argon atmosphere, and carrying out pyrolysis treatment for 1-8 h; e. after cooling, heating to 1200-2000 ℃ under argon atmosphere, and carrying out pyrolysis treatment for 1-8 h. The sodium ion battery prepared by taking the phenolic epoxy resin-based hard carbon material prepared by the method as the negative electrode material has the electrochemical performance characteristics of excellent reversible specific capacity, good cycling stability, high first coulombic efficiency and the like.
Description
Technical Field
The application relates to the technical field of sodium ion battery anode materials, in particular to a preparation method of a phenolic epoxy resin-based hard carbon anode material, the hard carbon anode material and a sodium ion battery using the hard carbon anode material as an anode material.
Background
Lithium ion batteries have the outstanding advantages of high energy density, high rate performance, high cycle performance and the like, have become important energy sources meeting the increasing demands of energy storage systems, and have been widely applied to consumer electronics and electric automobiles. However, since lithium reserves are limited and resources are unevenly distributed, resulting in a sharp increase in the cost of lithium ion batteries, it is highly demanded to find an inexpensive alternative energy source.
Sodium ion batteries are one of the novel energy storage devices expected to replace lithium ion batteries due to the abundant sodium resources. However, the intercalation compounds formed from sodium and graphite are thermodynamically unstable and sodium ionsThe ionic radius of (2) is greater than that of lithium ion +.>Resulting in graphite being unsuitable for storing sodium ions as a commercial negative electrode material for lithium ion batteries. Thus, there is currently a lack of negative electrode materials with good electrochemical properties for sodium ion batteries.
In recent years, hard carbon is considered as a promising negative electrode material for sodium ion batteries because of its large interlayer spacing, good structural stability and high reversible capacity. However, the existing resin hard carbon material has limited further development in the field of negative electrodes of sodium ion batteries due to poor reversible specific capacity and cycle performance.
Disclosure of Invention
In view of the above, in order to solve the problems of poor cycle performance and low reversible specific capacity of the resin hard carbon material in the prior art, the application applies the phenolic epoxy resin-based hard carbon material to the sodium ion battery for the first time, and the sodium ion battery prepared by adopting the anode material has excellent reversible specific capacity, good cycle stability and high first coulombic efficiency.
Specifically, the application provides a preparation method of a phenolic epoxy resin-based hard carbon anode material, which comprises the following steps: a. taking phenolic epoxy resin as a precursor, mixing the phenolic epoxy resin and maleic anhydride according to the mass ratio of 5:1-1:1, and uniformly stirring; b. transferring the mixture of the phenolic epoxy resin and the maleic anhydride into a heater, and heating at 120-180 ℃ for 8-12 h for curing; c. taking out the cured phenolic epoxy resin, and grinding the phenolic epoxy resin into powder; d. placing the powder into a reactor, heating to 400-800 ℃ under argon atmosphere, and carrying out pyrolysis treatment for 1-8 h; e. after cooling, heating to 1200-2000 ℃ under argon atmosphere, and carrying out pyrolysis treatment for 1-8 h.
The application also provides the phenolic epoxy resin-based hard carbon anode material prepared by the method.
The application also provides a sodium ion battery, which comprises a positive pole piece, a negative pole piece, an isolating film arranged between the positive pole piece and the negative pole piece and electrolyte; the negative electrode plate comprises a negative electrode current collector and negative electrode slurry arranged on the negative electrode current collector; the negative electrode slurry includes: the application provides a phenolic epoxy resin-based hard carbon anode material, a conductive agent, a binder and a solvent.
Compared with the existing resin hard carbon material, the preparation method of the phenolic epoxy resin-based hard carbon material provided by the application has the advantages that:
1. phenolic epoxy resins are used as precursors in the process of the application, which contain a large number of epoxy groups. In addition, the phenolic epoxy resin belongs to a resin material, has low cost and mature preparation technology, and has excellent reversible specific capacity, good cycle stability and higher first coulombic efficiency when being applied to the negative electrode of the sodium ion battery compared with other negative electrode materials when being prepared into a hard carbon material.
2. Maleic anhydride is used in the present application to react with phenolic epoxy resin.
The maleic anhydride selected by the method of the application is used as a curing agent to carry out curing reaction with the phenolic epoxy resin to form a new chemical bond, so that the originally dispersed macromolecular chain segments of the phenolic epoxy resin are connected into a reticular macromolecule with stable structure through the maleic anhydride.
There are at least two advantages to such a stable network: 1. and the circulation stability of the phenolic epoxy resin-based hard carbon anode material is improved. During the charge and discharge cycle, the stable microstructure can counteract part of mechanical stress generated during sodium ion intercalation/deintercalation, and the stability of electrochemical performance is improved, so that the capacity retention rate of the phenolic epoxy resin-based hard carbon material can reach 93.4% at most after 800 circles (data in the embodiment show). 2. The curing reaction enhances the crosslinking degree between the high molecular chain segments of the phenolic epoxy resin, the directional growth of the carbon layer can be inhibited in the subsequent carbonization process, more turbine-shaped graphite microstructures are formed, more nano micropores are formed, and the reversible specific capacity of the phenolic epoxy resin-based hard carbon material is increased by the additional sodium storage sites and the larger platform capacity is shown.
3. The method of the application adopts two-step pyrolysis.
The first-step pyrolysis in the present application may be considered as a pre-pyrolysis, with at least 3 advantages over the prior art one-step pyrolysis.
Firstly, the cured phenolic epoxy resin is subjected to heat treatment at the temperature of 400-800 ℃, so that partial impurities are eliminated, the microstructure order degree of the material is increased, the upper surface of the appearance becomes coarser, and higher reversible specific capacity and better rate capability are brought.
And compared with one-step pyrolysis, the method has the advantages that the preheating step is added, which is equivalent to the transitional process before high-temperature carbonization (1000 ℃) of one material is added, and the crosslinking density of a high molecular chain segment in the phenolic epoxy resin is improved. In the preheating and pyrolysis process, as the heat energy is not high, the movement capacity of the polymer chain segments is enhanced, the reticular polymer structures are not damaged, the polymer chains are more tightly crosslinked, and when the subsequent high-temperature carbonization is carried out, the crosslinked structure after the preheating and pyrolysis treatment is kept or the crosslinking degree is continuously enhanced as long as the temperature is not higher than 2000 ℃, so that the structural stability of the phenolic epoxy resin-based hard carbon material is certainly improved, and the better cycle stability is shown in the electrochemical characterization.
Finally, for the hard carbon cathode material of the sodium ion battery, the crosslinking density of the high molecular chains in the phenolic epoxy resin is enhanced due to the addition of the pre-pyrolysis step, so that the directional growth of the carbon layer in the high-temperature carbonization process is inhibited, the number of nano micropores is increased, and the larger platform capacity is shown in electrochemical characterization.
In addition, as can be seen from the experimental results of the examples and comparative examples of the present application, the finally prepared battery of the present application has at least the following 4 advantages:
1. the stable microstructure in the cured phenolic epoxy resin-based hard carbon material provides excellent cycle performance. After the application circulates for 800 circles, the capacity retention rate can reach 93.4% at maximum.
2. Has higher reversible specific capacity. The reversible specific capacity of the application can reach 539.0mAh g at most -1 。
3. The electrochemical performance is easier to regulate and control. The application mainly regulates and controls the microstructure of the hard carbon material through the pyrolysis temperature. As shown in table 1 and table 2 of the examples, phenolic epoxy resin based hard carbon materials prepared at different pyrolysis temperatures have different electrochemical properties when used as a negative electrode active material for sodium ion batteries.
4. Better rate capability. The application has the highest reversible capacity of 539.0mAh g under the current density of 0.1C -1 The reversible capacity can be kept at 422.0mAhg at maximum even if the current density is increased to 2C -1 。
In short, the preparation method of the phenolic epoxy resin-based hard carbon material is prepared by taking phenolic epoxy resin as a raw material through solidification and pyrolysis, the preparation method is simple, and the phenolic epoxy resin-based hard carbon material has the characteristics of high carbon yield, low cost, mature raw material preparation technology and the like, is beneficial to reducing the production cost of the material and improving the repeatability of the material preparation, and is easy for industrial production.
In addition, the sodium ion battery prepared by using the phenolic epoxy resin-based hard carbon material as a negative electrode material has the electrochemical performance characteristics of excellent reversible specific capacity, good cycle stability, high first coulombic efficiency and the like.
Drawings
Fig. 1 is an SEM image of the phenolic epoxy resin-based hard carbon material prepared in example 4.
Detailed Description
The application provides a preparation method of a phenolic epoxy resin-based hard carbon material, which comprises the following steps:
a. taking phenolic epoxy resin as a precursor, mixing the phenolic epoxy resin and maleic anhydride according to the mass ratio of 5:1-1:1, and uniformly stirring;
b. transferring the mixture of the phenolic epoxy resin and the maleic anhydride into a heater, and heating at 120-180 ℃ for 8-12 h for curing;
c. taking out the cured phenolic epoxy resin and grinding the phenolic epoxy resin into powder;
d. placing the powder into a reactor, heating to 400-800 ℃ under argon atmosphere, and carrying out pyrolysis treatment for 1-8 h;
e. after cooling, heating to 1200-2000 ℃ under argon atmosphere, and carrying out pyrolysis treatment for 1-8 h.
Wherein, in the step b, the heater may be a crucible. In step c, the apparatus used for grinding may be a vibratory sample grinder. In step d, the reactor may be a tube furnace.
In the step d, the heating rate is preferably 1 to 10 ℃/min. Because the excessive heating rate can lead to incomplete pyrolysis of the precursor, impurities and defects are not effectively eliminated, the specific surface area is excessively large, the structural regularity is reduced, and various electrochemical performances of the hard carbon anode material are reduced. The lower temperature rising rate is beneficial to reducing defects and impurities and reducing the specific surface area, so that the first coulombic efficiency and the cycling stability of the hard carbon anode material are improved.
In step e, the heating rate is preferably 2 to 10 ℃/min. Within this preferable temperature rise rate range, it is useful to reduce impurities and defects and to improve the structural regularity. In step e, the pyrolysis temperature is preferably 1400 to 1800 ℃.
The type of the novolac epoxy resin is not particularly limited in the present application, and is preferably one or more selected from the group consisting of phenol novolac epoxy resin, o-cresol novolac epoxy resin, and bisphenol a novolac epoxy resin.
The application also provides the phenolic epoxy resin-based hard carbon anode material prepared by the method.
The phenolic epoxy resin-based hard carbon material prepared by the application is macroscopic irregular block particles, and has a nanoscale micropore structure inside, wherein the aperture of the nanoscale micropore is smaller than 2nm.
The application also provides a sodium ion battery, which comprises a positive pole piece, a negative pole piece, an isolating film arranged between the positive pole piece and the negative pole piece and electrolyte; wherein, the negative pole piece includes: a negative electrode current collector and a negative electrode slurry arranged on the negative electrode current collector; the negative electrode slurry includes: the application provides a phenolic epoxy resin-based hard carbon anode material, a conductive agent, a binder and a solvent.
The electrolyte is not particularly limited in the present application, and a conventional electrolyte may be used, for example: the electrolyte solution can contain electrolyte sodium salt and organic solvent, wherein the electrolyte sodium salt can be sodium hexafluorophosphate (NaPF 6 ) Or sodium perchlorate (NaClO) 4 ) The organic solvent may be one or more selected from the group consisting of ethylene glycol dimethyl ether (DME), ethylene Carbonate (EC), propylene Carbonate (PC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC), and diethyl carbonate (DEC).
The technical scheme of the application is further described below through examples and drawings.
Example 1
The embodiment is used for explaining the preparation method of the phenolic epoxy resin-based hard carbon negative electrode material, the phenolic epoxy resin-based hard carbon negative electrode material prepared by the preparation method, and a sodium ion battery using the phenolic epoxy resin-based hard carbon negative electrode material.
a. Phenolic epoxy resin and maleic anhydride are mixed according to the mass ratio of 2.5:1 and stirred uniformly.
b. The mixture was transferred to a crucible and cured by heating at 180℃for 12 h.
c. And (3) preparing the cured phenolic epoxy resin into powder through a vibration sample grinder.
d. Transferring the obtained powder into a tube furnace, introducing argon, and performing a pre-pyrolysis step: raising the temperature from room temperature to 500 ℃ at a speed of 2 ℃/min and preserving the temperature for 1h;
e. after cooling to room temperature, a high temperature pyrolysis step is performed: raising the temperature from room temperature to 1200 ℃ at a speed of 5 ℃/min, and preserving the temperature for 1h.
And after cooling to room temperature, taking out a powder sample to obtain the phenolic epoxy resin-based hard carbon anode material of the embodiment 1.
The prepared phenolic epoxy resin-based hard carbon negative electrode material is a hard carbon material with irregular block-shaped macroscopic morphology and a nanoscale micropore structure inside, wherein the diameter of a pore canal of the nanoscale micropore structure is 0.38nm. The pore diameter of the nanometer micropore refers to the nanometer pore existing in the hard carbon and can not be characterized by the adsorption of gas molecules on the surface of the material, and is obtained by a small-angle X-ray diffraction test.
Uniformly mixing the powder sample, the carbon nano tube and sodium alginate according to the mass ratio of 7:2:1, adding a proper amount of deionized water, stirring and mixing for 7 hours to prepare uniformly distributed slurry, and coating the uniformly mixed slurry on a copper foil current collector. And (3) carrying out vacuum drying on the copper foil current collector coated with the slurry, and preparing the negative electrode plate after the copper foil current collector is completely dried. In a vacuum glove box in an argon atmosphere, a metal sodium sheet is used as a counter electrode, glass microfiber and foam nickel are respectively used as an electrolytic diaphragm and a gasket, and 1mol of NaPF is used 6 The mixed solution obtained by dissolving 1L of ethylene glycol dimethyl ether is taken as electrolyte, and the prepared pole piece is added to assemble the button cell C1.
Examples 2 to 7
These examples are provided to illustrate the preparation method of the phenolic epoxy resin based hard carbon negative electrode material, the phenolic epoxy resin based hard carbon negative electrode material prepared by the preparation method, and the sodium ion battery using the phenolic epoxy resin based hard carbon negative electrode material.
Using the same method as in example 1, except for the difference in reaction conditions as shown in table 1 below, phenolic epoxy resin-based hard carbon negative electrode materials were each prepared and assembled into cells C2-7, respectively.
In addition, the phenolic epoxy resin-based hard carbon anode materials prepared in examples 2-7 were hard carbon materials with irregular block-shaped macroscopic morphology and nano-scale micropore structures inside, wherein the pore diameters of the nano-scale micropore structures are shown in table 1, respectively.
TABLE 1
Comparative example 1
This comparative example is for explaining a method of preparing the phenolic resin-based hard carbon anode material of comparative example 1, and the phenolic resin-based hard carbon anode material prepared, and a sodium ion battery using the phenolic resin-based hard carbon anode material.
In this comparative example, a novolac epoxy-based hard carbon negative electrode material was produced by the same method as in example 1. Then, battery CC1 was assembled by the same method as in example 1, except that the phenolic epoxy resin was changed to phenolic resin.
Comparative example 2
This comparative example is for explaining a method of preparing the novolac epoxy-based hard carbon anode material of comparative example 2, and the novolac epoxy-based hard carbon anode material prepared, and a sodium ion battery using the novolac epoxy-based hard carbon anode material.
In this comparative example, a novolac epoxy-based hard carbon negative electrode material was produced by the same method as in example 1. Then, the following steps are performed instead of step d and step e in example 1, except that the step d pre-pyrolysis step in example 1 is omitted. The obtained powder sample was transferred to a tube furnace, argon gas was introduced, and the temperature was directly raised from room temperature to 1200 ℃ at a rate of 5 ℃/min, and the temperature was maintained for 1 hour, and then battery CC2 was assembled by the same method as in example 1.
Performance testing
Constant current charge and discharge tests were performed on the sodium ion batteries C1 to C7 and CC1 to CC2 prepared in examples 1 to 7 and comparative examples 1 to 2: the test voltage range is 0-2.5V, the current density is 0.1C=50mA/g, and the reversible specific capacity and the first coulomb efficiency of the sodium ion batteries prepared in each example and comparative example are obtained; current densities of 0.1C, 0.2C, 0.4C, 1C, 2C, 4C, 6C, and 8C, where 1c=500 mA/g, were obtained to obtain the rate performance of the sodium ion batteries prepared in each of the examples and comparative examples; the current density was 500mA/g, and the charge-discharge cycle was 800 weeks, to obtain the reversible specific capacity retention rates of the sodium ion batteries prepared in each of the examples and comparative examples. The results of the test are shown in table 2 below.
TABLE 2
As can be seen from table 2, the first coulombic efficiency, reversible specific capacity, rate capability, and cycle stability of the sodium ion battery prepared by using the phenolic epoxy resin-based hard carbon material in examples 1 to 7 were far superior to those of comparative example 1, and positive effects on the prepared sodium ion battery were verified when using phenolic epoxy resin as a precursor of the hard carbon material as compared with using phenolic resin.
The electrochemical performances of the sodium ion battery prepared by using the phenolic epoxy resin-based hard carbon material in examples 1-7, such as the first coulombic efficiency, reversible specific capacity, multiplying power performance and cycling stability, are far better than those of comparative example 2, and positive effects of the prepared sodium ion battery are verified by adopting a two-step pyrolysis method, namely a method of pre-pyrolysis and then pyrolysis, compared with a one-step pyrolysis method.
In addition, it can be seen that the electrochemical properties of the sodium ion battery prepared using the phenolic epoxy resin based hard carbon material in comparative examples 2 to 4 and examples 1 and 5 have a preferable range of positive effects of the high-temperature pyrolysis temperature on the prepared negative electrode material of the sodium ion battery, and the preferable range of the temperature is 1400 to 1800 ℃. When the phenolic epoxy resin-based hard carbon material is prepared in the preferable temperature range and is used for a negative electrode material of a sodium ion battery, the first coulomb efficiency, reversible specific capacity, rate capability and cycle stability of the sodium ion battery are all remarkably improved.
Claims (7)
1. The preparation method of the phenolic epoxy resin-based hard carbon anode material is characterized by comprising the following steps of:
a. taking phenol type phenolic epoxy resin as a precursor, mixing the phenol type phenolic epoxy resin and maleic anhydride according to the mass ratio of 2.5:1, and uniformly stirring;
b. transferring the mixture of the phenol type phenolic epoxy resin and the maleic anhydride into a heater, and heating at 180 ℃ for 8-12 h for curing;
c. taking out the cured phenol type phenolic epoxy resin and grinding the phenol type phenolic epoxy resin into powder;
d. placing the powder into a reactor, heating to 500 ℃ under argon atmosphere, and carrying out pyrolysis treatment for 1-8 h;
e. after cooling, heating to 1400-1800 ℃ under argon atmosphere, and carrying out pyrolysis treatment for 1-8 h.
2. The method according to claim 1, wherein in step d, the temperature increase rate is 1 to 10 ℃/min.
3. The method according to claim 1, wherein in step e, the temperature increase rate is 2 to 10 ℃/min.
4. A phenolic epoxy resin-based hard carbon negative electrode material prepared by the method of any one of claims 1-3.
5. The phenolic epoxy resin-based hard carbon negative electrode material of claim 4, wherein the phenolic epoxy resin-based hard carbon material is macroscopically irregular block-shaped particles, and a nanoscale microporous structure is present inside the particles, and the pore size of the nanoscale micropores is less than 2nm.
6. The sodium ion battery is characterized by comprising a positive pole piece, a negative pole piece, an isolating film arranged between the positive pole piece and the negative pole piece and electrolyte; the negative electrode plate comprises a negative electrode current collector and negative electrode slurry arranged on the negative electrode current collector; the negative electrode slurry includes: the phenolic epoxy resin-based hard carbon negative electrode material, conductive agent, binder and solvent according to any one of claims 4-5.
7. The sodium ion battery of claim 6, wherein the electrolyte comprises an electrolyte sodium salt and an organic solvent, wherein the electrolyte sodium salt is sodium hexafluorophosphate (NaPF 6 ) Or sodium perchlorate (NaClO) 4 ) The organic solvent is one or more selected from the group consisting of ethylene glycol dimethyl ether (DME), ethylene Carbonate (EC), propylene Carbonate (PC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC), and diethyl carbonate (DEC).
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