CN115010109A - Preparation method of novolac epoxy resin-based hard carbon material, hard carbon material and sodium ion battery - Google Patents
Preparation method of novolac epoxy resin-based hard carbon material, hard carbon material and sodium ion battery Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
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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
- 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
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- 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
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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
- H01M4/36—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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- 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
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- 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 invention provides a preparation method of a novolac epoxy resin-based hard carbon negative electrode 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 novolac epoxy resin and the maleic anhydride into a heater, and heating for 8-12 hours at 120-180 ℃ for curing; c. taking out the cured novolac epoxy resin, and grinding into powder; d. putting the powder into a reactor, heating to 400-800 ℃ in an argon atmosphere, and carrying out pyrolysis treatment for 1-8 h; e. and after cooling, heating to 1200-2000 ℃ in an argon atmosphere, and carrying out pyrolysis treatment for 1-8 h. The sodium ion battery prepared by taking the novolac epoxy resin-based hard carbon material prepared by the method as the negative electrode material has the characteristics of excellent reversible specific capacity, good cycling stability, higher first coulombic efficiency and other electrochemical properties.
Description
Technical Field
The invention relates to the technical field of negative electrode materials of sodium ion batteries, in particular to a preparation method of a phenolic epoxy resin-based hard carbon negative electrode material, the hard carbon negative electrode material and a sodium ion battery using the hard carbon negative electrode material as a negative electrode material.
Background
Lithium ion batteries have the outstanding advantages of high energy density, high rate performance, high cycle performance, etc., have become important energy sources meeting the increasing demands of energy storage systems, and have been widely applied to consumer electronics products and electric vehicles. However, since the lithium reserves are limited and the resources are unevenly distributed, the cost of the lithium ion battery is rapidly increased, and therefore, an inexpensive alternative energy source is urgently needed to be found.
The sodium ion battery is one of novel energy storage devices which are expected to replace lithium ion batteries due to abundant sodium resources. However, the intercalation compound formed by sodium and graphite is thermodynamically unstable, and sodium ions
Has an ionic radius larger than that of lithium ion
Resulting in graphite not being suitable for storing sodium ions as a commercial anode material for lithium ion batteries. Therefore, there is currently a lack of negative electrode materials with good electrochemical properties for sodium ion batteries.
In recent years, hard carbon has been 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 sodium ion battery negative electrodes 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 resin hard carbon materials in the prior art, the phenolic epoxy resin based hard carbon material is applied to the sodium ion battery for the first time, and the sodium ion battery prepared by adopting the negative electrode material has excellent reversible specific capacity, good cycle stability and high first coulombic efficiency.
Specifically, the invention provides a preparation method of a novolac epoxy resin-based hard carbon negative electrode 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 novolac epoxy resin and the maleic anhydride into a heater, and heating for 8-12 hours at 120-180 ℃ for curing; c. taking out the cured novolac epoxy resin, and grinding into powder; d. putting the powder into a reactor, heating to 400-800 ℃ in an argon atmosphere, and carrying out pyrolysis treatment for 1-8 h; e. and after cooling, heating to 1200-2000 ℃ in an argon atmosphere, and carrying out pyrolysis treatment for 1-8 h.
The invention also provides a phenolic epoxy resin-based hard carbon negative electrode material prepared by the method.
The invention also provides a sodium ion battery, which comprises a positive pole piece, a negative pole piece, an isolating membrane arranged between the positive pole piece and the negative pole piece, and electrolyte; the negative pole piece comprises a negative current collector and negative slurry arranged on the negative current collector; the negative electrode slurry includes: the invention provides a novolac epoxy resin-based hard carbon negative electrode material, a conductive agent, a binder and a solvent.
Compared with the prior resin hard carbon material, the preparation method of the novolac epoxy resin-based hard carbon material has the following advantages:
1. the process of the present invention uses a novolac epoxy resin as a precursor, which contains a large amount of epoxy groups. Moreover, the novolac epoxy resin belongs to a resin material, has low cost and mature preparation technology, and has excellent reversible specific capacity, good cycling stability and higher first coulombic efficiency compared with other cathode materials when being prepared into a hard carbon material applied to a sodium ion battery cathode.
2. Maleic anhydride is used in the present invention to react with novolac epoxy.
The method of the invention selects maleic anhydride as a curing agent to carry out curing reaction with the novolac epoxy resin to form a new chemical bond, so that the originally dispersed macromolecular chain segments of the novolac epoxy resin are connected into a reticular macromolecule with stable structure through the maleic anhydride.
Such a stable network has at least two advantages: 1. the circulation stability of the novolac epoxy resin-based hard carbon negative electrode material is improved. In the charge-discharge cycle process, the stable microstructure can offset part of mechanical stress generated by sodium ions during intercalation/deintercalation, and the stability of electrochemical performance is improved, so that the maximum capacity retention rate of the novolac epoxy resin-based hard carbon material can reach 93.4 percent after 800 cycles (as shown by data in the embodiment). 2. The curing reaction enhances the crosslinking degree among high molecular chain segments of the novolac epoxy resin, the directional growth of a carbon layer is inhibited in the subsequent carbonization process, more turbine-shaped graphite microstructures are formed, more nano micropores are formed, the additional sodium storage sites increase the reversible specific capacity of the novolac epoxy resin-based hard carbon material, and a larger platform capacity is represented.
3. In the process of the invention, two-step pyrolysis is employed.
The first pyrolysis step in the present invention can be considered as a pre-pyrolysis, and there is at least a 3 point advantage over the one-step pyrolysis of the prior art.
Firstly, the cured novolac epoxy resin is subjected to heat treatment at the temperature of 400-800 ℃, which is beneficial to eliminating partial impurities, increasing the microstructure order of the material, and enabling the surface on the appearance to be rougher, thereby bringing higher reversible specific capacity and better rate performance.
And secondly, compared with one-step pyrolysis, the step of pre-pyrolysis is added, which is equivalent to the addition of a transition process before high-temperature carbonization (>1000 ℃) of a material, and is beneficial to improving the crosslinking density of a high-molecular chain segment in the novolac epoxy resin. In the process of preheating and hydrolysis, as the heat energy is not high, the movement capacity of the high molecular chain segment is enhanced, and the reticular macromolecular structure is not damaged, so that the crosslinking of the high molecular chain is tighter, and when subsequent high-temperature carbonization is carried out, as long as the temperature is not more than 2000 ℃, the crosslinked structure after preheating and hydrolysis treatment can be kept or the crosslinking degree is continuously enhanced, so that the structural stability of the novolac epoxy resin-based hard carbon material is undoubtedly improved, and in the electrochemical characterization, more excellent circulation stability is expressed.
Finally, for the hard carbon cathode material of the sodium ion battery, due to the addition of the pre-pyrolysis step, the crosslinking density of high molecular chains in the novolac epoxy resin is enhanced, so that the directional growth of a carbon layer in the high-temperature carbonization process is inhibited, the number of nano micropores is increased, and a larger platform capacity is represented in the electrochemical characterization.
In addition, as can be seen from the experimental results of the examples and comparative examples of the present invention, the finally prepared batteries of the present invention have at least the following 4-point advantages:
1. the firm microstructure in the novolac epoxy resin-based hard carbon material after the curing reaction provides excellent cycle performance. After the method is circulated for 800 circles, the capacity retention rate can reach 93.4 percent to the maximum.
2. Has higher reversible specific capacity. The reversible specific capacity of the invention can reach 539.0mAh g at most -1 。
3. The electrochemical performance is easier to regulate and control. The microstructure of the hard carbon material is regulated and controlled mainly by pyrolysis temperature. As shown in tables 1 and 2 in the examples, novolac epoxy resin-based hard carbon materials prepared at different pyrolysis temperatures have different electrochemical properties when used as a negative active material of a sodium ion battery.
4. Better rate performance. The reversible capacity of the invention can reach 539.0mAh g at the maximum under the current density of 0.1C -1 Even if the current density is increased to 2C, the reversible capacity can be kept at 422.0mAhg at the highest value -1 。
In short, the preparation method of the novolac epoxy resin-based hard carbon material is characterized in that novolac epoxy resin is used as a raw material and is prepared through curing and pyrolysis, the preparation method is simple, the novolac epoxy resin-based hard carbon material has the characteristics of high carbon yield, low cost, mature raw material preparation technology and the like, the production cost of the material is reduced, the repeatability of material preparation is improved, and the industrial production is facilitated.
In addition, the sodium ion battery prepared by using the novolac epoxy resin-based hard carbon material as a negative electrode material has the characteristics of excellent reversible specific capacity, good cycling stability, higher first coulombic efficiency and other electrochemical properties.
Drawings
FIG. 1 is an SEM image of a novolac epoxy-based hard carbon material prepared in example 4.
Detailed Description
The invention provides a preparation method of a novolac epoxy resin-based hard carbon material, which comprises the following steps:
a. taking novolac epoxy resin as a precursor, mixing the novolac epoxy resin and maleic anhydride according to the mass ratio of 5: 1-1: 1, and uniformly stirring;
b. transferring the mixture of the novolac epoxy resin and the maleic anhydride into a heater, and heating for 8-12 hours at 120-180 ℃ for curing;
c. taking out the cured novolac epoxy resin, and grinding into powder;
d. putting the powder into a reactor, heating to 400-800 ℃ in an argon atmosphere, and carrying out pyrolysis treatment for 1-8 h;
e. and after cooling, heating to 1200-2000 ℃ in an argon atmosphere, and carrying out pyrolysis treatment for 1-8 h.
Wherein, in step b, the heater may be a crucible. In step c, the apparatus used for grinding may be a vibration sample grinder. In step d, the reactor may be a tube furnace.
In the step d, the heating rate is preferably 1-10 ℃/min. Because the precursor is not completely pyrolyzed due to an excessively high temperature rise rate, impurities and defects are not effectively eliminated, the specific surface area is excessively large, the structural regularity is reduced, and various electrochemical properties of the hard carbon negative electrode material are reduced. And the lower temperature rise rate is beneficial to reducing defects and impurities and reducing the specific surface area, so that the first coulombic efficiency and the cycle stability of the hard carbon negative electrode material are improved.
In the step e, the heating rate is preferably 2-10 ℃/min. Within the range of the preferable temperature rise rate, the method contributes to reduction of impurities and defects and improvement of structural regularity. In the step e, the pyrolysis temperature is preferably 1400-1800 ℃.
The type of the novolac epoxy resin is not particularly limited in the present invention, and is preferably one or more selected from the group consisting of phenol-type novolac epoxy resins, o-cresol-type novolac epoxy resins, and bisphenol a-type novolac epoxy resins.
The invention also provides the phenolic epoxy resin-based hard carbon negative electrode material prepared by the method.
The phenolic epoxy resin-based hard carbon material prepared by the invention is in an irregular blocky particle shape in a macroscopic view, and has a nano-scale micropore structure in the macroscopic view, and the aperture of the nano-scale micropores is less than 2 nm.
The invention also provides a sodium ion battery, which comprises a positive pole piece, a negative pole piece, an isolating membrane arranged between the positive pole piece and the negative pole piece, and electrolyte; wherein, negative pole piece includes: the negative electrode current collector comprises a negative electrode current collector and negative electrode slurry arranged on the negative electrode current collector; the negative electrode slurry includes: the invention provides a phenolic epoxy resin-based hard carbon negative electrode material, a conductive agent, a binder and a solvent.
In the present invention, the electrolyte is not particularly limited, 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), Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), and diethyl carbonate (DEC).
The technical solution of the present invention is further described below by way of examples and figures.
Example 1
This example is used to illustrate a method for preparing a novolac epoxy resin-based hard carbon negative electrode material, a novolac epoxy resin-based hard carbon negative electrode material prepared by the method, and a sodium ion battery using the novolac epoxy resin-based hard carbon negative electrode material.
a. Mixing the novolac epoxy resin and the maleic anhydride according to the mass ratio of 2.5:1, and uniformly stirring.
b. The mixture was transferred to a crucible and heated at 180 ℃ for 12h to cure.
c. And preparing the cured novolac epoxy resin into powder by a vibration sample grinding machine.
d. And transferring the obtained powder into a tube furnace, introducing argon, and performing a pre-pyrolysis step: heating from room temperature to 500 ℃ at the speed of 2 ℃/min and keeping the temperature for 1 h;
e. after cooling to room temperature, carrying out a high-temperature pyrolysis step: raising the temperature from room temperature to 1200 ℃ at the speed of 5 ℃/min, and keeping the temperature for 1 h.
And after cooling to room temperature, taking out a powder sample to obtain the novolac epoxy resin-based hard carbon negative electrode material of the embodiment 1.
The prepared novolac epoxy resin-based hard carbon negative electrode material is a hard carbon material which has an irregular blocky macroscopic appearance and a nano-scale microporous structure in the interior, wherein the diameter of a pore channel of the nano-scale microporous structure is 0.38 nm. The diameter of the pore channel of the nano micropore refers to the nano 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 the 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 mixed slurry on a copper foil current collector. And (4) carrying out vacuum drying on the copper foil current collector coated with the slurry, and after the copper foil current collector is completely dried, preparing the negative pole piece. In a vacuum glove box in argon atmosphere, a metal sodium sheet is taken as a counter electrode, glass microfiber and foam nickel are respectively taken as an electrolytic diaphragm and a gasket, and 1mol of NaPF 6 And (3) taking a mixed solution obtained by dissolving the mixture in 1L of ethylene glycol dimethyl ether as an electrolyte, and adding the prepared pole piece to assemble the button cell C1.
Examples 2 to 7
The examples are provided to illustrate the preparation method of the novolac epoxy resin-based hard carbon negative electrode material, the prepared novolac epoxy resin-based hard carbon negative electrode material, and a sodium ion battery using the novolac epoxy resin-based hard carbon negative electrode material.
Novolac epoxy resin-based hard carbon negative electrode materials were respectively prepared and assembled into cells C2-7 in the same manner as in example 1, except that the reaction conditions were different as shown in table 1 below.
In addition, the novolac epoxy resin-based hard carbon negative electrode materials prepared in examples 2 to 7 are hard carbon materials with irregular block shapes in macroscopic appearances and with nanoscale microporous structures in the interiors, wherein the pore diameters of the nanoscale microporous structures are respectively shown in table 1.
TABLE 1
Comparative example 1
This comparative example is used to illustrate the preparation method of the phenolic resin-based hard carbon negative electrode material of comparative example 1, the phenolic resin-based hard carbon negative electrode material prepared, and a sodium ion battery using the phenolic resin-based hard carbon negative electrode material.
In this comparative example, a novolac epoxy resin-based hard carbon negative electrode material was prepared in the same manner as in example 1. Then, a battery CC1 was assembled in the same manner as in example 1, except that the novolac epoxy resin was changed to a phenol resin.
Comparative example 2
This comparative example is used to illustrate the preparation method of the novolac epoxy resin-based hard carbon negative electrode material of comparative example 2, the prepared novolac epoxy resin-based hard carbon negative electrode material, and a sodium ion battery using the novolac epoxy resin-based hard carbon negative electrode material.
In this comparative example, a novolac epoxy resin-based hard carbon negative electrode material was prepared in the same manner as in example 1. Then, the following steps are performed instead of step d and step e in example 1, except that the pre-pyrolysis step in step d in example 1 is omitted: the resulting powder sample was transferred to a tube furnace, argon was introduced, the temperature was raised from room temperature to 1200 ℃ directly at a rate of 5 ℃/min, and the temperature was maintained for 1h, followed by assembly into a cell CC2 using the same method as in example 1.
Performance testing
The sodium ion batteries C1-C7 and CC1-CC2 prepared in examples 1-7 and comparative examples 1-2 were subjected to constant current charge and discharge test: the testing voltage range is 0-2.5V, the current density is 0.1C-50 mA/g, and the reversible specific capacity and the first coulombic efficiency of the sodium-ion battery prepared in each embodiment and each comparative example are obtained; current densities of 0.1C, 0.2C, 0.4C, 1C, 2C, 4C, 6C, and 8C, where 1C is 500mA/g, were obtained to obtain rate performance of the sodium ion batteries prepared in each of the examples and comparative examples; the current density is 500mA/g, and the reversible specific capacity retention rate of the sodium-ion battery prepared in each example and each comparative example is obtained after the charge-discharge cycle is 800 weeks. The results of the tests are shown in table 2 below.
TABLE 2
As can be seen from table 2, the electrochemical performances of the sodium ion batteries prepared in examples 1 to 7 using the novolac epoxy resin based hard carbon material, such as the first coulombic efficiency, the reversible specific capacity, the rate capability, and the cycle stability, are far superior to those of comparative example 1, and it is verified that, compared with the case of using the novolac epoxy resin as the precursor of the hard carbon material, the positive effect on the prepared sodium ion batteries is obtained when using the novolac epoxy resin as the precursor of the hard carbon material.
The electrochemical performances of the sodium ion batteries prepared by using the novolac epoxy resin-based hard carbon material in the embodiments 1 to 7, such as the first coulombic efficiency, the reversible specific capacity, the rate capability and the cycling stability, are far superior to those of the comparative example 2, and it is verified that compared with the one-step pyrolysis method, the two-step pyrolysis method, namely the method of first preheating pyrolysis and then high-temperature pyrolysis, is adopted, so that the positive effect on the prepared sodium ion batteries is achieved.
In addition, as can be seen from comparison of various electrochemical properties of the sodium ion batteries prepared by using the novolac epoxy resin-based hard carbon material in examples 2-4 and examples 1 and 5, a preferable range exists in which the high-temperature pyrolysis temperature has a positive effect on the prepared negative electrode material of the sodium ion battery, and the preferable temperature range is 1400-1800 ℃. When the novolac epoxy resin-based hard carbon material is prepared within the optimal temperature range and used as a negative electrode material of a sodium ion battery, the initial coulombic efficiency, reversible specific capacity, rate capability and cycling stability of the sodium ion battery are all improved more remarkably.
Claims (8)
1. The preparation method of the novolac epoxy resin-based hard carbon negative electrode material is characterized by comprising the following steps of:
a. taking novolac epoxy resin as a precursor, mixing the novolac epoxy resin and maleic anhydride according to the mass ratio of 5: 1-1: 1, and uniformly stirring;
b. transferring the mixture of the novolac epoxy resin and the maleic anhydride into a heater, and heating for 8-12 hours at 120-180 ℃ for curing;
c. taking out the cured novolac epoxy resin, and grinding into powder;
d. putting the powder into a reactor, heating to 400-800 ℃ in an argon atmosphere, and carrying out pyrolysis treatment for 1-8 h;
e. and after cooling, heating to 1200-2000 ℃ in an argon atmosphere, and carrying out pyrolysis treatment for 1-8 h.
2. The method of claim 1, wherein in step d, the temperature increase rate is 1-10 ℃/min.
3. The method according to claim 1, wherein in step e, the temperature rise rate is 2-10 ℃/min and the pyrolysis temperature is 1400-1800 ℃.
4. The method according to claim 1, wherein the novolac epoxy resin is one or more selected from the group consisting of phenol-novolac epoxy resins, o-cresol-novolac epoxy resins, and bisphenol a-novolac epoxy resins.
5. A novolac epoxy resin-based hard carbon negative electrode material prepared by the method of any one of claims 1 to 4.
6. The novolac epoxy resin-based hard carbon negative electrode material as claimed in claim 5, wherein the novolac epoxy resin-based hard carbon material is macroscopically irregular blocky particles, and a nano-scale micropore structure exists inside the particles, and the diameter of the nano-scale micropores is less than 2 nm.
7. A sodium ion battery is characterized by comprising a positive pole piece, a negative pole piece, a separation film and electrolyte, wherein the separation film is arranged between the positive pole piece and the negative pole piece; the negative pole piece comprises a negative current collector and negative slurry arranged on the negative current collector; the negative electrode slurry includes: the novolac epoxy resin-based hard carbon negative electrode material of any one of claims 5-6, a conductive agent, a binder and a solvent.
8. The sodium-ion battery of claim 7, wherein the electrolyte solution comprises sodium electrolyte salt and an organic solvent, wherein the sodium electrolyte 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), Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), and diethyl carbonate (DEC).
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