CN116812904A - Aromatic phenolic resin-based hard carbon material, sodium ion battery and preparation method thereof - Google Patents
Aromatic phenolic resin-based hard carbon material, sodium ion battery and preparation method thereof Download PDFInfo
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 78
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 72
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 56
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 50
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 39
- 238000000197 pyrolysis Methods 0.000 claims description 39
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 15
- 235000010290 biphenyl Nutrition 0.000 claims description 13
- 239000004305 biphenyl Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 230000000630 rising effect Effects 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000004321 preservation Methods 0.000 claims 2
- JRQJLSWAMYZFGP-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical compound OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 JRQJLSWAMYZFGP-UHFFFAOYSA-N 0.000 claims 1
- PBEHQFUSQJKBAS-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;phenol Chemical compound OC1=CC=CC=C1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 PBEHQFUSQJKBAS-UHFFFAOYSA-N 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 239000007773 negative electrode material Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 18
- 239000010405 anode material Substances 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- -1 aralkyl phenolic resin Chemical compound 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 101150093275 hcs1 gene Proteins 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101150030953 HCS2 gene Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The application provides an aromatic phenolic resin-based hard carbon material, and a preparation method and application thereof. The aromatic phenolic resin-based hard carbon material is prepared by pre-pyrolyzing aromatic phenolic resin powder at low temperature (400-900 ℃) and pyrolyzing the powder at high temperature (1000-1800 ℃). The prepared aromatic phenolic resin-based hard carbon material is used as a negative electrode material, and has the comprehensive performance advantages of charge-discharge capacity, cycle stability, first coulombic efficiency and the like when being applied to a sodium ion battery system.
Description
Technical Field
The application relates to the technical field of sodium ion batteries, in particular to an aromatic phenolic resin-based hard carbon material, a sodium ion battery and a preparation method thereof.
Background
In recent years, sodium ion batteries are considered as an important complement to lithium ion batteries. Much research effort has been directed to developing electrolytes and positive electrode materials for sodium ion batteries. The high-performance anode material plays the same important role in further improving the energy density of the sodium ion battery. Hard carbon anode materials are considered promising candidates for sodium ion battery anode materials due to their lower plateau voltage and acceptable capacity compared to alloy anode materials and conversion-based anode materials that have high plateau voltage and poor cycling stability.
At present, research on preparing a hard carbon anode material by using a part of resin is carried out, but initial coulombic efficiency and rate capability still need to be further improved.
Disclosure of Invention
Based on this, it is necessary to provide an aromatic phenolic resin-based hard carbon material, a preparation method thereof and an application in preparing sodium ion batteries. The prepared sodium ion battery has more excellent comprehensive performances such as initial coulombic efficiency, charge-discharge capacity, cycle stability and the like by adopting the aromatic phenolic resin-based hard carbon material as the negative electrode material.
The application adopts the following technical scheme:
the application provides a preparation method of an aromatic phenolic resin-based hard carbon material, which comprises the following steps: preparing aromatic phenolic resin powder; transferring the aromatic phenolic resin powder into a reaction furnace, heating to 400-900 ℃ under argon atmosphere, performing pre-pyrolysis treatment, and cooling to obtain a pre-pyrolysis product; and heating to 1000-1800 ℃ in an argon atmosphere, carrying out high-temperature pyrolysis treatment on the pre-pyrolysis product, and cooling to obtain the hard carbon material.
In some embodiments, the aromatic phenolic resin is selected from at least one of an aralkyl phenolic resin, a biphenyl phenolic resin, a bisphenol a phenolic resin.
Preferably, the aromatic phenolic resin is selected from biphenyl type phenolic resins.
In some of these embodiments, the warm-up rate of the pre-pyrolysis step is 1-10 ℃/min; and/or the temperature rising rate of the high-temperature pyrolysis step is 1-15 ℃/min.
In some of these embodiments, the temperature of the high temperature pyrolysis step is preferably 1400 to 1800 ℃.
The application also provides an aromatic phenolic resin-based hard carbon material, which is prepared by sequentially carrying out preheating pyrolysis treatment at 400-900 ℃ and cooling and then carrying out pyrolysis treatment at 1000-1800 ℃ on aromatic phenolic resin powder.
Wherein, the appearance of the aromatic phenolic resin based hard carbon material is: macroscopically irregular block-shaped particles, and nano-scale micropore structures exist in the particles. Preferably, the pore size of the nanoscale micropores is less than 2nm.
The application also provides a negative electrode plate which is prepared from the hard carbon material prepared by the method. Preferably, the negative electrode plate is prepared from a conductive agent, a binder, a solvent and a hard carbon material prepared by the method.
The application also provides a sodium ion battery which is characterized by comprising a positive pole piece, an isolating film, the negative pole piece and sodium ion electrolyte.
Compared with the prior art, the application has the core advantages that:
1) According to the method, the aromatic phenolic resin is used as a precursor, the precursor contains a large number of aromatic rings, raw materials are easy to obtain, and when the hard carbon material prepared by adopting the two-step heat treatment is applied to the negative electrode of the sodium ion battery, compared with other negative electrode materials, the prepared hard carbon negative electrode material has excellent first coulombic efficiency, charge-discharge capacity and cycle stability.
Specifically, the aromatic phenolic resin-based hard carbon material is used as a negative electrode material of a sodium ion battery, has higher reversible specific capacity and can reach 384.8mAh/g under the current density of 50 mA/g. The capacity of the sodium ion battery remains 219.9mAh/g even if the current density is increased to 1A/g. After 1000 cycles of the sodium ion battery, the capacity retention rate can reach 84.2% at maximum. Compared with other resin hard carbon materials, the charge-discharge capacity, the multiplying power performance and the cycle performance of the aromatic phenolic resin hard carbon material are improved to a certain extent.
2) In particular, the method of the present application employs a two-step heat treatment: the first heat treatment can be regarded as pre-pyrolysis, part of impurities are eliminated, the microstructure of the material becomes more ordered, the high-temperature pyrolysis is further carried out, and the charge-discharge performance capacity and the multiplying power can be improved as a whole.
Drawings
Fig. 1 is an SEM image of the aromatic phenolic resin-based hard carbon material prepared in example 4.
Detailed Description
The present application will be described in further detail with reference to specific examples so as to more clearly understand the present application by those skilled in the art. The following examples are given for illustration of the application only and are not intended to limit the scope of the application. All other embodiments obtained by those skilled in the art without creative efforts are within the protection scope of the present application based on the specific embodiments of the present application. In the examples of the present application, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise; in the embodiments of the present application, unless specifically indicated, all technical means used are conventional means well known to those skilled in the art.
In the present application, the aromatic phenol resin means: phenolic resin with benzene ring structure contains at least one benzene ring with a domain bond.
Wherein, the structural formula of biphenyl type phenolic resin is:
the structural formula of the aralkyl phenolic resin is as follows:
the structural formula of the bisphenol A type phenolic resin is as follows:
the structural formula of the aliphatic phenolic resin is as follows:
the source and physical and chemical indexes of the key materials for the test are described:
| raw materials | Commercial brand | Physical and chemical index | Source |
| Biphenyl type phenolic resin | BNH-851 | Hydroxyl equivalent (198-208 g/eq) | Hunan well original New Material science and technology Co.Ltd |
| Aralkyl phenolic resin | XYH-880 | Hydroxyl equivalent (172-180 g/eq) | Hunan well original New Material science and technology Co.Ltd |
| Bisphenol A type phenolic resin | BPA-18 | Hydroxyl equivalent (100-160 g/eq) | Jiangyin city Dongpeng International technology trade Co., ltd |
| Aliphatic phenolic resin | PF-8106 | Hydroxyl equivalent (104-110 g/eq) | Hunan well original New Material science and technology Co.Ltd |
Example 1
The embodiment provides a preparation method of an aromatic phenolic resin-based hard carbon material, which comprises the following steps:
s1, preparing biphenyl type phenolic resin into powder through a vibration sample grinder to obtain resin powder.
S2, transferring the resin powder prepared in the step S1 into a tube furnace, introducing argon, and performing pre-pyrolysis under the following process conditions: the temperature was raised from room temperature to 600℃at a rate of 1℃per minute, and the temperature was kept for 2 hours. Cooling to room temperature to obtain the pre-pyrolysis product.
S3, continuously carrying out high-temperature pyrolysis on the pre-pyrolysis product obtained in the step S2, wherein the process conditions are as follows: the temperature was raised from room temperature to 1000℃at a rate of 2℃per minute, and the temperature was kept for 1 hour. Cooling to room temperature to obtain the hard carbon material.
The embodiment also provides a battery application example, and the preparation and assembly method thereof comprises the following steps:
s1, preparing a negative electrode:
and uniformly mixing the prepared hard carbon material, carbon black and sodium alginate according to the mass ratio of 8:1:1, adding a proper amount of deionized water, stirring and mixing to obtain uniform slurry (the time is 5 h), and then coating the uniformly mixed slurry on a copper foil current collector. And (5) drying in vacuum to prepare the negative electrode plate.
S2, battery assembly:
in a glove box in an argon atmosphere, the negative electrode plate prepared in the step S1 is used as a separation film, a metal sodium plate is used as a counter electrode, foam nickel is used as a gasket, and 1mol/LNaPF is used 6 The ethylene glycol dimethyl ether solution is used as electrolyte to assemble the button cell HC1.
Example 2
The present embodiment provides a method for preparing an aromatic phenolic resin-based hard carbon material, which has substantially the same process steps as those of embodiment 1, and differs only in that:
the treatment temperature of the high-temperature pyrolysis in step S3 is adjusted to 1200 ℃.
The present embodiment also provides a battery application example, the preparation and assembly method of which is referred to in embodiment 1, and button battery HC2 is assembled.
Example 3
The present embodiment provides a method for preparing an aromatic phenolic resin-based hard carbon material, which has substantially the same process steps as those of embodiment 1, and differs only in that:
the treatment temperature of the pyrolysis in step S3 was adjusted to 1400 ℃.
The present embodiment also provides a battery application example, the preparation and assembly method of which is referred to in embodiment 1, and button battery HC3 is assembled.
Example 4
The present embodiment provides a method for preparing an aromatic phenolic resin-based hard carbon material, which has substantially the same process steps as those of embodiment 1, and differs only in that:
the treatment temperature of the high-temperature pyrolysis in the step S3 is adjusted to 1600 ℃.
The present embodiment also provides a battery application example, the preparation and assembly method of which is referred to in embodiment 1, and button battery HC4 is assembled.
Example 5
The present embodiment provides a method for preparing an aromatic phenolic resin-based hard carbon material, which has substantially the same process steps as those of embodiment 1, and differs only in that:
the treatment temperature of the high-temperature pyrolysis in step S3 is adjusted to 1800 ℃.
The present embodiment also provides a battery application example, the preparation and assembly method of which is referred to in embodiment 1, and button battery HC5 is assembled.
Example 6
The present embodiment provides a method for preparing an aromatic phenolic resin-based hard carbon material, which has substantially the same process steps as those of embodiment 1, and differs only in that:
in the step S1, an aralkyl phenolic resin is adopted to replace biphenyl phenolic resin;
in step S2, the process conditions of the pre-pyrolysis are: raising the temperature from room temperature to 700 ℃ at a speed of 1 ℃/min, and preserving the temperature for 4 hours;
and in the step S3, the treatment temperature of high-temperature pyrolysis is adjusted to 1600 ℃, and the temperature is kept for 5 hours.
The present embodiment also provides a battery application example, the preparation and assembly method of which is referred to in embodiment 1, and button battery HC6 is assembled.
Example 7
The present embodiment provides a method for preparing an aromatic phenolic resin-based hard carbon material, which has substantially the same process steps as those of embodiment 1, and differs only in that:
in the step S1, bisphenol A type phenolic resin is adopted to replace biphenyl type phenolic resin;
in step S2, the process conditions of the pre-pyrolysis are: raising the temperature from room temperature to 600 ℃ at a speed of 1 ℃/min, and preserving the temperature for 6 hours;
and in the step S3, the treatment temperature of high-temperature pyrolysis is adjusted to 1600 ℃, and the temperature is kept for 7 hours.
The present embodiment also provides a battery application example, the preparation and assembly method of which is referred to in embodiment 1, and button battery HC7 is assembled.
Comparative example 1
The comparative example provides a preparation method of a phenolic resin-based hard carbon material, which has the process steps basically the same as those of example 1, except that:
in step S1, an aliphatic phenolic resin is used to replace biphenyl phenolic resin.
This comparative example also provides an example of battery application, the preparation and assembly method of which is described in example 1, assembled into a button cell HCS1.
Comparative example 2
The comparative example provides a preparation method of a phenolic resin-based hard carbon material, which comprises the following steps:
s1, preparing biphenyl type phenolic resin into powder through a vibration sample grinder to obtain resin powder.
S2, transferring the resin powder prepared in the step S1 into a tube furnace, introducing argon, and performing one-step pyrolysis, wherein the process conditions are as follows: the temperature was raised from room temperature to 1000℃at a rate of 2℃per minute, and the temperature was kept for 1 hour. Cooling to room temperature to obtain the hard carbon material.
This comparative example also provides an example of battery application, the preparation and assembly method of which is described in example 1, assembled into button cell HCS2.
Comparative example 3
This comparative example refers to the best test example in CN110817833a—a preparation method of a resin-based hard carbon anode material, and the specific preparation method includes the following steps:
s1, fully carbonizing the biphenyl type phenolic resin serving as a framework at 500 ℃ for 5 hours.
S2, impregnating the sample obtained in the step S1 by using impregnant asphalt, wherein the ratio of the resin to the impregnant is 1:2.
S3, carbonizing the sample prepared in the step S2 at 450 ℃.
S4, crushing the carbonized material in the step S3 to obtain the material with the median diameter D50 of 20 mu m.
And S5, carbonizing the sample prepared in the step S4 at a high temperature of 1400 ℃ to obtain the anode material.
This comparative example also provides an example of battery application, for which the preparation and assembly method is described in example 1, assembled into button cell HCS3.
Comparative example 4
The comparative example refers to an optimal test example in CN114824257 A_a hard carbon anode material, a preparation method and application thereof, and the specific preparation method comprises the following steps:
s1, placing biphenyl type phenolic resin into a high-temperature vacuum atmosphere furnace for heat treatment, heating to 210 ℃ at a heating rate of 2 ℃/min, and preserving heat for 1h.
S2, introducing nitrogen into the high-temperature vacuum atmosphere furnace, continuously heating, and heating at a heating speed of 3 ℃/min for 223min; then the temperature rising speed is reduced to 1 ℃/min, the temperature rising time is 221min, the temperature is increased to 1100 ℃, and the temperature is kept for 1h. Finally, cooling to 25 ℃ at a cooling speed of 5 ℃/min.
S3, crushing the cooled material to be less than or equal to 2mm through a ceramic twin-roll crusher, and then finely crushing and classifying the cooled material by adopting an airflow crusher and a classifier to obtain the hard carbon anode material.
This comparative example also provides an example of battery application, for which the preparation and assembly method is described in example 1, assembled into button cell HCS4.
Application performance test:
the sodium ion batteries HC1 to HC7 and HCS1 to HCS4 prepared in the above examples and comparative examples were subjected to constant current charge and discharge test, respectively: the test voltage range is 0-2V, and the charge-discharge capacity and the first coulombic efficiency of the sodium ion battery prepared by each example and comparative example are obtained; current densities (unit: mA/g) of 50, 100, 200, 500, 1000, 2000 and 5000, the rate properties of the batteries prepared in each of the examples and comparative examples were obtained; the current density was 500mA/g and the charge and discharge cycle was 1000 weeks, to obtain the cycle retention rate of the charge and discharge performance of the sodium ion batteries prepared in each example and comparative example.
The results of the specific tests are shown in the following table:
as can be seen from the above table, the sodium ion batteries of the aromatic phenolic resin-based hard carbon materials prepared in examples 1 to 7 were far superior to those of comparative examples 1 to 4 in terms of initial coulombic efficiency, charge-discharge performance, and cycle retention rate.
In particular, compared with comparative example 2, the aromatic phenolic resin-based hard carbon materials prepared in examples 1 to 7 by the 2-step heat treatment method have better first coulombic efficiency, charge and discharge performance, cycle retention rate and other properties when applied to sodium ion battery systems.
Through observation and test, the hard carbon material prepared by the embodiment of the application is as follows: the macro morphology is irregular block-shaped, and the inside of the macro morphology is provided with a hard carbon material with a nanoscale micropore structure. Therein, an SEM image of the hard carbon material prepared in example 4 is shown in fig. 1.
In addition, it is worth noting that the inventor team, through extensive research, found that:
1) In the preparation method of the aromatic phenolic resin-based hard carbon material, the temperature of the first-step pre-pyrolysis is preferably controlled at 400-900 ℃, the temperature rising rate is controlled at 1-10 ℃/min, the temperature of the second-step high-temperature pyrolysis is preferably controlled at 1400-1800 ℃, the temperature rising rate is controlled at 1-15 ℃/min, and the comprehensive performance advantages such as first coulombic efficiency, charge-discharge performance, cycle retention rate and the like are integrally facilitated to be controlled.
2) When the technological conditions of the first-step pre-pyrolysis and the second-step high-temperature pyrolysis are the same, compared with bisphenol A type phenolic resin and aralkyl phenolic resin, the aromatic phenolic resin adopts the hard carbon material prepared by the biphenyl type phenolic resin as the anode material, and the overall comprehensive properties such as initial coulombic efficiency, charge-discharge performance, cycle retention rate and the like are better.
It should be noted that the above examples are only for further illustrating and describing the technical solution of the present application, and are not intended to limit the technical solution of the present application, and the method of the present application is only a preferred embodiment and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The preparation method of the aromatic phenolic resin-based hard carbon material is characterized by comprising the following steps of:
preparing aromatic phenolic resin powder;
transferring the aromatic phenolic resin powder into a reaction furnace, heating to 400-900 ℃ under argon atmosphere, performing pre-pyrolysis treatment, and cooling to obtain a pre-pyrolysis product;
and heating to 1000-1800 ℃ in an argon atmosphere, carrying out high-temperature pyrolysis treatment on the pre-pyrolysis product, and cooling to obtain the hard carbon material.
2. The method for producing an aromatic phenol resin-based hard carbon material according to claim 1, wherein the aromatic phenol resin is at least one selected from the group consisting of an aralkyl phenol resin, a biphenyl phenol resin and a bisphenol a phenol resin.
3. The method for producing an aromatic phenolic resin-based hard carbon material according to claim 2, wherein the aromatic phenolic resin is selected from biphenyl type phenolic resins.
4. The method for preparing an aromatic phenolic resin-based hard carbon material according to any one of claims 1 to 3, wherein the heating rate in the pre-pyrolysis step is 1-10 ℃/min, and the pre-pyrolysis heat preservation treatment is 1-10 h; and/or
The temperature rising rate of the high-temperature pyrolysis step is 1-15 ℃/min, and the high-temperature pyrolysis heat preservation treatment is 1-12 h.
5. The method for preparing an aromatic phenolic resin-based hard carbon material according to claim 4, wherein the temperature of the high-temperature pyrolysis step is 1400-1800 ℃.
6. The aromatic phenolic resin based hard carbon material is characterized in that the aromatic phenolic resin based hard carbon material is prepared by sequentially carrying out preheating pyrolysis treatment at 400-900 ℃ and cooling and then carrying out high-temperature pyrolysis treatment at 1000-1800 ℃.
7. The aromatic phenolic resin-based hard carbon material according to claim 6, wherein the morphology of the aromatic phenolic resin-based hard carbon material is: macroscopically irregular block-shaped particles, and nano-scale micropore structures exist in the particles.
8. A negative electrode sheet prepared from a hard carbon material prepared by the method of any one of claims 1 to 5.
9. The negative electrode tab of claim 8, prepared using a conductive agent, a binder, a solvent, and a hard carbon material prepared by the method of any one of claims 1 to 5.
10. A sodium ion battery comprising a positive electrode sheet, a separation film, a negative electrode sheet according to claim 8 or 9, and a sodium ion electrolyte.
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