CN116692831A - Phosphorus-doped phenolic resin-based hard carbon material, preparation method and application - Google Patents
Phosphorus-doped phenolic resin-based hard carbon material, preparation method and application Download PDFInfo
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- CN116692831A CN116692831A CN202310965199.0A CN202310965199A CN116692831A CN 116692831 A CN116692831 A CN 116692831A CN 202310965199 A CN202310965199 A CN 202310965199A CN 116692831 A CN116692831 A CN 116692831A
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- phenolic resin
- hard carbon
- carbon material
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 63
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 63
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 46
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 9
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims abstract 2
- 238000002156 mixing Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 10
- 239000004254 Ammonium phosphate Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 9
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 9
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 claims description 9
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 2
- 229960001553 phloroglucinol Drugs 0.000 claims description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 10
- 229910001415 sodium ion Inorganic materials 0.000 description 10
- 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 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application relates to the technical field of battery materials, and provides a phosphorus-doped phenolic resin-based hard carbon material, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Stirring and mixing a phenol monomer and an alkaline system to obtain a solution A; (2) Adding an aldehyde monomer and a phosphorus-containing reagent into the solution A obtained in the step (1), and stirring to obtain a solution B; (3) Adding polyvinyl alcohol into the solution B obtained in the step (2) to obtain phenolic resin; (4) Dissolving the phenolic resin obtained in the step (3) in alcohol, and performing crosslinking to obtain a phosphorus-doped phenolic resin matrix precursor; (5) Carbonizing the phosphorus-doped phenolic resin-based precursor obtained in the step (4) to obtain the phosphorus-doped phenolic resin-based hard carbon material. The preparation method of the phosphorus-doped phenolic resin-based hard carbon material can effectively improve the capacity of a battery.
Description
Technical Field
The application relates to the technical field of battery materials, in particular to a phosphorus-doped phenolic resin-based hard carbon material, a preparation method and application thereof.
Background
Energy sources have become an essential component of human society, and energy storage technology is becoming a popular research field. The lithium ion battery has the outstanding advantages of high energy density, long cycle life and the like, and has become an important power source for meeting the increasing demands of energy storage systems. However, since lithium is stored in the crust in a limited amount and resources are unevenly distributed, the cost of lithium is drastically increased, and a search for a substitute is urgently needed.
Sodium is used as the same group element of lithium, has many similar physical and chemical properties as lithium, has high content of sodium in the crust, sufficient resource reserve and low cost, and can be used as a good substitute of lithium. However, since the radius of sodium ions is too large and a stable compound cannot be formed with graphite, graphite cannot be used as a negative electrode material of a sodium ion battery. Therefore, to realize industrialization of sodium ion batteries, a low-cost and excellent-performance negative electrode material needs to be found.
Hard carbon has the advantages of excellent physical and chemical properties, low cost and the like, and becomes a promising negative electrode material of a sodium ion battery. The phenolic resin-based hard carbon material has high carbon residue rate, low cost and excellent sodium storage performance, and is one of the key points of hard carbon cathode research. For example, CN105355867A is a hard carbon negative electrode material for a high-performance lithium ion power battery, a preparation method and application thereof; the hard carbon negative electrode material of the sodium ion battery based on the phenolic resin of CN109742383A, and the preparation method and the application thereof are researched to a certain extent, but the energy density and the initial efficiency of the finally obtained battery finished product still have great progress space.
Disclosure of Invention
The application aims to provide a preparation method of a phosphorus-doped phenolic resin-based hard carbon material, which can effectively improve the capacity of a battery.
The embodiment of the application is realized by the following technical scheme: a preparation method of a phosphorus-doped phenolic resin-based hard carbon material comprises the following steps:
(1) Adding one or more of sodium hydroxide solution, potassium hydroxide, barium hydroxide, ammonia water and triethylamine into a phenol monomer, regulating the pH value of the solution to be more than 7, and continuously stirring at 40-50 ℃ to obtain solution A; wherein there is no particular limitation on the concentration of the solution A;
(2) Adding aldehyde monomer, ammonium phosphate, DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and phenylphosphoryl dichloride into the solution A obtained in the step (1) to obtain a solution B; wherein the mass fraction of the aldehyde monomer solution is 37wt%, and the mole ratio of the aldehyde monomer to the phenol monomer in the solution B is 1-2:1, a step of; the specific kind of DOPO is not limited.
(3) Continuously stirring the solution B obtained in the step (2) at 80-95 ℃ and continuously adding polyvinyl alcohol to perform polycondensation reaction to obtain phenolic resin;
(4) Dissolving the phenolic resin obtained in the step (3) in an alcohol solution, putting the solution into a high-pressure reaction kettle at 80-120 ℃ for crosslinking for 12-30 hours, and filtering and drying to obtain a phosphorus-doped phenolic resin matrix precursor;
(5) And (3) carrying out sectional carbonization on the phosphorus-doped phenolic resin-based precursor obtained in the step (4) under the inert gas atmosphere, wherein the carbonization program is that the heating rate is 1.5-2.5 ℃/min, the temperature is increased to 90-110 ℃ and kept for 1.5-2 hours, the temperature is increased to 250-300 ℃ and kept for 2-3 hours at 4-6 ℃/min, the temperature is increased to 500-600 ℃ and kept for 1.5-2 hours at the speed of 2-3 ℃/min, the heating rate is kept to 1000-1400 ℃ and kept for 2-3 hours, and finally the temperature is cooled to room temperature.
Further, the phenolic monomer in the step (1) is one or more of phenol, resorcinol, catechol and phloroglucinol.
Further, the aldehyde monomer in the step (2) is one or more of formaldehyde, benzaldehyde, furfural and terephthalaldehyde; the molar ratio of phenol monomer to aldehyde monomer is 1:2. the addition of the polar solution and the polyvinyl alcohol can improve the crosslinking degree of the phenolic resin polymer. The higher the crosslinking degree of the phenolic resin is, the crosslinking structure can be used for combining the growth of the carbon layer in the carbonization process, and the structure of the shorter carbon layer can improve the specific capacity and the cycle stability of the battery under the condition of unchanged interlayer spacing. And the higher the crosslinking degree is, the more regular the shape of the hard carbon is, and the proper surface defect degree is possessed, so that the sodium storage performance is improved.
Further, in the step (2), the contents of ammonium phosphate, DOPO and phenylphosphoryl dichloride respectively account for 0.1-3%, 0.1-1% and 0.1-1% of the mass fraction of the solution B; wherein the phosphorus-containing reagent reacts with the phenolic resin to form a heterocyclic structure with the phenolic resin in the form of a chemical bond. The electronegativity of the carbon element is greater than that of phosphorus, and the carbon element is an electron donor in a doped structure, so that a large number of defects and active sites can be generated in a carbon skeleton, and the adsorption capacity of sodium ions is improved to a great extent. The atomic radius of the phosphorus atoms is large, the spacing between graphite microcrystalline layers can be increased to a certain extent, and the sodium storage capacity of the hard carbon material is further improved. The equivalent bond of P-O-C, P =O is introduced by a chemical reaction mode, so that the content of oxygen-containing functional groups in the hard carbon is changed, and a certain interval between graphite microcrystal layers can be enlarged. Due to the introduction of oxygen atoms, more active sites can be provided for sodium ions, and the sodium storage performance is further improved.
According to the carbonization method in the step (5), a segmented carbonization process is adopted in the carbonization process, so that the carbon residue rate of the precursor is obviously improved, and the structural stability of the hard carbon material is good. Wherein, in the carbonization process, the stabilization treatment at 100 ℃ and 300 ℃ respectively removes redundant alcohol solution, ensures the structural stability of phenolic resin and reduces the volatilization caused by thermal cracking of the material. And the heat preservation treatment at 600 ℃ is to pre-carbonize the hard carbon material, regulate and control the growth of the carbon layer, and further improve the structural stability of the hard carbon material. And cooling to room temperature to obtain the phosphorus-doped phenolic resin-based hard carbon material.
The application also provides the phosphorus-doped phenolic resin-based hard carbon material prepared by the preparation method of the phosphorus-doped phenolic resin-based hard carbon material.
The application also provides application of the phosphorus-doped phenolic resin-based hard carbon material to a battery anode material.
The technical scheme of the embodiment of the application has at least the following advantages and beneficial effects: according to the phosphorus-doped phenolic resin-based hard carbon material, the polyvinyl alcohol is introduced during phenolic resin synthesis, so that the crosslinking degree can be remarkably improved, the appearance of the hard carbon is more regular, the phosphorus-doped phenolic resin-based hard carbon material has proper surface defect degree, and the sodium storage performance is further improved. And the addition of the phosphorus-containing reagent causes the phosphorus-containing reagent to form a heterocyclic structure with the phenolic resin in a chemical bond form. The electronegativity of the phosphorus element is greater than that of carbon, and the phosphorus element is an electron donor in a doped structure, so that a large number of active sites can be generated in a carbon skeleton, and the adsorption capacity of sodium ions is improved to a great extent. The atomic radius of the phosphorus atom is large, so that the inter-microcrystalline space of the graphite can be increased to a certain extent, and sites can be provided for storage of sodium ions. The equivalent bond of P-O-C, P =O is introduced, so that the content of oxygen-containing functional groups in the hard carbon is changed, and a certain interval between graphite microcrystalline layers can be enlarged. Due to the introduction of oxygen atoms, more active sites can be provided for sodium ions, and the sodium storage performance is improved. By the above action, when the material is applied to the negative electrode of a battery, the battery capacity can be remarkably improved.
Drawings
FIG. 1 is a scanning electron microscope image of a phosphorus-doped phenolic resin-based hard carbon material of example 1 of the present application;
fig. 2 is a graph showing the relationship between specific capacity and voltage during charge and discharge of the battery obtained in experimental example 2 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a preparation method of a phosphorus-doped phenolic resin-based hard carbon material, which comprises the following steps:
(1) Adding 45% sodium hydroxide solution into phenol solution, and stirring at 45deg.C to obtain solution A with pH of 7-7.5.
(2) Adding formaldehyde, ammonium phosphate, DOPO (structural formula is shown as below) and phenyl phosphoryl dichloride into the solution A obtained in the step (1) to obtain a solution B; wherein the mole ratio of phenol to formaldehyde is 1:2, the addition amounts of the ammonium phosphate, the DOPO and the phenylphosphoryl dichloride respectively account for 0.1 percent, 0.1 percent and 0.1 percent of the mass fraction of the solution B.
(3) The solution B was warmed to 95℃and 5% by weight of polyvinyl alcohol powder was added and stirring was continued until a phenolic resin was obtained.
(4) And (3) dissolving the phenolic resin obtained in the step (3) in an ethanol solution, then placing the solution into a high-pressure reaction kettle, and crosslinking the solution at 100 ℃ for 15 hours to obtain a phenolic resin-based precursor. Cooling to room temperature, filtering, drying and mechanically crushing to obtain powdered phenolic resin matrix precursor.
(5) And (3) carrying out sectional carbonization on the phosphorus-doped phenolic resin-based precursor obtained in the step (4) under the inert gas atmosphere, wherein the carbonization program is that the heating rate is 1.5 ℃/min, the temperature is increased to 90 ℃ and kept for 1.5 hours, the temperature is increased to 250 ℃ and kept for 2 hours at the speed of 4 ℃/min, the temperature is increased to 500 ℃ and kept for 1.5 hours at the speed of 2 ℃/min, the heating rate is kept to 1400 ℃ and kept for 2 hours at last, and finally the phenolic resin-based precursor is cooled to room temperature. Scanning Electron Microscope (SEM) detection is carried out on the phosphorus-doped phenolic resin-based hard carbon material obtained in the step, and the electron microscope diagram is shown in figure 1
Example 2
Example 2 provides a method for preparing a phosphorus-doped phenolic resin-based hard carbon material, which is different from example 1 in that step (2) is as follows: adding formaldehyde, ammonium phosphate, DOPO and phenyl phosphoryl dichloride into the solution A obtained in the step (1) to obtain a solution B; wherein the mole ratio of phenol to formaldehyde is 1: and 2, the contents of ammonium phosphate, DOPO and phenyl phosphoryl dichloride respectively account for 3%, 1% and 1% of the mass fraction of the solution B.
Example 3
Example 3 provides a method for preparing a phosphorus-doped phenolic resin-based hard carbon material, which is different from example 1 in that step (5), step (5) in this example is: and (3) carrying out sectional carbonization on the phosphorus-doped phenolic resin-based precursor obtained in the step (4) under the inert gas atmosphere, wherein the carbonization program is that the heating rate is 2.5 ℃/min, the temperature is raised to 110 ℃ and kept for 2 hours, the temperature is raised to 300 ℃ and kept for 3 hours at the speed of 6 ℃/min, the temperature is raised to 600 ℃ and kept for 2 hours at the speed of 3 ℃/min, the heating rate is kept to be raised to 1400 ℃ and kept for 3 hours at last, and finally the phenolic resin-based precursor is cooled to the room temperature.
Example 4
Example 4 provides a method for preparing a phosphorus-doped phenolic resin-based hard carbon material, which is different from example 1 in that step (5), step (5) in this example is: and (3) carrying out sectional carbonization on the phosphorus-doped phenolic resin-based precursor obtained in the step (4) under the inert gas atmosphere, wherein the carbonization program is that the heating rate is 2 ℃/min, the temperature is raised to 100 ℃, the temperature is kept for 2 hours, the temperature is raised to 300 ℃ at 5 ℃/min, the temperature is kept for 3 hours, the temperature is raised to 600 ℃ at the speed of 2 ℃/min, the temperature is kept for 2 hours, the heating rate is kept at 3 ℃/min, the temperature is raised to 1400 ℃ and the temperature is kept for 3 hours, and finally the cooling is carried out to the room temperature.
Comparative example 1
This comparative example provides a method for producing a negative electrode material, which differs from example 1 only in step (3). Step (3) of this comparative example does not add polyvinyl alcohol.
Comparative example 2
This comparative example provides a method for producing a negative electrode material, which is different from example 1 in step (2) and step (3). In step (2) of this comparative example, ammonium phosphate, DOPO, and phenylphosphoryl dichloride were not added. And (3) adding no polyvinyl alcohol.
Comparative example 3
This comparative example provides a method for producing a negative electrode material, which differs from example 1 only in step (2). In step (2) of this comparative example, ammonium phosphate, DOPO, and phenylphosphoryl dichloride were not added.
Experimental example 1
The materials prepared in examples 1 to 4 and comparative examples 1 to 3 were used as negative electrodes in battery assembly, respectively, in which the battery assembly was completed in a glove box filled with argon gas, and a button cell was assembled using a metal sodium sheet as positive electrode. Electrochemical testing was performed by an electrochemical workstation, using a constant current charge-discharge mode, at a current density of 0.1C. The results of the tests under the conditions of a discharge cut-off voltage of 0.05V and a charge cut-off voltage of 2.5V are shown in table 1 below (the average value was taken for each group of tests several times).
Table 1 battery capacities and initial efficiencies of examples 1 to 4 and comparative examples 1 to 3
As can be seen from table 1 above, the phosphorus-doped phenolic resin-based hard carbon material prepared by the method of the present application is used as a negative electrode material of a battery, and has a higher capacity on the premise of not low capacity retention rate and low initial efficiency after a plurality of cycles.
Experimental example 2
The materials obtained in example 3 were used in a battery according to the operation method in experimental example 1, and the specific capacity-voltage relationship of the battery during charge and discharge was measured, respectively, and the results are shown in fig. 2, in which two curves are a charge curve and a discharge curve, respectively, indicating the relationship between the charge capacity and the voltage and the relationship between the discharge capacity and the voltage during charge of the battery. Wherein, the discharge capacity of the battery reaches 422mAh/g, and the initial coulomb efficiency is 92%. The battery prepared by the material has better coulombic efficiency and higher capacity.
The above is only a preferred embodiment of the present application, and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. 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 phosphorus-doped phenolic resin-based hard carbon material is characterized by comprising the following steps of:
(1) Stirring and mixing a phenol monomer and an alkaline system to obtain a solution A;
(2) Adding an aldehyde monomer and a phosphorus-containing reagent into the solution A obtained in the step (1), and stirring to obtain a solution B;
(3) Adding polyvinyl alcohol into the solution B obtained in the step (2) to obtain phenolic resin;
(4) Dissolving the phenolic resin obtained in the step (3) in alcohol, and performing crosslinking to obtain a phosphorus-doped phenolic resin matrix precursor;
(5) Carbonizing the phosphorus-doped phenolic resin-based precursor obtained in the step (4) to obtain the phosphorus-doped phenolic resin-based hard carbon material.
2. The method for preparing the phosphorus-doped phenolic resin-based hard carbon material according to claim 1, wherein the alkaline substance of the alkaline system in the step (1) comprises one or more of sodium hydroxide, potassium hydroxide, barium hydroxide, ammonia water and triethylamine.
3. The method for preparing a phosphorus-doped phenolic resin-based hard carbon material according to claim 1, wherein the phenolic monomers in the step (1) include one or more of phenol, resorcinol, catechol, and phloroglucinol.
4. The method for preparing the phosphorus-doped phenolic resin-based hard carbon material according to claim 1, wherein the aldehyde monomer in the step (2) comprises one or more of formaldehyde, benzaldehyde, furfural and terephthalaldehyde;
the molar ratio of phenol monomer to aldehyde monomer is 1:1-2.
5. The method for preparing a phosphorus-doped phenolic resin-based hard carbon material according to claim 1, wherein the reaction temperature in the step (3) is 80-95 ℃; the reaction temperature in the step (4) is 80-120 ℃.
6. The method for preparing the phosphorus-doped phenolic resin-based hard carbon material according to claim 1, wherein the addition amount of the polyvinyl alcohol in the step (3) is 4-6% of the mass of the B solution.
7. The method for preparing a phosphorus-doped phenolic resin-based hard carbon material according to any one of claims 1 to 6, wherein the phosphorus-containing reagent in the step (2) comprises ammonium phosphate, DOPO and phenylphosphoryl dichloride, which respectively account for 0.1 to 3%, 0.1 to 1% and 0.1 to 1% of the mass fraction of the solution B.
8. The method for preparing a phosphorus-doped phenolic resin-based hard carbon material according to any one of claims 1 to 6, wherein the carbonization procedure in the step (5) is to heat up to 90 to 110 ℃ at a heating rate of 1.5 to 2.5 ℃/min for 1.5 to 2 hours, heat up to 250 to 300 ℃ at a heating rate of 4 to 6 ℃/min for 2 to 3 hours, heat up to 500 to 600 ℃ at a heating rate of 2 to 3 ℃/min for 1.5 to 2 hours, heat up to 1000 to 1400 ℃ at a heating rate of 2 to 3 ℃/min for 2 to 3 hours, and finally cool down to room temperature.
9. A phosphorus-doped phenolic resin-based hard carbon material prepared by the method for preparing a phosphorus-doped phenolic resin-based hard carbon material according to any one of claims 1 to 8.
10. Use of the phosphorus-doped phenolic resin-based hard carbon material according to claim 9 in a battery negative electrode material.
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