CN115893371A - Sulfur, nitrogen and phosphorus doped porous carbon material and preparation and application thereof - Google Patents
Sulfur, nitrogen and phosphorus doped porous carbon material and preparation and application thereof Download PDFInfo
- Publication number
- CN115893371A CN115893371A CN202211696930.6A CN202211696930A CN115893371A CN 115893371 A CN115893371 A CN 115893371A CN 202211696930 A CN202211696930 A CN 202211696930A CN 115893371 A CN115893371 A CN 115893371A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- sulfur
- porous carbon
- carbon material
- phosphorus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 160
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000011593 sulfur Substances 0.000 title claims abstract description 83
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 83
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 81
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 80
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 73
- 239000011574 phosphorus Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000003990 capacitor Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000007772 electrode material Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000002482 conductive additive Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001238 wet grinding Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000009837 dry grinding Methods 0.000 claims description 2
- 235000014786 phosphorus Nutrition 0.000 claims description 2
- 238000007581 slurry coating method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000005077 polysulfide Substances 0.000 abstract description 9
- 229920001021 polysulfide Polymers 0.000 abstract description 9
- 150000008117 polysulfides Polymers 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 13
- 229910052573 porcelain Inorganic materials 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- -1 LA133 Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
A sulfur, nitrogen and phosphorus doped porous carbon material and preparation and application thereof belong to the technical field of battery materials, and overcome the defect of poor electrical performance of a battery caused by low shuttle inhibition efficiency of a modification material to polysulfide in electrolyte in the prior art. The sulfur, nitrogen and phosphorus doped porous carbon material comprises, by mass, 0 & lt, 5% of nitrogen, 0 & lt, 2% of sulfur and 0 & lt, 2% of phosphorus. The porous carbon material prepared by the method has strong adsorption capacity to polysulfide, and the electrical properties of batteries and super capacitors prepared by the porous carbon material are obviously improved.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a sulfur, nitrogen and phosphorus doped porous carbon material and preparation and application thereof.
Background
The anode of the lithium-sulfur battery uses sulfur, the cathode uses metal lithium, the theoretical energy density of the battery is high, and the battery is expected to realize commercial replacement of the existing lithium ion battery. However, during charge and discharge cycles, the dissolution of polysulfides in the electrolyte and the shuttling effect between the positive and negative electrodes greatly affect battery performance and safety.
In order to solve the problem, a material having an adsorption effect on polysulfide is usually used to modify a diaphragm and a pole piece, or is added separately as a modifying layer to block the shuttle of polysulfide in an electrolyte.
However, the conventional modified materials inhibit the shuttle effect only by physical adsorption and blocking, have low efficiency, and cannot meet the requirements for long cycle life and high capacity batteries.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the shuttle inhibition efficiency of a modifying material to polysulfide in electrolyte is low, so that the battery has poor electrical property, thereby providing a sulfur, nitrogen and phosphorus doped porous carbon material, and preparation and application thereof.
Therefore, the invention provides the following technical scheme.
In a first aspect, the invention provides a sulfur, nitrogen and phosphorus doped porous carbon material, wherein the content of nitrogen element is more than 0 and less than or equal to 5 percent, the content of sulfur element is more than 0 and less than or equal to 2 percent, and the content of phosphorus element is more than 0 and less than or equal to 2 percent.
Further, at least one of the following conditions is satisfied:
(1) The specific surface area is 1000-3000m 2 /g；
(2) The sulfur, nitrogen and phosphorus doped porous carbon material is of a micro-mesoporous composite structure, and the pore size distribution is 0.6-10nm;
(3) The grain diameter is 5-50 μm.
In a second aspect, the invention provides a preparation method of a sulfur, nitrogen and phosphorus doped porous carbon material, which comprises the following steps:
step 1, mixing a phosphorus source, a nitrogen source and a carbon source, heating to 600-1000 ℃ under the protection of inert gas, preserving heat for 2-6h, and cooling to obtain a nitrogen and phosphorus doped precursor material;
step 2, mixing the precursor material doped with nitrogen and phosphorus with a sulfur simple substance, heating to 120-250 ℃ under the protection of inert gas, preserving heat for 6-12h, and cooling to obtain a sulfur-containing precursor;
and 3, heating the sulfur-containing precursor to 600-1300 ℃ under the protection of inert gas, and preserving heat for 1-6h to prepare the sulfur, nitrogen and phosphorus doped porous carbon material.
Further, the step 1 satisfies at least one of the conditions (1) to (6):
(1) A source of phosphorus, ammonium dihydrogen phosphate or diammonium hydrogen phosphate;
(2) The nitrogen source is ammonium dihydrogen phosphate or diammonium hydrogen phosphate;
(3) The carbon source is one or more of melamine, urea and glucose;
(4) The mass ratio of the sum of the phosphorus source and the nitrogen source to the carbon source is 1:1-1:5;
(5) The heating rate is 2-10 ℃/min;
(6) Mixing a phosphorus source, a nitrogen source and a carbon source, and then grinding.
Further, at least one of the conditions (1) to (5) is satisfied:
(1) In the step 2, the mass ratio of the nitrogen-phosphorus doped precursor material to the elemental sulfur is 1:2-10;
(2) In the step 2, the heating rate is 1-5 ℃/min;
(3) In the step 3, the heating rate is 2-10 ℃/min;
(4) In the step 3, the sulfur-containing precursor is ground and then heated;
(5) In the steps 1 to 3, the inert gas is at least one of nitrogen and argon.
In a third aspect, the invention provides a porous carbon material modified separator, wherein the porous carbon material is the sulfur, nitrogen and phosphorus doped porous carbon material or the sulfur, nitrogen and phosphorus doped porous carbon material prepared by the method.
In a fourth aspect, the invention provides a preparation method of a porous carbon material modified diaphragm, which comprises the following steps:
mixing the porous carbon material with a conductive additive and a binder, and adding a solvent to prepare slurry;
and coating the slurry on one side or two sides of the diaphragm, and drying to remove the solvent to obtain the diaphragm modified by the porous carbon material.
Further, at least one of the following conditions is satisfied:
(1) The solvent is one or more of deionized water, ethanol and N-methylpyrrolidone (NMP);
(2) The conductive additive is one or more of carbon black (SP), ketjen Black (KB) and Carbon Nano Tube (CNT);
(3) The binder is one or more of carboxymethyl cellulose (CMC), styrene-butadiene emulsion SBR, LA133, polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE);
(4) The thickness of the slurry coating is 50-200 microns;
(5) The drying temperature is 60-120 ℃;
(6) The mass ratio of the porous carbon material to the conductive additive to the binder is as follows: 80-97% of porous carbon material, 2-10% of conductive additive and 1-10% of binder.
In a fifth aspect, the invention provides a supercapacitor electrode material comprising the sulfur, nitrogen and phosphorus doped porous carbon material or the sulfur, nitrogen and phosphorus doped porous carbon material prepared according to the method.
In a sixth aspect, the invention provides a preparation method of a supercapacitor electrode material, which comprises the following steps:
mixing a sulfur, nitrogen and phosphorus doped porous carbon material with capacitance carbon, grinding and then carrying out ball milling to obtain a super capacitor electrode material;
optionally, the mass ratio of the sulfur, nitrogen and phosphorus doped porous carbon material to the capacitance carbon is 1:4-4:1;
optionally, the ball milling time is 1-6h; the ball milling mode is dry milling or wet milling, and ethanol or deionized water is added in the wet milling.
The technical scheme of the invention has the following advantages:
1. the sulfur, nitrogen and phosphorus doped porous carbon material provided by the invention contains, by mass, 0-5% of nitrogen element, 0-2% of sulfur element and 0-2% of phosphorus element. According to the invention, through the doping of the sulfur, nitrogen and phosphorus heteroatoms and the limitation of the doping amount, the adsorption of the porous carbon material to polysulfide can be enhanced, the conductivity of the porous carbon material is improved, and the reduction of the conductivity of the material due to excessive doping is avoided.
2. The sulfur, nitrogen and phosphorus doped porous carbon material provided by the invention meets at least one of the following conditions: (1) The specific surface area is 1000-3000m 2 (ii)/g; (2) a micro-mesoporous composite structure with pore size distribution of 0.6-10nm; (3) the grain diameter is 5-20 μm.
The high specific surface area allows the porous carbon material to have more active sites for adsorbing polysulfide; when used as an active material, the lithium ion composite material can provide more surface area and capacity for lithium ion adsorption. The micro-mesoporous composite structure is beneficial to the migration of ions, provides larger capacity under low multiplying power, does not obstruct the migration of ions under high multiplying power, and provides better multiplying power performance. The grain diameter is in the range, so that the pore utilization rate of the material cannot be reduced due to overlarge grain diameter, and the contact of the two-phase interface of the material and the electrolyte is facilitated; meanwhile, the conditions that more electron transfer resistances are possibly generated due to the fact that the particle size is too small and the uniformity is not good due to the agglomeration of materials are avoided.
3. The preparation method of the sulfur, nitrogen and phosphorus doped porous carbon material provided by the invention comprises the following steps:
step 1, mixing a phosphorus source, a nitrogen source and a carbon source, heating to 600-1000 ℃ under the protection of inert gas, preserving heat for 2-6h, and cooling to obtain a precursor material doped with nitrogen and phosphorus; step 2, mixing the precursor material doped with nitrogen and phosphorus with a sulfur simple substance, heating to 120-250 ℃ under the protection of inert gas, preserving heat for 6-12h, and cooling to obtain a sulfur-containing precursor; and 3, heating the sulfur-containing precursor to 600-1300 ℃ under the protection of inert gas, and preserving heat for 1-6h to prepare the sulfur, nitrogen and phosphorus doped porous carbon material.
According to the invention, a plurality of C-S are exposed on the surface of the porous carbon material by melting and filling sulfur into the carbon skeleton, most of sulfur is sublimated after the heat treatment in the step 3, and C originally bonded with sulfur on the surface of the porous carbon material has better affinity to sulfur, so that polysulfide in a lithium-sulfur battery can be adsorbed more favorably.
The invention adopts the sulfur simple substance to mix with the nitrogen and phosphorus doped precursor material for sulfur doping, only needs the waste gas end to process the tail gas, and has simple and convenient operation.
4. The double-electric-layer super capacitor stores energy by utilizing the porous structure and rich specific surface adsorption ions of the electrode material, no electrochemical reaction is generated in the energy storage process, and only the double-electric-layer effect of the electrode material is utilized, so that the energy density of the double-electric-layer super capacitor is low, and the power density is high. The supercapacitor stores energy through adsorption of ions on the surface of an active material, and the larger the specific surface area is, the more energy is stored. However, the conventional commercial electrode material for the super capacitor has a small specific surface and only contains a microporous structure, so that the conventional commercial electrode material is not beneficial to ion migration under high magnification, is not beneficial to the magnification performance of the super capacitor, and has low pore utilization rate. According to the invention, the porous carbon material containing the micro-mesoporous structure is mixed with the commercial electrode material (capacitance carbon), so that a higher specific surface area and a more appropriate pore structure are provided, and the energy density, the capacity retention rate under high power and the pore utilization rate of the super capacitor are improved.
The porous carbon material doped with the heteroatoms is beneficial to the infiltration of electrolyte and higher ion migration rate, improves the interface contact between an electrode material and the electrolyte and reduces the impedance of the super capacitor. According to the invention, the supercapacitor electrode is improved by adopting the porous carbon material with high specific surface area and adsorption activity so as to obtain higher energy density and better rate performance.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a preparation method of a sulfur, nitrogen and phosphorus doped porous carbon material, which comprises the following steps:
step 1, mixing 8g of diammonium hydrogen phosphate and 12g of glucose, grinding uniformly, placing the mixture in a porcelain ark, transferring the porcelain ark into a tube furnace, heating to 800 ℃ at a speed of 5 ℃/min under the protection of argon, preserving heat for 4 hours, and naturally cooling (namely cooling along with the furnace) to obtain a precursor material doped with nitrogen and phosphorus;
step 2, mixing the precursor material doped with nitrogen and phosphorus with 8g of sublimed sulfur, grinding uniformly, transferring into a porcelain ark, placing the porcelain ark into a tube furnace, heating the tube furnace to 200 ℃ at the speed of 1 ℃/min under the protection of argon, preserving heat for 12h, and naturally cooling to obtain a sulfur-containing precursor;
and 3, uniformly grinding the sulfur-containing precursor, transferring the sulfur-containing precursor into a ceramic square boat, placing the ceramic square boat into a tube furnace, heating to 1100 ℃ at a speed of 5 ℃/min under the protection of argon, preserving heat for 4 hours, and naturally cooling to obtain the sulfur, nitrogen and phosphorus doped porous carbon material.
The porous carbon material doped with sulfur, nitrogen and phosphorus prepared in the embodiment is doped with 1.3% of nitrogen element, 0.5% of sulfur element and 0.2% of phosphorus element.
The specific surface area is 1382m 2 (ii)/g; the pore size distribution is 2.3-6.8nm; the grain diameter is 30 +/-5 mu m.
Example 2
The embodiment provides a preparation method of a sulfur, nitrogen and phosphorus doped porous carbon material, which comprises the following steps:
step 1, mixing 8g of diammonium hydrogen phosphate and 10g of urea, uniformly grinding, placing the mixture in a porcelain ark, transferring the porcelain ark into a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the protection of argon, preserving heat for 6 hours, and naturally cooling to obtain a nitrogen and phosphorus doped precursor material;
step 2, mixing the precursor material doped with nitrogen and phosphorus with 6g of sublimed sulfur, grinding uniformly, transferring into a porcelain ark, placing the porcelain ark into a tube furnace, heating the tube furnace to 180 ℃ at a speed of 2 ℃/min under the protection of argon, preserving heat for 10h, and naturally cooling to obtain a sulfur-containing precursor;
and 3, uniformly grinding the sulfur-containing precursor, transferring the sulfur-containing precursor into a ceramic square boat, placing the ceramic square boat into a tube furnace, heating to 1300 ℃ at the speed of 2 ℃/min under the protection of argon, preserving heat for 2 hours, and naturally cooling to obtain the sulfur, nitrogen and phosphorus doped porous carbon material.
The porous carbon material doped with sulfur, nitrogen and phosphorus prepared in the embodiment is doped with 2.5% of nitrogen element, 0.36% of sulfur element and 0.16% of phosphorus element.
Specific surface area of 2316m 2 (iv) g; the pore size distribution is 0.6-5.1nm; the particle size is 10 +/-5 mu m.
Example 3
The embodiment provides a preparation method of a sulfur, nitrogen and phosphorus doped porous carbon material, which comprises the following steps:
step 1, mixing 5g of ammonium dihydrogen phosphate and 5g of melamine, grinding uniformly, placing the mixture in a porcelain ark, transferring the porcelain ark into a tube furnace, heating to 1000 ℃ at a speed of 8 ℃/min under the protection of argon, preserving the temperature for 2h, and naturally cooling to obtain a nitrogen and phosphorus doped precursor material;
step 2, mixing the precursor material doped with nitrogen and phosphorus with 5g of sublimed sulfur, uniformly grinding, transferring the mixture into a porcelain ark, placing the porcelain ark into a tube furnace, heating the tube furnace to 220 ℃ at a speed of 2 ℃/min under the protection of argon, preserving heat for 6h, and naturally cooling to obtain a sulfur-containing precursor;
and 3, uniformly grinding the sulfur-containing precursor, transferring the sulfur-containing precursor into a ceramic square boat, placing the ceramic square boat into a tubular furnace, heating to 1000 ℃ at a speed of 5 ℃/min under the protection of argon, preserving heat for 6 hours, and naturally cooling to obtain the sulfur, nitrogen and phosphorus doped porous carbon material.
The porous carbon material doped with sulfur, nitrogen and phosphorus prepared in the embodiment is doped with 3.1% of nitrogen element, 0.8% of sulfur element and 0.12% of phosphorus element.
The specific surface area is 2542m 2 (ii)/g; the pore size distribution is 0.8-4.3nm; the particle size is 12 +/-5 mu m.
Example 4
The embodiment provides a diaphragm modified by a porous carbon material, the porous carbon material adopts the sulfur, nitrogen and phosphorus doped porous carbon material prepared in the embodiment 2, and the preparation method comprises the following steps:
mixing 80mg of the porous carbon material with 10mg of conductive additive SP and 10mg of binder CMC/SBR emulsion, and adding 3g of solvent deionized water to prepare slurry;
coating the slurry on one side of the diaphragm, wherein the coating thickness is 100 micrometers; and drying at 80 ℃ to remove the solution, thereby obtaining the diaphragm modified by the porous carbon material.
Example 5
The embodiment provides a diaphragm modified by a porous carbon material, the porous carbon material adopts the sulfur, nitrogen and phosphorus doped porous carbon material prepared in the embodiment 3, and the preparation method comprises the following steps:
mixing 80mg of the porous carbon material, 10mg of conductive additive KB and 10mg of binder PVDF, and adding 3g of NMP to prepare slurry;
coating the slurry on one side of the diaphragm, wherein the coating thickness is 150 micrometers; and drying at 120 ℃ to remove the solution, thereby obtaining the diaphragm modified by the porous carbon material.
Example 6
The embodiment provides a supercapacitor electrode material, which is prepared by mixing 90mg of the sulfur, nitrogen and phosphorus doped porous carbon material prepared in the embodiment 1 and 90mg of capacitance carbon YP-50, and performing ball milling for 3 hours after grinding in a manner of adding ethanol for wet grinding and drying.
The embodiment also provides a preparation method of the supercapacitor electrode plate, the supercapacitor electrode material prepared in the embodiment is mixed with 10mg of PVDF and 10mg of SP in NMP, and the mixture is mixed for 2 hours by using a mixer to obtain supercapacitor electrode material slurry. And soaking the foamed nickel in the slurry for 10s, taking out and drying to obtain the pole piece.
Comparative example 1
This comparative example is substantially the same as example 1 except that it does not include step 2.
The porous carbon material doped with sulfur, nitrogen and phosphorus prepared in the embodiment is doped with 1.6% of nitrogen element, 0% of sulfur element and 0.2% of phosphorus element.
Test example 1
The porous carbon material modified membranes prepared in the embodiments 4 and 5 are respectively assembled into the lithium-sulfur button cell, the nitrogen and phosphorus doped porous carbon material prepared in the comparative example 1 is prepared into the porous carbon material modified membrane by the same process as the embodiment 4, and the lithium-sulfur button cell is assembled. The assembled cell was subjected to electrochemical performance testing.
The assembly process comprises the following steps: the negative electrode used was a 14mm diameter lithium sheet, the separator used was the separator prepared in comparative example 1 of examples 4 and 5, and cut into a 19mm diameter, and the positive electrode used 60% graphite, 20% sulfur, 10% SP, 10% PVDF coated on a copper foil, and dried and cut into a 12mm pole piece.
The test process comprises the following steps: the battery was subjected to a charge-discharge cycle test using the LAND test system. The test voltage interval is 1.6-2.8V, after circulating for 5 circles with 0.1C current, 0.2C circulates for 5 circles, 0.5C circulates for 5 circles, 1C circulates for 5 circles, 2C circulates for 5 circles, and then 1C circulates to 1000 circles.
The test results are shown in Table 1.
TABLE 1 Battery Electrical Properties
As can be seen from Table 1, the capacity, the cycle performance and the rate performance of the lithium-sulfur button battery assembled by the porous carbon material modified diaphragm prepared by the method are obviously improved.
Test example 2
A supercapacitor was prepared using the supercapacitor electrode material prepared in example 6, and a capacitor was prepared using a pure commercial capacitive carbon material as comparative example 2. And carrying out charge-discharge cycle test performance test on the assembled super capacitor.
The test process comprises the following steps: organic electrolyte (1M TEABF) for super capacitor 4 Acetonitrile ACN solution) with a test voltage interval of 0-2.5V, and performing performance test on the supercapacitor by using a LAND circulating system, wherein the test voltage interval is firstly circulated for 10 circles at 0.1A/g, then circulated for 10 circles at 0.2, 0.5, 1, 2, 3, 5 and 10A/g respectively, and finally circulated for 20000 circles at 1A/g.
The test results are shown in Table 2.
TABLE 2 ultracapacitor Electrical Properties
According to the table 2, the specific capacity, the rate capability and the cycle performance of the super capacitor prepared by the super capacitor electrode material are obviously improved.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The sulfur, nitrogen and phosphorus doped porous carbon material is characterized in that the content of nitrogen is more than 0 and less than or equal to 5 percent, the content of sulfur is more than 0 and less than or equal to 2 percent, and the content of phosphorus is more than 0 and less than or equal to 2 percent.
2. A sulfur, nitrogen, phosphorus doped porous carbon material according to claim 1, characterized in that at least one of the following conditions is fulfilled:
(1) The specific surface area is 1000-3000m 2 /g；
(2) The sulfur, nitrogen and phosphorus doped porous carbon material is of a micro-mesoporous composite structure, and the pore size distribution is 0.6-10nm;
(3) The grain diameter is 5-50 μm.
3. A method for preparing a sulfur, nitrogen, phosphorus doped porous carbon material according to claim 1 or 2, comprising the steps of:
step 1, mixing a phosphorus source, a nitrogen source and a carbon source, heating to 600-1000 ℃ under the protection of inert gas, preserving heat for 2-6h, and cooling to obtain a nitrogen and phosphorus doped precursor material;
step 2, mixing the precursor material doped with nitrogen and phosphorus with a sulfur simple substance, heating to 120-250 ℃ under the protection of inert gas, preserving heat for 6-12h, and cooling to obtain a sulfur-containing precursor;
and 3, heating the sulfur-containing precursor to 600-1300 ℃ under the protection of inert gas, and preserving heat for 1-6h to prepare the sulfur, nitrogen and phosphorus doped porous carbon material.
4. The method for producing a sulfur, nitrogen, phosphorus-doped porous carbon material according to claim 3, wherein the step 1 satisfies at least one of conditions (1) to (6):
(1) A source of phosphorus, ammonium dihydrogen phosphate or diammonium hydrogen phosphate;
(2) The nitrogen source is ammonium dihydrogen phosphate or diammonium hydrogen phosphate;
(3) The carbon source is one or more of melamine, urea and glucose;
(4) The mass ratio of the sum of the phosphorus source and the nitrogen source to the carbon source is 1:1-1:5;
(5) The heating rate is 2-10 ℃/min;
(6) Mixing a phosphorus source, a nitrogen source and a carbon source, and then grinding.
5. The method for producing a sulfur, nitrogen, phosphorus-doped porous carbon material according to claim 3, wherein at least one of conditions (1) to (5) is satisfied:
(1) In the step 2, the mass ratio of the nitrogen-phosphorus doped precursor material to the elemental sulfur is 1:2-10;
(2) In the step 2, the heating rate is 1-5 ℃/min;
(3) In the step 3, the heating rate is 2-10 ℃/min;
(4) In the step 3, the sulfur-containing precursor is ground and then heated;
(5) In the steps 1 to 3, the inert gas is at least one of nitrogen and argon.
6. A porous carbon material-modified separator, wherein the porous carbon material is the sulfur, nitrogen, or phosphorus-doped porous carbon material according to claim 1 or 2, or the sulfur, nitrogen, or phosphorus-doped porous carbon material produced by the method according to any one of claims 3 to 5.
7. The method for preparing a porous carbon material-modified separator according to claim 6, comprising the steps of:
mixing the porous carbon material with a conductive additive and a binder, and adding a solvent to prepare slurry;
and coating the slurry on one side or two sides of the diaphragm, and drying to remove the solvent to obtain the diaphragm modified by the porous carbon material.
8. The method for producing a porous carbon material-modified separator according to claim 7, characterized in that at least one of the following conditions is satisfied:
(1) The solvent is one or more of deionized water, ethanol and NMP;
(2) The conductive additive is one or more of SP, KB and CNT;
(3) The binder is one or more of CMC, SBR, LA133, PVDF and PTFE;
(4) The thickness of the slurry coating is 50-200 microns;
(5) The drying temperature is 60-120 ℃;
(6) The mass ratio of the porous carbon material to the conductive additive to the binder is as follows: 80-97% of porous carbon material, 2-10% of conductive additive and 1-10% of binder.
9. A supercapacitor electrode material comprising a sulfur, nitrogen, phosphorus doped porous carbon material according to claim 1 or 2 or a sulfur, nitrogen, phosphorus doped porous carbon material prepared according to the method of any one of claims 3 to 5.
10. The preparation method of the electrode material of the supercapacitor according to claim 9, characterized by comprising the following steps:
mixing a sulfur, nitrogen and phosphorus doped porous carbon material with capacitance carbon, grinding and then carrying out ball milling to obtain a super capacitor electrode material;
optionally, the mass ratio of the sulfur, nitrogen and phosphorus doped porous carbon material to the capacitance carbon is 1:4-4:1;
optionally, the ball milling time is 1-6h; the ball milling mode is dry milling or wet milling, and ethanol or deionized water is added in the wet milling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211696930.6A CN115893371A (en) | 2022-12-28 | 2022-12-28 | Sulfur, nitrogen and phosphorus doped porous carbon material and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211696930.6A CN115893371A (en) | 2022-12-28 | 2022-12-28 | Sulfur, nitrogen and phosphorus doped porous carbon material and preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115893371A true CN115893371A (en) | 2023-04-04 |
Family
ID=86493822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211696930.6A Pending CN115893371A (en) | 2022-12-28 | 2022-12-28 | Sulfur, nitrogen and phosphorus doped porous carbon material and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115893371A (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105938900A (en) * | 2016-06-20 | 2016-09-14 | 北京理工大学 | Research of surface-modified nitrogen-doped porous carbon-sulfur composite material in positive electrode of lithium-sulfur battery |
| CN107887613A (en) * | 2017-10-18 | 2018-04-06 | 温州大学 | Oxygen reduction electrode and preparation method and application based on three-dimensional netted nitrogen phosphorus sulphur codope porous carbon materials |
| CN108281628A (en) * | 2018-01-05 | 2018-07-13 | 武汉理工大学 | Zinc cobalt sulfide/nitrogen-doped carbon composite material and preparation method and application |
| CN108313999A (en) * | 2018-01-31 | 2018-07-24 | 华南理工大学 | A kind of preparation method of nitrogen, sulphur, phosphorus heteroatoms doping carbon material |
| CN108529619A (en) * | 2018-05-21 | 2018-09-14 | 桂林电子科技大学 | A kind of nitrogen sulphur codope porous carbon materials and its preparation method and application |
| CN109786691A (en) * | 2018-12-24 | 2019-05-21 | 肇庆市华师大光电产业研究院 | A kind of kalium ion battery negative electrode material and preparation method thereof |
| CN110176597A (en) * | 2019-06-20 | 2019-08-27 | 西北师范大学 | A kind of preparation and application of biomass carbon/sulphur composite material |
| CN113224464A (en) * | 2020-01-17 | 2021-08-06 | 南京理工大学 | Lithium-sulfur battery taking CoS/NS co-doped graphene composite material coated diaphragm as intermediate layer |
| CN113471455A (en) * | 2021-07-01 | 2021-10-01 | 湖南理工学院 | Cobalt disulfide/nitrogen and sulfur co-doped mesoporous carbon composite catalyst for zinc-air battery and preparation method thereof |
| CN113871607A (en) * | 2021-09-13 | 2021-12-31 | 常州大学 | Halide-doped carbon/sulfur positive electrode material and preparation method and application thereof |
| CN115020722A (en) * | 2022-06-15 | 2022-09-06 | 哈尔滨工业大学（威海） | Preparation method of bimetallic nitrogen-containing porous carbon catalyst |
| CN115411251A (en) * | 2022-09-23 | 2022-11-29 | 惠州亿纬锂能股份有限公司 | Negative electrode material and preparation method and application thereof |
-
2022
- 2022-12-28 CN CN202211696930.6A patent/CN115893371A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105938900A (en) * | 2016-06-20 | 2016-09-14 | 北京理工大学 | Research of surface-modified nitrogen-doped porous carbon-sulfur composite material in positive electrode of lithium-sulfur battery |
| CN107887613A (en) * | 2017-10-18 | 2018-04-06 | 温州大学 | Oxygen reduction electrode and preparation method and application based on three-dimensional netted nitrogen phosphorus sulphur codope porous carbon materials |
| CN108281628A (en) * | 2018-01-05 | 2018-07-13 | 武汉理工大学 | Zinc cobalt sulfide/nitrogen-doped carbon composite material and preparation method and application |
| CN108313999A (en) * | 2018-01-31 | 2018-07-24 | 华南理工大学 | A kind of preparation method of nitrogen, sulphur, phosphorus heteroatoms doping carbon material |
| CN108529619A (en) * | 2018-05-21 | 2018-09-14 | 桂林电子科技大学 | A kind of nitrogen sulphur codope porous carbon materials and its preparation method and application |
| CN109786691A (en) * | 2018-12-24 | 2019-05-21 | 肇庆市华师大光电产业研究院 | A kind of kalium ion battery negative electrode material and preparation method thereof |
| CN110176597A (en) * | 2019-06-20 | 2019-08-27 | 西北师范大学 | A kind of preparation and application of biomass carbon/sulphur composite material |
| CN113224464A (en) * | 2020-01-17 | 2021-08-06 | 南京理工大学 | Lithium-sulfur battery taking CoS/NS co-doped graphene composite material coated diaphragm as intermediate layer |
| CN113471455A (en) * | 2021-07-01 | 2021-10-01 | 湖南理工学院 | Cobalt disulfide/nitrogen and sulfur co-doped mesoporous carbon composite catalyst for zinc-air battery and preparation method thereof |
| CN113871607A (en) * | 2021-09-13 | 2021-12-31 | 常州大学 | Halide-doped carbon/sulfur positive electrode material and preparation method and application thereof |
| CN115020722A (en) * | 2022-06-15 | 2022-09-06 | 哈尔滨工业大学（威海） | Preparation method of bimetallic nitrogen-containing porous carbon catalyst |
| CN115411251A (en) * | 2022-09-23 | 2022-11-29 | 惠州亿纬锂能股份有限公司 | Negative electrode material and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| 张义永: "《锂硫电池原理及正极的设计与构建》", 30 April 2020, 冶金工业出版社, pages: 38 - 41 * |
| 曾晓苑: "《碳基复合材料的制备及其在能源存储中的应用》", 31 March 2021, 冶金工业出版社, pages: 319 - 320 * |
| 武鲁明等: "多孔碳材料的制备及其金属磷化物氧还原性能研究", 《无机盐工业》, 22 August 2022 (2022-08-22) * |
| 肖成伟: "《电动汽车工程手册 第4卷 动力蓄电池》", 31 January 2020, 机械工业出版社, pages: 408 - 409 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109314228B (en) | Sulfur-carbon composite and lithium-sulfur battery comprising same | |
| Wang et al. | A lightweight multifunctional interlayer of sulfur–nitrogen dual-doped graphene for ultrafast, long-life lithium–sulfur batteries | |
| Zheng et al. | Ultralight carbon flakes modified separator as an effective polysulfide barrier for lithium-sulfur batteries | |
| Shi et al. | Si nanoparticles adhering to a nitrogen-rich porous carbon framework and its application as a lithium-ion battery anode material | |
| WO2013073526A1 (en) | Electrode for electricity storage devices, electricity storage device, and method for producing electrode for electricity storage devices | |
| EP3168905A1 (en) | Carbon composites | |
| CN109417171B (en) | Adjustable and mass-producible synthesis of graded porous nanocarbon/sulfur composite cathodes | |
| Liao et al. | Novel flower-like hierarchical carbon sphere with multi-scale pores coated on PP separator for high-performance lithium-sulfur batteries | |
| Cheng et al. | Oxidized multiwall carbon nanotube modified separator for high performance lithium–sulfur batteries with high sulfur loading | |
| CN111244455A (en) | Silicon-carbon composite negative electrode material composite conductive agent of lithium ion battery, negative plate and preparation method of negative plate | |
| CN111263993B (en) | Sulfur-carbon composite material, preparation method thereof and lithium secondary battery comprising sulfur-carbon composite material | |
| Mao et al. | Electrospinning synthesis of Co 3 O 4@ C nanofibers as a high-performance anode for sodium ion batteries | |
| CN108232176B (en) | Lithium-sulfur battery cathode material and preparation method thereof | |
| CN113659125A (en) | Silicon-carbon composite material and preparation method thereof | |
| Yang et al. | Hollow MnO2 spheres/porous reduced graphene oxide as a cathode host for high-performance lithium-sulfur batteries | |
| Cao et al. | Transformation of ZIF-8 nanoparticles into 3D nitrogen-doped hierarchically porous carbon for Li–S batteries | |
| CN112768678A (en) | Negative electrode material, preparation method thereof and lithium ion battery | |
| Xiaogang et al. | DTT-doped MWCNT coating for checking shuttle effect of lithium-sulfur battery | |
| US20220293946A1 (en) | A Cathode Material and a Method of Preparing The Same | |
| CN116825951A (en) | Negative plate and sodium ion battery | |
| CN111244370A (en) | Polyamine carbon composite material, slurry, diaphragm, lithium-sulfur battery and preparation method | |
| CN110993883A (en) | Electrode plate and preparation method and application thereof | |
| CN116387472A (en) | Negative electrode slurry of sodium ion battery, negative electrode plate and sodium ion battery | |
| Cui et al. | Na-X zeolite templated and sulfur-impregnated porous carbon as the cathode for a high-performance Li–S battery | |
| CN115893371A (en) | Sulfur, nitrogen and phosphorus doped porous carbon material and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |