CN114678505B - Sulfur-phosphorus co-doped hard carbon composite material and preparation method thereof - Google Patents
Sulfur-phosphorus co-doped hard carbon composite material and preparation method thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000007833 carbon precursor Substances 0.000 claims abstract description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 8
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- 238000010000 carbonizing Methods 0.000 claims abstract description 7
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- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
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- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 6
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 5
- 239000005416 organic matter Substances 0.000 claims abstract description 5
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
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- 239000011257 shell material Substances 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- 239000000126 substance Substances 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
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- 239000000203 mixture Substances 0.000 claims description 4
- 239000005959 Fosthiazate Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- YASYVMFAVPKPKE-UHFFFAOYSA-N acephate Chemical compound COP(=O)(SC)NC(C)=O YASYVMFAVPKPKE-UHFFFAOYSA-N 0.000 claims description 3
- DUFVKSUJRWYZQP-UHFFFAOYSA-N fosthiazate Chemical compound CCC(C)SP(=O)(OCC)N1CCSC1=O DUFVKSUJRWYZQP-UHFFFAOYSA-N 0.000 claims description 3
- 229920005546 furfural resin Polymers 0.000 claims description 3
- NNKVPIKMPCQWCG-UHFFFAOYSA-N methamidophos Chemical compound COP(N)(=O)SC NNKVPIKMPCQWCG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 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 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 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
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
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- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
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- -1 sulfur-phosphorus compound Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
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- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
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- 239000011889 copper foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- LJOPFCHCRGVYCR-UHFFFAOYSA-N [C].[C].[S] Chemical compound [C].[C].[S] LJOPFCHCRGVYCR-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- BFZUFHPKKNHSAG-UHFFFAOYSA-N [N].[P].[S] Chemical compound [N].[P].[S] BFZUFHPKKNHSAG-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000005213 imbibition Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 229920000767 polyaniline Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 238000005096 rolling process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- 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
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Abstract
The invention discloses a sulfur-phosphorus co-doped hard carbon composite material and a preparation method thereof, wherein the composite material is of a core-shell structure, a shell is nitrogen-containing amorphous carbon, and the mass of the shell accounts for 1-10% of the mass of the composite material. The mass ratio of sulfur atom in the inner core is 1.11-1.88%, the mass ratio of phosphorus atom in the inner core is 1.88-2.23%, and the rest is hard carbon. The preparation method comprises the following steps: adding hydrocarbon, sulfur-phosphorus organic matter and nitrogen-containing polymer into an organic solvent to prepare an organic solution, adding the organic solution into a high-pressure reaction kettle for reaction, filtering, and freeze-drying the filtered powder to obtain a porous hard carbon precursor; adding dilute hydrochloric acid solution and porous hard carbon precursor into oxidant solution in turn, reacting for 12-72h at 0-4 ℃ after uniform ultrasonic dispersion, cleaning with 10% dilute hydrochloric acid, vacuum drying, grinding, transferring to a tubular furnace, and carbonizing in argon inert atmosphere to obtain the catalyst. The invention can improve the specific capacity, give consideration to the power performance and the first efficiency and reduce the impedance.
Description
Technical Field
The invention belongs to the field of preparation of lithium ion battery materials, and particularly relates to a sulfur-phosphorus co-doped hard carbon composite material and a preparation method of the sulfur-phosphorus co-doped hard carbon composite material.
Background
The hard carbon is non-graphitizable amorphous carbon, has large interlayer spacing, good rapid charge and discharge performance, and especially excellent low-temperature charge and discharge performance. At present, hard carbon is mainly prepared from high molecular polymer materials, such as coconut shells, starch, resin and the like, wherein the high molecular polymer generates air holes in the pyrolysis process, so that the specific surface area of the hard carbon is higher, moisture and oxygen are easily absorbed, side reactions are more, the first coulombic efficiency is lower, the effective specific capacity is lower (about 300 mAh/g), the electronic conductivity deviation (lower than one order of magnitude of graphite) is caused by a porous structure, and in order to further improve the electronic conductivity of the hard carbon material, a material with high conductivity needs to be doped and coated. For example, phosphorus doping improves the specific capacity of the material, nitrogen doping improves the electronic conductivity of the material, boron doping improves the interlayer spacing of the material, sulfur doping improves the rate capability of the material, but the existence of single element or compound doping only improves one performance of the material, while other performances are not improved. For example, chinese patent publication No. CN202110908449.8 discloses "a phosphorus-nitrogen doped biomass hard carbon material, a preparation method thereof, and an application thereof at 8/9/2021, in which phosphorus atoms are doped between carbon layers in a composite material prepared by the method, the carbon layer spacing is increased, and surface active sites are increased, and a negative electrode material has a higher specific capacity, good conductivity, small polarization, a lower first coulombic efficiency, and a good cycle performance, but has a problem that the first efficiency and the specific capacity cannot be considered at the same time.
Disclosure of Invention
The invention aims to overcome the defects and provide the sulfur-phosphorus co-doped hard carbon composite material which can improve the specific capacity, give consideration to the power performance and the first efficiency and reduce the resistance.
The invention also aims to provide a preparation method of the sulfur-phosphorus co-doped hard carbon composite material.
The invention relates to a sulfur-phosphorus co-doped hard carbon composite material, which comprises the following components in percentage by weight: the composite material is of a core-shell structure, the inner core is hard carbon containing sulfur and phosphorus, the outer shell is amorphous carbon containing nitrogen, and the mass of the outer shell accounts for 1-10% of the mass of the composite material.
The sulfur-phosphorus co-doped hard carbon composite material comprises the following components in parts by weight: the mass ratio of sulfur atoms in the inner core is 1.11-1.88%, the mass ratio of phosphorus atoms in the inner core is 1.88-2.23%, and the balance is hard carbon.
The preparation method of the sulfur-phosphorus co-doped hard carbon composite material comprises the following steps:
(1) According to the mass ratio of 100:1 to 20: 1-10, weighing hydrocarbon, sulfur-phosphorus organic matter and nitrogen-containing polymer, adding the hydrocarbon, sulfur-phosphorus organic matter and nitrogen-containing polymer into an organic solvent to prepare an organic solution, then adding the organic solution into a high-pressure reaction kettle, reacting for 1-6 h at the temperature of 100-200 ℃ and the pressure of 1-5 Mpa, filtering, and freeze-drying powder obtained after filtering for 24h at the temperature of-40 ℃ to obtain a porous hard carbon precursor;
(2) Preparing 0.5-5 wt% of oxidant solution, sequentially adding 10% of dilute hydrochloric acid solution (the volume is 5% of the oxidant solution), porous hard carbon precursor, wherein the mass ratio of the oxidant solution to the porous hard carbon precursor is 1-10, reacting at 0-4 ℃ for 12-72h after uniform ultrasonic dispersion, cleaning with 10% of dilute hydrochloric acid, vacuum drying at 80 ℃ for 24h, grinding until the granularity D50 is 5-20 micrometers, transferring to a tubular furnace, and carbonizing at 700-1000 ℃ for 1-6 h under the inert atmosphere of argon gas to obtain the hard carbon composite material.
The preparation method of the sulfur-phosphorus co-doped hard carbon composite material comprises the following steps: the hydrocarbon in the step (1) is one of phenolic resin, furfural resin, epoxy resin, coconut shell, starch, glucose or sucrose;
the preparation method of the sulfur-phosphorus co-doped hard carbon composite material comprises the following steps: the sulfur-phosphorus organic matter in the step (1) is one of methamidophos, acephate or fosthiazate;
the preparation method of the sulfur-phosphorus co-doped hard carbon composite material comprises the following steps: the nitrogen-containing polymer in the step (1) is one of aniline, thiophene, pyrrole or urea;
the preparation method of the sulfur-phosphorus co-doped hard carbon composite material comprises the following steps: the organic solvent in the step (1) is carbon tetrachloride or cyclohexane.
The preparation method of the sulfur-phosphorus co-doped hard carbon composite material comprises the following steps: the oxidant in the step (2) is (NH) 4 ) 2 S 2 O 8 、H 2 O 2 、K 2 Cr 2 O 7 Or KIO 3 To (3) is provided.
Compared with the prior art, the invention has obvious beneficial effects, and the technical scheme can be seen as follows: according to the invention, the phosphorus atoms are doped in the hard carbon of the inner core, the lithium storage active points of the material are improved by utilizing the hole formed by the catalytic action of the sulfur-phosphorus compound in the preparation process, the energy density is improved by utilizing the high specific capacity of the phosphorus, the sulfur atoms are doped between carbon layers, the carbon layer spacing is increased, the surface active sites are increased, the lithium ion migration rate can be greatly increased, and the power performance is improved. Meanwhile, sulfur atoms form a crosslinking effect between carbon-carbon chemical bonds, namely the carbon-sulfur-carbon chemical bonds improve the structural stability of the material and improve the cycle performance.
The shell is firstly coated with organic compounds such as aniline and the like, then the organic compounds such as polyaniline and the like are formed by polymerization and carbonized to obtain nitrogen-containing amorphous carbon which has the characteristics of high electronic conductivity and stable and strong structure, low impedance and the like of-C-N-chemical bond, and the cycle performance and the power performance are improved; meanwhile, the surface of the inner core is coated with an amorphous lifting material, so that the first efficiency is further improved.
Drawings
Fig. 1 is an SEM image of a hard carbon composite prepared in example 1.
Detailed Description
Example 1
A preparation method of a sulfur-phosphorus co-doped hard carbon composite material comprises the following steps:
(1) Weighing 100g of phenolic resin, 10g of methamidophos and 5g of aniline, adding the materials into 500ml of carbon tetrachloride, carrying out ultrasonic dispersion uniformly, transferring the mixture into a high-pressure reaction kettle, reacting for 3 hours at the temperature of 150 ℃ and the pressure of 3Mpa, filtering, and freeze-drying the obtained powder for 24 hours at the temperature of minus 40 ℃ to obtain a porous hard carbon precursor;
(2) Adding 5g (NH 4) 2S2O8 into 500ml deionized water to prepare a 1% solution, sequentially adding 10ml of dilute hydrochloric acid solution (10 wt%), 100g of porous hard carbon precursor, performing ultrasonic dispersion uniformly, reacting at 0-4 ℃ for 48h, cleaning with dilute hydrochloric acid (10 wt%), performing vacuum drying at 80 ℃ for 24h, grinding to 10 micrometers, transferring to a tubular furnace, and carbonizing at 800 ℃ for 3h under the inert atmosphere of argon to obtain the hard carbon composite material.
Example 2
A preparation method of a sulfur-phosphorus co-doped hard carbon composite material comprises the following steps:
(1) Weighing 100g of furfural resin, 1g of acephate and 1g of thiophene, adding the materials into 500ml of cyclohexane, performing ultrasonic dispersion uniformly, transferring the materials into a high-pressure reaction kettle, reacting for 6 hours at the temperature of 100 ℃ and the pressure of 5Mpa, filtering, and performing freeze drying on the obtained powder for 24 hours at the temperature of-40 ℃ to obtain a porous hard carbon precursor;
(2) Adding 1g of K2Cr2O7 into 200ml of deionized water to prepare a 0.5% solution, sequentially adding 1ml of dilute hydrochloric acid solution (10 wt%), 100g of porous hard carbon precursor, uniformly dispersing by ultrasonic, reacting at 0-4 ℃ for 12h, cleaning with dilute hydrochloric acid (10 wt%), drying at 80 ℃ in vacuum for 24h, grinding to 5 microns, transferring to a tube furnace, and carbonizing at 700 ℃ for 6h under the inert atmosphere of argon to obtain the hard carbon composite material.
Example 3
A preparation method of a sulfur-phosphorus co-doped hard carbon composite material comprises the following steps:
(1) Weighing 100g of coconut shell, 20g of fosthiazate and 10g of pyrrole, adding into 500ml of cyclohexane organic solvent, performing ultrasonic dispersion uniformly, transferring into a high-pressure reaction kettle, reacting for 1h at 200 ℃ and 1Mpa, filtering, and freeze-drying the obtained powder for 24h at-40 ℃ to obtain a porous hard carbon precursor;
(2) Adding 10g of H2O2 into 200ml of deionized water to prepare a 5wt% solution, sequentially adding 10ml of dilute hydrochloric acid solution (10 wt%), 100g of porous hard carbon precursor, performing ultrasonic dispersion uniformly, reacting at 0-4 ℃ for 72h, cleaning with dilute hydrochloric acid (10 wt%), performing vacuum drying at 80 ℃ for 24h, grinding to 20 micrometers, transferring to a tubular furnace, and carbonizing at 1000 ℃ for 1h under an argon inert atmosphere to obtain the hard carbon composite material.
Comparative example:
weighing 100g of phenolic resin, adding the phenolic resin into 500ml of carbon tetrachloride organic solvent, uniformly dispersing by ultrasonic, transferring the phenolic resin into a high-pressure reaction kettle, reacting at 150 ℃ and 3Mpa for 3h, filtering, and drying at 80 ℃ in vacuum for 24h to obtain a hard carbon precursor, grinding the hard carbon precursor to 10 micrometers, transferring the hard carbon precursor into a tubular furnace, and carbonizing the hard carbon precursor for 3h at 800 ℃ in an argon inert atmosphere to obtain the hard carbon composite material.
Test example 1: SEM test
Fig. 1 is an SEM image of the hard carbon composite material prepared in example 1, and it can be seen from fig. 1 that the material has a granular structure with a reasonable size distribution and a grain size of 3 to 8 μm.
Test example 2: physicochemical Properties and button cell test thereof
The hard carbon composite materials prepared in examples 1 to 3 and comparative example were subjected to particle size, tap density, specific surface area, interlayer distance, powder resistivity and specific capacity tests.
The test method comprises the following steps: GB/T-243358-2019 graphite cathode material for lithium ion batteries:
the hard carbon composite materials obtained in the examples 1-3 and the comparative example are respectively used as lithium ion battery cathode materials to assemble button cells A1, A2, A3 and B1; the preparation method comprises the following steps: adding a binder, a conductive agent and a solvent into the negative electrode material, stirring and pulping, coating the mixture on a copper foil, and drying and rolling the copper foil to obtain the copper-clad laminate. The binder used was LA132 binder, conductive agent SP, negative electrode materials prepared in examples 1 to 3 and comparative example, respectively, and the solvent was redistilled water in the following proportions: and (3) anode material: SP: LA132: double distilled water =95g:1g:4g:220mL, and preparing a negative pole piece; the electrolyte is LiPF6/EC + DEC (volume ratio is 1, concentration is 1.3 mol/L), the metal lithium sheet is a counter electrode, the diaphragm is made of Polyethylene (PE), the simulated battery is assembled in an argon-filled glove box, the electrochemical performance is performed on a Wuhan blue electricity CT2001A type battery tester, the charging and discharging voltage range is 0.00V-2.0V, and the charging and discharging rate is 0.1C. The multiplying power (2C, 0.1C) and the cycle performance (0.2C/0.2C, 200 times) of the button cell battery are tested at the same time. The test data are detailed in table 1.
As can be seen from table 1, the materials prepared in examples 1 to 3 have high specific capacity and first efficiency because the material is doped with phosphorus to increase the specific capacity of the material, nitrogen atoms reduce the electronic impedance of the material and increase the rate and cycle performance, and sulfur atoms increase the interlayer spacing increase rate of the material; meanwhile, the porous precursor prepared by the hydrothermal method has a porous structure, and the specific surface area of the porous precursor is improved. The example and comparative materials were also tested for sulfur and phosphorus content by a carbon sulfur analyzer and ICP, respectively.
TABLE 1 comparison of physicochemical parameters of examples 1-3 with comparative examples
Test example 3: soft package battery
Compositions prepared in examples 1-3 and comparative examplesThe composite material is used as a negative electrode material, and a negative electrode pole piece is prepared by using a ternary material (LiNi) 1/3 Co 1/3 Mn 1/3 O 2 ) As the positive electrode, liPF 6 (the solvent is EC + DEC, the volume ratio is 1, and the concentration is 1.3 mol/l) is used as an electrolyte, the celegard2400 is a diaphragm to prepare 2Ah soft package batteries C1, C2, C3 and D, and the three-element lithium battery is obtained, and the test results are detailed in tables 2-5.
TABLE 2 imbibition Capacity of negative plate
The liquid absorption capacity of the pole piece is shown in table 2, and as can be seen from table 2, the liquid absorption and retention capacities of the negative electrode in the examples 1 to 3 are obviously superior to those of the comparative example, and the analysis reason is as follows: the hard carbon cathode electrode prepared by a hydrothermal method is of a porous structure and a high specific surface area, and the liquid absorption and retention capacity of the cathode electrode is improved.
TABLE 3 comparison of the magnifications of examples 1-3 with comparative examples
Rate capability
The rate performance of the soft package battery is tested, the charging and discharging voltage range is 2.5-4.2V, the temperature is 25 +/-3.0 ℃, charging is carried out at 1.0C, 3.0C, 5.0C, 10.0C and 20.C, discharging is carried out at 1.0C, and the test results are shown in table 3. As can be seen from table 3, the rate charge performance of the pouch cells in examples 1-3 is significantly better than the comparative example, i.e., the charge time is shorter, the analytical reason is that: in the embodiment, the surface of the negative electrode material is coated with nitrogen atoms with high electronic conductivity to reduce impedance, and the prepared material is in a porous structure, so that the diffusion rate of lithium ions in the charging and discharging process is increased, and the rate capability of the lithium ions is improved.
Table 4 comparison of cycle performance of lithium ion batteries of examples 1-3 and comparative examples
And (3) testing the cycle performance:
the cycle performance test method comprises the following steps: the charging and discharging current is 3C/3C, the voltage range is 2.5-4.2V, the cycle number is 500 times, and the test result is shown in table 4. As can be seen from table 4, the cycle performance of the lithium ion battery prepared by using the hard carbon composite negative electrode material obtained in examples 1 to 3 is significantly better than that of the comparative example at each stage, because the nitrogen atoms promote the electronic conductivity and structural stability of the material in the structure of the nitrogen-phosphorus-sulfur doped hard carbon composite material by a hydrothermal method, and the porous material prepared by the hydrothermal method has liquid absorption and retention properties, thereby promoting the cycle performance of the material, and meanwhile, sufficient electrolyte improves the diffusion channel of lithium ions, reduces the diffusion resistance of lithium ions, improves the conductivity of the material, and improves the cycle performance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modifications, equivalent variations and modifications made on the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention without departing from the technical solution of the present invention.
Claims (5)
1. A sulfur and phosphorus co-doped hard carbon composite material is characterized in that: the composite material is of a core-shell structure, the inner core is hard carbon containing sulfur and phosphorus, the outer shell is amorphous carbon containing nitrogen, the mass proportion of the outer shell is 1-10% of the mass of the composite material, the mass proportion of sulfur atoms in the inner core is 1.11-1.88%, the mass proportion of phosphorus atoms in the inner core is 1.88-2.23%, and the balance is hard carbon;
the preparation method comprises the following steps:
(1) According to the mass ratio of 100:1 to 20: 1-10, weighing a hydrocarbon, a sulfur-phosphorus organic substance and a nitrogen-containing polymer monomer, adding the weighed hydrocarbon, the sulfur-phosphorus organic substance and the nitrogen-containing polymer monomer into an organic solvent to prepare an organic solution, then adding the organic solution into a high-pressure reaction kettle, reacting for 1-6 h at the temperature of 100-200 ℃ and the pressure of 1-5 Mpa, filtering, and freeze-drying powder obtained after filtering for 24h at the temperature of-40 ℃ to obtain a porous hard carbon precursor;
(2) Preparing 0.5-5 wt% of oxidant solution, sequentially adding 10% of dilute hydrochloric acid solution, wherein the volume of the dilute hydrochloric acid solution is 5% of the oxidant solution, the mass ratio of the oxidant solution to the porous hard carbon precursor is 1-10, the mixture is subjected to ultrasonic dispersion uniformly, reacting at the temperature of 0-4 ℃ for 12-72h, cleaning with 10% of dilute hydrochloric acid, vacuum drying at the temperature of 80 ℃ for 24h, grinding until the granularity D50 is 5-20 micrometers, transferring to a tubular furnace, and carbonizing at the temperature of 700-1000 ℃ for 1-6 h under the inert atmosphere of argon gas to obtain a hard carbon composite material;
the sulfur-phosphorus organic matter in the step (1) is one of methamidophos, acephate or fosthiazate.
2. The sulfur-phosphorus co-doped hard carbon composite material as claimed in claim 1, wherein: the hydrocarbon in the step (1) is one of phenolic resin, furfural resin, epoxy resin, coconut shell, starch, glucose or sucrose.
3. The sulfur-phosphorus co-doped hard carbon composite material as claimed in claim 1, wherein: the nitrogen-containing polymer monomer in the step (1) is one of aniline, thiophene, pyrrole or urea.
4. The sulfur-phosphorus co-doped hard carbon composite material as claimed in claim 1, wherein: the organic solvent in the step (1) is carbon tetrachloride or cyclohexane.
5. The sulfur-phosphorus co-doped hard carbon composite material as claimed in claim 1, wherein: the oxidant in the step (2) is (NH) 4 ） 2 S 2 O 8 、H 2 O 2 、K 2 Cr 2 O 7 Or KIO 3 To (3) is provided.
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