CN117239123A - Graphene anode material and preparation method thereof - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 49
- 239000010405 anode material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 11
- -1 transition metal chalcogenide Chemical class 0.000 claims abstract description 23
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000004964 aerogel Substances 0.000 claims abstract description 6
- 239000002071 nanotube Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910003266 NiCo Inorganic materials 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
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- 238000006243 chemical reaction Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000017 hydrogel Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- 229910052573 porcelain Inorganic materials 0.000 claims description 9
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 229910003472 fullerene Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- LGRDAQPMSDIUQJ-UHFFFAOYSA-N tripotassium;cobalt(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Co+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] LGRDAQPMSDIUQJ-UHFFFAOYSA-N 0.000 claims description 3
- ZVAVRBUTFWLEBK-UHFFFAOYSA-N NC1=CC(=C(C=C1)S)C1=CC=CC=C1 Chemical compound NC1=CC(=C(C=C1)S)C1=CC=CC=C1 ZVAVRBUTFWLEBK-UHFFFAOYSA-N 0.000 claims description 2
- 238000003287 bathing Methods 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000004575 stone Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- UCFIGPFUCRUDII-UHFFFAOYSA-N [Co](C#N)C#N.[K] Chemical compound [Co](C#N)C#N.[K] UCFIGPFUCRUDII-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of energy storage battery anode materials, in particular to a graphene anode material and a preparation method thereof, wherein the graphene anode material comprises transition metal chalcogenide and mercapto-functional graphene aerogel, and the stone prepared by the method is testedThe graphene anode material has excellent electrochemical performance, and the specific capacity and the multiplying power performance respectively reach 1000 mAh.g ‑1 And 95% or more.
Description
Technical Field
The invention relates to the field of energy storage battery anode materials, in particular to a graphene anode material and a preparation method thereof.
Background
Lithium ion batteries have been widely used in industrial and commercial fields (e.g., notebook computers, mobile communication devices, electric vehicles, etc.) due to their high energy density, long life, etc. However, conventional commercial graphite anode materials cannot meet the increasing demands, and anode materials with high energy density and long cycle life become research hotspots.
The graphene serving as a novel nanomaterial has excellent performances such as special two-dimensional single-layer extension carbon structure, excellent electrical conductivity, thermal conductivity, toughness, strength and the like, and has wide application prospects in various fields such as functional materials, energy sources and the like. The theoretical capacity of graphene is 774mAh/g, and the electron mobility is 10 000cm 2 V -1 s -1 A lithium ion diffusion coefficient of 10 -7 -10 - 6 cm 2 s -1 The graphene is expected to replace the traditional graphite to become a new generation of negative electrode material, and is notable that graphene is used as an electrode in practical application, stacking and even agglomeration easily occur in the charge and discharge process, so that the specific surface area of the electrode is reduced, the lithium intercalation capacity is reduced, and the electrochemical performance of a lithium ion battery is influenced.
Disclosure of Invention
The invention aims to: aiming at the technical problems, the invention provides a graphene anode material and a preparation method thereof.
The technical scheme adopted is as follows:
a graphene anode material comprises transition metal chalcogenide and mercapto-functionalized graphene aerogel.
Further, the transition metal chalcogenide includes transition metal sulfides and transition metal selenides.
Further, the transition metal sulfide and the transition metal selenide are transition metal sulfide micro-nanotubes and transition metal selenide micro-nanotubes, respectively.
Further, the transition metal sulfide is NiCo 2 S 4 。
Further, the methodThe transition metal selenide is CoSe 2 。
The invention also provides a preparation method of the graphene anode material, which comprises the following steps:
dissolving soluble cobalt salt and sodium citrate in water to obtain solution A, dissolving cobalt potassium cyanide in water to obtain solution B, fully mixing the solution A, the solution B and the micro-nano tube template under the action of ultrasound, standing the obtained suspension at room temperature for reaction for 5-10h, filtering out precipitate, washing, drying, placing the obtained product and selenium powder into a porcelain boat and placing into a tube furnace, then heating to 350-400 ℃ under nitrogen atmosphere for 3-5h, cooling to room temperature, washing the product with toluene to remove the micro-nano tube template, and drying to obtain CoSe 2 A micro-nanotube;
dissolving soluble cobalt salt and soluble nickel salt in isopropanol/glycerol mixed solution, adding and uniformly mixing a micro-nano tube template, transferring the obtained solution into a hydrothermal reaction kettle, sealing and heating to 180-200 ℃ for reaction for 5-10h, cooling to room temperature, filtering out precipitate, washing a product with toluene to remove the micro-nano tube template, and drying to obtain NiCo 2 S 4 A micro-nanotube;
mixing p-amino thiophenol and hydrochloric acid solution, ice-bathing, adding sodium nitrite solution and graphene oxide, stirring for reacting for 12-24h, adding CoSe 2 Micro-nano tube, niCo 2 S 4 And (3) carrying out ultrasonic dispersion on the micro-nano tube and the ascorbic acid, then placing the micro-nano tube and the ascorbic acid in a water bath kettle at 65-75 ℃ for continuous reaction for 6-12 hours, filtering out and washing to obtain hydrogel, soaking the hydrogel in ethanol solution to remove impurities, and freeze-drying.
Further, the volume ratio of the isopropyl alcohol to the glycerol in the isopropyl alcohol/glycerol mixed solution is 5-10:1.
further, the micro-nanotube template is a fullerene micro-nano whisker.
Further, the molar ratio of p-aminophenylthiophenol to sodium nitrite is 1:1-1.2.
Further, the graphene oxide is subjected to polyvinylpyrrolidone treatment in advance.
The invention has the beneficial effects that:
according to the graphene anode material, due to the fact that oxygen-containing functional groups exist in graphene oxide, the balance of electrostatic repulsion and van der Waals force exists between the graphene sheets, after ascorbic acid is added, the oxygen-containing functional groups of the graphene oxide are reduced and removed, electrostatic repulsion between the sheets is reduced, pi-pi conjugation acting force is enhanced, graphene sheets are mutually overlapped to form a graphene hydrogel with a three-dimensional structure, and the graphene aerogel can be obtained through freeze drying. Meanwhile, the three-dimensional porous structure is also beneficial to the infiltration and adsorption of electrolyte, the cycle performance of the battery is improved, the graphene is modified by grafting sulfhydryl, the sulfhydryl is electronegative, the three-dimensional porous structure has a certain electron-withdrawing capacity, the rapid transmission of lithium ions on the surface of the graphene can be promoted, and the electrochemical performance of the graphene is improved;
the transition metal chalcogenide has wide attention due to mechanical and thermal stability and excellent theoretical capacity, but the problems of poor volume change, dissolution of lithium polysulfide, poor conductivity and the like in the charge and discharge process lead to unsatisfactory cycle performance and rate performance.
Drawings
Fig. 1 is a microscopic morphology diagram of the graphene anode material prepared in example 1.
Detailed Description
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. The technology not mentioned in the present invention refers to the prior art, and unless otherwise indicated, the following examples and comparative examples are parallel tests, employing the same processing steps and parameters.
Example 1
A graphene anode material comprises CoSe 2 Micro-nano tube, niCo 2 S 4 The preparation method of the micro-nano tube and mercapto functional graphene aerogel comprises the following steps:
dissolving 2.98g of cobalt acetate and 4.64g of sodium citrate in 200ml of deionized water to obtain a solution A, dissolving 2.66g of cobalt potassium cyanide in 200ml of deionized water to obtain a solution B, fully mixing the solution A, the solution B and 5g of fullerene micro-nano whiskers under the action of ultrasound, standing the obtained suspension at room temperature for reaction for 8 hours, filtering out precipitate, repeatedly washing with deionized water and ethanol, drying, putting the obtained product and selenium powder into a porcelain boat according to a weight ratio of 1:2, placing the product and selenium powder into a tubular furnace (the selenium powder is at the front end of the porcelain boat, the product is at the rear end of the porcelain boat), heating to 350 ℃ under nitrogen atmosphere, preserving heat for 3 hours, cooling to room temperature, taking out, ultrasonically washing in 500ml of toluene for 60 minutes to remove fullerene micro-nano whiskers, and finally drying to obtain CoSe 2 A micro-nanotube;
dissolving 3.02g of copper nitrate trihydrate and 7.28g of cobalt nitrate hexahydrate in 300ml of isopropanol/glycerol mixed solution (the volume ratio of isopropanol to glycerol is 5:1), adding and uniformly mixing 5g of fullerene micro-nano whiskers, transferring the obtained solution into a hydrothermal reaction kettle, sealing and heating to 180 ℃ for reaction for 8 hours, cooling to room temperature, filtering out precipitate, placing in 500ml of toluene, ultrasonically washing for 60 minutes to remove the fullerene micro-nano whiskers, and drying to obtain NiCo 2 S 4 A micro-nanotube;
dispersing 10g of graphene oxide in 100ml of deionized water, adding 0.5g of polyvinylpyrrolidone, performing ultrasonic dispersion for 60min, filtering, drying, and adding 12.5g of p-amino thiophenol into 100ml of 1M hydrochloric acid solutionIn the process, stirring and mixing uniformly, then carrying out ice bath, dropwise adding 100ml of 1M sodium nitrite solution into the system, stirring for 30min, adding the graphene oxide, stirring and reacting for 12h, and then adding 1g of CoSe 2 Micro-nano tube, 1g NiCo 2 S 4 And (3) carrying out ultrasonic dispersion on the micro-nano tube and 10g of ascorbic acid for 30min, then placing the mixture in a water bath kettle at 70 ℃ for continuous reaction for 12h, filtering out the mixture to obtain hydrogel, soaking the hydrogel in a 20% ethanol solution for 24h, removing impurities, and freeze-drying the hydrogel.
Note that: the preparation method of the fullerene micro-nano whisker in the embodiment refers to the following documents;
xu Qingtao, zhu Guangxu, zhang Wenjun, kangning, plain philosophy conversion of fullerene C60 platelets to whiskers [ J ]. University of Qingdao technical university (natural science edition), 2021, (stage 1).
Example 2
Substantially the same as in example 1, except that CoSe 2 Micro-nano tube and NiCo 2 S 4 The dosage of the micro-nano tube is respectively 0.5g and 1g.
Example 3
Substantially the same as in example 1, except that CoSe 2 Micro-nano tube and NiCo 2 S 4 The dosage of the micro-nano tube is 1g and 0.5g respectively.
Example 4
Substantially the same as in example 1, except that CoSe 2 Micro-nano tube and NiCo 2 S 4 The dosage of the micro-nano tube is 0.5g and 0.5g respectively.
Comparative example 1: substantially the same as in example 1, except that CoSe was used 2 Powder instead of CoSe 2 Micro-nanotubes.
CoSe 2 The preparation method of the powder comprises the following steps:
dissolving 2.98g of cobalt acetate and 4.64g of sodium citrate in 200ml of deionized water to obtain a solution A, dissolving 2.66g of potassium cobalt cyanide in 200ml of deionized water to obtain a solution B, fully mixing the solution A and the solution B under the action of ultrasound, standing the obtained solution at room temperature for reaction for 5-10 hours, filtering out precipitate, repeatedly washing with deionized water and ethanol, drying, putting the obtained product and selenium powder into a porcelain boat according to a weight ratio of 1:2, and placing the porcelain boat and the selenium powder into a tubular furnace (selenium powder)At the front end of the porcelain boat and the rear end of the porcelain boat), then heating to 350 ℃ under nitrogen atmosphere, preserving heat for 3 hours, cooling to room temperature, taking out, placing in 500ml toluene, ultrasonic washing for 60 minutes, finally drying and grinding to obtain the CoSe 2 And (3) powder.
Comparative example 2: substantially the same as in example 1, except that substantially the same as in example 1 was used with NiCo 2 S 4 Powder instead of NiCo 2 S 4 Micro-nanotubes.
NiCo 2 S 4 The preparation method of the powder comprises the following steps:
dissolving 3.02g of copper nitrate trihydrate and 7.28g of cobalt nitrate hexahydrate in 300ml of isopropanol/glycerol mixed solution (the volume ratio of isopropanol to glycerol is 5:1), transferring the obtained solution into a hydrothermal reaction kettle, sealing, heating to 180 ℃ for reaction for 8 hours, cooling to room temperature, filtering out precipitate, placing in 500ml of toluene, ultrasonically washing for 60 minutes, drying and grinding to obtain NiCo 2 S 4 And (3) powder.
Comparative example 3: substantially the same as in example 1, except that CoSe was not added 2 Micro-nanotubes.
Comparative example 4: substantially the same as in example 1, except that NiCo was not added 2 S 4 Micro-nanotubes.
Comparative example 5: substantially the same as in example 1, except that graphene aerogel was not subjected to thiol-functionalization treatment, the preparation method was as follows:
dispersing 10g of graphene oxide in 100ml of deionized water, adding 0.5g of polyvinylpyrrolidone, performing ultrasonic dispersion for 60min, filtering, drying, adding the graphene oxide into 200ml of deionized water, stirring for 12h, and adding 1g of CoSe 2 Micro-nano tube, 1g NiCo 2 S 4 And (3) carrying out ultrasonic dispersion on the micro-nano tube and 10g of ascorbic acid for 30min, then placing the mixture in a water bath kettle at 70 ℃ for continuous reaction for 12h, filtering out the mixture to obtain hydrogel, soaking the hydrogel in a 20% ethanol solution for 24h, removing impurities, and freeze-drying the hydrogel.
Performance test: the graphene anode materials prepared in the embodiments 1-4 and the comparative examples 1-5 of the invention are assembled into button cells respectively, and performance test is carried out on a blue electric tester;
wherein, the positive electrode: a lithium sheet; and (3) a negative electrode: the prepared graphene anode material; a diaphragm: a polypropylene microporous membrane; the volume ratio of the electrolyte is 1:1:1 (ethylene carbonate), EDC (diethyl carbonate) and EMC (ethylmethyl carbonate) as solvents, liPF6 with a concentration of 1.0M as solute, and a test current density of 0.1 A.g -1 The test results are shown in table 1:
table 1:
；
as can be seen from the above Table 1, the graphene anode material prepared by the invention has excellent electrochemical performance, and the specific capacity and the rate capability reach 1000 mAh.g respectively -1 And 95% or more.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. The graphene anode material is characterized by comprising transition metal chalcogenide and mercapto-functionalized graphene aerogel;
the transition metal chalcogenides include transition metal sulfides and transition metal selenides;
the transition metal sulfide and the transition metal selenide are respectively transition metal sulfide micro-nanotubes and transition metal selenide micro-nanotubes.
2. The graphene anode material of claim 1, wherein the transition metal sulfide is NiCo 2 S 4 。
3. The graphene anode material of claim 2, wherein the transition metal selenide is CoSe 2 。
4. A method for preparing the graphene anode material according to claim 3, which is characterized by comprising the following steps:
dissolving soluble cobalt salt and sodium citrate in water to obtain solution A, dissolving cobalt potassium cyanide in water to obtain solution B, fully mixing the solution A, the solution B and the micro-nano tube template under the action of ultrasound, standing the obtained suspension at room temperature for reaction for 5-10h, filtering out precipitate, washing, drying, placing the obtained product and selenium powder into a porcelain boat and placing into a tube furnace, then heating to 350-400 ℃ under nitrogen atmosphere for 3-5h, cooling to room temperature, washing the product with toluene to remove the micro-nano tube template, and drying to obtain CoSe 2 A micro-nanotube;
dissolving soluble cobalt salt and soluble nickel salt in isopropanol/glycerol mixed solution, adding and uniformly mixing a micro-nano tube template, transferring the obtained solution into a hydrothermal reaction kettle, sealing and heating to 180-200 ℃ for reaction for 5-10h, cooling to room temperature, filtering out precipitate, washing a product with toluene to remove the micro-nano tube template, and drying to obtain NiCo 2 S 4 A micro-nanotube;
mixing p-amino thiophenol and hydrochloric acid solution, ice-bathing, adding sodium nitrite solution and graphene oxide, stirring for reacting for 12-24h, adding CoSe 2 Micro-nano tube, niCo 2 S 4 And (3) carrying out ultrasonic dispersion on the micro-nano tube and the ascorbic acid, then placing the micro-nano tube and the ascorbic acid in a water bath kettle at 65-75 ℃ for continuous reaction for 6-12 hours, filtering out and washing to obtain hydrogel, soaking the hydrogel in ethanol solution to remove impurities, and freeze-drying.
5. The method for preparing a graphene anode material according to claim 4, wherein the volume ratio of isopropyl alcohol to glycerol in the isopropyl alcohol/glycerol mixed solution is 5-10:1.
6. the method for preparing a graphene anode material according to claim 4, wherein the micro-nanotube template is a fullerene micro-nano whisker.
7. The method for preparing a graphene anode material according to claim 4, wherein the molar ratio of p-aminophenylthiophenol to sodium nitrite is 1:1-1.2.
8. The method for preparing a graphene anode material according to claim 4, wherein the graphene oxide is previously treated with polyvinylpyrrolidone.
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| CN202311521629.6A CN117239123B (en) | 2023-11-15 | 2023-11-15 | Graphene anode material and preparation method thereof |
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| CN202311521629.6A CN117239123B (en) | 2023-11-15 | 2023-11-15 | Graphene anode material and preparation method thereof |
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| CN117239123A true CN117239123A (en) | 2023-12-15 |
| CN117239123B CN117239123B (en) | 2024-01-12 |
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