CN114388763B - NiS/graphene@carbon composite material and preparation method and application thereof - Google Patents
NiS/graphene@carbon composite material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 113
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 235000010413 sodium alginate Nutrition 0.000 claims description 13
- 239000000661 sodium alginate Substances 0.000 claims description 13
- 229940005550 sodium alginate Drugs 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 9
- 229940038773 trisodium citrate Drugs 0.000 claims description 9
- 235000010408 potassium alginate Nutrition 0.000 claims description 8
- 239000000737 potassium alginate Substances 0.000 claims description 8
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 238000004729 solvothermal method Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004201 L-cysteine Substances 0.000 claims description 5
- 235000013878 L-cysteine Nutrition 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 2
- 229940072056 alginate Drugs 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229960002433 cysteine Drugs 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- PKIDNTKRVKSLDB-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;hydrate Chemical compound O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PKIDNTKRVKSLDB-UHFFFAOYSA-K 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229920001586 anionic polysaccharide Polymers 0.000 description 1
- 150000004836 anionic polysaccharides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 transition metal chalcogenide Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion battery electrode materials, in particular to a NiS/graphene@carbon composite material, and a preparation method and application thereof. According to the invention, nickel sulfide, graphene oxide and a carbon source are compounded, porous carbon is obtained after gel carbonization, the porous carbon has a large specific surface area, and the adhesion of the graphene oxide and the nickel sulfide is realized; the porous carbon has a cross-linked hole structure, and after the porous carbon is compounded with nickel sulfide, the nickel sulfide is attached to the porous carbon, so that the synergistic effect of the porous carbon and the porous carbon is improved, and the conductivity is further improved; according to the invention, porous carbon is adopted to replace graphene, and under the combined action of reduced graphene oxide, nickel sulfide and porous carbon, the conductivity of the graphene is close to that of a NiS@graphene material, so that the consumption of graphene is reduced, the cost is saved to a certain extent, and meanwhile, the electrode material with excellent conductivity is obtained.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery electrode materials, and particularly relates to a NiS/graphene@carbon composite material and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high working voltage, small volume, light weight, high energy, no memory effect, no pollution, small self discharge and long cycle life, so the lithium ion battery is an ideal energy source which is gradually developed; the lithium ion battery is a rechargeable battery, and works by means of reciprocating intercalation and deintercalation of lithium ions between a positive electrode and a negative electrode, lithium ions are deintercalated from the positive electrode during charging and then are intercalated into the negative electrode through an electrolyte, at the moment, the negative electrode is in a lithium-rich state, and the negative electrode is opposite during discharging, so that the electrochemical performance of the battery is improved and optimized, and the selection of a proper electrode material is important.
Nickel sulfide (NiS, ni) 3 S 2 、NiS 2 、Ni 3 S 4 Etc.) belong to narrow bandgap transition metal semiconductors, whose nanoparticles are a typical transition metal chalcogenide, have a higher specific capacity, excellent electrical conductivity,the lithium ion battery electrode material has the advantages of abundant reserves, low price and easy processing and preparation, and is a potential lithium ion battery electrode material; sulfur in nickel sulfide can react reversibly with metallic lithium, as compared to carbon materials, providing reversible capacity, by: ni (Ni) x S y +2yLi→xNi+yLi 2 S, S; although the reaction can provide higher capacity, the electrode active material is separated from the current collector due to larger volume change in the lithium intercalation and deintercalation process, so that the capacity is rapidly attenuated, meanwhile, the pure nickel sulfide nano particles are easy to agglomerate, have poor conductivity and poor recycling performance, and the performance of the pure nickel sulfide nano particles is greatly limited.
In the prior art, the nickel sulfide is technically modified by graphene to obtain a graphene@nickel sulfide composite material, and the graphene applied to the electrode material is generally expensive, so that the prepared graphene@nickel sulfide composite material is unfavorable for industrialized popularization and production, and the application of the graphene@nickel sulfide composite material is limited, so that the research in the prior art aims at modifying the carbon material by the graphene so as to improve and promote the electrical property of the electrode material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a NiS/graphene@carbon composite material and a preparation method and application thereof; according to the invention, nickel sulfide, graphene oxide and a carbon source are compounded, porous carbon is obtained after gel carbonization, the porous carbon has a large specific surface area, and the adhesion of the graphene oxide and the nickel sulfide is realized; the porous carbon has a cross-linked hole structure, and after the porous carbon is compounded with nickel sulfide, the nickel sulfide is attached to the porous carbon, so that the synergistic effect of the porous carbon and the porous carbon is improved, and the conductivity is further improved; according to the invention, porous carbon is adopted to replace graphene, and under the combined action of reduced graphene oxide, nickel sulfide and porous carbon, the conductivity of the graphene is close to that of a NiS@graphene material, so that the consumption of graphene is reduced, the cost is saved to a certain extent, and meanwhile, the electrode material with excellent conductivity is obtained.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a preparation method of a NiS/graphene@carbon composite material comprises the following steps:
(1) Mixing a nickel-containing salt, a sulfur source and a surfactant, and then performing solvothermal reaction to obtain nickel sulfide;
(2) Uniformly mixing a carbon source solution and graphene oxide, adding the nickel sulfide prepared in the step (1), removing residual bubbles after full mixing, and evaporating a solvent to obtain nickel sulfide/graphene oxide gel;
wherein the mass ratio of the carbon source to deionized water in the carbon source solution is 2-6:100, wherein the mass ratio of the carbon source to the graphene oxide is 1:0.05-0.1, and the mass ratio of the carbon source to the nickel sulfide is 1:0.5-1;
(3) Dropwise adding a pore-forming agent KOH onto the nickel sulfide/graphene oxide gel in the step (2), heating at 400-700 ℃ for 1.5-3h in nitrogen atmosphere, carbonizing at 900 ℃ for 0.5-1h, and cooling to room temperature to obtain a NiS/graphene oxide@carbon composite material;
(4) And (3) reducing the NiS/graphene oxide@carbon composite material in the step (3) to obtain the NiS/graphene@carbon composite material.
Preferably, the nickel-containing salt in the step (1) is selected from one of nickel chloride, nickel fluoride, nickel nitrate, nickel sulfate, nickel oxalate and nickel acetate.
Preferably, the sulfur source in the step (1) is selected from one of thiourea, L-cysteine and thioacetamide.
Preferably, the surfactant of step (1) is selected from trisodium citrate or a hydrate of trisodium citrate.
Preferably, the method of solvothermal reaction in the step (1) is as follows: mixing a nickel-containing salt, a sulfur source and a surfactant in a solvent in a reaction kettle, and then carrying out heat preservation reaction for 18-42h at 170-230 ℃;
wherein the ratio of the amount of surfactant, sulfur source and nickel-containing salt substance is 1-3:2-4:1, a step of; the solvent is one of deionized water, methanol, ethanol, glycol, ethylenediamine and N, N' -dimethylformamide.
Preferably, the carbon source in the step (2) is selected from sodium alginate or potassium alginate.
Preferably, the reduction reaction conditions of the step (4) are as follows: dispersing the NiS/graphene oxide@carbon composite material in deionized water, dropwise adding ammonia water until the pH value is 9-11, adding hydrazine hydrate into the mixture, uniformly mixing the mixture, and reacting the mixture at 90-120 ℃ for 24-48 hours to obtain the NiS/graphene@carbon composite material.
The invention also protects the NiS/graphene@carbon composite material prepared by the preparation method.
The invention also protects the application of the NiS/graphene@carbon composite material in preparing the lithium ion battery anode material.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a simple, green and effective preparation method of a NiS/graphene@carbon composite material; according to the invention, the nickel sulfide is prepared by adopting a conventional technical means, and graphene oxide is used as a precursor, the nickel sulfide, a carbon source solution and the graphene oxide are mixed, the graphene oxide has electronegativity and the capability of attracting electrons, and at the moment, the graphene oxide and a carbon source (sodium alginate or potassium alginate) are mutually attracted after being mixed, so that the graphene oxide is uniformly dispersed in the carbon source solution, and the nickel sulfide/graphene oxide gel is obtained; when nickel sulfide/graphene oxide gel is subjected to heat treatment, a carbon material with a cross-linked pore structure is obtained through a pore-forming agent, and meanwhile, graphene oxide and nickel sulfide are uniformly distributed on porous carbon, so that the porous carbon is used as a substrate, the porous carbon is used for replacing graphene, the conductivity is improved, and meanwhile, the use amount of the graphene is reduced, so that the cost is effectively saved to a certain extent;
and finally, carrying out reduction operation on the graphene oxide to remove oxygen-containing functional groups on the graphene oxide, generating reduced graphene oxide, partially recovering the conductivity of the graphene, and overcoming the technical defect that graphene sheets are easy to overlap.
2. Alginate is taken as a natural water-soluble anionic polysaccharide, and can synthesize high-strength hydrogel under mild conditions; in addition, hydrogel prepared from alginate can form a cross-linked structure through a dynamic covalent bond, so that self-repairing capability is realized, and the overall stability of the anode material is improved.
3. In the NiS/graphene@carbon composite material prepared by the method, graphene oxide is used as a precursor, and finally the graphene oxide is reduced to obtain reduced graphene oxide, wherein the reduced graphene oxide has the conductivity inferior to that of graphene, but the reduced graphene oxide, nickel sulfide and porous carbon have the conductivity similar to that of the NiS@graphene material under the combined action of the reduced graphene oxide, nickel sulfide and porous carbon.
Drawings
FIG. 1 is a graph of the results of a stability test of a working electrode prepared using the NiS/graphene @ carbon composite material of example 2 of the present invention cycled 100 times at a current density of 100 mA/g;
FIG. 2 is a graph of the results of a stability test for a working electrode made using the NiS/graphene @ carbon composite of example 2 of the present invention cycled 1000 times at a current density of 100 mA/g.
Detailed Description
The following detailed description of specific embodiments of the invention is, but it should be understood that the invention is not limited to specific embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental methods described in the examples of the present invention are conventional methods unless otherwise specified.
The following experimental methods and detection methods, if not specified, are all conventional methods; the following reagents and raw materials, unless otherwise specified, are commercially available.
Example 1
A preparation method of a NiS/graphene@carbon composite material comprises the following steps:
(1) Mixing nickel nitrate, thiourea and trisodium citrate in methanol in a reaction kettle, then carrying out thermal insulation reaction at 170 ℃ for 42 hours, and carrying out solvothermal reaction to obtain nickel sulfide;
wherein, the ratio of the amount of trisodium citrate, thiourea and nickel nitrate substances is 1:4:1, a step of;
(2) Uniformly mixing a sodium alginate solution and graphene oxide, adding the nickel sulfide prepared in the step (1), removing residual bubbles and evaporating a solvent after full mixing to obtain nickel sulfide/graphene oxide gel;
wherein, the mass ratio of sodium alginate to deionized water in the sodium alginate solution is 2:100, the mass ratio of sodium alginate to graphene oxide is 1:0.1, and the mass ratio of sodium alginate to nickel sulfide is 1:0.8;
(3) Dropwise adding a pore-forming agent KOH onto the nickel sulfide/graphene oxide gel in the step (2), heating at 400 ℃ for 3 hours in a nitrogen atmosphere, carbonizing at 900 ℃ for 1 hour, and cooling to room temperature to obtain a NiS/graphene oxide@carbon composite material;
(4) Reducing the NiS/graphene oxide@carbon composite material in the step (3), wherein the reduction reaction conditions are as follows: dispersing the NiS/graphene oxide@carbon composite material in deionized water, dropwise adding ammonia water until the pH value is 9, adding hydrazine hydrate into the solution, uniformly mixing the solution, and reacting the solution at 120 ℃ for 24 hours to obtain the NiS/graphene@carbon composite material.
Example 2
A preparation method of a NiS/graphene@carbon composite material comprises the following steps:
(1) Mixing nickel chloride hexahydrate, thioacetamide and trisodium citrate in ethylene glycol in a reaction kettle, then carrying out thermal insulation reaction at 200 ℃ for 36 hours, and carrying out solvothermal reaction to obtain nickel sulfide;
wherein the ratio of the amounts of trisodium citrate, thioacetamide and nickel chloride hexahydrate material is 2:3:1, a step of;
(2) Uniformly mixing a sodium alginate solution and graphene oxide, adding the nickel sulfide prepared in the step (1), removing residual bubbles and evaporating a solvent after full mixing to obtain nickel sulfide/graphene oxide gel;
wherein, the mass ratio of sodium alginate to deionized water in the sodium alginate solution is 4:100, the mass ratio of sodium alginate to graphene oxide is 1:0.08, and the mass ratio of sodium alginate to nickel sulfide is 1:0.5;
(3) Dropwise adding a pore-forming agent KOH onto the nickel sulfide/graphene oxide gel in the step (2), heating at 500 ℃ for 2 hours in a nitrogen atmosphere, carbonizing at 900 ℃ for 0.5 hour, and cooling to room temperature to obtain a NiS/graphene oxide@carbon composite material;
(4) Reducing the NiS/graphene oxide@carbon composite material in the step (3), wherein the reduction reaction conditions are as follows: dispersing the NiS/graphene oxide@carbon composite material in deionized water, dropwise adding ammonia water until the pH is 10, adding hydrazine hydrate into the solution, uniformly mixing the solution, and reacting the solution at 100 ℃ for 36 hours to obtain the NiS/graphene@carbon composite material.
Example 3
A preparation method of a NiS/graphene@carbon composite material comprises the following steps:
(1) Taking nickel acetate, L-cysteine and trisodium citrate hydrate, then mixing the nickel acetate, L-cysteine and trisodium citrate hydrate in deionized water in a reaction kettle, then carrying out thermal insulation reaction for 18 hours at 230 ℃, and carrying out solvothermal reaction to obtain nickel sulfide;
wherein, the ratio of the amount of the hydrate of trisodium citrate, L-cysteine and the amount of the nickel acetate substance is 3:2:1, a step of;
(2) Uniformly mixing a potassium alginate solution and graphene oxide, adding the nickel sulfide prepared in the step (1), removing residual bubbles after full mixing, and evaporating a solvent to obtain nickel sulfide/graphene oxide gel;
wherein, the mass ratio of the potassium alginate to the deionized water in the potassium alginate solution is 6:100, wherein the mass ratio of the potassium alginate to the graphene oxide is 1:0.05, and the mass ratio of the potassium alginate to the nickel sulfide is 1:1, a step of;
(3) Dropwise adding a pore-forming agent KOH onto the nickel sulfide/graphene oxide gel in the step (2), heating at 700 ℃ for 1.5 hours in a nitrogen atmosphere, carbonizing at 900 ℃ for 0.5 hour, and cooling to room temperature to obtain a NiS/graphene oxide@carbon composite material;
(4) Reducing the NiS/graphene oxide@carbon composite material in the step (3), wherein the reduction reaction conditions are as follows: dispersing the NiS/graphene oxide@carbon composite material in deionized water, dropwise adding ammonia water until the pH is 11, adding hydrazine hydrate into the solution, uniformly mixing the solution, and reacting the solution at 90 ℃ for 48 hours to obtain the NiS/graphene@carbon composite material.
According to the invention, an NiS/graphene@carbon composite material with excellent electrochemical performance is prepared in each of the embodiments 1-3, the NiS/graphene@carbon composite material prepared in the embodiment 2 is taken as an example, the NiS/graphene@carbon composite material, acetylene black and polyvinylidene fluoride are mixed according to the mass ratio of 80:10:10 to prepare slurry, then the slurry is uniformly coated on the surface of a copper foil, and a working electrode is obtained after drying, pressing and cutting, so that electrochemical performance detection is performed;
the lithium sheet is used as a counter electrode and is placed in electrolyte together with the working electrode, and the electrolyte is commercially available 1mol/L LiPF 6 Ec+dmc solution, and performing electrochemical performance detection, the test results are shown in fig. 1 and 2;
FIG. 1 is a graph of the results of a stability test of a working electrode at a current density of 100mA/g for 100 times, and the results of FIG. 1 show that the NiS/graphene@carbon composite material has good cycle stability within 100 times of the cycle, and the battery capacity is stable at 814mAh/g after 100 times of the cycle.
FIG. 2 is a graph of the results of a stability test of a working electrode at a current density of 100mA/g for 1000 cycles, and the results of FIG. 2 show that the NiS/graphene@carbon composite material has good cycle stability within 1000 cycles, and the battery capacity can reach 749mAh/g after 1000 cycles.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (8)
1. The preparation method of the NiS/graphene@carbon composite material is characterized by comprising the following steps of:
(1) Taking a nickel-containing salt, a sulfur source and a surfactant, and then performing solvothermal reaction to obtain nickel sulfide;
(2) Uniformly mixing a carbon source solution and graphene oxide, adding the nickel sulfide prepared in the step (1), removing residual bubbles after full mixing, and evaporating a solvent to obtain nickel sulfide/graphene oxide gel;
wherein the mass ratio of the carbon source to deionized water in the carbon source solution is 2-6:100, wherein the mass ratio of the carbon source to the graphene oxide is 1:0.05-0.1, and the mass ratio of the carbon source to the nickel sulfide is 1:0.5-1;
(3) Dropwise adding a pore-forming agent KOH onto the nickel sulfide/graphene oxide gel in the step (2), heating at 400-700 ℃ for 1.5-3h in nitrogen atmosphere, carbonizing at 900 ℃ for 0.5-1h, and cooling to room temperature to obtain a NiS/graphene oxide@carbon composite material;
(4) Reducing the NiS/graphene oxide@carbon composite material in the step (3) to obtain the NiS/graphene@carbon composite material;
the carbon source in the step (2) is selected from sodium alginate or potassium alginate.
2. The method for preparing a NiS/graphene @ carbon composite material according to claim 1, wherein the nickel-containing salt of step (1) is selected from one of nickel chloride, nickel fluoride, nickel nitrate, nickel sulfate, nickel oxalate, and nickel acetate.
3. The method for preparing the NiS/graphene @ carbon composite material according to claim 1, wherein the sulfur source in the step (1) is one selected from thiourea, L-cysteine and thioacetamide.
4. The method for preparing a NiS/graphene @ carbon composite material according to claim 1, wherein the surfactant in the step (1) is selected from trisodium citrate or a hydrate of trisodium citrate.
5. The method for preparing the NiS/graphene @ carbon composite material according to claim 1, wherein the method for solvothermal reaction in the step (1) is as follows: mixing a nickel-containing salt, a sulfur source and a surfactant in a solvent in a reaction kettle, and then carrying out heat preservation reaction for 18-42h at 170-230 ℃;
wherein the ratio of the amount of surfactant, sulfur source and nickel-containing salt substance is 1-3:2-4:1, a step of; the solvent is one of deionized water, methanol, ethanol, glycol, ethylenediamine and N, N' -dimethylformamide.
6. The method for preparing a NiS/graphene @ carbon composite material according to claim 1, wherein the reduction reaction conditions in the step (4) are as follows: dispersing the NiS/graphene oxide@carbon composite material in deionized water, dropwise adding ammonia water until the pH value is 9-11, adding hydrazine hydrate into the mixture, uniformly mixing the mixture, and reacting the mixture at 90-120 ℃ for 24-48 hours to obtain the NiS/graphene@carbon composite material.
7. A NiS/graphene @ carbon composite material made by the method of any one of claims 1-6.
8. Use of the NiS/graphene @ carbon composite material of claim 7 in the preparation of a lithium ion battery anode material.
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| CN104134783A (en) * | 2014-07-31 | 2014-11-05 | 北京科技大学 | Nano-NiS/graphene composite anode material and preparation method thereof |
| CN106654268A (en) * | 2016-12-09 | 2017-05-10 | 太原理工大学 | Method for preparing porous carbon material for lithium/sodium-ion battery |
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| CN113437277A (en) * | 2021-07-20 | 2021-09-24 | 广东工业大学 | Bi2S3/NiS2@ C negative electrode material, sodium ion battery and preparation method of sodium ion battery |
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| CN104134783A (en) * | 2014-07-31 | 2014-11-05 | 北京科技大学 | Nano-NiS/graphene composite anode material and preparation method thereof |
| CN106654268A (en) * | 2016-12-09 | 2017-05-10 | 太原理工大学 | Method for preparing porous carbon material for lithium/sodium-ion battery |
| CN110627134A (en) * | 2019-09-26 | 2019-12-31 | 广东工业大学 | Preparation method of cobalt-nickel sulfide electrode material and battery |
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