CN114242975B - Ternary composite material and preparation method and application thereof - Google Patents
Ternary composite material and preparation method and application thereof Download PDFInfo
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- CN114242975B CN114242975B CN202111482546.1A CN202111482546A CN114242975B CN 114242975 B CN114242975 B CN 114242975B CN 202111482546 A CN202111482546 A CN 202111482546A CN 114242975 B CN114242975 B CN 114242975B
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- molybdenum disulfide
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- 239000011206 ternary composite Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 59
- 239000002028 Biomass Substances 0.000 claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 29
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 26
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000007773 negative electrode material Substances 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 29
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 239000004201 L-cysteine Substances 0.000 claims description 7
- 235000013878 L-cysteine Nutrition 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012935 ammoniumperoxodisulfate Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 8
- 238000003487 electrochemical reaction Methods 0.000 abstract description 8
- 239000011229 interlayer Substances 0.000 abstract description 8
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 239000011734 sodium Substances 0.000 abstract description 8
- 239000002135 nanosheet Substances 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- -1 transition metal sulfide Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 235000003301 Ceiba pentandra Nutrition 0.000 description 1
- 244000146553 Ceiba pentandra Species 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to the technical field of battery materials, in particular to a ternary composite material, a preparation method and application thereof, wherein the application adopts biomass PC as a framework by a simple one-step hydrothermal method to grow MoS in situ 2 The nano sheet is coated with polypyrrole PPy on the surface of the material to prepare the biomass carbon/molybdenum sulfide@polypyrrole PC/MoS of the lamellar network 2 @PPy ternary sandwich structure composite material and MoS 2 The interlayer spacing is obviously increased, and the agglomeration phenomenon is also relieved; PC/MoS provided by the application 2 When the@PPy ternary composite material is applied to a negative electrode material of a sodium ion battery, the sandwich structure of the layered network enables the electrode material to be fully contacted with electrolyte, a large number of electrochemical reaction active sites are provided, and MoS is effectively relieved 2 The three-dimensional conductive network formed by the biomass carbon skeleton and the PPy in the long circulation process also effectively improves the conductivity of the material, accelerates the electrochemical reaction kinetics of the material, greatly improves the electrochemical sodium storage performance of the material, and can be widely used as a negative electrode material of a sodium ion battery.
Description
Technical Field
The application relates to the technical field of battery materials, in particular to a ternary composite material and a preparation method and application thereof.
Background
Since the successful commercialization of lithium ion batteries in 1991, great success has been achieved in portable energy storage. However, the scarcity of lithium resources has led to a continuous increase in the cost of lithium ion batteries, which makes it difficult to meet market demands. The sodium ion battery which is the alkali metal ion battery has a similar charge-discharge mechanism as the lithium ion battery, and sodium resources are far more abundant than lithium, meanwhile, the sodium ion battery has the advantages of low cost, high safety, good low-temperature performance and quick charge, is hopeful to be complemented with the multiple elements of the lithium iron phosphate and ternary lithium battery which are developed and mature, and becomes an ideal substitute of the lithium ion battery. However, commercial anode materials for lithium ion batteries are not suitable for use in sodium ion batteries. Therefore, the research of the negative electrode material of the sodium ion battery has important significance for the development of the sodium ion battery, and the development of the electrode material of the sodium ion battery with high performance, especially the negative electrode material, overcomes the difficulties of low energy density and poor cycle performance of the sodium ion battery, and can further accelerate the commercial pace of the sodium ion battery.
MoS 2 As typical two-dimensional lamellar transition metal sulfide, the layers are combined by weak van der Waals force, the interlayer spacing is larger (0.64 nm), the ion deintercalation is very favorable, and the theoretical specific capacity is as high as 670mAh/g. But MoS 2 The material also has obvious disadvantages as a negative electrode material of the sodium ion battery, and has low intrinsic conductivity, obvious volume effect in long circulation and slow sodium storage reaction kinetics. At present, moS is often promoted by constructing a multidimensional nano structure, compounding with conductive carbon materials and other modification means 2 Although the electrochemical sodium storage performance is improved to a certain extent, the application requirements can not be met.
In view of this, the present application aims to propose a new ternary composite material to better solve the above technical problems.
Disclosure of Invention
In order to solve the problems, the application provides a ternary composite material, a preparation method and application thereof, which aims to solve MoS 2 As a negative electrode material of the sodium ion battery, the material has the problems of low reversible capacity, unstable circulation, poor rate capability and the like.
The technical scheme adopted by the application is as follows:
a preparation method of a ternary composite material comprises the following preparation steps:
s1: preparation of biomass carbon/molybdenum disulfide material
Washing, drying and crushing biomass into biomass powder, dispersing the biomass powder, sodium molybdate dihydrate and L-cysteine in deionized water, uniformly mixing, transferring to a reaction kettle for hydrothermal reaction, collecting black precipitate after the reaction is finished, centrifugally cleaning for a plurality of times, freeze-drying to obtain a reaction product, and annealing the reaction product in an inert atmosphere to obtain a biomass carbon/molybdenum disulfide composite material;
s2: preparation of biomass carbon/molybdenum disulfide@polypyrrole ternary composite material
Dispersing the biomass carbon/molybdenum disulfide composite material and p-toluenesulfonic acid in deionized water, placing the deionized water in an ice water bath for stirring and cooling, dropwise adding pyrrole monomers, after uniform dispersion, dropwise adding an ammonium peroxodisulfate aqueous solution, fully soaking, collecting precipitate, centrifugally cleaning the precipitate, and freeze-drying to obtain the biomass carbon/molybdenum disulfide@polypyrrole ternary composite material.
Further, the biomass in S1 is a layered network structure biomass.
Further, the mass ratio of sodium molybdate dihydrate to L-cysteine in S1 is 2:5.
further, the hydrothermal reaction temperature in S1 is controlled at 150-220 ℃ and the reaction time is controlled at 18-36h.
Further, the freeze-drying time in S1 is 12-24 hours.
Further, the inert atmosphere in the S1 is argon, the annealing treatment temperature is 600-800 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 1-3h.
Further, the usage amount of pyrrole in S2 is 0.5-2 times of that of the biomass carbon/molybdenum disulfide composite material, and the mass ratio of p-toluenesulfonic acid, ammonium peroxodisulfate and pyrrole is 8:8:5.
further, the temperature of the ice water bath in the S2 is kept at 0-4 ℃, and the reaction time in the ice water bath is 12-24h.
The biomass carbon/molybdenum disulfide@polypyrrole ternary composite material prepared by the preparation method is prepared.
The biomass carbon/molybdenum disulfide@polypyrrole ternary composite material is applied to a sodium ion battery anode material.
The beneficial effects of the application are as follows:
1. the application adopts biomass with layered network structure (such as petals and PC) as a framework by a simple one-step hydrothermal method, and grows MoS in situ 2 The nano-sheet is coated with polypyrrole PPy on the surface of the material to prepare PC/MoS of the lamellar network 2 Ternary sandwich composite @ PPyMaterial, moS 2 The interlayer spacing is obviously increased, and the agglomeration phenomenon is also relieved;
2. the biomass adopted in the application is the petals of the layered network structure, has rich sources and low cost, and can be used for MoS 2 The polypyrrole carbon layer in the ternary composite material has good conductivity and controllable thickness, and is wrapped in PC/MoS 2 Surface energy stabilized MoS 2 The structure reduces the impedance, thereby effectively improving the application performance;
3. PC/MoS provided by the application 2 When the@PPy ternary composite material is applied to a negative electrode material of a sodium ion battery, the layered network core-shell structure of the ternary composite material enables the electrode material to be fully contacted with electrolyte, a large number of electrochemical reaction active sites are provided, and MoS is effectively relieved 2 The three-dimensional conductive network formed by the biomass carbon skeleton and the PPy in the long circulation process also effectively improves the conductivity of the material, accelerates the electrochemical reaction kinetics of the material, and greatly improves the electrochemical sodium storage performance of the material.
Drawings
FIG. 1 is PC/MoS prepared in example 1 2 SEM and elemental profile of the @ PPy ternary composite;
FIG. 2 is a PC/MoS prepared in example 1 2 XRD spectrum of the@PPy ternary composite material, scanning speed is 5 degrees/min, and scanning range is 5-80 degrees;
FIG. 3 is PC/MoS prepared in example 1 2 A Raman spectrum of the @ PPy ternary composite material;
FIG. 4 is a PC/MoS prepared in example 1 2 The @ PPy ternary composite material is used as a cycle performance diagram of a negative electrode of the sodium ion battery;
FIG. 5 is a PC/MoS prepared in example 1 2 And (3) taking the@PPy ternary composite material as a rate performance graph of a negative electrode of the sodium ion battery.
Detailed Description
In order that the application may be understood more fully, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended claims. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete. The various materials used in the examples, unless otherwise indicated, are commonly commercially available products.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The values disclosed in the embodiments of the present application are approximate values, and are not determined values. Where the error or experimental conditions allow, all values within the error range may be included without limiting the specific values disclosed in the embodiments of the present application.
The numerical ranges disclosed in the examples of the present application are intended to represent relative amounts of the components in the mixture, as well as ranges of temperatures or other parameters recited in the examples of other methods.
The preparation method of the ternary composite material provided by the application comprises the following preparation steps:
s1: preparation of biomass carbon/molybdenum disulfide material
Washing, drying and crushing biomass into biomass powder, dispersing the biomass powder, sodium molybdate dihydrate and L-cysteine in deionized water, uniformly mixing, transferring to a reaction kettle for hydrothermal reaction, collecting black precipitate after the reaction is finished, centrifugally cleaning for a plurality of times, freeze-drying to obtain a reaction product, and annealing the reaction product in an inert atmosphere to obtain a biomass carbon/molybdenum disulfide composite material;
s2: preparation of biomass carbon/molybdenum disulfide@polypyrrole ternary composite material
Dispersing the biomass carbon/molybdenum disulfide composite material and p-toluenesulfonic acid in deionized water, placing the deionized water in an ice water bath for stirring and cooling, dropwise adding pyrrole monomers, after uniform dispersion, dropwise adding an ammonium peroxodisulfate aqueous solution, fully soaking, collecting precipitate, centrifugally cleaning the precipitate, and freeze-drying to obtain the biomass carbon/molybdenum disulfide@polypyrrole ternary composite material.
Wherein the biomass in S1 is biomass with a layered network structure.
The mass ratio of the sodium molybdate dihydrate to the L-cysteine in the S1 is 2:5.
the hydrothermal reaction temperature in S1 is controlled at 150-220 ℃ and the reaction time is controlled at 18-36h.
The freeze drying time in S1 is 12-24h.
The inert atmosphere in the S1 is argon, the annealing treatment temperature is 600-800 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 1-3h.
The dosage of pyrrole in S2 is 0.5-2 times of that of biomass carbon/molybdenum disulfide composite material, and the mass ratio of p-toluenesulfonic acid, ammonium peroxodisulfate and pyrrole is 8:8:5.
and S2, keeping the temperature of the ice water bath at 0-4 ℃ and reacting for 12-24 hours in the ice water bath.
The application adopts the biomass PC with the layered network structure as the framework by a simple one-step hydrothermal method, and grows MoS in situ 2 The nano-sheet is coated with polypyrrole PPy on the surface of the material to prepare PC/MoS of the lamellar network 2 @PPy ternary sandwich structure composite material and MoS 2 The interlayer spacing is obviously increased, the agglomeration phenomenon is also relieved, the biomass adopted in the application is a layered network structure petal, the source is rich, the cost is low, and the biomass can be used for MoS 2 The polypyrrole coating layer in the ternary composite material has good conductivity and controllable thickness, and is wrapped in PC/MoS 2 Surface energy stabilized MoS 2 The structure reduces the impedance, thereby effectively improving the application performance; PC/MoS provided by the application 2 When the@PPy ternary composite material is applied to a negative electrode material of a sodium ion battery, the sandwich structure of the layered network enables the electrode material to be fully contacted with electrolyte, a large number of electrochemical reaction active sites are provided, and MoS is effectively relieved 2 Volume change during long circulation, biomass carbon boneThe three-dimensional conductive network formed by the frames and the PPy also effectively improves the conductivity of the material, quickens the electrochemical reaction kinetics of the material, greatly improves the electrochemical sodium storage performance of the material, and can be widely used as a negative electrode material of a sodium ion battery.
The following are specific examples of the present application:
preparation of biomass carbon/molybdenum disulfide@polypyrrole ternary composite material
S1: preparation of biomass carbon/molybdenum disulfide material
Weighing 1g of washed, dried and crushed kapok petal powder, dispersing 0.6g of sodium molybdate dihydrate and 1.5g L-cysteine in 60mL of deionized water, magnetically stirring for 30min, transferring the mixed solution into a polytetrafluoroethylene reaction kettle liner, carrying out heat preservation reaction for 24h at 200 ℃, naturally cooling, centrifugally washing the obtained sample with deionized water and ethanol for multiple times, carrying out freeze drying for 12h, carrying out heat preservation for 2h at 800 ℃ in Ar atmosphere at a heating rate of 5 ℃/min, and carrying out furnace cooling to obtain a biomass carbon/molybdenum disulfide sample;
s2: preparation of biomass carbon/molybdenum disulfide@polypyrrole ternary composite material
Taking 0.1g of the biomass carbon/molybdenum disulfide sample, dispersing 0.08g of p-toluenesulfonic acid in 10mL of deionized water for 30min by ultrasonic, cooling the solution in an ice bath, taking 0.05g of pyrrole monomer under stirring, slowly dripping into the solution, stirring for 30min, slowly dripping into an aqueous solution in which 0.08g of ammonium peroxodisulfate is dissolved, collecting precipitate after 12h, centrifugally cleaning the sample for multiple times by using deionized water and ethanol respectively, and freeze-drying for 12h to obtain the biomass carbon/molybdenum disulfide@polypyrrole PC/MoS 2 Sample of PPy ternary composite.
For PC/MoS prepared in this example 2 SEM, XRD and Raman characterization are carried out on the @ PPy material, the characterization result is shown in figure 1, and as shown in figure 1, the PC/MoS provided by the application 2 The PC framework of the layered network structure in the@PPy ternary composite material is uniformly distributed with a plurality of MoS sheets 2 MoS polymerized by nano-sheets 2 Nanoparticles with a diameter ranging from 150 to 200nm, the network structure rich in functional groups being capable of giving MoS during hydrothermal processes 2 The growth of the nanoplatelets provides a large number of electrochemically reactive active sites; moS (MoS) 2 The nano-sheet has a slightly rough surface, which is a PPy carbon layer coated on the surface of the material. The high coincidence of C, N element with Mo and S element distribution in the element distribution spectrogram further indicates MoS 2 The nano-sheet is stably anchored on a PC layered network framework under the tight package of PPy, and the layered network structure has larger specific surface area, can provide a large number of electrochemical sodium storage active sites and simultaneously ensure the stability of the structure, thereby effectively solving the problem of MoS 2 As a negative electrode material of the sodium ion battery, the material has the problems of low reversible capacity, unstable circulation, poor rate capability and the like.
FIG. 2 shows the PC/MoS prepared in this example 2 XRD testing of the @ PPy ternary composite, which analyzed PC/MoS 2 The lattice structure and phase composition of the @ PPy ternary composite material, shown in FIG. 2, appear to belong to MoS at about 9 °, 33 ° and 58 ° 2 (002) Characteristic peaks of (100) and (110) crystal planes, and MoS at the same time 2 The presence of a significantly smaller angular offset compared to the standard card indicates PC/MoS 2 MoS in@PPy ternary composite material 2 The interlayer spacing of the polymer is obviously increased and calculated to be 0.98nm which is far greater than unmodified MoS 2 The spacing between layers is 0.64nm, the PC/MoS provided by the application 2 Ternary composite material @ PPy modified to allow MoS in the composite material 2 Is significantly increased in the interlayer spacing, moS 2 The increase of the interlayer spacing of the sodium ion intercalation polymer is beneficial to the deintercalation of sodium ions with larger ionic radius, thereby better meeting the requirement of specific capacity when the sodium ion intercalation polymer is applied to the anode material of a sodium ion battery.
FIG. 3 is a PC/MoS prepared in this example 2 Raman spectrum of the @ PPy ternary composite material, see FIG. 3, PC/MoS of the present application 2 At 372cm @ PPy -1 And 404cm -1 The nearby absorption peaks respectively correspond to MoS 2 A kind of electronic deviceAnd A 1g Characteristic peak at 1347cm -1 And 1583cm -1 The nearby peaks correspond to the D peak and D peak of the carbon material respectivelyG peak, 968cm -1 The small peak at this point is a characteristic peak of PPy.
The biomass carbon/molybdenum disulfide@polypyrrole PC/MoS prepared in the embodiment 2 the@PPy ternary composite material is applied to a sodium ion battery anode material and comprises the following specific steps:
according to 8:1:1 weight ratio PC/MoS was weighed 2 Mixing and grinding a@PPy composite material, conductive carbon black and sodium carboxymethylcellulose (CMC) with a proper amount of deionized water to obtain a slurry; coating the slurry on a cut foam nickel current collector, vacuum drying, tabletting, transferring into a glove box filled with Ar atmosphere, and using PC/MoS 2 The active pole piece of @ PPy is an anode, the metal sodium is a cathode, the Whatman glass fiber is a diaphragm, and the 1M NaClO 4 EC-DMC (volume ratio 1:1, 5% fec was added) solution to assemble coin cells for electrolyte and cell cycling and rate performance were measured on a LAND CT2001A system.
For the PC/MoS 2 The @ PPy is an electrochemical performance test of the half-cell assembled from electrode materials. As shown in FIG. 4, PC/MoS is performed at a current density of 100mA/g and a voltage window of 0.01-3.0V 2 The initial discharge specific capacity of the@PPy electrode is up to 652.9mAh/g, the initial charge specific capacity is 435.1mAh/g, and the discharge specific capacity is still kept at 412mAh/g after 50 circles of circulation. The rate performance of the material at different current densities (0.1-2A/g) is shown in FIG. 5, PC/MoS with increasing current density 2 The @ PPy electrode exhibited excellent rate capability, with reversible specific discharge capacities reaching 391.4, 362.4, 323.2, 268.6 and 193.9mAh/g at current densities of 0.1, 0.2, 0.5, 1 and 2A/g, respectively, and rapidly reaching initial levels (391 mAh/g) as the current density was reduced from 2A/g back to 0.1A/g.
Referring to the specific examples and experimental characterization results, the application adopts petal biomass carbon as a framework by a simple one-step hydrothermal method to grow MoS in situ 2 The nano-sheet is coated with polypyrrole on the surface of the material to prepare PC/MoS of the lamellar network 2 @PPy ternary sandwich structure composite material and MoS 2 The interlayer spacing is obviously increased, and the agglomeration phenomenon is also relieved; the biomass adopted in the application is a layered network structure petal,it has rich sources and low cost, and can be used for MoS 2 The polypyrrole coating layer in the ternary composite material has good conductivity, controllable thickness and is wrapped in PC/MoS 2 Surface energy stabilized MoS 2 The structure reduces the impedance, thereby effectively improving the application performance; PC/MoS provided by the application 2 When the@PPy ternary composite material is applied to a negative electrode material of a sodium ion battery, the sandwich structure of the layered network enables the electrode material to be fully contacted with electrolyte, a large number of electrochemical reaction active sites are provided, and MoS is effectively relieved 2 The three-dimensional conductive network formed by the biomass carbon skeleton and the PPy in the long circulation process also effectively improves the conductivity of the material, accelerates the electrochemical reaction kinetics of the material, and greatly improves the electrochemical sodium storage performance of the material.
The foregoing examples illustrate only a few embodiments of the application and are described in detail herein without thereby limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (7)
1. The preparation method of the ternary composite material is characterized by comprising the following preparation steps:
s1: preparation of biomass carbon/molybdenum disulfide material
Washing, drying and crushing biomass into biomass powder, dispersing the biomass powder, sodium molybdate dihydrate and L-cysteine in deionized water, uniformly mixing, transferring to a reaction kettle for hydrothermal reaction, collecting black precipitate after the reaction is finished, centrifugally cleaning for a plurality of times, freeze-drying to obtain a reaction product, and annealing the reaction product in an inert atmosphere to obtain a biomass carbon/molybdenum disulfide composite material;
s2: preparation of biomass carbon/molybdenum disulfide@polypyrrole ternary composite material
Dispersing the biomass carbon/molybdenum disulfide composite material and p-toluenesulfonic acid in deionized water, placing the deionized water in an ice water bath for stirring and cooling, dropwise adding pyrrole monomers, after uniform dispersion, dropwise adding an ammonium peroxodisulfate aqueous solution, fully soaking, collecting precipitate, centrifugally cleaning the precipitate, and freeze-drying to obtain the biomass carbon/molybdenum disulfide@polypyrrole ternary composite material;
wherein the biomass in S1 is biomass with a layered network structure;
wherein the mass ratio of the sodium molybdate dihydrate to the L-cysteine in the S1 is 2:5, a step of;
wherein the dosage of pyrrole in S2 is 0.5-2 times of that of the biomass carbon/molybdenum disulfide composite material, and the mass ratio of p-toluenesulfonic acid, ammonium peroxodisulfate and pyrrole is 8:8:5.
2. the method for preparing a ternary composite material according to claim 1, wherein the hydrothermal reaction temperature in S1 is controlled to be 150-220 ℃ and the reaction time is controlled to be 18-36h.
3. The method of claim 1, wherein the freeze-drying time in S1 is 12-24 hours.
4. The method for preparing the ternary composite material according to claim 1, wherein the inert atmosphere in the step S1 is argon, the annealing treatment temperature is 600-800 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 1-3h.
5. The method for preparing a ternary composite material according to claim 1, wherein the temperature of the ice water bath in S2 is kept at 0-4 ℃, and the reaction time in the ice water bath is 12-24h.
6. A biomass carbon/molybdenum disulfide @ polypyrrole ternary composite material made by the method of any of claims 1-5.
7. The use of the biomass carbon/molybdenum disulfide @ polypyrrole ternary composite material as a negative electrode material of a sodium ion battery according to claim 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106517182A (en) * | 2016-11-08 | 2017-03-22 | 南昌航空大学 | Preparation method of biomass carbon adopting layered structure |
| CN106847547A (en) * | 2017-02-09 | 2017-06-13 | 同济大学 | Three-dimensional tubulose molybdenum bisuphide/polypyrrole composite electrode material for super capacitor and its preparation |
| CN111740080A (en) * | 2020-02-10 | 2020-10-02 | 天能电池集团股份有限公司 | Electrochemical sodium storage electrode made of composite nano material and preparation method thereof |
| CN112786870A (en) * | 2021-02-10 | 2021-05-11 | 广西师范大学 | Polypyrrole coated MoS2/C composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106517182A (en) * | 2016-11-08 | 2017-03-22 | 南昌航空大学 | Preparation method of biomass carbon adopting layered structure |
| CN106847547A (en) * | 2017-02-09 | 2017-06-13 | 同济大学 | Three-dimensional tubulose molybdenum bisuphide/polypyrrole composite electrode material for super capacitor and its preparation |
| CN111740080A (en) * | 2020-02-10 | 2020-10-02 | 天能电池集团股份有限公司 | Electrochemical sodium storage electrode made of composite nano material and preparation method thereof |
| CN112786870A (en) * | 2021-02-10 | 2021-05-11 | 广西师范大学 | Polypyrrole coated MoS2/C composite material and preparation method thereof |
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