CN115092961B - Preparation method and application of hollow spherical shell structured vanadium oxyhydroxide - Google Patents
Preparation method and application of hollow spherical shell structured vanadium oxyhydroxide Download PDFInfo
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- NNLCYUIKYSRIHF-UHFFFAOYSA-N [V].O(O)O Chemical compound [V].O(O)O NNLCYUIKYSRIHF-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 150000008117 polysulfides Polymers 0.000 claims abstract description 100
- 229920001021 polysulfide Polymers 0.000 claims abstract description 90
- 239000005077 polysulfide Substances 0.000 claims abstract description 90
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 31
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000004888 barrier function Effects 0.000 claims abstract description 28
- 229910018091 Li 2 S Inorganic materials 0.000 claims abstract description 26
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- -1 graphene compound Chemical class 0.000 claims abstract description 12
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 42
- 239000006185 dispersion Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 31
- 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 30
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 19
- QKDGGEBMABOMMW-UHFFFAOYSA-I [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] QKDGGEBMABOMMW-UHFFFAOYSA-I 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000013329 compounding Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 3
- 230000008384 membrane barrier Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003440 toxic substance Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 231100000167 toxic agent Toxicity 0.000 description 3
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a preparation method and application of a hollow spherical shell structure vanadium oxyhydroxide. The vanadium oxyhydroxide has a spherical shape, the diameter of 190-330nm and a hollow structure inside; the thickness of the spherical shell is 35-42nm, holes are distributed on the spherical shell, and the density of the holes is (3.85-4.52) multiplied by 10 ‑4 Individual/nm 2 The method comprises the steps of carrying out a first treatment on the surface of the The molecular formula of the vanadium oxyhydroxide is VOOH, and the structural formula is H-O-V=O. The hollow spherical shell structure vanadium oxyhydroxide is used for preparing a lithium sulfur battery diaphragm barrier layer; the hollow spherical shell structure vanadium oxyhydroxide is used for accommodating polysulfide; the hollow spherical shell structure vanadium oxyhydroxide is used for adsorbing polysulfide; the vanadium in the hydroxyl vanadium oxide with the specific hollow spherical shell structure and sulfur in polysulfide form a V-S chemical bond, so that the hydroxyl vanadium oxide with the hollow spherical shell structure and polysulfide form chemical adsorption; the hollow spherical shell structure vanadium oxyhydroxide and nitrogen doped graphene compound is used for catalyzing polysulfide, and the polysulfide is catalytically converted into Li 2 S。
Description
Technical Field
The invention relates to a preparation method and application of vanadium oxyhydroxide, in particular to application of a hollow spherical shell structure vanadium oxyhydroxide.
Background
With the continuous development of the electric automobile industry and the intellectualization and portability of portable electronic products, the demand for energy storage devices is also increasing, so that the development of energy storage devices with high energy density, high specific capacity, long cycle life and high safety factor is urgent, and the development of energy storage devices with high energy density, high specific capacity, long cycle life and high safety factor is urgentAmong the various novel energy storage devices, the secondary battery has received great attention from scientific research and industry because of the advantages of small volume, light weight, recycling and the like. Among the existing secondary batteries, lithium Sulfur Batteries (LSBs) have a high energy density (2500 Wh.kg) -1 ) And a high specific capacity (1675 mAh.g) -1 ) The positive electrode sulfur simple substance has the advantages of abundant reserves, low production cost, environmental friendliness and the like, and is considered as one of the next generation high-energy-density electrochemical energy storage devices with the highest application potential.
The lithium-sulfur battery mainly comprises a sulfur (S) anode, a metal lithium cathode, an electrolyte and a porous polyolefin microporous diaphragm. Currently, one of the main problems facing the practical use of lithium sulfur batteries is polysulfide (Li 2 S n (4.ltoreq.n.ltoreq.8)), which causes problems of capacity degradation, loss of active material, reduction in coulombic efficiency, self-discharge, and the like of the battery. The shuttle effect can be effectively relieved by constructing the diaphragm barrier layer, and the effect of the diaphragm barrier layer and polysulfide molecules can be seen at present. Materials that mitigate the shuttle effect have three functions: 1) Physical confinement; 2) Chemical adsorption; 3) Catalytic conversion of soluble polysulfides. Physical confinement refers to confining polysulfides within the pore structure of a material, such as hollow nanorods, hollow nanocubes, hollow microspheres, and the like; chemisorption is the formation of metal-S bonds by metal cations and polysulfide anions; catalytic conversion of soluble polysulfides is generally referred to as accelerating the liquid-solid reaction process, promoting the conversion of the soluble polysulfides to solid Li 2 S, avoiding accumulation of polysulfide in electrolyte.
In order to solve the technical problems, the invention designs a preparation method and application of the hollow spherical shell structure vanadium oxyhydroxide.
Disclosure of Invention
The invention aims to provide a preparation method and application of a hollow spherical shell structure vanadium oxyhydroxide. The invention uses the hollow spherical shell structure vanadium hydroxide (VOOH) to prepare the lithium sulfur battery diaphragm barrier layer, the barrier layer can be effectively dispersed in ethanol due to the function of the functional group (-OH), and the hollow sphereThe VOOH of the shell structure does not need to be simultaneously ultrasonically treated with the conductive agent, so that the appearance of the hollow spherical shell structure is prevented from being damaged by the ultrasonic treatment; successful combination of the barrier layer and the PP diaphragm is realized by a vacuum filtration method; the VOOH of the hollow spherical shell structure can contain polysulfide and can chemically adsorb polysulfide, so that polysulfide shuttling to the negative electrode is reduced; on the other hand, the vanadium oxyhydroxide and nitrogen-doped graphene compound with the hollow spherical shell structure can be used for catalytically converting polysulfide into Li 2 S, the barrier layer is used for effectively inhibiting the multi-sulfur shuttle, and the electrochemical performance of the lithium-sulfur battery is finally improved; the preparation method provided by the invention is simple and feasible, has low cost, reduces the use of toxic substance N-methyl pyrrolidone, and provides a feasible scheme for the application of the VOOH material with the hollow spherical shell structure to lithium-sulfur batteries.
The technical scheme of the invention is as follows: the vanadium oxyhydroxide with the hollow spherical shell structure has a spherical shape, a diameter of 190-330nm and a hollow structure inside; the thickness of the spherical shell is 35-42nm, holes are distributed on the spherical shell, and the density of the holes is (3.85-4.52) multiplied by 10 -4 Individual/nm 2 The method comprises the steps of carrying out a first treatment on the surface of the The molecular formula of the vanadium oxyhydroxide is VOOH, and the structural formula is H-O-V=O.
In the preparation method of the hollow spherical shell structure vanadium oxyhydroxide, the vanadium oxyhydroxide is prepared through the following steps:
(1) Adding ammonium metavanadate into deionized water and stirring to obtain a product A;
(2) Adding hydrochloric acid solution into the product A, then adding hydrazine hydrate solution, and continuously stirring to obtain a product B;
(3) And (3) carrying out hydrothermal reaction on the product B, cooling, and then using absolute ethyl alcohol and deionized water to mix, centrifugally clean, thereby obtaining the vanadium oxyhydroxide with a hollow spherical shell structure.
In the step (1), 0.234 to 0.250g of ammonium metavanadate is added into 40 to 50mL of deionized water, and the mixture is magnetically stirred for 0.5 to 1.5 hours at the temperature of between 10 and 30 ℃ at the rotating speed of between 350 and 390 r.min -1 ；
The steps ofIn the step (2), 1-1.2mL of hydrochloric acid solution is added into 40-50mLA product under the condition of magnetic stirring at the temperature of 10-30 ℃, then 2-3mL of hydrazine hydrate solution is added, and the magnetic stirring is continued for 0.5-1.5h at the temperature of 10-30 ℃ with the rotating speed of 350-390 r.min -1 ；
The concentration of the hydrochloric acid is 0.8-1.2 mol.L -1 The mass fraction of the hydrazine hydrate solution is 80-85%.
In the preparation method of the hollow spherical shell structure vanadium oxyhydroxide, in the step (3), the product B is subjected to a hydrothermal reaction at a temperature of 150-170 ℃ for 10-14 hours, cooled to 20-30 ℃, and then mixed with absolute ethyl alcohol and deionized water, centrifugally cleaned to a pH value of 6.8-7.2, thereby obtaining the hollow spherical shell structure vanadium oxyhydroxide.
The application of the hollow spherical shell structure vanadium oxyhydroxide is that the hollow spherical shell structure vanadium oxyhydroxide is used for preparing a lithium sulfur battery diaphragm barrier layer; the method specifically comprises the following steps:
(4) Adding the hollow spherical shell structure vanadium oxyhydroxide into absolute ethyl alcohol, and dispersing to obtain a C product;
(5) Reducing graphene oxide by using a hydrazine hydrate solution to prepare nitrogen-doped graphene, so as to obtain a D product;
(6) Dissolving the binder in N-methyl pyrrolidone and absolute ethyl alcohol, then adding the product D, carrying out ultrasonic dispersion, then adding the product C, and stirring to obtain the product E;
(7) And carrying out vacuum suction filtration on the E product by using a diaphragm to obtain a diaphragm modified by the E product, namely the diaphragm barrier layer of the lithium-sulfur battery.
In the application of the hollow spherical shell structure vanadium oxyhydroxide, in the step (4), 0.11-0.405g of hollow spherical shell structure vanadium oxyhydroxide is added into 20-30mL of absolute ethyl alcohol, and the mixture is magnetically stirred and dispersed for 2-4h, wherein the rotation speed of the magnetic stirring is as follows: 350-390 r.min -1 Obtaining a C product;
in the step (5), under the condition of ice bath, using an ultrasonic cell pulverizer to disperse graphene oxide in deionized water to obtain a dispersion liquid, wherein the concentration of the dispersion liquid is 1.8-2.2 mg.mL -1 Under magnetic stirring, adding 40-42.5% hydrazine hydrate dropwise into the dispersion liquid, and reacting at 70-90deg.CAfter cooling to 20-30 ℃ for 20-28h, cleaning to pH 6.8-7.2, and freeze-drying to obtain nitrogen-doped graphene powder to obtain a D product; the time of the magnetic stirring is 20-28h, and the rotating speed of the magnetic stirring is as follows: 350-390 r.min -1 ；
In the step (6), 0.005g of the binder PVDF is dissolved in 20-30mLN-
Adding methyl pyrrolidone and 180-190mL absolute ethyl alcohol, then adding 0.005-0.025g D product, performing ultrasonic dispersion, then adding 1.67-7.3mLC products, and magnetically stirring to obtain E product; the ultrasonic dispersion power is 200-240W, and the dispersion time is 3-5h; the time of the magnetic stirring is 2-4 hours, and the rotating speed of the magnetic stirring is as follows: 350-390 r.min -1 。
And (7) carrying out vacuum suction filtration on the E product by using a Celgard-2500PP membrane to obtain the lithium sulfur battery membrane barrier layer.
The application of the hollow spherical shell structure vanadium oxyhydroxide is that the hollow spherical shell structure vanadium oxyhydroxide is used for accommodating polysulfide; the polysulfide is polysulfide dissolved in electrolyte and formed by reaction with lithium ions in the discharge process of sulfur positive electrode, and the molecular formula of the polysulfide is Li 2 S n (n is more than or equal to 4 and less than or equal to 8), and the diameter of polysulfide molecules is 1-2nm.
The application of the hollow spherical shell structure vanadium oxyhydroxide is that the hollow spherical shell structure vanadium oxyhydroxide is used for adsorbing polysulfide; the vanadium in the hydroxyl vanadium oxide with the specific hollow spherical shell structure and sulfur in polysulfide form a V-S chemical bond, so that the hydroxyl vanadium oxide with the hollow spherical shell structure and polysulfide form chemical adsorption;
the polysulfide is polysulfide dissolved in electrolyte and formed by reaction with lithium ions in the discharge process of sulfur positive electrode, and the molecular formula of the polysulfide is Li 2 S n (n is more than or equal to 4 and less than or equal to 8), and the diameter of polysulfide molecules is 1-2nm.
The application of the hollow spherical shell structure vanadium oxyhydroxide applies the hollow spherical shell structure vanadium oxyhydroxide and nitrogen doped graphene compound to catalyze polysulfide, and the polysulfide is catalytically converted into Li 2 S；
The method for compounding the vanadium oxyhydroxide with the hollow spherical shell structure and the nitrogen-doped graphene specifically comprises the following steps:
(7) Adding the hollow microsphere vanadium oxyhydroxide into absolute ethyl alcohol, and dispersing to obtain a product C;
(8) Reducing graphene oxide by using a hydrazine hydrate solution to prepare nitrogen-doped graphene, so as to obtain a D product;
(9) Adding the product D into absolute ethyl alcohol, performing ultrasonic dispersion, adding the product C, and stirring to obtain a hollow spherical shell structure vanadium hydroxide and nitrogen doped graphene compound;
the polysulfide is polysulfide dissolved in electrolyte and formed by reaction with lithium ions in the discharge process of sulfur positive electrode, and the molecular formula of the polysulfide is Li 2 S n (n is more than or equal to 4 and less than or equal to 8), and the diameter of polysulfide molecules is 1-2nm.
In the application of the hollow spherical shell structure vanadium oxyhydroxide, in the step (7), 0.11-0.405g of the hollow spherical shell structure vanadium oxyhydroxide is added into 20-30mL of absolute ethyl alcohol, and the mixture is magnetically stirred and dispersed for 2-4h, wherein the rotation speed of the magnetic stirring is as follows: 350-390 r.min -1 Obtaining a C product;
in the step (8), under the condition of ice bath, using an ultrasonic cell pulverizer to disperse graphene oxide in deionized water to obtain a dispersion liquid, wherein the concentration of the dispersion liquid is 1.8-2.2 mg.mL -1 Under magnetic stirring, then dripping hydrazine hydrate with the mass fraction of 40-42.5% into the dispersion liquid, reacting for 20-28h at 70-90 ℃, cooling to 20-30 ℃, cleaning to pH of 6.8-7.2, and freeze-drying to obtain nitrogen-doped graphene powder to obtain a D product; the time of the magnetic stirring is 20-28h, and the rotating speed of the magnetic stirring is as follows: 350-390 r.min -1 ；
Adding 0.005-0.025g of D product into 180-190mL of absolute ethyl alcohol, performing ultrasonic dispersion, adding 1.67-7.3 g of mLC product, and magnetically stirring to obtain a hollow spherical shell structure vanadium hydroxide and nitrogen doped graphene compound; the ultrasonic dispersion power is 200-240W, and the dispersion time is 3-5h; the time of the magnetic stirring is 2-4 hours, and the rotating speed of the magnetic stirring is as follows: 350-390 r.min -1 。
Compared with the prior art, the invention has the following beneficial effects:
1. the VOOH (vanadium oxyhydroxide) of the hollow spherical shell structure prepared by the invention has spherical morphology, the diameter of 190-330nm and the hollow structure inside; the thickness of the spherical shell is 35-42nm, holes are distributed on the spherical shell, and the density of the holes is (3.85-4.52) multiplied by 10 -4 Individual/nm 2 The method comprises the steps of carrying out a first treatment on the surface of the The molecular formula of the vanadium oxyhydroxide is VOOH, the structural formula is H-O-V=O, polysulfide can be contained, and shuttle of polysulfide is reduced; due to the 'size effect', the thinner the shell thickness is, the shorter the ion diffusion distance is, the time required for ion diffusion is reduced, the ion migration is promoted, and the spherical shell thickness of 35-42nm can promote the lithium ion migration.
2. In the step (1), the reaction temperature is 10-30 ℃, the magnetic stirring time is 0.5-1.5h, and the rotating speed of the magnetic stirring is 350-390 r.min -1 The method comprises the steps of carrying out a first treatment on the surface of the In order to effectively dissolve ammonium metavanadate; in step (2), hydrochloric acid is added for the purpose of adding ammonium metavanadate (NH) 4 VO 3 ) VO in (2) 3 - Conversion to VO 2 + The purpose of the hydrazine hydrate is to make VO 2 + Conversion to V 3+ Finally, V (OH) is formed 2 NH 2 The magnetic stirring time is 0.5-1.5h after adding hydrazine hydrate, in order to make VO 2 + Completely converted into V (OH) 2 NH 2 The method comprises the steps of carrying out a first treatment on the surface of the In step (3), V (OH) is reacted under the reaction conditions 2 NH 2 VOOH can be generated, and the reaction equation is as follows: v (OH) 2 NH 2 +H 2 O→VOOH+NH 4 OH, the purpose of the centrifugal washing by mixing absolute ethanol and deionized water is to wash off unreacted hydrazine hydrate and generated NH 4 OH, the purpose of centrifugal cleaning is convenient for subsequent VOOH to disperse in absolute ethyl alcohol, and the preparation method is simple and the reaction period is short.
3. The invention uses the hollow spherical shell structure vanadium hydroxide to prepare the lithium sulfur battery diaphragm barrier layer, and specifically adds the hollow spherical shell structure VOOH into absolute ethyl alcohol through the step (4), and magnetically stirring and dispersing are carried out, wherein the step is mainly because of the existence of hydroxyl in the hollow spherical shell structure VOOH, so that the hollow spherical shell structure VOOH can be dispersed in the absolute ethyl alcohol, and the magnetic stirring condition is proper, and the specific magnetic stirring time is 2-4hVOOH can be effectively dispersed in the room, and the rotation speed of magnetic stirring is as follows: 350-390 r.min -1 The appearance of VOOH is not destroyed at the stirring speed; the nitrogen doped graphene (NG) powder is prepared through the step (5), and the concentration of the graphene oxide dispersion liquid in the step (5) is 1.8-2.2 mg.mL -1 The mass fraction of the hydrazine hydrate reducing agent is 40-42.5%, and when the hydrazine hydrate reducing agent reacts for 20-28 hours at 70-90 ℃, the nitrogen doped graphene with better conductivity can be prepared; step (6) dissolving 0.005g of a binder PVDF in 20-30 mLN-methyl pyrrolidone and 180-190mL of absolute ethyl alcohol, wherein the PVDF is used for preventing the barrier layer material from falling off on the membrane, and the reason why the PVDF is dissolved by using less N-methyl pyrrolidone is that the use of toxic substances N-methyl pyrrolidone is reduced; the addition of absolute ethanol does not affect the dissolution of PVDF and, in addition, it is also possible to disperse VOOH. The magnetic stirring time is 2-4h, and the rotating speed of the magnetic stirring is as follows: 350-390 r.min -1 The morphological characteristics of VOOH are not damaged, and the recombination of VOOH and nitrogen doped graphene can be realized; the step (7) realizes successful combination of the barrier layer and the PP diaphragm by a vacuum suction filtration method, and the preparation method provided by the invention is simple and feasible, has low cost, reduces the use of toxic substance N-methyl pyrrolidone, and provides a feasible scheme for the application of the material with the hollow spherical shell structure to lithium-sulfur batteries.
The diaphragm prepared by the invention can effectively inhibit the shuttle of polysulfide and improve the electrochemical performance of a lithium-sulfur battery. Its initial discharge capacity is 891.8 mAh.g -1 The capacity is still kept at 488.0 mAh.g after 600 cycles -1 The capacity fade rate at 1C was 0.075%. The research is beneficial to developing a high-performance lithium sulfur battery, promotes the development of the lithium sulfur battery towards the high specific capacity and long service life, and has important research significance in the field of energy conversion and storage.
4. The hollow spherical shell structure vanadium oxyhydroxide is used for accommodating polysulfide; the polysulfide is polysulfide dissolved in electrolyte and formed by reaction with lithium ions in the discharge process of sulfur positive electrode, and the molecular formula of the polysulfide is Li 2 S n (4.ltoreq.n.ltoreq.8) straight polysulfide moleculesThe diameter is 1-2nm. The hollow porous structure of the VOOH in particular provides a large amount of surface area, so that the hollow porous structure is fully contacted with polysulfide molecules, polysulfide molecules are adsorbed by van der waals force, and the polysulfide molecules enter the interior of the hollow VOOH, so that the hollow spherical shell structure vanadium oxyhydroxide can be used for accommodating polysulfide.
5. The hollow spherical shell structure vanadium oxyhydroxide is used for adsorbing polysulfide; the vanadium in the hydroxyl vanadium oxide with the specific hollow spherical shell structure and sulfur in polysulfide form a V-S chemical bond, so that the hydroxyl vanadium oxide with the hollow spherical shell structure and polysulfide form chemical adsorption; since the V element can form a V-S chemical bond with polysulfide, chemisorption is extremely stable,
6. the invention uses the hollow spherical shell structure vanadium oxyhydroxide and nitrogen doped graphene compound (VOOH/NG) for catalyzing polysulfide, and catalytically converts polysulfide into Li 2 S, S; due to the effect of hydroxyl in the hollow spherical shell structure VOOH, the hollow spherical shell structure VOOH can be uniformly dispersed in C 2 H 5 In OH, the recombination of VOOH and NG of the hollow spherical shell structure is realized. Specific VOOH/NG can mix Li 2 S n (n is more than or equal to 4 and less than or equal to 8) to be catalytically converted into Li 2 S, specifically, the following reaction, working electrode:
a counter electrode:
in conclusion, the invention oxidizes hydroxyl groups by adopting a hollow spherical shell structureVanadium (VOOH) is used for preparing a lithium-sulfur battery diaphragm barrier layer, the barrier layer can be effectively dispersed in ethanol due to the function of a functional group (-OH), and the VOOH of the hollow spherical shell structure does not need to be simultaneously ultrasonically treated with a conductive agent, so that the appearance of the hollow spherical shell structure is prevented from being damaged by the ultrasonic treatment; successful combination of the barrier layer and the PP diaphragm is realized by a vacuum filtration method; the VOOH of the hollow spherical shell structure can contain polysulfide and can chemically adsorb polysulfide, so that polysulfide shuttling to the negative electrode is reduced; on the other hand, the vanadium oxyhydroxide and nitrogen-doped graphene compound with the hollow spherical shell structure can be used for catalytically converting polysulfide into Li 2 S, the barrier layer is used for effectively inhibiting the multi-sulfur shuttle, and the electrochemical performance of the lithium-sulfur battery is finally improved; the preparation method provided by the invention is simple and feasible, has low cost, reduces the use of toxic substance N-methyl pyrrolidone, and provides a feasible scheme for the application of the VOOH material with the hollow spherical shell structure to lithium-sulfur batteries.
Drawings
FIG. 1 is XRD of VOOH prepared in examples 1-3 of the present invention;
FIG. 2 is SEM (a) and TEM (b) of VOOH prepared in examples 1-3 of the invention;
FIG. 3 is an SEM cross-section of VOOH/NG-PP prepared according to application examples 1-1, 1-2, 1-3 of the invention;
FIG. 4 is an SEM surface of the VOOH/NG-PP (b) of the invention PP (a) and prepared according to application examples 1-1, 1-2, 1-3;
FIG. 5 is a graph of the cycling performance of lithium sulfur batteries assembled based on commercial PP separator membranes, VOOH/NG-PP, and NG-PP prepared by application examples 1-1, 1-2, 1-3 of the invention;
FIG. 6 is a view showing the addition of Li to VOOH of practical example 2-1 of the present invention 2 S 6 Standing for 2h to obtain a visual experimental chart;
FIG. 7 is an ultraviolet spectrum of application example 3-1VOOH (a) after a visualization experiment, and FIG. 7 (b) is XPS of V2p of VOOH;
FIG. 8 is Li using the VOOH/NG electrode of example 4-3 2 S 6 Symmetrical battery test patterns.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not intended to be limiting.
Example 1: the vanadium oxyhydroxide with the hollow spherical shell structure has a spherical shape, a diameter of 190-330nm and a hollow structure inside; the thickness of the spherical shell is 35-42nm, holes are distributed on the spherical shell, and the density of the holes is (3.85-4.52) multiplied by 10 -4 Individual/nm 2 The method comprises the steps of carrying out a first treatment on the surface of the The molecular formula of the vanadium oxyhydroxide is VOOH, and the structural formula is H-O-V=O.
The preparation method of the hollow spherical shell structure vanadium oxyhydroxide comprises the following steps:
(1) Adding 0.234g of ammonium metavanadate into 40mL of deionized water, magnetically stirring at 30 ℃ for 0.5h at a rotational speed of 350 r.min -1 Obtaining a product A;
(2) Adding 1mL of hydrochloric acid solution into 40mLA product under the condition of 30 ℃ magnetic stirring, then adding 2mL of hydrazine hydrate solution, and continuing magnetic stirring for 0.5h at 30 ℃ with the rotating speed of 350 r.min -1 Obtaining a product B;
the concentration of the hydrochloric acid is 0.8mol.L -1 The mass fraction of the hydrazine hydrate solution is 80%.
(3) And (3) carrying out hydrothermal reaction on the product B, wherein the temperature of the hydrothermal reaction is 150 ℃, the reaction time is 10 hours, cooling to 20 ℃, and then, mixing absolute ethyl alcohol and deionized water, centrifugally cleaning until the pH value is 6.8, thereby obtaining the vanadium hydroxide with the hollow spherical shell structure.
Example 2: the vanadium oxyhydroxide with the hollow spherical shell structure has a spherical shape, a diameter of 190-330nm and a hollow structure inside; the thickness of the spherical shell is 35-42nm, holes are distributed on the spherical shell, and the density of the holes is (3.85-4.52) multiplied by 10 -4 Individual/nm 2 The method comprises the steps of carrying out a first treatment on the surface of the The molecular formula of the vanadium oxyhydroxide is VOOH, and the structural formula is H-O-V=O.
The preparation method of the hollow spherical shell structure vanadium oxyhydroxide comprises the following steps:
(1) Adding 0.24g of ammonium metavanadateAdding into 45mL deionized water, magnetically stirring at 20deg.C for 1 hr at a rotation speed of 370 r.min -1 Obtaining a product A;
(2) Adding 1.1mL of hydrochloric acid solution into 45mLA product under the condition of magnetic stirring at 20 ℃, then adding 2.5mL of hydrazine hydrate solution, and continuing magnetic stirring for 1h at 20 ℃ at the rotating speed of 370 r.min -1 Obtaining a product B;
the concentration of the hydrochloric acid is 1 mol.L -1 The mass fraction of the hydrazine hydrate solution is 83%.
(3) And (3) carrying out hydrothermal reaction on the product B, wherein the temperature of the hydrothermal reaction is 160 ℃, the reaction time is 12 hours, cooling to 25 ℃, and then, mixing absolute ethyl alcohol and deionized water, centrifugally cleaning until the pH value is 7, thereby obtaining the vanadium hydroxide with the hollow spherical shell structure.
Example 3: the vanadium oxyhydroxide with the hollow spherical shell structure has a spherical shape, a diameter of 190-330nm and a hollow structure inside; the thickness of the spherical shell is 35-42nm, holes are distributed on the spherical shell, and the density of the holes is (3.85-4.52) multiplied by 10 -4 Individual/nm 2 The method comprises the steps of carrying out a first treatment on the surface of the The molecular formula of the vanadium oxyhydroxide is VOOH, and the structural formula is H-O-V=O.
The preparation method of the hollow spherical shell structure vanadium oxyhydroxide comprises the following steps:
(1) Adding 0.250g of ammonium metavanadate into 50mL of deionized water, magnetically stirring at 10deg.C for 1.5h at a rotation speed of 390 r.min -1 Obtaining a product A;
(2) Adding 1.2mL of hydrochloric acid solution into 50mL of the product under the condition of magnetic stirring at 10 ℃, then adding 3mL of hydrazine hydrate solution, and continuing magnetic stirring for 1.5h at 10 ℃ with the rotating speed of 390 r.min -1 Obtaining a product B;
the concentration of the hydrochloric acid is 1.2 mol.L -1 The mass fraction of the hydrazine hydrate solution is 85%.
(3) And (3) carrying out hydrothermal reaction on the product B, wherein the temperature of the hydrothermal reaction is 170 ℃, the reaction time is 14 hours, cooling to 30 ℃, and then, mixing absolute ethyl alcohol and deionized water, centrifugally cleaning until the pH value is 7.2, thereby obtaining the vanadium hydroxide with the hollow spherical shell structure.
Experiments prove that:
1. as shown in fig. 1, by X-ray diffraction analysis (XRD), XRD of vanadium oxyhydroxide (fig. 1) exhibited peak positions corresponding one by one to standard pdf#74-1877 cards, with (020), (120), (031), (111), (131), (200), (151), (002) and (251) crystal planes corresponding to 14.1 °, 27.0 °, 36.4 °, 38.1 °, 43.4 °, 46.9 °, 52.8 °, 60.4 ° and 68.5 °, respectively; indicating that VOOH was successfully prepared.
2. Fig. 2 is SEM and TEM images of vanadium oxyhydroxide. The vanadium oxyhydroxide can be spherical, has the diameter of 190-330nm and has a hollow structure inside; the inside is a hollow structure; the thickness of the spherical shell is 35-42nm, holes are distributed on the spherical shell, and the density of the holes is (3.85-4.52) multiplied by 10 -4 Individual/nm 2 The hollow spherical shell structure vanadium oxyhydroxide disclosed by the invention.
Application example 1-1: the vanadium oxyhydroxide with the hollow spherical shell structure is used for preparing a lithium sulfur battery diaphragm barrier layer; the method specifically comprises the following steps:
(4) 0.11g of vanadium oxyhydroxide with a hollow spherical shell structure is added into 20mL of absolute ethyl alcohol, and is magnetically stirred and dispersed for 2h, wherein the rotating speed of the magnetic stirring is as follows: 350r min -1 Obtaining a C product;
(5) Under the condition of ice bath, graphene oxide is dispersed in deionized water by using an ultrasonic cyto-pulverizer to obtain a dispersion liquid, wherein the concentration of the dispersion liquid is 1.8 mg.mL -1 Dropwise adding hydrazine hydrate with the mass fraction of 40% into the dispersion liquid under magnetic stirring, reacting for 20 hours at 70 ℃, cooling to 20 ℃, cleaning to pH 6.8, and freeze-drying to obtain nitrogen-doped graphene powder to obtain a D product; the time of the magnetic stirring is 20h, and the rotating speed of the magnetic stirring is as follows: 350r min -1 ；
(6) Dissolving 0.005g of a binder PVDF into 20 mLN-methylpyrrolidone and 190mL of absolute ethyl alcohol, then adding 0.005g of D product, performing ultrasonic dispersion, adding 7.3 g of mLC product, and magnetically stirring to obtain E product; the ultrasonic dispersion power is 200W, and the dispersion time is 3h; the time of the magnetic stirring is 2h, and the rotating speed of the magnetic stirring is as follows: 350r min -1 ；
(7) And (3) carrying out vacuum suction filtration on the E product by using a Celgard-2500PP diaphragm to obtain the lithium-sulfur battery diaphragm barrier layer.
Application examples 1-2: the vanadium oxyhydroxide with the hollow spherical shell structure is used for preparing a lithium sulfur battery diaphragm barrier layer; the method specifically comprises the following steps:
(4) 0.25g of vanadium oxyhydroxide with a hollow spherical shell structure is added into 25mL of absolute ethyl alcohol, and is magnetically stirred and dispersed for 3 hours, wherein the rotating speed of the magnetic stirring is as follows: 370 r.min -1 Obtaining a C product;
(5) Under the condition of ice bath, graphene oxide is dispersed in deionized water by using an ultrasonic cell pulverizer to obtain dispersion liquid, wherein the concentration of the dispersion liquid is 2 mg/mL -1 Dropwise adding hydrazine hydrate with the mass fraction of 41% into the dispersion liquid under magnetic stirring, reacting for 24 hours at 80 ℃, cooling to 25 ℃, cleaning to pH 7, and freeze-drying to obtain nitrogen-doped graphene powder to obtain a D product; the time of the magnetic stirring is 24 hours, and the rotating speed of the magnetic stirring is as follows: 370 r.min -1 ；
(6) 0.005g of PVDF binder was dissolved in 25 mLN-methylpyrrolidone and 185mL absolute ethanol, then added with 0.025g of D product, dispersed by ultrasound, and then added with 2mLC
Magnetically stirring the product to obtain a product E; the ultrasonic dispersion power is 220W, and the dispersion time is 4h; the time of the magnetic stirring is 3h, and the rotating speed of the magnetic stirring is as follows: 370 r.min -1 ；
(7) And (3) carrying out vacuum suction filtration on the E product by using a Celgard-2500PP diaphragm to obtain the lithium-sulfur battery diaphragm barrier layer.
Application examples 1-3: the vanadium oxyhydroxide with the hollow spherical shell structure is used for preparing a lithium sulfur battery diaphragm barrier layer; the method specifically comprises the following steps:
(4) 0.405g of hollow spherical shell structure vanadium hydroxide is added into 30mL of absolute ethyl alcohol, and is magnetically stirred and dispersed for 4 hours, wherein the rotating speed of the magnetic stirring is as follows: 390 r.min -1 Obtaining a C product;
(5) Under the condition of ice bath, graphene oxide is dispersed in deionized water by using an ultrasonic cell pulverizer to obtain a dispersion liquid, wherein the concentration of the dispersion liquid is 2.2 mg.mL -1 Under magnetic stirring, adding hydrazine hydrate with mass fraction of 42.5% into the dispersion liquid dropwise, reacting at 90 ℃ for 28h, and coolingAfter the temperature reaches 30 ℃, cleaning until the pH value is 7.2, and obtaining nitrogen doped graphene powder after freeze drying to obtain a D product; the time of the magnetic stirring is 28h, and the rotating speed of the magnetic stirring is as follows: 390 r.min -1 ；
(6) Dissolving 0.005g of a binder PVDF in 30 mLN-methylpyrrolidone and 180mL of absolute ethyl alcohol, then adding 0.015g of product D, performing ultrasonic dispersion, adding 1.67 g of product mLC, and magnetically stirring to obtain product E; the ultrasonic dispersion power is 200-240W, and the dispersion time is 3-5h; the time of the magnetic stirring is 2-4 hours, and the rotating speed of the magnetic stirring is as follows: 350-390 r.min -1 ；
(7) And (3) carrying out vacuum suction filtration on the E product by using a Celgard-2500PP diaphragm to obtain the lithium-sulfur battery diaphragm barrier layer.
Experiments prove that:
1. as shown in FIG. 3, the thickness of the load barrier material VOOH/NG in VOOH/NG-PP was 16.09 μm.
2. As shown in fig. 4, the VOOH/NG barrier material in VOOH/NG-PP covered the pores of PP, compared to PP, which covered could block shuttling of polysulfide.
3. As shown in FIG. 5, the initial discharge capacity of VOOH/NG-PP at 1C was 891.8 mAh.g in PP, NG-PP and VOOH/NG-PP -1 The capacity is still kept at 488.0 mAh.g after 600 cycles -1 The capacity fade rate was 0.075%. While the initial discharge capacity of NG-PP is 880.7 mAh.g -1 The capacity is still kept at 398.9 mAh.g after 600 cycles -1 The capacity fade rate was 0.091%. The initial discharge capacity of PP was 733.9 mAh.g -1 The capacity remained at 259.3 mAh.g after 600 cycles -1 The capacity attenuation rate is 0.108%, and compared with the VOOH/NG-PP prepared by the invention, the VOOH/NG-PP has the most excellent cycle performance.
And MoS prepared by combining the VOOH/NG-PP with Li Lian-shan subject group 2 The electrochemical performance of the PP lithium sulfur battery separator barrier layer is compared as shown in the following table:
table 1 electrochemical performance comparison table
It can be seen from Table 1 that VOOH/NG-PP prepared by the present invention is compared with the prior art barrier layer material MoS 2 Compared with PP, the PP has excellent electrochemical performance, large capacity and long service life.
Application example 2-1: the hollow spherical shell structure vanadium oxyhydroxide is used for accommodating polysulfide; the polysulfide is polysulfide dissolved in electrolyte and formed by reaction with lithium ions in the discharge process of sulfur positive electrode, and the molecular formula of the polysulfide is Li 2 S n (n is more than or equal to 4 and less than or equal to 8), and the diameter of polysulfide molecules is 1-2nm.
Experiments prove that: as shown in FIG. 6, after the VOOH prepared by the present invention is added and left to stand for 2 hours, li of the VOOH-containing sample 2 S 6 Changes the color of (C) from yellow to colorless and transparent, and pure Li 2 S 6 Still yellow. Indicating that VOOH adsorbs polysulfide, i.e. the hollow spherical shell structure vanadium oxyhydroxide contains polysulfide.
Application example 3-1: the hollow spherical shell structure vanadium oxyhydroxide is used for adsorbing polysulfide; the vanadium in the hydroxyl vanadium oxide with the hollow spherical shell structure and sulfur in polysulfide form a V-S chemical bond, so that the hydroxyl vanadium oxide with the hollow spherical shell structure and polysulfide form chemical adsorption;
the polysulfide is polysulfide dissolved in electrolyte and formed by reaction with lithium ions in the discharge process of sulfur positive electrode, and the molecular formula of the polysulfide is Li 2 S n (n is more than or equal to 4 and less than or equal to 8), and the diameter of polysulfide molecules is 1-2nm.
Experiments prove that:
the UV-visible spectrum test of FIG. 7a shows that pure Li 2 S 6 Having two characteristic peaks at about 263 and 314nm, and after adding VOOH prepared according to the present invention, li containing VOOH 2 S 6 The overall intensity of (c) becomes weaker and even the characteristic peaks at 263 and 314nm disappear. Indicating that it can adsorb Li 2 S 6 Further chemisorption is demonstrated by figure 7b between VOOH and polysulfide, forming V-S chemical bonds between them.
Application example 4-1: the vanadium oxyhydroxide and nitrogen-doped graphene composite with the hollow spherical shell structure is used for catalyzing polysulfide, and polysulfide is catalytically converted into Li 2 S；
The method for compounding the vanadium oxyhydroxide with the hollow spherical shell structure and the nitrogen-doped graphene specifically comprises the following steps:
(7) 0.11g of vanadium oxyhydroxide with a hollow spherical shell structure is added into 20mL of absolute ethyl alcohol, and is magnetically stirred and dispersed for 2h, wherein the rotating speed of the magnetic stirring is as follows: 350r min -1 Obtaining a C product;
(8) Under the condition of ice bath, graphene oxide is dispersed in deionized water by using an ultrasonic cyto-pulverizer to obtain a dispersion liquid, wherein the concentration of the dispersion liquid is 1.8 mg.mL -1 Dropwise adding hydrazine hydrate with the mass fraction of 40% into the dispersion liquid under magnetic stirring, reacting for 20 hours at 70 ℃, cooling to 20 ℃, cleaning to pH 6.8, and freeze-drying to obtain nitrogen-doped graphene powder to obtain a D product; the time of the magnetic stirring is 20h, and the rotating speed of the magnetic stirring is as follows: 350r min -1 ；
(9) Adding 0.005g of D product into 180mL of absolute ethyl alcohol, performing ultrasonic dispersion, adding 1.67 g of mLC product, and magnetically stirring to obtain a hollow spherical shell structure vanadium hydroxide and nitrogen doped graphene compound (VOOH/NG); the ultrasonic dispersion power is 200W, and the dispersion time is 3h; the time of the magnetic stirring is 2h, and the rotating speed of the magnetic stirring is as follows: 350r min -1 。
Application example 4-2: the vanadium oxyhydroxide and nitrogen-doped graphene composite with the hollow spherical shell structure is used for catalyzing polysulfide, and polysulfide is catalytically converted into Li 2 S；
The method for compounding the vanadium oxyhydroxide with the hollow spherical shell structure and the nitrogen-doped graphene specifically comprises the following steps:
(7) 0.25g of vanadium oxyhydroxide with a hollow spherical shell structure is added into 25mL of absolute ethyl alcohol, and is magnetically stirred and dispersed for 3 hours, wherein the rotating speed of the magnetic stirring is as follows: 370 r.min -1 Obtaining a C product;
(8) Under the condition of ice bath, graphene oxide is dispersed in deionized water by using an ultrasonic cell pulverizer to obtain dispersion liquid, wherein the concentration of the dispersion liquid is 2 mg/mL -1 In the followingDropwise adding hydrazine hydrate with the mass fraction of 41% into the dispersion liquid under magnetic stirring, reacting for 24 hours at 80 ℃, cooling to 25 ℃, cleaning to pH 7, and freeze-drying to obtain nitrogen-doped graphene powder to obtain a D product; the time of the magnetic stirring is 24 hours, and the rotating speed of the magnetic stirring is as follows: 370 r.min -1 ；
(9) Adding 0.015g of D product into 185mL of absolute ethyl alcohol, performing ultrasonic dispersion, adding 4g of mLC product, and performing magnetic stirring to obtain a hollow spherical shell structure vanadium oxyhydroxide and nitrogen doped graphene compound (VOOH/NG); the ultrasonic dispersion power is 220W, and the dispersion time is 4h; the time of the magnetic stirring is 3h, and the rotating speed of the magnetic stirring is as follows: 370 r.min -1 。
Application example 4-1: the vanadium oxyhydroxide and nitrogen-doped graphene composite with the hollow spherical shell structure is used for catalyzing polysulfide, and polysulfide is catalytically converted into Li 2 S；
The method for compounding the vanadium oxyhydroxide with the hollow spherical shell structure and the nitrogen-doped graphene specifically comprises the following steps:
(7) 0.405g of hollow spherical shell structure vanadium hydroxide is added into 30mL of absolute ethyl alcohol, and is magnetically stirred and dispersed for 4 hours, wherein the rotating speed of the magnetic stirring is as follows: 390 r.min -1 Obtaining a C product;
(8) Under the condition of ice bath, graphene oxide is dispersed in deionized water by using an ultrasonic cell pulverizer to obtain a dispersion liquid, wherein the concentration of the dispersion liquid is 2.2 mg.mL -1 Dropwise adding hydrazine hydrate with the mass fraction of 42.5% into the dispersion liquid under magnetic stirring, reacting for 28 hours at 90 ℃, cooling to 30 ℃, cleaning to pH 7.2, and freeze-drying to obtain nitrogen-doped graphene powder to obtain a D product; the time of the magnetic stirring is 28h, and the rotating speed of the magnetic stirring is as follows: 390 r.min -1 ；
(9) Adding 0.025g of D product into 190mL of absolute ethyl alcohol, performing ultrasonic dispersion, adding 7.3 g of mLC product, and magnetically stirring to obtain a hollow spherical shell structure vanadium hydroxide and nitrogen doped graphene compound (VOOH/NG); the ultrasonic dispersion power is 240W, and the dispersion time is 5h; the time of the magnetic stirring is 4h, and the rotating speed of the magnetic stirring is as follows: 390 r.min -1 。
Experiments prove that:
examples 4-1, 4-2, 4-3 the data of FIG. 8 are optimal (corresponding example 4-3) As shown in FIG. 8, at a scan rate of 2mV/s, four peaks appear in the cyclic voltammograms of VOOH/NG. The peak currents of the respective peaks are a (-7.28 mA.mg) -1 )、b(8.25mA·mg -1 )、c(7.0mA·mg -1 ) And d (-8.48 mA.mg) -1 ) VOOH/NG was shown to catalyze polysulfide conversion with the conversion equation corresponding to each peak as follows:
peak a:
working electrode:
a counter electrode:peak b:
working electrode:
a counter electrode:peak c:
working electrode:
a counter electrode:peak d:
working electrode:
a counter electrode:
namely, the hollow spherical shell structure of the invention is vanadium hydroxide and nitrogenDoped graphene complexes can be used to catalyze polysulfides, which are catalytically converted to Li 2 S。
Claims (6)
1. The application of the hollow spherical shell structure vanadium oxyhydroxide is characterized in that: the vanadium oxyhydroxide has a spherical shape, the diameter of 190-330nm and a hollow structure inside; the thickness of the spherical shell is 35-42nm, holes are distributed on the spherical shell, and the density of the holes is (3.85-4.52) multiplied by 10 -4 Individual/nm 2 The method comprises the steps of carrying out a first treatment on the surface of the The molecular formula of the vanadium oxyhydroxide is VOOH, and the structural formula is H-O-V=O;
the vanadium oxyhydroxide is prepared by the following steps:
in the step (1), 0.234 to 0.250g of ammonium metavanadate is added into 40 to 50mL of deionized water, and the mixture is magnetically stirred for 0.5 to 1.5 hours at the temperature of 10 to 30 ℃ and the rotating speed of the magnetic stirring is 350 to 390 r.min -1 ；
In the step (2), 1-1.2mL of hydrochloric acid solution is added into 40-50mLA product under the condition of magnetic stirring at the temperature of 10-30 ℃, then 2-3mL of hydrazine hydrate solution is added, and the magnetic stirring is continued for 0.5-1.5h at the temperature of 10-30 ℃ with the rotating speed of 350-390 r.min -1 ；
The concentration of the hydrochloric acid is 0.8-1.2 mol.L -1 The mass fraction of the hydrazine hydrate solution is 80-85%;
in the step (3), the product B is subjected to a hydrothermal reaction at a temperature of 150-170 ℃ for 10-14 hours, cooled to 20-30 ℃, and then mixed and centrifugally cleaned to a pH value of 6.8-7.2 by using absolute ethyl alcohol and deionized water, so that vanadium hydroxide with a hollow spherical shell structure is obtained;
the vanadium oxyhydroxide with the hollow spherical shell structure is used for preparing a lithium sulfur battery diaphragm barrier layer; the method specifically comprises the following steps:
(4) Adding the hollow spherical shell structure vanadium oxyhydroxide into absolute ethyl alcohol, and dispersing to obtain a C product;
(5) Reducing graphene oxide by using a hydrazine hydrate solution to prepare nitrogen-doped graphene, so as to obtain a D product;
(6) Dissolving the binder in N-methyl pyrrolidone and absolute ethyl alcohol, then adding the product D, carrying out ultrasonic dispersion, then adding the product C, and stirring to obtain the product E;
(7) And carrying out vacuum suction filtration on the E product by using a diaphragm to obtain a diaphragm modified by the E product, namely the diaphragm barrier layer of the lithium-sulfur battery.
2. The use of the hollow spherical shell structured vanadium oxyhydroxide according to claim 1, characterized in that:
in the step (4), 0.11-0.405g of hollow spherical shell structure vanadium hydroxide is added into 20-30mL of absolute ethyl alcohol, and the mixture is magnetically stirred and dispersed for 2-4 hours, wherein the rotation speed of the magnetic stirring is as follows: 350-390 r.min -1 Obtaining a C product;
in the step (5), under the condition of ice bath, using an ultrasonic cell pulverizer to disperse graphene oxide in deionized water to obtain a dispersion liquid, wherein the concentration of the dispersion liquid is 1.8-2.2 mg.mL -1 Under magnetic stirring, then dripping hydrazine hydrate with the mass fraction of 40-42.5% into the dispersion liquid, reacting for 20-28h at 70-90 ℃, cooling to 20-30 ℃, cleaning to pH of 6.8-7.2, and freeze-drying to obtain nitrogen-doped graphene powder to obtain a D product; the time of the magnetic stirring is 20-28h, and the rotating speed of the magnetic stirring is as follows: 350-390 r.min -1 ；
In the step (6), 0.005g of a binder PVDF is dissolved in 20-30 mLN-methyl pyrrolidone and 180-190mL of absolute ethyl alcohol, then 0.005-0.025g of D product is added, ultrasonic dispersion is carried out, 1.67-7.3mLC products are added, and magnetic stirring is carried out, thus obtaining E product; the ultrasonic dispersion power is 200-240W, and the dispersion time is 3-5h; the time of the magnetic stirring is 2-4 hours, and the rotating speed of the magnetic stirring is as follows: 350-390 r.min -1 ；
In the step (7), the E product is subjected to vacuum suction filtration by using a Celgard-2500PP membrane, and the lithium sulfur battery membrane barrier layer is obtained.
3. The use of the hollow spherical shell structured vanadium oxyhydroxide according to claim 1, characterized in that: the hollow spherical shell structure vanadium oxyhydroxide is used for accommodating polysulfide; the polysulfide is polysulfide dissolved in electrolyte and formed by reaction with lithium ions in the discharge process of sulfur positive electrode, and the molecular formula of the polysulfide is Li 2 S n Polysulfide fraction with n being 4-8The diameter of the seed is 1-2nm.
4. The use of the hollow spherical shell structured vanadium oxyhydroxide according to claim 1, characterized in that: the hollow spherical shell structure vanadium oxyhydroxide is used for adsorbing polysulfide; the vanadium in the hydroxyl vanadium oxide with the specific hollow spherical shell structure and sulfur in polysulfide form a V-S chemical bond, so that the hydroxyl vanadium oxide with the hollow spherical shell structure and polysulfide form chemical adsorption;
the polysulfide is polysulfide dissolved in electrolyte and formed by reaction with lithium ions in the discharge process of sulfur positive electrode, and the molecular formula of the polysulfide is Li 2 S n N is more than or equal to 4 and less than or equal to 8, and the diameter of polysulfide molecules is 1-2nm.
5. The use of the hollow spherical shell structured vanadium oxyhydroxide according to claim 1, characterized in that: the vanadium oxyhydroxide and nitrogen-doped graphene composite with the hollow spherical shell structure is used for catalyzing polysulfide, and polysulfide is catalytically converted into Li 2 S；
The method for compounding the vanadium oxyhydroxide with the hollow spherical shell structure and the nitrogen-doped graphene specifically comprises the following steps:
(7) Adding the hollow microsphere vanadium oxyhydroxide into absolute ethyl alcohol, and dispersing to obtain a product C;
(8) Reducing graphene oxide by using a hydrazine hydrate solution to prepare nitrogen-doped graphene, so as to obtain a D product;
(9) Adding the product D into absolute ethyl alcohol, performing ultrasonic dispersion, adding the product C, and stirring to obtain a hollow spherical shell structure vanadium hydroxide and nitrogen doped graphene compound;
the polysulfide is polysulfide dissolved in electrolyte and formed by reaction with lithium ions in the discharge process of sulfur positive electrode, and the molecular formula of the polysulfide is Li 2 S n N is more than or equal to 4 and less than or equal to 8, and the diameter of polysulfide molecules is 1-2nm.
6. The use of the hollow spherical shell structured vanadium oxyhydroxide according to claim 5, characterized in that:
in the step (7)0.11-0.405g of hollow spherical shell structure vanadium hydroxide is added into 20-30mL of absolute ethyl alcohol, and the mixture is magnetically stirred and dispersed for 2-4h, wherein the rotation speed of the magnetic stirring is as follows: 350-390 r.min -1 Obtaining a C product;
in the step (8), under the condition of ice bath, using an ultrasonic cell pulverizer to disperse graphene oxide in deionized water to obtain a dispersion liquid, wherein the concentration of the dispersion liquid is 1.8-2.2 mg.mL -1 Under magnetic stirring, then dripping hydrazine hydrate with the mass fraction of 40-42.5% into the dispersion liquid, reacting for 20-28h at 70-90 ℃, cooling to 20-30 ℃, cleaning to pH of 6.8-7.2, and freeze-drying to obtain nitrogen-doped graphene powder to obtain a D product; the time of the magnetic stirring is 20-28h, and the rotating speed of the magnetic stirring is as follows: 350-390 r.min -1 ；
Adding 0.005-0.025g of D product into 180-190mL of absolute ethyl alcohol, performing ultrasonic dispersion, adding 1.67-7.3 g of mLC product, and magnetically stirring to obtain a hollow spherical shell structure vanadium hydroxide and nitrogen doped graphene compound; the ultrasonic dispersion power is 200-240W, and the dispersion time is 3-5h; the time of the magnetic stirring is 2-4 hours, and the rotating speed of the magnetic stirring is as follows: 350-390 r.min -1 。
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