CN105914374B - Composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure and its preparation method and application - Google Patents
Composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000011229 interlayer Substances 0.000 title claims abstract description 42
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 42
- 239000011733 molybdenum Substances 0.000 title claims abstract description 42
- 238000005253 cladding Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 33
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229960003638 dopamine Drugs 0.000 claims abstract description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004744 fabric Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 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 abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 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 abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 235000015393 sodium molybdate Nutrition 0.000 claims description 8
- 239000011684 sodium molybdate Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- 239000011669 selenium Substances 0.000 claims description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 38
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 37
- 238000000034 method Methods 0.000 abstract description 14
- 230000002441 reversible effect Effects 0.000 abstract description 7
- 229910016001 MoSe Inorganic materials 0.000 description 21
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 12
- 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 description 11
- 239000010410 layer Substances 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003346 selenoethers Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- -1 Sodium Molybdate Dihydrates Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000012546 transfer 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Composite material the invention discloses a kind of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure and its preparation method and application, this method includes：Selenium powder is dissolved in hydrazine hydrate, forms solution A；Sodium Molybdate Dihydrate is dissolved in water, forms solution B；Solution is mixed, reaction solution is formed, the vertical graphene collector material for being grown in carbon cloth is placed in the reaction solution, carries out hydro-thermal reaction, it is washed afterwards, dry, obtain VG MoSe2Nucleocapsid array structure；Dopamine hydrochloride is taken to be dissolved in water, then by VG MoSe2Nucleocapsid array structure is immersed in Dopamine hydrochloride aqueous solution, water-bath polymerization, washed drying；By dopamine polymerize nucleocapsid array structure, under hot conditions under protective atmosphere be carbonized to get.When the composite material of the structure is used as sodium ion negative material, with high reversible charge/discharge capacity, long circulation life and excellent high rate performance.
Description
Technical field
The present invention relates to anode material of lithium-ion battery technical fields, and in particular to and a kind of nitrogen-doped carbon cladding selenizing molybdenum/
Composite material of graphene nucleocapsid array interlayer structure and preparation method thereof and the application as anode material of lithium-ion battery.
Background technology
Energy crisis and environmental problem are the two big challenges that current mankind society faces, and reproducible New Energy is cleaned in exploitation
Source has become the active demand of today's society.Among current various new energy source technologies, lithium rechargeable battery is due to high energy
Metric density, high working voltage, advantages of environment protection have captured rapidly portable electronic market, and as electric vehicle and greatly
The primary selection of scale energy-storage system.But since lithium resource reserves are limited and are unevenly distributed, resulting in it can not effectively meet pair
The huge needs of power lithium-ion rechargeable battery, and the price with lithium associated materials has further been raised, increase its battery
Cost, so as to hinder the development of novel energy industry.Therefore the related energy storage technology of honest alternative lithium ion battery is developed
It is crucial as urgent problem.
Sodium is resourceful, and development cost is low, and sodium has the characteristics that similar insertion and abjection mechanism to lithium so that sodium ion
Secondary cell becomes the first choice of alternative lithium rechargeable battery, and as the research hotspot of today's society.But due to sodium from
Sub- radiusCompare lithium ionGreatly, sodium ion migrates slowly in electrode material, and deintercalation process is complicated, leads
Cause reversible capacity and high rate performance poor.Therefore the sodium-ion battery material with high reversible capacity and good circulation stability is explored
Material has great importance to the development of sodium ion secondary battery of new generation.The MoSe of layer structure2, due to larger layer
Spacing (0.67nm) is conducive to the insertion and abjection of sodium ion, and can be embedded in for sodium ion and provide big space, avoids embedding sodium
When volume expansion, so as to maintain the stabilization of structure, while there is higher storage sodium capacity (400-800mA hg-1), therefore
MoSe2Research as sodium ion negative material has become current research hotspot.But two-dimensional structure MoSe2Material is due to layer
With the van der Waals interaction of interlayer, easily reunite during charge discharge, cause the effective of electrolyte and active material
Contact reduces, electrode reversible capacity rapid decay.In addition, pure MoSe2Electronic conductivity is not high so that it is as sodium ion two
High rate performance is relatively low during primary cell cathode, it is difficult to bear the charge and discharge of larger current density.Therefore, two-dimensional layer MoSe is improved2
Structural stability and improve electronic conductivity be MoSe2Material is as sodium ion secondary battery negative material using urgently to be resolved hurrily
Key scientific problems.
At present, by by layer structure MoSe2It is compound with reduced graphene, inhibit its reunion, increase its electric conductivity, improve
Sodium ion diffusion rate.In addition, to MoSe2Surface modification or cladding are carried out, inhibits more selenizings of its charge and discharge process generation
The dissolving of object stores up the stability and high rate performance of sodium so as to improve it.Layer structure selenides surface is modified, carbon bag
It covers, the thickness of carbon thin layer, microstructure, doping situation, affects its interlayer spacing, electric conductivity and its electronics transfer speed
Rate stores up sodium performance so as to affect it.Although above method can improve MoSe to a certain extent2As sodium ion cathode
Chemical property, but the chemical properties such as its reversible capacity and high rate performance from industrial applications also there are a distance,
It is still necessary to improve.
The content of the invention
Object of the present invention is to provide a kind of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structures
Composite material and its preparation method and application, when the composite material of the structure is used as sodium ion negative material, with high reversible
Charge/discharge capacity, long circulation life and excellent high rate performance.
A kind of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure sodium ion negative material and its preparation side
Method, the MoSe2Nanometer sheet intersecting vertical is grown in vertical graphene array, and uniformly coats the carbon of one layer of N doping
Layer forms interlayer structure, and the carbon thickness of the N doping of the cladding is 5-10nm.
The present invention by with vertical graphene (VG) be skeleton, MoSe2Nanometer sheet intersecting vertical is grown in vertical graphene
On array, the carbon (NC) of N doping is cladding layer building nucleocapsid array interlayer structure VG MoSe2@NC composite materials, so as to obtain
High reversible capacity and excellent high rate performance.
A kind of preparation method of the composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure, bag
Include following steps：
(1) selenium powder is dissolved in hydrazine hydrate, forms solution A；
(2) Sodium Molybdate Dihydrate is dissolved in water, forms solution B；
(3) solution A with solution B is uniformly mixed, forms reaction solution, the vertical graphene collector material of carbon cloth will be grown in
Material is placed in the reaction solution, carries out hydro-thermal reaction, washed afterwards, dry, obtains VG-MoSe2Nucleocapsid array structure；
(4) Dopamine hydrochloride is taken to be dissolved in water, formed hydrochloric acid aqueous dopamine solution, then by step (3) obtained by VG-
MoSe2Nucleocapsid array structure is immersed in Dopamine hydrochloride aqueous solution, water-bath polymerization, and washed drying obtains dopamine polymerization
Nucleocapsid array structure；
(5) by the nucleocapsid array structure of dopamine polymerization obtained by step (4), carbonization is calcined under protective atmosphere, obtains nitrogen
Adulterate the composite material of carbon coating selenizing molybdenum/graphene nucleocapsid array interlayer structure, i.e. VG MoSe2@NC。
The preferred technical solution of the present invention is used as below：
In step (1), the concentration of selenium is 0.2-0.6mmolmL in the solution A-1(i.e. mmol/mL).
In step (2), the concentration of sodium molybdate is 0.02-0.1mmolmL in the solution B-1。
In step (3), the molar ratio of selenium and sodium molybdate in solution B is 1.5~2.5 in the solution A：1, it is further excellent
Choosing is 2：1.Further preferably, when 160-200 DEG C of progress hydro-thermal reaction 12-24 is small.
In step (4), the concentration of dopamine is 3-7mg mL in the Dopamine hydrochloride aqueous solution-1, at 70 DEG C -90 DEG C
When water-bath polymerization 12-24 is small, further preferably, water-bath temperature is 80 DEG C.
In step (5), either argon gas is under nitrogen or argon gas protection for nitrogen for the protective atmosphere, calcining heat
For 500-800 DEG C, when calcination time is 2-6 small.
The composite material of the nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure, MoSe2Content is
0.2-0.5mg cm-2。
The composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure is particularly as sodium-ion battery
Negative material, the VG@MoSe that will be obtained2The directly small section of@NC composite materials is as sodium-ion battery cathode assembled battery.Cathode
Preparation be by VG@MoSe obtained by step (5)2@NC composite materials are cut into slices, and membrane is using Whatman glass fibres, electrolysis
Liquid is with 1molL-1NaClO4For solute, volume ratio 1:1 ethylene carbonate (EC) is solvent with dimethyl carbonate (DMC),
And the fluorinated ethylene carbonate of 5.0wt.% is added in, cathode uses sodium piece, and the assembling process of battery is all full of argon gas
And water oxygen content is completed in the glove box less than 0.1ppm.
The lithium ion battery that assembles place 24 it is small when after carry out constant current charge-discharge test, charging/discharging voltage for 3.0V~
0.01V, capacity, charge-discharge performance and the multiplying power property of Xun Huan measurement negative electrode of lithium ion battery in 25 ± 1 DEG C of environment.
Compared with prior art, the invention has the advantages that：
(1) method that the present invention is combined using hydro-thermal, water-bath with calcining, the flexible nitrogen-doped carbon cladding selenizing molybdenum of preparation/
Graphene nucleocapsid array interlayer structure sodium ion negative material, of low cost, preparation process is simple, it is easy to accomplish a large amount of metaplasias
Production.
(2) the VG@MoSe prepared by2@NC are flexible nucleocapsid array interlayer structure, and nitrogen-doped carbon clad is thick for 5-10nm
Degree is conducive to improve the electric conductivity of material and the dissolving of more selenides during effective charge and discharge.
(3) the VG@MoSe prepared by2@NC are prepared into sodium ion cathode, then are direct shearing, eliminate the preparation of slurry,
The cumbersome electrode preparation process such as coating, drying.
(4) the VG@MoSe prepared by2@NC composite materials, vertical graphene skeleton provide good electron-transport and lead to
Road, the carbon coating layer of N doping improve the electric conductivity of electrode and inhibiting generated in charge and discharge process the dissolvings of more selenides from
And overcome the fast inferior position of decaying, realize with high circulation stability, high rate capability, high charge-discharge capacity sodium-ion battery
Cathode.
(5) this method is easy to operate, yield is big, and clad is uniform.The sandwich nucleocapsid array structure VG@that the present invention prepares
MoSe2@NC sodium ions negative material has flexible support, high specific discharge capacity, long circulating stability and excellent high rate performance etc.
Advantage has broad application prospects in novel energy field.
Description of the drawings
Fig. 1 is the composite wood of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure prepared by embodiment 1
The process schematic of material, wherein, (a) is to be grown in the vertical graphene (VG) of carbon cloth in Fig. 1, and (b) is VG-MoSe in Fig. 12Core
Shell array structure, (c) is VG@MoSe in Fig. 12@NC。
Fig. 2 is that the nitrogen-doped carbon prepared in embodiment 1 coats the composite wood of selenizing molybdenum/graphene nucleocapsid array interlayer structure
The XRD spectra of material.
Fig. 3 is the nucleocapsid array structure VG@MoSe prepared in embodiment 12Different multiples SEM figure, wherein, in Fig. 3 (a)
For the nucleocapsid array structure VG@MoSe prepared in embodiment 12Low range SEM figures, (b) is what is prepared in embodiment 1 in Fig. 3
Nucleocapsid array structure VG@MoSe2High magnification SEM figure.
Fig. 4 is that the composite material that nitrogen-doped carbon coats selenizing molybdenum/graphene nucleocapsid array interlayer structure is prepared in embodiment 1
Different multiples SEM figures and its photo in kind, wherein, (a) coats selenizing molybdenum/stone to prepare nitrogen-doped carbon in embodiment 1 in Fig. 4
The low range SEM of the composite material of black alkene nucleocapsid array interlayer structure schemes, and (b) is to prepare nitrogen-doped carbon bag in embodiment 1 in Fig. 4
The high magnification SEM figures of the composite material of selenizing molybdenum/graphene nucleocapsid array interlayer structure are covered, (c) is to be made in embodiment 1 in Fig. 4
The photo in kind of the composite material of standby nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure.
Fig. 5 is that the composite material that nitrogen-doped carbon coats selenizing molybdenum/graphene nucleocapsid array interlayer structure is prepared in embodiment 1
The circulating battery stability of preparation.
Fig. 6 is that the composite material that nitrogen-doped carbon coats selenizing molybdenum/graphene nucleocapsid array interlayer structure is prepared in embodiment 1
The battery high rate performance of preparation.
Specific embodiment
The present invention is made below by embodiment and further being illustrated, but the invention is not limited in following realities
Example.
Embodiment 1
(1) the selenium powder dispersing and dissolving of 4mmol is taken among the hydrazine hydrate of 10mL, under the conditions of 25 DEG C of room temperature, stirring
30min, forms the solution A of claret, and the concentration of selenium is 0.4mmolmL in solution A-1；
(2) 2mmol Sodium Molybdate Dihydrates is taken to be dissolved in 60mL deionized waters, form solution B, molybdic acid na concn in solution B
For 0.33mmolmL-1；
(3) solution A of 10mL and the solution B of 60mL are taken, is mixed evenly, is transferred among reaction kettle, then by 5 ×
Vertical graphene (VG) collector material that 5cm is grown in carbon cloth is placed in one, and when 200 DEG C of hydro-thermal reactions 24 are small, washs, does
It is dry, obtain VG-MoSe2Nucleocapsid array structure；
(4) Dopamine hydrochloride of 0.2g is weighed, is dissolved in 30mL deionized waters and forms solution, then by VG-MoSe2Core
Shell array structure impregnates wherein, when 80 DEG C of polymerisations 24 of water-bath are small, wash drying, obtains the nucleocapsid array that dopamine polymerize
Composite material；
(5) for the nucleocapsid array composite material polymerizeing dopamine under argon atmosphere, 600 DEG C of high temperature cabonizations 4 are small
When, obtain the composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure, i.e. VG@MoSe2@NC；
(6) by VG@MoSe2@NC composite materials are directly cut to small pieces, as sodium-ion battery electrode.By assembling button
Sodium ion half-cell, with VG@MoSe2@NC composite materials are half-cell anode, using whatman glass fibres as half-cell membrane,
With 1mol L-1NaClO4For solute, volume ratio 1:1 ethylene carbonate (EC) is solvent with dimethyl carbonate (DMC), and is added
Enter the fluorinated ethylene carbonate of 5.0wt.% for electrolyte, using sodium piece as button half-cell cathode, the assembling process of battery is all
It is completed in full of the glove box of argon gas and water oxygen content less than 0.1ppm.
With reference to hydro-thermal, water-bath prepares nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array with calcining the method being combined
The preparation process of interlayer structure as shown schematically in fig. 1, wherein, (a) is to be grown in the vertical graphene (VG) of carbon cloth in Fig. 1,
(b) is VG-MoSe in Fig. 12Nucleocapsid array structure, (c) is VG@MoSe in Fig. 12@NC。
Nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure sodium ion negative material passes through X-ray diffraction
Spectrum test (XRD), as shown in Fig. 2, preparing VG@MoSe for the present embodiment 12The XRD spectrum of@NC composite materials.It can according to Fig. 2
Know, VG@MoSe prepared by the present embodiment 12@NC composite materials have the diffraction maximum of VG, with MoSe2Diffraction maximum (JCPDS Card
No.29-0914).As shown in Fig. 3 (a-b), the carbon-coating VG-MoSe of uncoated N doping2SEM pictures, maintain vertical graphite
The structure of alkene array, and growing the vertical MoSe of one layer of cross-bridging on graphene film2Nanometer sheet, nanoscale twins thickness
For 20-30 nanometers.After foring carbon coating layer with carbonization by dopamine polymerization, as shown in Fig. 4 (a-b), it can be seen that vertical
The MoSe being grown on graphene2Nanometer sheet is thickening, and lamellar structure is difficult to distinguish, forms carbon-coated MoSe2.Such as Fig. 4 c institutes
Show, VG@MoSe2@NC have good flexibility.According to calculating of poor quality before and after reaction, nitrogen-doped carbon cladding selenizing can be calculated
Molybdenum/graphene nucleocapsid array interlayer structure sodium ion negative material (i.e. nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array folder
The composite material of core structure) in MoSe2Content be about 0.27mg cm-2。
Assembled lithium ion battery place 24 it is small when after carry out constant current charge-discharge test, charging/discharging voltage section is
3.0V~0.01V, capacity, charge-discharge performance and the multiplying power of Xun Huan measurement sodium-ion battery cathode in 25 ± 1 DEG C of environment
Characteristic.
After being assembled into lithium ion battery, various electrochemical property tests are carried out.As seen from Figure 5, sodium-ion battery exists
200mA g-1There is 785.6mAh g under current density-1Discharge capacity for the first time, by 400 times cycle after its discharge capacity still
So there are 534.8mAh g-1, coulombic efficiency maintains more than 99%, shows excellent capacity retention ratio and cyclical stability.
Fig. 6 show the high rate performance figure of negative material manufactured in the present embodiment, which shows very excellent high rate performance,
0.2,0.5,1.0 with 2.0A g-1Capacity respectively reaches 538,470,395 and 300mAh g under current density-1.When electric current from
2.0A g-1Return to 0.2A g-1When, and cycle 100 times after, battery capacity returns to 535mAh g-1。
Embodiment 2
(1) the selenium powder dispersing and dissolving of 3mmol is taken among the hydrazine hydrate of 10mL, under the conditions of 25 DEG C of room temperature, stirring
30min, forms the solution A of claret, and the concentration of selenium is 0.3mmolmL in solution A-1；
(2) 1.5mmol Sodium Molybdate Dihydrates is taken to be dissolved in 50mL deionized waters, form solution B, sodium molybdate is dense in solution B
It spends for 0.03mmolmL-1；
(3) solution A of 10mL and the solution B of 50mL are taken, is mixed evenly, is transferred among reaction kettle, then by 3 ×
Vertical graphene (VG) collector material that 3cm is grown in carbon cloth is placed in one, and when 200 DEG C of hydro-thermal reactions 16 are small, washs, does
It is dry, obtain VG-MoSe2Nucleocapsid array structure；
(4) Dopamine hydrochloride of 0.15g is weighed, is dissolved in 30mL deionized waters and forms solution, then by VG-MoSe2
Nucleocapsid array structure impregnates wherein, when 80 DEG C of water-bath polymerisations 18 are small, wash drying, obtains the nucleocapsid battle array that dopamine polymerize
Row composite material；
(5) the nucleocapsid array composite material polymerizeing dopamine is when calcining 3 is small at 700 DEG C under nitrogen protection atmosphere,
Obtain nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array composites sandwich structures, i.e. VG@MoSe2@NC；
(6) by VG@MoSe2@NC composite materials are directly cut to small pieces, as electrode.By assembling half electricity of button sodium ion
Pond, with VG@MoSe2@NC composite materials are half-cell anode, using whatman glass fibres as half-cell membrane, with 1molL- 1NaClO4For solute, volume ratio 1:1 ethylene carbonate (EC) is solvent with dimethyl carbonate (DMC), and is added in
5.0wt.% fluorinated ethylene carbonates are electrolyte, and using sodium piece as button half-cell cathode, the assembling process of battery is all being filled
Full argon gas and water oxygen content are completed in the glove box less than 0.1ppm.
According to calculating of poor quality before and after reaction, it is sandwich that nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array can be calculated
MoSe in structure sodium ion negative material2Content be about 0.25mg cm-2。
By nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure sodium ion cathode prepared by the present embodiment
After material is assembled into sodium ion secondary battery, various electrochemical property tests are carried out.Sodium-ion battery is in 200mA g-1Electric current is close
Degree is lower to have 789.3mAh g-1Discharge capacity for the first time, by 400 times cycle after its discharge capacity still have 536.8mAh g-1, coulombic efficiency maintains more than 99%, shows excellent capacity retention ratio and cyclical stability.It is prepared from the present embodiment
Negative material high rate performance figure in, which shows very excellent high rate performance, in 0.2,0.5,1.0 and 2.0A g-1
Capacity respectively reaches 539,471,394 and 302mAh g under current density-1.When electric current is from 2.0A g-1Return to 0.2A g-1When, and
After Xun Huan 100 times, battery capacity returns to 534mAh g-1。
Embodiment 3
(1) the selenium powder dispersing and dissolving of 6mmol is taken among the hydrazine hydrate of 10mL, under normal temperature condition, stirs 30min, shape
Into the solution A of claret, the concentration of selenium is 0.6mmolmL in solution A-1；
(2) Sodium Molybdate Dihydrate of 3mmol is taken to be dissolved in 60mL deionized waters, forms solution B, sodium molybdate is dense in solution B
It spends for 0.05mmolmL-1；
(3) solution A of 10mL and the solution B of 60mL are taken, is mixed evenly, is transferred among reaction kettle, then by 6 ×
Vertical graphene (VG) collector material that 6cm is grown in carbon cloth is placed in one, and when 200 DEG C of hydro-thermal reactions 12 are small, washs, does
It is dry, obtain VG-MoSe2Nucleocapsid array structure；
(4) Dopamine hydrochloride of 0.3g is weighed, is dissolved in 30mL deionized waters and forms solution, then by VG-MoSe2Core
Shell array structure impregnates wherein, when 80 DEG C of water-bath polymerisations 12 are small, wash drying, obtains the nucleocapsid array that dopamine polymerize
Composite material；
(5) the nucleocapsid array composite material polymerizeing dopamine is when calcining 2 is small at 800 DEG C under argon atmosphere,
Obtain nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array composites sandwich structures, i.e. VG@MoSe2@NC；
(6) by VG@MoSe2@NC composite materials are directly cut to small pieces, as electrode.By assembling half electricity of button sodium ion
Pond, with VG@MoSe2@NC composite materials are half-cell anode, using whatman glass fibres as half-cell membrane, with 1mol L- 1NaClO4For solute, volume ratio 1:1 ethylene carbonate (EC) is solvent with dimethyl carbonate (DMC), and is added in
5.0wt.% fluorinated ethylene carbonates are electrolyte, and using sodium piece as button half-cell cathode, the assembling process of battery is all being filled
Full argon gas and water oxygen content are completed in the glove box less than 0.1ppm.
According to calculating of poor quality before and after reaction, it is sandwich that nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array can be calculated
MoSe in structure sodium ion negative material2Content be about 0.26mg cm-2。
By nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure sodium ion cathode prepared by the present embodiment
After material is assembled into sodium ion secondary battery, various electrochemical property tests are carried out.Sodium-ion battery is in 200mA g-1Electric current is close
Degree is lower to have 783.5mAh g-1Discharge capacity for the first time, by 400 times cycle after its discharge capacity still have 535.8mAh g-1, coulombic efficiency maintains more than 99%, shows excellent capacity retention ratio and cyclical stability.It is prepared from the present embodiment
Negative material high rate performance figure in, which shows very excellent high rate performance, in 0.2,0.5,1.0 and 2.0A g-1
Capacity respectively reaches 538,474,396 and 301mAh g under current density-1.When electric current is from 2.0A g-1Return to 0.2A g-1When, and
After Xun Huan 100 times, battery capacity returns to 537mAh g-1。
A kind of flexible nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure sodium ion in Examples 1 to 3
Its maximum discharge capacity in difference under current density is as shown in table 1 after negative material is assembled into sodium-ion battery：
Table 1
Claims (10)
1. a kind of preparation method of the composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure, special
Sign is, comprises the following steps：
(1) selenium powder is dissolved in hydrazine hydrate, forms solution A；
(2) Sodium Molybdate Dihydrate is dissolved in water, forms solution B；
(3) solution A with solution B is uniformly mixed, forms reaction solution, the vertical graphene collector material for being grown in carbon cloth is put
In the reaction solution, hydro-thermal reaction is carried out, it is washed afterwards, dry, obtain VG-MoSe2Nucleocapsid array structure；
(4) Dopamine hydrochloride is taken to be dissolved in water, formed hydrochloric acid aqueous dopamine solution, then by step (3) obtained by VG-MoSe2
Nucleocapsid array structure is immersed in Dopamine hydrochloride aqueous solution, and water-bath polymerization, washed drying obtains the nucleocapsid of dopamine polymerization
Array structure；
(5) by the nucleocapsid array structure of dopamine polymerization obtained by step (4), carbonization is calcined under protective atmosphere, obtains N doping
The composite material of carbon coating selenizing molybdenum/graphene nucleocapsid array interlayer structure.
2. the composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure according to claim 1
Preparation method, which is characterized in that in step (1), in the solution A concentration of selenium be 0.2-0.6mmolmL-1。
3. the composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure according to claim 1
Preparation method, which is characterized in that in step (2), in the solution B concentration of sodium molybdate be 0.02-0.1mmolmL-1。
4. the composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure according to claim 1
Preparation method, which is characterized in that in step (3), in the solution A in selenium and solution B the molar ratio of sodium molybdate for 1.5~
2.5：1.
5. the composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure according to claim 1
Preparation method, which is characterized in that in step (3), 160-200 DEG C carry out hydro-thermal reaction 12-24 it is small when.
6. the composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure according to claim 1
Preparation method, which is characterized in that in step (4), in the Dopamine hydrochloride aqueous solution concentration of dopamine be 3-7mg
mL-1。
7. the composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure according to claim 1
Preparation method, which is characterized in that in step (4), when 70 DEG C of -90 DEG C of water-baths polymerization 12-24 are small.
8. the composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure according to claim 1
Preparation method, which is characterized in that in step (5), the protective atmosphere be nitrogen or argon gas, calcining heat 500-
800 DEG C, calcination time 2-6h.
9. the nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid prepared according to claim 1~8 any one of them preparation method
The composite material of array interlayer structure.
10. the composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure according to claim 9
Application as anode material of lithium-ion battery.
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| CN106669763B (en) * | 2016-12-30 | 2019-06-18 | 华南理工大学 | A kind of nitrogen-doped carbon cladding nano flower-like MoSe2Composite material and preparation and application |
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| CN107955598B (en) * | 2017-11-03 | 2019-12-31 | 东华大学 | Molybdenum selenide nanosheet/nitrogen-doped carbon core-shell structure composite material and preparation method and application thereof |
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| CN111573630A (en) * | 2020-04-29 | 2020-08-25 | 扬州大学 | Transition metal selenide/carbon positive electrode composite material and aluminum ion battery |
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| CN114420908A (en) * | 2022-01-11 | 2022-04-29 | 西北工业大学 | Graphene-loaded nitrogen-doped carbon-coated manganese selenide-based sodium/potassium ion battery cathode material and preparation method thereof |
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