CN109767926A - Bivalve layer sulfide based on ZIF-67 skeleton and the preparation method and application thereof - Google Patents

Bivalve layer sulfide based on ZIF-67 skeleton and the preparation method and application thereof Download PDF

Info

Publication number
CN109767926A
CN109767926A CN201811487891.2A CN201811487891A CN109767926A CN 109767926 A CN109767926 A CN 109767926A CN 201811487891 A CN201811487891 A CN 201811487891A CN 109767926 A CN109767926 A CN 109767926A
Authority
CN
China
Prior art keywords
zif
bivalve layer
skeleton structure
preparation
sulfide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811487891.2A
Other languages
Chinese (zh)
Other versions
CN109767926B (en
Inventor
王育乔
谢方
李梦恬
张亚轩
孙岳明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southeast University
Original Assignee
Southeast University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Southeast University filed Critical Southeast University
Priority to CN201811487891.2A priority Critical patent/CN109767926B/en
Publication of CN109767926A publication Critical patent/CN109767926A/en
Application granted granted Critical
Publication of CN109767926B publication Critical patent/CN109767926B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

Bivalve layer sulfide that the invention discloses a kind of based on ZIF-67 skeleton and the preparation method and application thereof, is expressed as CoS/MCo2S4, wherein inner shell materials are CoS, sheathing material MCo2S4, M can be Ni, Mn, Fe, Cu and Zn.Specifically include: a. prepares ZIF-67；B. nucleocapsid shape intermediate is prepared；C. bivalve layer sulfide electrode material is prepared；D. it assembles: the bivalve layer sulfide of preparation is applied to nickel foam surface-assembled supercapacitor.The present invention is developed with ZIF-67 skeleton bivalve layer structure feature, includes two different sulfide, while having both large specific surface area, the features such as active site is more, to effectively improve the specific capacity of supercapacitor.Structure of the invention has stable skeleton firm and cavity structure, can slow down supercapacitor electrode material structure collapses in charge and discharge process, and then be remarkably improved the cyclical stability of supercapacitor.In addition, the preparation method is easy to operate, favorable reproducibility is suitble to large-scale production.

Description

Bivalve layer sulfide based on ZIF-67 skeleton and the preparation method and application thereof
Technical field
The invention belongs to the technical field of material of the complex function with special appearance structure, and in particular to Yi Zhongji In the bivalve of ZIF-67 skeleton layer sulfide and the preparation method and application thereof.
Background technique
Supercapacitor is most potential one of energy storage device at present, have high power density, long circulation life, Fast charging and discharging, it is environmental-friendly many advantages, such as.The present invention provides a kind of high performance double based on ZIF-67 skeleton structure The preparation method of shell sulfide and its application method in supercapacitor.Layer sulfide structure in bivalve of the present invention Comprising monometallic sulfide and bimetallic sulfide, the theoretical specific capacitance of both sulfide is very high, is applied to supercapacitor When can embody synergistic effect.Double shell structurres based on ZIF-67 skeleton have stable skeleton and cavity structure, can subtract Slow supercapacitor electrode material structure collapses in charge and discharge process, to significantly improve the stable circulation of supercapacitor Property.Moreover, the features such as cavity structure of bivalve layer also makes the material have large specific surface area, and active site is more, into one Step improves the quality specific capacitance of supercapacitor.
In order to realize that this structure feature, the present invention pass through plasma erosion method and chemical vapor deposition using ZIF-67 skeleton Area method constructs bivalve layer sulfide CoS/MCo2S4Technology of preparing, as the electrode of supercapacitor, for improving super capacitor Device chemical property.With CoS/NiCo2S4For, using the preparation method of hereinafter embodiment 1, preparation based on ZIF-67 bone When the bivalve layer sulfide of frame structure assembles supercapacitor as electrode material: when current density is 1A/g, quality specific volume Amount is 1230F/g；After circulation 9000 times, specific capacity is maintained at 76% or more.We are expected to by simply and effectively making as a result, Preparation Method, obtaining has height ratio capacity, the supercapacitor of long circulation life and low cost of manufacture.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the present invention provides a kind of based on ZIF-67 skeleton Bivalve layer sulfide and the preparation method and application thereof, the first object of the present invention are to provide a kind of high performance based on ZIF-67 bone The bivalve layer sulfide of frame structure is used for supercapacitor；The second object of the present invention is to provide the ZIF-67 skeleton structure bivalve The preparation method of layer sulfide.
Technical solution: to achieve the above object, the present invention passes through plasma erosion method and chemical gas using ZIF-67 skeleton Phase sedimentation constructs bivalve layer sulfide CoS/MCo2S4, wherein inner shell materials are CoS, sheathing material MCo2S4, M can be with For one of several elements of Ni, Mn, Fe, Cu and Zn.
The present invention is achieved through the following technical solutions, and step includes:
Of the invention nanostructure bivalve layer sulfide powder and PVDF and acetylene black based on ZIF-67 skeleton structure with Mass ratio 8:1:1 is uniformly mixed, and is applied in the nickel foam pre-processed, about 1.5-2.5g/cm2.Smear the nickel foam completed As application of electrode in supercapacitor, the specific capacity and cycle life of supercapacitor are improved.
The utility model has the advantages that a kind of bivalve layer sulfide and preparation method thereof based on ZIF-67 skeleton provided by the invention with answer With, compared with prior art the present invention has the advantages that
1.) double shell structurres based on ZIF-67 skeleton have stable skeleton and cavity structure, can slow down super electricity Container electrode material structure collapses in charge and discharge process, to significantly improve the cyclical stability of supercapacitor.
2.) the bivalve layer sulfide based on ZIF-67 skeleton structure has the characteristics that large specific surface area, active site are more, and There is certain synergistic effect between two kinds of sulfide of inner casing and shell, chemical property can be effectively improved, made it have superior Chemical property.
3.) preparation method of ZIF-67 skeleton structure bivalve layer sulfide is simply direct, and avoids the not true of hydro-thermal method Qualitative, repeatability is high, low in cost, is suitble to large-scale production.
4.) preparation method is applied widely, the bivalve layer sulfide table based on ZIF-67 skeleton structure being finally synthesizing It is shown as CoS/MCo2S4, wherein M can be one of several elements of Ni, Mn, Fe, Cu and Zn.This experimental method is applicable to base In monometallic with synergy/bimetallic bivalve layer sulfide preparation of a variety of bivalves of ZIF-67 skeleton structure layer.
5.) the bivalve layer sulfide based on ZIF-67 skeleton structure of this method preparation is had excellent performance, with CoS/NiCo2S4 For, using the preparation method of hereinafter embodiment 1, the bivalve layer sulfide based on ZIF-67 skeleton structure of preparation is as electricity Pole material, when assembling supercapacitor: when current density is 1A/g, specific discharge capacity 1230F/g；Circulation 9000 is taken second place Afterwards, specific capacity is maintained at 76% or more.
Detailed description of the invention
Fig. 1 is the structural schematic diagram based on ZIF-67 skeleton structure bivalve layer sulfide；
Fig. 2 is the GCD figure for the active material that embodiment 1 obtains；
Fig. 3 is 9000 circle of active material circulation that embodiment 1 obtains；
Fig. 4 is the GCD figure for the active material that embodiment 2 obtains；
Fig. 5 is the GCD figure for the active material that embodiment 3 obtains；
Fig. 6 is the GCD figure for the active material that embodiment 4 obtains；
Fig. 7 is the GCD figure for the active material that embodiment 5 obtains；
Fig. 8 is the GCD figure for the active material that embodiment 6 obtains.
Specific embodiment
The present invention is prepared for a kind of for improving the double based on ZIF-67 skeleton structure of supercapacitor chemical property This material is expressed as CoS/MCo by shell sulfide2S4, wherein inner shell materials are CoS, sheathing material MCo2S4, M can be with For one of several elements of Ni, Mn, Fe, Cu and Zn.
The Redox reaction that electrode material occurs are as follows:
GCD process calculation equation is as follows:
Wherein Cs is quality specific capacitance, electric current when I is constant current charge-discharge, unit A；M is active material quality, single Position is g；Δ T is the discharge time during GCD, unit s；Δ V is voltage window, unit V；GCD (galvanostatic charge-discharge) is constant current charge-discharge.
The present invention is achieved through the following technical solutions, and experimental procedure includes:
A. ZIF-67 is prepared；
The methanol solution of cobalt nitrate is mixed with the methanol solution of methylimidazole, it is quiet in room temperature after magnetic agitation 30min It sets, is centrifuged, methanol cleaning, vacuum drying obtains the ZIF-67 material of the polyhedral of purple
B. nucleocapsid shape intermediate is prepared；
ZIF-67 powder obtained in step a is placed in M (NO3)2Ethanol solution, M can be Ni, Mn, Fe, Cu and Zn In any element, after magnetic agitation, eccentric cleaning is dried in vacuo later, obtains the intermediate powder of lilac: nucleocapsid shape The double-hydroxide of ZIF-67/ two-spot metal.
C. bivalve layer sulfide electrode material is prepared
Lilac powder obtained in step b is vulcanized using chemical vapour deposition technique method.
D. it assembles
The powder is applied in the nickel foam pre-processed, as electrode for assembling supercapacitor.
Embodiment
Technical solution of the present invention is described further below, with CoS/NiCo2S4For, other metallic elements CoS/MCo2S4The preparation method of material is similar, and elemental nickel need to be only changed to other metallic elements.It is of the invention based on ZIF- The structural schematic diagram of 67 skeleton structure bivalves layer sulfide is as shown in Figure 1.
Embodiment 1
A. the 25ml methanol solution of the cobalt nitrate containing 1mmol and the 25ml methanol solution of the methylimidazole containing 4mmol is quick It mixes, after magnetic agitation 30min, at room temperature, stands 9h；Later, centrifugation, methanol cleaning, vacuum drying, obtain the multi-panel of purple Body shape ZIF-67.
B. 50mg purple powder obtained in step a is taken to be placed in the 30ml ethanol solution of the nickel nitrate containing 100mg, magnetic agitation After 30min, eccentric cleaning is dried in vacuo later, obtains the intermediate of lilac: ZIF-67/ nickel cobalt double-hydroxide.
C. 50mg is taken to vulcanize using chemical vapour deposition technique method in intermediate obtained in step b, curing temperature 300 DEG C, vulcanization time 2h, heating rate is 10 DEG C/min, and sulphur source is sublimed sulfur, and the quality of sublimed sulfur is 100mg.
D. the bivalve layer sulfide described in will be powdered based on ZIF-67 skeleton structure, PVDF and acetylene black are with mass ratio 8:1:1 is uniformly mixed, and is applied in the nickel foam pre-processed, about 1.5-2.5g/cm2.The nickel foam completed is smeared as electricity Pole is for assembling supercapacitor.
Bivalve layer sulfide based on ZIF-67 skeleton structure prepared by the method for using the present embodiment is as electrode material group Supercapacitor is filled, wherein platinized platinum is to electrode, and saturation calomel is reference electrode, and active material is working electrode, uses 2M's The electrolyte of KOH carries out CV and GCD test.When current density is 1A/g, the specific discharge capacity of material is 1230F/g；GCD is followed After ring 9000 times, specific capacity is maintained at 76% or more compared to initial value, sees Fig. 2 and Fig. 3.
Embodiment 2
A. the 25ml methanol solution of the cobalt nitrate containing 1mmol and the 25ml methanol solution of the methylimidazole containing 4mmol is quick It mixes, after magnetic agitation 30min, at room temperature, stands 9h；Later, centrifugation, methanol cleaning, vacuum drying, obtain the multi-panel of purple Body shape ZIF-67.
B. 50mg purple powder obtained in step a is taken to be placed in the 30ml ethanol solution of the nickel nitrate containing 50mg, magnetic agitation After 60min, eccentric cleaning, vacuum drying obtains the ZIF-67/ nickel cobalt double-hydroxide of lilac.
C. 50mg is taken to vulcanize using chemical vapour deposition technique method in intermediate obtained in step b, curing temperature 300 DEG C, vulcanization time 4h, heating rate is 10 DEG C/min, and sulphur source is sublimed sulfur, and the quality of sublimed sulfur is 50mg.
D. the bivalve layer sulfide described in will be powdered based on ZIF-67 skeleton structure, PVDF and acetylene black are with mass ratio 8:1:1 is uniformly mixed, and is applied in the nickel foam pre-processed, about 1.5-2.5g/cm2.The nickel foam completed is smeared as electricity Pole is for assembling supercapacitor.
Bivalve layer sulfide based on ZIF-67 skeleton structure prepared by the method for using the present embodiment is as electrode material group Supercapacitor is filled, wherein platinized platinum is to electrode, and saturation calomel is reference electrode, and active material is working electrode, uses 2M's The electrolyte of KOH carries out CV and GCD test.When current density is 1A/g, the specific discharge capacity of material is 624F/g, sees Fig. 4.
Embodiment 3
A. the 25ml methanol solution of the cobalt nitrate containing 1mmol and the 25ml methanol solution of the methylimidazole containing 4mmol is quick It mixes, after magnetic agitation 30min, at room temperature, stands 9h；Later, centrifugation, methanol cleaning, vacuum drying, obtain the multi-panel of purple Body shape ZIF-67.
B. 50mg purple powder obtained in step a is taken to be placed in the 30ml ethanol solution of the nickel nitrate containing 150mg, magnetic agitation After 90min, eccentric cleaning, vacuum drying obtains the ZIF-67/ nickel cobalt double-hydroxide of lilac.
C. lilac powder obtained in step b is vulcanized using chemical vapour deposition technique method, curing temperature 500 DEG C, vulcanization time 2h, heating rate is 10 DEG C/min, and sulphur source is sublimed sulfur, and the quality of sublimed sulfur is 150mg.
D. the bivalve layer sulfide described in will be powdered based on ZIF-67 skeleton structure, PVDF and acetylene black are with mass ratio 8:1:1 is uniformly mixed, and is applied in the nickel foam pre-processed, about 1.5-2.5g/cm2.The nickel foam completed is smeared as electricity Pole is for assembling supercapacitor.
Bivalve layer sulfide based on ZIF-67 skeleton structure prepared by the method for using the present embodiment is as electrode material group Supercapacitor is filled, wherein platinized platinum is to electrode, and saturation calomel is reference electrode, and active material is working electrode, uses 2M's The electrolyte of KOH carries out CV and GCD test.When current density is 1A/g, the specific discharge capacity of material is 512F/g, sees Fig. 5.
Embodiment 4
A. the 25ml methanol solution of the cobalt nitrate containing 1mmol and the 25ml methanol solution of the methylimidazole containing 4mmol is quick It mixes, after magnetic agitation 30min, at room temperature, stands 9h；Later, centrifugation, methanol cleaning, vacuum drying, obtain the multi-panel of purple Body shape ZIF-67.
B. 50mg purple powder obtained in step a is taken to be placed in the 30ml ethanol solution of the nickel nitrate containing 200mg, magnetic agitation After 30min, eccentric cleaning, vacuum drying obtains the ZIF-67/ nickel cobalt double-hydroxide of lilac.
C. intermediate will be obtained in step b takes vulcanizing using chemical vapour deposition technique method for 50mg, curing temperature 400 DEG C, vulcanization time 3h, heating rate is 10 DEG C/min, and sulphur source is sublimed sulfur, the quality 200mg of sublimed sulfur.
D. the bivalve layer sulfide described in will be powdered based on ZIF-67 skeleton structure, PVDF and acetylene black are with mass ratio 8:1:1 is uniformly mixed, and is applied in the nickel foam pre-processed, about 1.5-2.5g/cm2.The nickel foam completed is smeared as electricity Pole is for assembling supercapacitor.
Bivalve layer sulfide based on ZIF-67 skeleton structure prepared by the method for using the present embodiment is as electrode material group Supercapacitor is filled, wherein platinized platinum is to electrode, and saturation calomel is reference electrode, and active material is working electrode, uses 2M's The electrolyte of KOH carries out CV and GCD test.When current density is 1A/g, the specific discharge capacity of material is 862F/g, sees Fig. 6.
Embodiment 5
A. the 25ml methanol solution of the cobalt nitrate containing 1mmol and the 25ml methanol solution of the methylimidazole containing 4mmol is quick It mixes, after magnetic agitation 30min, at room temperature, stands 9h；Later, centrifugation, methanol cleaning, vacuum drying, obtain the multi-panel of purple Body shape ZIF-67.
B. 50mg purple powder obtained in step a is taken to be placed in the 30ml ethanol solution of the nickel nitrate containing 100mg, magnetic agitation After 90min, eccentric cleaning, vacuum drying obtains the ZIF-67/ nickel cobalt double-hydroxide of lilac.
C. 50mg is taken to vulcanize using chemical vapour deposition technique method in intermediate obtained in step b, curing temperature 300 DEG C, vulcanization time 4h, heating rate is 10 DEG C/min, and sulphur source is sublimed sulfur, and the quality of sublimed sulfur is 100mg.
D. the bivalve layer sulfide described in will be powdered based on ZIF-67 skeleton structure, PVDF and acetylene black are with mass ratio 8:1:1 is uniformly mixed, and is applied in the nickel foam pre-processed, about 1.5-2.5g/cm2.The nickel foam completed is smeared as electricity Pole is for assembling supercapacitor.
Bivalve layer sulfide based on ZIF-67 skeleton structure prepared by the method for using the present embodiment is as electrode material group Supercapacitor is filled, wherein platinized platinum is to electrode, and saturation calomel is reference electrode, and active material is working electrode, uses 2M's The electrolyte of KOH carries out CV and GCD test.When current density is 1A/g, the specific discharge capacity of material is 762F/g, sees Fig. 7.
Embodiment 6
A. the 25ml methanol solution of the cobalt nitrate containing 1mmol and the 25ml methanol solution of the methylimidazole containing 4mmol is quick It mixes, after magnetic agitation 30min, at room temperature, stands 9h；Later, centrifugation, methanol cleaning, vacuum drying, obtain the multi-panel of purple Body shape ZIF-67.
B. 50mg purple powder obtained in step a is taken to be placed in the 30ml ethanol solution of the nickel nitrate containing 150mg, magnetic agitation After 30min, eccentric cleaning is dried in vacuo later, obtains the intermediate of lilac: ZIF-67/ nickel cobalt double-hydroxide.
C. 50mg is taken to vulcanize using chemical vapour deposition technique method in intermediate obtained in step b, curing temperature 300 DEG C, vulcanization time 4h, heating rate is 10 DEG C/min, and sulphur source is sublimed sulfur, and the quality of sublimed sulfur is 150mg.
D. the bivalve layer sulfide described in will be powdered based on ZIF-67 skeleton structure, PVDF and acetylene black are with mass ratio 8:1:1 is uniformly mixed, and is applied in the nickel foam pre-processed, about 1.5-2.5g/cm2.The nickel foam completed is smeared as electricity Pole is for assembling supercapacitor.
Bivalve layer sulfide based on ZIF-67 skeleton structure prepared by the method for using the present embodiment is super as electrode assembling When grade capacitor, wherein platinized platinum is to electrode, and saturation calomel is reference electrode, and active material is working electrode, uses the KOH of 2M Electrolyte carry out CV and GCD test.When current density is 1A/g, the specific discharge capacity of material is 963F/g, sees Fig. 8.
The present invention develops a kind of bivalve layer structure feature based on ZIF-67 skeleton, as shown in Figure 1, including two kinds of differences Sulfide, while large specific surface area is had both, the features such as active site is more, to effectively improve the specific volume of supercapacitor Amount.Double shell structurres based on ZIF-67 skeleton have stable skeleton and cavity structure, can slow down supercapacitor and fill Electrode material structure collapses in discharge process, and then the cyclical stability of supercapacitor can be significantly improved.In addition, the preparation Method is easy to operate, favorable reproducibility, is suitble to large-scale production.
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of bivalve layer sulfide based on ZIF-67 skeleton structure, which is characterized in that bivalve layer sulfide is expressed as CoS/MCo2S4, wherein inner shell materials are CoS, sheathing material MCo2S4, M is any including Ni, Mn, Fe, Cu and Zn A kind of element.
2. a kind of preparation method of bivalve layer sulfide based on ZIF-67 skeleton structure according to claim 1, special Sign is, includes the following steps:
A. ZIF-67 is prepared:
The methanol solution of cobalt nitrate is mixed with the methanol solution of methylimidazole, magnetic agitation is being stored at room temperature, centrifugation, first Alcohol cleaning, vacuum drying obtain the ZIF-67 material of the polyhedral of purple；
B. nucleocapsid shape intermediate is prepared:
ZIF-67 powder obtained in step a is placed in M (NO3)2Ethanol solution, after magnetic agitation, eccentric cleaning, vacuum is dry It is dry, obtain the intermediate powder of lilac: nucleocapsid shape ZIF-67/ two-spot metal hydroxides；
C. bivalve layer sulfide electrode material is prepared:
Lilac intermediate powder obtained in step b is vulcanized using chemical vapour deposition technique method to get ZIF-67 is based on The bivalve layer sulfide of skeleton structure.
3. the preparation method of the bivalve layer sulfide based on ZIF-67 skeleton structure according to claim 2, which is characterized in that In the step a, the concentration of the methanol solution of cobalt nitrate is 0.04M, and the concentration of the methanol solution of methylimidazole is 0.16M, The ratio of two kinds of solution mixing is 1:1.
4. the preparation method of the bivalve layer sulfide according to claim 2 based on ZIF-67 skeleton structure, feature exist In, in the step b, ZIF-67 powder and M (NO3)2The mass ratio of crystal is 1:X, and wherein X is 1,2,3,4.
5. the preparation method of the bivalve layer sulfide based on ZIF-67 skeleton structure according to claim 2, which is characterized in that In the step b, the amount of the corresponding ethyl alcohol of every 50mg ZIF-67 powder is 30mL.
6. the preparation method of the bivalve layer sulfide according to claim 2 based on ZIF-67 skeleton structure, feature exist In in the step b, magnetic agitation time, i.e. plasma erosion time are 30-120min.
7. the preparation method of the bivalve layer sulfide according to claim 2 based on ZIF-67 skeleton structure, feature exist In in the step c, the curing temperature of chemical vapour deposition technique is 300-500 DEG C, vulcanization time 2-4h, and heating rate is 10℃/min。
8. the preparation method of the bivalve layer sulfide according to claim 2 based on ZIF-67 skeleton structure, feature exist In in the step c, the sulphur source of chemical vapour deposition technique is sublimed sulfur, and the mass ratio of intermediate and sulphur source is 1:X, and wherein X is 1、2、3、4。
9. the bivalve layer sulfide according to claim 1 based on ZIF-67 skeleton structure, which is characterized in that be applied to super In grade capacitor.
10. ZIF-67 skeleton structure according to claim 9 bivalve layer sulfide, which is characterized in that be applied to super electricity In container method particularly includes: the bivalve layer sulfide described in will be powdered based on ZIF-67 skeleton structure, PVDF and acetylene It is black uniformly to be mixed with mass ratio 8:1:1, it is applied in the nickel foam pre-processed, application area 1.5-2.5g/cm2；It smears The nickel foam of completion is as electrode for assembling supercapacitor.
CN201811487891.2A 2018-12-06 2018-12-06 ZIF-67 framework-based double-shell sulfide and preparation method and application thereof Active CN109767926B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811487891.2A CN109767926B (en) 2018-12-06 2018-12-06 ZIF-67 framework-based double-shell sulfide and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811487891.2A CN109767926B (en) 2018-12-06 2018-12-06 ZIF-67 framework-based double-shell sulfide and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109767926A true CN109767926A (en) 2019-05-17
CN109767926B CN109767926B (en) 2021-02-09

Family

ID=66450549

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811487891.2A Active CN109767926B (en) 2018-12-06 2018-12-06 ZIF-67 framework-based double-shell sulfide and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109767926B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110068599A (en) * 2019-05-31 2019-07-30 吉林大学 One kind being based on CoFe2O4/Co3O4The formaldehyde gas sensor and preparation method thereof of duplex shell structure cubic materials
CN110575842A (en) * 2019-10-12 2019-12-17 福州大学 Preparation method of adjustable and controllable yolk-shell structure nitrogen-carbon-doped cobalt molybdenum sulfide counter electrode catalyst
CN110797206A (en) * 2019-10-31 2020-02-14 上海应用技术大学 Co-Mn-S composite material and preparation method and application thereof
CN110957146A (en) * 2019-11-12 2020-04-03 洛阳师范学院 Preparation method of supercapacitor composite electrode material and electrode
CN112216520A (en) * 2020-05-13 2021-01-12 江苏大学 Preparation method and application of composite electrode with MOF-derived Ni-Co-S nanoparticles growing on carbon cloth
CN114725411A (en) * 2022-04-02 2022-07-08 北京科技大学 Cobalt-based oxygen reduction electrocatalytic material and preparation method thereof
CN115410831A (en) * 2022-09-14 2022-11-29 桂林电子科技大学 Preparation method and application of NiMo-LDH @ Co-ZIF-67 porous core-shell structure composite material
CN114725411B (en) * 2022-04-02 2024-05-17 北京科技大学 Cobalt-based oxygen reduction electrocatalytic material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106298255A (en) * 2016-08-16 2017-01-04 中南大学 A kind of hollow sub-microsphere with multilamellar cobalt sulfide/cobalt oxide shell and its preparation method and application
CN107740135A (en) * 2017-09-30 2018-02-27 哈尔滨工业大学 A kind of hollow polyhedral preparation method and applications of meso-hole structure NiCoS
KR20180106166A (en) * 2017-03-17 2018-10-01 영남대학교 산학협력단 Preparation method of 3D hierarchical mesoporous NiCo2S4/Ni(OH)2 core-shell nanosheet arrays on 3-dimensional conductive carbon electrode and its application to high performance supercapacitors
CN108666553A (en) * 2018-05-11 2018-10-16 深圳大学 A kind of cobalt sulfide/carbon fiber composite and the preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106298255A (en) * 2016-08-16 2017-01-04 中南大学 A kind of hollow sub-microsphere with multilamellar cobalt sulfide/cobalt oxide shell and its preparation method and application
KR20180106166A (en) * 2017-03-17 2018-10-01 영남대학교 산학협력단 Preparation method of 3D hierarchical mesoporous NiCo2S4/Ni(OH)2 core-shell nanosheet arrays on 3-dimensional conductive carbon electrode and its application to high performance supercapacitors
CN107740135A (en) * 2017-09-30 2018-02-27 哈尔滨工业大学 A kind of hollow polyhedral preparation method and applications of meso-hole structure NiCoS
CN108666553A (en) * 2018-05-11 2018-10-16 深圳大学 A kind of cobalt sulfide/carbon fiber composite and the preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
L.W. YE: ""NiCo2S4/Co3S4 heterogeneous double-shelled nanocages for high-performance electrochemical energy storage"", 《MATERIALS LETTERS》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110068599A (en) * 2019-05-31 2019-07-30 吉林大学 One kind being based on CoFe2O4/Co3O4The formaldehyde gas sensor and preparation method thereof of duplex shell structure cubic materials
CN110575842A (en) * 2019-10-12 2019-12-17 福州大学 Preparation method of adjustable and controllable yolk-shell structure nitrogen-carbon-doped cobalt molybdenum sulfide counter electrode catalyst
CN110575842B (en) * 2019-10-12 2020-08-11 福州大学 Preparation method of adjustable and controllable yolk-shell structure nitrogen-carbon-doped cobalt molybdenum sulfide counter electrode catalyst
CN110797206A (en) * 2019-10-31 2020-02-14 上海应用技术大学 Co-Mn-S composite material and preparation method and application thereof
CN110957146A (en) * 2019-11-12 2020-04-03 洛阳师范学院 Preparation method of supercapacitor composite electrode material and electrode
CN112216520A (en) * 2020-05-13 2021-01-12 江苏大学 Preparation method and application of composite electrode with MOF-derived Ni-Co-S nanoparticles growing on carbon cloth
CN114725411A (en) * 2022-04-02 2022-07-08 北京科技大学 Cobalt-based oxygen reduction electrocatalytic material and preparation method thereof
CN114725411B (en) * 2022-04-02 2024-05-17 北京科技大学 Cobalt-based oxygen reduction electrocatalytic material and preparation method thereof
CN115410831A (en) * 2022-09-14 2022-11-29 桂林电子科技大学 Preparation method and application of NiMo-LDH @ Co-ZIF-67 porous core-shell structure composite material
CN115410831B (en) * 2022-09-14 2024-03-19 桂林电子科技大学 Preparation method and application of NiMo-LDH@Co-ZIF-67 porous core-shell structure composite material

Also Published As

Publication number Publication date
CN109767926B (en) 2021-02-09

Similar Documents

Publication Publication Date Title
CN109767926A (en) Bivalve layer sulfide based on ZIF-67 skeleton and the preparation method and application thereof
CN104517739B (en) Titania based electrode material for super capacitor and preparation method thereof
CN106229492A (en) A kind of preparation method of lead carbon battery negative pole based on ZIF 8 zeolite imidazole ester skeletal porous carbon nanomaterial
CN109485867A (en) A kind of preparation method and applications of metal organic framework compound
CN104393268B (en) The preparation method of the SnSb/ CNT composite negative pole material that a kind of aeroge is modified
CN105355925B (en) A kind of preparation method of three-dimensional order nickel skeleton load germanium base lithium cell cathode material
CN110310835B (en) Nano flower-shaped NiS @ NiCo2S4Micro-nano electrode material and preparation method and application thereof
CN106654262B (en) A kind of preparation method and application of hollow sphere nickel sulfide positive electrode
CN108807911A (en) A kind of aluminium ion battery and preparation method thereof
CN109599542A (en) A kind of phosphatization cobalt biomass carbon composite material and preparation method and application
CN110350184A (en) A kind of high capacity NiMoO for cell positive material4The preparation method of energy storage material
CN105633327B (en) A kind of TiS2For the aluminium ion secondary cell and its preparation process of anode
CN107978736B (en) Metal alloy/carbon tube/graphene sulfur-loaded composite cathode material and preparation method and application thereof
CN103117400A (en) Secondary lithium-air battery cathode catalyst
CN109494357B (en) Preparation and application of ferric fluoride doped nano titanium dioxide
CN107275627A (en) Mn doping hollow porous classifying nano ball electrode materials of CuS and its preparation method and application
CN105118683B (en) A kind of preparation method of cobalt molybdate composite manganese dioxide electrode material
CN109786725A (en) Independent self-supporting positive electrode and preparation method thereof and aluminium ion battery and preparation method thereof
CN107221446B (en) A kind of Co-Ni-Mn oxide composite and its preparation method and application
CN103943856B (en) A kind of preparation method of phthalocyanine-iron phosphate compound anode material of lithium
CN106340630B (en) A kind of SiO2The preparation method of/C composite nano materials and its application in lithium cell cathode material
CN110931267B (en) Nickel-cobalt-molybdenum ternary metal sulfide and preparation method and application thereof
CN106099093B (en) Titanium-based oxide K containing potassium2Ti8O17Preparation method and products thereof and application
CN109637838B (en) Preparation method and application of loofah-shaped hollow molybdenum disulfide material
CN112038106A (en) Electrode material, preparation method thereof and supercapacitor electrode

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant