CN109192949A - Suede shell hollow polyhedral Co is obtained by ZIF-67 multi-panel derivatization9S8@MoS2Method - Google Patents

Suede shell hollow polyhedral Co is obtained by ZIF-67 multi-panel derivatization9S8@MoS2Method Download PDF

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CN109192949A
CN109192949A CN201811011504.8A CN201811011504A CN109192949A CN 109192949 A CN109192949 A CN 109192949A CN 201811011504 A CN201811011504 A CN 201811011504A CN 109192949 A CN109192949 A CN 109192949A
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mos
suede
hollow polyhedral
shell
cos
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陈铭
李文龙
周克寒
沈超
韩悦
吴化雨
戴兰轩
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Yangzhou University
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Yangzhou University
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

Abstract

The invention discloses one kind to obtain suede shell hollow polyhedral Co by ZIF-67 multi-panel derivatization9S8@MoS2Method.Two-dimensional slice material MoS is grown in its inner surface after turning to α-CoS hollow polyhedral so that ZIF-67 is derivative2, form the Co of suede shell hollow polyhedral structure9S8@MoS2, suede shell hollow polyhedral Co9S8@MoS2, there is the amorphous carbon of N doping the electric conductivity of composite material can be improved, hollow structure can buffer bulk effect in charge and discharge process, while Co9S8Polyhedron theoretical specific capacity with higher itself, two-dimensional layer material MoS2Growth in situ, in polyhedron surfaces externally and internally, forms MoS in α-CoS2Suede shell further increases lithium storage content, promotes high rate performance, suede shell Co9S8@MoS2When as lithium ion battery negative material, Co9S8And MoS2Play synergistic effect, surface MoS2Increase lithium storage content, buffer volumes variation；Hollow Co9S8Skeleton further buffers the embedding de- bulk effect generated in the process of lithium ion, which is a kind of ion cathode material lithium with application prospect.

Description

Suede shell hollow polyhedral Co is obtained by ZIF-67 multi-panel derivatization9S8@MoS2's Method
Technical field
The invention belongs to lithium ion battery negative material production technical fields, and in particular to by ZIF-67 multi-panel derivatization Obtain suede shell hollow polyhedral Co9S8@MoS2Preparation method.
Background technique
Metal-organic framework material (MOFs) is a kind of coordination polymer quickly grown nearly ten years, refers to transition metal Ion and organic ligand pass through the crystalline porous material with periodic network structure being self-assembly of.It has high hole Rate, low-density, bigger serface, duct rule, aperture is adjustable and topological structure diversity and the advantages that Scalability, has Three-dimensional pore structure, generally using metal ion as tie point, it is that zeolite and carbon are received that organic ligand support, which constitutes space 3D and extends, The important novel porous materials of another class except mitron, are all widely used in catalysis, energy storage and separation.Currently, MOFs Have become the important research direction of multiple chemical branches such as inorganic chemistry, organic chemistry.Metal organic frame derivative has been made Electro-catalysis, photocatalysis, the biology load various fields such as medicine and lithium ion battery negative material are had been used for for a series of composite material, The controllable function in its adjustable aperture makes it better than traditional porous material.
Transient metal sulfide is a kind of important functional material occurred in recent years.Wherein, molybdenum disulfide (MoS2) because Its two-dimensional layered structure from S-Mo-S motif and by extensive research concern, these motifs are mutual by weak Van der Waals Effect is stacked.Especially the bigger serface that is assigned of anisotropic structure and high activity marginal position have them Interesting optics, electronics, physics and chemical property.Especially as lithium ion battery (LiBS) and sodium-ion battery (SIBS) Electrode material, MoS2The intercalation and removing that larger interlamellar spacing along c-axis is lithium/sodium ion in electrochemical reaction process provide Effective diffusion path has faster ion kinetics of diffusion and height ratio capacity.
So far, there are still more problems for electro-catalysis hydrolysis field for transition metal chalcogenide nano material, one is The promotion of single component material specific capacity approaches bottleneck, MoS2There are intrinsic low conductivity and large volume are swollen in cyclic process Swollen, this will lead to rate capacity difference and capacity is decayed rapidly.Therefore it studies MoS2It is supported on other carriers and improves its conduction Rate and the reduction capacity due to caused by volume expansion are decayed rapidly, and are introduced other metal sulfides and realized that the collaboration of material is made It is especially significant with just seeming.The second is transition metal chalcogenide is semiconductor, electron transfer rate is slow, therefore good leads Electric substrate realizes that good removal lithium embedded just becomes most important as the electrode material of ion battery.The third is the stabilization of battery Property and big multiplying power under charge and discharge problem, universal single transition metal sulfide is steady as the electrode material of lithium ion battery at present Charge-discharge performance under qualitative and big multiplying power is often poor.Therefore, how to design and prepare with good high rate performance and big Realize that preferable charge-discharge performance lithium ion battery electrode material is current urgent problem to be solved under multiplying power.
Summary of the invention
It is an object of the invention to propose that one kind obtains Co by ZIF-67 multi-panel derivatization9S8@MoS2Polyhedron suede shell Method.
The technical solution adopted by the present invention to solve the technical problems is:
One kind obtaining Co by ZIF-67 multi-panel derivatization9S8@MoS2The method of polyhedron suede shell, is obtained with ZIF-67 derivatization α-CoS hollow polyhedral as carrier, carry out MoS in the surfaces externally and internally of hollow polyhedral template2The growth in situ of piece, lazy Property gas under calcining form Co9S8@MoS2Polyhedron suede shell structure.Specifically comprise the following steps:
Hollow polyhedral α-CoS is dispersed in water by S1, and sodium molybdate is added and thiocarbamide stirs evenly, occurs under high temperature and pressure Hollow polyhedral α-CoS@MoS can be obtained in liquid phase reactor2；
S2, by hollow polyhedral α-CoS@MoS2It is calcined under an inert gas, suede shell hollow polyhedral Co can be obtained9S8@ MoS2。
In the step S1, α-CoS hollow polyhedral, sodium molybdate, thiocarbamide mass ratio be 1:0.5 ~ 10:0.5 ~ 50, lead to It crosses and designs the adjustable MoS of the ratio2The amount of nanometer sheet growth in situ on α-CoS hollow polyhedral.
In the step S1, liquid phase reactor temperature is 120 ~ 250 DEG C, by controlling the adjustable MoS of liquid phase reactor temperature2 The reaction rate of nanometer sheet growth in situ on α-CoS hollow polyhedral；The liquid phase reactor time is the h of 30 min ~ 2, passes through control The liquid phase reactor time processed can control MoS2Nanometer sheet growth thickness and surface coverage.
In the step S2, by hollow polyhedral α-CoS@MoS2It is calcined under protection of argon gas, calcination temperature 600 ~ 900 DEG C, 0.5 ~ 5 h of calcination time, heating rate is 1 ~ 10 DEG C/min, and with this condition, α-CoS hollow polyhedral crystal form turns Become more stable Co9S8, while improving MoS2The crystallinity of nanometer sheet, and organic ligand can be converted into shape in original structure At the N doping carbon-coating with good electric conductivity, the uniform suede shell hollow polyhedral Co of pattern can get9S8@MoS2Composite material.
Compared with prior art, the invention has the advantages that
(1) α-CoS hollow polyhedral pattern prepared is uniform, stable structure, has the Co of good pattern for subsequent preparation9S8@ MoS2Polyhedron suede shell structure provides advantage.
(2) by control process conditions, α-CoS hollow polyhedral crystal transfer is more stable Co9S8, improve simultaneously MoS2The crystallinity of nanometer sheet, and organic ligand can be converted into form the nitrogen-doped carbon with good electric conductivity in original structure Layer can get the uniform suede shell hollow polyhedral Co of pattern9S8@MoS2Composite material.
Detailed description of the invention
Fig. 1 is respectively the polyhedral transmission electron microscope picture of ZIF-67 of different amplification prepared by embodiment 2.
Fig. 2 is respectively the transmission electron microscope picture of the α-CoS hollow polyhedral of different amplification prepared by embodiment 2.
Fig. 3 is respectively the suede shell hollow polyhedral Co of different amplification prepared by embodiment 29S8@MoS2Transmission electron microscope Figure.
Fig. 4 is respectively the suede shell hollow polyhedral Co of different amplification prepared by embodiment 29S8@MoS2Scanning electron microscope Figure.
Fig. 5 is suede shell hollow polyhedral Co prepared by embodiment 29S8@MoS2XRD diagram.
Fig. 6 is suede shell hollow polyhedral Co prepared by embodiment 29S8@MoS2Lithium ion battery different multiplying under performance Figure.
Fig. 7 is suede shell hollow polyhedral Co prepared by embodiment 29S8@MoS2Lithium ion battery current density be 5A g-1Under long circulating performance map.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments with attached drawing pair The present invention is described in detail.
Suede shell hollow polyhedral Co of the present invention9S8@MoS2Composite material, unique nano Co9S8@MoS2Multi-panel Body suede shell structure, not only MoS2It is empty that the bulk effect that material generates during lithium ion is embedding de- provides effective buffering Between, its specific surface area is improved but also MoS2Active site be largely exposed, be more conducive to the quick of lithium ion Transmission；Transient metal sulfide and MoS are obtained after α-CoS hollow polyhedral calcined material2The synergistic effect of piece possesses it High specific capacity and high rate performance and excellent cyclical stability；And Co9S8@MoS2Polyhedron suede shell structure makes material Lithiumation/the bulk effect generated during lithiumation is gone to be effectively relieved, so that active material obtains in high current, long circulating To effective protection.Therefore, suede shell hollow polyhedral Co9S8@MoS2Composite material be it is a kind of have excellent performance, great application prospect Lithium ion battery negative material.
One, prepared by material
Embodiment 1:
1, α-CoS hollow polyhedral is prepared
Co(NO3)2·6H2291 mg of O and 328 mg of 2-methylimidazole, which is dissolved separately in 25 ml methanol solutions, to be mixed, room temperature 24 h of lower stirring, with ethanol washing 4 times, are done at 60 DEG C to be centrifuged 5 min in 6000 rpm after reaction after obtaining solid phase Dry 6 h forms ZIF-67 nanometer polyhedral.
It takes 30 mg ultrasonic disperse of ZIF-67 nanometer polyhedral in 30 ml ethanol solutions, 150 mg thioacetamides is added 24 h are reacted at a temperature of 40 DEG C, to be centrifuged 5 min in 5000 rpm after reaction, is respectively washed 3 times, is obtained with water and ethyl alcohol Shell wall thickness is the α-CoS hollow polyhedral of 40 nm.
Manufactured α-CoS hollow polyhedral, partial size are about 300 ~ 600 nm or so, and the middle section of ZIF-67 is carved completely Erosion, forms the α-CoS polyhedron of hollow structure, and surfacing is uniform, and wall thickness is controlled in 15 ~ 40 nm, and this structure has Great specific surface area and biggish hollow volume.
2, suede shell hollow polyhedral Co is prepared9S8@MoS2
Disperse 30 mg of α-CoS hollow polyhedral that obtained wall thickness is 40 nm in the molybdic acid that 30 mg are added in the water of 25 ml The thiocarbamide of sodium and 60 mg are stirred at room temperature 2 h and are then transferred into 120 DEG C of 2 h of reaction in the reaction kettle of 50 ml, wait react knot 5 min are centrifuged in 5000 rpm after beam, is respectively washed 3 times with water and ethyl alcohol, α-CoS@MoS can be obtained2Polyhedron suede shell structure, Since α-CoS hollow structure remains intact, MoS2Nanometer sheet is grown in a nanometer surfaces externally and internally for α-CoS hollow polyhedral, is formed Tapetum.
α-CoS@the MoS that will be obtained2Polyhedron suede shell structure 600 DEG C of 5 h of calcining under an argon atmosphere, heating rate 2 DEG C/min, suede shell hollow polyhedral Co can be obtained9S8@MoS2Composite material.
Embodiment 2:
1, α-CoS hollow polyhedral is prepared
Co(NO3)2·6H2291 mg of O and 656 mg of 2-methylimidazole, which is dissolved separately in 25 ml methanol solutions, to be mixed, room temperature Lower stirring for 24 hours, to be centrifuged 5 min in 6000 rpm after reaction, with ethanol washing 4 times, is done at 60 DEG C after obtaining solid phase Dry 6h forms ZIF-67 nanometer polyhedral.
It takes 30 mg ultrasonic disperse of ZIF-67 nanometer polyhedral in 30 ml ethanol solutions, 90 mg thioacetamides is added It is transferred to 50ml high-temperature high-pressure reaction kettle and reacts 5 h at a temperature of 100 DEG C, to be centrifuged 5 min in 5000 rpm after reaction, It is respectively washed 3 times with water and ethyl alcohol, obtains the α-CoS hollow polyhedral that shell wall thickness is 20 nm.
2, suede shell hollow polyhedral Co is prepared9S8@MoS2
Disperse 30 mg of α-CoS hollow polyhedral that obtained wall thickness is 20 nm in the molybdenum that 150 mg are added in the water of 25 ml The thiocarbamide of sour sodium and 750 mg are stirred at room temperature 2 h and are then transferred into 200 DEG C of 1 h of reaction in the reaction kettle of 50 ml, wait react After 5000 rpm be centrifuged 5 min, respectively washed 3 times with water and ethyl alcohol, suede shell hollow polyhedral α-CoS@can be obtained MoS2Composite material.
The suede shell hollow polyhedral α-CoS@MoS that will be obtained2800 DEG C of 2 h of calcining under an argon atmosphere, heating rate 5 DEG C/min, suede shell hollow polyhedral Co can be obtained9S8@MoS2Composite material.
Embodiment 3:
1, α-CoS hollow polyhedral is prepared
Co(NO3)2·6H2291 mg of O and 1312 mg of 2-methylimidazole, which is dissolved separately in 25 ml methanol solutions, to be mixed, room Temperature is lower to be stirred for 24 hours, to be centrifuged 5 min in 6000 rpm after reaction, with ethanol washing 4 times, after acquirement solid phase at 60 DEG C Dry 6h, forms ZIF-67 nanometer polyhedral.
It takes 30 mg ultrasonic disperse of ZIF-67 nanometer polyhedral in 30 ml ethanol solutions, 300 mg thioacetamides is added It is transferred to 50ml high-temperature high-pressure reaction kettle and reacts 10 min at a temperature of 200 DEG C, to be centrifuged 5 in 5000 rpm after reaction Min is respectively washed 3 times with water and ethyl alcohol, obtains the α-CoS hollow polyhedral that shell wall thickness is 15 nm.
2, suede shell hollow polyhedral Co is prepared9S8@MoS2
Disperse 30 mg of α-CoS hollow polyhedral that obtained wall thickness is 15 nm in the molybdenum that 300 mg are added in the water of 50 ml The thiocarbamide of sour sodium and 1.5 g are stirred at room temperature 2h and are then transferred into 250 DEG C of 10 min of reaction in the reaction kettle of 150 ml, to anti- 5 min are centrifuged in 5000 rpm after answering, is respectively washed 3 times with water and ethyl alcohol, suede shell hollow polyhedral α-CoS@can be obtained MoS2Composite material.
The suede shell hollow polyhedral α-CoS@MoS that will be obtained2Composite material is in argon gas as 900 DEG C of calcinings under inert gas 0.5 h, heating rate are 10 DEG C/min, and suede shell hollow polyhedral Co can be obtained9S8@MoS2Composite material.
Two, product is verified:
Under conditions of embodiment 2, the assembling of lithium ion battery is carried out using the electrode material of acquisition as negative electrode material, is below The material characterization and performance characterization of the embodiment 2 of selection:
Fig. 1 is the polyhedral transmission electron microscope picture of ZIF-67 under the different amplification prepared using the method for the present invention.It can from figure See: prepared product is that partial size is about 300-500 nm, and smooth surface.
Fig. 2 is the transmission electron microscope picture of the α-CoS hollow polyhedral under the different amplification prepared using the method for the present invention. From figure: prepared product is that partial size is about 300-500 nm, and wall thickness is about 20nm or so, and surface is smooth flat It is whole.
Fig. 3 is the suede shell hollow polyhedral Co prepared using the method for the present invention9S8@MoS2Transmission electron microscope picture.It can from figure See: pattern is uniform, Co9S8Keep its hollow structure, MoS2Tapetum is grown in Co9S8On skeleton.
Fig. 4 is the suede shell hollow polyhedral Co prepared using the method for the present invention9S8@MoS2Scanning electron microscope (SEM) photograph.It can from figure See: composite material pattern is uniform, MoS2Tapetum is grown in Co9S8On skeleton.
Fig. 5 is the suede shell hollow polyhedral Co prepared using the method for the present invention9S8@MoS2XRD diagram.From figure: Co9S8@ MoS2Crystal form is good, illustrates to successfully synthesize Co9S8@MoS2Composite material.
Fig. 6 is the suede shell hollow polyhedral Co of preparation9S8@MoS2Lithium ion battery different multiplying under performance map.Suede shell Hollow polyhedral Co9S8@MoS2As negative electrode of lithium ion battery current density respectively in 0.1A g-1, 0.2A g-1, 0.5A g-1, 1A g-1, 2A g-1, 5A g-1, 0.1A g-1Under specific discharge capacity, from the figure we can see that, in 5A g-1, when according to It is old to may remain in 600 mAh g-1Specific capacity, from 5A g-1To 0.1A g-1When, it remains to return to 820 mAh g-1, therefore suede Shell hollow polyhedral Co9S8@MoS2There is good high rate performance when as lithium ion battery negative material.
Fig. 7 is the suede shell hollow polyhedral Co of preparation9S8@MoS2Lithium ion battery current density be 5A g-1Under length Cycle performance figure.580 mAh g are still able to maintain after the circle of circulation 400-1It illustrates, suede shell hollow polyhedral Co9S8@MoS2Make For lithium ion battery negative material when, equally have good long circulating performance.The reason is that because its polyhedron suede shell knot Structure and Co9S8And MoS2Synergistic effect.
The instrument and equipment that the present invention uses is simple, and operating process is easy, and reaction process material requested is less toxic, harmless, and can Effectively to control the stoichiometric ratio of each component material, it is uniform to obtain size, is evenly distributed and pattern control is good, can be with Hollow Compound nano material for industrial mass production high quality.Suede shell hollow polyhedral Co prepared by the present invention9S8@ MoS2Skeleton be the Co obtained by MOFs derivatization9S8Hollow polyhedral structure, the amorphous carbon with N doping can be improved The electric conductivity of composite material, hollow structure can buffer bulk effect in charge and discharge process, while Co9S8Polyhedron itself has Higher theoretical specific capacity.Two-dimensional layer material MoS2Growth in situ, in polyhedron surfaces externally and internally, forms MoS in α-CoS2Suede shell, The lithium storage content of material is further increased, high rate performance is promoted.Suede shell hollow polyhedral Co9S8@MoS2It is negative as lithium ion battery When the material of pole, Co9S8And MoS2Play synergistic effect, surface MoS2Increase lithium storage content, buffer volumes variation；Hollow Co9S8Bone Frame further buffers the embedding de- bulk effect generated in the process of lithium ion, and hollow structure can also improve the high rate performance of material.

Claims (6)

1. one kind obtains Co by ZIF-67 multi-panel derivatization9S8@MoS2The method of polyhedron suede shell, which is characterized in that including such as Lower step:
Hollow polyhedral α-CoS is dispersed in water by S1, and sodium molybdate is added and thiocarbamide stirs evenly, liquid occurs in reaction kettle Hollow polyhedral α-CoS@MoS can be obtained in phase reaction2；
S2, by hollow polyhedral α-CoS@MoS2It is calcined under an inert gas, suede shell hollow polyhedral Co can be obtained9S8@ MoS2。
2. the method as described in claim 1, which is characterized in that in step S1, α-CoS hollow polyhedral, sodium molybdate, thiocarbamide Mass ratio is 1:0.5 ~ 10:0.5 ~ 50.
3. the method as described in claim 1, which is characterized in that in step S1, liquid phase reactor temperature is 120 ~ 250 DEG C, liquid phase Reaction time is the h of 30 min ~ 2.
4. the method as described in claim 1, which is characterized in that in step S2, by hollow polyhedral α-CoS@MoS2It is protected in argon gas It is calcined under shield.
5. the method as described in claim 1, which is characterized in that in step S2, calcination temperature is 600 ~ 900 DEG C, calcination time 0.5~5 h。
6. the method as described in claim 1, which is characterized in that in step S2, heating rate is 1 ~ 10 DEG C/min.
CN201811011504.8A 2018-08-31 2018-08-31 Suede shell hollow polyhedral Co is obtained by ZIF-67 multi-panel derivatization9S8@MoS2Method Pending CN109192949A (en)

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CN110120306B (en) * 2019-05-24 2021-04-23 桂林电子科技大学 Co-Mo-O-S spherical flower cluster structure composite material and preparation method and application thereof
CN110120306A (en) * 2019-05-24 2019-08-13 桂林电子科技大学 A kind of Co-Mo-O-S spherical shape flowers structural composite material and its preparation method and application
CN110299530A (en) * 2019-07-22 2019-10-01 福州大学 A kind of ZIF-67 base cobalt molybdenum oxide hollow Nano cage/graphene composite material and the preparation method and application thereof
CN111477847A (en) * 2020-04-08 2020-07-31 扬州大学 Box-shaped necklace multilevel structure Fe7S8/WS2@ C-CNFs lithium ion battery negative electrode material and preparation method thereof
CN111477847B (en) * 2020-04-08 2022-07-19 扬州大学 Box-shaped necklace multilevel structure Fe7S8/WS2@ C-CNFs lithium ion battery negative electrode material and preparation method thereof
CN111933455A (en) * 2020-06-12 2020-11-13 扬州大学 PNT @ NiCo-LDH composite material applied to supercapacitor and preparation method thereof
CN113346065A (en) * 2020-07-30 2021-09-03 广东格林赛福能源科技有限公司 Preparation method, material and application of high-performance CoSe/C-NS composite material
CN114512729A (en) * 2020-11-16 2022-05-17 比亚迪股份有限公司 Nanomaterial for negative electrode protection layer, negative electrode protection slurry, lithium negative electrode and lithium battery
CN114512729B (en) * 2020-11-16 2023-07-14 比亚迪股份有限公司 Nanomaterial, negative electrode protection slurry, lithium negative electrode and lithium battery
CN112635764A (en) * 2020-12-03 2021-04-09 江苏大学 CoS/Co9S8Preparation method of @ C core-shell structure nano composite sodium ion battery cathode material
CN112421065B (en) * 2020-12-04 2021-09-21 合肥工业大学 Carbon/molybdenum disulfide-sulfur molybdenum cobalt composite electrochemical catalyst material and preparation and application thereof
CN112421065A (en) * 2020-12-04 2021-02-26 合肥工业大学 Carbon/molybdenum disulfide-sulfur molybdenum cobalt composite electrochemical catalyst material and preparation and application thereof
CN113517438A (en) * 2021-04-23 2021-10-19 山东科技大学 Internal confinement heterojunction yolk-shell electrode material and preparation method and application thereof
CN113428850A (en) * 2021-06-23 2021-09-24 青岛科技大学 Method for preparing three-shell-layer phosphate hydroxide hollow nano cage material by layer-by-layer assembly method at room temperature
CN113428850B (en) * 2021-06-23 2023-09-01 青岛科技大学 Method for preparing three-shell layer hydrogen phosphate hollow nano cage material by layer-by-layer assembly method at room temperature

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Application publication date: 20190111