CN110048106A - A kind of cobalt sulfide and multistage carbon nano-structured composite material and preparation method and application - Google Patents

A kind of cobalt sulfide and multistage carbon nano-structured composite material and preparation method and application Download PDF

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CN110048106A
CN110048106A CN201910317689.3A CN201910317689A CN110048106A CN 110048106 A CN110048106 A CN 110048106A CN 201910317689 A CN201910317689 A CN 201910317689A CN 110048106 A CN110048106 A CN 110048106A
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cobalt
carbon nano
composite material
structured composite
preparation
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CN110048106B (en
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黄剑锋
席乔
李嘉胤
曹丽云
党欢
王璐
郭鹏辉
王海
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Shaanxi University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • 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
    • 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 present invention discloses a kind of cobalt sulfide and multistage carbon nano-structured composite material and preparation method and application, using the graphene of nitrogen sulphur codope as matrix, using metal catalytic generate carbon nanotube method on graphene in-situ growing carbon nano tube, cobalt granule is wrapped up in pipe, later vulcanizing treatment is carried out to cobalt granule again, generates a kind of material that cobalt sulfide is compound with multistage carbon structure.The clad structure it is ingenious in design solve the problems, such as transient metal sulfide as anode material of lithium-ion battery capacity attenuation, effectively inhibit the reuniting effect of transient metal sulfide particle, and carbon nanotube clad structure helps to alleviate the dusting effect of transient metal sulfide particle, and safe preparation process is easy to operate；The cobalt sulfide of preparation and multistage carbon nano-structured composite material can be applied to lithium ion battery and sodium ion battery electrode material.

Description

A kind of cobalt sulfide and multistage carbon nano-structured composite material and preparation method and application
Technical field
The invention belongs to nanometer field of energy source materials, be related to a kind of cobalt sulfide and multistage carbon nano-structured composite material and its Preparation method and application.
Background technique
Transient metal sulfide (MSs) due to its high theoretical capacity, inexpensive and good electronic conductivity and be considered It is one of the most potential candidate of anode material as sodium-ion battery (SIB).However, in duplicate embedding sodium and removing sodium The dissolution of the dusting effect of MSs and the intermediate sulfide of reaction in the electrolytic solution can all be led because of caused by volume expansion in the process The circulation volume of MSs is caused sharply to decline.Therefore, the research of MSs cyclical stability in lithium ion battery, sodium-ion battery is improved The problem of always researchers pay close attention to.
It is considered as overcoming above problem most efficient method that MSs is compound with carbon material.On the one hand, the carbon materials of high conductivity Material can be used as the matrix of MSs, have the function that effectively to disperse MSs nano particle；On the other hand, in the MSs electricity of carbon material cladding In extremely, carbon material can hinder electrolyte to contact with the direct of MSs as barrier, to inhibit to react being dissolved in for intermediate sulfide The utilization rate of electrode material is improved in electrolyte, further reaction is on more stable circulation volume.Importantly, different original The carbon material of sub (such as N, S, B etc.) doping, because local high reaction activity region can be generated and improve conduction by introducing foreign atom Property, to obtain higher sodium storge quality.Three-dimensional (3D) structure for establishing carbon material is also a selection well, Ke Yigeng The volume expansion of good adaptation MSs.However, inventing a kind of simple mild method to construct three-dimensional structure in situ and effectively disperse The preparation method of transient metal sulfide is still a huge challenge.
Summary of the invention
To overcome above-mentioned the deficiencies in the prior art, it is an object of the present invention to provide a kind of cobalt sulfide and multistage are carbon nano-structured multiple Condensation material and its preparation method and application, using the method for coating transient metal sulfide in the carbon nanotube of growth in situ, solution The problem of certainly transient metal sulfide is as anode material of lithium-ion battery capacity attenuation.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of preparation method of cobalt sulfide and multistage carbon nano-structured composite material, comprising the following steps:
1) it disperses graphene oxide, melamine, trithiocyanuric acid and cobalt salt in suitable deionized water, stirs Reaction is abundant, then freeze drying example；
It is 0.5-4mg/ml that the graphene oxide, which is distributed to the concentration in deionized water,；The graphene oxide, trimerization The mass ratio of cyanogen ammonia, trithiocyanuric acid and cobalt salt is 1:(1.2~25): (1.7~9): (1~22)；
2) heat treated sample: dry sample is placed in the tube furnace of inert gas shielding and is calcined；
The heat treatment process is warming up to 600~1000 DEG C using the heating rate of 2~20 DEG C/min, keeps the temperature 1~5h；
3) vulcanizing treatment, it is 1:(1~5 that the substance completed will be heat-treated in step 2) with sulphur powder in mass ratio) it mixes, so Vulcanizing treatment is carried out in the tube furnace of inert gas shielding afterwards；500~800 are warming up in sulfidation with 5~30 DEG C/min DEG C, keep the temperature 1~3h；It is taken out after sample natural cooling under inert gas shielding atmosphere to get sulphur is arrived after the completion of vulcanizing treatment Change cobalt and multistage carbon nano-structured composite material.
Further, the step 1) cobalt salt is one of cobalt acetate, cobalt nitrate, cobaltous sulfate and cobalt chloride.
Further, the step 1) whipping temp is 60 DEG C~120 DEG C, and mixing time is 1~10h.
Further, heat treatment process protective gas flow velocity is 0~300sccm in the step 2).
Further, protective gas flow velocity is 0~200sccm when vulcanizing treatment in the step 3).
A kind of cobalt sulfide and multistage carbon nano-structured composite material are as cathode of lithium battery active material or sode cell cathode The application of active material.
Advantageous effect of the invention is embodied in:
Cobalt sulfide of the invention and multistage carbon nano-structured composite material preparation method are with the graphene of nitrogen sulphur codope For matrix, the method for the carbon nanotube in-situ growing carbon nano tube on graphene is generated using metal catalytic, wraps up cobalt in pipe Grain, carries out vulcanizing treatment to cobalt granule later again, generates a kind of material that cobalt sulfide is compound with multistage carbon structure.The clad structure Ingenious in design solves the problems, such as that transient metal sulfide as anode material of lithium-ion battery capacity attenuation, effectively inhibited The reuniting effect of metal sulfide grain is crossed, and carbon nanotube clad structure helps to alleviate transient metal sulfide particle Dusting effect, safe preparation process are easy to operate；The cobalt sulfide of preparation and multistage carbon nano-structured composite material can be applied to lithium from Sub- battery and sodium ion battery electrode material.
Detailed description of the invention
Fig. 1 is the scanning electron microscopy (SEM) of cobalt sulfide prepared by embodiment 2 and multistage carbon nano-structured composite material Photo
Specific embodiment
The present invention is further elaborated With reference to embodiment, but the present invention is not limited to following implementation Example.
Embodiment 1
(1) 0.05g graphene oxide is distributed in 50ml deionized water, then 0.252g trimerization is added in ultrasound removing Cyanamide and 0.177g trithiocyanuric acid, 60 DEG C of stirring 30min.0.05g cobalt acetate is added.Continuation is stirred under conditions of 60 DEG C 1h.Then product is freeze-dried.
(2) presoma is placed in tube furnace, leads to argon gas protection, is warming up to 600 DEG C with the heating rate of 2 DEG C/min and protects Warm 2h, argon gas flow velocity are 0sccm.
(3) then product is mixed with sulphur powder with the mass ratio of 1:1, under conditions of argon gas protection, with the liter of 5 DEG C/min Warm rate is warming up to 500 DEG C and keeps the temperature 1h, and argon gas flow velocity is 50sccm；In inert gas shielding gas after the completion of vulcanizing treatment It is taken out after sample natural cooling under atmosphere to get cobalt sulfide and multistage carbon nano-structured composite material is arrived.
Embodiment 2
(1) 0.05g graphene oxide is distributed in 25ml deionized water, then 0.504g trimerization is added in ultrasound removing Cyanamide and 0.304g trithiocyanuric acid, 80 DEG C of stirring 30min.0.5g cobalt acetate is added.Continuation stirs 4h under conditions of 80 DEG C. Then product is freeze-dried.
(2) presoma is placed in tube furnace, leads to argon gas protection, is warming up to 700 DEG C with the heating rate of 5 DEG C/min and protects Warm 2h, argon gas flow velocity are 50sccm.
(3) then product is mixed with sulphur powder with the mass ratio of 1:2, under conditions of argon gas protection, with the liter of 5 DEG C/min Warm rate is warming up to 600 DEG C and keeps the temperature 1.5h, and argon gas flow velocity is 150sccm；It is protected after the completion of vulcanizing treatment in inert gas It protects under atmosphere and is taken out after sample natural cooling to get cobalt sulfide and multistage carbon nano-structured composite material is arrived.
Referring to Fig.1, Fig. 1 is the SEM photograph that the present embodiment prepares sample.Electricity is scanned with the S-4800 type of Japan Electronics Corporation Sub- microscope (SEM) carries out morphology observation, can significantly see three-dimensional made of being assembled into as the graphene of nanometer grade thickness Graphene grows carbon nano tube structure on graphene.It is carbon nano-structured that the two is built into three-dimensional multistage jointly.
Embodiment 3
(1) 0.1g graphene oxide is distributed in 40ml deionized water, then 1.26g melamine is added in ultrasound removing Amine and 0.708g trithiocyanuric acid, 70 DEG C of stirring 1h.0.8g cobalt chloride is added.Continuation stirs 1h under conditions of 70 DEG C.Then Product is freeze-dried.
(2) presoma is placed in tube furnace, leads to argon gas protection, is warming up to 800 DEG C simultaneously with the heating rate of 10 DEG C/min 2h is kept the temperature, argon gas flow velocity is 100sccm.
(3) then product is mixed with sulphur powder with the mass ratio of 1:2.5, under conditions of argon gas protection, with 5 DEG C/min's Heating rate is warming up to 700 DEG C and keeps the temperature 2h, and argon gas flow velocity is 200sccm；It is protected after the completion of vulcanizing treatment in inert gas It protects under atmosphere and is taken out after sample natural cooling to get cobalt sulfide and multistage carbon nano-structured composite material is arrived.
Embodiment 4
(1) 0.1g graphene oxide is distributed in 100ml deionized water, then 2.5g melamine is added in ultrasound removing Amine and 0.354g trithiocyanuric acid, 80 DEG C of stirring 2h.0.4g cobalt acetate is added.Continuation stirs 2h under conditions of 80 DEG C.Then Product is freeze-dried.
(2) presoma is placed in tube furnace, leads to argon gas protection, is warming up to 900 DEG C with the heating rate of 4 DEG C/min and protects Warm 2h, argon gas flow velocity are 150sccm.
(3) then product is mixed with sulphur powder with the mass ratio of 1:3, under conditions of argon gas protection, with 20 DEG C/min's Heating rate is warming up to 800 DEG C and keeps the temperature 2h, and argon gas flow velocity is 100sccm；It is protected after the completion of vulcanizing treatment in inert gas It protects under atmosphere and is taken out after sample natural cooling to get cobalt sulfide and multistage carbon nano-structured composite material is arrived.
Embodiment 5
(1) 50mg graphene oxide is distributed in 50ml deionized water, then 0.126g melamine is added in ultrasound removing Amine and 0.177g trithiocyanuric acid, 60 DEG C of stirring 1h.0.6g cobaltous sulfate is added.Continuation stirs 10h under conditions of 60 DEG C.Then Product is freeze-dried.
(2) presoma is placed in tube furnace, leads to argon gas protection, is warming up to 1000 DEG C simultaneously with the heating rate of 20 DEG C/min 2h is kept the temperature, argon gas flow velocity is 200sccm.
(3) then product is mixed with sulphur powder with the mass ratio of 1:4, under conditions of argon gas protection, with 10 DEG C/min's Heating rate is warming up to 600 DEG C and keeps the temperature 3h, and argon gas flow velocity is 50sccm；In inert gas shielding after the completion of vulcanizing treatment It is taken out after sample natural cooling under atmosphere to get cobalt sulfide and multistage carbon nano-structured composite material is arrived.
Embodiment 6
(1) 0.1g graphene oxide is distributed in 25ml deionized water, then 0.756g melamine is added in ultrasound removing Amine and 0.9g trithiocyanuric acid, 120 DEG C of stirring 1h.1g cobalt nitrate is added.Continuation stirs 3h under conditions of 120 DEG C.Then will Product is freeze-dried.
(2) presoma is placed in tube furnace, leads to argon gas protection, is warming up to 700 DEG C simultaneously with the heating rate of 10 DEG C/min 1h is kept the temperature, argon gas flow velocity is 300sccm.
(3) then product is mixed with sulphur powder with the mass ratio of 1:5, under conditions of argon gas protection, with the liter of 5 DEG C/min Warm rate is warming up to 700 DEG C and keeps the temperature 2h, and argon gas flow velocity is 0sccm；In inert gas shielding gas after the completion of vulcanizing treatment It is taken out after sample natural cooling under atmosphere to get cobalt sulfide and multistage carbon nano-structured composite material is arrived.
Embodiment 7
(1) 0.1g graphene oxide is distributed in 200ml deionized water, then 0.12g melamine is added in ultrasound removing Amine and 0.17g trithiocyanuric acid, 120 DEG C of stirring 1h.2.2g cobalt nitrate is added.Continuation stirs 3h under conditions of 120 DEG C.Then Product is freeze-dried.
(2) presoma is placed in tube furnace, leads to argon gas protection, is warming up to 600 DEG C simultaneously with the heating rate of 10 DEG C/min 5h is kept the temperature, argon gas flow velocity is 200sccm.
(3) then product is mixed with sulphur powder with the mass ratio of 1:3, under conditions of argon gas protection, with 30 DEG C/min's Heating rate is warming up to 700 DEG C and keeps the temperature 2h, and argon gas flow velocity is 0sccm；In inert gas shielding after the completion of vulcanizing treatment It is taken out after sample natural cooling under atmosphere to get cobalt sulfide and multistage carbon nano-structured composite material is arrived.
Finally it should be noted that: the above examples are only used to illustrate the technical scheme of the present invention rather than its limitations, to the greatest extent Pipe is described the invention in detail referring to above-described embodiment, it should be understood by those ordinary skilled in the art that: still may be used With modifications or equivalent substitutions are made to specific embodiments of the invention, and repaired without departing from any of spirit and scope of the invention Change or equivalent replacement, should all cover in present claims range.

Claims (7)

1. the preparation method of a kind of cobalt sulfide and multistage carbon nano-structured composite material, it is characterised in that the following steps are included:
1) it disperses graphene oxide, melamine, trithiocyanuric acid and cobalt salt in suitable deionized water, is stirred to react Sufficiently, then freeze drying example；
It is 0.5-4mg/ml that the graphene oxide, which is distributed to the concentration in deionized water,；The graphene oxide, melamine, The mass ratio of trithiocyanuric acid and cobalt salt is 1:(1.2~25): (1.7~9): (1~22)；
2) heat treated sample: dry sample is placed in the tube furnace of inert gas shielding and is calcined；
The heat treatment process is warming up to 600~1000 DEG C using the heating rate of 2~20 DEG C/min, keeps the temperature 1~5h；
3) vulcanizing treatment, it is 1:(1~5 that the substance completed will be heat-treated in step 2) with sulphur powder in mass ratio) it mixes, then exist Vulcanizing treatment is carried out in the tube furnace of inert gas shielding；500~800 DEG C are warming up to 5~30 DEG C/min in sulfidation, is protected 1~3h of temperature；Taken out after sample natural cooling under inert gas shielding atmosphere after the completion of vulcanizing treatment to get to cobalt sulfide with Multistage carbon nano-structured composite material.
2. the preparation method of cobalt sulfide according to claim 1 and multistage carbon nano-structured composite material, it is characterised in that: Step 1) the cobalt salt is one of cobalt acetate, cobalt nitrate, cobaltous sulfate and cobalt chloride.
3. the preparation method of cobalt sulfide according to claim 1 and multistage carbon nano-structured composite material, it is characterised in that: Step 1) the whipping temp is 60 DEG C~120 DEG C, and mixing time is 1~10h.
4. the preparation method of cobalt sulfide according to claim 1 and multistage carbon nano-structured composite material, it is characterised in that: Heat treatment process protective gas flow velocity is 0~300sccm in the step 2).
5. the preparation method of cobalt sulfide according to claim 1 and multistage carbon nano-structured composite material, it is characterised in that: Protective gas flow velocity is 0~200sccm when vulcanizing treatment in the step 3).
6. a kind of cobalt sulfide and multistage carbon nano-structured composite material of the method preparation of any one according to claim 1~5.
7. a kind of cobalt sulfide as claimed in claim 7 and multistage carbon nano-structured composite material are as cathode of lithium battery active material Or the application of sode cell negative electrode active material.
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CN112010353A (en) * 2020-09-04 2020-12-01 吉林大学 Metal sulfide nano material and preparation method and application thereof
CN112886016A (en) * 2021-02-04 2021-06-01 陕西科技大学 Preparation method of internal high-defect carbon nanotube composite material with through cobalt-nickel catalytic tube inner structure
CN113036121A (en) * 2021-03-05 2021-06-25 大连理工大学 Carbon-coated transition metal sulfide nanoflower structure, preparation method and application thereof

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