CN106169573A - A kind of preparation method of the composite of graphene coated sulfur family simple substance - Google Patents

A kind of preparation method of the composite of graphene coated sulfur family simple substance Download PDF

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Publication number
CN106169573A
CN106169573A CN201610874632.XA CN201610874632A CN106169573A CN 106169573 A CN106169573 A CN 106169573A CN 201610874632 A CN201610874632 A CN 201610874632A CN 106169573 A CN106169573 A CN 106169573A
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graphene
simple substance
preparation
composite
sulfur family
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陈远富
林杰
贺加瑞
王新强
于博
戚飞
郑斌杰
周金浩
赵燕
刘科
张万里
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University of Electronic Science and Technology of China
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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 the preparation method of the composite of a kind of graphene coated sulfur family simple substance, relate to nano composite material preparation field.The preparation method that the present invention provides uses spray drying treatment, graphene sheet layer is made to be coated with sulfur family simple substance, when being applied to lithium ion cell electrode, can effectively buffer sulfur family material bulk effect in electrochemical reaction, also improve the electric conductivity of material simultaneously, it is substantially reduced the impedance of battery, thus is effectively improved the chemical property of material.Preparation method of the present invention solves the preparation method of prior art Graphene sulfur family composite and is unfavorable for the problem of large-scale production, and the present invention has industrialization potential, by using spray drying treatment, shortens the production cycle；Preparation is simple, reaction condition gentle, therefore has the advantage of less energy consumption, low cost, can be applicable to high-capacity lithium ion cell electrode material.

Description

A kind of preparation method of the composite of graphene coated sulfur family simple substance
Technical field
The present invention relates to nano composite material preparation field, particularly a kind of redox graphene is formed with sulfur family simple substance The preparation method of composite, the composite that the present invention prepares is applicable to anode material for lithium-ion batteries.
Background technology
Graphene (Graphene) is that a kind of carbon atom is with sp2The hexangle type that hybrid form is formed is the two dimension of honeycomb lattice Material, special and perfect structure has contained abundant and peculiar physical phenomenon, make Graphene show many excellent mechanics, Calorifics, optically and electrically characteristic, at RF transistors, sensor, flexible transparent conductive film, lithium ion battery and super capacitor The fields such as device are with a wide range of applications, and have caused the very big concern of scientific circles.
In chalcogen, sulfur shows as insulating properties, and selenium shows as quasiconductor, and tellurium shows as metallicity.And chalcogen by In there being the highest theoretical capacity, in nature, Fengdu is high, cheap, environmentally friendly, thus in field of lithium ion battery In receive much attention.But, sulfur, selenium are due to its poorly conductive, change in volume in lithium ion battery charge and discharge cycles so that its Application in lithium ion battery is subject to certain restrictions.Therefore, improving its electric conductivity, the change of effective restricted volume becomes one Individual research emphasis.The electric conductivity of the superelevation that two-dimensional material Graphene is shown due to its special structure and good pliable and tough Property, therefore, Graphene can effectively improve above-mentioned problem with the composite of sulfur family.
In the past few decades, research worker is prepared for Graphene and the sulfur with different structure by different methods The composite of race.
Chinese patent " the mesoporous carbon-loaded based on three-dimensional grapheme self supporting structure of Application No. 201410076977.1 Sulfur/selenium flexible electrode and preparation method and application " in disclose mesoporous carbon-loaded based on three-dimensional grapheme self supporting structure Sulfur/selenium flexible electrode and preparation method and application, the method is with foam metal as masterplate, on metal matrix 700～1000 Growing three-dimensional Graphene skeleton at DEG C, then impregnates three-dimensional graphene framework such as in mesoporous carbon precursor solution 8～12 hours, Subsequently heat-treated drying 12～24 hours, carbonization 0.5～2 hours at 700～950 DEG C, obtain Graphene mesoporous carbon composite wood Material, last and sulfur/selenium is together put into the tube furnace under inert atmosphere, and is heated to 300～800 DEG C of insulations 5-10 hour, to obtain final product Mesoporous carbon-loaded sulfur/selenium flexible electrode to three-dimensional grapheme self supporting structure.The method complex process is loaded down with trivial details, and preparation process needs Wanting high temperature and noble gas, preparation time is long, limits industrialized production.
Chinese patent " selenium based on graphene sponge/sulfur carbon electrode and the preparation thereof of Application No. 201410074975.9 Method and application " disclose a kind of selenium/sulfur electrode based on graphene sponge structure and preparation method thereof.The method by hot soarfing from Graphene sheet layer be dispersed in pyrene solution, hydro-thermal prepares gel mass, the most again through lyophilization, subsequently 300～700 DEG C heat treatment 5～10 hours, obtain graphene sponge；Then graphene sponge and sulfur/selenium are put into the tube furnace of noble gas In 300～800 DEG C be incubated 5～10 hours, i.e. obtain the sulfur/selenium electrode material of graphene sponge.The method step is various, technique Complexity, energy consumption is big, needs longer manufacturing cycle.
Xu Jiantie et al. is at article ' Sulfur Graphene Nanostructured Cathodes via (" ball-milling method preparation has height to Ball-Milling for High-Performance Lithium Sulfur Batteries ' The nanostructured S-graphene anode material of lithium-sulfur cell performance ") in a literary composition with graphite and sulfur powder as raw material, ball milling 48 is little Time, then remove the sulfur of physical absorption at high annealing, then remove, with HCl treatment, the impurity that in mechanical milling process, ball grinder produces, Thus it is prepared for the graphene-sulfur positive electrode for lithium-sulfur cell.The method needs ball milling, annealing, the operation of acid treatment three step, Complex process, efficiency is low, and preparation time is the longest, it is impossible to large-scale production.
Zhang Jun et al. is at ' Sulfur nanocrystals anchored graphene composite with Highly improved electrochemical performance for lithium-sulfur batteries ' (" uses The nanocrystalline positive electrode of the sulfur being fixed on Graphene with high electrochemical performance in lithium-sulfur cell ") in a literary composition with oxidation Graphene, sulfur are raw material, by graphene oxide by ultrasonic disperse in sodium dodecyl benzene sulfonate aqueous solution, formed uniform Graphene oxide water solution, then sulfur nano particles is disperseed in deionized water, then transfer to water after above solution mixing In hot still, reacting 12 hours at 160 DEG C, the product obtained, by centrifugal, cleaning, dries a whole night at 60 DEG C.The method is Typical hydro-thermal method prepares nano material, and the response time is long, and production scale is little, it is impossible to carry out industrialized production.
Therefore, preparation time that the preparation method of current graphene-sulfur race composite generally needs to grow very much, cost are relatively High, be unfavorable for large-scale industrial production.
Summary of the invention
In view of the deficiencies in the prior art, it is an object of the invention to, it is provided that being combined of a kind of graphene coated sulfur family simple substance The preparation method of material, the method uses spray drying treatment technology, shortens the production cycle, it is possible to large-scale production Graphene The composite of cladding sulfur family simple substance；Preparation is simple, reaction temperature is low, therefore have less energy consumption, low cost excellent Gesture；The sulfur family composite of Graphene parcel prepared by the present invention has extraordinary application prospect in field of lithium ion battery.
Technical scheme is as follows:
The preparation method of the composite of a kind of graphene coated sulfur family simple substance, comprises the steps:
Step A: the aqueous dispersions stirring and evenly mixing of graphene oxide dispersion with sulfur family simple substance is formed mixed liquor；Wherein, Graphene oxide is 10: 2～8 with the mass ratio of sulfur family simple substance；
Step B: by step A gained mixed liquor through spray drying treatment, then redox graphene, it is thus achieved that Graphene The composite of cladding sulfur family simple substance.
Further, the aqueous dispersions of the sulfur family simple substance in described step A is nano dispersion fluid, and described chalcogen is Sulfur, selenium, tellurium.
In the present invention, it is preferred that, the graphene oxide in described step A is prepared by the Hummers method improved；
In the present invention, described graphene oxide dispersion is that graphene oxide is obtained by stirring supersound process with distilled water The uniform dispersion arrived；The concentration of described graphene oxide dispersion is preferably 0.5～5mg/ml.
Further, the spray drying treatment in step B of the present invention uses spray dryer, uses spray drying allow Product trends towards being formed spherical, it is achieved Graphene is preferably coated with, and can be with large-scale industrial production；Selection process is joined Number is as follows: inlet amount is 500～1000ml/h, and striker frequency is 40～60Hz, and intake air temperature is 120～180 DEG C.
In the present invention, in described step B redox graphene be by graphene oxide and reducing agent are reacted or Pass through thermal reduction.
In the present invention, suitable reducing agent all can use, and further, described reducing agent is hydrazine hydrate, hydroiodic acid, dimension Raw element C or sodium borohydride, above-mentioned reducing agent is the most conventional.
The invention have the advantages that
1, preparation method of the present invention uses spray drying treatment, shortens the production cycle, is suitable for large-scale production graphite The composite of alkene cladding sulfur family simple substance；Preparation is simple, reaction condition gentle, therefore has less energy consumption, low cost Advantage；Can be mass-produced, there is industrialization potential, can be applicable to cathode material for high capacity lithium ion battery.
The composite of the graphene coated sulfur family simple substance that 2, the present invention prepares can not only effectively buffer sulfur family material and exist Bulk effect in electrochemical reaction, also improves the electric conductivity of material simultaneously, is substantially reduced the impedance of battery, thus effectively Improve the chemical property of material.
Accompanying drawing explanation
Fig. 1 is the Raman collection of illustrative plates of the composite of the graphene coated sulfur family simple substance prepared by the present invention.
Fig. 2 is the scanning electron microscope diagram of the composite of the graphene coated sulfur family simple substance prepared by the present invention.
Fig. 3 is the transmission electron microscope figure of the composite of the graphene coated sulfur family simple substance prepared by the present invention.
Fig. 4 is the composite discharge and recharge for lithium-sulfur cell of the graphene coated sulfur family simple substance prepared by the present invention Curve.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with embodiment, the present invention is entered The elaboration of one step:
Embodiment 1:
The preparation method of the composite of a kind of graphene coated sulfur family simple substance, comprises the steps:
Step A: weigh 500 milligrams and be dissolved in 500ml deionized water, stirs 30min, supersound process 30 minutes, obtains all Even graphene oxide dispersion；
1 gram of sulfur simple substance is scattered in 100ml aqueous solution and prepares uniform dispersion, before measuring the aqueous dispersions addition of 10ml sulfur State in graphene oxide dispersion, supersound process 30 minutes, obtain uniform mixed solution；
Step B: by step A gained mixed liquor through spray drying treatment, inlet amount is 1000ml/h, and striker frequency is 50Hz, intake air temperature is 150 DEG C, and (graphene oxide-sulfur is multiple for the complex that prepared graphene oxide cladding sulfur family simple substance is formed Compound)；Then described graphene oxide-sulfur compound and hydroiodic acid are reacted 2 hours at 90 DEG C, prepare graphene coated sulfur The complex (graphene-sulfur complex) of simple substance.
Fig. 1 is the Raman collection of illustrative plates of the composite that Graphene prepared by the present embodiment is formed with sulfur family simple substance, can from Fig. 1 To find out, at 470cm-1、250cm-1And 220cm-1Peak represent the S--S in composite；At 1350cm-1And 1577cm-1The peak at place represents D peak and the G peak of Graphene respectively, therefore, figure can show that the present invention has prepared graphene coated through enforcement The composite of sulfur family simple substance.
Embodiment 2:
The preparation method of the composite of a kind of graphene coated sulfur family simple substance, comprises the steps:
Step A: weigh 2500 milligrams and be dissolved in 500ml deionized water, stirs 30min, supersound process 30 minutes, obtains all Even graphene oxide dispersion；
1 gram of sulfur simple substance is scattered in 100ml aqueous solution and prepares uniform dispersion, before measuring the aqueous dispersions addition of 60ml sulfur State in graphene oxide dispersion, supersound process 30 minutes, obtain uniform mixed solution；
Step B: by step A gained mixed liquor through spray drying treatment, inlet amount is 1500ml h-1, striker frequency is 50Hz, intake air temperature is 150 DEG C, prepares the complex (graphene oxide-sulfur compound) of graphene oxide cladding sulfur simple substance； Then described graphene oxide-sulfur compound and sodium borohydride are reacted 2 hours at 90 DEG C, prepare graphene coated sulfur simple substance Complex (graphene-sulfur complex).
Fig. 2 is the scanning electron microscope diagram of the composite of graphene coated sulfur simple substance prepared by the present embodiment.From Fig. 2 In it can be seen that in spray process, graphene oxide trends towards curling, and is wrapped up by sulfur, form Graphene parcel the answering of sulfur Compound.
Embodiment 3:
The preparation method of the composite of a kind of graphene coated sulfur family simple substance, comprises the steps:
Step A: weigh 1500 milligrams and be dissolved in 500ml deionized water, stirs 30min, supersound process 30 minutes, obtains all Even graphene oxide dispersion；
1 gram of sulfur simple substance is scattered in 100ml aqueous solution and prepares uniform dispersion, before measuring the aqueous dispersions addition of 60ml sulfur State in graphene oxide dispersion, supersound process 30 minutes, obtain uniform mixed solution；
Step B: by step A gained mixed liquor through spray drying treatment, inlet amount is 1000ml h-1, striker frequency is 50Hz, intake air temperature is 120 DEG C, prepares the complex (graphene oxide-sulfur compound) of graphene oxide cladding sulfur simple substance； Then described graphene oxide-sulfur compound and hydrazine hydrate are reacted 2 hours at 90 DEG C, prepare graphene coated sulfur simple substance Complex (graphene-sulfur complex).
Fig. 3 is the transmission electron microscope figure of the composite of graphene coated sulfur simple substance prepared by the present embodiment, from Fig. 3 In it can be seen that sulfur nano particles has been coated with by graphene nanometer sheet completely.
Embodiment 4:
The preparation method of the composite of a kind of graphene coated sulfur family simple substance, comprises the steps:
Step A: weigh 2500 milligrams and be dissolved in 500ml deionized water, stirs 30min, supersound process 30 minutes, obtains all Even graphene oxide dispersion；
1 gram of sulfur simple substance is scattered in 100ml aqueous solution and prepares uniform dispersion, before measuring the aqueous dispersions addition of 80ml sulfur State in graphene oxide dispersion, supersound process 30 minutes, obtain uniform mixed solution；
Step B: by step A gained mixed liquor through spray drying treatment, inlet amount is 1000ml h-1, striker frequency is 50Hz, intake air temperature is 150 DEG C, prepares the complex (graphene oxide-sulfur compound) of graphene oxide cladding sulfur simple substance； Then described graphene oxide-sulfur compound and sodium borohydride are reacted 2 hours at 90 DEG C, prepare graphene coated sulfur simple substance Complex (graphene-sulfur complex).
Fig. 4 be the composite of graphene coated sulfur simple substance prepared by the present embodiment as lithium ion battery negative material time Charging and discharging curve, Fig. 4 shows that the composite of graphene coated sulfur simple substance prepared by the present invention has the highest specific capacity.
Embodiment 5:
The preparation method of the composite of a kind of graphene coated sulfur family simple substance, comprises the steps:
Step A: weigh 1500 milligrams and be dissolved in 500ml deionized water, stirs 30min, supersound process 30 minutes, obtains all Even graphene oxide dispersion；
1 gram of sulfur simple substance is scattered in 100ml aqueous solution and prepares uniform dispersion, before measuring the aqueous dispersions addition of 30ml sulfur State in graphene oxide dispersion, supersound process 30 minutes, obtain uniform mixed solution；
Step B: by step A gained mixed liquor through spray drying treatment, inlet amount is 500ml h-1, striker frequency is 60Hz, intake air temperature is 150 DEG C, prepares the complex (graphene oxide-sulfur compound) of graphene oxide cladding sulfur simple substance； Then described graphene oxide-sulfur compound and hydroiodic acid are reacted 2 hours at 90 DEG C, prepare graphene coated sulfur simple substance Complex (graphene-sulfur complex).
Embodiment 6:
The preparation method of the composite of a kind of graphene coated sulfur family simple substance, comprises the steps:
Step A: weigh 250 milligrams and be dissolved in 500ml deionized water, stirs 30min, supersound process 30 minutes, obtains all Even graphene oxide dispersion；
1 gram of selenium simple substance is scattered in 100ml aqueous solution and prepares uniform dispersion, before measuring the aqueous dispersions addition of 10ml selenium State in graphene oxide dispersion, supersound process 30 minutes, obtain uniform mixed solution；
Step B: by step A gained mixed liquor through spray drying treatment, inlet amount is 2000ml h-1, striker frequency is 60Hz, intake air temperature is 180 DEG C, prepares the complex (graphene oxide-selenium compound) of graphene oxide cladding selenium simple substance； Then described graphene oxide-selenium compound and hydroiodic acid are reacted 2 hours at 90 DEG C, prepare graphene coated selenium simple substance Complex (Graphene-selenium compound).
Embodiment 7:
The preparation method of the composite of a kind of graphene coated sulfur family simple substance, comprises the steps:
Step A: weigh 250 milligrams and be dissolved in 500ml deionized water, stirs 30min, supersound process 30 minutes, obtains all Even graphene oxide dispersion；
1 gram of tellurium simple substance is scattered in 100ml aqueous solution and prepares uniform dispersion, before measuring the aqueous dispersions addition of 10ml tellurium State in graphene oxide dispersion, supersound process 30 minutes, obtain uniform mixed solution；
Step B: by step A gained mixed liquor through spray drying treatment, inlet amount is 1000ml h-1, striker frequency is 60Hz, intake air temperature is 180 DEG C, prepares the complex (graphene oxide-tellurium complex) of graphene oxide cladding tellurium simple substance； Then described graphene oxide-tellurium complex and hydroiodic acid are reacted 2 hours at 90 DEG C, prepare graphene coated tellurium simple substance Complex (Graphene-tellurium complex).
Above in association with accompanying drawing, embodiments of the invention are set forth, but the invention is not limited in above-mentioned concrete Embodiment, above-mentioned detailed description of the invention is only schematic rather than restrictive, and those of ordinary skill in the art exists Under the enlightenment of the present invention, in the case of without departing from present inventive concept and scope of the claimed protection, it may also be made that a lot of shape Formula, within these belong to the protection of the present invention.

Claims (8)

1. the preparation method of the composite of a graphene coated sulfur family simple substance, it is characterised in that comprise the steps:
Step A: the aqueous dispersions stirring and evenly mixing of graphene oxide dispersion with sulfur family simple substance is formed mixed liquor；Wherein, oxidation Graphene is 10: 2～8 with the mass ratio of sulfur family simple substance；
Step B: by step A gained mixed liquor through spray drying treatment, then redox graphene, it is thus achieved that graphene coated The composite of sulfur family simple substance.
The preparation method of the composite of graphene coated sulfur family simple substance the most according to claim 1, it is characterised in that institute The aqueous dispersions stating the sulfur family simple substance in step A is nano dispersion fluid, and described chalcogen is sulfur, selenium, tellurium.
The preparation method of the composite of graphene coated sulfur family simple substance the most according to claim 1 and 2, its feature exists In, the graphene oxide in described step A is prepared by the Hummers method improved.
The preparation method of the composite of graphene coated sulfur family simple substance the most according to claim 3, it is characterised in that institute Stating graphene oxide dispersion is the uniform dispersion that graphene oxide is obtained by stirring supersound process with distilled water.
The preparation method of the composite of graphene coated sulfur family simple substance the most according to claim 1, it is characterised in that institute The concentration stating graphene oxide dispersion is 0.5～5mg/ml.
The preparation method of the composite of graphene coated sulfur family simple substance the most according to claim 1, it is characterised in that institute Stating the spray drying treatment in step B and use spray dryer, technological parameter is as follows: inlet amount is 500～2000ml/h, striker Frequency is 40～60Hz, and intake air temperature is 120～180 DEG C.
The preparation method of the composite of graphene coated sulfur family simple substance the most according to claim 1, it is characterised in that institute Stating redox graphene in step B is by graphene oxide and reducing agent being reacted or pass through thermal reduction.
The preparation method of the composite of graphene coated sulfur family simple substance the most according to claim 5, it is characterised in that institute Stating reducing agent is hydrazine hydrate, hydroiodic acid, vitamin C or sodium borohydride.
CN201610874632.XA 2016-10-06 2016-10-06 A kind of preparation method of the composite of graphene coated sulfur family simple substance Pending CN106169573A (en)

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CN107706404A (en) * 2017-11-23 2018-02-16 东北师范大学 A kind of selenium cladding tin ash/graphene nanocomposite material prepares and its application
CN107863520A (en) * 2017-11-12 2018-03-30 四川大学 A kind of lithium sulfur battery anode material and preparation method thereof
CN107910536A (en) * 2017-12-27 2018-04-13 东北师范大学 A kind of selenium/graphene nanocomposite material prepares and its application
CN109950473A (en) * 2019-03-29 2019-06-28 柯良节 A kind of lithium-sulphur cell positive electrode and preparation method thereof
CN111370658A (en) * 2020-02-27 2020-07-03 肇庆市华师大光电产业研究院 Lithium-sulfur battery positive electrode material and preparation method thereof
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Application publication date: 20161130