CN109326786A - A kind of zinc sulphide containing sulphur vacancy/rGO composite material and preparation method and application - Google Patents

A kind of zinc sulphide containing sulphur vacancy/rGO composite material and preparation method and application Download PDF

Info

Publication number
CN109326786A
CN109326786A CN201811249226.XA CN201811249226A CN109326786A CN 109326786 A CN109326786 A CN 109326786A CN 201811249226 A CN201811249226 A CN 201811249226A CN 109326786 A CN109326786 A CN 109326786A
Authority
CN
China
Prior art keywords
solution
zns
rgo
preparation
added
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.)
Pending
Application number
CN201811249226.XA
Other languages
Chinese (zh)
Inventor
张昭良
郑德超
张景皓
辛颖
李倩
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.)
University of Jinan
Original Assignee
University of Jinan
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 University of Jinan filed Critical University of Jinan
Priority to CN201811249226.XA priority Critical patent/CN109326786A/en
Publication of CN109326786A publication Critical patent/CN109326786A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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
    • 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
    • H01M4/36—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
    • H01M2004/028—Positive 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 belongs to novel energy resource material technology fields, and in particular to a kind of zinc sulphide/rGO composite material and preparation method and application.A kind of preparation method of the zinc sulphide containing sulphur vacancy/rGO composite material: the preparation of ZnS/GO: carbon disulfide is added dropwise in ethylenediamine solution, solution A is named as；Graphene oxide GO is added in ethylene glycol solution and is ultrasonically treated, B solution is named as, B solution is added in solution A and continuously stirs to obtain mixed solution, zinc nitrate solution is added dropwise into mixture under stiring, heats after solution is cooled to room temperature, centrifugation, washing, dried object ZnS/GO；By the ZnS/GO of step (1) preparation under argon hydrogen gaseous mixture, high temperature reduction obtains the ZnS containing sulphur vacancy1‑x/rGO.The present invention carries sulphur method using one pot of a kind of simple, safe wet-chemical, has abandoned traditional melting diffusion method, has reduced loss, and the carrying capacity of active sulfur is up to 90%.

Description

A kind of zinc sulphide containing sulphur vacancy/rGO composite material and preparation method and application
Technical field
The invention belongs to novel energy resource material technology fields, and in particular to a kind of zinc sulphide/rGO composite material and its preparation side Method and application.
Background technique
Currently, environmental pollution and energy shortage have become mankind nowadays social development faces two big severe crises, It forces people to have to develop new green energy resource to replace traditional fossil energy.Wind energy, solar energy, tide energy etc. belong to Renewable energy, but due to the inhomogeneities of spatio-temporal distribution, need corresponding energy storage device to match.Cause This, develops a kind of safety, stablizes, and efficiently, environmentally friendly energy storage device is the core objective for alleviating the energy and environmental crisis.With people Increase sharply to mobile application equipment and extensive energy stores demand, the especially rapid development of electric car, such as cobalt The traditional lithium-ion batteries such as sour lithium, LiMn2O4 can no longer meet the demand of people.In the rechargeable battery of a new generation, due to High theoretical capacity (the 1675 mAh g of elemental sulfur-1) and lithium-sulfur cell specific energy for constituting of itself and lithium metal be more up to (2600 Wh kg-1), and resource reserve is abundant in nature for elemental sulfur, and it is cheap and environmental-friendly, make lithium-sulfur cell in electrochemistry There is good development prospect in terms of stored energy application.However, its practical application is still limited by factors, especially:It is living The insulating properties of property substance sulphur and discharging product,The shuttle effect of intermediate product polysulfide,Sulphur anode is in cyclic process Big volume change etc. seriously hinders the development and practical application of lithium-sulfur cell.
Now, low-sulfur carrying capacity and the shuttle effect of polysulfide are that two faced keys of lithium-sulfur cell commercialization are chosen War." energy and environment science " magazine (Energy Environ. Sci, 2017,10:1476-1486.) reports one as a result, Kind is using sulphur defect molybdenum disulfide nano sheet as positive electrode and is applied to lithium-sulfur cell, and active material sulphur carrying capacity is 78%, Under 0.5C, first circle specific discharge capacity is 1159 mAhg-1, average every circle capacity attenuation is 643 mAhg after 500 circulations-1, phase The average every circle capacity attenuation rate answered is 0.09%, and chemical property is poor.
Summary of the invention
In view of the problems of the existing technology, the object of the present invention is to provide a kind of zinc sulphide/rGO containing sulphur vacancy Composite material, the composite material have excellent chemical property.
The present invention also provides the preparation method of above-mentioned composite material, the preparation method is simple, easy.
The present invention also provides application of the above-mentioned composite material in lithium-sulfur cell.
The present invention to achieve the goals above used by technical solution are as follows:
A kind of preparation method of the zinc sulphide containing sulphur vacancy/rGO composite material, which is characterized in that use following steps:
(1) preparation of ZnS/GO: 0.1-0.136 mL carbon disulfide is added dropwise in 40-68mL ethylenediamine solution, name For solution A；30-60 mg graphene oxide GO is added in 50-80 mL ethylene glycol solution and is ultrasonically treated, B solution is named as, B solution is added in solution A and continuously stirs to obtain mixed solution, is to 34 mL concentration of mixed solution and dripping under stiring The zinc nitrate solution of 0.05 moL/L, heating reaction, after solution is cooled to room temperature, centrifugation for several times with ethanol washing, will be precipitated Object is in 30-60oDry 12 h, dried object ZnS/GO under C；
(2) ZnS1-xThe preparation of/rGO: by the ZnS/GO of step (1) preparation under argon hydrogen gaseous mixture, high temperature reduction is contained The ZnS in sulphur vacancy1-x/rGO。
Preferably, the time that graphene oxide is ultrasonically treated in ethylene glycol solution in step (1) is 10-50min, ultrasound Power is 450W；A, the mixed mixing time of two solution of B is 10-50min；The temperature reacted is heated described in step (1) is 140 oC-180 oC, soaking time 12h.
Preferably, the temperature of high temperature reduction described in step (2) is 400oC-800 oC, heating rate 3oC/min- 10 oC/min, soaking time are 6 h.
Preferably, gaseous mixture described in step (2) is the argon hydrogen gaseous mixture that hydrogen accounts for 5%-10%.
A kind of zinc sulphide containing sulphur vacancy/rGO composite material of above-mentioned preparation method preparation.
A kind of above-mentioned zinc sulphide containing sulphur vacancy/application of the rGO composite material in lithium sulfur battery anode material.
Above-mentioned lithium sulfur battery anode material is prepared using following methods:
(1) S-ZnS1-xThe preparation of/rGO: by 40 ml ZnS1-x/ rGO solution and 0.3-0.5 g Na2SO3With 1.2-1.5 g Na2S•9H2O is mixed and stirred for 30 min, and it is 1 moL/L H that 10 ml concentration, which are then added dropwise,2SO4, 12 h are stirred, centrifugation is received The prepared product of collection, filtering are washed with deionized to remove remaining Na2SO3And Na2S impurity is freeze-dried to obtain S- ZnS1-x/ rGO；
(2) preparation of slurry: S-ZnS prepared by step (1)1-x / rGO, conductive carbon are mixed with binder, are added corresponding molten 10 h are stirred in agent, are uniformly mixed and slurry is made, and slurry are uniformly coated on a current collector, dry, obtain positive electrode.
Preferably, ZnS described in step (1)1-xThe concentration of/rGO solution is 1-2 mg/mL.
Preferably, described in step (2) load sulphur after material, conductive carbon and binder mass ratio 8:1:1 or 7:2:1；Step Suddenly conductive carbon is acetylene black or Super.P in (2)；When binder is aqueous binders, binder is butadiene-styrene rubber or carboxymethyl Sodium cellulosate, the solvent in aqueous binders are water；When binder is oil-soluble binder, binder is Kynoar, oil The solvent of soluble binder is N-Methyl pyrrolidone.
Preferably, the collector in step (2) is aluminium foil, carbon coated aluminum foil, conductive carbon paper, conductive carbon felt or conductive carbon cloth, The drying is 50-90oDry 6-48 h under C.
The present invention is using the zinc sulphide in high concentration sulphur vacancy/rGO composite material as positive electrode and is assembled into button lithium sulphur Battery.Specific assemble method are as follows: uniformly coat slurry on a current collector, in 50-90oDry 6-48 h under C, finally It is cut into the round pole piece that diameter is 8 mm.It is anode with prepared pole piece, CeLgard 2300 is used as diaphragm, commercial metal Li Piece is as cathode.Add the group that ethers electrolyte or carbonates electrolyte complete battery in the glove box full of argon gas Dress.
The zinc sulphide in high concentration sulphur prepared by the present invention vacancy/rGO composite material, with this composite material assemble battery, At identical multiplying power 0.5C, first circle specific discharge capacity is 1168 mAh g-1, 500 circulation after still remain in 1018 mAh g-1, average every circle capacity attenuation rate is only 0.02%, shows excellent electro-chemical activity.We pass through in ZnS1-xOn/rGO Sulphur vacancy is manufactured, and using the load sulphur method of one pot of wet process, sulphur carrying capacity is up to 90%(weight).Meanwhile sulphur vacancy can also It is sent out by electronics transfer being anchored and converting in polysulfide as the high activity site of absorption and catalyzed conversion polysulfide Extremely important effect is waved, excellent chemical property is shown.
The utility model has the advantages that
(1) zinc sulphide in high concentration sulphur of the present invention vacancy/preparation method is simple for rGO composite material, it is low in cost.With this Lithium-sulfur cell as positive electrode assembling is capable of providing more sulphur vacancy active site in cyclic process to be chemically bonded The more sulphions of the intermediate product generated in oxidation-reduction process improve the benefit of active material to weaken the generation of shuttle effect With rate.
(2) present invention carries sulphur method using one pot of a kind of simple, safe wet-chemical, has abandoned traditional melting diffusion Method reduces loss, and the carrying capacity of active sulfur is up to 90%.
(3) prepared by the present invention that there is ZnS1-xThe lithium-sulfur cell of/rGO electrode material shows excellent chemical property, Having benefited from the presence in high concentration sulphur vacancy first, elemental sulfur can refill sulphur vacancy, and thus sulphur carrying capacity increases, and up to 90%；This Outside, the big specific surface of redox graphene can disperse active material more evenly, to provide more active sites；Have Excellent electric conductivity helps active material sulphur receiving and losing electrons.
(4) present invention is with ZnS1-xPositive electrode of/the rGO as lithium-sulfur cell, effectively inhibits shuttle effect, due to The presence in high concentration sulphur vacancy can pass through turning for electronics as the high activity site of absorption and catalyzed conversion polysulfide It moves, plays extremely important effect being anchored and converting in polysulfide, and show high stability, the electricity of high reversible capacity Chemical property.
Detailed description of the invention
Fig. 1 is ZnS in embodiment 11-x/rGO、S-ZnS1-x/ rGO and ZnS/rGO, S8XRD spectra.
Fig. 2 is S- ZnS in embodiment 11-xIn/rGO and comparative example 1,2 S-ZnS/rGO and S-rGO at 0.5C in Cycle performance figure in 500 circulations.
Fig. 3 is S- ZnS in embodiment 11-xHigh rate performance figure of/rGO, S-ZnS/rGO and the S-rGO under different multiplying.
Specific embodiment
The principle of the invention and feature are described with reference to the accompanying drawing, illustrated embodiment is served only for explaining the present invention, and Non-limiting the scope of the present invention.
Embodiment 1
The preparation of ZnS/GO: it firstly, carbon disulfide (0.136 mL) is added dropwise in ethylenediamine solution (68 mL), names For solution A.60 mg graphene oxide GO are added in 80 mL ethylene glycol solutions and are ultrasonically treated 30 min, ultrasonic power is 450W is named as B solution, and B solution is added in solution A to and is continuously stirred 30 min, is added dropwise under stiring into mixture 34 mL concentration are 0.05 moL/L zinc nitrate solution, are transferred them in autoclave 180o12 h are heated under C.It is cold to solution But it to after room temperature, is centrifuged, and with ethanol washing, by sediment 60oDry 12 h, dried object ZnS/GO under C.
ZnS1-xThe preparation of/rGO: by the collected ZnS/GO sample obtained under argon hydrogen gaseous mixture, wherein gaseous mixture is hydrogen Gas accounts for 10% argon hydrogen gaseous mixture, high temperature reduction, heating rate 5oC/min is warming up to 650oC keeps the temperature 6 h, is contained The ZnS in sulphur vacancy1-x/ rGO sample.
S-ZnS1-xThe preparation of/rGO: firstly, the ZnS for being 1mg/mL by 40ml concentration1-x/ rGO solution and 0.44 g Na2SO3With 1.44 g Na2S•9H2O is mixed and stirred for 30 min.Then, it is 1 moL/L H that 10 ml concentration, which are added dropwise,2SO4, then 12 h of secondary stirring, are collected by centrifugation prepared product, and filtering is washed with deionized to remove remaining Na2SO3And Na2S is miscellaneous Matter is freeze-dried to obtain S-ZnS1-x/rGO。
The preparation of slurry: 80 mg S-ZnS are weighed1-x/ rGO, 10 mg Super P and 10 mg PVDF, 200 μ L NMP stirs 10 h, is uniformly mixed and slurry is made.
The production of electrode slice: slurry is uniformly coated in carbon coated aluminum foil using knife coating, 80oDry 12 under C h.It is cut into the round pole piece that diameter is 8 mm.
The assembling of battery: being anode with prepared pole piece, and CeLgard 2300 is used as diaphragm, commercial metal Li piece conduct Cathode, 40 μ L ethers electrolyte of addition complete the assembling of battery in the glove box full of argon gas.
Electrochemical property test: the present invention using Wuhan Lan Bo Electronics Co., Ltd. 1 mA of indigo plant electricity LANHECT2001A, 2 mA charge and discharge instrument have carried out constant current charge-discharge and cycle performance test to it.
Fig. 1 is the ZnS prepared in the present embodiment1-xXRD spectra and ZnS/rGO and S of/the rGO before and after carrying sulphur8Mark Quasi- spectrogram, we can see that being successfully prepared ZnS from this figure1-x/ rGO sample, and active material elemental sulfur is successfully loaded In ZnS1-xThe surface /rGO.Fig. 2 is the S-ZnS under the multiplying power of 0.5C1-xTri- kinds of electrodes of/rGO, S-ZnS/rGO and S-rGO The cycle performance of material.It can be obtained from the figure that going out, the first circle specific discharge capacity of three kinds of materials is respectively 1168 mAh g-1、1059 mAh g-1With 759 mAh g-1.After 500 circulations, S-ZnS1-x/ rGO stills remain in 1018 mAh g-1Specific capacity, phase The average every circle capacity attenuation rate answered is only 0.02%.And the capacity of S-ZnS/rGO and S-rGO is kept at 540 mAh g-1 With 326 mAh g-1, corresponding average every circle capacity attenuation rate respectively up to 0.09% and 0.11%.Obviously, we it can be concluded that Conclusion S- ZnS1-x/ rGO shows excellent cyclical stability compared to S-ZnS/rGO and S-rGO.Fig. 3 is in different multiplying Under 0.2,0.5,1,2 and 4C, the high rate performance figure of three different materials, it can be seen that S- ZnS1-x/ rGO's is forthright again S-ZnS/rGO and S-rGO can be substantially better than.
Embodiment 2
The preparation of ZnS/GO: firstly, carbon disulfide (0.1 mL) is added dropwise in ethylenediamine solution (40 mL), it is named as A Solution.Later, 30 mg graphene oxide GO are added in 40 mL ethylene glycol solutions and are ultrasonically treated 20 min, ultrasonic power is 450W is named as B solution, and B solution is added in solution A to and is continuously stirred 30 min, is added dropwise under stiring into mixture 34 mL concentration are 0.05 moL/L zinc nitrate solution, are transferred them in autoclave 180o12 h are heated under C.It is cold to solution But it to after room temperature, is centrifuged, and with ethanol washing, by sediment 40oDry 12 h, dried object ZnS/GO under C.
ZnS1-xThe preparation of/rGO: by the collected ZnS/GO sample obtained under argon hydrogen gaseous mixture, wherein gaseous mixture is hydrogen Gas accounts for 10% argon hydrogen gaseous mixture, high temperature reduction, heating rate 3oC/min is warming up to 400oC keeps the temperature 6 h, is contained The ZnS in sulphur vacancy1-x/ rGO sample.
S-ZnS1-xThe preparation of/rGO: firstly, the ZnS for being 3 mg/mL by 40 ml concentration1-x/ rGO solution and 0.3 g Na2SO3With 1.2 g Na2S•9H2O is mixed and stirred for 30 min.Then, it is 1 moL/L H that 10 ml concentration, which are added dropwise,2SO4, again 12 h are stirred, prepared product is collected by centrifugation, filtering is washed with deionized to remove remaining Na2SO3And Na2S impurity, It is freeze-dried to obtain S-ZnS1-x/rGO。
The preparation of slurry: 70 mg S- ZnS are weighed1-x/ rGO, 20 mg Super P and 10 mg PVDF, 200 μ L NMP stirs 10 h, is uniformly mixed and slurry is made.
The production of electrode slice: slurry is uniformly coated in carbon coated aluminum foil using knife coating, 80oDry 12 under C h.It is cut into the round pole piece that diameter is 8 mm.
The assembling of battery: being anode with prepared pole piece, and CeLgard 2300 is used as diaphragm, commercial metal Li piece conduct Cathode, 40 μ L ethers electrolyte of addition complete the assembling of battery in the glove box full of argon gas.
Electrochemical property test: the present invention using Wuhan Lan Bo Electronics Co., Ltd. 1 mA of indigo plant electricity LANHECT2001A, 2 mA charge and discharge instrument have carried out constant current charge-discharge and cycle performance test to it.
Electrochemical property test is the result shows that have S-ZnS obtained in the present embodiment1-x/ rGO electrode material its in 0.5C Under first circle specific discharge capacity be 1120 mAh g-1, after 500 recycle, capacity attenuation to 930 mAh g-1, corresponding average Every circle capacity attenuation rate is 0.03%, and coulombic efficiency is close to 100%, good cycling stability.
Embodiment 3
The preparation of ZnS/GO: it firstly, carbon disulfide (0.116 mL) is added dropwise in ethylenediamine solution (50 mL), names For solution A.Later, 40 mg graphene oxide GO are added in 60 mL ethylene glycol solutions and are ultrasonically treated 50 min, ultrasonic function Rate is 450W, is named as B solution, and B solution is added in solution A and continuously stirs 30 min, under stiring into mixture It is 0.05 moL/L zinc nitrate solution that 34 mL concentration, which are added dropwise, is transferred them in autoclave 140o12 h are heated under C.To molten It after liquid is cooled to room temperature, is centrifuged, and with ethanol washing, by sediment in 30-60oDry 12 h, dried object are under C ZnS/GO。
ZnS1-xThe preparation of/rGO: by the collected ZnS/GO sample obtained under argon hydrogen gaseous mixture, wherein gaseous mixture is hydrogen Gas accounts for 10% argon hydrogen gaseous mixture, high temperature reduction, heating rate 10oC/min is warming up to 800oC keeps the temperature 6 h, is contained There is the ZnS in sulphur vacancy1-x/ rGO sample.
S-ZnS1-xThe preparation of/rGO: firstly, the ZnS for being 4 mg/mL by 40 ml concentration1-x/ rGO solution and 0.5 g Na2SO3With 1.5 g Na2S•9H2O is mixed and stirred for 30 min.Then, it is 1 moL/L H that 10 ml concentration, which are added dropwise,2SO4, again 12 h are stirred, prepared product is collected by centrifugation, filtering is washed with deionized to remove remaining Na2SO3And Na2S impurity, It is freeze-dried to obtain S-ZnS1-x/rGO。
The preparation of slurry: 80 mg S-ZnS are weighed1-x/ rGO, 10 mg Super P and 10 mg PVDF, 200 μ L NMP stirs 10h, is uniformly mixed and slurry is made.
The production of electrode slice: slurry is uniformly coated in carbon coated aluminum foil using knife coating, 80oDry 12 under C h.It is cut into the round pole piece that diameter is 8 mm.
The assembling of battery: being anode with prepared pole piece, and CeLgard 2300 is used as diaphragm, commercial metal Li piece conduct Cathode, 40 μ L ethers electrolyte of addition complete the assembling of battery in the glove box full of argon gas.
Electrochemical property test: the present invention using Wuhan Lan Bo Electronics Co., Ltd. 1 mA of indigo plant electricity LANHECT2001A, 2 mA
Charge and discharge instrument has carried out constant current charge-discharge and cycle performance test to it.
Electrochemical property test is the result shows that have S-ZnS obtained in the present embodiment1-x/ rGO electrode material its in 0.5C Under first circle specific discharge capacity be 900 mAh g-1, 500 circulation after capacity attenuation be 603 mAh g-1, corresponding average every Enclosing capacity attenuation rate is 0.07%, and for coulombic efficiency close to 95%, cyclical stability is preferable.
Embodiment 4
The preparation of ZnS/GO: it firstly, carbon disulfide (0.136 mL) is added dropwise in ethylenediamine solution (58 mL), names For solution A.Later, 60 mg graphene oxide GO are added in 70 mL ethylene glycol solutions and are ultrasonically treated 30 min, ultrasonic function Rate is 450W, is named as B solution, and B solution is added in solution A and continuously stirs 40 min, under stiring into mixture It is 0.05 moL/L zinc nitrate solution that 34 mL concentration, which are added dropwise, is transferred them in autoclave 180o12 h are heated under C.To molten It after liquid is cooled to room temperature, is centrifuged, and with ethanol washing, by sediment 60oDry 12 h, dried object ZnS/ under C GO。
ZnS1-xThe preparation of/rGO: by the collected ZnS/GO sample obtained under argon hydrogen gaseous mixture, wherein gaseous mixture is hydrogen Gas accounts for 10% argon hydrogen gaseous mixture, high temperature reduction, heating rate 6oC/min is warming up to 500oC keeps the temperature 4 h, is contained The ZnS in sulphur vacancy1-x/ rGO sample.
S-ZnS1-xThe preparation of/rGO: firstly, the ZnS for being 4 mg/mL by 40 ml concentration1-x/ rGO solution and 0.35 g Na2SO3With 1.25 g Na2S•9H2O is mixed and stirred for 30 min.Then, it is 1 moL/L H that 10 ml concentration, which are added dropwise,2SO4, again 12 h are stirred, prepared product is collected by centrifugation, filtering is washed with deionized to remove remaining Na2SO3And Na2S impurity, It is freeze-dried to obtain S-ZnS1-x/rGO。
The preparation of slurry: 80 mg S-ZnS are weighed1-x/ rGO, 10 mg Super P and 10 mg PVDF, 200 μ L NMP stirs 10 h, is uniformly mixed and slurry is made.
The production of electrode slice: slurry is uniformly coated in carbon coated aluminum foil using knife coating, 80oDry 12 under C h.It is cut into the round pole piece that diameter is 8 mm.
The assembling of battery: being anode with prepared pole piece, and CeLgard 2300 is used as diaphragm, commercial metal Li piece conduct Cathode, 40 μ L ethers electrolyte of addition complete the assembling of battery in the glove box full of argon gas.
Electrochemical property test: the present invention using Wuhan Lan Bo Electronics Co., Ltd. 1 mA of indigo plant electricity LANHECT2001A, 2 mA charge and discharge instrument have carried out constant current charge-discharge and cycle performance test to it.
Electrochemical property test is the result shows that have S-ZnS obtained in the present embodiment1-x/ rGO electrode material its in 0.5C Under first circle specific discharge capacity be 1011 mAh g-1, 500 circulation after capacity attenuation be 823 mAh g-1, corresponding average every Enclosing capacity attenuation rate is 0.04%, and coulombic efficiency is close to 97%, good cycling stability.
Comparative example 1
The preparation of ZnS/GO: it firstly, carbon disulfide (0.136 mL) is added dropwise in ethylenediamine solution (68 mL), names For solution A.Later, 60 mg graphene oxide GO are added in 80 mL ethylene glycol solutions and are ultrasonically treated 30 min, ultrasonic function Rate is 450W, is named as B solution, and B solution is added in solution A and continuously stirs 30 min, under stiring into mixture It is 0.05 moL/L zinc nitrate solution that 34 mL concentration, which are added dropwise, is transferred them in autoclave 180o12 h are heated under C.To molten It after liquid is cooled to room temperature, is centrifuged, and with ethanol washing, by sediment 60oDry 12 h, dried object ZnS/ under C GO。
The preparation of S-ZnS/rGO: firstly, the ZnS for being 1 mg/mL by 40 ml concentration1-x/ rGO solution and 0.44 g Na2SO3With 1.44 g Na2S•9H2O is mixed and stirred for 30 min.Then, it is 1 moL/L H that 10 ml concentration, which are added dropwise,2SO4, again 12 h are stirred, prepared product is collected by centrifugation, filtering is washed with deionized to remove remaining Na2SO3And Na2S impurity, It is freeze-dried to obtain S-ZnS1-x/rGO.The preparation of slurry: 80 mg S-ZnS are weighed1-x/ rGO, 10 mg Super P and 10 mg PVDF, 200 μ L NMP stir 10 h, are uniformly mixed and slurry is made.
The production of electrode slice: slurry is uniformly coated in carbon coated aluminum foil using knife coating, 80oDry 12 under C h.It is cut into the round pole piece that diameter is 8 mm.
The assembling of battery: being anode with prepared pole piece, and CeLgard 2300 is used as diaphragm, commercial metal Li piece conduct Cathode, 40 μ L ethers electrolyte of addition complete the assembling of battery in the glove box full of argon gas.
Electrochemical property test: the present invention using Wuhan Lan Bo Electronics Co., Ltd. 1 mA of indigo plant electricity LANHECT2001A, 2 mA charge and discharge instrument have carried out constant current charge-discharge and cycle performance test to it.
As shown in Figure 2 using S- ZnS/rGO as the lithium-sulfur cell of positive electrode, the head shown under the multiplying power of 0.5C Circle specific discharge capacity is 1059 mAh g-1, in 500 circulations, corresponding average every circle capacity attenuation rate increases to 0.09%.Phase Than the S- ZnS in embodiment 11-x/ rGO, chemical property are in a disadvantageous position.
Comparative example 2
The preparation of GO: 60 mg graphene oxide GO being added in 80 mL ethylene glycol solutions and are ultrasonically treated 30 min, ultrasonic function Rate is 450W, and continuously stirs 30 min, and above-mentioned solution is transferred in autoclave and 180o12 h are heated under C.To solution After being cooled to room temperature, centrifugation, ethanol washing for several times, by sediment 60oDry 12 h, dried object GO under C.
The preparation of rGO: by the collected GO sample obtained under argon hydrogen gaseous mixture, gaseous mixture is mixed for the argon hydrogen that hydrogen accounts for 10% Close gas, high temperature reduction, heating rate 5oC/min is warming up to 650oC keeps the temperature 6 h, obtains rGO sample.
The preparation of S-rGO: firstly, the rGO solution and 0.44 g Na that are 1 mg/mL by 40 ml concentration2SO3With 1.44 g Na2S•9H2O is mixed and stirred for 30min.Then, it is 1 moL/L H that 10 ml concentration, which are added dropwise,2SO4, 12 h are again stirring for, centrifugation is received The prepared product of collection, filtering are washed with deionized to remove remaining Na2SO3And Na2S impurity is freeze-dried to obtain S- rGO。
The preparation of slurry: weighing 80 mg rGO, 10 mg Super P and 10 mg PVDF, 200 μ L NMP, stirring 10h is uniformly mixed and slurry is made.
The production of electrode slice: slurry is uniformly coated in carbon coated aluminum foil using knife coating, 80oDry 12 under C h.It is cut into the round pole piece that diameter is 8 mm.
The assembling of battery: being anode with prepared pole piece, and CeLgard 2300 is used as diaphragm, commercial metal Li piece conduct Cathode, 40 μ L ethers electrolyte of addition complete the assembling of battery in the glove box full of argon gas.
Electrochemical property test: the present invention using Wuhan Lan Bo Electronics Co., Ltd. 1 mA of indigo plant electricity LANHECT2001A, 2 mA charge and discharge instrument have carried out constant current charge-discharge and cycle performance test to it.
Through detecting under the current density of 0.5C, the lithium-sulfur cell of preparation shows 759 mAh g-1First circle discharge specific volume Amount, after 500 recycle, special capacity fade to 326 mAh g-1, average every circle capacity attenuation rate of corresponding average every circle is big About 0.11%.Compared to S-ZnS in embodiment 11-x/ rGO, chemical property are obviously in a disadvantageous position.
Example discussed above is detailed description of the invention, it should be understood that these examples are only tool of the invention Body example, however it is not limited to the present invention, it is all in spirit of the invention any modification, supplementary, and equivalent replacement etc., It should be included within the scope of the present invention.

Claims (10)

1. a kind of preparation method of the zinc sulphide containing sulphur vacancy/rGO composite material, which is characterized in that use following steps:
(1) preparation of ZnS/GO: 0.1-0.136 mL carbon disulfide is added dropwise in 40-68mL ethylenediamine solution, name For solution A；30-60 mg graphene oxide GO is added in 50-80 mL ethylene glycol solution and is ultrasonically treated, B solution is named as, B solution is added in solution A and continuously stirs to obtain mixed solution, is to 34 mL concentration of mixed solution and dripping under stiring The zinc nitrate solution of 0.05 moL/L, heating reaction, after solution is cooled to room temperature, centrifugation for several times with ethanol washing, will be precipitated Object is in 30-60oDry 12 h, dried object ZnS/GO under C；
(2) ZnS1-xThe preparation of/rGO: by the ZnS/GO of step (1) preparation under argon hydrogen gaseous mixture, high temperature reduction is contained The ZnS in sulphur vacancy1-x/rGO。
2. preparation method according to claim 1, which is characterized in that graphene oxide is in ethylene glycol solution in step (1) The time of middle ultrasonic treatment is 10-50 min, ultrasonic power 450W；A, the mixed mixing time of two solution of B is 10-50 min；The temperature of heating reaction described in step (1) is 140oC-180 oC, soaking time are 12 h.
3. preparation method according to claim 1, which is characterized in that the temperature of high temperature reduction described in step (2) is 400oC-800 oC, heating rate 3oC/min-10 oC/min, soaking time are 6 h.
4. preparation method according to claim 1, which is characterized in that gaseous mixture described in step (2) is that hydrogen accounts for 5%- 10% argon hydrogen gaseous mixture.
5. a kind of zinc sulphide containing sulphur vacancy/rGO composite wood of the described in any item preparation method preparations of claim 1-4 Material.
6. zinc sulphide/rGO composite material described in a kind of claim 5 containing sulphur vacancy is in lithium sulfur battery anode material Using.
7. application according to claim 6, which is characterized in that the lithium sulfur battery anode material is prepared using following methods It forms:
(1) S-ZnS1-xThe preparation of/rGO: by 40 ml ZnS1-x/ rGO solution and 0.3-0.5 g Na2SO3With 1.2-1.5 g Na2S•9H2O is mixed and stirred for 30 min, and it is 1 moL/L H that 10 ml concentration, which are then added dropwise,2SO4, 12 h are stirred, centrifugation is received The prepared product of collection, filtering are washed with deionized to remove remaining Na2SO3And Na2S impurity is freeze-dried to obtain S- ZnS1-x/ rGO；
(2) preparation of slurry: S-ZnS prepared by step (1)1-x / rGO, conductive carbon are mixed with binder, are added corresponding molten 10 h are stirred in agent, are uniformly mixed and slurry is made, and slurry are uniformly coated on a current collector, dry, obtain positive electrode.
8. application according to claim 7, which is characterized in that ZnS described in step (1)1-xThe concentration of/rGO solution is 1- 4 mg/mL。
9. application according to claim 7, which is characterized in that material, conductive carbon and bonding after load sulphur described in step (2) The mass ratio 8:1:1 or 7:2:1 of agent；Conductive carbon is acetylene black or Super.P in step (2)；When binder is aqueous binders, Binder is butadiene-styrene rubber or sodium carboxymethylcellulose, and the solvent in aqueous binders is water；Binder is oil-soluble binder When, binder is Kynoar, and the solvent of oil-soluble binder is N-Methyl pyrrolidone.
10. application according to claim 7, which is characterized in that the collector in step (2) is aluminium foil, carbon coated aluminum foil, leads Electrical carbon paper, conductive carbon felt or conductive carbon cloth, the drying are 50-90oDry 6-48 h under C.
CN201811249226.XA 2018-10-25 2018-10-25 A kind of zinc sulphide containing sulphur vacancy/rGO composite material and preparation method and application Pending CN109326786A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811249226.XA CN109326786A (en) 2018-10-25 2018-10-25 A kind of zinc sulphide containing sulphur vacancy/rGO composite material and preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811249226.XA CN109326786A (en) 2018-10-25 2018-10-25 A kind of zinc sulphide containing sulphur vacancy/rGO composite material and preparation method and application

Publications (1)

Publication Number Publication Date
CN109326786A true CN109326786A (en) 2019-02-12

Family

ID=65261586

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811249226.XA Pending CN109326786A (en) 2018-10-25 2018-10-25 A kind of zinc sulphide containing sulphur vacancy/rGO composite material and preparation method and application

Country Status (1)

Country Link
CN (1) CN109326786A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113430533A (en) * 2021-06-23 2021-09-24 景德镇陶瓷大学 Nickel-cobalt-iron trimetal catalyst for in-situ growth of graphene through phosphorization and sulfuration and preparation method thereof
CN113488621A (en) * 2021-06-30 2021-10-08 肇庆市华师大光电产业研究院 Preparation method of high-performance sodium-sulfur battery positive electrode material
CN113502502A (en) * 2021-06-23 2021-10-15 景德镇陶瓷大学 Sulfur-doped graphene-coated nickel-cobalt bimetallic catalyst and preparation method thereof
CN113529128A (en) * 2021-06-23 2021-10-22 景德镇陶瓷大学 Sulfur-phosphorus co-doped in-situ growth graphene coated nickel-cobalt-iron hydrogen evolution catalyst and preparation method thereof
CN113529100A (en) * 2021-06-23 2021-10-22 景德镇陶瓷大学 Graphene-coated vulcanized nickel-cobalt-iron trimetal catalyst and preparation method thereof
CN113529127A (en) * 2021-06-23 2021-10-22 景德镇陶瓷大学 Tungsten metal catalyst for in-situ growth of sulfur and graphene and preparation method thereof
CN114177922A (en) * 2021-12-14 2022-03-15 西南科技大学 Composite catalyst for removing uranium in nuclear waste liquid and preparation method and application thereof
CN114349041A (en) * 2021-12-24 2022-04-15 杭州钱航船舶修造有限公司 Preparation method of zinc sulfide and cobalt sulfide core-shell cubic nanometer material suitable for sodium ion battery electrode
CN114824223A (en) * 2022-05-10 2022-07-29 扬州大学 MnS/carbon composite material with sulfur defect, and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102867963A (en) * 2012-09-29 2013-01-09 上海空间电源研究所 Anode active material of lithium sulfur battery and preparation method of anode active material
CN106927498A (en) * 2017-03-14 2017-07-07 中南大学 A kind of zinc sulfide nano-belt, preparation and its application in lithium sulfur battery anode material is prepared
US20180090802A1 (en) * 2016-09-27 2018-03-29 Samsung Electronics Co., Ltd. Cathode and lithium air battery including the same, and method of preparing the cathode
CN108232142A (en) * 2017-12-22 2018-06-29 中国科学院福建物质结构研究所 A kind of zinc sulphide/graphene composite material, preparation method and application
CN108539171A (en) * 2018-04-16 2018-09-14 济南大学 A kind of preparation method of the zinc sulphide with graphene oxide compound and its application in lithium sulfur battery anode material
CN108598427A (en) * 2018-04-26 2018-09-28 吉林大学 The method for improving cobalt sulfide charge and discharge cycles ability by coating redox graphene

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102867963A (en) * 2012-09-29 2013-01-09 上海空间电源研究所 Anode active material of lithium sulfur battery and preparation method of anode active material
US20180090802A1 (en) * 2016-09-27 2018-03-29 Samsung Electronics Co., Ltd. Cathode and lithium air battery including the same, and method of preparing the cathode
CN106927498A (en) * 2017-03-14 2017-07-07 中南大学 A kind of zinc sulfide nano-belt, preparation and its application in lithium sulfur battery anode material is prepared
CN108232142A (en) * 2017-12-22 2018-06-29 中国科学院福建物质结构研究所 A kind of zinc sulphide/graphene composite material, preparation method and application
CN108539171A (en) * 2018-04-16 2018-09-14 济南大学 A kind of preparation method of the zinc sulphide with graphene oxide compound and its application in lithium sulfur battery anode material
CN108598427A (en) * 2018-04-26 2018-09-28 吉林大学 The method for improving cobalt sulfide charge and discharge cycles ability by coating redox graphene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAIBIN LIN ET.AL: "Electrocatalysis of polysulfide conversion by sulfur-deficient MoS2 nanoflakes for lithium-sulfur batteries", 《ENERGY & ENVIRONMENTAL SCIENCE》 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113430533A (en) * 2021-06-23 2021-09-24 景德镇陶瓷大学 Nickel-cobalt-iron trimetal catalyst for in-situ growth of graphene through phosphorization and sulfuration and preparation method thereof
CN113502502A (en) * 2021-06-23 2021-10-15 景德镇陶瓷大学 Sulfur-doped graphene-coated nickel-cobalt bimetallic catalyst and preparation method thereof
CN113529128A (en) * 2021-06-23 2021-10-22 景德镇陶瓷大学 Sulfur-phosphorus co-doped in-situ growth graphene coated nickel-cobalt-iron hydrogen evolution catalyst and preparation method thereof
CN113529100A (en) * 2021-06-23 2021-10-22 景德镇陶瓷大学 Graphene-coated vulcanized nickel-cobalt-iron trimetal catalyst and preparation method thereof
CN113529127A (en) * 2021-06-23 2021-10-22 景德镇陶瓷大学 Tungsten metal catalyst for in-situ growth of sulfur and graphene and preparation method thereof
CN113488621A (en) * 2021-06-30 2021-10-08 肇庆市华师大光电产业研究院 Preparation method of high-performance sodium-sulfur battery positive electrode material
CN114177922A (en) * 2021-12-14 2022-03-15 西南科技大学 Composite catalyst for removing uranium in nuclear waste liquid and preparation method and application thereof
CN114177922B (en) * 2021-12-14 2023-09-01 西南科技大学 Composite catalyst for removing uranium in nuclear waste liquid and preparation method and application thereof
CN114349041A (en) * 2021-12-24 2022-04-15 杭州钱航船舶修造有限公司 Preparation method of zinc sulfide and cobalt sulfide core-shell cubic nanometer material suitable for sodium ion battery electrode
CN114349041B (en) * 2021-12-24 2024-03-15 杭州钱航船舶修造有限公司 Preparation method of zinc sulfide and cobalt sulfide core-shell cube nanomaterial suitable for sodium ion battery electrode
CN114824223A (en) * 2022-05-10 2022-07-29 扬州大学 MnS/carbon composite material with sulfur defect, and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN109326786A (en) A kind of zinc sulphide containing sulphur vacancy/rGO composite material and preparation method and application
CN107221716B (en) Rechargeable aqueous zinc ion battery
CN108539171B (en) Preparation method of zinc sulfide and graphene oxide compound and application of compound in positive electrode material of lithium-sulfur battery
CN107226475B (en) Potassium ion battery positive electrode material, preparation method thereof and potassium ion battery
CN107425185B (en) Preparation method of carbon nanotube-loaded molybdenum carbide material and application of carbon nanotube-loaded molybdenum carbide material in lithium-sulfur battery positive electrode material
CN109103399B (en) Functional diaphragm for lithium-sulfur battery, preparation method of functional diaphragm and application of functional diaphragm in lithium-sulfur battery
CN106450102A (en) Modified graphite separator for lithium-sulfur battery, preparation method of modified graphite separator and lithium-sulfur battery
CN109167035A (en) Carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion battery of preparation
CN104051733A (en) Vanadium selenide/carbon-based composite material, preparation method of material, and negative electrode of lithium ion battery
CN108199032B (en) Preparation of carbon-coated nano hollow bismuth simple substance and application of alkaline battery
CN110289408A (en) Nano-silicon and silicon/carbon composite and preparation method and application based on cutting scrap silicon
CN110085829A (en) A kind of MXene@C@Co9S8Compound and preparation method thereof
CN107902633A (en) A kind of selenizing pyrite material and its battery of preparation
CN110993944A (en) Aqueous ion battery and application thereof
CN108178157A (en) A kind of sodium-ion battery negative material and its application and preparation method
CN108963207A (en) A kind of carbon composite material and its preparation method and application of porous metals doping
CN110364732A (en) With the compound zinc load and preparation method and application of inorganic functional decorative layer in a kind of water system battery
CN109742439A (en) A kind of novel lithium-sulfur cell porous interlayer material, preparation method and application
CN108172406A (en) One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material
CN104779379A (en) Novel sulfur and carbon composite material for lithium secondary battery, and preparation method thereof
CN104993131B (en) A kind of lithium ion battery negative material NiS/Ni and preparation method thereof
CN110391415A (en) A kind of positive electrode active materials and the Zinc ion battery including the positive electrode active materials
CN109286002A (en) Thousand layers of Bark Biomass carbon load red phosphorus anode material of lithium-ion battery of one kind and preparation method thereof
CN112490414B (en) Tin dioxide and vanadium pentoxide composite electrode material and preparation method and application thereof
CN110783542A (en) Paper towel derived carbon fiber loaded MoS 2Preparation method of micro-flower composite material and application of micro-flower composite material in lithium-sulfur battery

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20190212

RJ01 Rejection of invention patent application after publication