CN105070895B - Method for preparing nanometer sulfur ball wrapped by manganese dioxide - Google Patents
Method for preparing nanometer sulfur ball wrapped by manganese dioxide Download PDFInfo
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- CN105070895B CN105070895B CN201510613304.XA CN201510613304A CN105070895B CN 105070895 B CN105070895 B CN 105070895B CN 201510613304 A CN201510613304 A CN 201510613304A CN 105070895 B CN105070895 B CN 105070895B
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- manganese dioxide
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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 provides a method for preparing a nanometer sulfur ball wrapped by manganese dioxide, belonging to the technical field of chemical batteries. The method comprises the following steps: mixing sodium thiosulfate solution and polyvinylpyrrolidone solution with the same volume, adding with concentrated hydrochloric acid, carrying out magnetic stirring for reaction, centrifuging, washing and collecting solid; dispersing the solid into water, adding with manganese sulfate, carrying out magnetic stirring for dissolving, then adding with potassium permanganate solution for reaction, centrifuging the final production, washing, and drying, and thus obtaining the anometer sulfur ball wrapped by manganese dioxide. The method is simple and feasible, the requirements on equipment are low, the production cost is low, the prepared nanometer sulfur ball wrapped by manganese dioxide is small in size and uniform in appearance, manganese dioxide wrapping outside can inhibit dissolving of polysulfides, and also can improve the electrical conductivity, and thus the effects of improving the coulombic efficiency and the cycling stability of the battery are achieved.
Description
Technical field
The invention belongs to chemical cell technical field, and in particular to manganese dioxide wraps up the preparation method of nano-sulfur ball.
Background technology
As developing rapidly for the portable electric appts such as mobile communication, electronic instrument and electric tool, and people are saved
Can environmental consciousness raising, can the secondary cell of multiple discharge and recharge be widely applied.Wherein, come across the nineties in 20th century
Lithium rechargeable battery be at present generally acknowledged in the world electrochmical power source of new generation, viable commercial product in portable set neck
Develop rapidly in domain.But in fields such as electric automobile, Aero-Space and defence equipments, current commercialization lithium rechargeable battery is received
It is limited to theoretical capacity, it is impossible to further significantly improve its energy density, far from the demand for meeting technology development.Therefore, need
The new chemical with features such as higher energy density, more long circulation life, low cost and environmental friendliness is researched and developed in a hurry
Power supply.
With lithium metal as negative pole, lithium-sulfur rechargeable battery (abbreviation lithium-sulfur cell) of the elemental sulfur for positive active material is theoretical
Energy density is up to 2600Wh/kg, and actual attainable energy density is 500 Wh/kg, and elemental sulfur low cost, to environment friend
It is good, meet the fields such as electric automobile, space technology and defence equipment to electrokinetic cell demand.
In discharge process, elemental sulfur is reduced to S to lithium-sulfur cell-2During have multiple intermediate states and generate, wherein
Li2Sn (4≤n≤8) is soluble in organic electrolyte, spreads from positive to negative pole, with the carrying out of electric discharge, finally gives birth in negative pole
Into Li2S is deposited, and Li2S does not dissolve in organic electrolyte, causes that lithium-sulfur cell cyclicity is poor, coulombic efficiency is low, self-discharge rate
High the problems such as, the paces which is practical are delayed.
The content of the invention
It is an object of the invention to propose that a kind of preparation cost is cheap, preparation method is simple, the preferable lithium of cyclical stability
Sulphur cell positive electrode material preparation method.
The present invention is comprised the following steps：
1）Prepare nano-sulfur ball：Isopyknic hypo solution is mixed with polyvinylpyrrolidonesolution solution, is added
Concentrated hydrochloric acid, magnetic agitation are reacted, and reaction is centrifuged after terminating, washing, collects solid；
2）Prepare the nano-sulfur ball of manganese dioxide parcel：The solid is dispersed in water, and adds manganese sulfate, magnetic force is stirred
After mixing dissolving, potassium permanganate solution is added, after question response terminates, end-product is centrifuged, washed, be dried, obtain manganese dioxide
Parcel nano-sulfur ball.
The advantage of present invention process is：Can prepare under room temperature, method simple possible, equipment requirements are simple, production cost compared with
It is low.The manganese dioxide parcel nano-sulfur ball size prepared is less（500nm~600nm）, pattern is homogeneous, the dioxy of outer layer covers
Change the dissolving that manganese can suppress polysulfide, electric conductivity can be improved again, the coulombic efficiency for improving battery can be reached with circulation surely
Qualitatively effect.
The present invention improves the cycle performance of battery to suppress the dissolving of polysulfide, is prepared for manganese dioxide parcel and receives
Rice sulfur ball.As manganese dioxide is quasiconductor, sulfur is insulator, and the electric conductivity of material can be improved after parcel, in addition, there is research
Show, the reaction of manganese dioxide and polysulfide generates thiosulfate, thiosulfate can further with polysulfide chemical combination, suppression
The dissolving of polysulfide processed.The present invention is prepared for nano level sulfur ball, and particle diameter is less, is conducive to improving the contact surface with electrolyte
Product, can suppress the dissolving of polysulfide, can improve electric conductivity again after coating manganese dioxide, can reach the coulomb for improving battery
The effect of efficiency and cyclical stability.
Magnetic agitation is conducive to generating the more homogeneous nano-sulfur ball of size, and size is in 400nm or so.Moisture is added to dissipate,
So that the manganese dioxide generated in aqueous solution is closely deposited in sulfur ball surface.
In addition, the step 1）In, the hypo solution concentration of input is 0.04M, the described poly- second of input
The mass fraction of alkene pyrrolidone solution is 0.02%.Under the conditions of this, the polyvinylpyrrolidone in aqueous solution can be self-assembled into
Hollow ball, can grow in polyvinylpyrrolidone hollow ball inside after adding concentrated hydrochloric acid and thiosulfuric acid reactant salt, final to prepare
Into nano-sulfur ball.
The step 1）In, the mass fraction of the concentrated hydrochloric acid is 37%, concentrated hydrochloric acid and the hypo solution of input
Volume ratio is 1.6: 100.This concentrated hydrochloric acid is excessive, is conducive to sodium thiosulfate to react generation nano-sulfur ball completely.
Step 1）In, the rotating speed of centrifugation is 7000r/min, and washing rotating speed is 6000r/min, and 10min is centrifuged.Under this rotating speed
Nano-sulfur ball in solution can be separated out completely, it is to avoid loss of product.
Step 2）The input quality of middle manganese sulfate and step 1）The volume ratio of middle hypo solution is 153mg:
100mL.The manganese sulfate of this amount is put into, the manganese dioxide that next step is generated can be enabled to coat nano-sulfur ball completely.
Step 2）The input quality of middle potassium permanganate manganese and step 1）The volume ratio of middle hypo solution is 67mg:
100mL.When manganese sulfate is 2.3 with the mass ratio of potassium permanganate:When 1, γ type manganese dioxide can be prepared.
Step 2）The rotating speed of middle centrifugation is 5000r/min, and the time is 10min.Under this centrifugal rotational speed, the product of synthesis can be with
It is centrifuged out completely.
Step 2）Dry temperature conditionss are 60 DEG C.Dry temperature is 60 DEG C, the too high meeting sulfur volatilization of temperature, sulfur content drop
It is low.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the nano-sulfur ball prepared using the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of the nano-sulfur ball of the manganese dioxide parcel prepared using the present invention.
Fig. 3 is the X-ray diffractogram of the nano-sulfur ball of the manganese dioxide parcel prepared using the present invention.
Fig. 4 is the thermogravimetric analysis figure of the nano-sulfur ball of the manganese dioxide parcel prepared using the present invention.
Fig. 5 is the charge and discharge of the nano-sulfur ball as lithium sulfur battery anode material of the manganese dioxide parcel prepared using the present invention
Electric cycle performance figure.
Specific embodiment
First, preparation technology is described in detail to the present invention with reference to embodiments.
Embodiment 1
1）Prepare nano-sulfur ball：The concentration of 100mL is gathered for 0.02% with 100mL concentration for 0.04M hypo solutions
Vinylpyrrolidone solution mixes, and adds 1.6mL concentrated hydrochloric acid（Mass fraction is 37%, similarly hereinafter）, magnetic agitation, during reaction 2h,
10min, 6000r/min centrifuge washing 10min are centrifuged under 7000r/min, solid is collected.
2）Prepare the nano-sulfur ball of manganese dioxide parcel：By step 1）The solid of middle collection is dispersed in 20mL water, is added
153mg manganese sulfates, after magnetic agitation dissolving, add potassium permanganate solutions of the 5mL containing 67mg, that is, obtain product,
10min is centrifuged under 5000r/min, is washed, 60 DEG C of freeze-day with constant temperature 12h.
Embodiment 2
1）Prepare nano-sulfur ball：The concentration of 200mL is gathered for 0.02% with 200mL concentration for 0.04M hypo solutions
Vinylpyrrolidone solution mixes, and adds 3.2mL concentrated hydrochloric acid, magnetic agitation during reaction 2h, to be centrifuged under 7000r/min
10min, 6000r/min centrifuge washing 10min, collects solid.
2）Prepare the nano-sulfur ball of manganese dioxide parcel：By step 1）The solid of middle collection is dispersed in 40mL water, is added
306mg manganese sulfates, after magnetic agitation dissolving, add potassium permanganate solutions of the 10mL containing 134mg, that is, obtain product,
10min is centrifuged under 5000r/min, is washed, 60 DEG C of freeze-day with constant temperature 12h.
Embodiment 3
1）Prepare nano-sulfur ball：The concentration of 500mL is gathered for 0.02% with 500mL concentration for 0.04M hypo solutions
Vinylpyrrolidone solution mixes, and adds 8mL concentrated hydrochloric acid, magnetic agitation during reaction 2h, 10min to be centrifuged under 7000r/min,
6000r/min centrifuge washing 10min, collect solid.
2）Prepare the nano-sulfur ball of manganese dioxide parcel：By step 1）The solid of middle collection is dispersed in 100mL water, is added
765mg manganese sulfates, after magnetic agitation dissolving, add potassium permanganate solutions of the 10mL containing 335mg, that is, obtain product,
10min is centrifuged under 5000r/min, is washed, 60 DEG C of freeze-day with constant temperature 12h.
2nd, product checking：
As shown in figure 1, being the scanning electron microscope (SEM) photograph of the nano-sulfur ball prepared using the inventive method.It can be seen that, prepared receives
The spherical looks of rice sulfur are homogeneous, and size is less, and diameter is in 500nm or so.
As shown in Fig. 2 being the scanning electron microscope (SEM) photograph of the nano-sulfur ball of the manganese dioxide parcel prepared using the inventive method.Can
See, prepared product is the nano-sulfur ball of manganese dioxide parcel, and preferably, diameter is in 500nm or so for manganese dioxide covered effect.
Fig. 3 is the X-ray powder diffraction figure of the nano-sulfur ball of the manganese dioxide parcel prepared using the inventive method.Can
See, the clad of sulfur ball surface is manganese dioxide, and after cladding, sulfur ball does not occur qualitative change.
Fig. 4 is the thermogravimetric analysis figure of the nano-sulfur ball of the manganese dioxide parcel prepared using the inventive method.It can be seen that, dioxy
The content for changing manganese is 34.80%, and sulfur content is 65.20%, and sulfur content is higher.
Fig. 5 is the charge and discharge of the nano-sulfur ball as lithium sulfur battery anode material of the manganese dioxide parcel prepared using the present invention
Electric cycle performance figure.Test under the electric current of 2C, initial specific capacity is close to 800mAh/g, still has 400mAh/ after 300 circle of circulation
The specific capacity of g or so.It can be seen that, the nano-sulfur ball electric conductivity after manganese dioxide cladding is preferable, with higher specific capacity and circulation
Stability.
Claims (7)
1. it is a kind of to prepare the method that manganese dioxide wraps up nano-sulfur ball, it is characterised in that to comprise the following steps：
1）Prepare nano-sulfur ball：Isopyknic hypo solution is mixed with polyvinylpyrrolidonesolution solution, dense salt is added
Acid, magnetic agitation are reacted, and reaction is centrifuged after terminating, washing, collects solid；The step 1）In, input it is described thio
Metabisulfite solution concentration is 0.04M, and the mass fraction of the polyvinylpyrrolidonesolution solution of input is 0.02%；
2）Prepare the nano-sulfur ball of manganese dioxide parcel：The solid is dispersed in water, and adds manganese sulfate, magnetic agitation is molten
Xie Hou, adds potassium permanganate solution, after question response terminates, end-product is centrifuged, washing, is dried, and obtains manganese dioxide parcel
Nano-sulfur ball.
2. preparation method according to claim 1, it is characterised in that the step 1）In, the mass fraction of the concentrated hydrochloric acid
For 37%, the concentrated hydrochloric acid of input is 1.6: 100 with the volume ratio of hypo solution.
3. preparation method according to claim 1, it is characterised in that step 1）In, the rotating speed of centrifugation is 7000r/min, is washed
Rotating speed is washed for 6000r/min, centrifugation 10min.
4. preparation method according to claim 1, it is characterised in that step 2）The input quality of middle manganese sulfate and step 1）
The volume ratio of middle hypo solution is 153mg: 100mL.
5. preparation method according to claim 1, it is characterised in that step 2）The input quality of middle potassium permanganate manganese and step
Rapid 1）The volume ratio of middle hypo solution is 67mg: 100mL.
6. preparation method according to claim 1, it is characterised in that step 2）The rotating speed of middle centrifugation is 5000r/min, when
Between be 10min.
7. preparation method according to claim 1, it is characterised in that step 2）Dry temperature conditionss are 60 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106129356B (en) * | 2016-07-14 | 2018-08-17 | 扬州大学 | A kind of preparation method of hollow meso-porous titanium dioxide manganese pipe/sulphur composite material |
| CN108878838B (en) * | 2018-06-29 | 2020-06-05 | 北京理工大学 | Method for coating polypyrrole on surface of hollow sulfur sphere |
| CN110416518B (en) * | 2019-07-30 | 2022-10-18 | 西京学院 | Nanometer material with yolk-eggshell structure and preparation method and application thereof |
| CN111403702B (en) * | 2020-03-13 | 2022-05-17 | 北京航空航天大学 | Sulfur-carrying material and positive electrode material for lithium-sulfur battery |
Citations (5)
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| EP0615301A1 (en) * | 1993-03-10 | 1994-09-14 | Alliant Techsystems Inc. | High rate electrochemical cell |
| CN101521284A (en) * | 2009-03-18 | 2009-09-02 | 广州市天球实业有限公司 | Lithium-iron disulfide disposable column type battery and preparation process thereof |
| CN103579590A (en) * | 2013-05-09 | 2014-02-12 | 中国地质大学（武汉） | Preparation method for coating anode material of lithium battery |
| CN103972518A (en) * | 2013-02-05 | 2014-08-06 | 中国科学院大连化学物理研究所 | Manganese dioxide/carbon nanocomposite, and preparation method and application thereof |
| CN104600316A (en) * | 2015-01-07 | 2015-05-06 | 上海大学 | Sulfur/polymer/graphene ternary composite and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0410362A (en) * | 1990-04-27 | 1992-01-14 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte cell |
| US7390336B2 (en) * | 2003-07-29 | 2008-06-24 | Solicore, Inc. | Polyimide-based lithium metal battery |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0615301A1 (en) * | 1993-03-10 | 1994-09-14 | Alliant Techsystems Inc. | High rate electrochemical cell |
| CN101521284A (en) * | 2009-03-18 | 2009-09-02 | 广州市天球实业有限公司 | Lithium-iron disulfide disposable column type battery and preparation process thereof |
| CN103972518A (en) * | 2013-02-05 | 2014-08-06 | 中国科学院大连化学物理研究所 | Manganese dioxide/carbon nanocomposite, and preparation method and application thereof |
| CN103579590A (en) * | 2013-05-09 | 2014-02-12 | 中国地质大学（武汉） | Preparation method for coating anode material of lithium battery |
| CN104600316A (en) * | 2015-01-07 | 2015-05-06 | 上海大学 | Sulfur/polymer/graphene ternary composite and preparation method thereof |
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