CN109585827A - A kind of preparation method of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material - Google Patents

A kind of preparation method of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material Download PDF

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CN109585827A
CN109585827A CN201811434105.2A CN201811434105A CN109585827A CN 109585827 A CN109585827 A CN 109585827A CN 201811434105 A CN201811434105 A CN 201811434105A CN 109585827 A CN109585827 A CN 109585827A
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carbon nanotube
sulfur doping
doping carbon
titanium dioxide
coated
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赖梦瑶
詹春燕
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Dongguan University of Technology
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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
    • 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
    • H01M4/62—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 electrode material fields, and in particular to a kind of preparation method of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material；Firstly, carbon nanotube is added in deionized water, decentralized processing, sodium sulfide solution is added, is added in reaction kettle, isothermal reaction, centrifuge separation is rinsed, vacuum drying, sulfur doping carbon nanotube is prepared, finally, the A liquid of concentrated ammonia liquor, tetraethyl titanate, organic solvent composition is added in sulfur doping carbon nano tube dispersion liquid, constant temperature stirring, is centrifugated, and rinses, coated by titanium dioxide sulfur doping carbon nanotube is prepared in vacuum drying, calcination processing；Coated by titanium dioxide sulfur doping carbon nanotube preparation process is easy to operate, it is low to prepare economic cost, can be realized large-scale production, the coated by titanium dioxide sulfur doping carbon nanotube being prepared possesses biggish specific surface area, higher electron transport ability and first charge-discharge capacity, cycle performance are excellent.

Description

A kind of preparation of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material Method
Technical field
The invention belongs to electrode material fields, and in particular to a kind of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulfur cell is just The preparation method of pole material.
Background technique
In recent years, the continuous growth of energy demand and getting worse for environmental pollution are sent out in global economy fast development Opening up, there is high-energy density, long circulation life, high security, environmentally protective and inexpensive secondary cell to have in new energy field It is of great importance, lithium-sulfur cell is one kind in secondary cell system being developed with higher energy density, using simple substance As a positive electrode active material, theoretical energy density reaches 2600Wh/kg for sulphur or sulphurous materials, and there is Sulphur ressource to enrich, environment The advantages that friendly, cheap.
But lithium-sulfur cell still has some problems at present, seriously hinders the practical application of lithium-sulfur cell, specifically Come, lithium-sulfur cell there is problems: firstly, the electron conduction of elemental sulfur and ionic conductivity are poor, sulfur materials are in room temperature Under the extremely low (conductivity only 5.0 × 10 of conductivity-30S·cm-1), the final product polysulfide of reaction, such compound can It is dissolved in electrolyte, declines the capacity attenuation of lithium-sulfur cell sharply, causes cycle performance of battery poor, is unfavorable for the high magnification of battery Performance；Secondly, the density of sulphur and lithium sulfide is respectively 2.36gcm-3And 1.66gcm-3, have up in charge and discharge process 42% volume expansion or contraction, this expansion will lead to the change of positive pattern and structure, lead to the de- of sulphur and conducting matrix grain From to cause the decaying of capacity.
In order to solve these problems of lithium-sulfur cell, the Chinese patent of Publication No. CN103500820A discloses one kind Sulphur/porous carbon enveloped carbon nanometer tube composite positive pole and preparation method thereof for lithium-sulfur cell, elemental sulfur dispersion are supported on It, should in duct inside porous carbon enveloped carbon nanometer tube complex carbon material and its in the pore structure of the nanoporous carbon structure on surface The network duct of complex carbon material nanoscale effectively inhibits the dissolution of more lithium sulfides to spread loss, makes it have higher work The utilization rate of property substance sulphur, substantially increases the cyclical stability of lithium-sulfur cell.
However, carbon cannot play effect of contraction to polysulfide when the network duct using carbon loads elemental sulfur, Polysulfide is still dissolved in electrolyte, declines the capacity attenuation of lithium-sulfur cell sharply, causes cycle performance of battery poor.
Summary of the invention
It is an object of the invention to: a kind of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material is provided Preparation method, the present invention is by preventing polysulfide to be dissolved in electrolyte, making in sulfur doping carbon nano tube surface cladding titanium dioxide At capacity attenuation, poor circulation the phenomenon that occur.
A kind of preparation method of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material, including walk as follows It is rapid:
The preparation of S1, sulfur doping carbon nanotube: carbon nanotube is added in deionized water, and wherein the quality of carbon nanotube is 20-300mg, deionized water volume are 30-150mL, and sodium sulfide solution is added to carbon nanometer by ultrasonic wave decentralized processing 3-5h In pipe dispersion liquid, the volume that sodium sulfide solution is added is 5-30mL, and the mass concentration of sodium sulfide solution is 5mg/L, will be mixed Liquid after conjunction is added in reaction kettle, isothermal reaction, and the isothermal reaction time is 6-20h, and isothermal reaction temperature is 120-180 DEG C, after the reaction was completed, passes it through centrifuge separation and obtain solid, then rinsed with deionized water and ethyl alcohol, carried out vacuum and done Dry, vacuum drying temperature is 50-100 DEG C, and sulfur doping carbon nanotube is prepared in vacuum drying time 24-36h；
The preparation of S2, coated by titanium dioxide sulfur doping carbon nanotube: concentrated ammonia liquor and tetraethyl titanate are added in organic solvent, Uniform stirring is denoted as A liquid, and wherein ammonia concn is 1%-30%, and tetraethyl titanate concentration is 1-35%, and step S1 is prepared Sulfur doping carbon nanotube be added in organic solvent, wherein the quality of sulfur doping carbon nanotube be 3-9g, organic solvent volume For 250-700mL, ultrasonic wave decentralized processing 3-5h, sulfur doping carbon nano tube dispersion liquid is obtained, A liquid is slowly added into sulfur doping In carbon nano tube dispersion liquid, constant temperature stirring, constant temperature whipping temp is 30-70 DEG C, mixing speed 800-1200r/min, stirring Time is 12-36, after the reaction was completed, pass it through centrifuge separation obtain solid, then with deionized water and ethyl alcohol flushing, by its into Row vacuum drying, vacuum drying temperature are 70-90 DEG C, vacuum drying time 24-36h, after the completion of dry, are calcined Processing, calcination temperature is that 500-700 DEG C of calcination time is 5-10h, and coated by titanium dioxide sulfur doping carbon nanotube is prepared.
Preferably, organic solvent described in step S2 is one or more of ethyl alcohol, cyclohexane, isopropyl acetone, acetone.
Beneficial effect
(1) step S1 is conducting matrix grain sulfur loaded using carbon nanotube, and relatively high carbon nanotube loaded of quality is prepared Sulphur, the dosage by adjusting vulcanized sodium and carbon nanotube can control the concentration of sulfur doping, realize controllably mixing to carbon nanotube Miscellaneous, in addition, the flexible structure of carbon nanotube can play buffer function to the volume expansion of sulphur, and carbon nanotube is electron-transport Conductive path is provided, to improve the electron transport ability of positive electrode surface.
(2) step S2 uniformly coats one layer of titanium dioxide in sulfur doping carbon nano tube surface by sol-gel coating method Titanium increases the specific surface area of sulfur doping carbon nanotube, to increase the interfacial surface area for storing lithium, increases simultaneously The titanium dioxide of the electron transmission ability of sulfur doping carbon nano tube surface, surface possesses stronger suction-operated to polysulfide, To inhibit the phenomenon that the active material of electrode gradually decreases generation, moreover it is possible to inhibit more lithium sulfides to be dissolved in electrolyte, make lithium sulphur The phenomenon that capacity attenuation of battery sharply declines, and internal resistance increases, and then the cycle performance of lithium-sulfur cell is improved, reduce battery The speed of capacity attenuation makes sulphur lithium battery possess preferable charge-discharge performance.
(3) preparation process of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material of the present invention is easy to operate, Prepare economic cost it is low, can be realized large-scale production, the coated by titanium dioxide sulfur doping carbon nanotube being prepared possess compared with Big specific surface area, higher electron transport ability and first charge-discharge capacity, cycle performance are excellent.
Detailed description of the invention
Fig. 1 is coated by titanium dioxide sulfur doping carbon nanotube flow diagram.
A, b, c are respectively carbon nanotube used in step S1 and the sulfur doping carbon nanotube being prepared in embodiment 1 in Fig. 2 The coated by titanium dioxide sulfur doping carbon nanotube SEM figure that step S2 is prepared in SEM figure, embodiment 1.
Fig. 3 is the coated by titanium dioxide sulfur doping carbon nanotube TEM figure that S2 is prepared.
Fig. 4 is the porous carbon nanotube lithium sulfur battery anode material cyclic voltammetry curve of sulfur doping that comparative example 3 is prepared Figure.
Fig. 5 is the coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material circulation that embodiment 5 is prepared Volt-ampere curve figure.
Specific embodiment
Combined with specific embodiments below, the present invention is furture elucidated；It should be understood that these embodiments are merely to illustrate the present invention Rather than the claimed range of the limitation present invention；It will further be understood that read the content lectured of the present invention it Afterwards, those skilled in the art can make various changes or modification to the present invention, and such equivalent forms are equally fallen within appended by the application Claims limited range.
Embodiment 1-5
A kind of preparation method of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material, includes the following steps:
The preparation of S1, sulfur doping carbon nanotube: carbon nanotube is added in deionized water, and ultrasonic wave decentralized processing will vulcanize Sodium water solution is added in carbon nano tube dispersion liquid, mixed liquid is added in reaction kettle, isothermal reaction, and reaction is completed Afterwards, it passes it through centrifuge separation and obtains solid, then rinsed with deionized water and ethyl alcohol, be dried in vacuo, be prepared Sulfur doping carbon nanotube.
The preparation of S2, coated by titanium dioxide sulfur doping carbon nanotube: concentrated ammonia liquor and tetraethyl titanate are added to organic molten In agent, uniform stirring is denoted as A liquid, the sulfur doping carbon nanotube that step S1 is prepared is added in organic solvent, ultrasonic wave Decentralized processing obtains sulfur doping carbon nano tube dispersion liquid, A liquid is slowly added into sulfur doping carbon nano tube dispersion liquid, constant temperature Stirring passes it through centrifuge separation and obtains solid, then rinsed with deionized water and ethyl alcohol, carried out vacuum after the reaction was completed It is dry, after the completion of vacuum drying, calcination processing is carried out, coated by titanium dioxide sulfur doping carbon nanotube is prepared.
As the present invention more preferred embodiment, the ultrasonic wave decentralized processing time described in step S1 is in embodiment 3-5h。
As the present invention more preferred embodiment, the quality of sodium sulfide solution described in step S1 is dense in embodiment Degree is 5mg/L.
As the present invention more preferred embodiment, in embodiment in process of vacuum drying described in step S1, vacuum Drying temperature is 50-100 DEG C, vacuum drying time 24-36h.
As the present invention more preferred embodiment, organic solvent described in step S2 is ethyl alcohol, ring second in embodiment One or more of alkane, isopropyl acetone, acetone.
As the present invention more preferred embodiment, the ultrasonic wave decentralized processing time described in step S2 is in embodiment 3-5h。
As the present invention more preferred embodiment, in embodiment in constant temperature whipping process described in step S2, constant temperature Whipping temp is 30-70 DEG C, mixing speed 800-1200r/min, mixing time 12-36h.
As the present invention more preferred embodiment, in embodiment in process of vacuum drying described in step S2, vacuum Drying temperature is 70-90 DEG C, vacuum drying time 24-36h.
Wherein, in the preparation process of embodiment 1-5 coated by titanium dioxide sulfur doping carbon nanotube, step S1 sulfur doping carbon is received In the preparation process of mitron, the quality of carbon nanotube is Amg, and deionized water volume is BmL, the volume that sodium sulfide solution is added For CmL, the isothermal reaction time is Dh, and isothermal reaction temperature is E DEG C, the system of step S2 coated by titanium dioxide sulfur doping carbon nanotube During standby, ammonia concn is F% in A liquid, and tetraethyl titanate concentration is G%, and sulfur doping carbon nanotube is added in organic solvent, The quality of sulfur doping carbon nanotube is Hg, and organic solvent volume ImL, calcination temperature is that J DEG C of calcination time is Kh, specific each See Table 1 for details for step related data.
Each step related data of table 1
Carbon nanotube used in step S1 and the sulfur doping carbon nanotube SEM being prepared figure are respectively such as a, b in Fig. 2 in embodiment 1 Shown, by the SEM figure a of carbon nanotube it can be seen that carbon nanotube caliber is comparatively uniform, carbon nanotube pipe range probably has 1- 2μm；By the SEM figure b for the sulfur doping carbon nanotube being prepared it can be seen that carbon nanotube still keeps intact form, show Sulfur doping does not have agglomeration in carbon nanotube pipe.
The coated by titanium dioxide sulfur doping carbon nanotube SEM that step S2 is prepared in embodiment 1 schemes as shown in c in Fig. 2, C is schemed by the coated by titanium dioxide sulfur doping carbon nanotube SEM being prepared it can be seen that coating in sulfur doping carbon nano tube surface One layer of fine and close titanium dioxide, and from Fig. 2 a carbon nanotube SEM figure, b sulfur doping carbon nanotube SEM figure, c dioxy Change the SEM figure of titanium cladding sulfur doping carbon nanotube by comparing it can be found that larger change does not occur for the form of carbon nanotube；Two Titanium-oxide-coated sulfur doping carbon nanotube TEM schemes the coated by titanium dioxide sulfur doping carbon nanotube as shown in figure 3, by being prepared TEM schemes it can be seen that carbon nanotube bending fold together, a thin layer of titanium dioxide is observed that on its surface, is in Reveal the form of buckle fold.
Comparative example 1
A kind of preparation method of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material, includes the following steps:
The preparation of S1, sulfur doping carbon nanotube: carbon nanotube is added in deionized water, and wherein the quality of carbon nanotube is 350mg, deionized water volume are 200mL, and sodium sulfide solution is added to carbon nano tube dispersion liquid by ultrasonic wave decentralized processing 1h In, the volume that sodium sulfide solution is added is 40mL, and the mass concentration of sodium sulfide solution is 2mg/L, by mixed liquid It is added in reaction kettle, isothermal reaction, the isothermal reaction time is 3h, and isothermal reaction temperature is 250 DEG C, after the reaction was completed, by it Solid is obtained by centrifuge separation, then is rinsed with deionized water and ethyl alcohol, is dried in vacuo, vacuum drying temperature is 130 DEG C, sulfur doping carbon nanotube is prepared in vacuum drying time 12h；
The preparation of S2, coated by titanium dioxide sulfur doping carbon nanotube: concentrated ammonia liquor and tetraethyl titanate are added in ethyl alcohol, uniformly Stirring, is denoted as A liquid, and wherein ammonia concn is 35%, and tetraethyl titanate concentration is 42%, the sulfur doping carbon that step S1 is prepared Nanotube is added in ethyl alcohol, and wherein the quality of sulfur doping carbon nanotube is 12g, and ethyl alcohol volume is 800mL, at ultrasonic wave dispersion 2h is managed, sulfur doping carbon nano tube dispersion liquid is obtained, A liquid is slowly added into sulfur doping carbon nano tube dispersion liquid, constant temperature stirring, Constant temperature whipping temp is 100 DEG C, mixing speed 400r/min, mixing time 40h, after the reaction was completed, passes it through centrifugation Separation obtains solid, then is rinsed with deionized water and ethyl alcohol, is dried in vacuo, and vacuum drying temperature is 110 DEG C, vacuum Drying time is 15h, after the completion of dry, is carried out calcination processing, and calcination temperature is that 850 DEG C of calcination times are 12h, preparation Obtain coated by titanium dioxide sulfur doping carbon nanotube.
Comparative example 2
The present embodiment provides a kind of preparation methods of sulfur doping carbon nanotube lithium-sulphur cell positive electrode material, compared with Example 1, this The preparation process of embodiment step S1 sulfur doping carbon nanotube is identical with embodiment 1, the difference is that, the present embodiment does not have There are the preparation process of step S2 coated by titanium dioxide sulfur doping carbon nanotube, i.e., no coated by titanium dioxide, sulfur doping carbon nanometer Pipe is final lithium sulfur battery anode material.
Comparative example 3
The present embodiment provides a kind of preparation methods of the porous carbon nanotube lithium sulfur battery anode material of sulfur doping, including walk as follows It is rapid:
Carbon nanotube is uniformly mixed with potassium hydroxide, then under inert gas atmosphere, 700 DEG C is gradually heated to, then protects It is cooled to room temperature after warm a period of time, is removed remaining KOH with acid, solid drying is filtered out, obtains porous carbon nanotube；It will system Standby obtained porous carbon nanotube and elemental sulfur 1:4 ratio in mass ratio mix, 150 DEG C of heat together 12h under protective atmosphere Obtain the porous carbon nanotube of sulfur doping.
Coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material and comparative example is prepared in embodiment 1-5 The lithium sulfur battery anode material that 1-3 is prepared carries out charge/discharge capacity test, and test result is as shown in table 2, (digital in table 2 1-5 respectively represents embodiment 1-5, and digital 6-8 respectively represents comparative example 1-3).
2 charge/discharge capacity test result of table
1 2 3 4 5 6 7 8
First charge-discharge capacity (mA h/g) 1513 1527 1625 1638 1589 1394 1349 1427
100th charge/discharge capacity (mA h/g) 1107 1114 1226 1273 1162 792 561 913
Charge/discharge capacity loses (mA h/g) 406 413 399 365 427 602 788 514
From 2 charge/discharge capacity test result of table: the coated by titanium dioxide sulfur doping carbon nanotube that embodiment 1-5 is prepared The minimum 1513 mA h/g of lithium sulfur battery anode material first charge-discharge capacity, the 100th charge/discharge capacity minimum 1107 MA h/g, charge/discharge capacity loss is up to 427mA h/g, and the lithium sulfur battery anode material that comparative example 1-3 is prepared is for the first time Charge/discharge capacity is up to 1427 mA h/g, and the 100th charge/discharge capacity is up to 913 mA h/g, charge/discharge capacity loss The coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material that minimum 514mA h/g, embodiment 1-5 are prepared First charge-discharge lowest value of capacity, the 100th charge/discharge capacity minimum are above the lithium-sulfur cell that comparative example 1-3 is prepared Positive electrode peak, and the coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material that embodiment 1-5 is prepared Material charge/discharge capacity loss peak is lower than the lithium sulfur battery anode material minimum that comparative example 1-3 is prepared, in conclusion The coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material that embodiment 1-5 is prepared is substantially better than comparative example 1- 3 lithium sulfur battery anode materials being prepared；The coated by titanium dioxide sulfur doping carbon nanotube lithium sulphur electricity that embodiment 4 is prepared Pond positive electrode first charge-discharge capacity is 1638 mA h/g, and the 100th charge/discharge capacity is 1273 mA h/g, charge and discharge capacitor Amount loss is 365mA h/g, is best in embodiment, therefore embodiment 4 is most preferred embodiment.
Comparative example 4
The porous carbon nanotube lithium sulfur battery anode material of sulfur doping and embodiment 5 that comparative example 3 is prepared are prepared Coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material is analyzed by cyclic voltammetry curve, and Fig. 4 is comparison The porous carbon nanotube lithium sulfur battery anode material cyclic voltammetry curve of the sulfur doping that example 3 is prepared, 1,2 respectively represent in Fig. 4 First lap, the second circle scanning curve, Fig. 5 is the coated by titanium dioxide sulfur doping carbon nanotube lithium sulphur that is prepared of embodiment 5 1,2 respectively represent first lap, the second circle scanning curve in cell positive material cyclic voltammetry curve Fig. 5, by following for Fig. 4, Fig. 5 Ring volt-ampere curve is it can be seen that first lap scans in the porous carbon nanotube lithium sulfur battery anode material cyclic voltammetry curve of sulfur doping When, oxidation peak-to-peak value is about 1.45mA, coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material circulation volt-ampere When first lap scans in curve, oxidation peak-to-peak value is about 2.39mA, and Fig. 5 cyclic voltammetry curve is compared and Fig. 4 cyclic voltammetric Curve is obviously sharp, and electric current is relatively large, shows that coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material possesses Higher electron transport ability, Fig. 5 coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material circulation volt-ampere curve Second circle scanning curve is shuffled compared to first lap scanning curve, is shown that polysulfide dissolves, is generated vacancy and hole, have Help and electrolyte contacts to promote the transmittability of electronics produce the phenomenon that shuffling.
The present invention be can be seen that with the comparing result of comparative example through the foregoing embodiment by sulfur doping carbon nanotube table Face cladding titanium dioxide, prevents polysulfide to be dissolved in electrolyte, caused by capacity attenuation, poor circulation the phenomenon that occur.
The above, only of the invention illustrates embodiment, not to the present invention in any form with substantial limitation, It should be pointed out that for those skilled in the art, under the premise of not departing from the method for the present invention, that makes several changes It also should be regarded as protection scope of the present invention into supplement；All those skilled in the art, do not depart from spirit of that invention and In the case where range, using the equivalent variations of a little change, modification and differentiation that disclosed above technology contents are made, it is Equivalent embodiment of the invention；Meanwhile any equivalent variations that all substantial technologicals according to the present invention do above-described embodiment Change, modification and differentiation, still fall within protection scope of the present invention.

Claims (9)

1. a kind of preparation method of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material, includes the following steps:
The preparation of S1, sulfur doping carbon nanotube: carbon nanotube is added in deionized water, ultrasonic wave decentralized processing 3-5h, will Sodium sulfide solution is added in carbon nano tube dispersion liquid, mixed liquid is added in reaction kettle, isothermal reaction, reaction Centrifuge separation is passed it through after the completion and obtains solid, then is rinsed with deionized water and ethyl alcohol, is dried in vacuo, vacuum is dry Dry temperature is 50-100 DEG C, and sulfur doping carbon nanotube is prepared in vacuum drying time 24-36h；
The preparation of S2, coated by titanium dioxide sulfur doping carbon nanotube: concentrated ammonia liquor and tetraethyl titanate are added in organic solvent, Uniform stirring is denoted as A liquid, and the sulfur doping carbon nanotube that step S1 is prepared is added in organic solvent, ultrasonic wave dispersion 3-5h is handled, sulfur doping carbon nano tube dispersion liquid is obtained, A liquid is slowly added into sulfur doping carbon nano tube dispersion liquid, constant temperature It is stirred to react, passes it through centrifuge separation after the reaction was completed and obtain solid, then rinsed with deionized water and ethyl alcohol, carried out true Sky is dry, and vacuum drying temperature is 70-90 DEG C, vacuum drying time 24-36h, after the completion of dry, is carried out at calcining Reason, is prepared coated by titanium dioxide sulfur doping carbon nanotube.
2. a kind of preparation of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material according to claim 1 Method, which is characterized in that the quality of carbon nanotube described in step S1 is 20-300mg, and deionized water volume is 30-150mL.
3. a kind of preparation of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material according to claim 1 Method, which is characterized in that the volume that sodium sulfide solution described in step S1 is added is 5-30mL, the quality of sodium sulfide solution Concentration is 5mg/L.
4. a kind of preparation of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material according to claim 1 Method, which is characterized in that during isothermal reaction described in step S1, the isothermal reaction time is 6-20h, and isothermal reaction temperature is 120-180℃。
5. a kind of preparation of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material according to claim 1 Method, which is characterized in that organic solvent described in step S2 is one or more of ethyl alcohol, cyclohexane, isopropyl acetone, acetone.
6. a kind of preparation of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material according to claim 1 Method, which is characterized in that ammonia concn is 1%-30% in A liquid described in step S2, and tetraethyl titanate concentration is 1-35%.
7. a kind of preparation of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material according to claim 1 Method, which is characterized in that sulfur doping carbon nanotube described in step S2 is added in organic solvent, the matter of sulfur doping carbon nanotube Amount is 3-9g, organic solvent volume 250-700mL.
8. a kind of preparation of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material according to claim 1 Method, which is characterized in that during constant temperature described in step S2 is stirred to react, constant temperature whipping temp is 30-70 DEG C, mixing speed For 800-1200r/min, mixing time 12-36h.
9. a kind of preparation of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material according to claim 1 Method, which is characterized in that in calcination process described in step S2, calcination temperature is 500-700 DEG C, calcination time 5-10h.
CN201811434105.2A 2018-11-28 2018-11-28 A kind of preparation method of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material Pending CN109585827A (en)

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Cited By (4)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110846888A (en) * 2019-11-27 2020-02-28 宁波大学 Preparation method of sulfur-doped titanium dioxide nano-fiber
CN111554934A (en) * 2020-05-14 2020-08-18 陕西科技大学 Biochar-loaded titanium dioxide for lithium-sulfur battery electrode and preparation method thereof
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CN113937294A (en) * 2021-09-30 2022-01-14 海南大学 Compound and method for inhibiting shuttle effect of lithium-sulfur battery positive electrode material
CN114620713A (en) * 2022-04-13 2022-06-14 楚能新能源股份有限公司 Preparation method of Na ion and nonmetal co-doped carbon nanotube and lithium ion battery

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