CN106356555A - Preparation method of carbon nanotube/conductive polymer double-modified sulfur composite cathode material - Google Patents
Preparation method of carbon nanotube/conductive polymer double-modified sulfur composite cathode material Download PDFInfo
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Abstract
The invention relates to the technical field of electrode material synthesis and particularly discloses a preparation method of a 3D-structure carbon nanotube/conductive polymer double-modified sulfur composite cathode material. In the method, with a carbon nanotube, polyaniline and sulfur as base materials, a sulfur composite cathode material with a 3D structure is prepared by the steps such as hydrothermal process, liquid-phase synthesis process and heat treatment. In combination with the advantages of easiness in preparation and chemical confinement of a conductive polymer and the 3D conductive network skeleton of the carbon nanotube, the electrode material realizes effective modification of sulfur and has the advantages of good cycle performance, high rate capability and the like when applied to lithium-sulfur batteries, and has a broad application prospect in the related fields such as mobile communication and portable digital products, electric automobiles and energy storage equipment. The whole method has relatively simple process and mild reaction conditions and is environmentally friendly and facilitates industrial large-scale production.
Description
Technical field
The invention belongs to electrode material synthesis technical field is and in particular to a kind of long-life, height ratio capacity and have 3d
The preparation method of the sulfur composite positive pole of the dual modification of carbon nano tube/conducting polymer of structure.
Background technology
Develop rapidly with scientific and technological, people propose many requirements to mobile electronic device: safer, faster, electric
Tankage is bigger, stand-by time is longer.And conventional lithium ion battery positive electrode such as LiFePO4 (170mah*g-1) etc., by
In having relatively low theoretical specific capacity, limit it and further develop.Lithium-sulfur cell is because having very high specific capacity
(1673mah*g-1) and energy density (2600wh*kg-1) cause the extensive concern of people, but with elemental sulfur for positive pole material
The lithium-sulfur cell of material also has some shortcomings and hinders its business-like paces, is in particular in the following aspects:
1. the insulating properties of elemental sulfur.Elemental sulfur is the insulator of electronics and ion at room temperature, and electronics at room temperature passes
Conductance is 5 × 10-30s*cm-1, ionic conductance is 10-15, lead to lithium-sulfur cell internal resistance to increase, active material utilization is low.Cause
This needs to add substantial amounts of conductive agent (as acetylene black, Ketjen black) when making electrode, has made the energy density of electrode system
Reduce.
2. the dissolving of polysulfides.Intermediate product polysulfide (the li that electrochemical reaction produces2sn, n ＞ 4) and in electrolysis
Dissolve in liquid, diffuse to cathode of lithium and react therewith, cause " shuttle effect ".In addition, insulating properties insoluble matter li2S and
li2s2In negative material surface deposition, the electrical contact of active substance is led to deteriorate, cyclical stability declines.
3. the change in volume of active substance.Elemental sulfur (2.07g/cm-3) and lithium sulfide (1.66g/cm-3) in discharge and recharge
Density variation in journey causes about 76% change in volume, leads to the destruction of electrode structure.
Therefore, how to hinder battery rapid decay, improve cycle performance of battery, improve active material utilization become
The emphasis of lithium-sulfur cell research.Wherein, application material with carbon element modifying and decorating sulfur positive pole is prepare sulfur-based composite anode material important
One of means.
Material with carbon element has the advantages that high conductivity, multidimensional structure, with low cost, is widely used in existing including lithium-sulfur cell
Interior many energy fields.For example Canadian nazar et al. opens the beginning that meso-porous carbon material is applied to lithium-sulfur cell, first
First having synthesized specific surface area is 1976 (m2*g-1), pore volume be 2.1 (cm3*g-1) mesoporous material cmk-3, then pass through heat treatment
It is filled with 70% sulfur in its duct, test result indicate that: cmk-3 meso-porous carbon material can improve the electric conductivity of complex,
Promote the transmission of electronic and ionic, improve active material utilization, the initial discharge specific capacity of cmk-3/s carbon-sulfur compound is up to
1320mah*g-1(referring to ji x, lee k t, nazar l f.nat.mater., 2009,8,500-506.).But due to many
Hole carbon has open pore passage structure, and sulfur, under long charge and discharge electro ultrafiltration, is equally possible and escapes out carbon pores road；In addition,
Most material with carbon elements are all the inactive apolar substances of chemical property, lack stronger chemistry and the lithium sulfide of polarity between
Active force is it is impossible to enough effectively suppress polysulfides to scatter and disappear in long-range charge and discharge cycles, and shuttle effect occurs.
Except material with carbon element, it is also a kind of important modified method with polymer-modified sulfur composite.Prepared by xiao et al.
Polyaniline pipe, then in its Surface coating sulfur and carry out vulcanization reaction, effectively inhibits scattering and disappearing, 0.1c's of polysulfides
After electric current density circulation 100 circle, specific capacity is maintained at 837mah*g-1(referring to l.xiao, y.cao, j.xiao, etc.,
adv.mater.2012,24,1176-1181.).Chen et al. utilizes conducting polymer pedot (3,4-rthylene dioxythiophene) to wrap
Wrap up in sulfur nano-particle, in 400ma*g-1Electric current density under circulation 50 circle, keep 930mah*g-1Specific capacity (referring to
h.chen,w.dong,j.ge and etc.,sci.rep,2013,3,1910.).
In sum, single material with carbon element or polymer each come with some shortcomings it is impossible to reach the ideal to sulfur
Modification.Therefore, present invention incorporates both advantages, comprehensive material with carbon element and conducting polymer are jointly modified to sulfur and changed
Property, efficiently solve the problems, such as lithium-sulfur cell, achieve preferable battery performance.
Content of the invention
It is an object of the invention to overcoming existing sulfur positive electrode above shortcomings, a kind of excellent performance being provided and has
Hope the preparation method of the sulfur combination electrode material of the dual modification of material with carbon element/conducting polymer of large-scale industrial production.The party
Method, with CNT, polyaniline and sulfur as base material, is prepared by methods such as hydro-thermal method, room temperature liquid phase synthesizing method and heat treatments
High performance sulfur composite positive pole.The technical scheme that the present invention is adopted for achieving the above object is specific as follows:
A kind of preparation method of the sulfur composite positive pole of the dual modification of carbon nano tube/conducting polymer of 3d structure, bag
Include following steps:
(1) preparation of amination CNT (e-cnt): CNT is distributed in the aqueous solution of ethylenediamine, by solution
It is heated to uniform temperature insulation and carries out hydro-thermal reaction, after the completion of reaction, be centrifugally separating to obtain amination CNT；
(2) preparation of CNT-sulfur compound (e-cnt/s): by step (1) gained amination CNT and five water sulfur
Sodium thiosulfate, Polyvinylpyrrolidone, sulphuric acid mixing, stirring is centrifugally separating to obtain e-cnt/s complex after a period of time；
(3) preparation of CNT-sulfur (the p@e-cnt/s) complex of polyaniline parcel: by step (2) gained e-cnt/
S complex, aniline, hydrochloric acid and Ammonium persulfate. are distributed in deionized water, and stirring is centrifugally separating to obtain p@e- after a period of time
Cnt/s complex.
According to such scheme, in step (1) first by the ethylenediamine for 1:1-4 for the mass ratio and CNT be added to from
In sub- water, by magnetic stirring apparatuss, uniform mixed solution, the guarantor of mixed solution hydro-thermal reaction are obtained with moderate-speed mixer 30-90min
Temperature is 60-120 DEG C, and the insulation reaction time is 2-6h.
According to such scheme, first amination CNT is disperseed in deionized water, to add five water sulfur in step (2)
Sodium thiosulfate, Polyvinylpyrrolidone, sulphuric acid, mixed solution moderate-speed mixer response time 2-8h at normal temperatures, wherein five water sulfur
The mass ratio of sodium thiosulfate, Polyvinylpyrrolidone, sulphuric acid and ethylenediamine is 11.7:0.1:2.5-7.5:1.
According to such scheme, step (3) first e-cnt/s complex is added in deionized water, ultrasonic disperse 30-
90min, then sequentially adds aniline, hydrochloric acid, Ammonium persulfate., room temperature moderate-speed mixer mixing 6-18h, wherein aniline, hydrochloric acid, over cure
Sour ammonium is 1.22:0.8-4.8:2:1 with the mass ratio of ethylenediamine.
According to such scheme, rotating speed during centrifugation turns/min, product deionized water and anhydrous second for 5000-8000
Alcohol washs, and temperature during vacuum drying is 40-80 DEG C, and drying time is 12-36h, and the hydrochloric acid mass concentration being used is 37%,
The h 2 so 4 concentration being used is 98%.
The sulfur composite positive pole that the present invention provides uniformly is interspersed in nano-sulfur by the CNT through amination treatment
In grain, form the structure (e-cnt/s) of similar armored concrete.Pretreated amination CNT is except improving complex
Electric conductivity, also has numerous functional groups, and these functional groups can produce chemical interactions and polysulfides between, and minimizing is filled
In discharge process, active substance scatters and disappears.Again in one layer of conductive polymer polyanaline of e-cnt/s external sheath, at heat of vulcanization
After reason, between polyaniline and elemental sulfur, produce strong chemical interactions, scattering and disappearing of polysulfides can be reduced further,
And then the stability of protection composite positive pole microstructure, promote the long-range cycle performance of electrode.
The invention has the benefit that technological process is relatively simple, reaction condition gentle, environmental friendliness is it is easy to industrialization
Large-scale production, the sulfur composite positive pole being prepared using the method is used for during lithium-sulfur cell having energy density height, follows
The advantages of ring performance is good, high rate performance is good, in the related neck such as mobile communication and Portable digital product, electric automobile, energy storage device
Domain has broad application prospects.
Brief description
Fig. 1 is the scanning electron microscopic picture of each intermediate material in the embodiment of the present invention 3 preparation process, and a is e-cnt, and b is e-
Cnt/s, c are p@e-cnt/s.
Fig. 2 is the p@e-cnt/s composite X-ray diffraction pattern of the embodiment of the present invention 3 preparation.
Fig. 3 be the embodiment of the present invention 3 preparation lithium sulfur battery anode material at room temperature single electric current circulation figure.
Specific embodiment
For making those of ordinary skill in the art fully understand technical scheme and beneficial effect, below in conjunction with concrete
Embodiment and accompanying drawing are carried out further.Following examples are merely to illustrate, and do not constitute limitation of the invention, on this basis
Any improvement carrying out each falls within protection scope of the present invention.
Embodiment 1
The first step, adds 0.1g ethylenediamine and 0.1g CNT, by electromagnetic agitation first in 100ml deionized water
Then the solution of mix homogeneously loaded in hydrothermal reaction kettle by device moderate-speed mixer mixing 30min, and setting drying baker reaction condition is
60 DEG C, heat time heating time was reacted for 2 hours.After reaction terminates, by product deionized water and dehydrated alcohol centrifuge washing
(5000 revs/min) three times, the precipitate that centrifugation is obtained is placed in vacuum drying oven, is dried 12 hours under conditions of 40 DEG C,
Obtain amination CNT (e-cnt), collect standby.
Second step, the e-cnt of previous step gained is distributed in 200ml deionized water, sequentially adds 1.17g five water thio
Sodium sulfate, 0.01g Polyvinylpyrrolidone and the sulphuric acid that 0.25g mass concentration is 98%, are stirred by magnetic stirrer middling speed
Mix mixing 2h.After reaction terminates, product deionized water and dehydrated alcohol centrifuge washing (5000 revs/min) three times will be centrifuged
The precipitate obtaining is placed in vacuum drying oven, 12h is dried, obtains amination CNT/sulfur compound (e- under conditions of 40 DEG C
Cnt/s), collection is standby.
3rd step, above-mentioned e-cnt/s complex is added in 100ml deionized water, ultrasonic disperse 30min, is formed all
Even solution.Then 0.122g aniline, 0.08g hydrochloric acid (hydrochloric acid mass concentration is 37%) and 0.2g are sequentially added in solution
Ammonium persulfate., is mixed 6 hours by magnetic stirrer moderate-speed mixer.After reaction terminates, by product deionized water and anhydrous second
Alcohol centrifuge washing (5000 revs/min) three times, the precipitate that centrifugation is obtained is placed in vacuum drying oven, is dried under conditions of 40 DEG C
12 hours, obtain final product the amination CNT/sulfur compound (p@e-cnt/s) of polyaniline-coated.
For understanding the CNT-sulfur compound performance of the polyaniline parcel of embodiment 1 preparation, we are made into lithium
Sulfur battery has simultaneously carried out dependence test.First p@e-cnt/s complex, acetylene black and Kynoar according to mass ratio 75:
The proportioning of 15:10 is mixed, the more appropriate n- methyl pyrrolidone (nmp) of Deca thereto, then carries out mix and blend, stirs
Time of mixing is 2 hours.The slurry stirring is coated on aluminium foil, aluminium foil is carried out vacuum drying treatment and obtains anode electrode
Piece.Vacuum drying Absolute truth reciprocal of duty cycle is 100pa, 60 DEG C of baking temperature, and drying time is 12 hours.With lithium metal as negative pole
Piece, polypropylene porous film is battery diaphragm, and electrolyte prescription is that double trifluoromethanesulfonimide lithiums (litfsi) of 1mol/l are molten
Solution is in the mixed solution of 1,3- dioxolane (dol) and glycol dimethyl ether (dme) (volume ratio is 1:1), then adds
Lithium nitrate (the lino of 0.1mol/l3), it is assembled into 2025 type button cells in the glove box of argon gas atmosphere, then carry out electrochemistry
Performance test (test voltage is interval to be 1.4-2.8v).
Embodiment 2
The first step, is added 0.1g ethylenediamine and 0.25g CNT first in 100ml deionized water, is stirred by electromagnetism
Mix device moderate-speed mixer mixing 60min, then load the solution of mix homogeneously in hydrothermal reaction kettle, drying baker reaction condition is set
For 90 DEG C, heat time heating time was reacted for 4 hours.After reaction terminates, by product deionized water and dehydrated alcohol centrifuge washing
(6000 revs/min) three times, the precipitate that centrifugation is obtained is placed in vacuum drying oven, is dried 24 hours under conditions of 60 DEG C,
Obtain amination CNT (e-cnt), collect standby.
Second step, the e-cnt of previous step gained is distributed in 200ml deionized water, sequentially adds 1.17g five water thio
Sodium sulfate, 0.01g Polyvinylpyrrolidone and the sulphuric acid that 0.5g mass concentration is 98%, by magnetic stirrer moderate-speed mixer
Mixing 6h.After reaction terminates, centrifugation is obtained by product deionized water and dehydrated alcohol centrifuge washing (6000 revs/min) three times
The precipitate taking is placed in vacuum drying oven, 24h is dried under conditions of 60 DEG C, obtains amination CNT/sulfur compound (e-
Cnt/s), collection is standby.
3rd step, above-mentioned e-cnt/s complex is added in 100ml deionized water, ultrasonic disperse 60min, is formed all
Even solution.Then 0.122g aniline, 0.2g hydrochloric acid (hydrochloric acid mass concentration is 37%) and 0.2g are sequentially added in solution
Ammonium persulfate., is mixed 10 hours by magnetic stirrer moderate-speed mixer.After reaction terminates, by product deionized water and anhydrous second
Alcohol centrifuge washing (6000 revs/min) three times, the precipitate that centrifugation is obtained is placed in vacuum drying oven, is dried under conditions of 60 DEG C
24 hours, obtain final product the amination CNT/sulfur compound (p@e-cnt/s) of polyaniline-coated.
The making of lithium-sulfur cell: p@e-cnt/s complex, acetylene black and Kynoar according to mass ratio 75:15:10
Proportioning mixed, then to the appropriate n- methyl pyrrolidone (nmp) of Deca in solution, then carry out mix and blend, stirring
Time is 2 hours.The slurry stirring is coated on aluminium foil, aluminium foil is carried out vacuum drying treatment and obtains anode electrode
Piece.Vacuum drying Absolute truth reciprocal of duty cycle is 100pa, 60 DEG C of baking temperature, and drying time is 12 hours.With lithium metal as negative pole
Piece, polypropylene porous film is battery diaphragm, and electrolyte prescription is that double trifluoromethanesulfonimide lithiums (litfsi) of 1mol/l are molten
Solution is in the mixed solution of 1,3- dioxolane (dol) and glycol dimethyl ether (dme) (volume ratio is 1:1), then adds 0.1mol/
Lithium nitrate (the lino of l3), it is assembled into 2025 type button cells in the glove box of argon gas atmosphere, then carry out chemical property survey
Examination (test voltage is interval to be 1.4-2.8v).
Embodiment 3
The first step, adds 0.1g ethylenediamine and 0.4g CNT, by electromagnetic agitation first in 100ml deionized water
Then the solution of mix homogeneously loaded in hydrothermal reaction kettle by device moderate-speed mixer mixing 90min, and setting drying baker reaction condition is
120 DEG C, heat time heating time is reacted for 6h.After reaction terminates, by product deionized water and dehydrated alcohol centrifuge washing (8000
Rev/min) three times, the precipitate that centrifugation is obtained is placed in vacuum drying oven, is dried 36 hours, obtains amine under conditions of 80 DEG C
Carbon nano tube (e-cnt), collects standby.
Second step, the e-cnt of previous step gained is distributed in 200ml deionized water, sequentially adds 1.17g five water thio
Sodium sulfate, 0.01g Polyvinylpyrrolidone and the sulphuric acid that 0.75g mass concentration is 98%, are stirred by magnetic stirrer middling speed
Mix mixing 8h.After reaction terminates, product deionized water and dehydrated alcohol centrifuge washing (8000 revs/min) three times will be centrifuged
The precipitate obtaining is placed in vacuum drying oven, 36h is dried, obtains amination CNT/sulfur compound (e- under conditions of 80 DEG C
Cnt/s), collection is standby.
3rd step, above-mentioned e-cnt/s complex is added in 100ml deionized water, ultrasonic disperse 90min, is formed all
Even solution.Then 0.122g aniline, 0.48g hydrochloric acid (hydrochloric acid mass concentration is 37%) and 0.2g are sequentially added in solution
Ammonium persulfate., is mixed 15 hours by magnetic stirrer moderate-speed mixer.After reaction terminates, by product deionized water and anhydrous second
Alcohol centrifuge washing (8000 revs/min) three times, the precipitate that centrifugation is obtained is placed in vacuum drying oven, is dried under conditions of 80 DEG C
36 hours, obtain final product the amination CNT/sulfur compound (p@e-cnt/s) of polyaniline-coated.
The making of lithium-sulfur cell: p@e-cnt/s complex, acetylene black and Kynoar according to mass ratio 75:15:10
Proportioning mixed, then the n- methyl pyrrolidone (nmp) that Deca is appropriate, then carry out mix and blend, mixing time is 2 little
When.The slurry stirring is coated on aluminium foil, aluminium foil is carried out obtain after vacuum drying treatment with positive electrical pole piece.Vacuum is done
Dry Absolute truth reciprocal of duty cycle is 100pa, 60 DEG C of baking temperature, and drying time is 12 hours.With lithium metal as negative plate, polypropylene is many
Pore membrane is battery diaphragm, and electrolyte prescription is that double trifluoromethanesulfonimide lithiums (litfsi) of 1mol/l are dissolved in 1,3- dioxy
Pentane (dol) and the mixed solution of glycol dimethyl ether (dme) (volume ratio is 1:1), then the lithium nitrate adding 0.1mol/l
(lino3), it is assembled into 2025 type button cells in the glove box of argon gas atmosphere, then carry out electrochemical property test (test electricity
It is 1.4-2.8v between nip).
The appearance structure that p@e-cnt/s composite prepared by the inventive method has been carried out with sem, tem and xrd characterizes
And the test of chemical property, further confirmed that the load sulfur content of composite by tga, below with embodiment 3 simultaneously
Illustrate as a example test result.
Fig. 1 is the scanning electron microscope (SEM) photograph of each intermediate material in the embodiment of the present invention 3 preparation process, and wherein 1-a receives for amination carbon
Mitron, 1-b is CNT/sulfur composite construction, and 1-c is p@e-cnt/s composite.From figure 1 it will be seen that through modification
What CNT was still good maintains primary tubular structure, and tube wall becomes relative smooth；It is formed as schemed after being combined with sulfur
The reinforced concrete structure of 1-b, finally wraps up polyaniline and is packaged into composite construction further.Fig. 2 is p@e-cnt/s composite
X-ray diffraction pattern it can be seen that mainly present is the characteristic diffraction peak (jcpds no.08-0247) of sulfur.Fig. 3 is p@e-
Cnt/s composite is as the current cycle figure of lithium sulfur battery anode material constant current charge-discharge at room temperature.In 0.2c (1c=
1673mah*g-1) electric current density under, first discharge capacity be 1273mah*g-1, after discharge and recharge 200 times, discharge capacity still has
763mah*g-1, coulombic efficiency is close to 100%.This illustrate this material be effectively combined conducting polymer and CNT for
The modification advantage of sulfur, effectively inhibits scattering and disappearing of polysulfides, has stable cycle performance.
Claims (5)
1. the preparation method of the sulfur composite positive pole of the dual modification of carbon nano tube/conducting polymer of a kind of 3d structure, it is special
Levy and be, comprise the following steps:
(1) preparation of amination CNT: CNT is distributed in the aqueous solution of ethylenediamine, solution is heated to a constant temperature
Degree insulation carries out hydro-thermal reaction, is centrifugally separating to obtain amination CNT after the completion of reaction；
(2) preparation of CNT-sulfur compound: by step (1) gained amination CNT and five water sodium thiosulfate, poly- second
Alkene pyrrolidone, sulphuric acid mixing, stirring is centrifugally separating to obtain CNT-sulfur compound after a period of time；
(3) preparation of the CNT-sulfur compound of polyaniline parcel: by step (2) gained CNT-sulfur compound, benzene
Amine, hydrochloric acid and Ammonium persulfate. are distributed in deionized water, and stirring is centrifugally separating to obtain the carbon of polyaniline parcel after a period of time
Nanotube-sulfur compound.
2. sulfur composite positive pole as claimed in claim 1 preparation method it is characterised in that: first by matter in step (1)
Amount is added in deionized water, by magnetic stirring apparatuss with moderate-speed mixer 30- than the ethylenediamine for 1:1-4 and CNT
90min obtains uniform mixed solution, and the holding temperature of mixed solution hydro-thermal reaction is 60-120 DEG C, and the insulation reaction time is 2-
6h.
3. sulfur composite positive pole as claimed in claim 1 preparation method it is characterised in that: first by amine in step (2)
Carbon nano tube disperses in deionized water, to add five water sodium thiosulfate, Polyvinylpyrrolidone, sulphuric acid, mixed solution
Moderate-speed mixer response time 2-8h at normal temperatures, wherein five water sodium thiosulfate, Polyvinylpyrrolidone, sulphuric acid and ethylenediamine
Mass ratio is 11.7:0.1:2.5-7.5:1.
4. sulfur composite positive pole as claimed in claim 1 preparation method it is characterised in that: carbon is received by step (3) first
Mitron-sulfur compound is added in deionized water, ultrasonic disperse 30-90min, then sequentially adds aniline, hydrochloric acid, persulfuric acid
Ammonium, room temperature moderate-speed mixer mixing 6-18h, the wherein mass ratio of aniline, hydrochloric acid, Ammonium persulfate. and ethylenediamine are 1.22:0.8-
4.8:2:1.
5. sulfur composite positive pole as claimed in claim 1 preparation method it is characterised in that: rotating speed during centrifugation is
5000-8000 turns/min, product deionized water and absolute ethanol washing, and temperature during vacuum drying is 40-80 DEG C, when being dried
Between be 12-36h, the hydrochloric acid mass concentration being used be 37%, the h 2 so 4 concentration being used be 98%.
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