CN104766967A - Preparation method of S/C composite material used in positive pole of Li-S battery - Google Patents
Preparation method of S/C composite material used in positive pole of Li-S battery Download PDFInfo
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- H—ELECTRICITY
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Abstract
The invention discloses a preparation method of an S/C composite material used in a positive pole of a Li-S battery. The S/C composite material is formed by compositing a carbon carrier and elemental sulfur. The preparation method includes following steps: (A) pre-treating the carbon carrier with an acid; and (B) supporting the elemental sulfur onto the carbon carrier as a carrier at a high temperature to obtain the S/C composite material. In the preparation method, by means of electronegativity of oxygen-containing groups (such as a carboxyl group, a carbonyl group, a hydroxyl group and the like) being rich in the carbon carrier pre-treated by the acid and a large specific surface area, effective immobilization of a sulfur active substance is achieved, thereby more effectively inhibiting loss of the active substances during charging/discharging of a positive pole material. The circulation stability and rate capability of an electrode can be greatly improved, thereby obtaining the high-performance S/C composite positive pole material.
Description
Technical field
The present invention relates to a kind of lithium sulfur battery anode material, particularly relate to the preparation method of a kind of lithium-sulphur cell positive electrode sulphur/carbon composite.
Background technology
Day by day commercial lithium rechargeable battery is limited to theoretical capacity, cannot significantly improve its energy density further, and fuel cell is yet more difficult practical at short notice, and the technology grasped at present far can not meet the demand of development.Therefore, in a hurry need to research and develop the mechanism of new electrochemical power sources with features such as more high-energy-density, more long circulation life, low cost and environmental friendliness.
Take lithium metal as negative pole, elemental sulfur is that the lithium-sulfur rechargeable battery (abbreviation lithium-sulfur cell) of positive active material is paid close attention to widely because the advantages such as its theoretical capacity is high, raw material sources is wide, cheap and environmentally friendly receive, and is considered to the candidate of lithium-ion battery system most potentiality of future generation.But, this dissolving of polysulfide produced in discharge process of sulfur electrode and the effect of shuttling back and forth caused thus, directly results in that active material utilization reduces, the problem of electrode cycle stability and high-rate charge-discharge capability difference, the requirement of people can't be met at present, constrain the practical application of lithium-sulfur cell.
Make a general survey of the development of lithium-sulfur cell in recent years both at home and abroad, its research mainly concentrates on the composite positive pole aspect preparing sulphur.Wherein, conventional sulfur-donor is the material with carbon element that conductivity is good, have graded porous structure, as carbon nano-tube, Graphene, mesoporous carbon, carbon black etc., and conducting polymer is as polypyrrole, polyaniline, polythiophene etc., with the sulfenyl composite material that these conductive materials are prepared for carrier and elemental sulfur compound, active material elemental sulfur can be filled because carrier material has abundant pore structure, the high-specific surface area simultaneously had has certain suction-operated to the polysulfide after electric discharge, prevent the loss of active material, thus improve the cycle performance of battery.
But the cycle performance of sulfur-based composite anode material prepared by said method still can not close people's satisfaction.Recently, the people such as Song (J.Mater.Chem.A, 2014, DOI:10.1039/c4ta03625e) propose one more effectively to improve one's methods, the core concept of the method adds lipoic acid in the electrolytic solution, utilize the chemistry of this additive in lithium-sulfur cell first discharge process and electrochemical polymerization, the electronegative protective layer of one deck is formed on the surface at sulphur/carbon black composite positive pole, due to many sulphions band homocharge that this protective layer and sulphur are formed in discharge process, utilize jack per line to repel and stop many sulphions to leave positive electrode surface, effectively prevent the loss of polysulfide.But, simultaneously the fatal defects of the method can generate hydrogen in the sad process being polymerized of additive sulfur, therefore, brings very troublesome inflatable problem in battery charge and discharge process.
The present invention is intended to by the improvement to preparation method, to improve the performance of sulfenyl composite electrode.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of lithium-sulphur cell positive electrode sulphur/carbon composite, the material with carbon element acid such as mesoporous carbon are carried out preliminary treatment by described method, be carrier load elemental sulfur at relatively high temperatures with it, the method is extremely easy but very effective, sulphur/the carbon composite anode material of preparation can suppress the loss of positive electrode active material in charge and discharge process effectively, has excellent cycle performance and high rate performance.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A preparation method for lithium-sulphur cell positive electrode sulphur/carbon composite, is characterized in that, comprise the following steps:
(1) acid treatment of carbon carrier: added by carbon carrier in concentrated acid, reacts at 20 ~ 80 DEG C, and suction filtration after cooling, is washed with water to neutrality, vacuumize;
(2) preparation of sulphur/carbon composite: after the carbon carrier after the acid treatment obtain step (1) and elemental sulfur mixed grinding, heat treatment at 160 ~ 250 DEG C in inert gas atmosphere, obtains described sulphur/carbon composite.
Lithium-sulfur battery composite anode material of the present invention is composited by carbon carrier and elemental sulfur, first preliminary treatment is carried out in carbon carrier acid during preparation, then with it for carrier, adopt load elemental sulfur under higher temperature.The elecrtonegativity of the oxy radical (as groups such as carboxyl, carbonyl, hydroxyls) that after the method utilizes low-kappa number, carbon support material is rich in and large specific area realize effectively fixing sulphur active material, more effectively suppress the loss of positive electrode active material in charge and discharge process, thus obtain high performance sulphur/carbon composite anode material.
In step (1), described carbon carrier comprises carbon black, mesoporous carbon, carbon nano-tube, Graphene etc.; Also can be the various carbon support material doped with elements such as N, P.
In step (1), the preferred red fuming nitric acid (RFNA) of described concentrated acid, the concentrated sulfuric acid or their mixture; When described concentrated acid is nitration mixture, the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 1: 3 ~ 3: 1.
In step (1), the described acid treatment reaction time is preferably 2 ~ 8h.Vacuumize temperature is 60 ~ 120 DEG C.
In step (2), the quality proportioning of the carbon carrier after described acid treatment and sulphur is 4: 1 ~ 1: 4.
In step (2), described heat treatment time is preferably 8 ~ 24h.
Described inert gas atmosphere preferred nitrogen or argon gas.
The present invention has following useful technique effect:
(1) material with carbon element such as the present invention's mesoporous carbon of adopting low-kappa number to cross is carrier, and these carriers have classifying porous and large specific area, thus can load elemental sulfur effectively.What is more important, owing to having abundant oxy radical through acid-treated carbon support material surface, as carboxyl, carbonyl, hydroxyl etc., make carrier surface electronegative, many sulphions band homocharge of the easy loss that this and composite positive pole are formed in battery charge and discharge process, Coulomb repulsion makes many sulphions be effectively fixed on positive pole, thus sulphur active material can be fixed, restrained effectively the loss of active material in electrode process, improve cyclical stability and the high rate performance of electrode, obtain high-performance sulphur/carbon composite anode material.
(2) the present invention adopts the sulfurizing of higher temperatures method, is carried on by sulphur active material in the carbon support material that low-kappa number crosses, overcomes sulphur problem pockety in sulphur/carbon composite.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not limited with embodiment, but is limited by claim.
Accompanying drawing explanation
Fig. 1 is that the mesoporous carbon (a) that the obtained low-kappa number of embodiment 1 is crossed is schemed with the Zeta of undressed mesoporous carbon (b).
Fig. 2 be the obtained low-kappa number of embodiment 1 cross mesoporous carbon, undressed mesoporous carbon and they respectively with the infrared spectrogram of the composite material of sulphur.
Fig. 3 is the X ray diffracting spectrum of mesoporous carbon, sulphur/mesoporous carbon composite material A-MC@S and the high-temperature process sulphur that the obtained low-kappa number of embodiment 1 is crossed.
Fig. 4 is the transmission electron microscope photo of sulphur/mesoporous carbon composite material A-MC@S that embodiment 1 obtains.
Fig. 5 is the cycle performance figure of sulphur/mesoporous carbon composite material A-MC@S that embodiment 1 obtains.
Fig. 6 is the high rate performance figure of sulphur/mesoporous carbon composite material A-MC@S that embodiment 1 obtains.
Embodiment
Below by specific embodiment, technical solutions according to the invention are further described in detail, but are necessary to point out that following examples are only for the description to summary of the invention, do not form limiting the scope of the invention.
Embodiment 1
A preparation method for lithium-sulphur cell positive electrode sulphur/carbon composite, step is as follows:
(1) acid treatment of mesoporous carbon: add in round-bottomed flask by the mesoporous carbon of 0.25g, then adds the 15mL concentrated sulfuric acid (18M), 5mL red fuming nitric acid (RFNA) (16M) successively.Stirring reaction 5h at 50 DEG C, after cooling, suction filtration, is washed with water to neutrality, and vacuumize at 80 DEG C, gained sample is designated as A-MC.
(2) preparation of sulphur/mesoporous carbon composite material: after the A-MC obtain step (1) and sulphur are the ratio mixed grinding of 3: 2 with mass ratio, put into the airtight reactor being full of the 10mL of argon gas, with 180 DEG C of heat treatment 12h in Muffle furnace, obtain described sulphur/mesoporous carbon composite material, be designated as A-MC@S.
In contrast, directly adopt mesoporous carbon (being designated as MC) to prepare sulphur/mesoporous carbon composite material according to the method identical with step (2), be designated as MC@S.
Fig. 1 is the A-MC of the present embodiment synthesis and the Zeta figure of undressed mesoporous carbon.Result shows, and the Zeta potential of A-MC is low to moderate-38.7mV, and the Zeta potential of undressed mesoporous carbon only has-1.94mV.A-MC, with a large amount of negative electrical charges, makes A-MC show good dispersion in water.
Fig. 2 is the A-MC of the present embodiment synthesis, undressed mesoporous carbon and their infrared spectrograms of composite material of being formed with sulphur respectively, is MC, MC@S, A-MC@S and A-MC from top to bottom successively.Can find out, the A-MC sample after acid treatment, at 1724cm
-1and 1585cm
-1there is the characteristic peak of carbonyl (-C=O), carboxyl (-COOH) respectively in place.It is oxidized that this illustrates that acid treatment makes mesoporous carbon be in the carbon of isoreactivity position, edge, and the existence of these oxy radicals is the electronegative reason places of mesoporous carbon.
Fig. 3 is the X ray diffracting spectrum of A-MC and the A-MC@S of the present embodiment synthesis, and a, b, c are A-MC, S and A-MC@S respectively.As seen from the figure, A-MC is unbodied state; After 180 DEG C of process, simple sulphur still remains orthogonal crystalline phase, and the sulphur crystalline phase in A-MC@S becomes monoclinic sulphur (JCPDS65-1101) from original rhombic sulfur (JCPDS 08-0247), illustrate that sulphur is successfully adsorbed by A-MC.
Fig. 4 is the transmission electron microscope photo of the A-MC@S of the present embodiment synthesis.As seen from the figure, sulphur is evenly distributed in mesoporous carbon, and beyond mesoporous carbon, do not have unnecessary sulphur, illustrates under the heat treatment temperature of the present embodiment, and sulphur enters in the micropore of mesoporous carbon/mesoporous.
Fig. 5 is the charge-discharge performance figure of the A-MC@S of the present embodiment synthesis.As seen from the figure, through 50 circulations, the specific discharge capacity of A-MC@S, still up to 486mAh/g, far above the specific discharge capacity (108mAh/g) of MC@S and bright sulfur, shows superior cycle performance and higher specific capacity.
Fig. 6 is the high rate performance figure of the A-MC@S of the present embodiment synthesis.As seen from the figure, the high rate performance of A-MC@S is much better than the high rate performance of bright sulfur.
Visible, through acid-treated mesoporous carbon, not only there is graded porous structure and large specific area, can load elemental sulfur effectively.What is more important, owing to having abundant oxy radical through acid-treated mesoporous carbon surface, make mesoporous carbon surface band negative electrical charge, many sulphions band homocharge of the easy loss that this and composite positive pole are formed in battery charge and discharge process, Coulomb repulsion makes many sulphions be effectively fixed on positive pole, thus sulphur active material can be fixed, restrained effectively the loss of active material in electrode process, improve cyclical stability and the high rate performance of electrode, thus obtain high performance sulphur/carbon composite anode material.
Embodiment 2
A preparation method for lithium-sulphur cell positive electrode sulphur/carbon composite, step is as follows:
(1) acid treatment of carbon black: add in round-bottomed flask by the carbon black of 0.25g, then adds the 15mL concentrated sulfuric acid, 5mL red fuming nitric acid (RFNA) successively.Stirring reaction 5h at 50 DEG C, after cooling, suction filtration, is washed with water to neutrality, and vacuumize at 80 DEG C.
(2) preparation of sulphur/carbon black composite material: after the carbon black obtain step (1) and sulphur are the ratio mixed grinding of 3: 2 with mass ratio, put into the airtight reactor being full of the 10mL of argon gas, with 180 DEG C of heat treatment 12h in Muffle furnace, obtain described sulphur/carbon black composite material.
Embodiment 1 is similar to prepared sulphur/carbon black composite material and carries out dependence test and sign, conclusion and embodiment 1 basic simlarity.
Embodiment 3
A preparation method for lithium-sulphur cell positive electrode sulphur/carbon composite, step is as follows:
(1) acid treatment of carbon nano-tube: add in round-bottomed flask by the carbon nano-tube of 0.25g, then adds the 15mL concentrated sulfuric acid, 5mL red fuming nitric acid (RFNA) successively.Stirring reaction 5h at 50 DEG C, after cooling, suction filtration, is washed with water to neutrality, and vacuumize at 80 DEG C.
(2) preparation of sulphur/carbon nano tube compound material: after the carbon nano-tube obtain step (1) and sulphur are the ratio mixed grinding of 3: 2 with mass ratio, put into the airtight reactor being full of the 10mL of argon gas, with 180 DEG C of heat treatment 12h in Muffle furnace, obtain described sulphur/carbon nano tube compound material.
Embodiment 1 is similar to prepared sulphur/carbon nano tube compound material and carries out dependence test and sign, conclusion and embodiment 1 basic simlarity.
Embodiment 4
A preparation method for lithium-sulphur cell positive electrode sulphur/carbon composite, step is as follows:
(1) acid treatment of mesoporous carbon: add in round-bottomed flask by the mesoporous carbon of 0.25g, then adds the 15mL concentrated sulfuric acid, 5mL red fuming nitric acid (RFNA) successively.Stirring reaction 3h at 65 DEG C, after cooling, suction filtration, washing is to neutral, and vacuumize at 80 DEG C.
(2) preparation of sulphur/mesoporous carbon composite material: after the acid-treated mesoporous carbon obtain step (1) and sulphur are the ratio mixed grinding of 4: 1 with mass ratio, put into the airtight reactor being full of the 10mL of argon gas, with 180 DEG C of heat treatment 4h in Muffle furnace, obtain described sulphur/mesoporous carbon composite material.
Embodiment 1 is similar to prepared sulphur/mesoporous carbon composite material and carries out dependence test and sign, conclusion and embodiment 1 basic simlarity.
Embodiment 5
A preparation method for lithium-sulphur cell positive electrode sulphur/carbon composite, step is as follows:
(1) acidifying of mesoporous carbon: add in round-bottomed flask by the mesoporous carbon of 0.25g, then adds the 15mL concentrated sulfuric acid, 5mL red fuming nitric acid (RFNA) successively.Stirring reaction 8h at 80 DEG C, after cooling, suction filtration, washing is to neutral, and vacuumize at 80 DEG C.
(2) preparation of sulphur/mesoporous carbon composite material: after the acid-treated mesoporous carbon obtain step (1) and sulphur are the ratio mixed grinding of 1: 2 with mass ratio, put into the airtight reactor being full of the 10mL of argon gas, with 180 DEG C of heat treatment 8h in Muffle furnace, obtain described sulphur/mesoporous carbon composite material.
Embodiment 1 is similar to prepared sulphur/mesoporous carbon composite material and carries out dependence test and sign, conclusion and embodiment 1 basic simlarity.
Embodiment 6
A preparation method for lithium-sulphur cell positive electrode sulphur/carbon composite, step is as follows:
(1) acidifying of mesoporous carbon: add in round-bottomed flask by the mesoporous carbon of 0.25g, then adds the 15mL concentrated sulfuric acid, 5mL red fuming nitric acid (RFNA) successively.Stirring reaction 5h at 50 DEG C, after cooling, suction filtration, washing is to neutral, and vacuumize at 80 DEG C;
(2) preparation of sulphur/mesoporous carbon composite material: after the acidifying mesoporous carbon obtain step (1) and sulphur are the ratio mixed grinding of 1: 4 with mass ratio, put into the airtight reactor being full of the 10mL of argon gas, with 180 DEG C of heat treatment 24h in Muffle furnace, obtain described sulphur/mesoporous carbon composite material.
Embodiment 1 is similar to prepared sulphur/mesoporous carbon composite material and carries out dependence test and sign, conclusion and embodiment 1 basic simlarity.
Embodiment 7
A preparation method for lithium-sulphur cell positive electrode sulphur/carbon composite, step is as follows:
(1) acidifying of mesoporous carbon: add in round-bottomed flask by the mesoporous carbon of 0.25g, then adds the 5mL concentrated sulfuric acid, 15mL red fuming nitric acid (RFNA) successively.Stirring reaction 5h at 50 DEG C, after cooling, suction filtration, washing is to neutral, and vacuumize at 80 DEG C;
(2) preparation of sulphur/mesoporous carbon composite material: after the acidifying mesoporous carbon obtain step (1) and sulphur are the ratio mixed grinding of 2: 3 with mass ratio, put into the airtight reactor being full of the 10mL of argon gas, with 180 DEG C of heat treatment 10h in Muffle furnace, obtain described sulphur/mesoporous carbon composite material.
Embodiment 1 is similar to prepared sulphur/mesoporous carbon composite material and carries out dependence test and sign, conclusion and embodiment 1 basic simlarity.
Claims (7)
1. a preparation method for lithium-sulphur cell positive electrode sulphur/carbon composite, is characterized in that, comprise the following steps:
(1) acid treatment of carbon carrier: added by carbon carrier in concentrated acid, reacts at 20 ~ 80 DEG C, and suction filtration after cooling, is washed with water to neutrality, vacuumize;
(2) preparation of sulphur/carbon composite: after the carbon carrier after the acid treatment obtain step (1) and elemental sulfur mixed grinding, heat treatment at 160 ~ 250 DEG C in inert gas atmosphere, obtains described sulphur/carbon composite.
2. the preparation method of lithium-sulphur cell positive electrode sulphur/carbon composite according to claim 1, it is characterized in that: in step (1), described carbon carrier is carbon black, mesoporous carbon, carbon nano-tube or Graphene; Or the carbon black of N or P element doping, mesoporous carbon, carbon nano-tube or Graphene.
3. the preparation method of lithium-sulphur cell positive electrode sulphur/carbon composite according to claim 1, is characterized in that: in step (1), described concentrated acid is red fuming nitric acid (RFNA), the concentrated sulfuric acid or their mixture; When described concentrated acid is nitration mixture, the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 1:3 ~ 3:1.
4. the preparation method of lithium-sulphur cell positive electrode sulphur/carbon composite according to claim 1, it is characterized in that: in step (1), the described reaction time is 2 ~ 8h.
5. the preparation method of lithium-sulphur cell positive electrode sulphur/carbon composite according to claim 1, it is characterized in that: in step (2), the carbon carrier after described acid treatment and the mass ratio of sulphur are 4:1 ~ 1:4.
6. the preparation method of lithium-sulphur cell positive electrode sulphur/carbon composite according to claim 1, it is characterized in that: in step (2), described heat treatment time is 8 ~ 24h.
7. the preparation method of lithium-sulphur cell positive electrode sulphur/carbon composite according to claim 1, is characterized in that: described inert gas atmosphere is nitrogen or argon gas.
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| CN105374998A (en) * | 2015-10-16 | 2016-03-02 | 广东烛光新能源科技有限公司 | Sulfur-containing electrode material, lithium sulfur battery containing electrode material and preparation method of sulfur-containing electrode material |
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| CN107706378A (en) * | 2017-09-26 | 2018-02-16 | 西南大学 | The preparation method of the porous lithium sulfur battery anode material of high-performance based on rich carbon/oxygen functional group and application |
| CN111065600A (en) * | 2017-10-30 | 2020-04-24 | 株式会社Lg化学 | Sulfur-carbon composite material and preparation method thereof |
| US20200152971A1 (en) * | 2017-10-30 | 2020-05-14 | Lg Chem, Ltd. | Sulfur-carbon composite and method for preparing same |
| US11611066B2 (en) * | 2017-10-30 | 2023-03-21 | Lg Energy Solution, Ltd. | Sulfur-carbon composite and method for preparing same |
| CN110867563A (en) * | 2018-08-28 | 2020-03-06 | 南京理工大学 | Preparation method of bamboo-shaped graphene tube/sulfur composite material |
| CN112662204A (en) * | 2020-12-23 | 2021-04-16 | 哈尔滨工业大学 | Preparation method of porous/hollow-like carbon black material for lithium-sulfur battery |
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Application publication date: 20150708 |