CN102315424B - Composite anode material for lithium sulfur battery, preparation method and application thereof - Google Patents
Composite anode material for lithium sulfur battery, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a high-performance sulfur and set-appearance conductive polymer composite anode material for the anode of a lithium sulfur battery and a preparation technique thereof, belonging to the field of chemical power supplies. The composite anode material for the lithium sulfur battery provided by the invention is a sulfur and conductive polymer nanotube composite anode material. The sulfur is dispersed and absorbed on the surface of the conductive polymer nanotube and in the conductive polymer nanotube to form a hollow fibrous structure. The invention uses high-conductivity polymers with good adsorbability to the sulfur and the reduced product thereof as a conductive phase in a sulfur electrode, uses a co-heating method and a liquid sulfur infiltration method to enable the polymers to be evenly combined with the sulfur to obtain a composite electrode material, and solves the problems that the sulfur electrode and the reduced product thereof in the lithium sulfur battery are apt to be dissolved in organic electrolytes, the battery circulation performance is poor because of the non-conductivity of the sulfur and the like. The sixtieth cycling capacity of the composite material is larger than 650mAh/g and the electrochemical cycling stability is good.
Description
Technical field
The present invention relates to a kind of composite anode material for lithium sulfur battery, especially relate to a kind of sulphur-polymer composites as lithium-sulphur cell positive electrode and preparation method thereof and application, belong to field of chemical power source.
Background technology
At present, along with development such as various multifunctional portable electronic products and electric motor car, energy storage fields, demand to the reversible secondary cell using is increasing, therefore the reversible secondary cell that exploitation has a high-energy-density becomes study hotspot, especially adopts lithium metal to cause especially people's extensive concern as the high-energy-density lithium battery of electrode.One of limiting factor that it is main is the application of height ratio capacity positive pole.Use sulphur is that the lithium-sulfur rechargeable battery of positive electrode has the advantage such as high-energy-density, abundant raw materials, wherein sulphur is that positive pole comprises: inorganic sulphide, organic disulfide, poly-organic disulfide, organic polysulfide, carbon-sulphur polymer, poly-thio-compounds and elemental sulfur.Wherein the specific discharge capacity of elemental sulfur is 1675mAh/g, be that in the positive electrode understood of current people, specific capacity is the highest, pollution-free, the low cost of elemental sulfur and nature reserves are abundant etc., and advantage becomes a rising class positive pole material of secondary lithium battery.But also there are two urgent problems in lithium-sulfur cell, the one, be insulator as the sulphur of electrode material, the problems such as the chemical property of sulphur in electrode is not good and utilance is low will be caused, so conventionally select one or more electronic conductors compound object that improves conductivity that reaches with it; Another many lithium sulfides that are discharge process produces are soluble in organic electrolyte, cause the active material of electrode to reduce gradually, and due to the principle of shuttling back and forth, the many lithium sulfides that dissolve can reach on the negative pole lithium sheet of battery through barrier film, the product electric conductivity such as lithium sulfide that generates is poor and do not dissolve, cause the corrosion of battery cathode and the increase of the internal resistance of cell, cause the cycle performance variation of battery, capacity is progressively decayed.Along with the understanding to these problems, people have carried out a series of research: C.du.Liang in the selection of conductive phase and the control of pattern, etal. (Chemistry ofMaterials 21 (2009) 4724-4730) use mesoporous carbon as conductive phase, sulphur is infiltrated to mesoporous carbon under heating condition and form a kind of compound, 50 reversible capacities of this compound reach 700mAh/g; B.Zhang, the conductive phase that et al. (Electrochimica Acta 54 (2009) 3708-3713) uses is acetylene black, 50 reversible capacities of the compound forming with sulphur under heating condition are 500mAh/g; L.X.Yuan, it is 650mAh/g that et al. (Journal ofPower Sources 189 (2009) 1141-1146) adopts multi-walled carbon nano-tubes and sulphur to form 60 reversible specific capacities of electrically conductive composite.Can find out, because the high conductivity of above-mentioned conductive phase and special pattern can limit the diffusion of many lithium sulfides, therefore the cycle performance of lithium-sulfur cell is greatly improved, but the synthesis technique complexity of mesoporous carbon and multi-walled carbon nano-tubes, cost is high, so be necessary to find new alternative electric conducting material.
Summary of the invention
The problem such as the circulating battery that the object of the invention is the non-conductive property of the soluble property in organic bath and sulphur itself for the sulphur utmost point and reduzate thereof in lithium-sulfur cell and cause is poor, provides a kind of composite anode material for lithium sulfur battery.
The present invention utilizes the conductivity of polymer, strong adsorption effect and specific nanotube-shaped pattern, prepares a kind of composite sulfur material containing conducting polymer, solves the problems referred to above.
A kind of composite anode material for lithium sulfur battery provided by the invention, is sulphur-conductive polymer nanometer pipe composite positive pole, and described sulphur content is loose to be adsorbed in the tube-surface and pipe of described conductive polymer nanometer pipe, forms the filamentary structure of hollow.
The external diameter of described hollow fiber structure is 100～200nm, and the internal diameter of described hollow fiber structure is 50～80nm.Preferably, described sulphur accounts for 15～56% of described composite positive pole total weight, is preferably 40～56%.
Preferably, described conducting polymer is selected from polypyrrole, poly-propylamine, polythiophene, polyacetylene or their derivative.
Conductive polymer nanometer pipe described in the present invention can be synthetic by selfdecomposition soft template method.The reaction mechanism of the method is: make a certain proportion of oxidant and methyl orange in the aqueous solution, first form fibrous complex compound, under the oxidation of oxidant, make the monomer of conducting polymer at complex compound fiber surface polymerization reaction take place, along with the carrying out of polymerization reaction, oxidant is reduced and causes the decomposition of complex compound fiber gradually, thereby leaves nanotube-shaped conducting polymer fibres.The method preparation technology is simple, easy to operate, employing cost of material is cheap, products therefrom is the controlled nanotube of size uniform.
Preferably, the preparation method of the conductive polymer nanometer pipe described in the present invention, comprise the following steps: in the methyl orange solution of the 0.004-0.006mol/L of 100ml, drip the variable valency metal chloride of 0.004-0.006mol, and then add the polymer monomer of 0.004-0.006mol, room temperature reaction 8-24 hour, collects product, obtains conductive polymer nanometer pipe.
Described oxidant is the chloride of variable valency metal, as FeCl
3, CrCl
3deng.
Sulphur-conductive polymer nanometer pipe composite positive pole of the present invention can be with hot method or liquid phase sulphur infiltration method are synthetic altogether.
Adopt and be total to hot legal system for sulphur-conductive polymer nanometer pipe composite positive pole; comprise the following steps: be (1～3) by mass ratio: 1 sublimed sulfur and conductive polymer nanometer pipe mix; under vacuum or protective atmosphere, in 150～250 DEG C of insulation 3～6h, obtain sulphur-conductive polymer nanometer pipe composite positive pole after naturally cooling to room temperature.
In above-mentioned hot method altogether, described is mortar mill or planetary type ball-milling by the mixed method of conducting polymer and sublimed sulfur.Described protective gas can be argon gas or nitrogen.
In above-mentioned hot method altogether, the lower sulphur of described heat treatment temperature (150～250 DEG C) is molten state, sulphur now has low viscosity and is easy to wetting conductive polymer nanometer pipe, and sulphur has larger volatilization under higher temperature, and sulphur steam can enter in the micropore of conductive polymer nanometer pipe substrate.Temperature retention time is 3-6 hour, can enter in the pipe of conducting base with the sulphur that ensures molten state.
Adopt liquid phase sulphur infiltration method to prepare sulphur-conductive polymer nanometer pipe composite positive pole, comprise the following steps:
(1) by complete sublimed sulfur melting, then cooling rapidly in air or water, then be dissolved in non-polar solven, after filtration, obtain the solution of sulfur content 8～12wt%;
(2) conductive polymer nanometer pipe is immersed in the solution of step 1 gained, stir after 10～30 minutes and leave standstill, after filtering, products therefrom is dried at 50～100 DEG C under vacuum or protective atmosphere, obtains sulphur-conductive polymer nanometer pipe composite positive pole.
In above-mentioned liquid phase sulphur infiltration method, also can by products therefrom again repeating step 2 obtain sulphur-conductive polymer nanometer pipe composite positive pole of required sulfur content.
In above-mentioned liquid phase sulphur infiltration method, described in air or water rapidly cooling object be the high-temperature-phase in order to keep sulphur.
In above-mentioned liquid phase sulphur infiltration method, described non-polar solven is mainly selected according to the similar principle that mixes, and is CS
2, CCl
4, toluene etc.
In the present invention, related heat treatment process can adopt under vacuum or protective atmosphere and carry out, and protective gas can be argon gas or nitrogen.
In above-mentioned hot method altogether and liquid phase sulphur infiltration method, described conductive polymer nanometer pipe and sublimed sulfur before use, need be dry respectively under vacuum condition.Described dry run can adopt under vacuum or protective atmosphere carries out, and protective gas can be argon gas or nitrogen.
The present invention adopts the feature of sulphur-conducting polymer composite anode material that said method obtains as follows:
(1) conducting polymer matrix is nanotube, its size uniform, and the transmission that the network being intertwined to form is electric charge provides more path;
(2) sulphur is all evenly distributed in by two kinds of diverse ways in the surface or pipe of conductive polymer nanometer pipe, and sulphur and conducting polymer matrix Contact are tight, improves the conductivity of composite material.
(3) content of sulphur in composite positive pole is controlled, and the capacity of composite positive pole is controlled
Conducting polymer is due to its loose appearance structure, sulphur is had to certain suction-operated, sulphur is attracted in the micropore of nanotube-shaped conducting polymer matrix, effectively limit sulphur or many lithium sulfides diffuse out electrode matrix, and increase the sulphur of insulator and contacting of conductive phase, more reflecting points that combine with lithium are provided.And the electron channel that the network configuration that conductive polymer nanometer pipe forms provides can contribute to improve the conductivity of electrode.
The present invention adopts the polymer that sulphur and reduzate thereof are had good adsorption and itself have high conductivity as the conductive phase in sulfur electrode, adopt altogether the hot method and sulphur infiltration method to make it with sulphur evenly in conjunction with obtaining combination electrode material, solved the non-conductive property of soluble property in organic bath of the sulphur utmost point in lithium-sulfur cell and reduzate thereof and sulphur itself and the problem such as the circulating battery that causes is poor.Material provided by the present invention can be used for using as positive electrode in lithium-sulfur cell, and the 60th circulation volume of this composite material is greater than 650mAh/g, and has good electrochemistry cyclical stability.
Brief description of the drawings
Fig. 1 is the TEM shape appearance figure of sulphur-Pt/Polypyrrole composite material in embodiment 2.
Fig. 2 is that the discharge capacity of gained composite electrode in bright sulfur electrode and embodiment is with the situation of change of cycle-index.
Embodiment
For further setting forth content of the present invention, substantive features and marked improvement, hereby enumerate following examples and be described in detail as follows, but be not limited only to embodiment.
The conducting polymer the present invention relates to is explanation as an example of polypyrrole and polyaniline example, and its preparation method is: the FeCl that adds 0.005mol in the methyl orange aqueous solution that is 0.005mol/L in 100ml concentration
3, electromagnetic agitation evenly rear formation is wadding fibrous, then adds 0.005mol pyrroles or aniline monomer, stirs 12 hours under room temperature; Product obtains polypyrrole pipe at 80 DEG C of vacuum dryings after alternately cleaning with deionized water and alcohol.
Comparative example 1
Sublimed sulfur powder and acetylene black and Pluronic F-127 (PEO) are made to slurry in the ratio of 5: 3: 2 in Acetonitrile, coat on aluminium foil and be dried, make thus electrode film.Taking metallic lithium foil as to electrode, Celgard company of U.S. polypropylene screen is barrier film, 1M LiCF
3sO
3/ TEGDME is electrolyte, in the voltage range of 1-3V, and 0.1mA/cm
2current density under discharge and recharge experiment.The experimental result of gained is as shown in table 1 below.As can be seen from the table, the capacity attenuation of bright sulfur electrode is very fast, and after the 60th circulation, reversible capacity, from initial value 698.1mAh/g, decays to 97.6mAh/g, and capacity attenuation rate reaches 86.1%.
Embodiment 1
First the vacuumize 10h at 50 DEG C by sulphur and polypyrrole respectively.Be to mix final vacuum at 2: 1 to be sealed in glass container in mass ratio by sulphur and polypyrrole, then under 150 DEG C of conditions, be incubated 4 hours, obtain sulfur content after naturally cooling and be sulphur-Pt/Polypyrrole composite material (SPT1) of 56%.Electrode preparation method and battery assembling, test condition are all with comparative example 1.Test result is in table 1.
Embodiment 2
Raw-material dry as embodiment 1.Be that after 1: 1 sulphur and polypyrrole mix, to obtain sulfur content by the method for embodiment 1 be sulphur-Pt/Polypyrrole composite material (SPT2) of 40% by mass ratio.Electrode preparation method and battery assembling, test condition are all with comparative example 1.Test result is in table 1.Data from table 1 can be found out, compare bright sulfur electrode, and the cycle performance of composite electrode has had large increase.
Embodiment 3
Raw-material dry as embodiment 1.Sulphur is 140 DEG C of complete meltings, cooling rapidly in air or water, then it is dissolved in to CS
2in, after filtration, obtain the filtrate of sulfur-bearing 10%.Appropriate polypyrrole nanotube is immersed to the CS of above sulphur
2solution, stirs after 10 minutes and to leave standstill 20 minutes, then the product vacuum drying at 50 DEG C after filtering is obtained to sulfur content and be sulphur-Pt/Polypyrrole composite material (SPI1) of 15%.Electrode preparation method and battery assembling, test condition are all with comparative example 1.Test result is in table 1.
Embodiment 4
Sulphur-the Pt/Polypyrrole composite material obtaining in appropriate embodiment 3 (SPI1) is immersed to the CS of sulfur-bearing 10% left and right
2solution, obtaining sulfur content by the method for embodiment 3 is sulphur-polypyrrole material (SPI2) of 24%.Electrode preparation method and battery assembling, test condition are all with comparative example 1.Test result is in table 1.
Embodiment 5
By the synthetic method of polypyrrole nanotube in embodiment, synthesize polyaniline nanotube taking aniline as monomer.Raw-material dry as embodiment 1.After the sulphur that is 1: 1 by mass ratio and polyaniline mix, obtaining sulfur content by the method for embodiment 1 is sulphur-polyaniline composite material (S-PAnl) of 40%.Electrode preparation method and battery assembling, test condition are all with comparative example 1.Test result is in table 1.
Embodiment 6
Press the CS of method configuration sulfur-bearing 10% left and right in embodiment 3
2solution.Then appropriate polyaniline nanotube is immersed in above solution, stir after 10 minutes and to leave standstill 20 minutes, then the product vacuum drying at 50 DEG C after filtering is obtained to sulfur content and be sulphur-polyaniline composite material (S-PAn2) of 15%.Electrode preparation method and battery assembling, test condition are all with comparative example 1.Test result is in table 1.
Embodiment 7
By the synthetic method of polypyrrole nanotube in embodiment, synthesize polyaniline nanotube taking aniline as monomer.Raw-material dry as embodiment 1.The sulphur that is 1: 1 by mass ratio and polyaniline mix final vacuum and are sealed in glass container, then under 250 DEG C of conditions, are incubated 3 hours, obtain sulfur content after naturally cooling and be sulphur-polyaniline composite material of 40%.Electrode preparation method and battery assembling, test condition are all with comparative example 1.Test result is substantially the same manner as Example 5.
Embodiment 8
By the synthetic method of polypyrrole nanotube in embodiment, synthesize polyaniline nanotube taking aniline as monomer.Raw-material dry as embodiment 1.The sulphur that is 3: 1 by mass ratio and polyaniline mix final vacuum and are sealed in glass container, then under 200 DEG C of conditions, are incubated 6 hours, obtain sulfur content after naturally cooling and be sulphur-polyaniline composite material of 50%.Electrode preparation method and battery assembling, test condition are all with comparative example 1.Test result is substantially the same manner as Example 5.
Table 1
Data listed from table 1 can be found out, are total to the standby composite positive pole of hot legal system, all have higher capability retention, are all greatly improved compared with the electrode material in comparative example.
Related polar solvent C in above-described embodiment
2s can be by CCl
4or toluene substitutes, gained composite material after testing, its result with use polar solvent C
2basic identical when S.
Above-described embodiment gained composite material, detects through TEM, and its structure is all hollow fiber, and its external diameter is 100～200nm, and internal diameter is 50～80nm.
Claims (6)
1. a composite anode material for lithium sulfur battery, is characterized in that, is sulphur-conductive polymer nanometer pipe composite positive pole, and described sulphur content is loose to be adsorbed in the tube-surface and pipe of described conductive polymer nanometer pipe, forms the filamentary structure of hollow; The external diameter of described hollow fiber structure is 100～200nm, and the internal diameter of described hollow fiber structure is 50～80nm; Described sulphur accounts for 15～56% of described composite positive pole total weight; Described conducting polymer is selected from polypyrrole, poly-propylamine, polythiophene, polyacetylene or their derivative; Described conductive polymer nanometer pipe is synthetic by selfdecomposition soft template method, comprise the following steps: in the methyl orange solution of the 0.004-0.006mol/L of every 100ml, drip the variable valency metal chloride of 0.004-0.006mol, and then add the polymer monomer of 0.004-0.006mol, room temperature reaction 8-24 hour, collect product, obtain conductive polymer nanometer pipe.
2. the preparation method of composite anode material for lithium sulfur battery as claimed in claim 1; for hot method altogether; comprise the following steps: be (1～3) by mass ratio: 1 sublimed sulfur and conductive polymer nanometer pipe mix; under vacuum or protective atmosphere, in 150～250 DEG C of insulation 3～6h, obtain sulphur-conductive polymer nanometer pipe composite positive pole after naturally cooling to room temperature.
3. the preparation method of composite anode material for lithium sulfur battery as claimed in claim 2, is characterized in that, described is mortar mill or planetary type ball-milling by the mixed method of conducting polymer and sublimed sulfur.
4. the preparation method of composite anode material for lithium sulfur battery as claimed in claim 1, is liquid phase sulphur infiltration method, comprises the following steps:
(1) by complete sublimed sulfur melting, then cooling rapidly in air or water, then be dissolved in non-polar solven, after filtration, obtain the solution of sulfur content 8～12wt%;
(2) conductive polymer nanometer pipe is immersed in the solution of step 1 gained, stir after 10～30 minutes and leave standstill, after filtering, products therefrom is dried under vacuum or protective atmosphere; Obtain sulphur-conductive polymer nanometer pipe composite positive pole.
5. the preparation method of composite anode material for lithium sulfur battery as claimed in claim 4, is characterized in that, described non-polar solven is selected from CS
2, CCl
4or toluene.
Composite anode material for lithium sulfur battery as claimed in claim 1 in lithium-sulfur cell as the application of positive electrode.
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| DE102010043400A1 (en) * | 2010-11-04 | 2012-05-10 | Robert Bosch Gmbh | Cathode material for lithium-sulfur cell |
| CN103247776B (en) * | 2012-02-07 | 2016-02-17 | 苏州宝时得电动工具有限公司 | The preparation method of electrode composite material |
| CN103259000A (en) * | 2013-04-25 | 2013-08-21 | 浙江师范大学 | Polypyrrole hollow microsphere/ sulfur composite material as well as preparation method and application thereof |
| CN104577050B (en) * | 2013-10-17 | 2017-07-07 | 清华大学 | Active material of lithium ion battery electrode and preparation method thereof |
| CN104157839A (en) * | 2014-08-22 | 2014-11-19 | 南京中储新能源有限公司 | Polyaniline nanotube-sulfur composite material and secondary battery |
| CN104157829B (en) * | 2014-08-22 | 2016-01-20 | 南京中储新能源有限公司 | A kind of secondary aluminium cell comprising sulphur carbon composite based on polyaniline nanotube |
| CN104201336A (en) * | 2014-09-10 | 2014-12-10 | 南京中储新能源有限公司 | Polyaniline nano array-based sulfur composite material, preparation method thereof and secondary battery |
| CN104835966B (en) * | 2015-04-30 | 2018-08-14 | 奇瑞汽车股份有限公司 | A kind of lithium sulfur battery anode material and preparation method thereof |
| CN105762341A (en) * | 2016-03-04 | 2016-07-13 | 河源广工大协同创新研究院 | Preparation method of nano-sulfur/annular polypyrrole composite positive electrode material |
| CN105958033B (en) * | 2016-07-04 | 2018-07-06 | 吉林大学 | A kind of preparation method and application of non-graphitized carbon nanotube/sulphur composite material |
| CN106299317A (en) * | 2016-11-03 | 2017-01-04 | 深圳市沃特玛电池有限公司 | A kind of lithium sulfur battery anode material and preparation method thereof, lithium-sulfur cell |
| CN107275580B (en) * | 2017-07-10 | 2020-05-22 | 华南理工大学 | Lithium-sulfur battery positive electrode material with long cycle life and high specific capacity, lithium-sulfur battery positive electrode and preparation of lithium-sulfur battery positive electrode |
| CN109256554B (en) * | 2018-09-28 | 2020-08-28 | 河南科技学院 | Vulcanized polymer composite material and preparation method and application thereof |
| CN109616647B (en) * | 2018-12-10 | 2021-09-28 | 安徽师范大学 | Three-dimensional ordered porous hydrogel-loaded sulfur particle composite material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
| CN109802105B (en) * | 2018-12-24 | 2021-12-28 | 肇庆市华师大光电产业研究院 | Polyaniline nanotube-packaged metal nanowire array/sulfur composite material, controllable preparation method and application |
| CN112542579B (en) * | 2020-12-24 | 2021-09-21 | 太原理工大学 | Conductive Janus film, preparation method and application of conductive Janus film in preparation of lithium-sulfur battery anode |
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