CN103647104B - Lithium-sulfur battery - Google Patents

Lithium-sulfur battery Download PDF

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Publication number
CN103647104B
CN103647104B CN201310698877.8A CN201310698877A CN103647104B CN 103647104 B CN103647104 B CN 103647104B CN 201310698877 A CN201310698877 A CN 201310698877A CN 103647104 B CN103647104 B CN 103647104B
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battery
sulfur
lithium
barrier layer
positive pole
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CN103647104A (en
Inventor
温兆银
马国强
靳俊
张高校
王清松
吴相伟
张敬超
吴梅芬
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Jiangsu Zhongke Zhaoneng New Energy Technology Co., Ltd
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Shanghai Institute of Ceramics of CAS
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a lithium-sulfur battery. The lithium-sulfur battery comprises a sulfur positive electrode, a diaphragm, electrolyte and a metal lithium negative electrode, wherein a barrier layer which is formed by a conductive macromolecular nano material is arranged between the sulfur positive electrode and the diaphragm, and the thickness of the barrier layer is 5nm to 10 micrometers. Proved by an experiment, the primary discharging specific capacity of the lithium-sulfur battery can reach 520mAh/g under the 2C multiplying power, the discharging specific capacity after the battery is used for 200 weeks still can reach 528.1mAh/g, the capacity retention rate is more than 65 percent after the battery is circularly discharged for 60 times, the cycling performance and the multiplying power performance are good, and the application value is remarkable.

Description

A kind of lithium-sulfur cell
Technical field
The present invention relates to a kind of lithium-sulfur cell, belong to technical field of electrochemistry.
Background technology
With social development, the portable type electronic product such as mobile phone, portable computer, electric motor car, digital camera, i-pad It is flooded with the life of people.Wherein lithium battery, as main energy storage device, occupies leading position in mini-plant, but It is, the raising portable life being required with people that traditional lithium battery can not meet human wants.Thus, have The lithium battery of future generation of high specific energy, high security, high service life and low cost is sent to great expectations.
Positive pole is the key improving battery specific energy.Sulfur is just having theoretical specific capacity and the 2600wh/kg of 1675mah/g Energy density, be ten times of commercial transition metal oxide positive pole theoretical specific capacity and specific energy at present, and sulfur be in nature Rich content, cheap, environmentally safe close friend in boundary, therefore sulfur positive pole are just becoming most promising lithium battery One of pole material.
Although sulfur is just having plurality of advantages, active material utilization is low, cycle performance is poor, coulombic efficiency is low lacks Fall into become and limit its wide variety of key factor.The low conductivity of wherein sulfur is low mainly former of its active material utilization Cause.Meanwhile, in discharge process, the many lithium sulfides of cell reaction intermediate product can be dissolved in ethers electrolyte, afterwards many sulfurations Lithium migrates in the electrolytic solution, penetrates barrier film and reaches cathode of lithium and react, and generates simple lithium sulfide that is insoluble and insulating (li2S or li2s2), this side reaction greatly reduces cell active materials utilization rate, then, in battery charging process In, the simple lithium sulfide of a part can be reduced into many lithium sulfides by lithium and is dissolved in electrolyte again and move to anode, and now Oxidation reaction between many lithium sulfides and lithium also occurs simultaneously, and this process is referred to as the effect that shuttles.Simultaneously as simple vulcanize Lithium insolubility in the electrolytic solution, in turn results in the decay of battery capacity, and therefore, shuttle effect is also that coulombic efficiency is low, electric The main cause of pond cycle performance difference.
Researchers adopt distinct methods to reduce the shuttle effect in battery charge and discharge process, and then improve cell performance Energy.By using various material with carbon elements, such as using CNT, Graphene, mesoporous carbon storage sulfur, sulfur being limited in the hole of material with carbon element Limit the dissolving of many lithium sulfides in road or using the high specific surface area of material with carbon element, be beneficial to suppression shuttle effect and improve battery Performance;Using conducting polymers such as polypyrrole, polyaniline, polythiophenes as the memory bank of sulfur, many lithium sulfides can not only be limited Dissolving, the activity of conducting polymer itself also can improve the performance of battery;Add lino in electrolyte3, this additive can promote Enter the generation of cathode of lithium surface passivated membrane, stop the directly contact of many lithium sulfides and cathode of lithium in electrolyte, and then improve battery Performance;Meanwhile, using nano-oxide as adsorbent, can substantially adsorb many lithium sulfides, and then reduce shuttle effect to electricity The impact of pond performance.
Above-mentioned measure is all to set about inside cell electrode structure, though shuttle effect can be reduced to a certain extent to battery The impact of performance, but, used material is prepared complicated, relatively costly, is not easy to large-scale production;And changing with regard to electrolyte Kind then be only capable of improve battery coulombic efficiency, but cannot be avoided the dissolving in the electrolytic solution of many lithium sulfides, therefore to circulating battery Performance improvement is little.
Content of the invention
For the problems referred to above existing for prior art, the present invention is intended to provide one kind not only can reduce shuttle effect pair The impact of battery performance, and the lithium-sulfur cell of good circulation performance and high rate performance can be had.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of lithium-sulfur cell, including sulfur positive pole, barrier film, electrolyte and lithium anode it is characterised in that: sulfur positive pole with It is provided with the barrier layer being formed by conducting polymer nano material, the thickness on described barrier layer is 5nm~10 μm between barrier film.
As a kind of preferred version, the thickness on described barrier layer is 50nm~5 μm.
As a kind of preferred version, described conducting polymer nano material is nanofiber, nanotube or nano thin-film.
As further preferred scheme, described conducting polymer select polypyrrole, polyaniline, polyacrylonitrile, polythiophene, Polyacetylene or poly- 3,4- ethylenedioxy thiophene.
Oxide impregnation method, coprecipitation, electrochemical deposition method, chemical vapour deposition technique, physics can be passed through in described barrier layer The known technologies such as infusion process, physical vaporous deposition, plasma spraying method, plasma sputtering method, double-deck the tape casting are integrated in group Become the surface of the sulfur carbon composite layer of sulfur positive pole it is recommended that its growth in situ is made in the sulfur of composition sulfur positive pole using oxide impregnation method The surface of carbon composite layer.
Described oxide impregnation method includes operating as follows:
A) first sulfur positive pole is placed in the conducting polymer aqueous solution of 0.05~2mol/l and soaks 5~15 seconds, then take out It is placed in the aqueous oxidizing agent solution of 0.05~4mol/l and soak 5~15 seconds again;Circulate operation 1~10 time;
B) the sulfur positive pole after processing is carried out, is dried;
C) remove the barrier layer being grown in the collection liquid surface forming sulfur positive pole.
Described oxidant is preferably ferric chloride or Ammonium persulfate..
Described barrier layer can also be manufactured separately by following methods:
I) conducting polymer nano material is scattered in solvent, makes the dispersion liquid that formation concentration is 0.2~2g/l;
Ii) dispersion liquid of preparation is carried out with sucking filtration, washing, is dried.
Described solvent includes water, ethanol, acetone, chloroform, at least one in oxolane.
The present invention sets about in itself from battery structure, arranges one layer of barrier layer between anode and barrier film, effectively hinders Stop the dissolving in the electrolytic solution of many lithium sulfides and migration has occurred corruption to negative pole with it is therefore prevented that many lithium sulfides penetrate barrier film and migrate Erosion reaction, and then reduce the impact to battery performance for the shuttle effect;And the presence on barrier layer is also not significantly affected by battery The migration of internal electronics and ion, it is also possible to improve the wettability of electrode and electrolyte liquor, improves active material utilization, can simultaneously Enough directly contacts that can stop positive pole and negative pole when battery diaphragm ruptures, play protective action, improve battery security.
In the present invention, the presence one side on barrier layer can stop lithium-sulfur cell electric discharge intermediate product dissolving in the electrolytic solution And migration, meanwhile, weak chemical bond that conducting polymer and many lithium sulfides and sulfur are formed can the many lithium sulfides of active adsorption, stop it Dissolving in the electrolytic solution and migration, and then prevent many lithium sulfides from migrating to negative pole through barrier film and corrosion reaction occurs, and then Improve cycle performance of battery;Further, since the conductance ability of conducting polymer itself, loose porous barrier layer will not stop electricity The solution contact with electrode for the liquid, thus the presence on barrier layer will not significantly reduce the internal resistance of cell, increase electrochemical reaction potential barrier;Phase Instead, because it is more preferable to the wettability of electrolyte, the presence on barrier layer can reduce cell interface resistance on the contrary, is conducive to improving electricity Pole material ions electrical conductivity.
It is demonstrated experimentally that lithium-sulfur cell provided by the present invention, under 2c multiplying power, first discharge specific capacity is up to 520mah/ G, using the specific discharge capacity after 200 weeks still up to 528.1mah/g, and the capability retention circulating after electric discharge 60 times surpasses Cross 65%, have good cycle performance and high rate performance, there is significance using value.
Brief description
Fig. 1 be embodiment 2 prepared by the cyclic voltammetry curve (cv curve) of lithium-sulfur cell and this battery in different cycles Discharge curve;
Fig. 2 is the circulation of embodiment 2 gained battery (setting barrier layer) and comparative example 1 gained battery (being not provided with barrier layer) Performance comparision;Wherein: a curve represents embodiment 2 gained battery, b curve represents comparative example 1 gained battery.
Fig. 3 compares for embodiment 2 gained battery (setting barrier layer) cycle performance under different discharge-rates;Wherein: a Curve represents 1c multiplying power, and b curve represents 2c multiplying power.
The surface topography map of sulfur positive pole after embodiment 4 immersion treatment for the Fig. 4.
The shape appearance figure (sem photo) of the polypyrrole nanotube that Fig. 5 is obtained by embodiment 5.
The shape appearance figure (tem photo) of the polypyrrole nano fiber that Fig. 6 is obtained by embodiment 6;
Fig. 7 be embodiment 5(using polypyrrole nanotube sucking filtration film forming as barrier layer) and embodiment 6(with polypyrrole nanometer Fiber sucking filtration film forming is as barrier layer) and comparative example 2(be not provided with barrier layer) cycle performance of gained battery compares;Wherein: a is bent Line represents embodiment 5 gained battery, and b curve represents embodiment 6 gained battery;C represents comparative example 2 gained battery.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than restriction the scope of the present invention.
Comparative example 1
After the mass ratio that cmk-8 mesoporous carbon and sulfur are pressed 1:2 is mix homogeneously, using glass capsulation, it is placed in and adds at 300 DEG C Hot 4h, so that s can fully penetrate in the duct of mesoporous carbon, obtains sulfur carbon composite;By the sulfur obtaining carbon composite, Cmc(hydroxymethyl cellulose)+sbr(butadiene-styrene rubber), acetylene black presses the mass ratio of 8:1:1 uniform stirring is obtained slurry in aqueous Material, coats on aluminium foil and is dried, thus make electrode film;The electrode film obtaining is cut into the directly circle for 14mm Piece, obtains final product sulfur positive pole;With lithium metal as negative pole, as barrier film, electrolyte is the litfsi(bis- (trifluoro of 1mol/l to celgard film Pyrovinic acid) imine lithium) dol(1,3 dioxolanes)/dme(glycol dimethyl ether)/pyr14Tfsi(1- butyl -1- methylpyrrole Double (trifluoromethane sulfonyl group) imines of alkane) (1/1/1, v/v/v), the assembling of whole battery all completes in glove box.Therein The preparation of sulfur carbon composite is referring to described in journal of power sources196 (2011) 3,655 3658.
Comparative example 2
After ketjen black (kb) and sulfur mix homogeneously, under 155 DEG C of vacuum conditions, it is incubated 12h.The sulfur carbon obtaining is multiple Condensation material, cmc+sbr, acetylene black press the mass ratio prepared slurry of uniform stirring in aqueous of 8:1:1, coat on aluminium foil And be dried, thus make electrode film;The electrode film obtaining is cut into the directly disk for 14mm, obtains final product sulfur positive pole;With gold Genus lithium is negative pole, and as barrier film, electrolyte is containing 0.1mol/llino to celgard film3The 1mol/l litfsi of (lithium nitrate) (two (trifluoromethane sulfonic acid) imine lithium) dol(1,3 dioxolanes)/dme(glycol dimethyl ether) (1/1, v/v).Whole battery Assembling all complete in glove box.The preparation of sulfur carbon composite therein is referring to solid state ionics192 Described in (2011) 347 350.
Embodiment 1
Sulfur positive pole described in comparative example 1 is first soaked in 10 seconds in the polypyrrole aqueous solution of 1mol/l, proposes afterwards, then It is placed in the ammonium persulfate aqueous solution of 1mol/l and soaks 10 seconds, so move in circles 3 times, obtain electrode material according to comparative example 1 Described in method assembled battery being tested, test result is as shown in table 1.
Embodiment 2
Sulfur positive pole described in comparative example 1 is first soaked in after 10 seconds in the polypyrrole aqueous solution of 1mol/l and proposes, then be placed in Soak 10 seconds in the ammonium persulfate aqueous solution of 1mol/l, so move in circles 5 times, obtain electrode material according to institute in comparative example 1 State method assembled battery and tested, test result is as shown in table 1.The cv curve of gained battery and its putting in different cycles Electric curve is as shown in Figure 1: the cv curve of this battery shows two oxidation peak, corresponding to the life of many lithium sulfides and simple lithium sulfide Become, it is also be stepped up that oxidation peak area increases explanation discharge capacity with circulation.
Fig. 2 is following of the present embodiment gained battery (setting barrier layer) and comparative example 1 gained battery (being not provided with barrier layer) Ring Performance comparision;Wherein: a curve represents the present embodiment gained battery, b curve represents comparative example 1 gained battery.As seen from Figure 2: After setting barrier layer, the change of battery discharge specific capacity is substantially divided into three parts., in former weeks, battery capacity is slightly for Part I Micro- have decay, and corresponding to a small amount of sulfur being present in electrode surface, it is dissolved in electrolyte in cyclic process, causes the effect that shuttles Should, cause the decay of battery capacity, now also correspond to battery coulombic efficiency not high;More than 100 after Part II is are followed Ring, leads to corresponding to there being one layer of barrier layer the reason the raising of battery discharge specific capacity, raising between electrode and electrolyte Active substance sulfur can not be fully used in circulation early stage, and with the carrying out circulated, increasing sulfur is utilized, therefore, The specific discharge capacity of battery also can more and more higher;Part III is rear tens circulations of battery, declining corresponding to battery capacity Subtract, the main cause of battery capacity decay is the destruction on barrier layer, after tens circulations of experience, barrier layer is destroyed, and leads to Electrode is exposed, and shuttle effect causes the capacity attenuation of battery.
Fig. 3 compares for the present embodiment gained battery (setting barrier layer) cycle performance under different discharge-rates;Wherein: A curve represents 1c multiplying power, and b curve represents 2c multiplying power.As seen from Figure 3: the present embodiment gained battery (setting barrier layer) is at 2c times Under rate, first discharge specific capacity reaches 520mah/g, and after 200 weeks, battery discharge specific capacity reaches 528.1mah/g, illustrates to have good Good cycle performance and high rate performance.
Embodiment 3
Sulfur positive pole described in comparative example 1 is first soaked in after 10 seconds in the polyaniline aqueous solution of 0.5mol/l and proposes, then put Soak 10 seconds in the ammonium persulfate aqueous solution of 0.5mol/l, so move in circles 3 times, obtain electrode material according to comparative example 1 Described in method assembled battery being tested, test result is as shown in table 1.
Embodiment 4
Sulfur positive pole described in comparative example 1 is first soaked in 10 seconds in the polyaniline aqueous solution solution of 0.5mol/l, afterwards Propose, then be placed in the ammonium persulfate aqueous solution of 0.5mol/l soak 10 seconds, so move in circles 5 times, obtain electrode material by According to method assembled battery described in comparative example 1 and tested, test result is as shown in table 1.
Fig. 4 is the surface sem figure of the sulfur positive pole after the present embodiment immersion treatment, as seen from Figure 4: using said method energy Prepare polyaniline barrier layer in sulfur positive electrode surface, this barrier layer is made up of the polyaniline particles of below 100nm, have big The polyaniline particles of specific surface area are more beneficial for adsorbing polysulfide, desirably prevent its dissolving in the electrolytic solution and migration, And then raising battery performance.
Embodiment 5
First, polypyrrole nanotube is prepared using the soft template method that ferric nitrate and methyl orange are constituted, concrete preparation side Method reference literature: described in journal of power sources196 (2011) 6,951 6955.Gained polypyrrole nanotube A diameter of 150nm, length is 10~20 μm.The sem photo of obtained polypyrrole nanotube is as shown in figure 5, afterwards using taking out Filtering method is obtained polypyrrole nano thin-film, using the polypyrrole nano thin-film that obtains as barrier layer, described in comparative example 2 Sulfur positive pole, tests battery performance, and test result is as shown in table 1.
Embodiment 6
First, using ctab as surfactant, polypyrrole nanofibers are prepared, concrete preparation method is with reference to literary composition Offer: described in electrochemistry communications10 (2008) 1,819 1822.Gained polypyrrole nanofibers Tem photo as shown in Figure 6: a diameter of 50nm of gained fiber, hinged together between fiber, be therefore easy to sucking filtration Film forming., as barrier layer, using the sulfur positive pole described in comparative example 2, test is electric for the polypyrrole nano thin-film being obtained using sucking filtration Pond performance, test result is as shown in table 1.
Fig. 7 be embodiment 5(using polypyrrole nanotube sucking filtration film forming as barrier layer) and embodiment 6(with polypyrrole nanometer Fiber sucking filtration film forming is as barrier layer) and comparative example 2(be not provided with barrier layer) cycle performance of gained battery compares;Wherein: a is bent Line represents embodiment 5 gained battery, and b curve represents embodiment 6 gained battery;C represents comparative example 2 gained battery.Can by Fig. 7 See: using polypyrrole nanofibers and polypyrrole nanotube as barrier layer, battery first discharge specific capacity does not substantially reduce, But the capacity attenuation in battery former week is but significantly suppressed, and shows good cycle performance;And due to shuttling Effect is suppressed, and battery coulombic efficiency is also significantly improved.
Embodiment 7
First, the aqueous solution of the Ammonium persulfate. of 0.2mol/l is added drop-wise to the polypyrrole solution (water+ethanol work of 0.2mol/l For solvent) in, afterwards through filtering, washing, drying prepares polypyrrole nano-particle.With gained polypyrrole nano-particle, second Acetylene black, cmc+sbr are uniformly mixed with aqueous for 8:1:1 according to mass ratio and obtain slurry.Gained slurry is coated to Sulfur positive electrode surface described in comparative example 2, tests battery performance.Test result is as shown in table 1.
Table 1 battery performance test data
From result in table 1: the setting on barrier layer can significantly improve the cycle performance of lithium-sulfur cell, this is due to resistance The presence of barrier can stop the dissolving in the electrolytic solution of many lithium sulfides and migration, can effectively prevent many lithium sulfides from migrating to negative pole And with it, corrosion reaction occurs, and then be conducive to improving the cycle performance of lithium-sulfur cell.
Finally be necessary described herein be: above example is served only for technical scheme is made detailed further It is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to the above of the present invention for ground explanation Some the nonessential improvement made and adjustment belong to protection scope of the present invention.

Claims (2)

1. a kind of lithium-sulfur cell, including sulfur positive pole, barrier film, electrolyte and lithium anode it is characterised in that: sulfur positive pole with every Intermembranous be provided with the barrier layer being formed by conducting polymer nano material, the thickness on described barrier layer is 5nm~10 μm;And described resistance The preparation of barrier includes operating as follows:
A) first sulfur positive pole is placed in the polypyrrole aqueous solution of 1mol/l and soaks 10 seconds, then take out the persulfuric acid being placed in 1mol/l Soak again in aqueous ammonium 10 seconds;Circulate operation 3~5 times;
B) the sulfur positive pole after processing is carried out, is dried;
C) remove the barrier layer being grown in the collection liquid surface forming sulfur positive pole.
2. lithium-sulfur cell as claimed in claim 1 it is characterised in that: the thickness on described barrier layer be 50nm~5 μm.
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CN105428699B (en) * 2014-09-23 2018-04-03 中国科学院大连化学物理研究所 A kind of composite structured lithium-sulfur cell
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CN104600251A (en) * 2014-12-26 2015-05-06 中南大学 Lithium-sulfur battery positive electrode and preparation method thereof
CN104659407B (en) * 2015-02-26 2017-01-25 广东烛光新能源科技有限公司 Lithium-sulfur battery and preparation method thereof
CN104934632A (en) * 2015-04-28 2015-09-23 常州大学 Lithium-sulfur battery and preparation method thereof
CN105047982A (en) * 2015-06-01 2015-11-11 常州大学 Lithium sulfur battery based on modification of graphene oxide thin film
CN105552282B (en) * 2015-11-13 2019-04-23 北京理工大学 Lithium-sulfur cell based on Functional carbon fiber cloth as positive barrier layer
WO2017181108A1 (en) * 2016-04-14 2017-10-19 The Regents Of The University Of Michigan Templated synthesis of shape-controlled polymeric nanofibers by chemical vapor deposition (cvd) in liquid crystals
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