CN104716381A - Method for protecting negative electrode of lithium sulfur battery - Google Patents
Method for protecting negative electrode of lithium sulfur battery Download PDFInfo
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Abstract
The invention discloses a method for protecting the negative electrode of a lithium sulfur battery. A lithium sulfur battery negative electrode protection additive layer is adhered to the surface of the anode of the lithium sulfur battery. An additive component forming the protection additive layer can be an inorganic compound or an organic compound; the inorganic compound is one or above two of metal oxides, nonmetal oxides, sulfides, phosphides, nitrides, borides and fluorides; and the organic compound is one or above two of ionic liquid molecules, amino acids, polycation electrolytes, polyanion electrolytes, cationic surfactants, polyoxyether and polythioether. The morphology of the liquid metal protection layer is dynamically changing, and does not physically shed or crack due to continuous dissolution and deposition of the lithium metal in order to effectively protect the negative electrode.
Description
Technical field
Generality of the present invention relates to lithium-sulfur cell, more specifically relates in lithium-sulfur cell the protection comprising lithium anode.
Background technology
Lithium-sulfur cell has had people starting research and development in the nineties in last century, but quiet afterwards a period of time.Now, there is due to it performances such as incomparable high-energy-density, again receive the attention of research staff.Recent years, correlative study both domestic and external work was rather active, at present on the occasion of the key stage of technological break-through.This kind of typical rechargeable battery comprises using lithium metal as active material, using lithium metal alloy as active material or using lithium metal/carbon complex as the anode of active anode material.This battery contains the negative electrode of sulphur as active material.
When charging to lithium-sulfur cell, anode place lithium ion is reduced into lithium metal, and simultaneously at the oxidized formation polysulfide of negative electrode place lithium sulfide material and sulphur, lithium ion is released in the electrolyte connecting negative electrode and positive electrode.During electric discharge, anode place lithium metal is oxidized to lithium ion, and this lithium ion is released in electrolyte, participates in reduction reaction and forms lithium sulfide material simultaneously at negative electrode place lithium ion and sulphur.
Sulphur is widespread in nature, and data show, sulphur is probably 0.048wt% in the abundance of occurring in nature, and belongs to the natural resources not yet made full use of.The sulphur of occurring in nature mainly exists with elemental sulfur (S8) form thermodynamically stable under normal temperature, and its basic physics performance allows research staff be applied on lithium battery very excited for sulphur.Elemental sulfur has the features, particularly Li/S such as the large and low-density of hypotoxicity, cheap, storage and has very high theoretical energy density, and elemental sulfur specific capacity is up to 1,675mAh/g, specific energy, especially up to 2,600Wh/kg, is the positive electrode that specific capacity known is at present the highest.
Although have as above advantage, lithium-sulfur cell also has suitable distance from practical, current subject matter comprises: the lithium metal of (1) negative pole reacts with the polysulfide being dissolved in electrolyte, the elemental sulfur of side of the positive electrode then little by little generates polysulfide and enters electrolyte, and then react with lithium metal, finally cause the loss of both positive and negative polarity active material and region to cave in; (2) in lithium-sulfur cell discharge process, after the polysulfide of formation enters electrolyte, highly enriched polysulfide causes electrolyte viscosity to raise, and cause electrolyte conductivity to reduce, battery performance significantly declines; (3) working temperature of lithium-sulfur cell system is up to 300 ~ 400 DEG C, and this needs exotic material costly and complicated preparation technology to prevent battery from burning.In addition, because elemental sulfur is at room temperature non-conductive, can not use as positive electrode separately, so usually it is mixed to improve positive pole zone conductivity with a certain amount of electric conducting material when preparing lithium-sulfur cell, but excessive hybrid conductive material, can make again the specific energy of lithium-sulfur cell significantly reduce.
Dissolve " shuttling back and forth " effect of moving and causing for polysulfide, current solution is very limited, and people are many, and the angle from electrolysis additive and barrier film is set about.1) " electrochemistry journal " (Electrochimica Acta70; 2012; 344 – 348) report the work that Sheng S.Zhang adds additive lithium nitrate in the electrolytic solution; adding of lithium nitrate can make cathode of lithium surface form protective layer; but this protective layer can consume gradually, will lose efficacy gradually after tens charge and discharge cycles.2) " power source magazine " (Journal of Power Sources183,2008,441 – 445) describe another method, namely add toluene, methyl acetate etc. in the electrolytic solution to suppress the dissolving of polysulfide, but this method easily causes the decline of electrolytic conductivity.3) the third method uses composite polymer gel electrolyte separator, as Chinese invention patent 201110110093.X and " power source magazine " (Journal of Power Sources212, 2012, 179-185) disclosed report, gel electrolyte is by polymer, plasticizer (lithium salts solvent, ionic liquid etc.) and the gel polymeric network with appropriate microporous structure that formed by certain method of lithium salts, the liquid electrolyte molecule be fixed in micro-structural is utilized to realize ionic conduction by the polymer network system of solvent swell, the network configuration of its uniqueness makes gel have the cohesiveness of solid and the dispersion conductibility of liquid simultaneously.Because electrolyte solution quilt " coated " is in polymer network, the dissolving of polysulfide is suppressed, thus the problem of sulphur active material loss may be solved to a certain extent; But gel electrolyte separator conductivity and intensity are all lower.4) the 4th kind of method prepares macroion optionally electrolyte membrance, as the disclosed report of " power and energy magazine " (Journalof Power Sources246 (2014) 253-259), the barrier film being representative with Nafion perfluorosulfonic acid ion conductive membranes has higher lithium ion selective penetrated property and the obstructing capacity of polysulfide, thus effectively can suppress the diffusion of polysulfide from positive pole to negative pole.But the material cost of this kind of barrier film is higher, and ionic conductivity is lower, be difficult to meet real requirement.5) Lung biopsy deposits one deck SEI film or sputtering one deck lithium ion permselective membrane in negative terminal surface, and this film is inorganic ceramic membrane, has larger fragility.And the feature of lithium-sulfur cell to be change in volume larger, the dissolving of lithium ion and the pattern of deposition are not fixed, and therefore this solid ceramic film is difficult to the investigation tolerating battery long-time running.
Summary of the invention
The object of the invention is to solve the problem, a kind of method that lithium-sulfur cell negative pole is protected is provided.
For achieving the above object, the technical solution used in the present invention is:
Anode surface in lithium-sulfur cell adheres to one deck lithium-sulfur cell negative pole protection additive layer; The additive composition forming protection additive layer is inorganic compound or organic compound;
Inorganic compound is one or two or more kinds in metal oxide, nonmetal oxide, sulfide, phosphide, nitride, boride, fluoride;
Organic compound is one or two or more kinds in ionic liquid molecules, amino acids, polycation electrolyte, polyanion electrolyte, cationic surfactant, polyoxyether, polythiaether.
Its protection additive layer is that 1nm-500nm is thick.
Protect the material of additive layer by one or two or more kinds in metallic bond, coordinate bond, intermolecular force together with the lithium metal complexing of anode surface, and the interaction force of protection additive layer material and lithium metal is greater than the active force in protective layer and electrolyte solution between solvent molecule.
Mineral-type additive be generally inorganic molecules material, combined by metallic bond or coordinate bond and electrode.The molecular weight of organic additive between tens to several thousand, and usually containing carboxyl, amino, phosphate, sulfonic group, nitrato, itrile group, hydroxyl etc. can with the functional group of lithium ion generation electron coordinate effect.
Described anode be using lithium metal as active anode material or with lithium alloy as the material of active anode or using lithium carbon complex as active anode material.
Be set forth in lithium-sulfur cell the anode surface process of adhering to one deck lithium-sulfur cell negative pole protection additive layer be: add in the electrolyte solution of lithium-sulfur cell and have lithium-sulfur cell negative pole to protect additive, described additive is inorganic compound or organic compound;
Inorganic compound is one or two or more kinds in metal oxide, nonmetal oxide, sulfide, phosphide, nitride, boride, fluoride;
Organic compound is one or two or more kinds in ionic liquid molecules, amino acids, polyelectrolyte, cationic surfactant, polyoxyether, polythiaether; Between the mass concentration 0.01% ~ 1% of additive in electrolyte solution.
After assembling lithium-sulfur cell, make lithium-sulfur cell anode and the electrolyte solution contacts containing additive; By one or two or more kinds method in natural absorption, heat treatment, discharge and recharge, ultrasonic, microwave, additive is adsorbed on described anode surface, makes it to isolate with described electrolyte solution.
Assembling lithium-sulfur cell process is:
Lithium-sulfur cell anode be using lithium metal as active anode material or with lithium alloy as the material of active anode or using lithium carbon complex as active anode material; Lithium-sulfur cell negative electrode is carbon-sulfur compound; Between anode and negative electrode, membrane for polymer is set; Make anode and negative electrode and the electrolyte solution contacts containing additive.
The described electrolyte solution containing additive consists of: ether solvent, lithium salts (concentration is between 1% ~ 50%), additive (content is between 0.1% ~ 1%).
Described ether solvent is the mixed solvent of one or two or more kinds in dioxolanes (DOL), glycol dimethyl ether (DME), oxolane, methyltetrahydrofuran, tetraethylene glycol dimethyl ether.
Described lithium salts is lithium hexafluoro phosphate, perfluor sulfonyl imine lithium, perfluor sulfonyl lithium.
Described additive is inorganic compound or organic compound;
Inorganic compound is one or two or more kinds in Ludox, n-BuLi, phosphoric sulfide, phosphotungstic acid lithium, silicotungstate lithium, butyl titanate, silester, thionyl chloride, lithium hydroxide, zirconyl nitrate;
Organic compound is imidazole type ion liquid, tartaric acid, triphenylphosphine, perfluorinated sulfonic resin, polyethylene glycol, polyvinyl formal, silane coupler, heptose hydrochlorate, gluconic acid sodium salt, sodium alginate, sodium ammonium triacetate (N TA), edetate (EDETATE SODIUM or four sodium), diethylenetriamine pentacarboxylic acid salt (DTPA), monoethanolamine, diethanol amine, triethanolamine, ethylenediamine tetraacetic methene sodium phosphate (EDTMPS), diethylene triamine pentamethylene phosphonic salt (DETPMPS), amine three methene phosphate, lithium citrate, there is HPMA (HPMA), polyacrylic acid (PAA), poly-hydroxy acrylic acid, maleic acrylic copolymer, one or two or more kinds in polyacrylamide.
Beneficial effect:
Lithium-sulfur cell negative pole protection additive provided by the invention has following characteristics and beneficial effect:
1) by adding additive in lithium-sulfur cell electrolyte, making additive be attached to negative terminal surface, stopping that the polysulfide in electrolyte directly contacts with anode.Wherein, the pattern of lithium coat of metal is dynamic change, because of the continuous dissolving of lithium metal and deposition, physics can not occur and comes off or ftracture.Wherein, conventional electrolyte solution directly contacts with protective layer, not with protective layer generation chemical reaction, does not dissolve protective layer.Thus play the effect of protection negative pole.
2) this additive can be deposited on lithium-sulfur cell lithium-sulfur cell negative terminal surface dynamically, and forms diaphragm by metallic bond, coordinate bond, intermolecular force together with lithium metal complexing, thus stops polysulfide and lithium metal generation chemical reaction.And along with the deposition and resolution of negative electrode lithium ion, additive is adsorbed on negative terminal surface all the time, there is corresponding change according to the pattern of negative pole, can not come off.
3) feature of this kind of additive is without solid form, and the active force between additive molecule and lithium metal is greater than the active force between itself and conventional electrolysis liquid solvent.This can be selected by simple laboratory facilities, lithium metal is placed in the lithium-sulfur cell electrolyte containing additive, if the additive level in electrolyte obviously reduces, then illustrates that this additive is adsorbed on metal lithium electrode surface.
4) lithium-sulfur cell negative pole protection additive provided by the invention does not affect original battery packaging technology, practical, has performance, technique and multiple advantage economically compared with traditional additive.
Accompanying drawing explanation
The lithium-sulfur cell performance of the electrolyte assembling containing negative pole protection additive of Fig. 1 prepared by embodiment 1;
Fig. 2 is common not containing the lithium-sulfur cell performance of the electrolyte assembling of negative pole protection additive;
The lithium-sulfur cell performance of the electrolyte assembling containing negative pole protection additive of Fig. 3 prepared by embodiment 2;
The lithium-sulfur cell performance of the electrolyte assembling containing negative pole protection additive of Fig. 4 prepared by embodiment 3.
Embodiment
Further describe the lithium-sulfur cell negative pole protection additive and using method thereof that the present invention relates to by the following examples.Embodiment 1:
Added by 0.25g diethylenetriamine pentacarboxylic acid salt (DTPA) in LiTFSI/ (DME+DOL) electrolyte of 10g concentration 1M, strong agitation obtains clarifying electrolyte.Adopt composite membrane obtained above to assemble lithium sulphur button cell, it is carbon-sulfur compound (58% fills sulfur content, PVDF binding agent) just very, and battery is with 0.1 rate charge-discharge 16 circulation, and average coulombic efficiencies is 97.5%(Fig. 1);
And when adopting non-additive electrolyte, other conditions are constant, and the average coulombic efficiencies of battery only has 88%(Fig. 2).
Embodiment 2:
Add in LiTFSI/ (DME+DOL) electrolyte of 10g concentration 1M by 0.4 ethylenediamine tetraacetic methene sodium phosphate (EDTMPS), strong agitation obtains clarifying electrolyte.Adopt electrolyte obtained above to assemble lithium sulphur button cell, it is carbon-sulfur compound (58% fills sulfur content, PVDF binding agent) just very.Battery is with 0.1 rate charge-discharge 13 circulation, and average coulombic efficiencies is 97.3%(Fig. 3).
Embodiment 3:
0.504 donaxine three methene phosphate being added in LiTFSI/ (DME+DOL) electrolyte of 12 ml concn 1M, dissolving completely through stirring, obtain clarifying electrolyte.Adopt electrolyte obtained above to assemble lithium sulphur button cell, it is carbon-sulfur compound (58% fills sulfur content, PVDF binding agent) just very.Battery is with 0.1 rate charge-discharge 37 circulation, and average coulombic efficiencies is 98.7%(Fig. 4).
Embodiment 4:
Add in the LiTFSI/DME electrolyte of 10g concentration 1M by 0.5 ethylenediamine tetraacetic methene sodium phosphate (EDTMPS), strong agitation obtains the electrolyte containing negative pole protection additive.
Embodiment 5:
Add in the LiTFSI/DME electrolyte of 10g concentration 1M by 0.3 poly-perfluorinated sulfonic acid lithium (EW=1100), strong agitation obtains the electrolyte containing negative pole protection additive.
Embodiment 6:
Added by 0.4 lithium citrate in the LiTFSI/DME electrolyte of 10g concentration 1M, strong agitation obtains the electrolyte containing negative pole protection additive.
Embodiment 7:
Added by 0.6 silicotungstate lithium in the LiTFSI/DME electrolyte of 10g concentration 1M, strong agitation obtains the electrolyte containing negative pole protection additive.
Claims (8)
1. protect a method for lithium-sulfur cell negative pole, it is characterized in that:
Anode surface in lithium-sulfur cell adheres to one deck lithium-sulfur cell negative pole protection additive layer; The additive composition forming protection additive layer is inorganic compound or organic compound;
Inorganic compound is one or two or more kinds in metal oxide, nonmetal oxide, sulfide, phosphide, nitride, boride, fluoride;
Organic compound is one or two or more kinds in ionic liquid molecules, amino acids, polycation electrolyte, polyanion electrolyte, cationic surfactant, polyoxyether, polythiaether.
2. the method for claim 1, is characterized in that: its protection additive layer is that 1nm-500nm is thick.
3. the method for claim 1; it is characterized in that: protect the material of additive layer by one or two or more kinds in metallic bond, coordinate bond, intermolecular force together with the lithium metal complexing of anode surface, and the interaction force of protection additive layer material and lithium metal is greater than the active force in protective layer and electrolyte solution between solvent molecule.
4. the method for claim 1, is characterized in that: described anode be using lithium metal as active anode material or with lithium alloy as the material of active anode or using lithium carbon complex as active anode material.
5. the method for claim 1, is characterized in that:
Be set forth in lithium-sulfur cell the anode surface process of adhering to one deck lithium-sulfur cell negative pole protection additive layer be: add in the electrolyte solution of lithium-sulfur cell and have lithium-sulfur cell negative pole to protect additive, described additive is inorganic compound or organic compound;
Inorganic compound is one or two or more kinds in metal oxide, nonmetal oxide, sulfide, phosphide, nitride, boride, fluoride;
Organic compound is one or two or more kinds in ionic liquid molecules, amino acids, polyelectrolyte, cationic surfactant, polyoxyether, polythiaether; Between the mass concentration 0.01% ~ 1% of additive in electrolyte solution;
After assembling lithium-sulfur cell, make lithium-sulfur cell anode and the electrolyte solution contacts containing additive; By one or two or more kinds method in natural absorption, heat treatment, discharge and recharge, ultrasonic, microwave, additive is adsorbed on described anode surface, makes it to isolate with described electrolyte solution.
6. method as claimed in claim 5, is characterized in that:
Assembling lithium-sulfur cell process is:
Lithium-sulfur cell anode be using lithium metal as active anode material or with lithium alloy as the material of active anode or using lithium carbon complex as active anode material;
Lithium-sulfur cell negative electrode is carbon-sulfur compound; Between anode and negative electrode, membrane for polymer is set;
Make anode and negative electrode and the electrolyte solution contacts containing additive.
7. the method as described in claim 5 or 6, is characterized in that:
The described electrolyte solution containing additive consists of: ether solvent, lithium salts and additive;
Described ether solvent is the mixed solvent of one or two or more kinds in dioxolanes, glycol dimethyl ether, oxolane, methyltetrahydrofuran, tetraethylene glycol dimethyl ether;
Described lithium salts is lithium hexafluoro phosphate, perfluor sulfonyl imine lithium, perfluor sulfonyl lithium, concentration 1wt%-50wt%; Additive level is 0.1-1wt%.
8. the method as described in claim 1 or 5, is characterized in that:
Described additive is inorganic compound or organic compound;
Inorganic compound is one or two or more kinds in Ludox, n-BuLi, phosphoric sulfide, phosphotungstic acid lithium, silicotungstate lithium, butyl titanate, silester, thionyl chloride, lithium hydroxide, zirconyl nitrate;
Organic compound is imidazole type ion liquid, tartaric acid, triphenylphosphine, perfluorinated sulfonic resin, polyethylene glycol, polyvinyl formal, silane coupler, heptose hydrochlorate, gluconic acid sodium salt, sodium alginate, sodium ammonium triacetate, edetate, diethylenetriamine pentacarboxylic acid salt, monoethanolamine, diethanol amine, triethanolamine, ethylenediamine tetraacetic methene sodium phosphate, diethylene triamine pentamethylene phosphonic salt, amine three methene phosphate, lithium citrate, there is HPMA, polyacrylic acid, poly-hydroxy acrylic acid, maleic acrylic copolymer, one or two or more kinds in polyacrylamide.
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| CN106450455A (en) * | 2016-10-20 | 2017-02-22 | 重庆工业职业技术学院 | High-efficiency lithium-sulfur battery additive and application method thereof |
| CN107221704A (en) * | 2017-06-29 | 2017-09-29 | 中国科学院长春应用化学研究所 | A kind of electrolyte for lithium secondary batteries and lithia gas secondary cell |
| CN107689442A (en) * | 2016-08-05 | 2018-02-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Lithium metal composite, its preparation method and application with cladding Rotating fields |
| CN107834117A (en) * | 2016-09-16 | 2018-03-23 | 株式会社东芝 | Secondary cell, battery bag and vehicle |
| CN107919491A (en) * | 2016-10-10 | 2018-04-17 | 中国科学院成都有机化学有限公司 | A kind of graphene-based protective layer in lithium anodes surface and corresponding lithium-sulfur cell |
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