CN103985840A - Lithium negative electrode with functional protective layer and lithium sulfur battery - Google Patents
Lithium negative electrode with functional protective layer and lithium sulfur battery Download PDFInfo
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- CN103985840A CN103985840A CN201410245358.0A CN201410245358A CN103985840A CN 103985840 A CN103985840 A CN 103985840A CN 201410245358 A CN201410245358 A CN 201410245358A CN 103985840 A CN103985840 A CN 103985840A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a lithium negative electrode with a functional protective layer and a lithium sulfur battery. The lithium negative electrode is provided with a functional protective layer which is coated on the surface and includes a conductive polymer. In the lithium sulfur battery, the functional protective layer of the lithium negative electrode is contacted with an electrolyte, so that a stable interface is formed between the electrolyte and a base body of the lithium negative electrode.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of lithium-sulfur cell that there is the cathode of lithium of functional protection layer and comprise above-mentioned cathode of lithium.
Background technology
Along with social development, the portable type electronic products such as mobile phone, portable computer, electric motor car, digital camera, I-pad are flooded with people's life.Wherein lithium battery is as main energy storage device, dominate in mini-plant, and still, along with the raising that people require portable life, traditional lithium battery can not meet human wants.Thereby, have high specific energy, high security, high useful life and cheaply lithium battery of future generation be sent to great expectations.
Positive pole is the key that improves battery specific energy.Sulphur is just having the theoretical specific capacity of 1675mAh/g and the energy density of 2600Wh/Kg, the anodal theoretical specific capacity of current commercial transition metal oxide and specific energy ten times, and sulphur is occurring in nature rich content, cheap, environmentally safe close friend, so sulphur positive pole becomes one of lithium electricity positive electrode having most development prospect.
Although sulphur is just having plurality of advantages, active material utilization is low, cycle performance is poor, coulomb low key factor that limits its extensive use that becomes of efficiency.Wherein the low conductivity of sulphur is the main cause that its active material utilization is low.Meanwhile, in discharge process, the many lithium sulfides of cell reaction intermediate product can be dissolved in ethers electrolyte, and many lithium sulfides move in electrolyte afterwards, penetrate barrier film arrive cathode of lithium and with its generation corrosion reaction, generate simple lithium sulfide (Li insoluble and insulation
2s or Li
2s
2), this side reaction greatly reduce cell active materials utilance, then, in battery charging process, the simple lithium sulfide of a part can be reduced into many lithium sulfides by lithium and again be dissolved in electrolyte and move to anode, and now the oxidation reaction between many lithium sulfides and lithium also occurs simultaneously, this process is referred to as the effect of shuttling back and forth.Meanwhile, due to the insolubility of simple lithium sulfide in electrolyte, and then cause the decay of battery capacity, therefore, the effect of shuttling back and forth is also the main cause that coulomb efficiency is low, cycle performance of battery is poor.
Researchers adopt diverse ways to reduce the effect of shuttling back and forth in battery charge and discharge process, and then improve battery performance.Adopt various material with carbon elements, as adopt carbon nano-tube, Graphene, mesoporous carbon to store sulphur, sulphur be limited in the duct of material with carbon element or utilize specific area that material with carbon element is high to limit the dissolving of many lithium sulfides, the inhibition of effect and the raising (Angew.Chem.Int.Ed.2013 of battery performance are conducive to shuttle back and forth, 52,2 – 18); Adopt the conducting polymers such as polypyrrole, polyaniline, polythiophene as the memory bank of sulphur, can not only limit the dissolving of many lithium sulfides, the activity of conducting polymer itself also can improve the performance (Electrochemistry Communications31 (2013) 10 – 12) of battery; Meanwhile, adopt nano-oxide as adsorbent, can obviously adsorb many lithium sulfides, and then reduce and shuttle back and forth effect to the impact of battery performance (Accounts of chemical research46.5 (2012): 1135-1143.).
On measure be to set about from battery electrode inside configuration, though can reduce to a certain extent the impact of effect on battery performance of shuttling back and forth, still, it is higher that the material that uses is prepared complicated cost, is not easy to large-scale production.Meanwhile, the problem of the negative pole aspect of lithium-sulfur cell is serious and complicated, and relevant research but seldom.
The problem of the negative pole aspect of lithium-sulfur cell mainly comprises following three aspects: first, because the Fermi level of lithium metal is lower, therefore lithium metal is unsettled to electrolyte, the SEI film forming between them is unsettled, and can in cyclic process, be consumed, can cause like this loss of electrolyte and cathode of lithium, therefore in order to mate sulphur positive pole, the cathode of lithium of lithium-sulfur cell must be excessive, has reduced the energy density of battery.In addition, adopt lithium metal the same as the battery of negative pole with other, in the long-term charge and discharge process of battery, the nonuniform deposition of lithium has caused the growth of lithium Zhi Jing, and the lasting growth of lithium Zhi Jing likely can puncture barrier film, causes the problem of fail safe.Simultaneously, for lithium-sulfur cell, because the many lithium sulfides of intermediate product of cell electrochemical reaction can be dissolved in electrolyte, they migrate to cathode of lithium and react with it and generate lithium sulfide soluble and insulation, the generation of lithium sulfide not only can cause the loss of active material, causes battery capacity decay, and the polarization that can improve battery, in charging process, the positive negative reaction between many lithium sulfides and lithium sulfide occurs simultaneously simultaneously, reduces the coulomb efficiency of battery.
Research work for lithium-sulfur cell cathode of lithium is considerably less, but for common cathode of lithium, being summarized as follows of related work: part work launches around electrolysis additive, such as adding AlI in electrolyte
3, Li
2cO
3(J.Electrochem.Soc.144 (1997) 1709.), LiNO
3(Journal of Power Sources196 (2011) 9839 – 9843), ionic liquid (J.Phys.Chem.C2013,117,4431-4440) etc., impel in electrochemical process and form more stable SEI film at negative pole, but these additives but can progressively be consumed in electrochemical reaction process, thereby be difficult to obtain highly stable chemical property, and or expensive, affect the practicalization of battery; A part is operated in cathode of lithium surface-coated polymer (Journal of Power Sources244 (2013) 363-368), the having of polymer is beneficial to reduces cathode of lithium and contacts with the direct of electrolyte, reduce the generation of irreversible reaction between cathode of lithium and electrolyte, and then obtain comparatively stable SEI film, but the therefore still migration of sluggish electronic and ionic to a certain extent of nonconducting polymer; In addition, at cathode of lithium superficial growth Li
3the lithium ion conductors such as N (Journal of Power Sources196 (2011) 8091 – 8097) or LiPON (Rare Metals Materials and engineering 39 (2010) 1664-1667) can solve above three problems really to a great extent simultaneously, but, growth technique is but very complicated, and it is very unsettled that Li3N reacts with water in air, and the conductivity of LiPON is not high enough.Also some research is incorporated into cathode of lithium surface (Electrochimica Acta103 (2013) 199 – 205) by monomers such as pyrroles, and obtain good effect, but the preparation of material designs complicated electrochemical process, be unfavorable for large-scale application.Although there has been document to pyrrole monomer, the modification of cathode of lithium to be studied, pyrrole monomer is not through doping oxidation, and itself is non-conductive, and it only can have stabilization to SEI, but can cause the generation of battery polarization, so be not suitable for lithium-sulfur cell.Therefore, this area in the urgent need to a kind of safe, stable, coulomb efficiency is high, battery capacity decays little lithium-sulfur cell.
Summary of the invention
The present invention is intended to overcome the defect of existing lithium-sulfur cell, the invention provides a kind of lithium-sulfur cell that has the cathode of lithium of functional protection layer and comprise this cathode of lithium.
The invention provides a kind of cathode of lithium with functional protection layer, described cathode of lithium have be coated in surface, the functional protection layer that comprises conducting polymer.
Cathode of lithium of the present invention contains functional protection layer, as shown below, and functional protection layer is positioned at the surface of cathode of lithium, and functional protection layer is comprised of conductive polymers based material.Functional protection layer can be stablized the interface of electrolyte and negative pole, forms stable SEI film; Can prevent that lithium serious in charge and discharge process from propping up crystals growth, improve battery security simultaneously; In addition, functional protection layer can physically separate many lithium sulfides that lithium-sulfur cell produces in charge and discharge process and contact with the direct of cathode of lithium, prevents the generation of corrosion reaction.Therefore, functional protection layer can effectively improve lithium-sulfur cell coulomb efficiency, reduces the active material loss causing due to many lithium sulfides and cathode of lithium corrosion reaction, prevents the growth of lithium Zhi Jing.In a word, cathode of lithium finishing one deck functional protection layer can effectively improve the cyclical stability of battery, improves battery coulomb efficiency.
Preferably, the matrix of described cathode of lithium is lithium metal or lithium alloy.
Preferably, described conducting polymer is at least one in polypyrrole, polyaniline, polythiophene, polyacetylene, polyacrylonitrile, poly-ethylenedioxy thiophene and derivative thereof.
Preferably, the thickness of stating functional protection layer is 10nm～100 μ m, preferably 1 μ m.
The present invention also provides a kind of lithium-sulfur cell that comprises above-mentioned arbitrary cathode of lithium, and in described lithium-sulfur cell, the functional protection layer of cathode of lithium contacts with electrolyte, makes to form stable interface between electrolyte and the matrix of cathode of lithium.
Beneficial effect of the present invention:
The cathode of lithium that the present invention prepares by easy mode, can be used in preparation safety, stable, coulomb efficiency is high, battery capacity decays little lithium-sulfur cell, is easy to realize industrialization, and industrial applicability is strong.
Accompanying drawing explanation
Fig. 1 is the structural representation of the lithium-sulfur cell for preparing in an embodiment in the present invention;
Fig. 2 is not for having the surperficial SEM shape appearance figure in an embodiment in the lithium sheet of functional protection layer and the present invention with the lithium sheet of functional protection layer;
Fig. 3 for the AC impedance figure without the lithium-sulfur cell in an embodiment in the lithium-sulfur cell of functional protection layer and the present invention with functional protection layer over time;
Fig. 4 is for having the cycle performance of lithium-sulfur cell and the variation of coulomb efficiency of functional protection layer in an embodiment in the lithium-sulfur cell without functional protection layer and the present invention.
Embodiment
Below in conjunction with accompanying drawing and following execution mode, further illustrate the present invention, should be understood that accompanying drawing and following execution mode are only for the present invention is described, and unrestricted the present invention.
Relate to a kind of cathode of lithium and lithium-sulfur cell containing functional protection layer herein.Cathode of lithium of the present invention contains functional protection layer, and as shown in Figure 1, functional protection layer is positioned at the surface of cathode of lithium, and functional protection layer is comprised of conductive polymers based material.Functional protection layer can be stablized the interface between electrolyte and cathode of lithium, forms stable SEI film, reduces the consumption to electrolyte and cathode of lithium in the long-term cyclic process of battery; In addition, functional protection layer can physically stop the growth of lithium Zhi Jing, prevents that lithium Zhi Jing from penetrating barrier film and causing the problem of fail safe; In addition; functional protection layer can physically separate many lithium sulfides that lithium-sulfur cell produces in charge and discharge process and contact with the direct of cathode of lithium; the generation that prevents corrosion reaction generates lithium sulfide soluble and insulation, can reduce loss and the electrode polarization of active material in cyclic process.Therefore, functional protection layer can effectively improve lithium-sulfur cell coulomb efficiency, reduces the active material loss causing due to many lithium sulfides and cathode of lithium corrosion reaction, prevents the growth of lithium Zhi Jing.In a word, cathode of lithium finishing one deck functional protection layer can effectively improve the cyclical stability of battery, improves battery coulomb efficiency.
The invention provides a kind of cathode of lithium with functional protection layer, and a kind of lithium-sulfur cell, comprise the cathode of lithium with functional protection layer, belong to technical field of electrochemistry.
Described cathode of lithium and lithium-sulfur cell, cathode of lithium mainly comprises lithium metal and other lithium alloys.
Described cathode of lithium and lithium-sulfur cell, functional protection layer comprises conductive polymers based material.
Described cathode of lithium and lithium-sulfur cell, the thickness of functional protection layer is 10nm～100 μ m, optimum thickness is 1 μ m.
Described functional protection layer, conducting polymer materials comprises: polypyrrole (PPy), polyaniline (PANI), polythiophene (PTh), polyacetylene, polyacrylonitrile (PAN), poly-ethylenedioxy thiophene (PEDOT) and derivative thereof.
Functional protection layer can be single conducting polymer, also can be conducting polymer materials from the compound of other materials, can also be the compound that different conducting polymer materials form.
In a word, functional protection layer can improve the contact performance of electrolyte and negative pole in the situation that not affecting electrode conductivuty, helps to form stable SEI film; Contacting of the isolated polysulfide of machinery and cathode of lithium simultaneously, prevent from, between them, corrosion reaction occurs and cause active material from loss and electrode polarization; Can stop the growth of lithium Zhi Jing, improve the fail safe of battery simultaneously.Adopt method set forth in the present invention, even if the sulfur content that carries of electrode anode active material reaches 2.5mg/cm
2, in electrode, sulfur content is up to 60%, and under 0.2C multiplying power, the specific discharge capacity of battery is still up to 875mAh/g after 200 weeks, and average coulomb efficiency reaches 89.2%, far above the lithium-sulfur cell that does not add functional protection layer.
Fig. 1 is the structural representation of the lithium-sulfur cell for preparing in an embodiment in the present invention;
Fig. 2 is not for having the surperficial SEM shape appearance figure in an embodiment in the lithium sheet of functional protection layer and the present invention with the lithium sheet of functional protection layer;
Fig. 3 for the AC impedance figure without the lithium-sulfur cell in an embodiment in the lithium-sulfur cell of functional protection layer and the present invention with functional protection layer over time;
Fig. 4 is for having the cycle performance of lithium-sulfur cell and the variation of coulomb efficiency of functional protection layer in an embodiment in the lithium-sulfur cell without functional protection layer and the present invention.
Below in conjunction with accompanying drawing and following execution mode, further illustrate the present invention; should understand; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention., those skilled in the art can do in suitable scope and be selected by explanation herein the temperature that following example is concrete, time etc. are only also examples in OK range,, and do not really want to be defined in the below concrete numerical value of example.
Comparative example 1
After Ketjen black (KB) and sulphur are mixed, under 155 ℃ of vacuum conditions, be incubated 12h.The sulphur carbon composite obtaining, CMC (CMC)+SBR (butadiene-styrene rubber), acetylene black (8:1:1) uniform stirring in the aqueous solution make slurry, coat on aluminium foil and are dried, and make thus electrode film.The electrode film obtaining is cut into the disk that diameter is 14mm, take lithium metal as negative pole, and Celgard film is as barrier film, and electrolyte is 1M LiTFSI (two (trifluoromethane sulfonic acid) imine lithium) DOL (1,3 dioxolanes)/DME (glycol dimethyl ether) (1/1, v/v).The assembling of whole battery all completes in glove box.
Embodiment 1
Adopt the nitromethane dispersion liquid (1wt% of PEDOT-co-PEG (polyethylene glycol) copolymer; from sigma) be coated in a side of cathode of lithium; be placed on dry 30min in glove box; repeat afterwards above-mentioned engineering 4 times; obtain PEDOT-PEG copolymer as the cathode of lithium of protective layer, the anodal assembling of the sulphur electrode in DOL/DME solution/comparative example 1 of the cathode of lithium/1MLiTFSI with protective layer that employing obtains.Fig. 2 has shown to have the cathode of lithium of PEDOT-co-PEG protective layer and original cathode of lithium surface topography, and as shown in (b) in Fig. 2, comparatively speaking, the cathode of lithium surface with protective layer becomes coarse.Simultaneously; for the impact of Study of functional protective layer on electrode and the generation of electrolyte SEI film; we have assembled respectively the cathode of lithium that adopts original cathode of lithium and have functional barrier layer and have assembled symmetrical battery, have measured their ac impedance spectroscopy over time, and test result as shown in Figure 3.As shown in (a) in Fig. 3, along with the prolongation of battery standing time, the battery impedance of original cathode of lithium assembling continues to increase, until be just stabilized in 172 Ω left and right after 192h; And as shown in (b) in Fig. 3, thering is the battery of the cathode of lithium assembling on functional barrier layer, after 96h, the impedance stabilization of battery is in 92 Ω left and right.Show that there is no the cathode of lithium of functional protection layer is unsettled to electrolyte, its thickness that generates SEI film increases gradually, has consumed lithium and electrolyte on the one hand, and in addition, the impedance of the SEI film that it is claimed is higher, can affect the generation of electrochemical reaction.And after having added functional protection layer, the stability of electrode pair electrolyte greatly improves, and the impedance of SEI film is also lower, is conducive to the generation of electrochemical reaction.Fig. 4 has shown the variation that whether adopts functional protection layer cycle performance of battery and coulomb efficiency; as shown in three curves below in Fig. 4; the interpolation of functional protection layer, can significantly improve the cycle performance of battery, especially the capacity attenuation in former weeks of battery is had to obvious inhibitory action.Finally, after 200 weeks, the specific discharge capacity of battery reaches 875mAh/g, far above the battery that does not add functional protection layer, and as in Fig. 4 above as shown in three curves, has the also obviously raising of coulomb efficiency of the battery of functional protection layer.In Fig. 4,0.2C represents to adopt the current density of 335mA/g to measure; 0.5C represents to adopt the current density of 837.5mA/g to measure.
Embodiment 2
First, adopt chemical method to prepare polypyrrole particle, concrete grammar is: aqueous dispersions (solution A) and the 0.1M ammonium persulfate solution (solution B) of preparing first respectively 0.1M pyrrole monomer, the in the situation that of rapid stirring, solution A is added drop-wise in solution B afterwards, reaction continues 12h at normal temperatures.Adopt afterwards deionized water and ethanol alternately to rinse product three times, filter and obtain product.The lower 60 ℃ of dry 24h of vacuum.Afterwards product is dispersed in nitromethane, adopts the method that is similar to embodiment 1, obtain adopting polypyrrole as the cathode of lithium of functional protection layer, assembling lithium-sulfur cell, test battery performance, result is as shown in table 1.
Embodiment 3
First, adopt chemical method to prepare polyaniline particle, concrete grammar is: aqueous dispersions (solution A) and the 0.1M ammonium persulfate solution (solution B) of preparing first respectively 0.1M aniline monomer, the in the situation that of rapid stirring, solution A is added drop-wise in solution B afterwards, reaction continues 12h at normal temperatures.Adopt afterwards deionized water and ethanol alternately to rinse product three times, filter and obtain product.The lower 60 ℃ of dry 24h of vacuum.Afterwards product is dispersed in nitromethane, adopts the method that is similar to embodiment 1, obtain adopting polypyrrole as the cathode of lithium of functional protection layer, assembling lithium-sulfur cell, test battery performance, result is as shown in table 1.
Embodiment 4
Adopt the nitromethane dispersion liquid (1wt% of PPy-co-PCL (polycaprolactone) copolymer; from sigma) adopt the method be similar to embodiment 1; obtain adopting PPy-co-PAL copolymer as the cathode of lithium of functional protection layer; assembling lithium-sulfur cell; test battery performance, result is as shown in table 1.
Embodiment 5
First, adopt chemical method to prepare PEDOT particle, concrete grammar is: aqueous dispersions (solution A) and the 0.1M ammonium persulfate solution (solution B) of preparing first respectively 0.1MEDOT monomer, the in the situation that of rapid stirring, solution A is added drop-wise in solution B afterwards, reaction continues 12h at normal temperatures.Adopt afterwards deionized water and ethanol alternately to rinse product three times, filter and obtain product.The lower 60 ℃ of dry 24h of vacuum.Afterwards product is dispersed in nitromethane, adopts the method that is similar to embodiment 1, obtain adopting PEDOT as the cathode of lithium of functional protection layer, assembling lithium-sulfur cell, test battery performance, result is as shown in table 1.
Table 1
Listed data and each figure result from table 1; functional protection layer the cycle performance that can obviously improve battery is set; this is because SEI film is stablized in the existence of functional protection layer, can stop the direct growth that contacts, can suppress lithium Zhi Jing simultaneously of many lithium sulfides and cathode of lithium.
Claims (5)
1. a cathode of lithium with functional protection layer, is characterized in that, described cathode of lithium have be coated in surface, the functional protection layer that comprises conducting polymer.
2. cathode of lithium according to claim 1, is characterized in that, the matrix of described cathode of lithium is lithium metal or lithium alloy.
3. cathode of lithium according to claim 1 and 2, is characterized in that, described conducting polymer is at least one in polypyrrole, polyaniline, polythiophene, polyacetylene, polyacrylonitrile, poly-ethylenedioxy thiophene and derivative thereof.
4. according to arbitrary described cathode of lithium in claim 1-3, it is characterized in that, the thickness of described functional protection layer is 10nm-100 μ m, preferably 1 μ m.
5. a lithium-sulfur cell that comprises arbitrary described cathode of lithium in claim 1-4, is characterized in that, in described lithium-sulfur cell, the functional protection layer of cathode of lithium contacts with electrolyte, makes to form stable interface between electrolyte and the matrix of cathode of lithium.
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| CN105322132A (en) * | 2014-07-31 | 2016-02-10 | 中国科学院上海硅酸盐研究所 | Positive electrode of lithium-sulfur battery with multifunctional elastic protection layer |
| CN105845891A (en) * | 2016-05-13 | 2016-08-10 | 清华大学 | Metal lithium negative electrode with dual-layer structure |
| CN106340616A (en) * | 2016-09-30 | 2017-01-18 | 上海空间电源研究所 | Lithium cathode used for lithium battery and provided with sandwich structure and preparation method thereof |
| CN106450229A (en) * | 2016-11-22 | 2017-02-22 | 深圳市鑫永丰科技有限公司 | Lithium metal powder coated by conductive polymer and preparation method and device of lithium metal powder |
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| CN105322132A (en) * | 2014-07-31 | 2016-02-10 | 中国科学院上海硅酸盐研究所 | Positive electrode of lithium-sulfur battery with multifunctional elastic protection layer |
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