CN103490027A - Membrane for lithium-sulfur battery and preparation method of membrane - Google Patents
Membrane for lithium-sulfur battery and preparation method of membrane Download PDFInfo
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Abstract
The invention discloses a membrane for a lithium-sulfur battery and a preparation method of the membrane. The membrane for the lithium-sulfur battery is composed of an ordinary battery membrane and a porous blocking layer loaded on the ordinary battery membrane. The porous barrier layer can permit lithium ions to pass through, but has blocking and absorption effects for a lithium polysulfide intermediate formed during charging and discharging processes of a sulfur positive electrode, so that active material sulfur can be limited on one side of the positive electrode, the situation that the sulfur positive electrode causes irreversible capacity fading since the lithium polysulfide intermediate formed during a cyclic process is dissolved in electrolyte can be prevented, and the cycle performance of the sulfur positive electrode is improved. Meanwhile, according to the membrane, a shuttle effect of the polysulfide to a lithium negative electrode further can be reduced, a sulfur-containing passivating layer is prevented from being formed on the surface of the lithium negative electrode during the cyclic process of the battery, and the cycle performance of the lithium negative electrode is improved. The invention further discloses the lithium-sulfur battery using the membrane, and the battery has high cycle capacity and excellent stable cycle performance. The membrane for the lithium-sulfur battery disclosed by the invention is simple in preparation method, raw materials are easily available, and the membrane is suitable for large-scale production, and has extremely high practicability.
Description
Technical field
The invention belongs to field of electrochemical power source, be specifically related to barrier film and preparation method thereof for a kind of lithium-sulfur cell, and the application of barrier film in lithium-sulfur cell and high volume energy density type energy storage device for described lithium-sulfur cell.
Background technology
Lithium-sulfur cell refers to that it is anodal adopting elemental sulfur, and lithium metal is negative pole, realizes a class novel metal lithium secondary battery of mutually changing between chemical energy and electric energy by the bielectron electrochemical reaction between sulphur and lithium.In lithium-sulfur cell, as anodal sulphur with as the lithium of negative pole, all there is very high theoretical capacity (Li:3860mA h g
-1, S:1675mA h g
-1), this makes lithium-sulfur cell have very high theoretical energy density (about 2600W h kg
-1), adapt to the development trend of strict mobile device to volume restrictions at present.
Yet the electrochemistry of lithium-sulfur cell has also been brought a series of serious problems, thereby hindered the practical application of battery.At first, ion and the electronic conductance of sulphur and its discharging product lithium sulfide are low, make the active material utilization of sulphur low, and cause the internal resistance of battery significantly to increase, thereby make battery show larger polarization in charge and discharge process, have reduced the energy efficiency of battery.Secondly, elemental sulfur, in its discharge process, can generate a series of many lithium sulfides intermediate (Li that are soluble in electrolyte
2s
x, x=4-8), these many lithium sulfides meeting strippings, in electrolyte, cause the sulphur positive pole irreversible capacity loss to occur in cyclic process.Simultaneously, the many lithium sulfides that are dissolved in electrolyte can move on cathode of lithium by " effect of shuttling back and forth ", and forming one deck main component is Li
2s
2and Li
2the electrochemistry inert layer of S, further damage the performance of battery.
In order to solve above these problems, people's and electrolyte anodal to sulphur usually carry out modification, attempt that active material sulphur is remained on to positive pole upper, improve the cycle performance of battery.A kind of lithium-sulfur cell positive pole is disclosed in Chinese patent CN1354529, in this positive pole, sulfenyl positive active material, conductive additive and binding agent all are filled in porous current collector, utilize anodal loose structure to disperse sulphur, thereby improve the utilance of sulfenyl positive active material; Simultaneously, loose structure also helps many lithium sulfides of absorption intermediate, improves the cycle performance of sulphur positive pole.Yet, because the aperture size in porous current collector is larger, to absorption and the maintenance poor effect of many lithium sulfides intermediate, thereby make sulphur stripping phenomenon in cyclic process obvious, cause circulation volume to descend rapidly.Use the lithium-sulfur cell cycle life of this sulphur positive pole only 10 to enclose.
Positive electrode and preparation method thereof for a kind of lithium-sulfur cell is disclosed in Chinese patent application CN103151524A, positive electrode comprises sulphur composite material and Carbon Materials, preparation process is, sulphur is assembled in the hole of metallic organic framework (MOF), prepare the sulphur composite material, then it is loaded on Carbon Materials.Utilize the polysulfide that the strong adsorption capacity of MOF material produces lithium-sulfur cell in charge and discharge process to be limited in its duct, stop it to be dissolved in electrolyte and migrate to negative pole, thereby will improve capacity and the cycle performance of lithium-sulfur cell.Yet because the pore volume of adopted MOF material is less, so the load capacity of sulphur in MOF is low, thereby be unfavorable for improving the content of sulphur in positive pole, the practicality of this class sulphur positive pole is poor.
Disclose a kind of electrolyte for lithium-sulfur cell in Chinese patent CN1487620, it comprises the salt with acid imide anion.This electrolyte can also comprise and has organic cations salt.When lithium-sulfur cell comprises the salt during as electrolyte with acid imide anion, the utilance of sulphur is improved, and cycle life characteristics and flash-over characteristic for example discharge capacity and average discharge volt also are improved.But this electrolyte can not fundamentally solve generation and the problems of dissolution of many lithium sulfides, use the lithium-sulfur cell of this electrolyte still to exist the sulphur stripping obvious, the shortcoming that cycle life is short.
Based on above reason, the present invention selects the lithium-sulfur cell barrier film as research object, by being set on the common batteries barrier film, one deck take micropore (<2nm) as main porous barrier layer, the present inventor is surprised to find, this porous barrier layer has good selection permeability, can allow lithium ion to pass through, the many lithium sulfides intermediate simultaneously the sulphur positive pole formed in charge and discharge process has and stops and suction-operated, thereby active material sulphur can be limited in to an anodal side, prevent that the sulphur positive pole is dissolved in the decay of electrolyte generation irreversible capacity because of the many lithium sulfides intermediate formed in cyclic process, improve the cycle performance of sulphur positive pole.In addition, described barrier film can also weaken the shuttle back and forth effect of polysulfide to cathode of lithium, prevents from forming the sulfur-bearing passivation layer on the cathode of lithium surface in the circulating battery process, improves the cycle performance of cathode of lithium.Use the lithium-sulfur cell of this barrier film to show high circulation volume and excellent stable circulation.
Summary of the invention
The purpose of this invention is to provide barrier film and preparation method thereof for a kind of lithium-sulfur cell, preferably, further improve the cyclical stability of lithium-sulfur cell by the porous barrier layer of selecting specific micropore size.
The invention provides a kind of lithium-sulfur cell barrier film, described barrier film by the common batteries barrier film and on it porous barrier layer of load form, it is characterized in that, described porous barrier layer is the pore type barrier layer, its micropore size size allows lithium ion to pass through, and many lithium sulfides intermediate that the sulphur positive pole is formed in charge and discharge process has and stops and suction-operated.Described porous barrier layer thickness is 10-100 μ m, and specific area is 200-4500m
2g
-1, preferred 400-3000m
2g
-1, pore volume is 0.1-3cm
3g
-1, preferred 0.5-2cm
3g
-1, micropore size is 0.3-2nm, preferably 0.3-1.5nm; Described porous can contain mesoporous and macropore in barrier layer, and its intermediary hole aperture is 2-50nm, and macropore diameter is 50-500nm, preferably 50-200nm.By selecting specific micropore size, the present invention is surprised to find, when adopting micropore size to be 0.6-2nm, prepared lithium-sulfur cell show better circulation volume and cyclical stability.
Described common batteries barrier film can be membrane for polymer, as polyethylene (PE) barrier film, polypropylene (PP) barrier film, polyimides (PI) barrier film, or its compound (as polypropylene, polyethylene (PP/PE/PP) barrier film) barrier film etc., it can be also the nonwoven fabrics barrier film, as the glass fibre non-woven barrier film, the non-woven fabrics of synthetic fiber barrier film, ceramic fiber paper barrier film etc.
In described porous barrier layer, Micropore volume accounts for the 30%-100% of total pore volume, preferably 60%-90%.
Described porous barrier layer consists of porous carrier.
Described porous carrier is selected from one or more in microporous carbon carrier and non-carbon porous carrier.
Described microporous carbon carrier is selected from one or more in electric capacity activated carbon, micropore carbon molecular sieve and high temperature pyrolysis carbon.
Described high temperature pyrolysis carbon is organic compound high temperature pyrolysis carbon.
Described organic compound is selected from saccharide compound, one or more in oxygen-containing polymers and polycyclic arene compound;
Wherein, described saccharide compound is selected from monose compound, disaccharide compound, one or more in three sugar compounds and compound of polysaccharide;
Described monose compound is selected from one or more in glucose, fructose, galactolipin and ribose;
Described disaccharide compound is selected from one or more in maltose, sucrose and lactose;
Described three sugar compounds are selected from one or more in gossypose and maltotriose;
Described compound of polysaccharide is selected from one or more in starch, cellulose, shitosan, alginic acid and glycogen;
Described oxygen-containing polymers is selected from one or more of the polymer that there is oxy radical on the main chains such as polyethylene glycol oxide (PEO), polyethylene glycol (PEG), polyacrylamide (PAM), polymethyl methacrylate (PMMA) or side chain;
Described polycyclic arene compound is selected from one or more in pitch, coal tar and catalytic cracking slurry oil;
In further research, a large amount of experimental results finds to adopt non-carbon porous carriers can stop and adsorb many lithium sulfides intermediate that the sulphur positive pole forms in charge and discharge process equally, and further improves other performances of carrier, as mechanical strength etc.Non-carbon porous carrier specifically is selected from one or more in micropore conducting polymer, micropore metal, micropore metal oxide, micropore semiconductive ceramic, micropore metal-organic backbone Coordination Polymers and non-carbon micro porous molecular sieve.
Wherein, described micropore conducting polymer is selected from one or more in polyaniline, polyacetylene, polyhenylene, polypyrrole and polythiophene;
Described micropore metal is selected from one or more in micropore gold, micropore platinum, micropore aluminium, micropore ruthenium, microporous nickel and micropore titanium;
Described micropore metal oxide is selected from one or more in micropore tri-iron tetroxide, micropore titanium dioxide and micropore ruthenium-oxide;
Described micropore semiconductive ceramic is selected from one or more in micro-pore silicon carbide and micropore zinc oxide;
Described micropore metal-organic backbone Coordination Polymers is selected from one or more in MIL-100 (Cr), MIL-101 (Cr) and MOF-5;
Described non-carbon micro porous molecular sieve is selected from one or more in 3A molecular sieve, 5A molecular sieve, 10X molecular sieve and 13X molecular sieve.
Described barrier film also can contain one or more in mesoporous carrier and macropore carrier.
Described mesoporous carrier is selected one or more in mesoporous carbon carrier and the mesoporous carrier of non-carbon.
Described mesoporous carbon carrier is selected one or more in phosphorus-ordered mesoporous carbon carrier and unordered mesoporous carbon carrier;
Wherein, described phosphorus-ordered mesoporous carbon carrier selects CMK-3 mesoporous carbon, CMK-5 mesoporous carbon etc. to have one or more in the mesoporous carbon carrier of order mesoporous structure;
Described unordered mesoporous carbon carrier is selected duct irregular structure, one or more in the porous carbon carrier of pore-size distribution in mesoporous scope.
The mesoporous carrier of described non-carbon is selected one or more in the mesoporous carrier of orderly non-carbon and the mesoporous carrier of unordered non-carbon;
Wherein, the mesoporous carrier of described orderly non-carbon selects SBA-15, MCM-41 etc. to have one or more in the mesoporous carrier of non-carbon of order mesoporous structure;
The mesoporous carrier of described unordered non-carbon is selected duct irregular structure, one or more in the mesoporous carrier of non-carbon of pore-size distribution in mesoporous scope.
Described macropore carrier is selected from one or more in macropore carbon carrier and non-carbon macropore carrier;
Wherein, ordered big hole carbon carrier and pore passage structure that described macropore carbon carrier selection has the regular pore canal structure are irregular, one or more in the unordered macropore carbon carrier of pore-size distribution in the macropore scope;
Orderly non-carbon macropore carrier and pore passage structure that described non-carbon macropore carrier selection has the regular pore canal structure are irregular, one or more in the unordered non-carbon macropore carrier of pore-size distribution in the macropore scope.
Can contain mesoporous and macropore in described porous carrier in order to form the classification pore passage structure in porous carrier.
Its pore passage structure of mesoporous and macropore comprised in described porous carrier can be orderly, can be also unordered.
But load elemental sulfur in described porous barrier layer, the content of sulphur in described barrier layer is the 0-85%(mass fraction).
The present invention provides the preparation method of a kind of above-mentioned lithium-sulfur cell with barrier film equally, it is characterized in that, described method comprises following steps:
(1) respectively for the preparation of the porous carrier, mesoporous carrier and the macropore carrier that form the porous barrier layer;
(2) described porous carrier, mesoporous carrier and macropore carrier are coated on the common batteries barrier film and form the porous barrier layer;
(3) by the barrier film of above-mentioned preparation drying and for lithium-sulfur cell.
Described method after respectively for the preparation of the porous carrier, mesoporous carrier and the macropore carrier that form the porous barrier layer, also can comprise sulphur is introduced to this step in porous carrier.
The present invention provides a kind of lithium-sulfur cell equally, comprises above-mentioned lithium-sulfur cell barrier film, cathode of lithium, sulphur positive pole and organic electrolyte;
Preferably, described sulphur positive pole is that sulphur, conductive additive and binding agent are made through blend, slurrying, smear, dry technological process;
Preferably, described conductive additive is one or more in carbon black, Super-P, Ketjen black;
Preferably, described binding agent and coordinative solvent are one or more in Kynoar (PVDF) (1-METHYLPYRROLIDONE (NMP) of take is solvent) or polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), butadiene-styrene rubber/sodium carboxymethylcellulose, sodium alginate (SA), gelatin (all take water as solvent);
Preferably, described organic electrolyte is ether electrolyte, and concentration is 0.1-2M, preferably 0.5-1.5M;
Preferably, in described ether electrolyte, solvent is selected from least one in DOX, glycol dimethyl ether and TRIGLYME, and solute is selected from least one in lithium hexafluoro phosphate, lithium perchlorate, lithium iodide and two (trimethyl fluoride sulfonyl) imine lithium.
In addition, the application of the lithium-sulfur cell that the invention described above provides in preparing high-energy-density type energy storage device, also belong to protection scope of the present invention.
The accompanying drawing explanation
The lithium-sulfur cell that Fig. 1 is embodiment 1 and membrane configuration schematic diagram.
The cycle performance of the lithium-sulfur cell that Fig. 2 is embodiment 1 under the 0.1C multiplying power.
The lithium-sulfur cell that Fig. 3 is embodiment 5 and membrane configuration schematic diagram.
The cycle performance of the lithium-sulfur cell that Fig. 4 is embodiment 5 under the 0.1C multiplying power.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Experimental technique described in following embodiment, if no special instructions, be conventional method; Described reagent and material, all can obtain from commercial channels.
Embodiment 1 is without the preparation of barrier film and the application in lithium-sulfur cell for sulphur type lithium-sulfur cell
The porous carrier adopted in experiment is electric capacity activated carbon (purchased from Japanese Kuraray company), and specific area is 920m
2g
-1, pore volume is 0.50cm
3g
-1, average pore size is 2.0nm.
Above-mentioned porous carrier is coated to the porous barrier layer that the upper formation of plain polypropylene single-layer septum (purchased from Japanese Asahi Kasei Corporation, thickness is 25 μ m) thickness is 25 μ m, dry rear standby.
By sulphur powder (purchased from traditional Chinese medicines reagent Co., Ltd) and carbon black, binding agent Kynoar in mass ratio 8:0.5:1.5 mix, and add the solvent 1-METHYLPYRROLIDONE, through technological processes such as slurrying, smear, dryings, obtain the sulphur positive pole.
Take the lithium sheet as negative pole, the barrier film, sulphur positive pole and the organic electrolyte assembling lithium-sulfur cell that coordinate above-mentioned preparation, organic electrolyte is selected ether electrolyte, and (concentration is 1 of 1M lithium hexafluoro phosphate, 3-dioxolanes/glycol dimethyl ether mixed solution, wherein DOX and glycol dimethyl ether volume ratio are 1:1).
Use discharges and recharges instrument above-mentioned lithium-sulfur cell is carried out to the test of room temperature constant current charge-discharge, and the test voltage interval is 1.5-2.5V.Battery capacity and charge-discharge magnification are all with the Mass Calculation of sulphur.Lithium-sulfur cell (is equivalent to current density 168mA g in the 0.1C multiplying power
-1) under the first circle discharge capacity be 1100mA h g
-1, first circle enclosed pasture efficiency is 89.5%, and from the second circle, enclosed pasture efficiency maintains 100% left and right always, and after 50 circle circulations, discharge capacity is still possessed 810mA h g
-1, demonstrate good cycle performance.
In the situation that do not change other experiment conditions, use different porous carriers to be coated on various common diaphragms and prepare the porous barrier layer, and assemble lithium-sulfur cell with the lithium-sulfur cell obtained with barrier film, record battery performance as shown in table 1 below.As seen from the table, use the lithium-sulfur cell of above-mentioned preparation all to show high circulation volume and good cyclical stability with the lithium-sulfur cell of barrier film.
Barrier film prepared based on different porous carriers by table 1 performance comparison during for lithium-sulfur cell
Annotate: polymer MIL-100 (Cr) is the Coordination Polymers (Materiaux Institut Lavoisier) of chromium and trimesic acid formation
Comparative Examples 1.1
Other condition is identical with embodiment 1, adopts the plain polypropylene barrier film when difference only is to assemble lithium-sulfur cell, the first circle discharge capacity of the lithium-sulfur cell of assembling under the 0.1C multiplying power be 850mA h g
-1, the discharge capacity after 143%, the 50 circle circulation of first circle enclosed pasture efficiency is 20mA h g
-1.First circle enclosed pasture efficiency is greater than 100%, and the sharp-decay of follow-up capacity, illustrates that there is the effect of shuttling back and forth significantly in the lithium-sulfur cell adopted without porous barrier layer common diaphragm, and the effect of simultaneously shuttling back and forth causes significant capacity attenuation.
Comparative Examples 1.2
Other conditions are identical with embodiment 1, and difference only is that the average pore size of used electric capacity active carbon is 2.1nm, the first circle discharge capacity of the lithium-sulfur cell of assembling under the 0.1C multiplying power be 860mA h g
-1, the discharge capacity after 50 circle circulations is 640mA h g
-1.
Comparative Examples 1.3
Other conditions are identical with embodiment 1, and difference only is that the average pore size of used electric capacity active carbon is 0.2nm, the first circle discharge capacity of the lithium-sulfur cell of assembling under the 0.1C multiplying power be 800mA h g
-1, the discharge capacity after 50 circle circulations is 76mA h g
-1.
By table 1, embodiment 1 and Comparative Examples 1.1,1.2 and 1.3 more known, the selection of using the lithium-sulfur cell with microporous carbon barrier layer barrier film of the present invention to show high circulation volume and excellent stable circulation, particularly micropore size has a significant effect to discharge capacity and cycle performance.For example, using the electric capacity active carbon in embodiment 1 as porous carrier, after its first circle discharge capacity and 50 circle circulations, discharge capacity is significantly better than the technique effect of Comparative Examples 1.2 and 1.3.
In addition, with respect to the microporous carbon carrier, non-carbon porous carrier provided by the invention (as, micropore tri-iron tetroxide, micropore metal-organic backbone Coordination Polymers, as the 13X molecular sieve) has better mechanical strength (as puncture intensity).
Embodiment 2 is without the preparation of barrier film and the application in lithium-sulfur cell for sulphur type lithium-sulfur cell
The porous carrier adopted in experiment is electric capacity activated carbon (purchased from Japanese Kuraray company), and specific area is 920m
2g
-1, pore volume is 0.50cm
3g
-1, average pore size is 0.6nm.Except porous carrier, also used CMK-3 phosphorus-ordered mesoporous carbon carrier (purchased from Nanjing pioneer Nono-material Science & Technology Ltd.) in experiment, specific area is 1430m
2g
-1, pore volume is 1.51cm
3g
-1, average pore size is 3.8nm.The consumption of two kinds of porous carriers is the 3:1(mass ratio).
After fully being mixed, two kinds of porous carriers are coated to the porous barrier layer that the upper formation of three layers of barrier film of plain polypropylene/polyethylene/polypropylene (purchased from U.S. Celgard, 40 μ m) thickness is 40 μ m, and dry rear standby.
By sulphur powder (purchased from traditional Chinese medicines reagent Co., Ltd) and Super-P, binding agent Kynoar in mass ratio 7:1.5:1.5 mix, and add the solvent 1-METHYLPYRROLIDONE, through technological processes such as slurrying, smear, dryings, obtain the sulphur positive pole.
Take the lithium sheet as negative pole, coordinate barrier film, sulphur positive pole and the organic electrolyte assembling lithium-sulfur cell of above-mentioned preparation, organic electrolyte is selected ether electrolyte (the TRIGLYME solution that concentration is the 1M lithium perchlorate).
Use discharges and recharges instrument above-mentioned lithium-sulfur cell is carried out to the test of room temperature constant current charge-discharge, and the test voltage interval is 1.5-2.5V.Battery capacity and charge-discharge magnification are all with the Mass Calculation of sulphur.The first circle discharge capacity of lithium-sulfur cell under the 0.1C multiplying power is 1540mA h g
-1, first circle enclosed pasture efficiency is 98%, and from the second circle, enclosed pasture efficiency maintains 100% left and right always, and after 50 circle circulations, discharge capacity is still possessed 1160mA h g
-1, demonstrate good cycle performance.
The comparative example 2.1
Other conditions are identical with embodiment 2, and difference has only been used the CMK-3 phosphorus-ordered mesoporous carbon carrier, do not use electric capacity activated carbon porous carrier, the first circle discharge capacity of the lithium-sulfur cell of assembling under the 0.1C multiplying power be 720mA h g
-1, the discharge capacity after 50 circle circulations is 215mA h g
-1, capacity attenuation is very fast, illustrates that the microporous carbon barrier layer in barrier film can significantly suppress the effect of shuttling back and forth, thereby improves the cycle performance of lithium-sulfur cell.
Embodiment 3 is without the preparation of barrier film and the application in lithium-sulfur cell for sulphur type lithium-sulfur cell
The porous carrier adopted in experiment is electric capacity activated carbon (purchased from Japanese Kuraray company), and specific area is 920m
2g
-1, pore volume is 0.50cm
3g
-1, average pore size is 0.6nm.Except porous carrier, also used the mesoporous carrier of the orderly non-carbon of SBA-15 (purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd.) in experiment, specific area is 600m
2g
-1, pore volume is 0.52cm
3g
-1, average pore size is 8nm, and utilizes the monodisperse silica nanosphere of diameter 250nm to scribe again standby three-dimensional ordered macroporous carbon, specific area 200m
2g
-1, pore volume 2.5cm
3g
-1, average pore size is 250nm.The consumption of three kinds of porous carriers is the 1:1:1(mass ratio).
After fully being mixed, three kinds of porous carriers are coated to the porous barrier layer that the upper formation of fibreglass diaphragm (purchased from U.S. Whatman, thickness is 500 μ m) thickness is 100 μ m, and dry rear standby.
By sulphur powder (purchased from traditional Chinese medicines reagent Co., Ltd) and Ketjen black, binding agent sodium alginate in mass ratio 8:1:1 mix, and add aqueous solvent, through technological processes such as slurrying, smear, dryings, obtain the sulphur positive pole.
Take the lithium sheet as negative pole, coordinate barrier film, sulphur positive pole and the organic electrolyte assembling lithium-sulfur cell of above-mentioned preparation, organic electrolyte is selected ether electrolyte (the TRIGLYME solution that concentration is the 1M lithium perchlorate).
Use discharges and recharges instrument above-mentioned lithium-sulfur cell is carried out to the test of room temperature constant current charge-discharge, and the test voltage interval is 1.5-2.5V.Battery capacity and charge-discharge magnification are all with the Mass Calculation of sulphur.The first circle discharge capacity of lithium-sulfur cell under the 0.1C multiplying power is 1480mA h g
-1, first circle enclosed pasture efficiency is 83%, and from the second circle, enclosed pasture efficiency maintains 100% left and right always, and after 50 circle circulations, discharge capacity is still possessed 980mA h g
-1, demonstrate good cycle performance.
The comparative example 3.1
Other conditions are identical with embodiment 3, and difference is not use electric capacity activated carbon porous carrier in the porous barrier layer of barrier film.The first circle discharge capacity of the lithium-sulfur cell of assembling under the 0.1C multiplying power is 720mA h g
-1, the discharge capacity after 50 circle circulations is 89mA h g
-1.Adopt mesoporous and lithium-sulfur cell capacity attenuation macropore porous barrier layer very fast, illustrate that the microporous carbon barrier layer can significantly suppress the effect of shuttling back and forth, thereby improve the cycle performance of lithium-sulfur cell.
Embodiment 4 is without the preparation of barrier film and the application in lithium-sulfur cell for sulphur type lithium-sulfur cell
The carrier material adopted in experiment is that sodium alginate (purchased from traditional Chinese medicines reagent Co., Ltd) adds the porous carbon of thermosetting in inert atmosphere (argon gas) under 800 ℃, this porous carbon has by micropore, the mesoporous and common classification pore passage structure formed of macropore, and its specific area is 1750m
2g
-1, pore volume is 2cm
3g
-1, average micropore size is 0.6nm, Micropore volume is 0.5cm
3g
-1, average mesoporous aperture is 6nm, average macropore diameter is 150nm.
Above-mentioned porous carrier materials is coated to the porous barrier layer that the upper formation thickness of common polythene single-layer septum (purchased from the eastern combustion of Japan, thickness is 25 μ m) is 25 μ m, dry rear standby.
By sulphur powder (purchased from traditional Chinese medicines reagent Co., Ltd) and carbon black, binding agent sodium carboxymethylcellulose in mass ratio 8:0.5:1.5 mix, and add aqueous solvent, through technological processes such as slurrying, smear, dryings, obtain the sulphur positive pole.
Take the lithium sheet as negative pole, the barrier film, sulphur positive pole and the organic electrolyte assembling lithium-sulfur cell that coordinate above-mentioned preparation, organic electrolyte is selected ether electrolyte, and (concentration is 1 of 1M lithium hexafluoro phosphate, 3-dioxolanes/glycol dimethyl ether mixed solution, wherein DOX and glycol dimethyl ether volume ratio are 1:1).
Use discharges and recharges instrument above-mentioned lithium-sulfur cell is carried out to the test of room temperature constant current charge-discharge, and the test voltage interval is 1.5-2.5V.Battery capacity and charge-discharge magnification are all with the Mass Calculation of sulphur.The first circle discharge capacity of lithium-sulfur cell under the 0.1C multiplying power is 1520mA h g
-1, first circle enclosed pasture efficiency is 86.5%, and from the second circle, enclosed pasture efficiency maintains 100% left and right always, and after 50 circle circulations, discharge capacity is still possessed 930mA h g
-1, demonstrate good cycle performance.
The preparation of barrier film and the application in lithium-sulfur cell for embodiment 5 sulfur-type lithium-sulfur cells
The porous carrier adopted in experiment is electric capacity activated carbon (purchased from Japanese Kuraray company), and specific area is 920m
2g
-1, pore volume is 0.50cm
3g
-1, average pore size is 0.6nm.By sulphur powder (purchased from traditional Chinese medicines reagent Co., Ltd) and electric capacity activated carbon in mass ratio 1:1 mix, by mode of heating, sulphur is loaded in activated carbon afterwards, make sulfur content 50%(mass fraction) porous carrier.
Porous carrier after above-mentioned sulfur loaded is coated to the porous barrier layer that the upper formation of plain polypropylene single-layer septum (purchased from Japanese Asahi Kasei Corporation, thickness is 25 μ m) thickness is 25 μ m, dry rear standby.
By sulphur powder and carbon black, binding agent Kynoar in mass ratio 8:0.5:1.5 mix, and add the solvent 1-METHYLPYRROLIDONE, through technological processes such as slurrying, smear, dryings, obtain the sulphur positive pole.
Take the lithium sheet as negative pole, the barrier film, sulphur positive pole and the organic electrolyte assembling lithium-sulfur cell that coordinate above-mentioned preparation, organic electrolyte is selected ether electrolyte, and (concentration is 1 of 1M lithium hexafluoro phosphate, 3-dioxolanes/glycol dimethyl ether mixed solution, wherein DOX and glycol dimethyl ether volume ratio are 1:1).
Use discharges and recharges instrument above-mentioned lithium-sulfur cell is carried out to the test of room temperature constant current charge-discharge, and the test voltage interval is 1.5-2.5V.Battery capacity and charge-discharge magnification all calculate with the gross mass of sulphur in barrier film and sulphur positive pole.Lithium-sulfur cell (is equivalent to current density 168mA g in the 0.1C multiplying power
-1) under the first circle discharge capacity be 940mA h g
-1, first circle enclosed pasture efficiency is 92%, and from the second circle, enclosed pasture efficiency maintains 100% left and right always, and after 50 circle circulations, discharge capacity is still possessed 830mA h g
-1, demonstrate good cycle performance.
The preparation of barrier film and the application in lithium-sulfur cell for embodiment 6 sulfur-type lithium-sulfur cells
The porous carrier adopted in experiment is electric capacity activated carbon (purchased from Japanese Kuraray company), and specific area is 920m
2g
-1, pore volume is 0.50cm
3g
-1, average pore size is 0.6nm.Except porous carrier, also used CMK-3 phosphorus-ordered mesoporous carbon carrier (purchased from Nanjing pioneer Nono-material Science & Technology Ltd.) in experiment, specific area is 1430m
2g
-1, pore volume is 1.51cm
3g
-1, average pore size is 3.8nm.The consumption of two kinds of porous carriers is the 3:1(mass ratio).
By two kinds of porous carriers and sulphur powder (purchased from traditional Chinese medicines reagent Co., Ltd) by different quality than fully mixing.By mode of heating, sulphur is loaded in activated carbon afterwards, make the porous carrier with different sulfur contents.
The porous carrier of above-mentioned preparation is coated to the porous barrier layer that the upper formation of three layers of barrier film of plain polypropylene/polyethylene/polypropylene (purchased from U.S. Celgard, 40 μ m) thickness is 40 μ m, dry rear standby.
By sulphur powder and Super-P, binding agent Kynoar in mass ratio 7:1.5:1.5 mix, and add the solvent 1-METHYLPYRROLIDONE, through technological processes such as slurrying, smear, dryings, obtain the sulphur positive pole.
Take the lithium sheet as negative pole, coordinate barrier film, sulphur positive pole and the organic electrolyte assembling lithium-sulfur cell of above-mentioned preparation, organic electrolyte is selected ether electrolyte (the TRIGLYME solution that concentration is the 1M lithium perchlorate).
Use discharges and recharges instrument above-mentioned lithium-sulfur cell is carried out to the test of room temperature constant current charge-discharge, and the test voltage interval is 1.5-2.5V, and the test multiplying power is 0.1C.Battery capacity and charge-discharge magnification all calculate with the gross mass of sulphur in barrier film and sulphur positive pole.As can be seen from Table 2, the sulfur content on barrier film in the porous barrier layer is at the 20%-60%(mass fraction) between while changing, use the lithium-sulfur cell of above-mentioned preparation all to show high circulation volume and good cyclical stability with the lithium-sulfur cell of barrier film.
The performance comparison when barrier film of the different sulfur contents of table 2 is used for lithium-sulfur cell
The preparation of barrier film and the application in lithium-sulfur cell for embodiment 7 sulfur-type lithium-sulfur cells
The carrier material adopted in experiment is that sodium alginate (purchased from traditional Chinese medicines reagent Co., Ltd) adds the porous carbon of thermosetting in inert atmosphere (argon gas) under 800 ℃, this porous carbon has by micropore, the mesoporous and common classification pore passage structure formed of macropore, and its specific area is 1750m
2g
-1, pore volume is 2cm
3g
-1, average micropore size is 0.6nm, Micropore volume is 0.5cm
3g
-1, average mesoporous aperture is 6nm, average macropore diameter is 150nm.
The porous carrier of above-mentioned preparation is mixed than fully by different quality with sulphur powder (purchased from traditional Chinese medicines reagent Co., Ltd), by mode of heating, sulphur is loaded in porous carrier afterwards, make the porous carrier with different sulfur contents.
The porous carrier materials of above-mentioned preparation is coated to the porous barrier layer that the upper formation thickness of common polythene single-layer septum (purchased from the eastern combustion of Japan, thickness is 25 μ m) is 25 μ m, dry rear standby.
By sulphur powder (purchased from traditional Chinese medicines reagent Co., Ltd) and carbon black, binding agent sodium carboxymethylcellulose in mass ratio 8:0.5:1.5 mix, and add aqueous solvent, through technological processes such as slurrying, smear, dryings, obtain the sulphur positive pole.
Take the lithium sheet as negative pole, the barrier film, sulphur positive pole and the organic electrolyte assembling lithium-sulfur cell that coordinate above-mentioned preparation, organic electrolyte is selected ether electrolyte, and (concentration is 1 of 1M lithium hexafluoro phosphate, 3-dioxolanes/glycol dimethyl ether mixed solution, wherein DOX and glycol dimethyl ether volume ratio are 1:1).
Use discharges and recharges instrument above-mentioned lithium-sulfur cell is carried out to the test of room temperature constant current charge-discharge, and the test voltage interval is 1.5-2.5V, and the test multiplying power is 0.1C.Battery capacity and charge-discharge magnification all calculate with the gross mass of sulphur in barrier film and sulphur positive pole.As can be seen from Table 2, the sulfur content on barrier film in the porous barrier layer is at the 15%-80%(mass fraction) between while changing, use the lithium-sulfur cell of above-mentioned preparation all to show high circulation volume and good cyclical stability with the lithium-sulfur cell of barrier film.
The performance comparison when barrier film of the different sulfur contents of table 3 is used for lithium-sulfur cell
To sum up, lithium-sulfur cell of the present invention can effectively stop and adsorb with barrier film many lithium sulfides intermediate that the sulphur positive pole forms in charge and discharge process, thereby active material sulphur can be limited in to an anodal side, prevent that the sulphur positive pole from, because the many lithium sulfides intermediate formed in cyclic process is dissolved in the decay of electrolyte generation irreversible capacity, improving the cycle performance of sulphur positive pole.Simultaneously, described barrier film can also weaken the shuttle back and forth effect of polysulfide to cathode of lithium, prevents from forming the sulfur-bearing passivation layer on the cathode of lithium surface in the circulating battery process, improves the cycle performance of cathode of lithium.Use the lithium-sulfur cell of barrier film of the present invention to show high circulation volume and excellent stable circulation.Lithium-sulfur cell of the present invention is simple by the barrier film preparation method, and raw material is easy to get, and suitable for mass production possesses very high practicality.
Claims (8)
1. a lithium-sulfur cell barrier film, described barrier film by the common batteries barrier film and on it porous barrier layer of load form, described porous barrier layer is the pore type barrier layer, its micropore size size allows lithium ion to pass through, and many lithium sulfides intermediate that the sulphur positive pole is formed in charge and discharge process has and stops and suction-operated, it is characterized in that, described porous barrier layer thickness is 10-100 μ m, and specific area is 200-4500m
2g
-1, preferred 400-3000m
2g
-1, pore volume is 0.1-3cm
3g
-1, preferred 0.5-2cm
3g
-1, micropore size is 0.3-2nm, preferred 0.3-1.5nm, and described porous can contain mesoporous and macropore in barrier layer, and its intermediary hole aperture is 2-50nm, and macropore diameter is 50-500nm, preferably 50-200nm.
2. lithium-sulfur cell barrier film according to claim 1, it is characterized in that, described common batteries barrier film can be membrane for polymer, as polyethylene (PE) barrier film, polypropylene (PP) barrier film, polyimides (PI) barrier film, or its compound (as polypropylene, polyethylene (PP/PE/PP) barrier film) barrier film etc., can be also the nonwoven fabrics barrier film, as the glass fibre non-woven barrier film, the non-woven fabrics of synthetic fiber barrier film, the ceramic fiber paper barrier film.
3. lithium-sulfur cell barrier film according to claim 1, is characterized in that, in described porous barrier layer, Micropore volume accounts for the 30%-100% of total pore volume, preferred 60%-90%, or preferably described porous barrier layer consists of porous carrier; More preferably, described porous carrier is selected from one or more in microporous carbon carrier and non-carbon porous carrier; Further preferably, described microporous carbon carrier is selected from one or more in electric capacity activated carbon, micropore carbon molecular sieve and high temperature pyrolysis carbon; Particularly, described high temperature pyrolysis carbon is preferably organic compound high temperature pyrolysis carbon, and described organic compound is preferably selected from saccharide compound, one or more in oxygen-containing polymers and polycyclic arene compound
Wherein, described saccharide compound is selected from monose compound, disaccharide compound, one or more in three sugar compounds and compound of polysaccharide;
Described monose compound is selected from one or more in glucose, fructose, galactolipin and ribose;
Described disaccharide compound is selected from one or more in maltose, sucrose and lactose;
Described three sugar compounds are selected from one or more in gossypose and maltotriose;
Described compound of polysaccharide is selected from one or more in starch, cellulose, shitosan, alginic acid and glycogen;
Described oxygen-containing polymers is selected from one or more of the polymer that there is oxy radical on polyethylene glycol oxide (PEO), polyethylene glycol (PEG), polyacrylamide (PAM), these main chains of polymethyl methacrylate (PMMA) or side chain;
Described polycyclic arene compound is selected from one or more in pitch, coal tar and catalytic cracking slurry oil.
4. lithium-sulfur cell barrier film according to claim 3, it is characterized in that, described non-carbon porous carrier specifically is selected from one or more in micropore conducting polymer, micropore metal, micropore metal oxide, micropore semiconductive ceramic, micropore metal-organic backbone Coordination Polymers and non-carbon micro porous molecular sieve;
Wherein, described micropore conducting polymer is selected from one or more in polyaniline, polyacetylene, polyhenylene, polypyrrole and polythiophene;
Described micropore metal is selected from one or more in micropore gold, micropore platinum, micropore aluminium, micropore ruthenium, microporous nickel and micropore titanium;
Described micropore metal oxide is selected from one or more in micropore tri-iron tetroxide, micropore titanium dioxide and micropore ruthenium-oxide;
Described micropore semiconductive ceramic is selected from one or more in micro-pore silicon carbide and micropore zinc oxide;
Described micropore metal-organic backbone Coordination Polymers is selected from one or more in MIL-100 (Cr), MIL-101 (Cr) and MOF-5;
Described non-carbon micro porous molecular sieve is selected from one or more in 3A molecular sieve, 5A molecular sieve, 10X molecular sieve and 13X molecular sieve.
5. lithium-sulfur cell barrier film according to claim 4, is characterized in that, described barrier film also can contain one or more in mesoporous carrier and macropore carrier; Preferably, described mesoporous carrier is selected one or more in mesoporous carbon carrier and the mesoporous carrier of non-carbon; More preferably, described mesoporous carbon carrier is selected one or more in phosphorus-ordered mesoporous carbon carrier and unordered mesoporous carbon carrier;
Wherein, described phosphorus-ordered mesoporous carbon carrier selects CMK-3 mesoporous carbon, CMK-5 mesoporous carbon etc. to have one or more in the mesoporous carbon carrier of order mesoporous structure;
Described unordered mesoporous carbon carrier is selected duct irregular structure, one or more in the porous carbon carrier of pore-size distribution in mesoporous scope;
Preferably, the mesoporous carrier of described non-carbon is selected one or more in the mesoporous carrier of orderly non-carbon and the mesoporous carrier of unordered non-carbon;
Wherein, the mesoporous carrier of described orderly non-carbon selects SBA-15, MCM-41 etc. to have one or more in the mesoporous carrier of non-carbon of order mesoporous structure;
The mesoporous carrier of described unordered non-carbon is selected duct irregular structure, one or more in the mesoporous carrier of non-carbon of pore-size distribution in mesoporous scope;
Also preferably, described macropore carrier is selected from one or more in macropore carbon carrier and non-carbon macropore carrier;
Wherein, ordered big hole carbon carrier and pore passage structure that described macropore carbon carrier selection has the regular pore canal structure are irregular, one or more in the unordered macropore carbon carrier of pore-size distribution in the macropore scope;
Orderly non-carbon macropore carrier and pore passage structure that described non-carbon macropore carrier selection has the regular pore canal structure are irregular, one or more in the unordered non-carbon macropore carrier of pore-size distribution in the macropore scope;
Preferably, can contain mesoporous and macropore in described porous carrier in order to form the classification pore passage structure in porous carrier;
Preferably, its pore passage structure of mesoporous and macropore comprised in described porous carrier can be orderly, can be also unordered;
Preferably, but load elemental sulfur in described porous barrier layer, and the content of sulphur in described barrier layer is for being greater than 0 to 85 quality %.
6. one kind as the preparation method of lithium-sulfur cell as described in claim 1-5 with barrier film, it is characterized in that, described method comprises following steps:
(1) respectively for the preparation of the porous carrier, mesoporous carrier and the macropore carrier that form the porous barrier layer;
(2) described porous carrier, mesoporous carrier and macropore carrier are coated on the common batteries barrier film and form the porous barrier layer;
(3) by the barrier film of above-mentioned preparation drying and for lithium-sulfur cell.
Preferably, described method after respectively for the preparation of the porous carrier, mesoporous carrier and the macropore carrier that form the porous barrier layer, can be introduced sulphur in porous carrier.
7. a lithium-sulfur cell, comprise the described lithium-sulfur cell barrier film of claim 1-5, cathode of lithium, sulphur positive pole and organic electrolyte;
Preferably, described sulphur positive pole is that sulphur, conductive additive and binding agent are made through blend, slurrying, smear, dry technological process;
Preferably, described conductive additive is one or more in carbon black, Super-P, Ketjen black;
Preferably, described binding agent and coordinative solvent are one or more in Kynoar (PVDF) (1-METHYLPYRROLIDONE (NMP) of take is solvent) or polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), butadiene-styrene rubber/sodium carboxymethylcellulose, sodium alginate (SA), gelatin (all take water as solvent);
Preferably, described organic electrolyte is ether electrolyte, and concentration is 0.1-2M, preferably 0.5-1.5M;
Preferably, in described ether electrolyte, solvent is selected from least one in DOX, glycol dimethyl ether and TRIGLYME, and solute is selected from least one in lithium hexafluoro phosphate, lithium perchlorate, lithium iodide and two (trimethyl fluoride sulfonyl) imine lithium.
8. the application of lithium-sulfur cell in preparing high-energy-density type energy storage device according to claim 7.
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