CN105280867A - Modified diaphragm special for Li-S battery, preparation method of modified diaphragm and Li-S battery - Google Patents
Modified diaphragm special for Li-S battery, preparation method of modified diaphragm and Li-S battery Download PDFInfo
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- CN105280867A CN105280867A CN201510598350.7A CN201510598350A CN105280867A CN 105280867 A CN105280867 A CN 105280867A CN 201510598350 A CN201510598350 A CN 201510598350A CN 105280867 A CN105280867 A CN 105280867A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
In a modified diaphragm special for a Li-S battery, the surface at one side, close to a positive electrode, of a general diaphragm is coated with a Ketjen black coated metal oxide modified coating layer added with a conductive agent. A preparation method of the modified diaphragm special for the Li-S battery comprises the following steps of sequentially mixing Ketjen black and an aqueous solution of a metal oxide inorganic salt, carrying out dispersion, drying and calcinations to prepare a paste, and applying the paste at one side, close to the positive electrode, of a commercial diaphragm to obtain the modified diaphragm. The invention also discloses the Li-S battery applying the modified diaphragm special for the Li-S battery. The Li-S battery is prepared by taking metal lithium as a negative electrode, applying a Ketjen balck-sulfur composite material onto an aluminum foil to serve as the positive electrode, taking a mixture of LiTFSI, lithium nitrate, 1,3-dioxolane and glycol dimethyl ether as an electrolyte and assembling the modified diaphragm special for the Li-S battery. With the modified diaphragm disclosed by the invention, a "shuttle effect" of polysulfide lithium in the Li-S battery can be prevented, the electrochemical performance and the capacity of the Li-S battery are improved, the cycle lifetime of the Li-S battery is prolonged, and the modified diaphragm is suitably used for production at a large scale.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly the lithium-sulfur cell of dedicated modified barrier film of a kind of lithium-sulfur cell and preparation method thereof and composition thereof.
Background technology
A kind of model electrochemical energy-storage system that lithium sulphur (Li-S) battery is take lithium as negative pole (theoretical specific capacity 3860mAh/g), sulphur is positive pole (theoretical specific capacity 1675mAh/g), theoretical specific energy can reach 2600Wh/kg, much larger than the commercial Li-ion battery of present stage, and sulphur rich reserves, cheapness, low toxicity or nontoxic feature make this system great commercial value on earth.But the electrochemistry of lithium-sulfur cell has much serious problem to be badly in need of solving.First, the conductivity of active material sulphur and discharging product thereof is very low, reduces the energy efficiency of battery; Secondly, the many lithium sulfides of intermediate product of electrochemical reaction are soluble in electrolyte and produce irreversible capacitance loss, reduce utilance and the cycle performance of sulphur, and increase ion migration resistance; Meanwhile, the many lithium sulfides be dissolved in organic electrolyte migrate to cathode of lithium due to " effect of shuttling back and forth ", form the chemical property that SEI film reduces battery further.
To shuttle back and forth effect, sulphur poorly conductive, these three subject matters of volumetric expansion to solve lithium-sulfur cell polysulfide, in the last few years, people mainly carried out modification to sulphur positive pole, such as, by porous activated carbon, and carbon nano-tube, the material with carbon elements such as Graphene and sulphur compound.As Chinese patent CN103456929A discloses a kind of lithium-sulphur cell positive electrode, this positive electrode is composited by elemental sulfur and the classifying porous charcoal of three-dimensional; Preparation method first prepares the precursor complex of three-dimensional classifying porous charcoal by solvent-thermal method, obtain three-dimensional classifying porous charcoal after carbonization, then with sulphur compound, namely obtain lithium sulfur battery anode material.This three-dimensional classifying porous charcoal has multiple level cavernous structure be made up of mesopore and micropore, and it is mutually through between cavernous structure, there is very large specific area, active material elemental sulfur (quality of fault sulphur accounts for 50 ~ 90% of three-dimensional classifying porous carbonaceous amount) can be held in a large number, and central hole structure contributes to suppressing sulphur simple substance and polysulfide dissolving in the electrolytic solution, keep higher active substances in cathode materials utilance, be also conducive to the raising of lithium-sulfur cell cycle performance.
As Chinese patent CN103682280A discloses a kind of lithium sulfur battery anode material, comprise sulfur granules, conductive additive and Graphene.With graphene oxide, conductive additive and sulfur granules for raw material, spraying dry is carried out after conductive additive and sulfur granules being heat-treated, then the conductive additive obtained, sulfur compound are mixed with graphene oxide, adopt reducing agent redox graphene, obtain lithium sulfur battery anode material.Conductive additive and sulfur granules form conductive network, improve the conductivity of positive electrode; The conductivity of Graphene excellence further increases the conductivity of positive electrode; Graphene effectively can also suppress the dissolving of polysulfide, improves the cycle performance of lithium-sulfur cell.But still can not suppress completely the modification of positive electrode " effect of shuttling back and forth " of polysulfide, the carbon-based material used in positive pole modification can only fetter the many lithium sulfides of part, the capacity of lithium-sulfur cell and energy still can decline very soon, and therefore wanting to obtain high performance lithium-sulfur cell only only can not carry out modification to sulphur positive pole.
In order to the effect of shuttling back and forth of many lithium sulfides better can be suppressed, many lithium sulfides that the absorption of one deck barrier layer is escaped from positive pole can be added between sulfur-based positive electrode and barrier film.As Chinese patent CN103647104A discloses a kind of lithium-sulfur cell, the barrier layer formed by conducting polymer nano material is provided with between sulphur positive pole and barrier film, the high conductivity on barrier layer facilitates the transmission of ion and electronics on the one hand, lithium-sulfur cell electric discharge intermediate product dissolution and transport in the electrolytic solution can be stoped on the other hand, and then improve cycle performance of battery.Chinese patent CN103490027A discloses a kind of lithium-sulfur cell barrier film, described lithium-sulfur cell barrier film by common batteries barrier film and on it Porous barriers of load form.Porous barriers can allow lithium ion to pass through, but has stop and suction-operated to many lithium sulfides intermediate that sulphur positive pole is formed in charge and discharge process.Its Porous barriers is the activated carbon bought of market or the porous carbon prepared of laboratory.But these conducting polymer composites and the absorption major part of porous carbon materials to many lithium sulfides are a kind of physical absorptions based on Van der Waals force, limited sorption capacity.Therefore, study barrier layer and the barrier film compound of a kind of more excellent absorption and catalytic performance, the chemical property improving battery has further been very necessary.
Summary of the invention
Technical problem to be solved by this invention is, overcome the deficiency and defect mentioned in above background technology, dedicated modified barrier film of a kind of lithium-sulfur cell and preparation method thereof and lithium-sulfur cell are provided, on the basis of carbon sulphur anode composite modification, modification is carried out to the barrier film of battery, improves the electrochemical properties of lithium-sulfur cell further.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is for providing a kind of lithium-sulfur cell dedicated modified barrier film, comprise septum body and be coated on the modified coating of septum body by positive pole one side surface, described modified coating is Ketjen black coated metal oxide coating; Be added with conductive agent in modified coating, conductive agent adds NMP (1-METHYLPYRROLIDONE) as dispersant after mixing with Ketjen black coated metal oxide, be uniformly coated on membrane surface.
The dedicated modified barrier film of above-mentioned lithium-sulfur cell, preferably, described septum body is commercial barrier film Celgard2400; Described conductive agent is one or more in Super-P (conductive carbon black), BP2000 (Cabot conductive black), acetylene black.
The dedicated modified barrier film of above-mentioned lithium-sulfur cell, preferably, the thickness of described modified coating is 50-200 μm; Mass ratio >=1 of Ketjen black and metal oxide in modified coating.
As a total inventive concept, the present invention also provides the preparation method of the dedicated modified barrier film of a kind of above-mentioned lithium-sulfur cell, comprises the following steps:
(1) metal inorganic salt is dissolved in ultra-pure water, adds Ketjen black, then carry out disperseing, dry, heat treatment, obtain Ketjen black-metal oxide compounds;
(2) add organic solvent after being mixed with conductive agent, adhesive by the Ketjen black-metal oxide compounds obtained after step (1) and stir into slurry;
(3) Ketjen black obtained after step (2)-burning compound slurry is uniformly coated on barrier film by positive pole side surface on and dry, namely obtain the dedicated modified barrier film of lithium-sulfur cell.
Above-mentioned preparation method, preferably, in described step (1), metal inorganic salt is one or several in metal nitrate, metal sulfate, metal acetate, metal oxalate, metal carbonate; Described metal nitrate is manganese nitrate, cerous nitrate, lanthanum nitrate, yttrium nitrate, Titanium Nitrate, nickel nitrate, magnesium nitrate, copper nitrate, one or more in ferric nitrate and cobalt nitrate; Described metal sulfate is manganese sulfate, cerous sulfate, lanthanum sulfate, yttrium sulfate, titanium sulfate, nickelous sulfate, magnesium sulfate, copper sulphate, one or more in ferric sulfate and cobaltous sulfate; Described metal acetate is manganese acetate, lanthanum acetate, yttrium acetate, nickel acetate, magnesium acetate, copper acetate, one or more in ferric acetate and cobalt acetate; Described metal oxalate is manganese oxalate, cerium oxalate, lanthanum oxalate, yttrium oxalate, nickel oxalate, one or more in ferric oxalate and cobalt oxalate; Described metal carbonate is manganese carbonate, cerous carbonate, lanthanum carbonate, yttrium carbonate, nickelous carbonate, magnesium carbonate, copper carbonate, ferric carbonate, one or several in cobalt carbonate, and the model of Ketjen black is one or more in EC300, EC600JD, ECP300 and ECP600JD.
Above-mentioned preparation method, preferably, in described step (1), is separated into ultrasonic disperse, and the power of ultrasonic disperse is 100W-500W, and jitter time is 1-5h; Described bake out temperature is 50-100 DEG C, and drying time is 12-24h; Described heat treatment carries out in inert gas filled atmosphere furnace, and heat treated temperature is 400-800 DEG C, and the time is 4-6h; Described inert gas is nitrogen or argon gas.
Above-mentioned preparation method, preferably, in described step (2), the quality proportioning of Ketjen black-metal oxide compounds, conductive agent and adhesive is 5-7:1:2-4; Described adhesive is PVDF (polyvinyladine floride); Described organic solvent is NMP (1-METHYLPYRROLIDONE).
Above-mentioned preparation method, preferably, in described step (2), mixing speed is 600-1000r/min, and mixing time is 1-3h; In described step (3), bake out temperature is 50-100 DEG C, and drying time is 12-24h.
As a total inventive concept, the present invention also provides a kind of lithium-sulfur cell, comprise positive pole, negative pole, electrolyte and the dedicated modified barrier film of above-mentioned lithium-sulfur cell, described just very Ketjen black-sulphur anode composite, described negative pole is lithium metal, described electrolyte is the mixture of the sub-acid amides lithium of bis trifluoromethyl sulfonic acid, lithium nitrate, DOX and glycol dimethyl ether.Wherein solvent is the mixture of DOX and glycol dimethyl ether, and volume ratio is 1:1, and the sub-acid amides lithium concentration of bis trifluoromethyl sulfonic acid is 1-3M, and lithium nitrate concentration is 0.1-0.3M.
Above-mentioned lithium-sulfur cell, preferably, the preparation method of described Ketjen black-sulphur anode composite is: sulphur and Ketjen black mixed according to the ratio of mass ratio >=1 and be placed in ball mill, under the rotating speed of 300-800r/min, rotate 6-12 hour; Finally be placed in nitrogen or argon gas atmosphere, heat treatment 6-12 hour at 155 DEG C, make sulphur fully enter into the duct of Ketjen black, namely obtain this Ketjen black-sulphur anode composite.
The present invention is mainly based on following thinking: the common diaphragm that selection lithium-sulfur cell is commonly used is as modification object, the surface of general commercial barrier film by positive pole side is coated with the Porous barriers of one deck nano carbon-base (as Ketjen black) and metal oxide compound, and using this barrier film as lithium-sulfur cell dedicated diaphragm, with carbon sulphur composite material for positive electrode assembles lithium-sulfur cell.The Porous barriers of nano carbon-base Ketjen black and metal oxide compound allows lithium ion to pass through, and the many lithium sulfides simultaneously produced positive pole have stop and suction-operated.The non-bonding electrons that wherein metal oxide exists can form chemical bond with many lithium sulfides, therefore metal oxide add the absorption being more conducive to many lithium sulfides, as the lithium-sulfur cell on many lithium sulfides barrier layer, there is higher capacity and more excellent cycle performance than the simple nano carbon-base material that uses; Many lithium sulfides of metal oxide and absorption, as the carrier of metal oxide, are limited in its nanoscale duct, greatly strengthen the adsorption capacity on diagram modification barrier layer, improve capacity and the cycle life of lithium-sulfur cell by Ketjen black.
Compared to prior art, the present invention has following advantage:
(1) Ketjen black-metal oxide composite is applied in the side of lithium-sulfur cell barrier film by positive pole as many lithium sulfides barrier layer by the present invention, many lithium sulfides barrier layer allows lithium ion to pass through, the many lithium sulfides simultaneously produced positive pole have stop and suction-operated, wherein metal oxide add the absorption being more conducive to many lithium sulfides, as the lithium-sulfur cell on many lithium sulfides barrier layer, there is higher capacity and more excellent cycle performance than simple nano carbon-base material (as Ketjen black) that uses.
(2) Ketjen black is compared with other porous carbon materials, as industrialization product low price, and Ketjen black is nano-scale particle, specific area is high, larger than general activated carbon more than 3 times of conductivity, greatly strengthen the adsorption capacity on diagram modification barrier layer, improve capacity and the cycle life of lithium-sulfur cell.
(3) preparation method of the present invention is simple, does not need development of new barrier film, and only needing on existing commercialization barrier film, be coated with one deck diagram modification material can use, and greatly saves time and expense that Development and Production new types of diaphragm produces.
(4) advantages such as Ketjen black-metal oxide modified lithium-sulfur cell dedicated diaphragm that prepared by the present invention also has high conductivity, good chemical stability, excellent cycle performance and high rate performance, pollution-free.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is introduced simply, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is Ketjen black-manganese oxide compound transmission electron microscope picture prepared by the embodiment of the present invention 1.
Fig. 2 is Ketjen black-manganese oxide compound high-resolution-ration transmission electric-lens figure prepared by the embodiment of the present invention 1.
Fig. 3 is the embodiment of the present invention 1, and lithium-sulfur cell prepared by comparative example 1 and 2 carries out cycle performance curve chart under 1C.
Fig. 4 is the embodiment of the present invention 1, the coulombic efficiency curve chart that lithium-sulfur cell prepared by comparative example 1 and 2 circulates under 1C.
Embodiment
For the ease of understanding the present invention, hereafter will describe more comprehensively, meticulously inventing to do herein in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, it is identical that hereinafter used all technical terms and those skilled in the art understand implication usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Unless otherwise specified, the various raw material, reagent, instrument and equipment etc. used in the present invention are all bought by market and are obtained or prepare by existing method.
Embodiment 1:
The dedicated modified barrier film of a kind of lithium-sulfur cell of the present invention, comprise commercial barrier film Celgard2400 and be coated on the modified coating of commercial barrier film Celgard2400 by positive pole one side surface, modified coating is the coated Ketjen black-Coated With Manganese Oxide of Ketjen black; Conductive agent Super-P is added with in modified coating; The thickness of modified coating is 100 μm; In modified coating, the mass ratio of Ketjen black and metal oxide is about 5:1.
The dedicated modified barrier film preparation method of the present embodiment lithium-sulfur cell, comprises the following steps:
(1) 0.3g manganese sulfate is dissolved in 100mL ultra-pure water and forms solution A;
(2) 1g Ketjen black is added solution A, with the ultrasonic power ultrasonic disperse 2 hours of 500W;
(3) solution suction filtration step (2) obtained also dries 24h with 80 DEG C in an oven;
(4) step (3) being dried the pressed powder obtained is positioned in tube-type atmosphere furnace, and in the nitrogen atmosphere of flowing, heat treatment 4h at 800 DEG C, obtains Ketjen black-manganese oxide compound;
(5) get the Ketjen black-manganese oxide compound of the above-mentioned preparation of 0.7g, 0.1gSuper-P, 0.2gPVDF mix, and add 8gNMP, within 2 hours, form diagram modification slurry with the speed high-speed stirred of 1000r/min;
(6) with automatic coating machine, the Ketjen black of above-mentioned preparation-manganese oxide diagram modification slurry is uniformly coated on Celgard2400 barrier film by the surface of positive pole side, coating thickness is 100 μm, coated modified diaphragm is placed on 80 DEG C of oven dry 24h in air dry oven, namely obtains the dedicated modified barrier film of lithium-sulfur cell.
The preparation method of the present embodiment lithium-sulfur cell, comprises the following steps:
(1) Ketjen black-sulphur positive electrode preparation: after 1g Ketjen black and the mixing of 2g sulphur, rotate 12 hours under the rotating speed of 800r/min with ball mill, subsequently the mixture of Ketjen black and sulphur is placed in tube furnace, under the nitrogen atmosphere of flowing, 155 DEG C of heat treatments 10 hours, obtain Ketjen black-sulphur composite positive pole;
(2) preparation of Ketjen black-sulphur anode composite: the Ketjen black-sulphur composite positive pole getting the above-mentioned preparation of 0.8g, 0.1gSuper-P, 0.1gPVDF mixes, add 4gNMP, within 2 hours, form Ketjen black-sulphur anode sizing agent with the speed high-speed stirred of 1000r/min, be uniformly coated on aluminium foil with automatic coating machine by Ketjen black-sulphur anode sizing agent, thickness is 200 μm, coated positive pole is placed on 80 DEG C of oven dry 24h in air dry oven, namely obtains Ketjen black-sulphur anode composite;
(3) lithium-sulfur cell is assembled: Ketjen black-sulphur anode composite step (2) obtained, the dedicated modified barrier film of lithium-sulfur cell prepared by the present embodiment, cathode of lithium, organic electrolyte 1MLiTFSI (the sub-acid amides lithium of bis trifluoromethyl sulfonic acid)+0.1MLiNO
3(lithium nitrate)+DOL (DOX)/DME (glycol dimethyl ether) (1/1, v/v), prepares button lithium-sulfur cell in water oxygen content is lower than the glove box of 1ppm.
If Fig. 1 is Ketjen black-manganese oxide compound transmission electron microscope (TEM) photo figure prepared by the present embodiment, Fig. 2 is Ketjen black-manganese oxide compound high-resolution-ration transmission electric-lens (HRTEM) photo figure prepared by the present embodiment, the Ketjen black prepared as seen from Figure 1-manganese oxide compound pattern is Ketjen black coated manganese oxide, the nano particle wrapped up by Ketjen black in TEM photo is manganese oxide nano granule, clearly can see the lattice phase of manganese oxide from Fig. 2.
Under 1C, carry out cycle performance test to lithium-sulfur cell prepared by the present embodiment, as shown in Figure 3, under 1C, first discharge specific capacity is 1163mAh/g to loop test result, and the specific discharge capacity after 200 times that circulates still reaches 1004mAh/g; As shown in Figure 4, the coulombic efficiency of battery is higher than 99% for coulombic efficiency.
Embodiment 2:
The dedicated modified barrier film of a kind of lithium-sulfur cell of the present invention, comprise commercial barrier film Celgard2400 and be coated on the modified coating of commercial barrier film Celgard2400 by positive pole one side surface, modified coating is the coated Ketjen black-Coated With Manganese Oxide of Ketjen black; Conductive agent Super-P is added with in modified coating; The thickness of modified coating is 100 μm; In modified coating, the mass ratio of Ketjen black and metal oxide is about 4:1.
The preparation method of the dedicated modified barrier film of the present embodiment lithium-sulfur cell, comprises the following steps:
(1) 0.4g manganese nitrate is dissolved in 100mL ultra-pure water and forms solution A;
(2) 1g Ketjen black is added solution A, with the ultrasonic power ultrasonic disperse 2 hours of 500W;
(3) solution suction filtration step (2) obtained and in an oven 80 DEG C dry 24h;
(4) step (3) being dried the pressed powder obtained is positioned in tube-type atmosphere furnace, and in the nitrogen atmosphere of flowing, heat treatment 4h at 500 DEG C, obtains Ketjen black-manganese oxide compound;
(5) get the Ketjen black-manganese oxide compound of the above-mentioned preparation of 0.7g, 0.1gSuper-P, 0.2gPVDF mix, and add 8gNMP, within 2 hours, form diagram modification slurry with the speed high-speed stirred of 1000r/min;
(6) with automatic coating machine, the Ketjen black of above-mentioned preparation-manganese oxide diagram modification slurry is uniformly coated on Celgard2400 barrier film by the surface of positive pole side, coating thickness is 100 μm, coated modified diaphragm is placed on 80 DEG C of oven dry 24h in air dry oven, namely obtains the dedicated modified barrier film of lithium-sulfur cell.
The preparation method of the present embodiment lithium-sulfur cell, comprises the following steps:
(1) Ketjen black-sulphur positive electrode preparation: after 1g Ketjen black and the mixing of 2g sulphur, rotate 12 hours under the rotating speed of 800r/min with ball mill, subsequently the mixture of Ketjen black and sulphur is placed in tube furnace, under the argon gas atmosphere of flowing, 155 DEG C of heat treatments 10 hours, obtain Ketjen black-sulphur composite positive pole;
(2) preparation of Ketjen black-sulphur anode composite: the Ketjen black-sulphur composite positive pole getting the above-mentioned preparation of 0.8g, 0.1gSuper-P, 0.1gPVDF mixes, add 4gNMP, within 2 hours, form Ketjen black-sulphur anode sizing agent with the speed high-speed stirred of 1000r/min, be uniformly coated on aluminium foil with automatic coating machine by Ketjen black-sulphur anode sizing agent, thickness is 200 μm, coated positive pole is placed on 80 DEG C of oven dry 24h in air dry oven, namely obtains Ketjen black-sulphur anode composite;
(3) lithium-sulfur cell is assembled: Ketjen black-sulphur anode composite step (2) obtained, the dedicated modified barrier film of lithium-sulfur cell prepared by the present embodiment, cathode of lithium, organic electrolyte 1MLiTFSI (the sub-acid amides lithium of bis trifluoromethyl sulfonic acid)+0.1MLiNO
3(lithium nitrate)+DOL (DOX)/DME (glycol dimethyl ether) (1/1, v/v), prepares button lithium-sulfur cell in water oxygen content is lower than the glove box of 1ppm.
Under 1C, carry out cycle performance test to lithium-sulfur cell prepared by the present embodiment, under 1C, first discharge specific capacity is 1150mAh/g, and the specific discharge capacity after 200 times that circulates still reaches 1000mAh/g, and the coulombic efficiency of battery is higher than 98%.
Embodiment 3:
The dedicated modified barrier film of a kind of lithium-sulfur cell of the present invention, comprise commercial barrier film Celgard2400 and be coated on the modified coating of commercial barrier film Celgard2400 by positive pole one side surface, modified coating is Ketjen black coated Ketjen black-lanthana coating; Conductive agent Super-P is added with in modified coating; The thickness of modified coating is 100 μm; In modified coating, the mass ratio of Ketjen black and metal oxide is about 3:1.
The preparation method of the dedicated modified barrier film of the present embodiment lithium-sulfur cell, comprises the following steps:
(1) 0.4g lanthanum nitrate is dissolved in 100mL ultra-pure water and forms solution A;
(2) 1g Ketjen black is added solution A, with the ultrasonic power ultrasonic disperse 2 hours of 500W;
(3) solution suction filtration step (2) obtained and in an oven 80 DEG C dry 24h;
(4) be positioned in tube-type atmosphere furnace by the pressed powder that step (3) obtains, in the nitrogen atmosphere of flowing, heat treatment 4h at 450 DEG C, obtains Ketjen black-lanthanum oxide compound;
(5) get Ketjen black-lanthanum oxide compound prepared by 0.7g step (4), 0.1gSuper-P, 0.2gPVDF mix, and add 8gNMP, within 2 hours, form diagram modification slurry with the speed high-speed stirred of 1000r/min;
(6) Celgard2400 barrier film is uniformly coated on by the surface of positive pole side with Ketjen black-lanthana diagram modification slurry that step (5) is prepared by automatic coating machine, coating thickness is 100 μm, coated modified diaphragm is placed on 80 DEG C of oven dry 24h in air dry oven, namely obtains the dedicated modified barrier film of lithium-sulfur cell.
The preparation method of the present embodiment lithium-sulfur cell, comprises the following steps:
(1) Ketjen black-sulphur positive electrode preparation: after 1g Ketjen black and the mixing of 2g sulphur, rotate 12 hours under the rotating speed of 800r/min with ball mill, subsequently the mixture of Ketjen black and sulphur is placed in tube furnace, under the nitrogen atmosphere of flowing, 155 DEG C of heat treatments 10 hours, obtain Ketjen black-sulphur composite positive pole;
(2) preparation of Ketjen black-sulphur anode composite: get 0.8g Ketjen black-sulphur composite positive pole, 0.1gSuper-P, 0.1gPVDF mixes, add 4gNMP, within 2 hours, form Ketjen black-sulphur anode sizing agent with the speed high-speed stirred of 1000r/min, be uniformly coated on aluminium foil with automatic coating machine by Ketjen black-sulphur anode sizing agent, thickness is 200 μm, coated positive pole is placed on 80 DEG C of oven dry 24h in air dry oven, namely obtains Ketjen black-sulphur anode composite;
(3) lithium-sulfur cell is assembled: Ketjen black-sulphur anode composite step (2) obtained, Ketjen black-lanthana lithium-sulfur cell modified diaphragm prepared by the present embodiment, cathode of lithium, organic electrolyte 1MLiTFSI (the sub-acid amides lithium of bis trifluoromethyl sulfonic acid)+0.1MLiNO
3(lithium nitrate)+DOL (DOX)/DME (glycol dimethyl ether) (1/1, v/v), prepares button lithium-sulfur cell in water oxygen content is lower than the glove box of 1ppm.
Under 1C, carry out cycle performance test to lithium-sulfur cell prepared by the present embodiment, under 1C, first discharge specific capacity is 1180mAh/g, and the specific discharge capacity after 200 times that circulates still reaches 1020mAh/g, and the coulombic efficiency of battery is higher than 97%.
Embodiment 4:
The dedicated modified barrier film of a kind of lithium-sulfur cell of the present invention, comprise commercial barrier film Celgard2400 and be coated on the modified coating of commercial barrier film Celgard2400 by positive pole one side surface, modified coating is the coated Ketjen black-cerium oxide of Ketjen black; Conductive agent Super-P is added with in modified coating; The thickness of modified coating is 100 μm; In modified coating, the mass ratio of Ketjen black and metal oxide is about 2.5:1.
The preparation method of the dedicated modified barrier film of the present embodiment lithium-sulfur cell, comprises the following steps:
(1) 0.5g cerous nitrate is dissolved in 100mL ultra-pure water and forms solution A;
(2) 1g Ketjen black is added solution A, with the ultrasonic power ultrasonic disperse 2 hours of 500W;
(3) solution suction filtration step (2) obtained and in an oven 80 DEG C dry 24h;
(4) be positioned in tube-type atmosphere furnace by the pressed powder that step (3) obtains, in the nitrogen atmosphere of flowing, heat treatment 4h at 500 DEG C, obtains Ketjen black-cerium oxide compound;
(5) get Ketjen black-cerium oxide compound prepared by 0.7g step (4), 0.1gSuper-P, 0.2gPVDF mix, and add 8gNMP, within 2 hours, form diagram modification slurry with the speed high-speed stirred of 1000r/min;
(6) Celgard2400 barrier film is uniformly coated on by the surface of positive pole side with Ketjen black-cerium oxide diagram modification slurry that step (5) is prepared by automatic coating machine, coating thickness is 100 μm, coated modified diaphragm is placed on 80 DEG C of oven dry 24h in air dry oven, namely obtains the dedicated modified barrier film of lithium-sulfur cell.
The preparation method of the present embodiment lithium-sulfur cell, comprises the following steps:
(1) Ketjen black-sulphur positive electrode preparation: after 1g Ketjen black and the mixing of 2g sulphur, rotate 12 hours under the rotating speed of 800r/min with ball mill, subsequently the mixture of Ketjen black and sulphur is placed in tube furnace, under the nitrogen atmosphere of flowing, 155 DEG C of heat treatments 10 hours, obtain Ketjen black-sulphur composite positive pole;
(2) preparation of Ketjen black-sulphur anode composite: get 0.8g Ketjen black-sulphur composite positive pole, 0.1gSuper-P, 0.1gPVDF mixes, add 4gNMP, within 2 hours, form Ketjen black-sulphur anode sizing agent with the speed high-speed stirred of 1000r/min, be uniformly coated on aluminium foil with automatic coating machine by Ketjen black-sulphur anode sizing agent, thickness is 200 μm, coated positive pole is placed on 80 DEG C of oven dry 24h in air dry oven, namely obtains Ketjen black-sulphur anode composite;
(3) lithium-sulfur cell is assembled: Ketjen black-sulphur anode composite step (2) obtained, lithium-sulfur cell modified diaphragm prepared by the present embodiment, cathode of lithium, organic electrolyte 1MLiTFSI (the sub-acid amides lithium of bis trifluoromethyl sulfonic acid)+0.1MLiNO
3(lithium nitrate)+DOL (DOX)/DME (glycol dimethyl ether) (1/1, v/v), prepares button lithium-sulfur cell in water oxygen content is lower than the glove box of 1ppm.
Under 1C, carry out cycle performance test to lithium-sulfur cell prepared by the present embodiment, under 1C, first discharge specific capacity is 1100mAh/g, and the specific discharge capacity after 200 times that circulates still reaches 982mAh/g, and the coulombic efficiency of battery is higher than 97%.
Embodiment 5:
The dedicated modified barrier film of a kind of lithium-sulfur cell of the present invention, comprise commercial barrier film Celgard2400 and be coated on the modified coating of commercial barrier film Celgard2400 by positive pole one side surface, modified coating is the coated Ketjen black-magnesium oxide coating of Ketjen black; Conductive agent Super-P is added with in modified coating; The thickness of modified coating is 100 μm; In modified coating, the mass ratio of Ketjen black and metal oxide is about 3.5:1.
The preparation method of the dedicated modified barrier film of the present embodiment lithium-sulfur cell, comprises the following steps:
(1) 0.4g magnesium acetate is dissolved in 100mL ultra-pure water and forms solution A;
(2) 1g Ketjen black is added solution A, with the ultrasonic power ultrasonic disperse 2 hours of 500W;
(3) solution suction filtration step (2) obtained and in an oven 80 DEG C dry 24h;
(4) be positioned in tube-type atmosphere furnace by the pressed powder that step (3) obtains, in the nitrogen atmosphere of flowing, heat treatment 4h at 700 DEG C, obtains Ketjen black-magnesium oxide compound;
(5) get 0.7g Ketjen black-magnesium oxide compound, 0.1gSuper-P, 0.2gPVDF mix, and add 8gNMP, within 2 hours, form diagram modification slurry with the speed high-speed stirred of 1000r/min;
(6) with automatic coating machine, Ketjen black-magnesium oxide diagram modification slurry is uniformly coated on Celgard2400 barrier film by the surface of positive pole side, coating thickness is 100 μm, coated modified diaphragm is placed on 80 DEG C of oven dry 24h in air dry oven, namely obtains Ketjen black-magnesium oxide lithium-sulfur cell modified diaphragm.
The preparation method of the present embodiment lithium-sulfur cell, comprises the following steps:
(1) Ketjen black-sulphur positive electrode preparation: after 1g Ketjen black and the mixing of 2g sulphur, rotate 12 hours under the rotating speed of 800r/min with ball mill, subsequently the mixture of Ketjen black and sulphur is placed in tube furnace, under the nitrogen atmosphere of flowing, 155 DEG C of heat treatments 10 hours, obtain Ketjen black-sulphur composite positive pole;
(2) preparation of Ketjen black-sulphur anode composite: get 0.8g Ketjen black-sulphur composite positive pole, 0.1gSuper-P, 0.1gPVDF mixes, add 4gNMP, within 2 hours, form Ketjen black-sulphur anode sizing agent with the speed high-speed stirred of 1000r/min, be uniformly coated on aluminium foil with automatic coating machine by Ketjen black-sulphur anode sizing agent, thickness is 200 μm, coated positive pole is placed on 80 DEG C of oven dry 24h in air dry oven, namely obtains Ketjen black-sulphur anode composite;
(3) lithium-sulfur cell is assembled: Ketjen black-sulphur anode composite step (2) obtained, lithium-sulfur cell modified diaphragm prepared by the present embodiment, cathode of lithium, organic electrolyte 1MLiTFSI (the sub-acid amides lithium of bis trifluoromethyl sulfonic acid)+0.1MLiNO
3(lithium nitrate)+DOL (DOX)/DME (glycol dimethyl ether) (1/1, v/v), prepares button lithium-sulfur cell in water oxygen content is lower than the glove box of 1ppm.
Under 1C, carry out cycle performance test to lithium-sulfur cell prepared by the present embodiment, under 1C, first discharge specific capacity is 1120mAh/g, and the specific discharge capacity after 200 times that circulates still reaches 967mAh/g, and the coulombic efficiency of battery is higher than 95%.
Comparative example 1:
A kind of lithium-sulfur cell barrier film, comprises commercial barrier film Celgard2400 and is coated on the Ketjen black coating of commercial barrier film Celgard2400 by positive pole one side surface; Conductive agent Super-P is added with in Ketjen black coating; Ketjen black coating is 100 μm.
The method of this comparative example lithium-sulfur cell barrier film and lithium-sulfur cell thereof, comprises the following steps:
The above-mentioned preparation of lithium-sulfur cell dedicated diaphragm and the preparation of lithium-sulfur cell thereof, comprise the following steps:
(1) get 0.7g Ketjen black, 0.1gSuper-P, 0.2gPVDF mix, and add 8gNMP, within 2 hours, form diagram modification slurry with the speed high-speed stirred of 1000r/min;
(2) with automatic coating machine, Ketjen black slurry is uniformly coated on Celgard2400 barrier film by the surface of positive pole side, coating thickness is 100 μm, coated modified diaphragm is placed on 80 DEG C of oven dry 24h in air dry oven and namely obtains Ketjen black lithium-sulfur cell barrier film;
(3) by after 1g Ketjen black and the mixing of 2g sulphur, rotate 12 hours under the rotating speed of 800r/min with ball mill, subsequently the mixture of Ketjen black and sulphur is placed in tube furnace, under the nitrogen atmosphere of flowing, within 10 hours, obtains Ketjen black-sulphur composite positive pole 155 DEG C of heat treatments;
(4) 0.8g Ketjen black-sulphur composite positive pole is got, 0.1gSuper-P, 0.1gPVDF mixes, add 4gNMP, within 2 hours, Ketjen black-sulphur anode sizing agent is formed with the speed high-speed stirred of 1000r/min, be uniformly coated on aluminium foil with automatic coating machine by Ketjen black-sulphur anode sizing agent, thickness is 200 μm, coated positive pole is placed on 80 DEG C of oven dry 24h in air dry oven and namely obtains Ketjen black-sulphur anode composite;
(5) Ketjen black-sulphur anode composite step (4) obtained, the Ketjen black lithium-sulfur cell barrier film that step (2) obtains, cathode of lithium, organic electrolyte 1MLiTFSI (the sub-acid amides lithium of bis trifluoromethyl sulfonic acid)+0.1MLiNO
3(lithium nitrate)+DOL (DOX)/DME (glycol dimethyl ether) (1/1, v/v), prepares button lithium-sulfur cell in water oxygen content is lower than the glove box of 1ppm.
Under 1C, carry out cycle performance test to lithium-sulfur cell prepared by this comparative example, as shown in Figure 3, under 1C, first discharge specific capacity is 1081mAh/g to loop test result, and the specific discharge capacity after 200 times that circulates reaches 780mAh/g; As shown in Figure 4, the coulombic efficiency of battery is higher than 93% for coulombic efficiency.
Comparative example 2:
The barrier film that this comparative example uses is general commercial barrier film Celgard2400.
The preparation method of the present embodiment lithium-sulfur cell, comprises the following steps:
(1) Ketjen black-sulphur positive electrode preparation: after 1g Ketjen black and the mixing of 2g sulphur, rotate 12 hours under the rotating speed of 800r/min with ball mill, subsequently the mixture of Ketjen black and sulphur is placed in tube furnace, under the nitrogen atmosphere of flowing, within 10 hours, obtain Ketjen black-sulphur composite positive pole 155 DEG C of heat treatments;
(2) preparation of Ketjen black-sulphur anode composite: get 0.8g Ketjen black-sulphur composite positive pole, 0.1gSuper-P, 0.1gPVDF mixes, add 4gNMP, within 2 hours, Ketjen black-sulphur anode sizing agent is formed with the speed high-speed stirred of 1000r/min, be uniformly coated on aluminium foil with automatic coating machine by Ketjen black-sulphur anode sizing agent, thickness is 200 μm, coated positive pole is placed on 80 DEG C of oven dry 24h in air dry oven and namely obtains Ketjen black-sulphur anode composite;
(3) lithium-sulfur cell is assembled: Ketjen black-sulphur anode composite step (2) obtained, commercial barrier film Celgard2400, cathode of lithium, organic electrolyte 1MLiTFSI (the sub-acid amides lithium of bis trifluoromethyl sulfonic acid)+0.1MLiNO
3(lithium nitrate)+DOL (DOX)/DME (glycol dimethyl ether) (1/1, v/v), prepares button lithium-sulfur cell in water oxygen content is lower than the glove box of 1ppm.
Under 1C, carry out cycle performance test to lithium-sulfur cell prepared by this comparative example, as shown in Figure 3, under 1C, first discharge specific capacity is 897mAh/g to loop test result, and the specific discharge capacity after 200 times that circulates reaches 557mAh/g; As shown in Figure 4, the coulombic efficiency of battery is higher than 80% for coulombic efficiency.
Analyze from Fig. 3 and Fig. 4, the dedicated modified barrier film of the lithium-sulfur cell being covered with Ketjen black-metal oxide compounds that the present invention uses, compared to the barrier film not being covered with Ketjen black-burning compound, obvious conductivity and the chemical stability that can improve battery, and there is better cycle performance and high rate performance, for the high request meeting battery provides reliable quality assurance.
Claims (10)
1. the dedicated modified barrier film of lithium-sulfur cell, is characterized in that, comprise septum body and be coated on the modified coating of septum body by positive pole one side surface, described modified coating is Ketjen black coated metal oxide coating; Conductive agent is added with in modified coating.
2. the dedicated modified barrier film of lithium-sulfur cell as claimed in claim 1, it is characterized in that, described septum body is commercial barrier film Celgard2400; Described conductive agent is one or more in Super-P, BP2000, acetylene black.
3. the dedicated modified barrier film of lithium-sulfur cell as claimed in claim 1, it is characterized in that, the thickness of described modified coating is 50-200 μm; Mass ratio >=1 of Ketjen black and metal oxide in modified coating.
4. a preparation method for the dedicated modified barrier film of the lithium-sulfur cell as described in any one of claims 1 to 3, is characterized in that, comprise the following steps:
(1) metal inorganic salt is dissolved in ultra-pure water, adds Ketjen black, then carry out disperseing, dry, heat treatment, obtain Ketjen black-metal oxide compounds;
(2) add organic solvent after being mixed with conductive agent, adhesive by the Ketjen black-metal oxide compounds obtained after step (1) and stir into slurry;
(3) Ketjen black obtained after step (2)-burning compound slurry is uniformly coated on barrier film by positive pole side surface on and dry, namely obtain the dedicated modified barrier film of lithium-sulfur cell.
5. preparation method according to claim 4, is characterized in that, in described step (1), metal inorganic salt is one or several in metal nitrate, metal sulfate, metal acetate, metal oxalate, metal carbonate; Described metal nitrate is manganese nitrate, cerous nitrate, lanthanum nitrate, yttrium nitrate, Titanium Nitrate, nickel nitrate, magnesium nitrate, copper nitrate, one or more in ferric nitrate and cobalt nitrate; Described metal sulfate is manganese sulfate, cerous sulfate, lanthanum sulfate, yttrium sulfate, titanium sulfate, nickelous sulfate, magnesium sulfate, copper sulphate, one or more in ferric sulfate and cobaltous sulfate; Described metal acetate is manganese acetate, lanthanum acetate, yttrium acetate, nickel acetate, magnesium acetate, copper acetate, one or more in ferric acetate and cobalt acetate; Described metal oxalate is manganese oxalate, cerium oxalate, lanthanum oxalate, yttrium oxalate, nickel oxalate, one or more in ferric oxalate and cobalt oxalate; Described metal carbonate is manganese carbonate, cerous carbonate, lanthanum carbonate, yttrium carbonate, nickelous carbonate, magnesium carbonate, copper carbonate, ferric carbonate, one or several in cobalt carbonate; The model of Ketjen black is one or more in EC300, EC600JD, ECP300 and ECP600JD.
6. preparation method according to claim 4, is characterized in that, in described step (1), is separated into ultrasonic disperse, and the power of ultrasonic disperse is 100W-500W, and jitter time is 1-5h; Described bake out temperature is 50-100 DEG C, and drying time is 12-24h; Described heat treatment carries out in inert gas filled atmosphere furnace, and heat treated temperature is 400-800 DEG C, and the time is 4-6h; Described inert gas is nitrogen or argon gas.
7. preparation method according to claim 4, is characterized in that, in described step (2), the quality proportioning of Ketjen black-metal oxide compounds, conductive agent and adhesive is 5-7:1:2-4; Described adhesive is PVDF; Described organic solvent is NMP.
8. preparation method according to claim 4, is characterized in that, in described step (2), mixing speed is 600-1000r/min, and mixing time is 1-3h; In described step (3), bake out temperature is 50-100 DEG C, and drying time is 12-24h.
9. a lithium-sulfur cell, comprise positive pole, negative pole, electrolyte and barrier film, it is characterized in that, described barrier film is the dedicated modified barrier film of lithium-sulfur cell described in any one of claims 1 to 3, described just very Ketjen black-sulphur anode composite, described negative pole is lithium metal, and described electrolyte is the mixture of the sub-acid amides lithium of bis trifluoromethyl sulfonic acid, lithium nitrate, DOX and glycol dimethyl ether.
10. lithium-sulfur cell according to claim 9, it is characterized in that, the preparation method of described Ketjen black-sulphur anode composite is: sulphur and Ketjen black mixed according to the ratio of mass ratio >=1 and be placed in ball mill, under the rotating speed of 300-800r/min, rotate 6-12 hour; Finally be placed in nitrogen or argon gas atmosphere, heat treatment 6-12 hour at 155 DEG C, make sulphur fully enter into the duct of Ketjen black, namely obtain this Ketjen black-sulphur anode composite.
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