CN105280867B - A kind of dedicated modified barrier film of lithium-sulfur cell and preparation method thereof and lithium-sulfur cell - Google Patents
A kind of dedicated modified barrier film of lithium-sulfur cell and preparation method thereof and lithium-sulfur cell Download PDFInfo
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- 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
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Abstract
A kind of dedicated modified barrier film of lithium-sulfur cell, one layer of Ketjen black coated metal oxide modified coating for being added with conductive agent is coated with by the surface of positive pole side in common diaphragm.The preparation method of the dedicated modified barrier film of the lithium-sulfur cell includes mixing Ketjen black with the aqueous solution of metal oxides inorganic salt successively, after scattered, drying, calcining, slurry is made and is coated on commercial barrier film by positive pole side drying gained.The invention also discloses the lithium-sulfur cell using the dedicated modified barrier film of lithium-sulfur cell, using lithium metal as negative pole, using Ketjen black sulphur composite coated on aluminium foil as positive pole, by bis trifluoromethyl sulfonic acid Asia acid amides lithium, lithium nitrate, 1, the mixture of 3 dioxolanes and glycol dimethyl ether assembles as electrolyte, and the dedicated modified barrier film of the lithium-sulfur cell.The modified diaphragm of the present invention can suppress " the shuttle effect " of more lithium sulfides in lithium-sulfur cell, improve the chemical property, capacity and cycle life of lithium-sulfur cell, suitable for large-scale production.
Description
Technical field
The present invention relates to field of lithium ion battery, more particularly to a kind of dedicated modified barrier film of lithium-sulfur cell and preparation method thereof
And its lithium-sulfur cell of composition.
Background technology
It by negative pole (theoretical specific capacity 3860mAh/g), sulphur of lithium is positive pole (theoretical specific capacity that lithium sulphur (Li-S) battery, which is,
A kind of model electrochemical energy-storage system 1675mAh/g), theory than energy up to 2600Wh/kg, much larger than business at this stage
Change lithium ion battery, and sulphur on earth rich reserves, it is cheap, less toxic or nontoxic the characteristics of make the system great commercial value.
But the electrochemistry of lithium-sulfur cell has the problem of many serious to be badly in need of solving.First, active material sulphur and its electricity of discharging product
Conductance is very low, reduces the energy efficiency of battery；Secondly, the more lithium sulfides of intermediate product of electrochemical reaction are soluble in electrolyte production
Raw irreversible capacitance loss, reduces the utilization rate and cycle performance of sulphur, and increases ion migration resistance；Meanwhile it has been dissolved in
More lithium sulfides in machine electrolyte are migrated to cathode of lithium due to " shuttle effect ", and forming SEI films further reduces the electrification of battery
Learn performance.
In order to solve lithium-sulfur cell polysulfide shuttle effect, sulphur poorly conductive, volumetric expansion these three subject matters, closely
Over a little years, people are mainly modified to sulphur positive pole, for example, by the carbon materials such as porous activated carbon, CNT, graphene with
Sulphur is compound.As the A of Chinese patent CN 103456929 disclose a kind of lithium-sulphur cell positive electrode, the positive electrode is by elemental sulfur and three
Classifying porous charcoal is tieed up to be combined；Preparation method is to first pass through forerunner's bluk recombination that solvent-thermal method prepares three-dimensional classifying porous charcoal
Thing, three-dimensional classifying porous charcoal is obtained after carbonization, then it is compound with sulphur, that is, obtain lithium sulfur battery anode material.The three-dimensional is classifying porous
Charcoal has multiple level cavernous structures being made up of mesopore and micropore, and is mutually communicated between cavernous structure, has very big ratio
Surface area, active material elemental sulfur (quality with reference to sulphur accounts for the 50~90% of three-dimensional classifying porous carbonaceous amount) can be largely accommodated,
And central hole structure helps to suppress the dissolving of sulphur simple substance and polysulfide in the electrolytic solution, keeps higher positive electrode to live
Property material utilization, is also beneficial to the raising of lithium-sulfur cell cycle performance.
As the A of Chinese patent CN 103682280 disclose a kind of lithium sulfur battery anode material, including sulfur granules, conduction add
Add agent and graphene.Using graphene oxide, conductive additive and sulfur granules as raw material, conductive additive and sulfur granules are subjected to heat
It is spray-dried, is then mixed obtained conductive additive, sulfur compound with graphene oxide, using reducing agent after processing
Redox graphene, obtain lithium sulfur battery anode material.Conductive additive and sulfur granules form conductive network, improve positive pole
The electric conductivity of material；The excellent electric conductivity of graphene further increases the electric conductivity of positive electrode；Graphene can also be effective
Suppress the dissolving of polysulfide, improve the cycle performance of lithium-sulfur cell.But the modification to positive electrode still can not be complete
Suppress " the shuttle effect " of polysulfide, the carbon-based material that positive pole is used in being modified can only fetter the more lithium sulfides in part, lithium sulphur electricity
The capacity and energy in pond can still decline quickly, therefore want to obtain high performance lithium-sulfur cell only only sulphur positive pole can not be entered
Row is modified.
In order to preferably suppress the shuttle effect of more lithium sulfides, one layer can be added between sulfur-based positive electrode and barrier film
More lithium sulfides of the barrier layer absorption from positive pole escape.As the A of Chinese patent CN 103647104 disclose a kind of lithium-sulfur cell,
The barrier layer formed by conducting polymer nano material is provided between sulphur positive pole and barrier film, on the one hand the high conductivity on barrier layer promotes
The transmission of ion and electronics, the dissolving and migration of lithium-sulfur cell electric discharge intermediate product in the electrolytic solution on the other hand can be prevented,
And then improve cycle performance of battery.The A of Chinese patent CN 103490027 disclose a kind of lithium-sulfur cell barrier film, the lithium sulphur electricity
Pond is formed with barrier film by common batteries barrier film with the Porous barriers loaded thereon.Porous barriers can allow lithium ion to lead to
Cross, but the more lithium sulfide intermediates formed to sulphur positive pole in charge and discharge process have stop and suction-operated.Its Porous barriers
Porous carbon prepared by activated carbon or laboratory for market purchase.But these conducting polymer composites and porous carbon materials pair
It is a kind of physical absorption based on Van der Waals force that the absorption of more lithium sulfides is most of, limited sorption capacity.Therefore, research is a kind of more
Excellent absorption and the barrier layer of catalytic performance and barrier film are compound, and the chemical property for further improving battery has been very must
Will.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention in background above technology and defect, there is provided one
Kind dedicated modified barrier film of lithium-sulfur cell and preparation method thereof and lithium-sulfur cell, on the basis of the modification of carbon sulphur anode composite, to electricity
The barrier film in pond is modified, and further improves the electrochemical properties of lithium-sulfur cell.
In order to solve the above technical problems, technical scheme proposed by the present invention for provide a kind of lithium-sulfur cell it is dedicated modified every
Film, including septum body and be coated on septum body lean on the side surface of positive pole one modified coating, the modified coating is Ketjen black
Coated metal oxide coating；Conductive agent is added with modified coating, conductive agent mixes with Ketjen black coated metal oxide
NMP (1-METHYLPYRROLIDONE) is added after even and is used as dispersant, is uniformly coated on membrane surface.
The dedicated modified barrier film of above-mentioned lithium-sulfur cell, it is preferred that the septum body is commercial barrier film Celgard2400；
The conductive agent is the 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, it is preferred that the thickness of the modified coating is 50-200 μm；It is modified to apply
Mass ratio >=1 of Ketjen black and metal oxide in layer.
The inventive concept total as one, the present invention also provide a kind of preparation of the dedicated modified barrier film of above-mentioned lithium-sulfur cell
Method, comprise the following steps：
(1) metal inorganic salt is dissolved in ultra-pure water, adds Ketjen black, then disperseed, dried, be heat-treated, obtained
Ketjen black-metal oxide compounds；
(2) added after the Ketjen black-metal oxide compounds obtained after step (1) are mixed with conductive agent, adhesive
Organic solvent stirs into slurry；
(3) Ketjen black obtained after step (2)-metal oxide complex slurry is uniformly coated on barrier film and leans on positive pole side
Surface on and dry, that is, obtain the dedicated modified barrier film of lithium-sulfur cell.
Above-mentioned preparation method, it is preferred that in the step (1), metal inorganic salt is metal nitrate, metal sulfate
One or several kinds in salt, metal acetate, metal oxalate, metal carbonate；The metal nitrate is manganese nitrate, nitre
Sour cerium, lanthanum nitrate, yttrium nitrate, Titanium Nitrate, nickel nitrate, magnesium nitrate, copper nitrate, the one or more in ferric nitrate and cobalt nitrate；
The metal sulfate is manganese sulfate, cerous sulfate, lanthanum sulfate, yttrium sulfate, titanium sulfate, nickel sulfate, magnesium sulfate, copper sulphate, sulfuric acid
One or more in iron and cobaltous sulfate；The metal acetate is manganese acetate, lanthanum acetate, yttrium acetate, nickel acetate, magnesium acetate,
Copper acetate, the one or more in ferric acetate and cobalt acetate；The metal oxalate is manganese oxalate, cerium oxalate, lanthanum oxalate, oxalic acid
Yttrium, nickel oxalate, the one or more in ferric oxalate and cobalt oxalate；The metal carbonate is manganese carbonate, cerous carbonate, lanthanum carbonate,
Yttrium carbonate, nickelous carbonate, magnesium carbonate, copper carbonate, ferric carbonate, the one or several kinds in cobalt carbonate, the model of Ketjen black
One or more in EC300, EC600JD, ECP300 and ECP600JD.
Above-mentioned preparation method, it is preferred that in the step (1), be separated into ultrasonic disperse, the power of ultrasonic disperse is
100W-500W, jitter time 1-5h；The drying temperature is 50-100 DEG C, drying time 12-24h；The heat treatment is
Carried out in inert gas filled atmosphere furnace, the temperature of heat treatment is 400-800 DEG C, time 4-6h；The inert gas
For nitrogen or argon gas.
Above-mentioned preparation method, it is preferred that in the step (2), Ketjen black-metal oxide compounds, conductive agent and
The quality proportioning of adhesive is 5-7:1:2-4；Described adhesive is PVDF (polyvinyladine floride)；The organic solvent is NMP (N-
Methyl pyrrolidone).
Above-mentioned preparation method, it is preferred that in the step (2), mixing speed 600-1000r/min, mixing time
For 1-3h；In the step (3), drying temperature is 50-100 DEG C, drying time 12-24h.
The inventive concept total as one, the present invention also provide a kind of lithium-sulfur cell, including positive pole, negative pole, electrolyte and
The dedicated modified barrier film of above-mentioned lithium-sulfur cell, the just extremely Ketjen black-sulphur anode composite, the negative pole is lithium metal, described
Electrolyte is the mixture of bis trifluoromethyl sulfonic acid Asia acid amides lithium, lithium nitrate, 1,3- dioxolanes and glycol dimethyl ether.Wherein
Solvent is the mixture of DOX and glycol dimethyl ether, volume ratio 1：1, bis trifluoromethyl sulfonic acid Asia acid amides lithium is dense
It is 0.1-0.3M to spend for 1-3M, nitric acid lithium concentration.
Above-mentioned lithium-sulfur cell, it is preferred that the preparation method of the Ketjen black-sulphur anode composite is：By sulphur and Ketjen black
According to being placed in after the ratio mixing of mass ratio >=1 in ball mill, 6-12 hours are rotated under 300-800r/min rotating speed；Finally
It is placed in nitrogen or argon gas atmosphere, 6-12 hours is heat-treated at 155 DEG C, makes sulphur well into the duct to Ketjen black,
Obtain the Ketjen black-sulphur anode composite.
Present invention is primarily based on following thinking：The conventional common diaphragm of lithium-sulfur cell is selected as modified object, common
Commercial barrier film is by one layer of nano carbon-base (such as Ketjen black) of coating on the surface of positive pole side and the compound porous resistance of metal oxide
Barrier, and using this barrier film as lithium-sulfur cell dedicated diaphragm, lithium-sulfur cell is assembled by positive electrode of carbon sulphur composite.Receive
The carbon-based Ketjen black of rice and the compound Porous barriers of metal oxide allow lithium ion by while vulcanizing to caused by positive pole more
Lithium has stop and suction-operated.Non- bonding electrons can form chemical bond with more lithium sulfides wherein existing for metal oxide,
Therefore the addition of metal oxide is more beneficial for the absorption of more lithium sulfides, than using nano carbon-base material as more lithium sulfides merely
The lithium-sulfur cell on barrier layer has higher capacity and more excellent cycle performance；Carrier of the Ketjen black as metal oxide,
Metal oxide and more lithium sulfides of absorption are limited in its nanoscale duct, greatly strengthen the suction on diagram modification barrier layer
Attached ability, improve the capacity and cycle life of lithium-sulfur cell.
Compared to prior art, the present invention has the advantage that：
(1) Ketjen black-metal oxide composite is applied and made in lithium-sulfur cell barrier film by the side of positive pole by the present invention
For more lithium sulfide barrier layers, more lithium sulfide barrier layers allow lithium ions by while having resistance to more lithium sulfides caused by positive pole
Gear and suction-operated, the addition of wherein metal oxide are more beneficial for the absorption of more lithium sulfides, than using nano-sized carbon base material merely
Expect that (such as Ketjen black) has higher capacity and more excellent cycle performance as the lithium-sulfur cell on more lithium sulfide barrier layers.
(2) Ketjen black is cheap as industrialization product compared with other porous carbon materials, and Ketjen black is nanoscale
Particle, specific surface area is high, and electric conductivity is bigger than in general activated carbon more than 3 times, greatly strengthen the absorption on diagram modification barrier layer
Ability, improve the capacity and cycle life of lithium-sulfur cell.
(3) preparation method of the invention is simple, it is not necessary to develops new types of diaphragm, it is only necessary on existing commercialization barrier film
One layer of diagram modification material of coating can be used, and greatly save time and expense caused by Development and Production new types of diaphragm.
(4) Ketjen black-metal oxide modified lithium-sulfur cell dedicated diaphragm prepared by the present invention also has high conductivity, good
Good chemical stability, excellent cycle performance and high rate performance, it is pollution-free the advantages that.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, make required in being described below to embodiment
Accompanying drawing is simply introduced, it should be apparent that, drawings in the following description are some embodiments of the present invention, for this area
For those of ordinary skill, on the premise of not paying creative work, other accompanying drawings 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 map under 1C.
Fig. 4 is the embodiment of the present invention 1, the coulombic efficiency curve that lithium-sulfur cell prepared by comparative example 1 and 2 circulates under 1C
Figure.
Embodiment
For the ease of understanding the present invention, below in conjunction with Figure of description and preferred embodiment to invent herein do it is more complete
Face, meticulously describe, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical terms used hereinafter are generally understood that implication phase with those skilled in the art
Together.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention's
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of dedicated modified barrier film of lithium-sulfur cell of the invention, including commercial barrier film Celgard2400 and it is coated on commercialization
Barrier film Celgard2400 leans on the modified coating of the side surface of positive pole one, and modified coating is that Ketjen black coats Ketjen black-manganese oxide painting
Layer；Conductive agent Super-P is added with modified coating；The thickness of modified coating is 100 μm；Ketjen black and metal in modified coating
The mass ratio of 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 sulfates are dissolved in 100mL ultra-pure waters and form solution A；
(2) 1g Ketjen blacks are added into solution A, with 500W ultrasonic power ultrasonic disperse 2 hours；
(3) solution for obtaining step (2) filters and in an oven with 80 DEG C of drying 24h；
(4) solid powder that step (3) drying obtains is positioned in tube-type atmosphere furnace, in the nitrogen atmosphere of flowing,
4h is heat-treated at 800 DEG C, obtains Ketjen black-manganese oxide compound；
(5) Ketjen black-manganese oxide compound of the above-mentioned preparations of 0.7g is taken, 0.1g Super-P, 0.2g PVDF mixing, is added
Enter 8g NMP, diagram modification slurry is formed in 2 hours with 1000r/min speed high-speed stirred；
(6) Ketjen black of above-mentioned preparation-manganese oxide diagram modification slurry is uniformly coated on automatic coating machine
Celgard2400 barrier films are by the surface of positive pole side, coating thickness is 100 μm, and coated modified diaphragm is placed on into air blast
80 DEG C of drying 24h, that is, obtain the dedicated modified barrier film of lithium-sulfur cell in drying box.
The preparation method of the present embodiment lithium-sulfur cell, comprises the following steps：
(1) prepared by Ketjen black-sulphur positive electrode：After 1g Ketjen blacks and 2g sulphur are mixed, with ball mill 800r/min's
Rotate 12 hours under rotating speed, then the mixture of Ketjen black and sulphur is placed in tube furnace, under the nitrogen atmosphere of flowing,
155 DEG C are heat-treated 10 hours, obtain Ketjen black-sulphur composite positive pole；
(2) preparation of Ketjen black-sulphur anode composite：Take Ketjen black-sulphur composite positive pole of the above-mentioned preparations of 0.8g, 0.1g
Super-P, 0.1g PVDF are mixed, and add 4g NMP, and Ketjen black-sulphur is formed within 2 hours with 1000r/min speed high-speed stirred
Anode sizing agent, Ketjen black-sulphur anode sizing agent is uniformly coated on aluminium foil with automatic coating machine, thickness is 200 μm, will be coated
Positive pole be placed in air dry oven 80 DEG C of drying 24h, that is, obtain Ketjen black-sulphur anode composite；
(3) lithium-sulfur cell is assembled：The Ketjen black that step (2) is obtained-sulphur anode composite, lithium sulphur electricity manufactured in the present embodiment
The dedicated modified barrier film in pond, cathode of lithium, organic electrolyte 1M LiTFSI (bis trifluoromethyl sulfonic acid Asia acid amides lithium)+0.1M LiNO3
(lithium nitrate)+DOL (DOX)/DME (glycol dimethyl ether) (1/1, v/v), it is less than 1ppm hand in water oxygen content
Button lithium-sulfur cell is prepared in casing.
If Fig. 1 is Ketjen black manufactured in the present embodiment-manganese oxide compound transmission electron microscope (TEM) photo figure, Fig. 2 is this reality
Apply Ketjen black-manganese oxide compound high-resolution-ration transmission electric-lens (HRTEM) photo figure of example preparation, the section prepared as seen from Figure 1
Qin Hei-manganese oxide compound pattern is Ketjen black coated manganese oxide, and the nano particle wrapped up in TEM photos by Ketjen black is oxidation
Manganese nano particle, the lattice phase of manganese oxide can be clearly seen that from Fig. 2.
Carry out cycle performance test under 1C to lithium-sulfur cell manufactured in the present embodiment, institute in loop test result such as Fig. 3
Show, first discharge specific capacity is 1163mAh/g under 1C, and specific discharge capacity still reaches 1004mAh/g after circulating 200 times；Coulomb effect
As shown in Figure 4, the coulombic efficiency of battery is higher than 99% to rate.
Embodiment 2：
A kind of dedicated modified barrier film of lithium-sulfur cell of the invention, including commercial barrier film Celgard2400 and it is coated on commercialization
Barrier film Celgard2400 leans on the modified coating of the side surface of positive pole one, and modified coating is that Ketjen black coats Ketjen black-manganese oxide painting
Layer；Conductive agent Super-P is added with modified coating；The thickness of modified coating is 100 μm；Ketjen black and metal in modified coating
The mass ratio of 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 nitrates are dissolved in 100mL ultra-pure waters and form solution A；
(2) 1g Ketjen blacks are added into solution A, with 500W ultrasonic power ultrasonic disperse 2 hours；
(3) solution obtained step (2) filter and in an oven 80 DEG C dry 24h；
(4) solid powder that step (3) drying obtains is positioned in tube-type atmosphere furnace, in the nitrogen atmosphere of flowing,
4h is heat-treated at 500 DEG C, obtains Ketjen black-manganese oxide compound；
(5) Ketjen black-manganese oxide compound of the above-mentioned preparations of 0.7g is taken, 0.1g Super-P, 0.2g PVDF mixing, is added
Enter 8g NMP, diagram modification slurry is formed in 2 hours with 1000r/min speed high-speed stirred；
(6) Ketjen black of above-mentioned preparation-manganese oxide diagram modification slurry is uniformly coated on automatic coating machine
Celgard2400 barrier films are by the surface of positive pole side, coating thickness is 100 μm, and coated modified diaphragm is placed on into air blast
80 DEG C of drying 24h, that is, obtain the dedicated modified barrier film of lithium-sulfur cell in drying box.
The preparation method of the present embodiment lithium-sulfur cell, comprises the following steps：
(1) prepared by Ketjen black-sulphur positive electrode：After 1g Ketjen blacks and 2g sulphur are mixed, with ball mill 800r/min's
Rotate 12 hours under rotating speed, then the mixture of Ketjen black and sulphur is placed in tube furnace, under the argon gas atmosphere of flowing,
155 DEG C are heat-treated 10 hours, obtain Ketjen black-sulphur composite positive pole；
(2) preparation of Ketjen black-sulphur anode composite：Take Ketjen black-sulphur composite positive pole of the above-mentioned preparations of 0.8g, 0.1g
Super-P, 0.1g PVDF are mixed, and add 4g NMP, and Ketjen black-sulphur is formed within 2 hours with 1000r/min speed high-speed stirred
Anode sizing agent, Ketjen black-sulphur anode sizing agent is uniformly coated on aluminium foil with automatic coating machine, thickness is 200 μm, will be coated
Positive pole be placed in air dry oven 80 DEG C of drying 24h, that is, obtain Ketjen black-sulphur anode composite；
(3) lithium-sulfur cell is assembled：The Ketjen black that step (2) is obtained-sulphur anode composite, lithium sulphur electricity manufactured in the present embodiment
The dedicated modified barrier film in pond, cathode of lithium, organic electrolyte 1M LiTFSI (bis trifluoromethyl sulfonic acid Asia acid amides lithium)+0.1M LiNO3
(lithium nitrate)+DOL (DOX)/DME (glycol dimethyl ether) (1/1, v/v), it is less than 1ppm hand in water oxygen content
Button lithium-sulfur cell is prepared in casing.
Cycle performance test is carried out under 1C to lithium-sulfur cell manufactured in the present embodiment, first discharge specific capacity is under 1C
1150mAh/g, specific discharge capacity still reaches 1000mAh/g after circulating 200 times, and the coulombic efficiency of battery is higher than 98%.
Embodiment 3：
A kind of dedicated modified barrier film of lithium-sulfur cell of the invention, including commercial barrier film Celgard2400 and it is coated on commercialization
Barrier film Celgard2400 leans on the modified coating of the side surface of positive pole one, and modified coating is that Ketjen black coats Ketjen black-lanthana painting
Layer；Conductive agent Super-P is added with modified coating；The thickness of modified coating is 100 μm；Ketjen black and metal in modified coating
The mass ratio of 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 nitrates are dissolved in 100mL ultra-pure waters and form solution A；
(2) 1g Ketjen blacks are added into solution A, with 500W ultrasonic power ultrasonic disperse 2 hours；
(3) solution obtained step (2) filter and in an oven 80 DEG C dry 24h；
(4) solid powder that step (3) obtains is positioned in tube-type atmosphere furnace, in the nitrogen atmosphere of flowing, 450
4h is heat-treated at DEG C, obtains Ketjen black-lanthanum oxide compound；
(5) Ketjen black-lanthanum oxide compound for taking 0.7g steps (4) to prepare, 0.1g Super-P, 0.2g PVDF mixing,
8g NMP are added, diagram modification slurry is formed in 2 hours with 1000r/min speed high-speed stirred；
(6) Ketjen black for being prepared step (5) with automatic coating machine-lanthana diagram modification slurry is uniformly coated on
Celgard2400 barrier films are by the surface of positive pole side, coating thickness is 100 μm, and coated modified diaphragm is placed on into air blast
80 DEG C of drying 24h, that is, obtain the dedicated modified barrier film of lithium-sulfur cell in drying box.
The preparation method of the present embodiment lithium-sulfur cell, comprises the following steps：
(1) prepared by Ketjen black-sulphur positive electrode：After 1g Ketjen blacks and 2g sulphur are mixed, with ball mill 800r/min's
Rotate 12 hours under rotating speed, then the mixture of Ketjen black and sulphur is placed in tube furnace, under the nitrogen atmosphere of flowing,
155 DEG C are heat-treated 10 hours, obtain Ketjen black-sulphur composite positive pole；
(2) preparation of Ketjen black-sulphur anode composite：Take 0.8g Ketjen blacks-sulphur composite positive pole, 0.1g Super-P,
0.1g PVDF are mixed, and add 4g NMP, and Ketjen black-sulphur anode sizing agent is formed within 2 hours with 1000r/min speed high-speed stirred,
Ketjen black-sulphur anode sizing agent is uniformly coated on aluminium foil with automatic coating machine, thickness is 200 μm, and coated positive pole is put
80 DEG C of drying 24h, that is, obtain Ketjen black-sulphur anode composite in air dry oven；
(3) lithium-sulfur cell is assembled：The Ketjen black that step (2) is obtained-sulphur anode composite, section's qin manufactured in the present embodiment
Black-lanthana lithium-sulfur cell modified diaphragm, cathode of lithium, organic electrolyte 1M LiTFSI (bis trifluoromethyl sulfonic acid Asia acid amides lithium)+
0.1M LiNO3(lithium nitrate)+DOL (DOX)/DME (glycol dimethyl ether) (1/1, v/v) is low in water oxygen content
Button lithium-sulfur cell is prepared in 1ppm glove box.
Cycle performance test is carried out under 1C to lithium-sulfur cell manufactured in the present embodiment, first discharge specific capacity is under 1C
1180mAh/g, specific discharge capacity still reaches 1020mAh/g after circulating 200 times, and the coulombic efficiency of battery is higher than 97%.
Embodiment 4：
A kind of dedicated modified barrier film of lithium-sulfur cell of the invention, including commercial barrier film Celgard2400 and it is coated on commercialization
Barrier film Celgard2400 leans on the modified coating of the side surface of positive pole one, and modified coating is that Ketjen black coats Ketjen black-cerium oxide painting
Layer；Conductive agent Super-P is added with modified coating；The thickness of modified coating is 100 μm；Ketjen black and metal in modified coating
The mass ratio of 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 nitrates are dissolved in 100mL ultra-pure waters and form solution A；
(2) 1g Ketjen blacks are added into solution A, with 500W ultrasonic power ultrasonic disperse 2 hours；
(3) solution obtained step (2) filter and in an oven 80 DEG C dry 24h；
(4) solid powder that step (3) obtains is positioned in tube-type atmosphere furnace, in the nitrogen atmosphere of flowing, 500
4h is heat-treated at DEG C, obtains Ketjen black-cerium oxide compound；
(5) Ketjen black-cerium oxide compound for taking 0.7g steps (4) to prepare, 0.1g Super-P, 0.2g PVDF mixing,
8g NMP are added, diagram modification slurry is formed in 2 hours with 1000r/min speed high-speed stirred；
(6) Ketjen black for being prepared step (5) with automatic coating machine-cerium oxide diagram modification slurry is uniformly coated on
Celgard2400 barrier films are by the surface of positive pole side, coating thickness is 100 μm, and coated modified diaphragm is placed on into air blast
80 DEG C of drying 24h, that is, obtain the dedicated modified barrier film of lithium-sulfur cell in drying box.
The preparation method of the present embodiment lithium-sulfur cell, comprises the following steps：
(1) prepared by Ketjen black-sulphur positive electrode：After 1g Ketjen blacks and 2g sulphur are mixed, with ball mill 800r/min's
Rotate 12 hours under rotating speed, then the mixture of Ketjen black and sulphur is placed in tube furnace, under the nitrogen atmosphere of flowing,
155 DEG C are heat-treated 10 hours, obtain Ketjen black-sulphur composite positive pole；
(2) preparation of Ketjen black-sulphur anode composite：Take 0.8g Ketjen blacks-sulphur composite positive pole, 0.1g Super-P,
0.1g PVDF are mixed, and add 4g NMP, and Ketjen black-sulphur anode sizing agent is formed within 2 hours with 1000r/min speed high-speed stirred,
Ketjen black-sulphur anode sizing agent is uniformly coated on aluminium foil with automatic coating machine, thickness is 200 μm, and coated positive pole is put
80 DEG C of drying 24h, that is, obtain Ketjen black-sulphur anode composite in air dry oven；
(3) lithium-sulfur cell is assembled：The Ketjen black that step (2) is obtained-sulphur anode composite, lithium sulphur electricity manufactured in the present embodiment
Pond modified diaphragm, cathode of lithium, organic electrolyte 1M LiTFSI (bis trifluoromethyl sulfonic acid Asia acid amides lithium)+0.1M LiNO3(nitric acid
Lithium)+DOL (DOX)/DME (glycol dimethyl ether) (1/1, v/v), in glove box of the water oxygen content less than 1ppm
Prepare button lithium-sulfur cell.
Cycle performance test is carried out under 1C to lithium-sulfur cell manufactured in the present embodiment, first discharge specific capacity is under 1C
1100mAh/g, specific discharge capacity still reaches 982mAh/g after circulating 200 times, and the coulombic efficiency of battery is higher than 97%.
Embodiment 5：
A kind of dedicated modified barrier film of lithium-sulfur cell of the invention, including commercial barrier film Celgard2400 and it is coated on commercialization
Barrier film Celgard2400 leans on the modified coating of the side surface of positive pole one, and modified coating is that Ketjen black coats Ketjen black-magnesia painting
Layer；Conductive agent Super-P is added with modified coating；The thickness of modified coating is 100 μm；Ketjen black and metal in modified coating
The mass ratio of 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 acetates are dissolved in 100mL ultra-pure waters and form solution A；
(2) 1g Ketjen blacks are added into solution A, with 500W ultrasonic power ultrasonic disperse 2 hours；
(3) solution obtained step (2) filter and in an oven 80 DEG C dry 24h；
(4) solid powder that step (3) obtains is positioned in tube-type atmosphere furnace, in the nitrogen atmosphere of flowing, 700
4h is heat-treated at DEG C, obtains Ketjen black-magnesia compound；
(5) 0.7g Ketjen blacks-magnesia compound is taken, 0.1g Super-P, 0.2g PVDF mixing, adds 8g NMP, with
1000r/min speed high-speed stirred forms diagram modification slurry in 2 hours；
(6) Ketjen black-magnesia diagram modification slurry is uniformly coated on Celgard2400 barrier films and leaned on automatic coating machine
On the surface of positive pole side, coating thickness is 100 μm, and coated modified diaphragm is placed on into 80 DEG C of drying in air dry oven
24h, that is, obtain Ketjen black-magnesia lithium-sulfur cell modified diaphragm.
The preparation method of the present embodiment lithium-sulfur cell, comprises the following steps：
(1) prepared by Ketjen black-sulphur positive electrode：After 1g Ketjen blacks and 2g sulphur are mixed, with ball mill 800r/min's
Rotate 12 hours under rotating speed, then the mixture of Ketjen black and sulphur is placed in tube furnace, under the nitrogen atmosphere of flowing,
155 DEG C are heat-treated 10 hours, obtain Ketjen black-sulphur composite positive pole；
(2) preparation of Ketjen black-sulphur anode composite：Take 0.8g Ketjen blacks-sulphur composite positive pole, 0.1g Super-P,
0.1g PVDF are mixed, and add 4g NMP, and Ketjen black-sulphur anode sizing agent is formed within 2 hours with 1000r/min speed high-speed stirred,
Ketjen black-sulphur anode sizing agent is uniformly coated on aluminium foil with automatic coating machine, thickness is 200 μm, and coated positive pole is put
80 DEG C of drying 24h, that is, obtain Ketjen black-sulphur anode composite in air dry oven；
(3) lithium-sulfur cell is assembled：The Ketjen black that step (2) is obtained-sulphur anode composite, lithium sulphur electricity manufactured in the present embodiment
Pond modified diaphragm, cathode of lithium, organic electrolyte 1M LiTFSI (bis trifluoromethyl sulfonic acid Asia acid amides lithium)+0.1M LiNO3(nitric acid
Lithium)+DOL (DOX)/DME (glycol dimethyl ether) (1/1, v/v), in glove box of the water oxygen content less than 1ppm
Prepare button lithium-sulfur cell.
Cycle performance test is carried out under 1C to lithium-sulfur cell manufactured in the present embodiment, first discharge specific capacity is under 1C
1120mAh/g, specific discharge capacity still reaches 967mAh/g after circulating 200 times, and the coulombic efficiency of battery is higher than 95%.
Comparative example 1：
A kind of lithium-sulfur cell barrier film, including commercial barrier film Celgard2400 and be coated on commercial barrier film Celgard2400 and lean on
The Ketjen black coating of the side surface of positive pole one；Conductive agent Super-P is added with Ketjen black coating；Ketjen black coating is 100 μm.
The method of this comparative example lithium-sulfur cell barrier film and its lithium-sulfur cell, comprises the following steps：
The preparation of above-mentioned lithium-sulfur cell dedicated diaphragm and its preparation of lithium-sulfur cell, comprise the following steps：
(1) 0.7g Ketjen blacks are taken, 0.1g Super-P, 0.2g PVDF mixing, 8g NMP are added, with 1000r/min speed
Spend high-speed stirred and form diagram modification slurry in 2 hours；
(2) Ketjen black slurry is uniformly coated on surface of the Celgard2400 barrier films by positive pole side with automatic coating machine
On, coating thickness is 100 μm, and coated modified diaphragm is placed on into 80 DEG C of drying 24h in air dry oven obtains Ketjen black
Lithium-sulfur cell barrier film；
(3) after mixing 1g Ketjen blacks and 2g sulphur, rotated 12 hours under 800r/min rotating speed with ball mill, then will
The mixture of Ketjen black and sulphur is placed in tube furnace, and under the nitrogen atmosphere of flowing, section is obtained within 10 hours in 155 DEG C of heat treatments
Qin Hei-sulphur composite positive pole；
(4) 0.8g Ketjen blacks-sulphur composite positive pole is taken, 0.1g Super-P, 0.1g PVDF mixing, adds 4g NMP,
Ketjen black-sulphur anode sizing agent is formed with 1000r/min speed high-speed stirred 2 hours, with automatic coating machine by Ketjen black-sulphur just
Pole slurry is uniformly coated on aluminium foil, and thickness is 200 μm, and coated positive pole is placed on into 80 DEG C of drying 24h in air dry oven
Obtain Ketjen black-sulphur anode composite；
(5) Ketjen black for obtaining step (4)-sulphur anode composite, the Ketjen black lithium-sulfur cell barrier film that step (2) obtains,
Cathode of lithium, organic electrolyte 1M LiTFSI (bis trifluoromethyl sulfonic acid Asia acid amides lithium)+0.1M LiNO3(lithium nitrate)+DOL (1,
3- dioxolanes)/DME (glycol dimethyl ether) (1/1, v/v), prepare button lithium in glove box of the water oxygen content less than 1ppm
Sulphur battery.
To this comparative example prepare lithium-sulfur cell cycle performance test is carried out under 1C, loop test result as shown in figure 3,
First discharge specific capacity is 1081mAh/g under 1C, and specific discharge capacity reaches 780mAh/g after circulating 200 times；Coulombic efficiency such as Fig. 4
Shown in, the coulombic efficiency of battery is higher than 93%.
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) prepared by Ketjen black-sulphur positive electrode：After 1g Ketjen blacks and 2g sulphur are mixed, with ball mill 800r/min's
Rotate 12 hours under rotating speed, then the mixture of Ketjen black and sulphur is placed in tube furnace, under the nitrogen atmosphere of flowing,
155 DEG C of heat treatments obtain Ketjen black-sulphur composite positive pole in 10 hours；
(2) preparation of Ketjen black-sulphur anode composite：Take 0.8g Ketjen blacks-sulphur composite positive pole, 0.1g Super-P,
0.1g PVDF are mixed, and add 4g NMP, and Ketjen black-sulphur anode sizing agent is formed within 2 hours with 1000r/min speed high-speed stirred,
Ketjen black-sulphur anode sizing agent is uniformly coated on aluminium foil with automatic coating machine, thickness is 200 μm, and coated positive pole is put
80 DEG C of drying 24h obtain Ketjen black-sulphur anode composite in air dry oven；
(3) lithium-sulfur cell is assembled：The Ketjen black that step (2) is obtained-sulphur anode composite, commercial barrier film Celgard2400,
Cathode of lithium, organic electrolyte 1M LiTFSI (bis trifluoromethyl sulfonic acid Asia acid amides lithium)+0.1M LiNO3(lithium nitrate)+DOL (1,
3- dioxolanes)/DME (glycol dimethyl ether) (1/1, v/v), prepare button lithium in glove box of the water oxygen content less than 1ppm
Sulphur battery.
The lithium-sulfur cell prepared to this comparative example carries out cycle performance test under 1C, institute in loop test result such as Fig. 3
Show, first discharge specific capacity is 897mAh/g under 1C, and specific discharge capacity reaches 557mAh/g after circulating 200 times；Coulombic efficiency is such as
Shown in Fig. 4, the coulombic efficiency of battery is higher than 80%.
Analyzed from Fig. 3 and Fig. 4, the lithium-sulfur cell for being covered with Ketjen black-metal oxide compounds that the present invention uses is special
With modified diaphragm, compared to the barrier film for not being covered with Ketjen black-metal oxide complex, hence it is evident that electrical conductivity and the change of battery can be improved
Stability is learned, and there is more preferable cycle performance and high rate performance, to meet that the high request of battery provides reliable quality assurance.
Claims (7)
- A kind of 1. preparation method of the dedicated modified barrier film of lithium-sulfur cell, it is characterised in that the dedicated modified barrier film of lithium-sulfur cell, Including septum body and modified coating of the septum body by the side surface of positive pole one is coated on, the modified coating is that Ketjen black coats Coating of metal oxides；Conductive agent is added with modified coating；The preparation method of the dedicated modified barrier film of lithium-sulfur cell includes Following steps：(1) metal inorganic salt is dissolved in ultra-pure water, adds Ketjen black, then disperseed, dried, be heat-treated, obtain section's qin Black-metal oxide compounds；(2) added after the Ketjen black-metal oxide compounds obtained after step (1) are mixed with conductive agent, adhesive organic Stirring solvent is into slurry；(3) Ketjen black obtained after step (2)-metal oxide complex slurry is uniformly coated on table of the barrier film by positive pole side On face and dry, that is, obtain the dedicated modified barrier film of lithium-sulfur cell.
- 2. preparation method according to claim 1, it is characterised in that in the step (1), metal inorganic salt is metal nitre One or several kinds in hydrochlorate, metal sulfate, metal acetate, metal oxalate, metal carbonate；The metal nitrate Salt is manganese nitrate, cerous nitrate, lanthanum nitrate, yttrium nitrate, Titanium Nitrate, nickel nitrate, magnesium nitrate, copper nitrate, in ferric nitrate and cobalt nitrate One or more；The metal sulfate is manganese sulfate, cerous sulfate, lanthanum sulfate, yttrium sulfate, titanium sulfate, nickel sulfate, sulfuric acid Magnesium, copper sulphate, the one or more in ferric sulfate and cobaltous sulfate；The metal acetate is manganese acetate, lanthanum acetate, yttrium acetate, Nickel acetate, magnesium acetate, copper acetate, the one or more in ferric acetate and cobalt acetate；The metal oxalate is manganese oxalate, oxalic acid Cerium, lanthanum oxalate, yttrium oxalate, nickel oxalate, the one or more in ferric oxalate and cobalt oxalate；The metal carbonate is manganese carbonate, Cerous carbonate, lanthanum carbonate, yttrium carbonate, nickelous carbonate, magnesium carbonate, copper carbonate, ferric carbonate, the one or several kinds in cobalt carbonate；Section's qin One or more in black model EC300, EC600JD, ECP300 and ECP600JD.
- 3. preparation method according to claim 1, it is characterised in that in the step (1), be separated into ultrasonic disperse, surpass The scattered power of sound is 100W-500W, jitter time 1-5h；The drying temperature is 50-100 DEG C, drying time 12- 24h；The heat treatment is carried out in inert gas filled atmosphere furnace, and the temperature of heat treatment is 400-800 DEG C, time 4- 6h；The inert gas is nitrogen or argon gas.
- 4. preparation method according to claim 1, it is characterised in that in the step (2), Ketjen black-metal oxide The quality proportioning of compound, conductive agent and adhesive is 5-7:1:2-4；Described adhesive is PVDF；The organic solvent is NMP。
- 5. preparation method according to claim 1, it is characterised in that in the step (2), mixing speed 600- 1000r/min, mixing time 1-3h；In the step (3), drying temperature is 50-100 DEG C, drying time 12-24h.
- 6. preparation method as claimed in claim 1, it is characterised in that the septum body is commercial barrier film Celgard2400； The conductive agent is the one or more in Super-P, BP2000, acetylene black.
- 7. preparation method as claimed in claim 1, it is characterised in that the thickness of the modified coating is 50-200 μm；It is modified Mass ratio >=1 of Ketjen black and metal oxide in coating.
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| CN107785523B (en) * | 2016-08-31 | 2019-12-03 | 清华大学 | Lithium-sulfur cell diaphragm and lithium-sulfur cell |
| CN107785524B (en) * | 2016-08-31 | 2019-12-03 | 清华大学 | The preparation method of lithium-sulfur cell diaphragm |
| CN108270030B (en) * | 2016-12-30 | 2020-09-22 | 福建新峰二维材料科技有限公司 | Lithium-sulfur full battery and preparation method thereof |
| CN108666536B (en) * | 2017-03-31 | 2020-10-27 | 北京化工大学 | Preparation method of modified diaphragm of lithium-sulfur battery |
| CN108565386B (en) * | 2018-04-08 | 2021-06-25 | 珠海鹏辉能源有限公司 | Lithium-sulfur battery diaphragm and preparation method thereof, and lithium-sulfur battery and preparation method thereof |
| KR102415167B1 (en) | 2018-10-26 | 2022-07-01 | 주식회사 엘지에너지솔루션 | Functional separator, method for preparing the same and lithium secondary battery including the same |
| CN109698303A (en) * | 2018-12-03 | 2019-04-30 | 江苏理工学院 | A kind of electronic conductive material and its preparation and the application in lithium-sulfur cell coated separator |
| CN109921124B (en) * | 2019-03-06 | 2022-04-29 | 四川大学 | Recycling method of waste lithium ion battery anode material |
| CN113725558B (en) * | 2021-07-29 | 2022-09-13 | 长沙矿冶研究院有限责任公司 | Lithium-sulfur battery modified diaphragm and preparation method thereof |
| CN115360478B (en) * | 2022-07-13 | 2024-03-29 | 南昌大学 | In-situ growth carbon nanotube type ferric phosphate modified lithium sulfur battery diaphragm, preparation method thereof and lithium sulfur battery |
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