CN105977434B - A kind of spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm and preparation method thereof and the lithium-sulfur cell with the diaphragm - Google Patents
A kind of spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm and preparation method thereof and the lithium-sulfur cell with the diaphragm 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
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- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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- H—ELECTRICITY
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- 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
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Abstract
Cerium modified lithium-sulfur cell diaphragm and preparation method thereof is aoxidized the invention discloses a kind of spherical hollow, the modified diaphragm includes septum body, the side of the septum body is coated with modified coating, it include spherical hollow cerium oxide, conductive agent and adhesive in the modified coating, which can effectively prevent the shuttle of polysulfide.The invention also discloses a kind of lithium-sulfur cells with the modified diaphragm, including anode, cathode, electrolyte and diaphragm, the just extremely Ketjen black-sulphur anode composite, the cathode is lithium metal, the electrolyte is bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, 1, the mixture of 3- dioxolanes and glycol dimethyl ether, the diaphragm is that above-mentioned spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm or is the diaphragm that above-mentioned preparation method is prepared, and the diaphragm is coated with anode of the side close to lithium-sulfur cell of modified coating.Lithium-sulfur cell specific capacity is high for this, has extended cycle life.
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to it is a kind of aoxidize cerium modified lithium-sulfur cell diaphragm, its
Preparation method and lithium-sulfur cell with the diaphragm.
Background technique
It is positive (theoretical specific capacity that lithium sulphur (Li-S) battery, which is by cathode (theoretical specific capacity 3860mAh/g), sulphur of lithium,
A kind of model electrochemical energy-storage system 1675mAh/g), theoretical specific energy is up to 2600Wh/kg, much larger than business at this stage
Change lithium ion battery.In addition, the sulphur as positive electrode is also equipped with rich reserves, good in economic efficiency, less toxic advantage, so that should
System great commercial value.However, lithium-sulfur cell there is also some problems in practical applications, the conductance of (1) sulphur is specifically included that
Rate is very low, and at room temperature about 5 × 10-30S/cm must add conductive agent when as electrode material, this inevitably reduces anode
The energy density of material；(2) the more lithium sulfides of the intermediate product of electrochemical reaction are soluble in electrolyte and generate " shuttle effect ", drop
The low utilization rate and cycle performance of sulphur, increases ion migration resistance, while discharging product Li2S2And Li2S can be in sulfur electrode
Surface deposition, forms solid electrolyte interface film (SEI), and utilization efficiency and cycle performance is caused to decline；(3) sulphur anode exists
Acute variation leads to the unstable of battery cathode structure to the volume occurred in charge and discharge process repeatedly so that cycle life and
Special capacity fade.
For lithium-sulfur cell sulphur poorly conductive, polysulfide shuttle effect, volume expansion these three main problems, scientific research work
Authors are modified mainly for sulphur anode, such as carbon material supported with porous, electrically conductives such as active carbon, carbon nanotube, graphenes
Sulphur, these conductive porous carbon materials increase the electric conductivity of sulphur anode, have mitigated the bulk effect in charge and discharge process, and can be with
The more lithium sulfides of solubility that partial adsorbates generate in charge and discharge process.However only positive electrode is modified and still cannot
Completely inhibit " the shuttle effect " of polysulfide.Therefore, there is one kind to be developed that can preferably inhibit polysulfide shuttle effect
Technical solution, to further increase the performance of lithium-sulfur cell.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Cerium modified lithium-sulfur cell diaphragm of the spherical hollow of kind and preparation method thereof and the lithium-sulfur cell with the diaphragm, the modification
Diaphragm can effectively prevent the shuttle of polysulfide, using the lithium-sulfur cell specific capacity height of the diaphragm, have extended cycle life.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm, including septum body, the side of the septum body
It is coated with modified coating, includes spherical hollow cerium oxide, conductive agent and adhesive in the modified coating.In septum body
Side is coated with the modified coating containing spherical hollow cerium oxide, carries out to the polysulfide generated in lithium-sulfur cell charge and discharge process
Stop, adsorb and be catalyzed, cerium oxide is lanthanide metal oxide, and extranuclear strucure is unstable, is easy to lose or obtain
Electronics, therefore cerium oxide is good oxidation reduction catalyst.Polysulfide can be adsorbed onto sphere by spherical hollow cerium oxide
Inside, cerium oxide can be come into full contact with the polysulfide of absorption, considerably increase contact of the polysulfide with cerium oxide
Area enhances the catalytic action of cerium oxide；Also, polysulfide is bound after the cerium oxide absorption polysulfide of spherical hollow
It in sphere, is not easy to escape again, increases the modified coating to the absorption property of polysulfide, restrained effectively lithium sulphur electricity
The shuttle effect of polysulfide in pond, improves the specific capacity and cycle life of lithium-sulfur cell.
Above-mentioned spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm, it is preferred that the modified coating with a thickness of 20-
100μm；The conductive agent is one of Ketjen black, conductive black Super-P, conductive black BP2000 and acetylene black or several
Kind.Modified coating is thicker, wherein the cerium oxide contained is more, correspondingly can also get over to the absorption of polysulfide and catalytic performance
Good, still, modified coating is blocked up and will affect the energy density of lithium-sulfur cell, comprehensively considers absorption, catalysis to polysulfide
The energy density of performance and battery selects 20-100 μm of modified coating thickness more appropriate.
Above-mentioned spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm, it is preferred that in the modified coating, spherical hollow
The mass ratio of cerium oxide, conductive agent and adhesive is (5-8): (4-1): 1.More cerium oxide is added in modified coating to be increased
Add the absorption and catalytic action to polysulfide, a certain amount of conductive agent, which is added, can increase the electric conductivity of modified diaphragm, be conducive to
Electron-transport.
Above-mentioned spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm, it is preferred that the septum body be polyethylene every
Film or polypropylene diaphragm；Described adhesive is polyvinylidene fluoride binder.
The inventive concept total as one, another aspect of the present invention provide a kind of above-mentioned spherical hollow aoxidize it is cerium modified
The preparation method of lithium-sulfur cell diaphragm, comprising the following steps:
(1) spherical hollow cerium oxide, conductive agent and adhesive are added in organic solvent, are then stirred to obtain diaphragm
Modified slurry；
(2) the diagram modification slurry that step (1) obtains is uniformly coated on a side surface of septum body and is dried,
Cerium modified lithium-sulfur cell diaphragm is aoxidized up to the spherical hollow.
The diaphragm preparation method is easy to operate, only need to be coated with one layer of modified slurry in existing commercialized septum body side
, without developing new types of diaphragm, development and production new types of diaphragm the time it takes and expense is greatly saved.
Above-mentioned preparation method, it is preferred that in the step (1), spherical hollow cerium oxide is prepared by following steps:
(1.1) six nitric hydrate ceriums and citric acid are added in ultrapure water according to the molar ratio of 1:1-3, be stirred to
Solution clarification；
(1.2) step (1.1) acquired solution is spray-dried, obtains the mixed powder of dry cerous nitrate and citric acid
End；
(1.3) mixed-powder obtained by step (1.2) calcine up to the spherical hollow cerium oxide.
It is mixed into citric acid as complexing agent in cerous nitrate, advantageously forms the cerium oxide of spherical hollow；Also, it is forging
Citric acid heat resolve generates carbon dioxide gas and is conducive to form cavity in the inside of spherical cerium oxide during burning.Using spray
Mist drying-granulating method prepares spherical hollow cerium oxide, and simple process and low cost is suitable for large-scale industrial production, and
The pattern of cerium oxide has controllability in production process.
Above-mentioned preparation method, it is preferred that in the step (1.2), the inlet temperature of spray-drying operation is 200-250
DEG C, blower frequency is 50-60Hz, wriggling revolution speed 20-30r/min, is divided into 4s between cleansing pin；In the step (1.3), calcining
The temperature of operation is 400-600 DEG C, calcination time 3-6h.
Above-mentioned preparation method, it is preferred that in the step (1), organic solvent is N-Methyl pyrrolidone, the N- first
The mass ratio of base pyrrolidones and adhesive is 19-49:1.Since diaphragm is hydrophobic material, oil binder can only be used
Such as Kynoar (PVDF), and N-Methyl pyrrolidone (NMP) is the organic molten of good dissolution polyvinylidene fluoride binder
Agent；N-Methyl pyrrolidone and polyvinylidene fluoride binder are most suitable for slurry than its viscosity in range in the quality of 19-49:1 and apply
Cloth if too grout will be unable to bond, and will appear the case where being unevenly coated if slurry is too thick on diaphragm.
Above-mentioned preparation method, it is preferred that in the step (1), the mixing speed of stirring operation is 600-1000r/
Min, mixing time 1-3h；In the step (2), the temperature of drying operation is 50-80 DEG C, drying time 12-24h.
The inventive concept total as one, another aspect of the present invention provide a kind of lithium-sulfur cell, including anode, cathode,
Electrolyte and diaphragm, described just extremely Ketjen black-sulphur anode composite, the cathode are lithium metal, and the electrolyte is double three
Methyl fluoride sulfonic acid Asia amide lithium, lithium nitrate, 1,3-dioxolane and glycol dimethyl ether mixture, the diaphragm be it is above-mentioned
The diaphragm that spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm or is prepared for above-mentioned preparation method, the diaphragm apply
It is furnished with anode of the side close to lithium-sulfur cell of modified coating.The lithium-sulfur cell using Ketjen black to the sulphur anode of lithium-sulfur cell into
Row is modified, and is increased the electric conductivity of sulphur anode, has been mitigated the bulk effect in lithium-sulfur cell charge and discharge process, and can partial adsorbates
The polysulfide generated in charge and discharge process；In addition, the lithium-sulfur cell aoxidizes cerium modified diaphragm using above-mentioned spherical hollow, and
The side that diaphragm is coated with modified coating is disposed proximate to the anode of lithium-sulfur cell, which can be effectively to charge and discharge
The polysulfide generated in the process is stopped, adsorbed and is catalyzed, and effectively inhibits the shuttle effect of polysulfide, and then improve lithium
The performance of sulphur battery.The lithium-sulfur cell has higher specific capacity and more excellent cyclicity compared with existing lithium-sulfur cell
Energy.
Compared with the prior art, the advantages of the present invention are as follows:
(1) present invention applies spherical hollow cerium oxide in lithium-sulfur cell diaphragm by the side of anode as more lithium sulfides
Barrier layer, this barrier layer allow lithium ion to pass through, and the more lithium sulfides generated for anode have the work of blocking, absorption and catalysis
With wherein the addition of conductive agent increases the electric conductivity on this barrier layer and the wellability of electrolyte, the lithium-sulfur cell and use
Pure nano carbon-base material (such as Ketjen black) as more lithium sulfide barrier layers lithium-sulfur cell compare have higher specific capacity and
Superior cycle performance.
(2) spherical hollow cerium oxide of the invention uses the preparation method of mist projection granulating, and simple process and low cost is fitted
For large-scale industrial production, and the pattern of cerium oxide has controllability.
(3) diaphragm preparation method of the invention is simple, do not need exploitation new types of diaphragm, it is only necessary to it is existing commercialization every
One layer of diagram modification material is coated on film can be used, and time caused by development and production new types of diaphragm and expense is greatly saved
With.
(4) spherical hollow that the present invention is prepared aoxidizes cerium modified lithium-sulfur cell diaphragm and existing conductive carbon is modified
Lithium-sulfur cell diaphragm compare have better chemical stability.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the structural schematic diagram of lithium-sulfur cell of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of gained spherical hollow cerium oxide in the embodiment of the present invention 1.
Fig. 3 is the cycle performance curve of the embodiment of the present invention 1, comparative example 1 and 2 gained lithium-sulfur cell of comparative example at 1C.
Fig. 4 is the coulomb that the embodiment of the present invention 1, comparative example 1 and 2 gained lithium-sulfur cell of comparative example recycle 100 times at 1C
Efficiency.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
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 spherical hollow of the invention aoxidizes cerium modified lithium-sulfur cell diaphragm and preparation method thereof, with the diaphragm
The embodiment of lithium-sulfur cell.
The spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm and uses a kind of commercial diaphragm Celgard2400 (polypropylene
Diaphragm) it is used as septum body, one layer of modified coating is coated in a side surface of the septum body.The modified coating is spherical hollow
Cerium oxide, is also added with conductive agent Ketjen black and adhesive PVDF (Kynoar) in modified coating, in modified coating
The mass ratio of spherical hollow cerium oxide, Ketjen black and PVDF be 6:3:1, modified coating with a thickness of 20 μm.
The spherical hollow aoxidize the preparation method of cerium modified lithium-sulfur cell diaphragm the following steps are included:
(1) monohydrate potassium of the six nitric hydrate ceriums of 0.01mol and 0.03mol is placed in a beaker, 100ml is added
Ultrapure water, magnetic agitation mix 1h to solution clarification；
(2) solution after above-mentioned stirring is spray-dried by small spraying drying instrument, spray drying condition are as follows: into
200 DEG C of temperature of mouth, blower frequency 50Hz, wriggling revolution speed 20r/min, cleansing pin interval 4s obtain dry nitre in collector
The mixed-powder of sour cerium and citric acid；
(3) mixed-powder obtained above is put into batch-type furnace, 500 DEG C of calcining 4h, obtain spherical hollow in air
Cerium oxide；
(4) the spherical hollow cerium oxide for taking the 0.06g above method to be prepared, 0.03g Ketjen black, 0.01g PVDF mixing
0.3g N-Methyl pyrrolidone is added, 1h is stirred with the mixing speed of 1000r/min to get diagram modification slurry is arrived；
(5) the diagram modification slurry of above-mentioned preparation is uniformly coated on Celgard2400 diaphragm one using automatic coating machine
On the surface of side, coating thickness is 20 μm, and coating is completed to be placed in 60 DEG C of air dry ovens and dries 8h, be placed on vacuum drying oven
In at 60 DEG C vacuum drying 12h cerium modified lithium-sulfur cell diaphragm is aoxidized to get the spherical hollow to the present embodiment.
Fig. 2 is the scanning electron microscope (SEM) photograph of spherical hollow cerium oxide prepared in the present embodiment, by Fig. 2 it will be clear that
The pattern of cerium oxide is spherical shape, and is hollow structure.
The preparation method of lithium-sulfur cell in the present embodiment includes the following steps:
(1) Ketjen black-sulphur positive electrode preparation: 1g Ketjen black is taken, with ball mill 800r/min's after the mixing of 4g sulphur
The mixture of Ketjen black and sulphur, is then placed in tube furnace by positive and negative rotation alternate rotation 6h under revolving speed, in the nitrogen gas of flowing
Under atmosphere, it is heat-treated 10h at 155 DEG C, obtains Ketjen black-sulphur composite positive pole；
(2) Ketjen black-sulphur anode composite preparation: Ketjen black-sulphur composite positive pole, 0.1g of the above-mentioned preparation of 0.8g is taken
Conductive black Super-P and 0.1g PVDF are simultaneously mixed, and 4g NMP is added, and stir 2h formation section with the speed of 1000r/min
Then Ketjen black-sulphur anode sizing agent is uniformly coated on utter misery aluminium foil, thickness by Qin Hei-sulphur anode sizing agent with automatic coating machine
It is 150 μm, coated anode is placed in 80 DEG C of baking 10h in air dry oven, is placed in vacuum drying oven 60 DEG C of vacuum later and dries
12h is done to get Ketjen black-sulphur anode composite is arrived；
(3) lithium-sulfur cell is assembled: in the Ketjen black that step (2) is obtained-sulphur anode composite, spherical shape manufactured in the present embodiment
Sky aoxidizes cerium modified lithium-sulfur cell diaphragm, cathode of lithium, organic electrolyte (1M bis trifluoromethyl sulfonic acid Asia amide lithium (LiTFSI)
+ 0.1M lithium nitrate (LiNO3)+1,3-dioxolane (DOL)/glycol dimethyl ether (DME) (1/1, v/v)), it is low in water oxygen content
Button lithium-sulfur cell is prepared in the argon gas glove box of 1ppm, spherical hollow is aoxidized into cerium modified lithium-sulfur cell diaphragm and is coated with
The side of modified coating is arranged close to anode, and the structure of the lithium-sulfur cell is as shown in Figure 1.
Cycle performance test, loop test result such as Fig. 3 and Fig. 4 are carried out at 1C to lithium-sulfur cell manufactured in the present embodiment
It is shown.As seen from Figure 3 (in figure the curve of the top be the present embodiment lithium-sulfur cell test data), the lithium-sulfur cell is at 1C
First discharge specific capacity is 1063mAh/g, and specific discharge capacity still reaches 974mAh/g after circulation 100 times；From fig. 4, it can be seen that the electricity
After pond recycles 100 times, coulombic efficiency is higher than 98%.
Embodiment 2
A kind of spherical hollow of the invention aoxidizes cerium modified lithium-sulfur cell diaphragm and preparation method thereof, with the diaphragm
The embodiment of lithium-sulfur cell.
The spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm and uses commercialization diaphragm Celgard2400 as diaphragm sheet
Body is coated with one layer of modified coating in a side surface of the septum body.The modified coating is spherical hollow cerium oxide, modified
Conductive agent Super-P and adhesive PVDF are also added in coating, spherical hollow cerium oxide in modified coating, Super-P and
The mass ratio of PVDF be 7:2:1, modified coating with a thickness of 30 μm.
The spherical hollow aoxidize the preparation method of cerium modified lithium-sulfur cell diaphragm the following steps are included:
(1) monohydrate potassium of the six nitric hydrate ceriums of 0.02mol and 0.04mol is placed in a beaker, 150ml is added
Ultrapure water, magnetic agitation mix 1h to solution clarification；
(2) solution after above-mentioned stirring is spray-dried by small spraying drying instrument, spray drying condition are as follows: into
220 DEG C of temperature of mouth, blower frequency 55Hz, wriggling revolution speed 25r/min, cleansing pin interval 4s obtain dry nitre in collector
The mixed-powder of sour cerium and citric acid；
(3) mixed-powder obtained above is put into batch-type furnace, 600 DEG C of calcining 3h, obtain spherical hollow in air
Cerium oxide；
(4) the spherical hollow cerium oxide for taking the 0.7g above method to be prepared, 0.2g Super-P, 0.1g PVDF mixing
4g N-Methyl pyrrolidone is added, 2h is stirred with the mixing speed of 800r/min to get diagram modification slurry is arrived；
(5) the diagram modification slurry of above-mentioned preparation is uniformly coated on Celgard2400 diaphragm one using automatic coating machine
On the surface of side, coating thickness is 30 μm, and coating is completed to be placed in 70 DEG C of air dry ovens and dries 10h, be placed on vacuum baking
Vacuum drying aoxidizes cerium modified lithium-sulfur cell diaphragm for 24 hours at 50 DEG C to get the spherical hollow to the present embodiment in case.
The preparation method of lithium-sulfur cell in the present embodiment includes the following steps:
(1) Ketjen black-sulphur positive electrode preparation: 1g Ketjen black is taken, with ball mill 800r/min's after the mixing of 3g sulphur
The mixture of Ketjen black and sulphur, is then placed in tube furnace by positive and negative rotation alternate rotation 8h under revolving speed, in the nitrogen gas of flowing
Under atmosphere, it is heat-treated 10h at 155 DEG C, obtains Ketjen black-sulphur composite positive pole；
(2) Ketjen black-sulphur anode composite preparation: Ketjen black-sulphur composite positive pole, 0.1g of the above-mentioned preparation of 0.8g is taken
Conductive black Super-P and 0.1g PVDF are simultaneously mixed, and 4g NMP is added, and stir 3h formation section with the speed of 800r/min
Then Ketjen black-sulphur anode sizing agent is uniformly coated on utter misery aluminium foil, thickness by Qin Hei-sulphur anode sizing agent with automatic coating machine
It is 120 μm, coated anode is placed in 80 DEG C of baking 10h in air dry oven, is placed in vacuum drying oven 60 DEG C of vacuum later and dries
12h is done to get Ketjen black-sulphur anode composite is arrived；
(3) lithium-sulfur cell is assembled: in the Ketjen black that step (2) is obtained-sulphur anode composite, spherical shape manufactured in the present embodiment
Sky aoxidizes cerium modified lithium-sulfur cell diaphragm, cathode of lithium, organic electrolyte (1M LiTFSI+0.1M LiNO3+DOL/DME(1/
1, v/v) button lithium-sulfur cell), is prepared in argon gas glove box of the water oxygen content lower than 1ppm, spherical hollow is aoxidized cerium modified
Lithium-sulfur cell diaphragm be coated with the side of modified coating and be arranged close to anode, the structure of lithium-sulfur cell is as shown in Figure 1.
Cycle performance test is carried out at 1C to lithium-sulfur cell manufactured in the present embodiment, which puts for the first time at 1C
Electric specific capacity is 1150mAh/g, and specific discharge capacity still reaches 1000mAh/g after circulation 100 times, and the coulombic efficiency of battery is higher than
99%.
Embodiment 3
A kind of spherical hollow of the invention aoxidizes cerium modified lithium-sulfur cell diaphragm and preparation method thereof, with the diaphragm
The embodiment of lithium-sulfur cell.
The spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm and uses commercialization diaphragm Celgard2400 as diaphragm sheet
Body is coated with one layer of modified coating in a side surface of the septum body.The modified coating is spherical hollow cerium oxide, modified
Conductive agent BP2000 and adhesive PVDF, spherical hollow cerium oxide, BP2000 and PVDF in modified coating are also added in coating
Mass ratio be 5:4:1, modified coating with a thickness of 50 μm.
The spherical hollow aoxidize the preparation method of cerium modified lithium-sulfur cell diaphragm the following steps are included:
(1) monohydrate potassium of the six nitric hydrate ceriums of 0.02mol and 0.06mol is placed in a beaker, 200ml is added
Ultrapure water, magnetic agitation mix 2h to solution clarification；
(2) solution after above-mentioned stirring is spray-dried by small spraying drying instrument, spray drying condition are as follows: into
200 DEG C of temperature of mouth, blower frequency 60Hz, wriggling revolution speed 30r/min, cleansing pin interval 4s obtain dry nitre in collector
The mixed-powder of sour cerium and citric acid；
(3) mixed-powder obtained above is put into batch-type furnace, 500 DEG C of calcining 5h, obtain spherical hollow in air
Cerium oxide；
(4) the spherical hollow cerium oxide for taking the 0.5g above method to be prepared, 0.4g BP2000,0.1g PVDF mixing add
Enter 3g N-Methyl pyrrolidone, 3h is stirred with the mixing speed of 600r/min to get diagram modification slurry is arrived；
(5) the diagram modification slurry of above-mentioned preparation is uniformly coated on Celgard2400 diaphragm one using automatic coating machine
On the surface of side, coating thickness is 50 μm, and coating is completed to be placed in 60 DEG C of air dry ovens and dries 8h, be placed on vacuum drying oven
In at 80 DEG C vacuum drying 12h cerium modified lithium-sulfur cell diaphragm is aoxidized to get the spherical hollow to the present embodiment.
The preparation method of lithium-sulfur cell in the present embodiment includes the following steps:
(1) Ketjen black-sulphur positive electrode preparation: 1g Ketjen black is taken, with ball mill 700r/min's after the mixing of 4g sulphur
The mixture of Ketjen black and sulphur, is then placed in tube furnace by positive and negative rotation alternate rotation 10h under revolving speed, in the nitrogen gas of flowing
Under atmosphere, it is heat-treated 10h at 155 DEG C, obtains Ketjen black-sulphur composite positive pole；
(2) Ketjen black-sulphur anode composite preparation: Ketjen black-sulphur composite positive pole, 0.1g of the above-mentioned preparation of 0.8g is taken
Conductive black Super-P and 0.1g PVDF are simultaneously mixed, and 3g NMP is added, and stir 2h formation section with the speed of 1000r/min
Then Ketjen black-sulphur anode sizing agent is uniformly coated on utter misery aluminium foil, thickness by Qin Hei-sulphur anode sizing agent with automatic coating machine
It is 250 μm, coated anode is placed in 80 DEG C of baking 10h in air dry oven, is placed in vacuum drying oven 60 DEG C of vacuum later and dries
12h is done to get Ketjen black-sulphur anode composite is arrived；
(3) lithium-sulfur cell is assembled: in the Ketjen black that step (2) is obtained-sulphur anode composite, spherical shape manufactured in the present embodiment
Sky aoxidizes cerium modified lithium-sulfur cell diaphragm, cathode of lithium, organic electrolyte (1M LiTFSI+0.1M LiNO3+DOL/DME(1/
1, v/v) button lithium-sulfur cell), is prepared in argon gas glove box of the water oxygen content lower than 1ppm, spherical hollow is aoxidized cerium modified
Lithium-sulfur cell diaphragm be coated with the side of modified coating and be arranged close to anode, the structure of lithium-sulfur cell is as shown in Figure 1.
Cycle performance test is carried out at 1C to lithium-sulfur cell manufactured in the present embodiment, which puts for the first time at 1C
Electric specific capacity is 1020mAh/g, and specific discharge capacity still reaches 950mAh/g after circulation 100 times, and the coulombic efficiency of battery is higher than
97%.
Embodiment 4
A kind of spherical hollow of the invention aoxidizes cerium modified lithium-sulfur cell diaphragm and preparation method thereof, with the diaphragm
The embodiment of lithium-sulfur cell.
The spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm and uses commercialization diaphragm Celgard2400 as diaphragm sheet
Body is coated with one layer of modified coating in a side surface of the septum body.The modified coating is spherical hollow cerium oxide, modified
Conductive agent acetylene black and adhesive PVDF, spherical hollow cerium oxide, acetylene black and PVDF in modified coating are also added in coating
Mass ratio be 8:1:1, modified coating with a thickness of 70 μm.
The spherical hollow aoxidize the preparation method of cerium modified lithium-sulfur cell diaphragm the following steps are included:
(1) monohydrate potassium of the six nitric hydrate ceriums of 0.01mol and 0.03mol is placed in a beaker, 200ml is added
Ultrapure water, magnetic agitation mix 1h to solution clarification；
(2) solution after above-mentioned stirring is spray-dried by small spraying drying instrument, spray drying condition are as follows: into
250 DEG C of temperature of mouth, blower frequency 50Hz, wriggling revolution speed 20r/min, cleansing pin interval 4s obtain dry nitre in collector
The mixed-powder of sour cerium and citric acid；
(3) mixed-powder obtained above is put into batch-type furnace, 500 DEG C of calcining 4h, obtain spherical hollow in air
Cerium oxide；
(4) the spherical hollow cerium oxide for taking the 0.8g above method to be prepared, 0.1g acetylene black, 0.1g PVDF mixing add
Enter 3.3g N-Methyl pyrrolidone, 2h is stirred with the mixing speed of 700r/min to get diagram modification slurry is arrived；
(5) the diagram modification slurry of above-mentioned preparation is uniformly coated on Celgard2400 diaphragm one using automatic coating machine
On the surface of side, coating thickness is 70 μm, and coating is completed to be placed in 80 DEG C of air dry ovens and dries 6h, be placed on vacuum drying oven
In at 60 DEG C vacuum drying 12h cerium modified lithium-sulfur cell diaphragm is aoxidized to get the spherical hollow to the present embodiment.
The preparation method of lithium-sulfur cell in the present embodiment includes the following steps:
(1) Ketjen black-sulphur positive electrode preparation: 1g Ketjen black is taken, with ball mill 900r/min's after the mixing of 2g sulphur
The mixture of Ketjen black and sulphur, is then placed in tube furnace by positive and negative rotation alternate rotation 5h under revolving speed, in the nitrogen gas of flowing
Under atmosphere, it is heat-treated 10h at 155 DEG C, obtains Ketjen black-sulphur composite positive pole；
(2) Ketjen black-sulphur anode composite preparation: Ketjen black-sulphur composite positive pole, 0.2g of the above-mentioned preparation of 0.7g is taken
Conductive black Super-P and 0.1g PVDF are simultaneously mixed, and 3g NMP is added, and stir 2h formation section with the speed of 1000r/min
Then Ketjen black-sulphur anode sizing agent is uniformly coated on utter misery aluminium foil, thickness by Qin Hei-sulphur anode sizing agent with automatic coating machine
It is 300 μm, coated anode is placed in 80 DEG C of baking 10h in air dry oven, is placed in vacuum drying oven 60 DEG C of vacuum later and dries
12h is done to get Ketjen black-sulphur anode composite is arrived；
(3) lithium-sulfur cell is assembled: in the Ketjen black that step (2) is obtained-sulphur anode composite, spherical shape manufactured in the present embodiment
Sky aoxidizes cerium modified lithium-sulfur cell diaphragm, cathode of lithium, organic electrolyte (1M LiTFSI+0.1M LiNO3+DOL/DME(1/
1, v/v) button lithium-sulfur cell), is prepared in argon gas glove box of the water oxygen content lower than 1ppm, spherical hollow is aoxidized cerium modified
Lithium-sulfur cell diaphragm be coated with the side of modified coating and be arranged close to anode, the structure of lithium-sulfur cell is as shown in Figure 1.
Cycle performance test is carried out at 1C to lithium-sulfur cell manufactured in the present embodiment, which puts for the first time at 1C
Electric specific capacity is 1000mAh/g, and specific discharge capacity still reaches 910mAh/g after circulation 100 times, and the coulombic efficiency of battery is higher than
98%.
Embodiment 5
A kind of spherical hollow of the invention aoxidizes cerium modified lithium-sulfur cell diaphragm and preparation method thereof, with the diaphragm
The embodiment of lithium-sulfur cell.
The spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm and uses commercialization diaphragm Celgard2400 as diaphragm sheet
Body is coated with one layer of modified coating in a side surface of the septum body.The modified coating is spherical hollow cerium oxide, modified
Conductive agent Ketjen black and adhesive PVDF, spherical hollow cerium oxide, Ketjen black and PVDF in modified coating are also added in coating
Mass ratio be 7:2:1, modified coating with a thickness of 80 μm.
The spherical hollow aoxidize the preparation method of cerium modified lithium-sulfur cell diaphragm the following steps are included:
(1) monohydrate potassium of the six nitric hydrate ceriums of 0.01mol and 0.03mol is placed in a beaker, 150ml is added
Ultrapure water, magnetic agitation mix 1h to solution clarification；
(2) solution after above-mentioned stirring is spray-dried by small spraying drying instrument, spray drying condition are as follows: into
200 DEG C of temperature of mouth, blower frequency 60Hz, wriggling revolution speed 20r/min, cleansing pin interval 4s obtain dry nitre in collector
The mixed-powder of sour cerium and citric acid；
(3) mixed-powder obtained above is put into batch-type furnace, 500 DEG C of calcining 6h, obtain spherical hollow in air
Cerium oxide；
(4) the spherical hollow cerium oxide for taking the 0.7g above method to be prepared, 0.2g Ketjen black, 0.1g PVDF mixing add
Enter 2.5g N-Methyl pyrrolidone, 2h is stirred with the mixing speed of 1000r/min to get diagram modification slurry is arrived；
(5) the diagram modification slurry of above-mentioned preparation is uniformly coated on Celgard2400 diaphragm one using automatic coating machine
On the surface of side, coating thickness is 80 μm, and coating is completed to be placed in 60 DEG C of air dry ovens and dries 8h, be placed on vacuum drying oven
In at 65 DEG C vacuum drying 18h cerium modified lithium-sulfur cell diaphragm is aoxidized to get the spherical hollow to the present embodiment.
The preparation method of lithium-sulfur cell in the present embodiment includes the following steps:
(1) Ketjen black-sulphur positive electrode preparation: 1g Ketjen black is taken, with ball mill in 1000r/min after the mixing of 3.5g sulphur
Revolving speed under positive and negative rotation alternate rotation 4h, then the mixture of Ketjen black and sulphur is placed in tube furnace, in the nitrogen of flowing
Under atmosphere, it is heat-treated 10h at 155 DEG C, obtains Ketjen black-sulphur composite positive pole；
(2) Ketjen black-sulphur anode composite preparation: Ketjen black-sulphur composite positive pole, 0.1g of the above-mentioned preparation of 0.8g is taken
Conductive black Super-P and 0.1g PVDF are simultaneously mixed, and 3.5g NMP is added, and are formed with the speed stirring 2h of 1000r/min
Then Ketjen black-sulphur anode sizing agent is uniformly coated on utter misery aluminium foil by Ketjen black-sulphur anode sizing agent with automatic coating machine, thick
Degree is 300 μm, and coated anode is placed in 80 DEG C of baking 8h in air dry oven, is placed in vacuum drying oven 60 DEG C of vacuum later and dries
12h is done to get Ketjen black-sulphur anode composite is arrived；
(3) lithium-sulfur cell is assembled: in the Ketjen black that step (2) is obtained-sulphur anode composite, spherical shape manufactured in the present embodiment
Sky aoxidizes cerium modified lithium-sulfur cell diaphragm, cathode of lithium, organic electrolyte (1M LiTFSI+0.1M LiNO3+DOL/DME(1/
1, v/v) button lithium-sulfur cell), is prepared in argon gas glove box of the water oxygen content lower than 1ppm, spherical hollow is aoxidized cerium modified
Lithium-sulfur cell diaphragm be coated with the side of modified coating and be arranged close to anode, the structure of lithium-sulfur cell is as shown in Figure 1.
Cycle performance test is carried out at 1C to lithium-sulfur cell manufactured in the present embodiment, which puts for the first time at 1C
Electric specific capacity is 1100mAh/g, and specific discharge capacity still reaches 980mAh/g after circulation 100 times, and the coulombic efficiency of battery is higher than
97%.
Embodiment 6
A kind of spherical hollow of the invention aoxidizes cerium modified lithium-sulfur cell diaphragm and preparation method thereof, with the diaphragm
The embodiment of lithium-sulfur cell.
The spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm and uses commercialization diaphragm Celgard2400 as diaphragm sheet
Body is coated with one layer of modified coating in a side surface of the septum body.The modified coating is spherical hollow cerium oxide, modified
Conduction BP2000 and adhesive Kynoar are also added in coating, spherical hollow cerium oxide in modified coating, BP2000 and
The mass ratio of PVDF be 8:1:1, modified coating with a thickness of 100 μm.
The spherical hollow aoxidize the preparation method of cerium modified lithium-sulfur cell diaphragm the following steps are included:
(1) monohydrate potassium of the six nitric hydrate ceriums of 0.01mol and 0.01mol is placed in a beaker, 100ml is added
Ultrapure water, magnetic agitation mix 1h to solution clarification；
(2) solution after above-mentioned stirring is spray-dried by small spraying drying instrument, spray drying condition are as follows: into
200 DEG C of temperature of mouth, blower frequency 50Hz, wriggling revolution speed 20r/min, cleansing pin interval 4s obtain dry nitre in collector
The mixed-powder of sour cerium and citric acid；
(3) mixed-powder obtained above is put into batch-type furnace, 400 DEG C of calcining 4h, obtain spherical hollow in air
Cerium oxide；
(4) the spherical hollow cerium oxide for taking the 0.4g above method to be prepared, 0.05g conductive agent BP2000,0.05g
1.2g N-Methyl pyrrolidone is added in PVDF mixing, is starched with the mixing speed stirring 1h of 1000r/min to get to diagram modification
Material；
(5) the diagram modification slurry of above-mentioned preparation is uniformly coated on Celgard2400 diaphragm one using automatic coating machine
On the surface of side, coating thickness is 10 μm, and coating is completed to be placed in 60 DEG C of air dry ovens and dries 8h, be placed on vacuum drying oven
In at 60 DEG C vacuum drying 12h cerium modified lithium-sulfur cell diaphragm is aoxidized to get the spherical hollow to the present embodiment.
The preparation method of lithium-sulfur cell in the present embodiment includes the following steps:
(1) Ketjen black-sulphur positive electrode preparation: 1g Ketjen black is taken, with ball mill 800r/min's after the mixing of 4g sulphur
The mixture of Ketjen black and sulphur, is then placed in tube furnace by positive and negative rotation alternate rotation 6h under revolving speed, in the nitrogen gas of flowing
Under atmosphere, it is heat-treated 10h at 155 DEG C, obtains Ketjen black-sulphur composite positive pole；
(2) Ketjen black-sulphur anode composite preparation: take Ketjen black-sulphur positive electrode of the above-mentioned preparation of 0.8g, 0.1g conductive
Carbon black Super-P and 0.1g PVDF are simultaneously mixed, and 4g NMP is added, and stir 2h formation section qin with the speed of 1000r/min
Then Ketjen black-sulphur anode sizing agent is uniformly coated on utter misery aluminium foil by black-sulphur anode sizing agent with automatic coating machine, with a thickness of
250 μm, coated anode is placed in 80 DEG C of baking 10h in air dry oven, is placed in vacuum drying oven 60 DEG C of vacuum dryings later
12h to get arrive Ketjen black-sulphur anode composite；
(3) lithium-sulfur cell is assembled: in the Ketjen black that step (2) is obtained-sulphur anode composite, spherical shape manufactured in the present embodiment
Sky aoxidizes cerium modified lithium-sulfur cell diaphragm, cathode of lithium, organic electrolyte (1M LiTFSI+0.1M LiNO3+DOL/DME(1/
1, v/v) button lithium-sulfur cell), is prepared in argon gas glove box of the water oxygen content lower than 1ppm, spherical hollow is aoxidized cerium modified
Lithium-sulfur cell diaphragm be coated with the side of modified coating and be arranged close to anode, the structure of lithium-sulfur cell is as shown in Figure 1.
Cycle performance test is carried out at 1C to lithium-sulfur cell manufactured in the present embodiment, which puts for the first time at 1C
Electric specific capacity is 1000mAh/g, and specific discharge capacity still reaches 890mAh/g after circulation 100 times, and the coulombic efficiency of battery is higher than
99%.
Comparative example 1
A kind of lithium-sulfur cell diaphragm uses commercial diaphragm Celgard2400 as septum body, the one of the septum body
Side surface is coated with one layer of Ketjen black coating.In the Ketjen black coating be added with conductive agent Super-P, Ketjen black coating with a thickness of
20μm。
The lithium-sulfur cell diaphragm of this comparative example and the preparation method of lithium-sulfur cell the following steps are included:
(1) 0.06g Ketjen black, 0.01g Super-P and 0.03g PVDF mixing are taken, 2.4g NMP is added, with 1000r/
The mixing speed of min stirs 1h to get coating paste is arrived；
(2) slurry of above-mentioned preparation is uniformly coated on to the surface of Celgard2400 diaphragm side using automatic coating machine
On, coating thickness is 10 μm, and coating is completed to be placed in 60 DEG C of air dry ovens to dry 8h, is placed in vacuum drying oven at 60 DEG C later
Vacuum drying 12h is to get the lithium-sulfur cell modified diaphragm for arriving this comparative example.
(3) Ketjen black-sulphur positive electrode preparation: with ball mill 800r/min's after taking 1g Ketjen black and 4g sulphur to mix
The mixture of Ketjen black and sulphur, is then placed in tube furnace by positive and negative rotation alternate rotation 6h under revolving speed, in the nitrogen gas of flowing
Under atmosphere, in 155 DEG C of heat treatment 10h, Ketjen black-sulphur composite positive pole is obtained；
(4) Ketjen black-sulphur positive electrode of the above-mentioned preparation of 0.8g, 0.1g Ketjen black-sulphur anode composite preparation: are taken
Super-P and 0.1g PVDF is simultaneously mixed, and 5g NMP is added, and forms Ketjen black-sulphur with the speed stirring 2h of 1000r/min
Then Ketjen black-sulphur anode sizing agent is uniformly coated on utter misery aluminium foil by anode sizing agent with automatic coating machine, with a thickness of 150 μm,
Coated anode is placed in 60 DEG C of baking 8h in air dry oven, be placed in vacuum drying oven later 60 DEG C of vacuum drying 12h to get
To Ketjen black-sulphur anode composite；
(5) lithium-sulfur cell: the Ketjen black that step (4) is obtained-sulphur anode composite, the Ketjen black that step (2) obtains is assembled
Modified lithium-sulfur cell diaphragm, cathode of lithium, organic electrolyte (1M LiTFSI+0.1M LiNO3+ DOL/DME (1/1, v/v)),
Water oxygen content prepares button lithium-sulfur cell in the argon gas glove box lower than 1ppm.
Cycle performance test, loop test result such as Fig. 3 and Fig. 4 are carried out at 1C to the lithium-sulfur cell of this comparative example preparation
Shown, as seen from Figure 3, first discharge specific capacity is 900mAh/g under battery 1C, and specific discharge capacity reaches after circulation 100 times
750mAh/g；From fig. 4, it can be seen that coulombic efficiency was higher than for 90% (being lower than embodiment 1) after the circulating battery 100 times.
Comparative example 2
The diaphragm that this comparative example uses is general commercial diaphragm Celgard2400, the preparation side of this comparative example lithium-sulfur cell
Method the following steps are included:
(1) Ketjen black-sulphur positive electrode preparation: 10g alcohol is added after taking 1g Ketjen black and 4g sulphur to mix, uses ball mill
The positive and negative rotation alternate rotation 4h under the revolving speed of 800r/min takes out ball grinder and is placed in air dry oven at 45 DEG C dry 12h, with
The mixture of Ketjen black and sulphur is placed on afterwards in the reaction kettle liner of polytetrafluoroethylene (PTFE) and is placed in 155 DEG C of heat treatment 10 in batch-type furnace
Hour, obtain Ketjen black-sulphur composite positive pole；
(2) Ketjen black-sulphur positive electrode of the above-mentioned preparation of 0.8g, 0.1g Ketjen black-sulphur anode composite preparation: are taken
Super-P and 0.1g PVDF is simultaneously mixed, and 5g NMP is added, and stirs 6min, deaeration with the speed deaeration of 2000r/min
Ketjen black-stream anode sizing agent is obtained after 1min, Ketjen black-sulphur anode sizing agent is then uniformly coated on painting with automatic coating machine
On charcoal aluminium foil, with a thickness of 150 μm, coated anode is placed in 60 DEG C of baking 8h in air dry oven, be placed on vacuum drying oven
In 60 DEG C of vacuum drying 12h to get arrive Ketjen black-sulphur anode composite；
(3) lithium-sulfur cell: the Ketjen black that step (2) is obtained-sulphur anode composite, general commercial diaphragm is assembled
Celgard2400, cathode of lithium, organic electrolyte (1M LiTFSI+0.1M LiNO3+ DOL/DME (1/1, v/v)), contain in water oxygen
Amount prepares button lithium-sulfur cell in the argon gas glove box lower than 1ppm.
Cycle performance test, loop test result such as Fig. 3 and Fig. 4 are carried out at 1C to the lithium-sulfur cell of this comparative example preparation
Shown, as seen from Figure 3, battery first discharge specific capacity at 1C is 693mAh/g, and specific discharge capacity reaches after circulation 100 times
430mAh/g；From fig. 4, it can be seen that coulombic efficiency was higher than for 80% (being lower than embodiment 1) after the circulating battery 100 times.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of spherical hollow aoxidizes the preparation method of cerium modified lithium-sulfur cell diaphragm, the spherical hollow aoxidizes cerium modified
Lithium-sulfur cell diaphragm includes septum body, and the side of the septum body is coated with modified coating, includes in the modified coating
There are spherical hollow cerium oxide, conductive agent and adhesive；
The preparation method comprises the following steps:
(1) spherical hollow cerium oxide, conductive agent and adhesive are added in organic solvent, are then stirred to obtain diagram modification
Slurry；
(2) the diagram modification slurry that step (1) obtains is uniformly coated on a side surface of septum body and is dried to get
The spherical hollow aoxidizes cerium modified lithium-sulfur cell diaphragm；
In the step (1), spherical hollow cerium oxide is prepared by following steps:
(1.1) six nitric hydrate ceriums and citric acid are added in ultrapure water according to the molar ratio of 1:1-3, are stirred to solution
Clarification；
(1.2) step (1.1) acquired solution is spray-dried, obtains the mixed-powder of dry cerous nitrate and citric acid；
(1.3) mixed-powder obtained by step (1.2) calcine up to the spherical hollow cerium oxide.
2. preparation method according to claim 1, it is characterised in that: the modified coating with a thickness of 20-100 μm；Institute
Stating conductive agent is one or more of Ketjen black, conductive black Super-P, conductive black BP2000 and acetylene black.
3. preparation method according to claim 1, it is characterised in that: in the modified coating, spherical hollow cerium oxide is led
The mass ratio of electric agent and adhesive is (5-8): (4-1): 1.
4. preparation method according to claim 1, it is characterised in that: the septum body is polyethylene diagrams or polypropylene
Diaphragm；Described adhesive is polyvinylidene fluoride binder.
5. preparation method according to claim 1, it is characterised in that: in the step (1.2), spray-drying operation into
Mouthful temperature is 200-250 DEG C, and blower frequency is 50-60Hz, wriggling revolution speed 20-30r/min, is divided into 4s between cleansing pin；It is described
In step (1.3), the temperature of calcination operation is 400-600 DEG C, calcination time 3-6h.
6. preparation method according to claim 1, it is characterised in that: in the step (1), organic solvent is N- methyl pyrrole
The mass ratio of pyrrolidone, the N-Methyl pyrrolidone and adhesive is 19-49:1.
7. preparation method according to claim 1, it is characterised in that: in the step (1), the mixing speed of stirring operation
For 600-1000r/min, mixing time 1-3h；In the step (2), the temperature of drying operation is 50-80 DEG C, drying time
For 12-24h.
8. a kind of lithium-sulfur cell, including anode, cathode, electrolyte and diaphragm, it is characterised in that: the just extremely Ketjen black-
Sulphur anode composite, the cathode are lithium metal, and the electrolyte is bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, 1,3- bis-
The mixture of butyl oxide link and glycol dimethyl ether, the diaphragm are preparation method of any of claims 1-7 preparation
Obtained diaphragm, the diaphragm are coated with anode of the side close to lithium-sulfur cell of modified coating.
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| 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 |
| CN110649208B (en) * | 2018-09-29 | 2022-06-17 | 合肥工业大学 | Lithium-sulfur battery composite diaphragm 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 |
| CN111969164A (en) * | 2020-09-18 | 2020-11-20 | 合肥工业大学 | Composite modified diaphragm for lithium-sulfur battery and preparation method thereof |
| CN112811459A (en) * | 2020-12-31 | 2021-05-18 | 刘岩 | CeO (CeO)2Iron-coated nickel-doped lithium manganate positive electrode material 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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| CN1948157A (en) * | 2006-11-09 | 2007-04-18 | 上海大学 | Hollow bead shaped nano-cerium oxide and its preparation method |
| CN103490027A (en) * | 2013-08-12 | 2014-01-01 | 中国科学院化学研究所 | Membrane for lithium-sulfur battery and preparation method of membrane |
| CN104868086A (en) * | 2015-05-26 | 2015-08-26 | 广东烛光新能源科技有限公司 | Composite porous isolating membrane and preparation method thereof |
| CN105280867A (en) * | 2015-09-18 | 2016-01-27 | 长沙矿冶研究院有限责任公司 | Modified diaphragm special for Li-S battery, preparation method of modified diaphragm and Li-S battery |
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| CN1948157A (en) * | 2006-11-09 | 2007-04-18 | 上海大学 | Hollow bead shaped nano-cerium oxide and its preparation method |
| CN103490027A (en) * | 2013-08-12 | 2014-01-01 | 中国科学院化学研究所 | Membrane for lithium-sulfur battery and preparation method of membrane |
| CN104868086A (en) * | 2015-05-26 | 2015-08-26 | 广东烛光新能源科技有限公司 | Composite porous isolating membrane and preparation method thereof |
| CN105280867A (en) * | 2015-09-18 | 2016-01-27 | 长沙矿冶研究院有限责任公司 | Modified diaphragm special for Li-S battery, preparation method of modified diaphragm and Li-S battery |
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