CN107275575A - A kind of preparation method of cladded type lithium sulphur positive electrode - Google Patents
A kind of preparation method of cladded type lithium sulphur positive electrode Download PDFInfo
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- CN107275575A CN107275575A CN201710504230.5A CN201710504230A CN107275575A CN 107275575 A CN107275575 A CN 107275575A CN 201710504230 A CN201710504230 A CN 201710504230A CN 107275575 A CN107275575 A CN 107275575A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation method of cladded type lithium sulphur positive electrode, methods described prepares nano-sulfur using sulfuric acid and sodium thiosulfate reaction, by silicon dioxide coated nano sulphur and prepares microballoon, improves the cycle performance of lithium-sulfur cell；It is cladding material that Tungstenic compound is selected in the present invention, with novelty, cost is low, environment-friendly, clad can not only effectively suppress the side reaction between electrolyte and positive electrode, dissolving of transition metal etc. in material can also be suppressed, the cycle performance etc. under the cyclical stability and high magnification of material is effectively enhanced.
Description
Technical field
The present invention relates to battery material field, and in particular to a kind of preparation method of cladded type lithium sulphur positive electrode.
Background technology
New energy industry is that the current whole world improves an important development direction of energy shortage and environmental protection.Lithium-ion electric
Pond is due to high operating voltage, and memory-less effect, self discharge is small, energy density is big and the advantage that has extended cycle life, by
To extensive concern.Current lithium ion battery mainly develops towards high-energy-density, low production cost, high safety direction.
By negative pole of lithium metal, elemental sulfur for the theoretical specific energy of the lithium-sulfur cell of positive pole can reach 2600Wh/kg (lithium and
The theoretical specific capacity of sulphur is respectively 3860mAh/g and 1675mAh/g), much larger than used commercialization secondary cell at this stage.
In addition, cheap, the environment-friendly characteristic of elemental sulfur makes the energy storage system great commercial value again.But in the prior art, lithium
Not high to the utilization rate of positive active material sulphur in sulphur battery, its Capacity fading is serious, and cycle performance is poor, and electrochemistry
Performance is not good.In order to improve the performance of lithium-sulfur cell, current people are directed to the research of the positive electrode modification to lithium-sulfur cell,
To improve its electric conductivity and cycle performance.For example sulphur is filled out in mesoporous carbon space, the addition of mesoporous carbon improves electric conductivity；This
There is research worker to be modified using conducting polymer to sulphur outside, the addition of conducting polymer can be effectively improved lithium sulphur electricity
The cycle performance in pond.Although however, above-mentioned can improve the electric conductivity of lithium-sulfur cell to the method that sulphur positive electrode is modified
Or its cycle performance is improved, but the energy density of obtained lithium-sulfur cell is reduced, that is to say, that it is this that sulphur positive electrode is entered
The modified method of row can not improve the performance of lithium-sulfur cell on the whole.
Surface coating is one of current effective ways for improving anode material for lithium-ion batteries deficiency, and clad can not only have
Effect suppresses the side reaction between electrolyte and positive electrode, can also suppress dissolving of transition metal etc. in material, reinforcing material
Cycle performance under cyclical stability and high magnification etc., is effectively improved the chemical property of material.
The content of the invention
The present invention provides a kind of preparation method of cladded type lithium sulphur positive electrode, and methods described uses sulfuric acid and thiosulfuric acid
Sodium reaction prepares nano-sulfur, by silicon dioxide coated nano sulphur and prepares microballoon, improves the cycle performance of lithium-sulfur cell；This
From Tungstenic compound to coat material in invention, with novelty, cost is low, environment-friendly, and clad can not only effectively press down
Side reaction between electrolyte and positive electrode processed, can also suppress dissolving of transition metal etc. in material, effectively enhance material
Cyclical stability and high magnification under cycle performance etc..
To achieve these goals, the present invention provides a kind of preparation method of cladded type lithium sulphur positive electrode, this method bag
Include following steps：
（1）Prepare silica nanometer sulphur
Count by weight, the 35-40 parts of poly-vinyl alcohol solutions of mass fraction 5%, 10-12 parts of sodium thiosulfate and 12- are weighed respectively
15 parts of 10mol/L sulfuric acid are placed in beaker, and stirring mixing is placed in ultrasonic disperse 10-15min under 300-400W, then stands old
Change 4-6h, filter cake is collected by filtration and with water washing is distilled 3-5 times, filter cake must be washed by collecting, and be counted by weight, be weighed respectively
45-50 parts of distilled water, 10-15 parts without water glycol, 4-6 parts of polyvinyl alcohol and 6-8 parts of washing filter cakes, it is ultrasonic under 300-400W
Scattered 10-15min, is prepared into modified dispersion liquid；
The modification dispersion liquid pH to 10-11 for choosing the above-mentioned preparation of the ammoniacal liquor of mass fraction 12% regulation is placed in conical flask, is collected
Obtain alkalization modified liquid, then in mass ratio 1:8, the tetraethyl orthosilicate ethylene glycol solution of mass fraction 7% is added dropwise in conical beaker,
It is 80-100min to control time for adding, after being added dropwise to complete, sealing reaction 3-5h, then filters and collects filter cake, uses anhydrous second
After glycol is washed 3-5 times, 5-6h is dried at 50-60 DEG C, silica nanometer sulphur is prepared；
（2）Prepare covering liquid
Tungstenic compound is dissolved in deionized water, is stirred well to and is completely dissolved, is well mixed；
（3）Cladding
The covering liquid prepared, above-mentioned silica nanometer sulphur are added in ball grinder, with 300-500r/min rotating speed ball milling
4-6h is mixed, mixed liquor is obtained；
After the mixed liquor vacuum drying after mill, with 15 DEG C/min speed from room temperature to 120-220 DEG C, in 180-220
Constant temperature pre-burning 3-6h at DEG C, then it is warming up to 250-300 DEG C, in calcining at constant temperature 8- at 250-300 DEG C with 10 DEG C/min speed
10h, is finally down to room temperature with 5 DEG C/min at the uniform velocity rate of temperature fall, after being fully ground, and obtains cladded type lithium sulphur positive electrode.
It is preferred that, described Tungstenic compound uses ammonium metatungstate, and described ammonium metatungstate is above-mentioned silica nanometer
The 1wt%-3wt% of sulfur nutrient.
The invention has the advantages that and remarkable result：
（1）The present invention prepares nano-sulfur using sulfuric acid and sodium thiosulfate reaction, by silicon dioxide coated nano sulphur and prepares
Microballoon, improves the cycle performance of lithium-sulfur cell.
（2）From Tungstenic compound to coat material in the present invention, with novelty, cost is low, environment-friendly, clad
The side reaction between electrolyte and positive electrode can not only effectively be suppressed, dissolving of transition metal etc. in material can also be suppressed, had
Effect enhances cycle performance under the cyclical stability and high magnification of material etc..
Embodiment
Embodiment one
Count by weight, respectively 35 parts of poly-vinyl alcohol solutions of mass fraction 5% of weighing, 10 parts of sodium thiosulfate and 12 parts
10mol/L sulfuric acid is placed in beaker, and stirring mixing is placed in ultrasonic disperse 10min under 300W, and subsequent still aging 4h, filtering is received
Collect filter cake and with water washing is distilled 3 times, filter cake must be washed by collecting, and be counted by weight, and 45 parts of distilled water, 10 parts of nothings are weighed respectively
Water glycol, 4 parts of polyvinyl alcohol and 6 parts of washing filter cakes, the ultrasonic disperse 10min under 300W are prepared into modified dispersion liquid；
The modification dispersion liquid pH to 10-11 for choosing the above-mentioned preparation of the ammoniacal liquor of mass fraction 12% regulation is placed in conical flask, is collected
Obtain alkalization modified liquid, then in mass ratio 1:8, the tetraethyl orthosilicate ethylene glycol solution of mass fraction 7% is added dropwise in conical beaker,
It is 80min to control time for adding, after being added dropwise to complete, sealing reaction 3h, then filters and collects filter cake, is washed with without water glycol
Wash after 3 times, 5h is dried at 50 DEG C, silica nanometer sulphur is prepared.
Tungstenic compound is dissolved in deionized water, is stirred well to and is completely dissolved, is well mixed, obtain covering liquid；Institute
The Tungstenic compound stated uses ammonium metatungstate, and described ammonium metatungstate is the 1wt% of above-mentioned silica nanometer sulfur nutrient.
The covering liquid prepared, above-mentioned silica nanometer sulphur are added in ball grinder, with 300r/min rotating speed ball milling
4h is mixed, mixed liquor is obtained；
After the mixed liquor vacuum drying after mill, with 15 DEG C/min speed from room temperature to 180 DEG C, the constant temperature at 180 DEG C
Pre-burning 3h, then it is warming up to 250 DEG C, in calcining at constant temperature 8h at 250 DEG C with 10 DEG C/min speed, finally min with 5 DEG C/at the uniform velocity
Rate of temperature fall is down to room temperature, after being fully ground, and obtains cladded type lithium sulphur positive electrode.
Embodiment two
Count by weight, respectively 40 parts of poly-vinyl alcohol solutions of mass fraction 5% of weighing, 12 parts of sodium thiosulfate and 15 parts
10mol/L sulfuric acid is placed in beaker, and stirring mixing is placed in ultrasonic disperse 15min under 400W, and subsequent still aging 6h, filtering is received
Collect filter cake and with water washing is distilled 5 times, filter cake must be washed by collecting, and be counted by weight, and 50 parts of distilled water, 15 parts of nothings are weighed respectively
Water glycol, 6 parts of polyvinyl alcohol and 8 parts of washing filter cakes, the ultrasonic disperse 15min under 400W are prepared into modified dispersion liquid；
The modification dispersion liquid pH to 10-11 for choosing the above-mentioned preparation of the ammoniacal liquor of mass fraction 12% regulation is placed in conical flask, is collected
Obtain alkalization modified liquid, then in mass ratio 1:8, the tetraethyl orthosilicate ethylene glycol solution of mass fraction 7% is added dropwise in conical beaker,
It is 100min to control time for adding, after being added dropwise to complete, sealing reaction 5h, then filters and collects filter cake, with without water glycol
After washing 5 times, 6h is dried at 60 DEG C, silica nanometer sulphur is prepared.
Tungstenic compound is dissolved in deionized water, is stirred well to and is completely dissolved, is well mixed, obtain covering liquid；Institute
The Tungstenic compound stated uses ammonium metatungstate, and described ammonium metatungstate is the 3wt% of above-mentioned silica nanometer sulfur nutrient.
The covering liquid prepared, above-mentioned silica nanometer sulphur are added in ball grinder, with 500r/min rotating speed ball milling
6h is mixed, mixed liquor is obtained；
After the mixed liquor vacuum drying after mill, with 15 DEG C/min speed from room temperature to 220 DEG C, the constant temperature at 220 DEG C
Pre-burning 6h, then it is warming up to 300 DEG C, in calcining at constant temperature 10h at 300 DEG C with 10 DEG C/min speed, finally min with 5 DEG C/at the uniform velocity
Rate of temperature fall is down to room temperature, after being fully ground, and obtains cladded type lithium sulphur positive electrode.
Comparative example
Commercially available sulphur lithium anode material.
Above-described embodiment one, two and comparative example products therefrom are used into NMP as solvent, by active material: SP: PVDF
Be configured to slurry that solid content be 70% at=90: 5: 5 is evenly applied on Al paper tinsels, and positive pole is made.Negative pole is from diameter 14mm's
Metal lithium sheet, electrolyte selects 1mol LiFP6 (EC：DMC：EMC=1:1:1, v/v), with negative electrode casing-shell fragment-pad-lithium
Battery is packaged by the order of piece-electrolyte-barrier film-positive plate-pad-anode cover, and whole process is all filled with argon
Completed in the glove box of gas.Electric performance test is carried out in the case where test temperature is 25 DEG C, after tested the material of the embodiment one and two
Compared with the product of comparative example, first charge-discharge reversible capacity improves 16-18%, and service life brings up to more than 10%.
Claims (2)
1. a kind of preparation method of cladded type lithium sulphur positive electrode, this method comprises the following steps：
（1）Prepare silica nanometer sulphur
Count by weight, the 35-40 parts of poly-vinyl alcohol solutions of mass fraction 5%, 10-12 parts of sodium thiosulfate and 12- are weighed respectively
15 parts of 10mol/L sulfuric acid are placed in beaker, and stirring mixing is placed in ultrasonic disperse 10-15min under 300-400W, then stands old
Change 4-6h, filter cake is collected by filtration and with water washing is distilled 3-5 times, filter cake must be washed by collecting, and be counted by weight, be weighed respectively
45-50 parts of distilled water, 10-15 parts without water glycol, 4-6 parts of polyvinyl alcohol and 6-8 parts of washing filter cakes, it is ultrasonic under 300-400W
Scattered 10-15min, is prepared into modified dispersion liquid；
The modification dispersion liquid pH to 10-11 for choosing the above-mentioned preparation of the ammoniacal liquor of mass fraction 12% regulation is placed in conical flask, is collected
Obtain alkalization modified liquid, then in mass ratio 1:8, the tetraethyl orthosilicate ethylene glycol solution of mass fraction 7% is added dropwise in conical beaker,
It is 80-100min to control time for adding, after being added dropwise to complete, sealing reaction 3-5h, then filters and collects filter cake, uses anhydrous second
After glycol is washed 3-5 times, 5-6h is dried at 50-60 DEG C, silica nanometer sulphur is prepared；
（2）Prepare covering liquid
Tungstenic compound is dissolved in deionized water, is stirred well to and is completely dissolved, is well mixed；
（3）Cladding
The covering liquid prepared, above-mentioned silica nanometer sulphur are added in ball grinder, with 300-500r/min rotating speed ball milling
4-6h is mixed, mixed liquor is obtained；
After the mixed liquor vacuum drying after mill, with 15 DEG C/min speed from room temperature to 120-220 DEG C, in 180-220
Constant temperature pre-burning 3-6h at DEG C, then it is warming up to 250-300 DEG C, in calcining at constant temperature 8- at 250-300 DEG C with 10 DEG C/min speed
10h, is finally down to room temperature with 5 DEG C/min at the uniform velocity rate of temperature fall, after being fully ground, and obtains cladded type lithium sulphur positive electrode.
2. the method as described in claim 1, it is characterised in that described Tungstenic compound uses ammonium metatungstate, described is inclined
Ammonium tungstate is the 1wt%-3wt% of above-mentioned silica nanometer sulfur nutrient.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108063257A (en) * | 2017-12-14 | 2018-05-22 | 厦门大学 | A kind of preparation method and applications of metal shell layer cladding sulphur composite positive pole |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106654223A (en) * | 2017-01-16 | 2017-05-10 | 北京理工大学 | Modification method for tungsten-containing compound coated positive electrode material of lithium ion battery |
| CN106784637A (en) * | 2016-12-30 | 2017-05-31 | 梅庆波 | A kind of preparation method of high-energy-density lithium-sulphur cell positive electrode material |
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- 2017-06-28 CN CN201710504230.5A patent/CN107275575A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784637A (en) * | 2016-12-30 | 2017-05-31 | 梅庆波 | A kind of preparation method of high-energy-density lithium-sulphur cell positive electrode material |
| CN106654223A (en) * | 2017-01-16 | 2017-05-10 | 北京理工大学 | Modification method for tungsten-containing compound coated positive electrode material of lithium ion battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108063257A (en) * | 2017-12-14 | 2018-05-22 | 厦门大学 | A kind of preparation method and applications of metal shell layer cladding sulphur composite positive pole |
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Application publication date: 20171020 |