CN106374095B - A kind of preparation method of the composite material as lithium sulfur battery anode material - Google Patents
A kind of preparation method of the composite material as lithium sulfur battery anode material Download PDFInfo
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Abstract
The invention belongs to lithium sulfur battery anode material preparation field, specifically a kind of layered inorganic compound/conducting polymer/sulphur composite material preparation method as lithium sulfur battery anode material.The present invention is compound in nanoscale by polymer and inorganic layered compounds, and sulphur is sandwiched in piece interlayer, the shuttle effect of sulphur is prevented;Stratified material such as spring can buffer volumes expansion stress, keep material inherent structure reduce volume expanded caused by active material lose, improve material circulation performance;There is stratified material of organo-mineral complexing itself potential response cation to exchange attribute, and being compounded in charge and discharge process with sulphur has synergistic effect, improve the high rate performance of battery;Lamellar compound interlamellar spacing is adjustable, and suitable interlamellar spacing is conducive to Li+Transmission.Present invention process step is simple, easy to operate, and layered inorganic compound/conducting polymer/sulphur composite material has good application prospect in lithium sulfur battery anode material.
Description
Technical field
The invention belongs to lithium sulfur battery anode material preparation fields, specifically a kind of to be used as lithium sulfur battery anode material
Layered inorganic compound/conducting polymer/sulphur composite material preparation method.
Background technique
With the fast development of mobile electronic device and new-energy automobile, the mankind are to secondary energy storage battery specific energy and compare function
The requirement of rate is higher and higher.Lithium ion battery is one of now widely used secondary cell, wherein the positive material having been commercialized
Expect that theoretical capacity is lower, limited by theoretical specific capacity, further promotion energy density is extremely difficult, is not able to satisfy future
Develop demand to high-energy density secondary battery, lithium-sulfur cell due to very high storage lithium theoretical specific capacity 1675mAh/g,
And elemental sulfur has rich content, cheap, environmental-friendly as anode, it is considered to be a kind of very promising next-generation high
Energy density secondary cell.
The development of lithium-sulfur cell also faces very big challenge simultaneously, and elemental sulfur is the insulator of electronics and ion at room temperature
(5×10-3S/cm, room temperature), cannot be used separately as positive electrode, need to carry out sulphur and other conductive materials it is compound, with
Improve the conductive capability of electrode material;In addition in charge and discharge process sulphur intermediate product polysulfide (Li2Sx, x > 2), having
It dissolves, can be migrated between positive and negative anodes in machine electrolyte, is i.e. generation shuttle effect, lead to the loss of active material, capacity attenuation
Quickly;And volume change of the sulphur in charge and discharge process is larger, is fully converted to Li by sulphur2Volume expansion about 80%, draws when S
It plays active material differentiation and falls off, and then capacity is caused to be decayed rapidly, a series of this problem results in positive active material benefit
It is low and circulating battery stability is poor with rate.
To solve the above problems, people are special using the metal electrology characteristic of conducting polymer, redox active and storage lithium
Property and sulphur it is compound be used as positive electrode, with limit polysulfide dissolution improve electric conductivity.Simple chemistry cladding can be improved
The electric conductivity of material reduces charge transfer impedance, but active material caused by sulphur volume expansion cannot effectively be overcome to be lost.
The present invention is based on the basis of conducting polymer in-stiu coating sulphur, layered inorganic compound is introduced, its current potential is utilized
Response cation exchange attribute and sulphur, which are compounded in charge and discharge process, has synergistic effect, improves the high rate performance of battery, stratiform
Compound layer spacing is adjustable, and suitable interlamellar spacing is conducive to Li+Transmission, stratified material such as spring can buffer volumes expansion answer
Power keeps the inherent structure of material, improves layered inorganic compound/conduction of the cycle performance preparation structure function admirable of battery
Polymer nanocomposites, sulphur double team is simple in interlayer step, it is easy to operate, there is good application prospect.
Summary of the invention
The present invention in order to solve the problems, such as that lithium-sulphur cell positive electrode active material utilization rate is low and circulating battery stability is poor,
Provide a kind of layered inorganic compound/conducting polymer/sulphur composite material preparation side as lithium sulfur battery anode material
Method.
The present invention is achieved by the following technical solutions: a kind of layered inorganic chemical combination as lithium sulfur battery anode material
Object/conducting polymer/sulphur composite material preparation method, includes the following steps:
(1) delamination of layered inorganic compound: layered inorganic compound being dispersed, and adds intercalator, stirs 5 ~ 48h,
Layered inorganic compound delamination forms single layer compound;
(2) polymer monomer intercalation, sulphur content dissipate: polymer monomer solution being added in single layer compound solution, is used
After 100 ~ 5000r/min of revolving speed is stirred 1 ~ 10h of dispersion, elemental sulfur is added, 10 ~ 60 min of ultrasonic disperse is stirred for 1 ~ 5h,
It is dispersed in sulphur simple substance in mixed solution;
(3) polymerization cladding: at the uniform velocity dropwise addition oxidant into mixed solution, oxidant and polymer monomer molar ratio be 1:1 ~
2:1, time for adding are controlled in 10 ~ 120min;
(4) layered inorganic compound reassembles: at the uniform velocity dropwise addition concentration is 0.5 ~ 3M sour (inorganic) or alkali is (inorganic) to mixed
It closes in solution, time for adding is controlled in 10 ~ 80min, reassembles single layer compound, so that polymer and elemental sulfur be sandwiched
In interlayer, after reaction with the alternately washing, filtering of organic solvent and deionized water, it is dried to obtain layered inorganic compound/lead
Electric polymer/sulphur composite material.
When it is implemented, the interlamellar spacing of inorganic layered compounds can be adjusted by adjusting the additive amount of polymer.Certainly,
The additive amount of elemental sulfur can have an impact interlamellar spacing, but when realizing that interlamellar spacing is adjusted mainly by adjusting polymer
Additive amount.
Compared with prior art, the invention has the following advantages that (1) by polymer and inorganic layered compounds in nanometer
Scale is compound, and sulphur is sandwiched in interlayer, the shuttle effect of sulphur is prevented;(2) stratified material such as spring can buffer volumes expansion
Stress keeps the inherent structure of material, improves the cycle performance of battery;(3) stratified material of organo-mineral complexing itself has
Potential response cation exchanges attribute, and being compounded in charge and discharge process with sulphur has synergistic effect, improves the forthright again of battery
Energy;(4) lamellar compound interlamellar spacing is adjustable, and suitable interlamellar spacing is conducive to Li+Transmission.(5) Inorganic whisker layer
Shape compound is cheap, resourceful, and synthetic method is simple.Therefore present invention process step is simple, easy to operate, layered inorganic
Compound/conducting polymer/sulphur composite material has good application prospect in lithium sulfur battery anode material.
Detailed description of the invention
Fig. 1 is basic zirconium phosphate/polypyrrole/sulphur composite material XRD diagram that embodiment 2 prepares.
Fig. 2 is the 2025 type button cells that prepare of embodiment 2 first charge-discharge figure under different multiplying.It can be with by figure
Find out: basic zirconium phosphate/polypyrrole/sulphur composite material has good high rate performance as lithium sulfur battery anode material.
Fig. 3 is the 1st, 3,5 charge and discharge electrograph of 2025 type button cell that embodiment 4 prepares.As seen from the figure: covering
De- soil/polypyrrole/sulphur composite material is stablized as 5 specific discharge capacities before lithium sulfur battery anode material in 1000mAh/g.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained in the case where not making creative work precursor belongs to the model that the present invention protects
It encloses.
Preferably, laminate inorganic compound of the present invention is metal phosphate, clay, at least one in layered oxide
Kind.The preferred basic zirconium phosphate of the metal phosphate, phosphoric acid tin, the preferred montmorillonite of the clay, the layered oxide are excellent
Select vanadium oxide, molybdenum trioxide, manganese oxide.When it is implemented, intercalator need to be determined according to used layered inorganic compound.
In the present invention, the concentration after the dispersion of step (1) laminate inorganic compound is preferably 1 ~ 50mM, and more preferably 10
~15mM。
The polymer monomer is preferably at least one of pyrroles, aniline, acrylonitrile, thiophene in the present invention.At this
In some embodiments of invention, any one polymer monomer can be combined with other one or more polymer monomers, shape
At the polymer in lithium sulfur battery anode material.
In the present invention, the preferred granularity of the elemental sulfur is 1 ~ 5 μm, more preferably 3 ~ 5 μm.Present invention preferably employs
Elemental sulfur is 99% or more purity.
The oxidant preferably uses iron chloride, ammonium persulfate, sodium peroxydisulfate, one in potassium peroxydisulfate in the present invention
Kind.
When it is implemented, the acid is one of sulfuric acid, hydrochloric acid, phosphoric acid, the alkali is sodium hydroxide, hydroxide
One kind of potassium.
When concrete application, the organic solvent is dehydrated alcohol, acetone, butanol or carbon tetrachloride.
The present invention is explained further below in conjunction with example, but embodiment does not limit in any form the present invention.
Embodiment 1:
(1) delamination of montmorillonite: preparing 1mM montmorillonite solution, and add 15mM sulfuric acid, stirs 5h.
(2) polymer monomer intercalation, sulphur content dissipate: 20mM acrylonitrile monemer being added to after being acidified in montmorillonite solution, made
After carrying out dispersion 5h with revolving speed 100r/min, in montmorillonite and polyacrylonitrile gross mass: simple substance is added in sulphur simple substance=1:1 ratio
Sulphur, ultrasonic disperse 30min reuse in high-speed mixer stirring and stir 1 h, divide 5 μm of 99% sulphur simple substance granularity of purity uniformly
It is dispersed in mixed solution.
(3) polymerization cladding: being slowly added dropwise 30mM sodium peroxydisulfate into mixed solution, and time for adding is controlled in 10min.Over cure
The molar ratio of sour sodium and acrylonitrile monemer is 1:1.
(4) layered inorganic compound reassembles: it is 0.5M potassium hydroxide into mixed solution that concentration, which is added dropwise, time for adding
Control reassembles single layer compound in 60min, to sandwiching polyacrylonitrile and elemental sulfur in interlayer, after reaction
With the alternately washing, filtering of acetone and deionized water, it is dried to obtain montmorillonite/polyacrylonitrile/sulphur composite material.
Embodiment 2:
(1) delamination of layered inorganic compound: 15mM phosphoric acid aqueous zirconium is prepared, and adds the 20 mM tetrabutyl of intercalator
Ammonium hydroxide stirs 6h, forms transparent colloidal solution after delamination.
(2) polymer monomer intercalation, sulphur content dissipate: 20mM pyrrole monomer being added to after delamination in solution, revolving speed is used
After 800r/min carries out dispersion 4h, in basic zirconium phosphate and polypyrrole gross mass: elemental sulfur, ultrasound point is added in sulphur simple substance=4:6 ratio
40 min are dissipated, reuses in high-speed mixer stirring and stirs 4h, 3 μm of 99% sulphur simple substance granularity of purity is made to be dispersed in mixing
In solution.
(3) polymerization cladding: being slowly added dropwise 30mM iron chloride into mixed solution, and time for adding is controlled in 120 min.Chlorination
The molar ratio of iron and pyrrole monomer is 2:1.
(4) layered inorganic compound reassembles: it is 3M hydrochloric acid into mixed solution that concentration, which is added dropwise, and time for adding control exists
60min reassembles single layer compound, to sandwiching polypyrrole and elemental sulfur in interlayer, after reaction with ethyl alcohol and
Deionized water alternately washing, filtering, is dried to obtain basic zirconium phosphate/polypyrrole/sulphur composite material.
(5) basic zirconium phosphate/polypyrrole/sulphur composite material that will be prepared: super P:PVDF is mixed in the ratio of 7:2:1,
Add NMP to stir 2h, form uniform slurries, be coated on aluminium foil, drying obtains lithium-sulphur cell positive electrode piece.
(6) by positive plate manufactured in the present embodiment and lithium piece, diaphragm (glass fibre), electrolyte (1mol/L trifluoromethyl
Sulfimide lithium is dissolved in 1,3-dioxolane, glycol dimethyl ether) it is assembled into 2025 type button cells progress electro-chemical test,
Test result is shown in Fig. 2.0.02C first discharge specific capacity reaches 1480mAh/g, 0.2C first discharge specific capacity 1285mAh/g,
948 mAh/g of 0.5C first discharge specific capacity 1150mAh/g, 1C first discharge specific capacity.
The production method of 2025 type button cells is the common knowledge of this field, the present invention in above-mentioned and other embodiments
Herein without being described in detail.
Embodiment 3:
(1) delamination of layered inorganic compound: 5mM phosphoric acid tin aqueous solution is prepared, and adds intercalator 10mM tetrabutylammonium hydrogen
Amine-oxides stir 12h, form transparent colloidal solution after delamination.
(2) polymer monomer intercalation, sulphur content dissipate: 10mM pyrrole monomer being added to after delamination in solution, revolving speed is used
After 2000r/min carries out dispersion 1h, in phosphoric acid tin and polypyrrole gross mass: elemental sulfur, ultrasound is added in sulphur simple substance=3:7 ratio
Disperse 60min, reuses in high-speed mixer stirring and stir 4h, 3 μm of 99% sulphur simple substance granularity of purity is made to be dispersed in mixing
In solution.
(3) polymerization cladding: being slowly added dropwise 15mM iron chloride into mixed solution, and time for adding is controlled in 80 min.Chlorination
The molar ratio of iron and pyrrole monomer is 1.5:1.
(4) layered inorganic compound reassembles: it is 2M sulfuric acid into mixed solution that concentration, which is added dropwise, and time for adding control exists
80min reassembles single layer compound, to sandwiching polypyrrole and elemental sulfur in interlayer, after reaction with butanol and
Deionized water alternately washing, filtering, is dried to obtain phosphoric acid tin/polypyrrole/sulphur composite material.
Embodiment 4:
(1) delamination of montmorillonite: preparing 50mM montmorillonite solution, and add 80mM sulfuric acid, stirs 8h.
(2) polymer monomer intercalation, sulphur content dissipate: 20mM pyrrole monomer being added to after being acidified in montmorillonite solution, used
After revolving speed 600r/min carries out dispersion 3h, in montmorillonite and polypyrrole gross mass: elemental sulfur is added in sulphur simple substance=3:7 ratio, surpasses
Sound disperses 30min, reuses in high-speed mixer stirring and stirs 2h, is dispersed in 3 μm of 99% sulphur simple substance granularity of purity mixed
It closes in solution.
(3) polymerization cladding: being slowly added dropwise 30mM ammonium persulfate into mixed solution, and time for adding is controlled in 60min.Over cure
The molar ratio of sour ammonium and pyrrole monomer is 1.5:1.
(4) layered inorganic compound reassembles: it is 2M sodium hydroxide into mixed solution that concentration, which is added dropwise, time for adding control
System reassembles single layer compound in 10min, to sandwiching polypyrrole and elemental sulfur in interlayer, uses second after reaction
The alternately washing, filtering of pure and mild deionized water, is dried to obtain montmorillonite/polypyrrole/sulphur composite material.
(5) montmorillonite/polypyrrole/sulphur composite material that will be prepared: super P:PVDF is mixed in the ratio of 8:1:1,
Add NMP to stir 2h, form uniform slurries, be coated on aluminium foil, drying obtains lithium-sulphur cell positive electrode piece.
(6) by positive plate manufactured in the present embodiment and lithium piece, diaphragm (glass fibre), electrolyte (1 mol/L trifluoromethyl
Sulfimide lithium is dissolved in 1,3-dioxolane, glycol dimethyl ether) it is assembled into 2025 type button cells progress electro-chemical test,
Test result is shown in Fig. 3.0.2C electricity specific capacity is stablized in 1000mAh/g, and coulombic efficiency reaches 100%.
Embodiment 5:
(1) delamination of layered inorganic compound: 10mM vanadium oxide aqueous solution is prepared, and adds intercalator 20mM tetrabutylammonium hydrogen
Amine-oxides stir 6h, form transparent colloidal solution after delamination.
(2) polymer monomer intercalation, sulphur content dissipate: 15mM aniline monomer being added to after delamination in solution, revolving speed is used
After 700r/min carries out dispersion 3h, in vanadium oxide and polyaniline gross mass: elemental sulfur, ultrasound point is added in sulphur simple substance=4:6 ratio
60min is dissipated, reuses in high-speed mixer stirring and stirs 4h, so that 3 μm of 99% sulphur simple substance granularity of purity is dispersed in mixing molten
In liquid.
(3) polymerization cladding: being slowly added dropwise 20mM ammonium persulfate into mixed solution, and time for adding is controlled in 120min.It crosses
The molar ratio of ammonium sulfate and aniline monomer is 2:1.
(4) layered inorganic compound reassembles: it is 3M hydrochloric acid into mixed solution that concentration, which is added dropwise, and time for adding control exists
60min reassembles single layer compound, to sandwiching polyaniline and elemental sulfur in interlayer, after reaction with ethyl alcohol and
Deionized water alternately washing, filtering, is dried to obtain vanadium oxide/polyaniline/sulphur composite material.
(5) vanadium oxide/polyaniline/sulphur composite material that will be prepared: super P:PVDF is mixed in the ratio of 8:1:1,
Add NMP to stir 2h, form uniform slurries, be coated on aluminium foil, drying obtains lithium-sulphur cell positive electrode piece.
(6) by positive plate manufactured in the present embodiment and lithium piece, diaphragm (glass fibre), electrolyte (1mol/L trifluoromethyl
Sulfimide lithium is dissolved in 1,3-dioxolane, glycol dimethyl ether) it is assembled into 2025 type button cells progress electro-chemical test.
Embodiment 6:
(1) delamination of layered inorganic compound: 20mM molybdenum trioxide aqueous solution is prepared, and adds the intercalator 20mM tetrabutyl
Ammonium hydroxide stirs 48h, forms transparent colloidal solution after delamination.
(2) polymer monomer intercalation, sulphur content dissipate: 20mM thiophene monomer being added to after delamination in solution, revolving speed is used
After 5000r/min carries out dispersion 10h, in molybdenum trioxide and polythiophene gross mass: elemental sulfur is added in sulphur simple substance=3:7 ratio, surpasses
Sound disperses 10min, reuses in high-speed mixer stirring and stirs 5h, is dispersed in 1 μm of 99% sulphur simple substance granularity of purity mixed
It closes in solution.
(3) polymerization cladding: being slowly added dropwise 25mM potassium peroxydisulfate into mixed solution, and time for adding is controlled in 80min.Over cure
The molar ratio of sour potassium and thiophene monomer is 1:1.
(4) layered inorganic compound reassembles: it is 3M phosphoric acid into mixed solution that concentration, which is added dropwise, and time for adding control exists
80min reassembles single layer compound, to sandwiching polythiophene and elemental sulfur in interlayer, after reaction with four chlorinations
Carbon and deionized water alternately washing, filtering, are dried to obtain molybdenum trioxide/polythiophene/sulphur composite material.
Comparative example 1:
(1) sulphur content dissipates: weighing 0.3 g elemental sulfur ultrasonic disperse 20min in 200mL ultrapure water, reuses high-speed stirred
4h is stirred in machine stirring, is dispersed in 3 μm of 99% elemental sulfur granularity of purity in mixed solution.
(2) polymerization cladding: in polypyrrole gross mass: 0.2g pyrrole monomer, ultrasonic disperse is added in sulphur simple substance=4:6 ratio
Iron chloride is slowly added dropwise into mixed solution in 30min in whipping process, and the molar ratio of iron chloride and pyrrole monomer is 2:1, drop
Control continues to stir 5h after dripping in 120min between added-time.
(3) by the polypyrrole prepared/sulphur positive electrode: super P:PVDF is mixed in the ratio of 7:2:1, and NMP is added to stir
2h is mixed, uniform slurries are formed, is coated on aluminium foil, drying obtains lithium-sulphur cell positive electrode piece.
(4) by positive plate manufactured in the present embodiment and lithium piece, diaphragm (glass fibre), electrolyte (1 mol/L trifluoromethyl
Sulfimide lithium is dissolved in 1,3-dioxolane, glycol dimethyl ether) it is assembled into 2025 type button cells progress electro-chemical test.
0.2C first discharge specific capacity 758mAh/g is differed farther out with the 0.2C first discharge specific capacity of embodiment 4, it is possible thereby to illustrate
The addition of layered inorganic compound can effectively improve lithium-sulfur cell performance.
Claims (8)
1. a kind of layered inorganic compound/conducting polymer/sulphur composite material preparation side as lithium sulfur battery anode material
Method, which comprises the steps of:
(1) delamination of layered inorganic compound: layered inorganic compound being dispersed, and adds intercalator, stirs 5 ~ 48h, stratiform
Inorganic compound delamination forms single layer compound;
(2) polymer monomer intercalation, sulphur content dissipate: polymer monomer solution being added in single layer compound solution, revolving speed is used
After 100 ~ 5000r/min is stirred 1 ~ 10h of dispersion, elemental sulfur is added, 10 ~ 60min of ultrasonic disperse is stirred for 1 ~ 5h, makes sulphur
Simple substance is dispersed in mixed solution;
(3) polymerization cladding: at the uniform velocity dropwise addition oxidant into mixed solution, oxidant and polymer monomer molar ratio are 1:1 ~ 2:1,
Time for adding is controlled in 10 ~ 120min;
(4) layered inorganic compound reassembles: at the uniform velocity dropwise addition concentration is the mixed solution of 0.5 ~ 3M acid or alkali to step (3)
In, time for adding is controlled in 10 ~ 80min, reassembles single layer compound, to sandwiching polymer and elemental sulfur in layer
Between, after reaction with the alternately washing, filtering of organic solvent and deionized water, it is poly- to be dried to obtain layered inorganic compound/conduction
Close object/sulphur composite material.
2. a kind of layered inorganic compound/conducting polymer as lithium sulfur battery anode material according to claim 1/
The preparation method of sulphur composite material, which is characterized in that layered inorganic compound is metal phosphate, clay, stratiform oxidation
At least one of object.
3. a kind of layered inorganic compound/conducting polymer as lithium sulfur battery anode material according to claim 2/
The preparation method of sulphur composite material, which is characterized in that the concentration after the dispersion of step (1) laminate inorganic compound is 1 ~ 50mM.
4. a kind of layered inorganic compound/conducting polymer as lithium sulfur battery anode material according to claim 1/
The preparation method of sulphur composite material, which is characterized in that the polymer monomer be pyrroles, aniline, acrylonitrile, in thiophene at least
It is a kind of.
5. a kind of layered inorganic compound/conducting polymer as lithium sulfur battery anode material according to claim 3/
The preparation method of sulphur composite material, which is characterized in that the granularity of the elemental sulfur is 1 ~ 5 μm.
6. a kind of layered inorganic compound/conducting polymer as lithium sulfur battery anode material according to claim 1/
The preparation method of sulphur composite material, which is characterized in that the oxidant is iron chloride, ammonium persulfate, sodium peroxydisulfate, persulfuric acid
One of potassium.
7. a kind of layered inorganic compound/conducting polymer as lithium sulfur battery anode material according to claim 1/
The preparation method of sulphur composite material, which is characterized in that the acid is one of sulfuric acid, hydrochloric acid, phosphoric acid, and the alkali is hydrogen
One kind of sodium oxide molybdena, potassium hydroxide.
8. a kind of layered inorganic compound/conducting polymer as lithium sulfur battery anode material according to claim 1/
The preparation method of sulphur composite material, which is characterized in that the organic solvent is dehydrated alcohol, acetone, butanol or carbon tetrachloride.
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CN107591523A (en) * | 2017-08-22 | 2018-01-16 | 桂林电子科技大学 | A kind of iron, nickel dopped activated carbon sulfur materials and its preparation method and application |
CN109888198B (en) * | 2018-12-27 | 2020-11-17 | 北京航空航天大学 | Metal intercalation molybdenum oxide material and preparation method and application thereof |
CN110534742B (en) * | 2019-07-16 | 2021-05-28 | 江汉大学 | Preparation method of lithium-sulfur battery positive electrode composite material |
CN110660977B (en) * | 2019-08-23 | 2021-08-03 | 太原理工大学 | Lithium-sulfur electrochemical energy storage system and preparation method thereof |
CN110911616A (en) * | 2019-11-26 | 2020-03-24 | 电子科技大学 | High-temperature-resistant multifunctional diaphragm for lithium-sulfur battery and preparation method thereof |
CN112928276A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Composite sulfur positive electrode material and preparation method and application thereof |
CN112103487B (en) * | 2020-09-14 | 2021-12-14 | 广东省科学院化工研究所 | Bentonite/sulfur composite material and preparation method and application thereof |
CN112331837A (en) * | 2020-11-24 | 2021-02-05 | 中国科学院物理研究所 | Organic-inorganic composite electrode material and preparation method and application thereof |
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CN105409032A (en) * | 2013-06-21 | 2016-03-16 | 魁北克电力公司 | All-solid-state lithium-sulphur electrochemical cells and production methods thereof |
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