CN106450224B - A kind of anode composite material of lithium sulfur battery and preparation method thereof based on macroporous absorbent resin - Google Patents
A kind of anode composite material of lithium sulfur battery and preparation method thereof based on macroporous absorbent resin Download PDFInfo
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- CN106450224B CN106450224B CN201611023202.3A CN201611023202A CN106450224B CN 106450224 B CN106450224 B CN 106450224B CN 201611023202 A CN201611023202 A CN 201611023202A CN 106450224 B CN106450224 B CN 106450224B
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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 anode composite material of lithium sulfur battery and preparation method thereof based on macroporous absorbent resin, when application is as lithium sulfur battery anode material, with high discharge for the first time specific discharge capacity and excellent cycle performance.The present invention can effectively inhibit the dissolution and inhibition " shuttle effect " of polysulfide in battery charge and discharge process, improve the cycle performance of lithium-sulfur cell.And preparation process of the present invention is simple, low in raw material price is conducive to the development of lithium-sulfur cell.
Description
Technical field
The present invention relates to a kind of anode composite material of lithium sulfur battery and preparation method thereof based on macroporous absorbent resin, belongs to
Cell positive material, especially secondary battery positive electrode material field.
Background technique
With the continuous aggravation of environmental pollution got worse with energy crisis, Novel high-specific capacity flexible and height are found and developed
The cheap positive electrode of specific energy is the hot spot studied at present.Since elemental sulfur has, specific capacity is high, price is low, environmental-friendly etc.
Feature, it is considered to be one of most promising positive electrode.Using lithium piece as cathode in lithium-sulfur cell, the theoretical specific capacity of sulphur is up to
The theoretical energy density of 1675mAh/g, battery are up to 2600Wh/kg.Compared with traditional lithium ion battery, lithium-sulfur cell can
It realizes its 3 to 5 times of energy density, there is great application prospect.
But lithium-sulphur cell positive electrode has following three aspects: (1) poorly conductive of sulphur, battery polarization is serious,
Cause the utilization rate of sulphur low, and is unfavorable for the high rate capability of battery；(2) polysulfide that lithium-sulfur cell charge and discharge process generates
It is soluble in organic electrolyte, gradually decreases the active material of electrode, leads to the poor circulation of battery, capacity is gradually decayed；
(3) for sulphur in charge and discharge process, volume change is larger, may influence electrode stability, causes to recycle unstable, or even causes to pacify
Full problem.
Currently, people mainly improve from the following aspects in order to overcome the problems, such as lithium-sulphur cell positive electrode: (1) adulterating
Conductive phase substance improves its electric conductivity；(2) synthesis clad structure inhibits the dissolution of polysulfide；(3) pre- void space structure is protected
Hold the stability of material；(4) to support materials doped chemical or functional group and sulphur and polysulfide generate interaction to
Inhibit its dissolution.
Summary of the invention
For defect existing for existing lithium sulfur battery anode material, it is an object of the invention to invent a kind of to solve simultaneously
The positive electrode of the certainly above various problems.
An object of the present invention is to provide a kind of low in cost, and it is convenient that raw material obtains, and can improve the capacity of lithium-sulfur cell
And the anode composite material of lithium sulfur battery based on macroporous absorbent resin of cycle performance.
Simple the second object of the present invention is to provide a kind of preparation method, it is convenient that raw material obtains, and is suitble to industrial applications
The preparation method of anode composite material of lithium sulfur battery based on macroporous absorbent resin, gained composite material is as lithium-sulphur cell positive electrode
Cycle performance substantially improves when material is applied.
A kind of anode composite material of lithium sulfur battery based on macroporous absorbent resin carries sulphur using macroporous absorbent resin as matrix
After obtain macroporous absorbent resin/sulphur composite material, the load sulfur content of the composite material is 60%-70%.
The present invention successfully prepares lithium-sulphur cell positive electrode directly as sulfur materials are carried using macroporous absorbent resin for the first time.The material
The dissolution of polysulfide can be reduced, inhibits shuttle effect, to improve the cycle performance of lithium-sulfur cell.Further, since macropore
It is big to adsorb the cheap of resin, yield, and obtains conveniently, it is made to be very suitable to be produced and applied on a large scale.
The partial size of the macroporous absorbent resin is 1-5 μm, specific surface area 500-1000m2/ g, pore size distribution range 2-
100nm。
The macroporous absorbent resin is polar macroporous adsorption resin.
It is described the present invention provides a kind of preparation method of anode composite material of lithium sulfur battery based on macroporous absorbent resin
Composite material is prepared by the following method to obtain:
Scheme one: sulphur is injected in macroporous absorbent resin, is carried sulphur I and is obtained macroporous absorbent resin/sulphur composite material；
Alternatively,
Scheme two: using macroporous absorbent resin as matrix, after growth in situ carbon material, then by carry sulphur II obtain macroporous absorption
Resin/sulphur composite material.
In scheme two, with macroporous absorbent resin for outer skeleton, the porous carbon conducting agent phase of growth in situ, reinforcing material is led
Electrically, and being uniformly distributed for aperture can be improved, then passes through the subsequent combination for carrying sulphur process.The capacity of lithium-sulfur cell is improved,
It is more more excellent than the general porous positive electrode performance for carrying sulfur materials preparation.
In scheme two, the process of the growth in situ porous carbon materials are as follows: carbon source is soluble in water, macroporous absorption tree is added
Rouge is ultrasonically treated after mixing evenly, in a high pressure reaction kettle, hydro-thermal reaction is carried out under conditions of 160-200 DEG C, is filtered, washing,
It is dry under vacuum condition；
The carbon source is selected from one or more of glucose, sucrose, fructose or starch.
The mass ratio of the carbon source and macroporous absorbent resin is 3:1-8:1.
It carries sulphur I and carries the detailed process of sulphur II are as follows: elemental sulfur is added, in pressure 0.1-100Pa, temperature is 150-180 DEG C
Under conditions of handle I, keep pressure, II be further processed under conditions of being cooled to 100-120 DEG C, vacuum state is kept to be cooled to
Room temperature.
The hydro-thermal reaction time is 4-10h.
The processing I time is 0.5-2h.
The processing II time is 1-3h.
Before using macroporous absorbent resin, first it is pre-processed, preprocess method are as follows: by macroporous absorbent resin water
After washing, 2-3h is impregnated with the HCl solution ultrasound that mass fraction is 5%-10%, and washing is to mass fraction being 3%- after neutrality
10% NaOH solution ultrasound impregnates 2-3h, and using mass fraction after washing to neutrality again is 98% ethanol washing, filters, vacuum is dry
It is dry.
The porous carbon materials include but is not limited to microporous carbon, mesoporous carbon or level carbon.
Compared with the prior art, the present invention has the following beneficial effects:
1. the present invention realizes for the first time prepares lithium sulphur electricity for this high molecular material of macroporous absorbent resin as framework material
Pond positive electrode.
It can effectively inhibit the dissolution and inhibition " shuttle effect " of polysulfide in charge and discharge process.
It is used as the positive electrode of lithium-sulfur cell, there is following technical effect:
(1) inventor has found the close theory of discharge performance for the first time that the present invention carries sulphur positive electrode using macroporous absorbent resin
Capacity, performance is better than most positive electrodes at present for the first time；
(2) the lithium sulfur battery anode material battery performance that inventor's discovery joined macroporous absorbent resin is better than not being added big
The performance of macroporous adsorbent resin.Referring to data of the present invention: carrying sulphur composite positive pole using macroporous absorbent resin prepared by the present invention
It is assembled into button cell (embodiment 1) with cathode of lithium, under room temperature in 0.2C constant current charge-discharge, first discharge specific capacity reaches
To 1606.6mAh/g, close to theoretical value, capacity is 1167.9mAh/g after circulation 200 times, and average coulombic efficiency is 92%.And
The present invention is filled with the macroporous absorbent resin composite material (embodiment 2) of porous carbon, further enhances the electric conductivity of material, mentions
The high capacity of lithium-sulfur cell, cycle performance data are substantially better than the porous carbon supported sulfur materials of comparative example 3.
2. macroporous absorbent resin abundant raw material and cheap has very big as the framework material in lithium-sulphur cell positive electrode
Price advantage.
3. preparation process is simple, Yi Shixian industrialization.
In conclusion macroporous absorbent resin is a kind of cheap organic material, it is applied to as sulfur materials are carried
Lithium-sulfur cell field can reduce the dissolution of polysulfide, improve the cycle performance of lithium-sulfur cell.The present invention is by inhaling macropore
Attached resin and sulphur progress are compound, are prepared for can be used for the positive electrode of lithium-sulfur cell, and the lithium-sulfur cell capacity assembled is high, recycles
Performance is good.And the electric conductivity that positive electrode is improved using the structure that the means of conductive porous carbon filling are formed, is effectively pressed down
The problem of having made lithium-sulfur cell capacity attenuation is conducive to the industrialization of lithium-sulfur cell.
Detailed description of the invention
Fig. 1 is the SEM figure of polar macroporous adsorption resin used in embodiment；
Fig. 2 is the isothermal adsorption desorption figure obtained by embodiment 1；
Fig. 3 is 200 discharge capacity curve graphs of the lithium-sulfur cell obtained by embodiment 1；
Fig. 4 is 200 discharge capacity curve graphs of the lithium-sulfur cell obtained by embodiment 2.
Specific embodiment
The following examples but are not limited the scope of the invention to further explanation of the invention.
Elemental sulfur used in following embodiment and comparative example is sublimed sulfur, and preferably granularity is 10nm-1 μm, pole piece system
Standby middle sulfenyl composite active material, conductive agent and binder mass ratio 7:2:1, wherein conductive agent is acetylene black, and binder is poly-
Vinylidene, solvent are N-Methyl pyrrolidone, and collector is aluminium foil.
Embodiment 1
It pre-processes polar macroporous absorbent resin: choosing less than 2 μm samples of partial size, sufficiently cleaned with deionized water, then
2-3h is impregnated with the HCl solution ultrasound that mass fraction is 10%, is washed molten to the neutral NaOH for being followed by 5% with mass fraction
Liquid ultrasound impregnates 2-3h, filters after being cleaned again with mass fraction for 98% ethyl alcohol after washing to neutrality, finally gained sample exists
It is sufficiently dry under vacuum condition.
Above-mentioned pretreated polar macroporous adsorption resin dusty material is uniformly mixed with elemental sulfur 1:2, then by material
Material is placed in quartz boat, is heated to 160 DEG C of constant temperature 1.5h under vacuum conditions with the heating rate of 2 DEG C/min, keeps this true
Empty condition is simultaneously cooled to 120 DEG C, constant temperature 2h, keeps the vacuum condition and is cooled to room temperature.Sample is further ground, it is dry,
It is made and carries sulfur materials, carrying sulfur content is 66.7%.
Battery assembly and electrochemical property test:
Obtained composite positive pole, conductive black, Kynoar (PVDF) is uniform according to the mass ratio of 7:2:1
Mixing, is added appropriate NMP, stirs 12h at room temperature, be then coated in aluminum foil current collector, and tabletting obtains lithium-sulfur cell after drying
Positive plate makees cathode, LiTFSI/DOL:DEM (1:1 volume ratio, DOL:1, the 3- dioxolanes of 1mol/L with lithium piece；DME: second
Glycol dimethyl ether) it is electrolyte, Celgard2400 is diaphragm, and nickel foam is support chip, is assembled in the glove box of argon atmosphere
CR2016 type button cell.The battery assembled placement is subjected to electrochemical property test afterwards for 24 hours, test temperature is room temperature, is put
Electric size of current is 0.2C (1C=1675mA/g), and test voltage range is 1.0~3.0V.
Test result shows that under 0.2C discharge-rate, battery discharges specific discharge capacity for the first time for 1606.6mAh/g, connects
Nearly theoretical capacity, charge and discharge 200 times are 1167.9mAh/g later, and average coulombic efficiency is 92%.
Embodiment 2
The technical process for pre-processing polar macroporous adsorption resin powder is same as Example 1.
First 10g glucose is dissolved in 50mL deionized water, 50 DEG C or so acceleration dissolutions is slightly moderately heated to, weighs at 2g
The polar macroporous adsorption resin managed is added in above-mentioned solution, is ultrasonically treated 12h after mixing evenly, is then transferred to together poly-
In the autoclave of tetrafluoroethene liner, kettle cover, 180 DEG C of hydro-thermal reaction 6h are screwed.Kettle is opened after Temperature fall to room temperature
Lid, the product in kettle is transferred in centrifuge tube.A large amount of deionized waters are added in centrifuge tube, and 3000rpm is centrifuged after mixing evenly
10min, removes supernatant liquid, then plus deionization wash twice after use instead after dehydrated alcohol washs three times repetitive operations several times, most
Afterwards by sample 80 DEG C of dry 12h under vacuum conditions, resin composite materials are obtained.
Material obtained above is uniformly mixed with elemental sulfur 1:2, then material is placed in quartz boat, in vacuum item
160 DEG C of constant temperature 1.5h are heated to the heating rate of 2 DEG C/min under part, keep the vacuum condition and are cooled to 120 DEG C, constant temperature
2h keeps the vacuum condition and is cooled to room temperature.Sample is further ground, it is dry, it is made and carries sulfur materials, carrying sulfur content is
66.7%.
Button cell is assembled according to method described in embodiment 1, and carries out electrochemical property test, test result shows
Under 0.2C discharge-rate, battery discharges specific discharge capacity for the first time for 1558.3mAhg-1, it is after charge and discharge 200 times
1339.0mAhg-1, average coulombic efficiency is 95%.
Comparative example 1
It pre-processes nonpolar macroporous adsorption resin: choosing less than 2 μm samples of partial size, sufficiently rinsed with deionized water, then
The HCl solution flushing for being 10% with mass fraction is washed afterwards for several times to neutrality, is then rushed with the NaOH solution that mass fraction is 5%
It washes and washs afterwards to neutrality for several times, then the ethyl alcohol for being 98% with mass fraction rinses for several times, finally by gained sample in vacuum condition
It is lower sufficiently dry.
Above-mentioned pretreated nonpolar macroporous adsorption resin dusty material is uniformly mixed with elemental sulfur 1:2, then will
Material is placed in quartz boat, is heated to 160 DEG C of constant temperature 1.5h under vacuum conditions with the heating rate of 2 DEG C/min, and keeping should
Vacuum condition is simultaneously cooled to 120 DEG C, constant temperature 2h, keeps the vacuum condition and is cooled to room temperature.Sample is further ground, is done
It is dry, it is made and carries sulfur materials, carrying sulfur content is 66.7%.
Button cell is assembled according to method described in embodiment 1, and carries out electrochemical property test, test result shows
Under 0.2C discharge-rate, battery discharges specific discharge capacity for the first time for 759.8mAhg-1, it is after charge and discharge 200 times
321.1mAhg-1, average coulombic efficiency is 90%.
Comparative example 2
Porous carbon supported sulfur materials preparation:
First 10g glucose is dissolved in 50mL deionized water, 50 DEG C or so acceleration dissolutions is slightly moderately heated to, stirs evenly
After be ultrasonically treated 12h, be then transferred to together in the autoclave of polytetrafluoroethyllining lining, screw kettle cover, 180 DEG C of hydro-thermals are anti-
Answer 6h.Kettle cover is opened after Temperature fall to room temperature, the product in kettle is transferred in centrifuge tube.It is added in centrifuge tube a large amount of
3000rpm is centrifuged 10min to deionized water after mixing evenly, removes supernatant liquid, then plus deionization wash twice after use instead it is anhydrous
After three times repetitive operations several times of ethanol washing, finally by 12h dry at sample under vacuum conditions 80 DEG C.Partial size is chosen less than 5 μ
The porous carbon dust of m.
Porous carbon powder material obtained above is uniformly mixed with elemental sulfur 1:2, material is then placed in quartz boat
In, 160 DEG C of constant temperature 1.5h are heated to the heating rate of 2 DEG C/min under vacuum conditions, the vacuum condition is kept and is cooled to
It 120 DEG C, constant temperature 2h, keeps the vacuum condition and is cooled to room temperature.Sample is further ground, it is dry, it is made and carries sulfur materials, carry
Sulfur content is 66.7%.
Button cell is assembled according to method described in embodiment 1, and carries out electrochemical property test, test result shows
Under 0.2C discharge-rate, battery discharges specific discharge capacity for the first time for 948.7mAhg-1, it is after charge and discharge 200 times
635.7mAhg-1, average coulombic efficiency is 92%.
Comparative example 3
The technical process for pre-processing polar macroporous adsorption resin powder is same as Example 1.
Above-mentioned pretreated polar macroporous adsorption resin dusty material is uniformly mixed with elemental sulfur 1:2, then by material
Material is placed in quartz boat, is heated to 120 DEG C under vacuum conditions with the heating rate of 2 DEG C/min, constant temperature 2h keeps the vacuum
Condition is simultaneously cooled to room temperature.Sample is further ground, it is dry, it is made and carries sulfur materials, carrying sulfur content is 66.7%.
Button cell is assembled according to method described in embodiment 1, and carries out electrochemical property test, test result shows
Under 0.2C discharge-rate, battery discharges specific discharge capacity for the first time for 1348.5mAhg-1, it is after charge and discharge 200 times
792.7mAhg-1, average coulombic efficiency is 91%.
Comparative example 4
The technical process for pre-processing polar macroporous adsorption resin powder is same as Example 1.
Above-mentioned pretreated polar macroporous adsorption resin dusty material is uniformly mixed with elemental sulfur 1:2, then by material
Material is placed in quartz boat, is heated to 160 DEG C, constant temperature 1.5h under vacuum conditions with the heating rate of 2 DEG C/min, keeps this true
Empty condition is simultaneously cooled to room temperature.Sample is further ground, it is dry, it is made and carries sulfur materials, carrying sulfur content is 66.7%.
Button cell is assembled according to method described in embodiment 1, and carries out electrochemical property test, test result shows
Under 0.2C discharge-rate, battery discharges specific discharge capacity for the first time for 1424.7mAhg-1, it is after charge and discharge 200 times
876.5mAhg-1, average coulombic efficiency is 92%.
Comparative example 5
The technical process for pre-processing polar macroporous adsorption resin powder is same as Example 1.
Sulphur is infused using chemical reaction method: weighing the above-mentioned pretreated polar macroporous adsorption resin material of 0.25g, is added to
In the dehydrated alcohol of 50mL；It is ultrasonically treated 1h；Then in the Na that 3.875g is wherein added2S2O3·5H2O, then slowly add thereto
The hydrochloric acid solution (1mol/L) for entering 35mL, is stirred to react 12h at room temperature；Then, it is centrifuged, filters, washing to neutrality；Finally by institute
Lower 60 DEG C of sample vacuum condition dry 10h are obtained, obtain carrying sulfur materials, carrying sulfur content is 66.7%.
Button cell is assembled according to method described in embodiment 1, and carries out electrochemical property test, test result shows
Under 0.2C discharge-rate, battery discharges specific discharge capacity for the first time for 1405.4mAhg-1, it is after charge and discharge 200 times
921.7mAhg-1, average coulombic efficiency is 94%.
Comparative example 6
The technical process for pre-processing polar macroporous adsorption resin powder is same as Example 1.
First 10g glucose is dissolved in 50mL deionized water, 50 DEG C or so acceleration dissolutions is slightly moderately heated to, weighs at 2g
The macroporous absorbent resin managed is added in above-mentioned solution, is ultrasonically treated 12h after mixing evenly, is then transferred to polytetrafluoro together
In the autoclave of ethylene liner, kettle cover, 180 DEG C of hydro-thermal reaction 12h are screwed.Kettle cover is opened after Temperature fall to room temperature,
Product in kettle is transferred in centrifuge tube.A large amount of deionized waters are added in centrifuge tube, and 3000rpm is centrifuged after mixing evenly
10min, removes supernatant liquid, then plus deionization wash twice after use instead after dehydrated alcohol washs three times repetitive operations several times, most
Afterwards by 12h dry at sample under vacuum conditions 80 DEG C.
Material obtained above is uniformly mixed with elemental sulfur 1:2, then material is placed in quartz boat, in vacuum item
160 DEG C of constant temperature 1.5h are heated to the heating rate of 2 DEG C/min under part, keep the vacuum condition and are cooled to 120 DEG C, constant temperature
2h keeps the vacuum condition and is cooled to room temperature.Sample is further ground, it is dry, it is made and carries sulfur materials, carrying sulfur content is
66.7%.
Button cell is assembled according to method described in embodiment 1, and carries out electrochemical property test, test result shows
Under 0.2C discharge-rate, battery discharges specific discharge capacity for the first time for 1401.5mAhg-1, it is after charge and discharge 200 times
987.9mAhg-1, average coulombic efficiency is 91%.
Claims (7)
1. a kind of anode composite material of lithium sulfur battery based on macroporous absorbent resin, which is characterized in that be with macroporous absorbent resin
Matrix obtains macroporous absorbent resin/sulphur composite material after carrying sulphur, and the load sulfur content of the composite material is 60%-70%；It is described big
Macroporous adsorbent resin is polar macroporous adsorption resin.
2. composite material according to claim 1, which is characterized in that the partial size of the macroporous absorbent resin is 1-5 μm, than
Surface area is 500-1000m2/ g, pore size distribution range 2-100nm.
3. the preparation method of any one of the claim 1-2 composite material, which is characterized in that the composite material passes through following
Method is prepared: scheme one: sulphur being injected in macroporous absorbent resin, sulphur I is carried and obtains macroporous absorbent resin/sulphur composite material；
Alternatively, scheme two: using macroporous absorbent resin as matrix, after growth in situ porous carbon materials, then obtaining macropore by load sulphur II and inhale
Attached resin/sulphur composite material；
It carries sulphur I and carries the detailed process of sulphur II are as follows: elemental sulfur is added, in pressure 0.1-100Pa, the item that temperature is 150-180 DEG C
I is handled under part, keeps pressure, II is further processed under conditions of being cooled to 100-120 DEG C, and vacuum state is kept to be cooled to room
Temperature.
4. preparation method according to claim 3, which is characterized in that in scheme two, the growth in situ porous carbon materials
Process are as follows: carbon source is soluble in water, be added macroporous absorbent resin, be ultrasonically treated after mixing evenly, in a high pressure reaction kettle,
Hydro-thermal reaction is carried out under conditions of 160-200 DEG C, is filtered, and washing is dry under vacuum condition；
The carbon source is selected from one or more of glucose, sucrose, fructose or starch；
The mass ratio of the carbon source and macroporous absorbent resin is 3:1-8:1.
5. preparation method according to claim 3, which is characterized in that before using macroporous absorbent resin, first carried out to it
Pretreatment, preprocess method are as follows: after being washed with water, impregnated, washed into the HCl solution ultrasound that mass fraction is 5%-10%
Property after impregnated with the NaOH solution ultrasound that mass fraction is 3%-10%, washing is to mass fraction being again 98% ethyl alcohol after neutrality
Washing is filtered, vacuum drying.
6. the preparation method according to claim 4, which is characterized in that the hydro-thermal reaction time is 4-10h.
7. preparation method according to claim 3, which is characterized in that the processing I time is 0.5-2h, the processing II
Time is 1-3h.
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| KR20020020312A (en) * | 2000-09-08 | 2002-03-15 | 김순택 | Montmorillonite/sulfur complex compound, cathode active material comprising the same and lithium secondary battery employing the cathode active material |
| CN101916849B (en) * | 2010-08-17 | 2012-09-05 | 上海交通大学 | Sulfur-based composite anode material for secondary battery and preparation method thereof |
| CN102185127A (en) * | 2011-04-07 | 2011-09-14 | 武汉理工大学 | Lithium sulphur battery anode piece added with absorbent and lithium sulphur battery |
| WO2012150062A1 (en) * | 2011-05-02 | 2012-11-08 | Robert Bosch Gmbh | Polyacrylonitrile-sulfur composite material |
| CN104183836A (en) * | 2014-03-03 | 2014-12-03 | 河南师范大学 | Positive electrode composite material for lithium sulfur battery |
| CN105375000A (en) * | 2015-10-16 | 2016-03-02 | 广东烛光新能源科技有限公司 | Sulfur-containing electrode material and preparation method thereof |
| CN105529460A (en) * | 2015-11-23 | 2016-04-27 | 湘潭大学 | Lithium-sulfur battery cathode material of lithium-sulfur battery, preparation method of cathode material and lithium-sulfur battery |
| CN105633377A (en) * | 2016-02-21 | 2016-06-01 | 钟玲珑 | Preparation method for aluminium oxide hollow sphere lithium-sulfur battery positive electrode material |
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