CN102324507A - Preparation method for lithium-sulfur battery composite anode material - Google Patents
Preparation method for lithium-sulfur battery composite anode material Download PDFInfo
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Abstract
The present invention discloses a preparation method for a lithium-sulfur battery composite anode material. The preparation method comprises the following steps: (1) chemically activating vapor deposited carbon fiber through a solid base; (2) uniformly mixing the activated vapor deposited carbon fiber and a sulfur; (3) heating and holding in the presence of the inert atmosphere, such that the sulfur enters pores of the vapor deposited carbon fiber through a capillary action to obtain the sulfur-vapor deposited carbon fiber composite material. According to the present invention, the used vapor deposited carbon fiber has excellent electrical conductivity, good mechanical property and large aspect ratio, such that the natural three-dimensional conductive network is easily formed so as to improve the conductivity of the sulfur electrode, and improve the cycle performance of the lithium-sulfur battery.
Description
Technical field
The invention belongs to the new energy materials field, be specifically related to a kind of lithium-sulfur cell and use the composite positive pole preparation method.
Background technology
The traditional resource and the energy are in short supply day by day, environmental problem is on the rise, and the development and use new forms of energy and the new energy store and switch technology has become the energy strategy emphasis of various countries, and electric automobile is realized one of focus that the quilt of new energy technology is paid close attention to especially.The key of electric automobile success or not is battery.Just need develop the battery and the required supplementary material of high-energy-density, high-specific-power, ability quick charge, life-span length, safety, low environment pollution, reasonable price in order electric automobile to be pushed to industry.
Advantages such as lithium ion battery has specific energy height, stable operating voltage, memory-less effect, have extended cycle life and environmental pollution is little, thereby become the focus of electrokinetic cell research.Present technology is the most ripe, application battery the most extensive, that commercialization is the most successful is the sour lithium (LiCoO of cobalt
2) material cell, its theoretical specific capacity is 274 mAh/g, but the lithium cobaltate cathode material cost is high, fail safe is on the low side.LiMn2O4 (LiMn
2O
4) and LiFePO4 (LiFePO
4) the relative cobalt acid of material lithium has stronger price advantage, but their theoretical specific capacity is not high: LiFePO4 is 176 mAh/g, and LiMn2O4 is 148 mAh/g.These materials can not satisfy the requirement of high-energy-density, therefore need exploitation to have high power capacity, high-energy-density and good reversible novel anode material or battery system.
Lithium-sulfur cell has height ratio capacity (1675 mAh/g) and high-energy-density (2600 Wh/kg).In addition, with sulphur be positive electrode make it in the source, aspect such as cost, environmental friendliness also shows incomparable advantage.Lithium-sulfur cell is the chemical power source of future generation that has development potentiality and application prospect.
At present, there are several very big problems in lithium-sulfur cell: elemental sulfur is the insulator of electronics and ion with final discharging product; Intermediate product polysulfide in the discharge process is dissolved in the electrolyte, causes the irreversible loss and the capacity attenuation of active material.For this reason, how improving conductivity in the anodal cyclic process of sulphur, the distribution of improving sulphur, the diffusion that suppresses polysulfide is the research emphasis of sulfenyl positive electrode.
Done more work to lithium-sulphur cell positive electrode investigation of materials person.Wherein, Material with carbon element has characteristics such as outstanding conductivity, high specific area and microcellular structure; Material with carbon element and sulphur are compounded with the diffusion that is beneficial to the conductivity that improves the sulphur positive pole, the distribution of improving sulphur and inhibition polysulfide, thereby the sulphur carbon composite anode material is researcher's favor extremely.
(Electrochemical Acta such as W.Zheng; 2006; 51:1330-1335.) with sulphur and the CNT mixed with 5: 1; Under the argon gas atmosphere protection, be heated to 150 ℃ of insulation 10h earlier sulphur is entered under capillary force in the CNT pipe, be heated to 350 ℃ of insulation 4h then with the sulphur of evaporation at the CNT outer wall.Adopt 1MLiPF
6/ EC: DMC: EMC (volume ratio 1: 1: 1) electrolyte, be assembled into battery with the lithium sheet after, test according to the speed of discharging and recharging of 60mA/g, the initial specific capacity of battery is 700mAh/g.Sulphur and CNT are compounded with the conductivity that is beneficial to the raising electrode, but CNT is not easy to disperse, the easy aggravation of reuniting of preparation process at composite material influences the even distribution of sulphur content cloth, has limited the performance of battery first discharge specific capacity.
(carbon 2008,46:229-235.) sodium metasilicate and sucrose synthesized the mesopore charcoal with certain proportion mixing copolymerization for Wang J. etc.Adopt 200 ℃ of insulation 6h, the heating cycle of 300 ℃ of insulation 3h is total to hot sulphur and mesopore carbon mixture then, prepares the sulphur carbon composite.Adopting EMITFSI ionic liquid and LiTFSI lithium salts is electrolyte, is assembled into behind the battery according to the charging and discharging currents density measurement of 50mA/g, and the battery first discharge specific capacity reaches 1200mAh/g, and 50 circulations afterwards capacity remain on more than the 500mAh/g.Adopt mesopore charcoal and the compound first discharge specific capacity of sulphur to be greatly improved, but capacity attenuation is very fast.
Jia-jia Chen etc. (Electrochemical Acta, 2010,55:8062-8066.) adopt the solvent exchange method to prepare sulphur/carbon/carbon nano tube compound anode material.Be dispersed in lauryl sodium sulfate after CNT put into the red fuming nitric acid (RFNA) purification process, sulphur is dissolved in the oxolane.Two kinds of solution are mixed in certain proportion, and strong agitation.Repeatedly clean away lauryl sodium sulfate with distilled water, obtain the composite material that carbon nano tube surface covers sulphur.When discharging and recharging with the current density of 300mA/g, the about 1200mAh/g of specific capacity first of battery.
Chinese patent (CN 101891930A) has been announced sulfur-based composite anode material of a kind of carbon nanotubes and preparation method thereof.The acrylonitrile itaconic acid monomer is compound in the carbon nano tube surface original position, mixing with sulphur, through heat treatment sulphur is dispersed in the matrix of acrylonitrile itaconic acid copolymer dehydrocyclization formation then.30 capacity of circulation remain on more than the 600mAh/g after forming battery.This method helps the dispersion of CNT and the even distribution of sulphur, but synthesis technique is complicated.
(Journal of Power Sources such as Wang Jiazhao; 2011,196,7030-7034.) adopt solvent-thermal method to synthesize Graphene; Make the composite material that sulfur content is 22wt.% with Graphene and sulphur vapour deposition are compound then; Carry out the constant current charge-discharge test with the 50mA/g current density after being assembled into battery, the battery first discharge specific capacity reaches 1611mAh/g, and 40 times circulation back capacity remains on 600mAh/g.The specific capacity first of battery is near theoretical value, but capacity attenuation is serious.
Summary of the invention
Existing lithium-sulfur cell cycle performance is relatively poor, one of them reason be sulfur electrode in cyclic process conductivity variation, it is significant therefore to keep the stable conductive network of electrode.The raw material of wood-charcoal material that is adopted in the existing research has carbon black, CNT and mesoporous carbon etc.; They all have good conductivity; But CNT is not easy to disperse, and has influenced the even dispersion of sulphur, and carbon black and mesoporous carbon all are nano-sized powders or microballoon; In cyclic process, reunite easily, aggravated the deterioration of sulfur electrode performance.To this problem, we propose vapor-grown carbon fibers is applied to the electrode of lithium-sulfur cell.The vapour deposition carbon fiber has advantages such as good conductivity, draw ratio is big, thermal conductivity is good, can be barricaded as natural network by bridge between them, helps the diffusion of electrical conductivity and lithium ion.In addition, the draw ratio that carbon fiber is big can strengthen collector, bonding agent and active material particle between engaging force, the meaning positive to the stable generation of electrode structure.
In order to improve the anodal capacity performance of sulphur, to improve the lithium-sulfur cell cycle performance, the present invention provides a kind of lithium-sulfur cell composite positive pole preparation method.
The object of the invention is realized through following technical scheme:
A kind of preparation method of lithium-sulfur cell composite positive pole may further comprise the steps:
(1) the vapour deposition carbon fiber was mixed with mass ratio with solid base in 1: 1～1: 5, under inert atmosphere protection, 600～1000 ℃ of following heat tracing 1～4h, extremely neutral with diluted acid and deionized water wash after taking out, drying obtains the vapour deposition carbon fiber after the activation.
(2) the vapour deposition carbon fiber after the activation being mixed with sulphur, is to take out behind solvent ball milling 1～5h with the organic solvent, and ultrasonic dispersion 5～60min is in 40～90 ℃ of following vacuumizes;
(3) under inert atmosphere protection, mixture behind the ball milling is incubated 4～10h in 120～400 ℃ of scopes, cool to room temperature with the furnace and obtain composite positive pole.
Vapour deposition carbon fiber diameter 50～200nm that the present invention preferably uses, length 5～20 μ m.It has outstanding conductivity, good mechanical properties and big draw ratio, is prone to form natural three-dimensional conductive network.The vapour deposition carbon fiber can directly directly be buied from market; As X series and S series vapour deposition carbon fiber that can to adopt Japan clear and diameter company be 50～150nm, or the day of TaiWan, China company be the serial vapour deposition carbon fiber of 100～200nm etc. with the diameter of cause company.
The preferred embodiment of the invention is that the mass ratio with vapour deposition carbon fiber after sulphur and the activation is controlled at and was advisable in 1: 3～10: 1.
The preferred embodiment of the invention also comprises:
The solid base material that uses is in potassium hydroxide, NaOH, the lithium hydroxide one or several.
Inert atmosphere is a kind of in nitrogen, the argon gas or two kinds.
Diluted acid is a kind of in watery hydrochloric acid, dilute sulfuric acid, the rare nitric acid.
Organic solvent medium is one or more in acetone, isopropyl alcohol, n-butanol, normal propyl alcohol, the absolute ethyl alcohol.
Sulphur is a kind of in sublimed sulfur, the elementary sulfur or two kinds.
The resulting composite positive pole of the present invention, the mass content of sulphur in composite material is 15%～70%.
A kind of lithium-sulfur cell composite positive pole of the present invention preparation method has following advantage:
(1) a kind of lithium-sulfur cell composite positive pole of the present invention.Through with solid base activation vapour deposition carbon fiber, make carbon fiber form micropore and mesopore, increased the specific area and the pore volume of carbon fiber.Compound through vapour deposition carbon fiber and sulphur after the activation are heated altogether, help the performance of vapour deposition carbon fiber high conductivity, and improve the distribution of sulphur.Vapour deposition carbon fiber with big L/D ratio is difficult for reuniting, and their bridges are taken and formed three-dimensional conductive network, helps infiltration, the diffusion of lithium ion and the stablizing of cyclic process electrode structure of electrolyte.
(2) adopt that the composite sulfur of the present invention's preparation is anodal to be assembled into button cell with cathode of lithium, when 0.2C (335mA/g) constant current charge-discharge, first discharge specific capacity reaches 1350mAh/g under the room temperature, and circulating, capacity remains on 600mAh/g after 50 times.The compound specific discharge capacity that improves battery of vapour deposition carbon fiber and sulphur has improved the cycle performance of battery to a certain extent.
(3) the present invention adopts thermal process, is easy in industry, implement.Have advantages such as synthetic method is simple, utilization rate of raw materials is high, the pattern of material composition is controlled.
Description of drawings
Fig. 1 is the XRD figure of vapour deposition carbon fiber (a) after the activation that obtains by embodiment 2, sulphur-vapour deposition carbon fibre composite (b) and sulphur (c).
Fig. 2 is the lithium-sulfur cell composite positive pole FESEM photo that obtains by embodiment 3.
Fig. 3 is the cycle performance curve of lithium-sulfur cell composite positive pole in lithium-sulfur cell that obtains by embodiment 3.
Fig. 4 is the first charge-discharge curve of lithium-sulfur cell composite positive pole in lithium-sulfur cell that obtains by embodiment 4.
Embodiment
Below in conjunction with embodiment, the present invention is done further explain, but be not restricted to the protection range of invention.
Embodiment 1
, put into resistance furnace after mixing and heat than mixing NaOH and gas phase deposit carbon fiber with 3: 1 alkali charcoals.Under nitrogen protection, cool to room temperature behind 900 ℃ of following heat tracing 2h with the furnace and take out.With in the dilute sulfuric acid and potassium hydroxide, again with deionized water wash to neutral, 110 ℃ of following dryings obtain the vapour deposition carbon fiber after the activation then.
Through the potassium hydroxide activation, the specific area of vapour deposition carbon fiber obviously increases.After 900 ℃ of activation, the carbon fiber specific area is 41.1m
2/ g, pore volume are 0.201m
3/ g.
Vapour deposition carbon fiber after the activation is mixed with the mass ratio of elementary sulfur with 3: 1, puts into ball grinder,, be to take out behind the solvent ball milling 2h with acetone, ultrasonic dispersion 15min is in 60 ℃ of following vacuumizes.
In argon gas atmosphere protection down, mixture behind the ball milling is warming up to 155 ℃ is incubated 6h, take out after cooling to room temperature with the furnace.Gained composite positive pole, its sulfur content are 17.2wt.%.
Electrochemical property test:
Electrode slice and button cell assembling thereof all prepare according to following mode: embodiment 1 prepared vapour deposition carbon fiber/sulphur composite material, conductive black Super P, bonding agent PVDF are evenly mixed according to mass ratio at 8: 1: 1; Drip an amount of solvent (NMP); Be coated on the aluminum foil current collector 60 ℃ of vacuumize 15h after grinding to form uniform sizing material.Strike out the electrode slice that diameter is 10mm.With the metal lithium sheet is negative pole, in being full of the glove box of argon gas, is assembled into the CR2025 button cell, and at room temperature (25 ℃) carry out the constant current charge-discharge test with 0.2C, and first discharge specific capacity is 1163mAh/g.At room temperature carry out the constant current charge-discharge test with 0.05C, first discharge specific capacity is 1203mAh/g.
Take by weighing potassium hydroxide and gas phase deposit carbon fiber with 4: 1 alkali charcoal ratios, mix.Under the argon gas atmosphere protection, 800 ℃ of following heat tracing 2h cool to room temperature with the furnace and take out.With in the watery hydrochloric acid and potassium hydroxide, again with deionized water wash to neutral, 120 ℃ of following dryings obtain the vapour deposition carbon fiber after the activation.In the argon gas atmosphere after 800 ℃ of following activation vapour deposition carbon fiber specific area be 40.4m
2/ g, pore volume are 0.160m
3/ g.
Vapour deposition carbon fiber after the activation is mixed with the mass ratio of sublimed sulfur with 3: 1, puts into ball grinder,, be to take out behind the solvent ball milling 2h with the absolute ethyl alcohol, disperse 10min to obtain suspended nitride, with suspended nitride in 55 ℃ of following vacuumizes.
In argon gas atmosphere, mixture behind the ball milling is warming up to 155 ℃ of insulation 6h, cool to room temperature with the furnace and obtain sulphur-vapour deposition carbon fiber composite positive pole.Its sulfur content is 15.1wt.%.
Fig. 1 is the XRD figure of vapour deposition carbon fiber after lithium-sulfur cell composite positive pole, sulphur, the activation.Can know that by figure the collection of illustrative plates of composite material is very similar with carbon fiber, the characteristic peak of sulphur only embodies at a place a little to some extent.
Embodiment 3
Vapour deposition carbon fiber after the activation (according to embodiment 2 method gained) is mixed with the mass ratio of sublimed sulfur with 3: 2; Put into ball grinder; With the absolute ethyl alcohol is to take out behind the solvent ball milling 2h, put into the ultrasonic dispersion of beaker 12min and obtain suspended nitride, with suspended nitride in 57 ℃ of following vacuumizes.
In argon gas atmosphere, mixture behind the ball milling is warming up to 155 ℃ of insulation 6h, cool to room temperature with the furnace.Gained sulphur/vapour deposition carbon fibre composite sulfur content is 28.4wt.%.
Fig. 2 is embodiment 2 composite positive pole SEM figure.The consistent appearance of vapour deposition carbon fiber after the pattern of composite material and the activation is not seen the bulky grain sulphur of deposition, and the bridge that well intersects between the composite fiber is taken.
Electrode preparation and electrochemical property test method are identical with embodiment 1.
According to the lithium-sulfur cell composite positive pole 0.2C charge-discharge test of embodiment 3 preparation, its first discharge specific capacity is 1350mAh/g, circulates that capacity remains on 600mAh/g after 50 times, sees Fig. 3.
Embodiment 4
Alkali charcoals ratio with 3: 1 mixes NaOH and gas phase deposit carbon fiber.Under the nitrogen atmosphere protection, cool to room temperature behind 800 ℃ of following heat tracing 2h with the furnace and take out.With in the dilute sulfuric acid and potassium hydroxide, again with deionized water wash to neutral, drying obtains the vapour deposition carbon fiber after the activation.In the nitrogen atmosphere, after 800 ℃ of activation, the carbon fiber specific area is 47.8m
2/ g, pore volume are 0.186m
3/ g.
Vapour deposition carbon fiber after the activation is mixed with the mass ratio of elementary sulfur with 1: 5,, be to take out behind the solvent ball milling 3h with the absolute ethyl alcohol, ultrasonic dispersion 12min is in 55 ℃ of following vacuumizes.
In argon gas atmosphere, mixture behind the ball milling is warming up to 155 ℃ of insulation 6h, continue to be warming up to 300 ℃ of insulation 1.5h then, cool to room temperature with the furnace and obtain composite positive pole.Its sulfur content is 30.3wt.%.
Electrode preparation and electrochemical property test method are identical with embodiment 1.
According to the lithium-sulfur cell composite positive pole 0.2C charge-discharge test of embodiment 3 preparations, its first discharge specific capacity is 1310mAh/g, sees Fig. 4.
Embodiment 5
Take by weighing lithium hydroxide and gas phase deposit carbon fiber with 2.5: 1 alkali charcoal ratios, mix.Under the argon gas atmosphere protection,, cool to room temperature with the furnace and take out in 700 ℃ of heat tracing 2h.With in the dilute sulfuric acid and potassium hydroxide, again with deionized water wash to neutral, 120 ℃ of following dryings obtain the vapour deposition carbon fiber after the activation.In the argon gas atmosphere after 800 ℃ of following activation vapour deposition carbon fiber specific area be 34.4m
2/ g, pore volume are 0.147m
3/ g.
Vapour deposition carbon fiber after the activation is mixed with the mass ratio of sublimed sulfur with 1: 10, is to take out behind the solvent ball milling 3h with acetone, and ultrasonic dispersion 20min is in 58 ℃ of following vacuumizes.
In nitrogen atmosphere, mixture behind the ball milling is warming up to 155 ℃ of insulation 6h, be warming up to 300 ℃ of insulation 3h then, cool to room temperature with the furnace and obtain composite positive pole.The composite material sulfur content is 46.8wt.%.
Electrode preparation and electrochemical property test method are identical with embodiment 1.
According to the lithium-sulfur cell composite positive pole 0.2C charge-discharge test of embodiment 4 preparations, its first discharge specific capacity is 1236mAh/g.
Claims (8)
1. lithium-sulfur cell composite positive pole preparation method is characterized in that the preparation method may further comprise the steps:
(1) the vapour deposition carbon fiber was evenly mixed with mass ratio with solid base in 1: 1～1: 5; Under inert atmosphere protection; 600～1000 ℃ of following heat tracing 1～4h, extremely neutral with diluted acid and deionized water wash after taking out, 90～150 ℃ of dryings obtain the vapour deposition carbon fiber after the activation;
(2) the vapour deposition carbon fiber after the activation being mixed with sulphur, is to take out behind solvent ball milling 1～5h with the organic solvent, and ultrasonic dispersion 5～60min is in 40～90 ℃ of following vacuumizes;
(3) under inert atmosphere protection, mixture behind the ball milling is incubated 4～10h in 120～400 ℃ of scopes, cool to room temperature with the furnace, obtain lithium-sulfur cell with sulphur/vapour deposition carbon fiber composite positive pole.
2. require described a kind of lithium-sulfur cell composite positive pole preparation method according to right 1, it is characterized in that: the vapour deposition carbon fiber diameter 50～200nm of use, length 5～20 μ m.
3. according to claim 1 or 2 said a kind of lithium-sulfur cell composite positive pole preparation methods, it is characterized in that: the mass ratio of vapour deposition carbon fiber is 1: 3～10: 1 after described sulphur and the activation.
4. according to the said a kind of lithium-sulfur cell composite positive pole preparation method of claim 1, it is characterized in that: described organic solvent is one or more in acetone, isopropyl alcohol, n-butanol, normal propyl alcohol, the absolute ethyl alcohol.
5. require said a kind of lithium-sulfur cell composite positive pole preparation method according to right 1, it is characterized in that: used sulphur is a kind of of sublimed sulfur, elementary sulfur or two kinds.
6. according to the said a kind of lithium-sulfur cell composite positive pole preparation method of claim 1, it is characterized in that: the solid base that uses is in potassium hydroxide, NaOH, the lithium hydroxide one or several.
7. according to the said a kind of lithium-sulfur cell composite positive pole preparation method of claim 1, it is characterized in that: described inert atmosphere is a kind of in nitrogen, the argon gas or two kinds.
8. according to the said a kind of lithium-sulfur cell composite positive pole preparation method of claim 1, it is characterized in that: described diluted acid is one or several in watery hydrochloric acid, dilute sulfuric acid, the rare nitric acid.
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| CN104600266A (en) * | 2015-01-09 | 2015-05-06 | 上海大学 | Method for preparing carbon fibre cloth loaded sulphur composite material |
| WO2016192389A1 (en) * | 2015-06-03 | 2016-12-08 | 中国地质大学（武汉） | Lithium sulfur battery composite positive electrode material and preparation method thereof |
| CN105932235A (en) * | 2016-05-05 | 2016-09-07 | 北京化工大学 | Halloysite-based positive electrode material of lithium-sulfur battery and preparation method for positive electrode material |
| CN105932235B (en) * | 2016-05-05 | 2018-10-23 | 北京化工大学 | A kind of lithium sulfur battery anode material and preparation method thereof based on galapectite |
| CN105826540A (en) * | 2016-06-03 | 2016-08-03 | 合肥工业大学 | Lithium-sulfur battery composite anode material and preparation method and application thereof |
| CN106025216B (en) * | 2016-06-16 | 2018-10-09 | 广东工业大学 | Lithium sulfur battery anode material, preparation method and lithium-sulfur cell |
| CN108511723A (en) * | 2018-04-03 | 2018-09-07 | 中南大学 | A kind of mangaic acid cobalt/NC/S composite material and preparation methods and the application as lithium-sulfur rechargeable battery anode material |
| CN108511723B (en) * | 2018-04-03 | 2020-06-09 | 中南大学 | Cobalt manganate/NC/S composite material, preparation method thereof and application of cobalt manganate/NC/S composite material as positive electrode material of lithium-sulfur secondary battery |
| CN109860532A (en) * | 2018-12-18 | 2019-06-07 | 南京信息工程大学 | A kind of lithium-sulfur cell peanut shell carbon/sulphur anode composite preparation method |
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