CN107293715A - A kind of lithium-sulphur cell positive electrode S/CNT CeO2The preparation method of composite - Google Patents

A kind of lithium-sulphur cell positive electrode S/CNT CeO2The preparation method of composite Download PDF

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CN107293715A
CN107293715A CN201710468046.XA CN201710468046A CN107293715A CN 107293715 A CN107293715 A CN 107293715A CN 201710468046 A CN201710468046 A CN 201710468046A CN 107293715 A CN107293715 A CN 107293715A
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lithium
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CN107293715B (en
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吕春祥
肖登极
袁淑霞
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Shanxi Institute of Coal Chemistry of CAS
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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
    • H01M4/364—Composites as mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

A kind of lithium-sulphur cell positive electrode S/CNT CeO2The preparation method of composite is ultrasonically treated formation carbon nano tube suspension in the mixed solution for add CNT triethylene glycol and water；Cerous nitrate and hexa are added sequentially in suspension, and stirred, is fitted into afterwards in ptfe autoclave and is reacted at 100 200 DEG C；Reaction product be put into inert atmosphere in 400 1000 DEG C reaction, it is cold go after take out product, obtained CNT CeO2After product and sulphur powder mixing are reacted again, S/CNT CeO are obtained2Composite.The present invention, which has, carries sulfur content height, and specific discharge capacity is high, the advantage of good cycling stability.

Description

A kind of lithium-sulphur cell positive electrode S/CNT-CeO2The preparation method of composite
Technical field
The invention belongs to lithium-sulfur cell technical field, more particularly to a kind of positive pole S/CNT-CeO2The system of composite Preparation Method.
Background technology
With the progress of electronics technology, portable electrical appliance gradually develops to light, thin, small direction, the business of electric automobile Industry needs safety, the electrical source of power of long endurance, and people are to high safety factor, low cost, high-energy-density and circulation longevity Order long secondary cell demand increasingly urgent.The secondary electricity such as lithium ion battery and lead-acid accumulator, nickel-cadmium cell and Ni-MH battery Pond is compared, with operating voltage is high, energy density is big, have extended cycle life, self-discharge rate is small, low stain and memory-less effect etc. are excellent Point, after commercialization, obtains swift and violent development.In recent years, the research and development of lithium ion battery negative material achieved important breakthrough, The specific capacity of novel silicon base and tin-based material is improved largely compared with carbon-based material, but the Recent Progresses In The Development of positive electrode but compares It is slower.At present, the positive electrode theoretical specific capacity of several commercializations is both less than 200mAh/g, the lithium ion battery energy of composition Density only has 150~180Wh/kg, and there is certain potential safety hazard.Therefore, find and develop Novel high-specific capacity flexible and height Safe, the cheap positive electrode of specific energy is the focus studied at present.
Lithium-sulfur rechargeable battery be using lithium metal as negative pole, elemental sulfur or sulfenyl composite as positive pole secondary electricity Pond.In theory, lithium after sulphur completely reaction with generating Li2S, can be achieved 2 electron reactions, and its theoretical specific capacity is up to 1675mAh/ G, reaches 2600Wh/kg, actual energy density can reach at present with the secondary cell system theoretical energy density that sulphur and lithium metal are built To 566Wh/kg, and elemental sulfur light weight, ABUNDANT NATUREAL RESOURSES is cheap, environment-friendly, is most potential high power capacity electricity Pole material.
But, there is problems with as positive pole in elemental sulfur：(1) elemental sulfur is electronics and ion insulator at room temperature； (2) elemental sulfur can be reduced into the long-chain polysulphides for dissolving in electrolyte in discharge process, on the one hand cause active material It is lost in, another aspect long-chain polysulphides, which are dissolved in electrolyte, can increase electrolysis fluid viscosity, deteriorate its ionic conductivity；(3) it is dissolved in The long-chain polysulphides of electrolyte can be diffused into lithium anode, occur self discharge reaction, be reduced to short-chain polysulphides again Positive pole is spread back, causes serious cathode of lithium to corrode and relatively low coulombic efficiency, this process is referred to as shuttle effect；(4) charge and discharge The contraction and expansion of volume can occur for sulfur electrode in electric process, and the physical arrangement of electrode is destroyed to a certain extent.These problems are led Lithium-sulfur cell is caused to there is the deficiencies such as active material utilization is low, electrochemical reversibility is poor and capacity attenuation is fast.
In recent years, researcher had carried out a large amount of exploratory developments in terms of positive electrode, electrolyte and negative material.Gao Xing The research work of energy sulfenyl composite, is concentrated mainly on two aspects, and one is by sulphur absorption in the duct of porous material, separately One is in the conductive high molecular polymer protective layer of elemental sulfur Surface coating.Wherein, the high-ratio surface and hole of porous material Structure is conducive to being uniformly distributed and loading for sulphur, by the way that sulphur is evenly spread in duct or space, can be obviously improved sulphur just The electric conductivity of pole.Meanwhile, it can also limit the loss by dissolution of polysulfide using micropore, mesoporous stronger absorption property.Research It is typically all carbon material that person, which pays close attention to more porous material, but traditional carbon material specific surface area is smaller, pore passage structure uniformity Difference, pore-size distribution is uneven, and causing the composite prepared to carry, sulfur content is small, sulphur skewness；And the work in pore passage structure Property material can dissolve into electrolyte formation polysulfide, it is thus extremely limited to the inhibitory action of shuttle effect.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art to carry sulfur content height there is provided one kind, and discharge specific volume Amount is high, the lithium-sulphur cell positive electrode S/CNT-CeO of good cycling stability2The preparation method of composite.
Preparation method of the present invention comprises the following steps：
(1) it is ultrasound 10-40min in 0.5-2 mixed solution CNT to be added into the volume ratio of triethylene glycol and water, Form the suspension that carbon nanotube concentration is 1-10g/L；
(2) cerous nitrate and hexa are added sequentially in above-mentioned suspension, and stirred, in the suspension of formation Nitric acid cerium concentration is 0.005-0.1mol/L, and the concentration of hexa is 0.001-0.25mol/L；
(3) step (2) above-mentioned suspension is fitted into ptfe autoclave, 1-10h is reacted at 100-200 DEG C；
(4) step (3) reaction product is put into inert atmosphere, 400-1000 DEG C reaction 1-5h, it is cold go after take out product, Produce product CNT-CeO2；
(5) step (4) product and sulphur powder are mixed by 0.5-5 of mass ratio, reacts 1-5h at 100-200 DEG C, produce production Thing S/CNT-CeO2Composite.
Further, the volume ratio of triethylene glycol and water is preferably 1-1.5 in the step (1).
Further, the ultrasonic time of suspension is preferably 20-30mim in the step (1).
Further, the concentration of CNT is preferably 3-5g/L in suspension in the step (1).
Further, the concentration of cerous nitrate is preferably 0.05-0.075mol/L in the step (2).Further, it is described The concentration that hexamethylene tetramine is added in step (2) is preferably 0.01-0.20mol/L.
Further, reaction temperature is preferably 100-200 DEG C in ptfe autoclave in the step (3), reaction Time is preferably 3-5h.
Further, inert atmosphere is nitrogen or argon gas in the step (4).
Further, the reaction temperature of tube furnace is preferably 500-1000 DEG C in the step (4), and the reaction time is 2- 3h。
Further, sulphur and CNT-CeO in step (5)2Ratio best in quality is 3-5.
Further, reaction temperature is preferably 120-180 DEG C in the step (5), and the reaction time is preferably 2-3h.
The present invention has the advantages that：
(1) CNT formation three-dimensional conductive path, improves the electric conductivity of electrode；
(2) cerium oxide of nano-scale can effectively suppress shuttle effect, improve the lithium-sulfur cell life-span.
(3) S/CNT-CeO prepared by the present invention2Composite can improve the electric conductivity of sulphur, suppress shuttle effect, improve sulphur Utilization rate, with carrying sulfur content high (being more than 50%), first discharge specific capacity height (0.2CmAg-1Shi Shouci electric discharges are more than 1200mAhg-1), (600 specific capacities of discharge and recharge still have 500mAhg to cyclical stability during 0.2C-1)。
Brief description of the drawings
Fig. 1 is CNT-CeO2Field emission scanning electron microscope picture.
Fig. 2 is S/CNT-CeO2Flied emission Scanning Electron microscope photograph.
Fig. 3 is S/CNT-CeO2The cycle life for the lithium-sulfur cell that anode composite piece is assembled into.
Embodiment
Below with reference to specific embodiment, make further elaboration to the present invention.It should be understood that described in the invention Embodiment, only as presently preferred embodiments of the present invention, rather than for limiting embodiments of the invention.In addition, according to the present invention Central scope and principle, those skilled in the art can easily make various corresponding changes and modification to the present invention, These do not make the change and modification made under the premise of creative work, belong to required by the application appended claims Protection domain.
Embodiment 1
(1) it is ultrasound 10min, shape in 0.5 mixed solution CNT to be added into the volume ratio of triethylene glycol and water Into the suspension that carbon nanotube concentration is 1g/L；
(2) cerous nitrate and hexa are added sequentially in above-mentioned suspension, and stirred, in the suspension of formation Nitric acid cerium concentration is 0.005mol/L, and the concentration of hexa is 0.001mol/L.
(3) above-mentioned suspension is fitted into heating response in ptfe autoclave, 2h is reacted at 100 DEG C.
(4) above-mentioned reaction product is put into nitrogen protective gas, 400 DEG C reaction 1h, it is cold go after take out product, produce Product CNT-CeO2；
(5) by the product and sulphur powder in above-mentioned (4) using mass ratio as 0.5 mixing, 1h is reacted at 140 DEG C, product S/ is produced CNT-CeO2 composites.
(6) the Integration Assembly And Checkout method of button cell：By S/CNT-CeO2Composite, conductive carbon black, PVDF press the ︰ 1 of 8 ︰ 1 Mass ratio be scattered in NMP, be uniformly mixed and made into slurry, be coated on aluminium foil, diameter 14mm positive pole is struck out after drying Piece, negative pole is made with metal lithium sheet, and electrolyte is 1M LiTFSI/DME ︰ DOL (1 ︰ 1), is assembled into the glove box full of argon gas CR2025 button cells.Battery carries out discharge and recharge with 0.2C charge-discharge magnification and followed in 1.5-3.0V discharge and recharge is interval Ring stability test.
Embodiment 2
(1) it is ultrasound 20min, shape in 0.8 mixed solution CNT to be added into the volume ratio of triethylene glycol and water Into the suspension that carbon nanotube concentration is 3g/L；
(2) cerous nitrate and hexa are added sequentially in above-mentioned suspension, and stirred, in the suspension of formation Nitric acid cerium concentration is 0.01mol/L, and the concentration of hexa is 0.01mol/L；
(3) above-mentioned suspension is fitted into heating response in ptfe autoclave, 3h is reacted at 120 DEG C.
(4) above-mentioned reaction product is put into argon gas protective gas, 600 DEG C reaction 2h, it is cold go after take out product, produce production Thing CNT-CeO2；
(5) above-mentioned product and sulphur powder are reacted 2h at 160 DEG C, produces product S/CNT-CeO using mass ratio as 1.2 mixing2 Composite.
(6) the Integration Assembly And Checkout method of button cell：By S/CNT-CeO2Composite, conductive carbon black, PVDF press the ︰ 1 of 8 ︰ 1 Mass ratio be scattered in NMP, be uniformly mixed and made into slurry, be coated on aluminium foil, diameter 14mm positive pole is struck out after drying Piece, negative pole is made with metal lithium sheet, and electrolyte is 1M LiTFSI/DME ︰ DOL (1 ︰ 1), is assembled into the glove box full of argon gas CR2025 button cells.Battery carries out discharge and recharge with 0.2C charge-discharge magnification and followed in 1.5-3.0V discharge and recharge is interval Ring stability test.
Embodiment 3
(1) it is ultrasound 30min, shape in 1.5 mixed solution CNT to be added into the volume ratio of triethylene glycol and water Into the suspension that carbon pipe concentration is 5g/L；
(2) cerous nitrate and hexa are added sequentially in above-mentioned suspension, and stirred, in the suspension of formation Nitric acid cerium concentration is 0.05mol/L, and the concentration of hexa is 0.05mol/L；
(3) above-mentioned suspension is fitted into heating response in ptfe autoclave, 5h is reacted at 150 DEG C；
(4) above-mentioned reaction product is put into nitrogen protective gas, 700 DEG C reaction 3h, it is cold go after take out product, produce production Thing CNT-CeO2；
(5) above-mentioned product and sulphur powder are reacted 3h at 180 DEG C, produces product S/CNT-CeO using mass ratio as 3 mixing2It is multiple Condensation material.
(6) the Integration Assembly And Checkout method of button cell：By S/CNT-CeO2Composite, conductive carbon black, PVDF press the ︰ 1 of 8 ︰ 1 Mass ratio be scattered in NMP, be uniformly mixed and made into slurry, be coated on aluminium foil, diameter 14mm positive pole is struck out after drying Piece, negative pole is made with metal lithium sheet, and electrolyte is 1M LiTFSI/DME ︰ DOL (1 ︰ 1), is assembled into the glove box full of argon gas CR2025 button cells.Battery carries out discharge and recharge with 0.2C charge-discharge magnification and followed in 1.5-3.0V discharge and recharge is interval Ring stability test.
Embodiment 4
(1) it is ultrasound 25min, shape in 1.7 mixed solution CNT to be added into the volume ratio of triethylene glycol and water Into the suspension that carbon nanotube concentration is 7g/L；
(2) cerous nitrate and hexa are added sequentially in above-mentioned (1) in suspension, and stirred, formation it is outstanding Nitric acid cerium concentration is 0.07mol/L in supernatant liquid, and the concentration of hexa is 0.1mol/L；
(3) above-mentioned suspension is fitted into heating response in ptfe autoclave, 7h is reacted at 170 DEG C；
(4) above-mentioned reaction product is put into nitrogen protective gas, 800 DEG C reaction 3.5h, it is cold go after take out product, produce Product CNT-CeO2；
(5) product and sulphur powder in will be above-mentioned react 3.5h at 170 DEG C, produce product S/ using mass ratio as 3.5 mixing CNT-CeO2Composite.
(6) the Integration Assembly And Checkout method of button cell：By S/CNT-CeO2Composite, conductive carbon black, PVDF press the ︰ 1 of 8 ︰ 1 Mass ratio be scattered in NMP, be uniformly mixed and made into slurry, be coated on aluminium foil, diameter 14mm positive pole is struck out after drying Piece, negative pole is made with metal lithium sheet, and electrolyte is 1M LiTFSI/DME ︰ DOL (1 ︰ 1), is assembled into the glove box full of argon gas CR2025 button cells.Battery carries out discharge and recharge with 0.2C charge-discharge magnification and followed in 1.5-3.0V discharge and recharge is interval Ring stability test.
Case study on implementation 5：
(1) it is ultrasound 10-40min, shape in 2 mixed solution CNT to be added into the volume ratio of triethylene glycol and water Into the suspension that carbon nanotube concentration is 10g/L；
(2) cerous nitrate and hexa are added sequentially in above-mentioned suspension, and stirred, in the suspension of formation Nitric acid cerium concentration is 0.1mol/L, and the concentration of hexa is 0.25mol/L；
(3) suspension in above-mentioned (2) is fitted into heating response in ptfe autoclave, 10h is reacted at 180 DEG C；
(4) above-mentioned reaction product is put into argon gas protective gas, 1000 DEG C reaction 5h, it is cold go after take out product, produce Product CNT-CeO2；
(5) above-mentioned product and sulphur powder are reacted 5h at 200 DEG C, produces product S/CNT-CeO using mass ratio as 5 mixing2It is multiple Condensation material.
(6) the Integration Assembly And Checkout method of button cell：By S/CNT-CeO2Composite, conductive carbon black, PVDF press the ︰ 1 of 8 ︰ 1 Mass ratio be scattered in NMP, be uniformly mixed and made into slurry, be coated on aluminium foil, diameter 14mm positive pole is struck out after drying Piece, negative pole is made with metal lithium sheet, and electrolyte is 1M LiTFSI/DME ︰ DOL (1 ︰ 1), is assembled into the glove box full of argon gas CR2025 button cells.Battery carries out discharge and recharge with 0.2C charge-discharge magnification and followed in 1.5-3.0V discharge and recharge is interval Ring stability test.
Table 1 is embodiment test result

Claims (11)

1. a kind of lithium-sulphur cell positive electrode S/CNT-CeO2The preparation method of composite, it is characterised in that comprise the following steps：
（1）It is ultrasound 10-40min in 0.5-2 mixed solution that CNT is added into the volume ratio of triethylene glycol and water, is formed Carbon nanotube concentration is 1-10g/L suspension；
（2）Cerous nitrate and hexa are added sequentially in above-mentioned suspension, and stirred, nitric acid in the suspension of formation Cerium concentration is 0.005-0.1 mol/L, and the concentration of hexa is 0.001-0.25 mol/L；
（3）By step（2）Above-mentioned suspension is fitted into ptfe autoclave, and 1-10h is reacted at 100-200 DEG C；
（4）By step（3）Reaction product is put into inert atmosphere, 400-1000 DEG C reaction 1-5h, it is cold go after take out product, produce Product CNT-CeO2；
（5）By step（4）Product and sulphur powder are mixed by 0.5-5 of mass ratio, and 1-5h is reacted at 100-200 DEG C, produce product S/ CNT-CeO2Composite.
2. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as claimed in claim 12The preparation method of composite, its feature exists In the step（1）The volume ratio of middle triethylene glycol and water is 1-1.5.
3. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as claimed in claim 12The preparation method of composite, its feature exists In the step（1）The ultrasonic time of middle suspension is 20-30mim.
4. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as claimed in claim 12The preparation method of composite, its feature exists In the step（1）The concentration of CNT is 3-5g/L in middle suspension.
5. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as claimed in claim 12The preparation method of composite, its feature exists In the step（2）The concentration of middle cerous nitrate is 0.05-0.075 mol/L.
6. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as claimed in claim 12The preparation method of composite, its feature exists In the step（2）The middle concentration for adding hexamethylene tetramine is 0.01-0.20 mol/L.
7. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as claimed in claim 12The preparation method of composite, its feature exists In the step（3）Reaction temperature is 100-200 DEG C in middle ptfe autoclave, and the reaction time is 3-5h.
8. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as claimed in claim 12The preparation method of composite, its feature exists In the step（4）Middle inert atmosphere is nitrogen or argon gas.
9. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as claimed in claim 12The preparation method of composite, its feature exists In the step（4）The reaction temperature of middle tube furnace is 500-1000 DEG C, and the reaction time is 2-3h.
10. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as claimed in claim 12The preparation method of composite, its feature It is step（5）Middle sulphur and CNT-CeO2Mass ratio is 3-5.
11. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as claimed in claim 12The preparation method of composite, its feature It is the step（5）Middle reaction temperature is 120-180 DEG C, and the reaction time is 2-3h.
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CN108232164A (en) * 2018-01-15 2018-06-29 中南大学 A kind of lithium sulfur battery anode material and preparation method thereof
CN108232164B (en) * 2018-01-15 2020-08-07 中南大学 Lithium-sulfur battery positive electrode material and preparation method thereof
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