CN107293715B - A kind of lithium-sulphur cell positive electrode S/CNT-CeO2The preparation method of composite material - Google Patents

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

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CN107293715B
CN107293715B CN201710468046.XA CN201710468046A CN107293715B CN 107293715 B CN107293715 B CN 107293715B CN 201710468046 A CN201710468046 A CN 201710468046A CN 107293715 B CN107293715 B CN 107293715B
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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
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Abstract

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

Description

A kind of lithium-sulphur cell positive electrode S/CNT-CeO2The preparation method of composite material
Technical field
The invention belongs to lithium-sulfur cell technical fields, more particularly to a kind of anode S/CNT-CeO2The system of composite material Preparation Method.
Background technique
With the progress of electronics technology, portable electrical appliance gradually develops to light, thin, small direction, the quotient of electric car Industry needs the electrical source of power of safety, long cruising ability, and people are to high safety factor, low cost, high-energy density and circulation longevity The long secondary cell demand of life is increasingly urgent to.The secondary electricity such as lithium ion battery and lead-acid accumulator, nickel-cadmium cell and nickel-metal hydride battery Pond is compared, and has that operating voltage is high, energy density is big, have extended cycle life, self-discharge rate is small, low pollution 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 Relatively slowly.Currently, 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 are some potential safety problemss.Therefore, find and develop Novel high-specific capacity flexible and height Safe, the cheap positive electrode of specific energy is the hot spot studied at present.
Lithium-sulfur rechargeable battery is the secondary electricity of elemental sulfur or sulfenyl composite material as anode using lithium metal as cathode Pond.Theoretically, Li is generated after lithium reacts completely with sulphur2S is, it can be achieved that 2 electron reactions, theoretical specific capacity are up to 1675mAh/ G reaches 2600Wh/kg with the secondary cell system theoretical energy density of sulphur and lithium metal building, and actual energy density can reach at present To 566Wh/kg, and elemental sulfur light weight, ABUNDANT NATUREAL RESOURSES is cheap, and it is environmental-friendly, it is most potential high capacity electricity Pole material.
But elemental sulfur has the following problems as anode: (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 during discharge, on the one hand cause active material It is lost, another aspect long-chain polysulphides, which are dissolved in electrolyte, will 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, and self discharge reaction occurs, is reduced to short-chain polysulphides again Anode is spread back, serious cathode of lithium corrosion and lower coulombic efficiency, this process is caused to be known as shuttle effect；(4) charge and discharge The contraction and expansion of volume can occur for sulfur electrode in electric process, destroy the physical structure of electrode to a certain extent.These problems are led Cause lithium-sulfur cell there are active material utilizations it is low, electrochemical reversibility is poor and capacity attenuation is fast the deficiencies of.
In recent years, researcher positive electrode, electrolyte and in terms of carried out a large amount of exploratory developments.Gao Xing The research work of energy sulfenyl composite material is concentrated mainly on two aspects, first is that sulphur is adsorbed in the duct of porous material, separately One is high molecular polymer protective layer in elemental sulfur surface coated with conductive.Wherein, the high-ratio surface and hole of porous material Structure is conducive to being uniformly distributed and loading for sulphur, by evenly spreading to sulphur in duct or gap, can be obviously improved sulphur just The electric conductivity of pole.Meanwhile the loss by dissolution of polysulfide can also be limited 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, cellular structure consistency Difference, pore-size distribution is uneven, and causing the composite material of preparation to carry, sulfur content is small, sulphur is unevenly distributed；And the work in cellular structure Property substance can dissolve and form polysulfide into electrolyte, thus it is extremely limited to the inhibiting effect of shuttle effect.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of load sulfur content height, discharge specific volume Amount is high, the lithium-sulphur cell positive electrode S/CNT-CeO of good cycling stability2The preparation method of composite material.
Preparation method of the present invention the following steps are included:
(1) volume ratio of triethylene glycol and water is added in carbon nanotube is ultrasound 10- in the mixed solution of 0.5-2 40min forms 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 0.001-0.25 mol/L；
(3) step (2) above-mentioned suspension is fitted into ptfe autoclave, reacts 1-10h at 100-200 DEG C；
(4) step (3) reaction product is put into inert atmosphere, 400-1000 DEG C of reaction 1-5h, it is cold go after take out product, Up to product CNT-CeO2；
(5) step (4) product and sulphur powder are mixed with mass ratio for 0.5-5,1-5h is reacted at 100-200 DEG C to get production Object S/CNT-CeO2Composite material.
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 carbon nanotube 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, described It is preferably 0.01-0.20mol/L that the concentration of hexamethylene tetramine is added in step (2).
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), reaction time 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 invention has the following beneficial effects:
(1) carbon nanotube forms three-dimensional conductive access, improves the electric conductivity of electrode；
(2) cerium oxide of nano-scale can effectively inhibit shuttle effect, improve the lithium-sulfur cell service life.
(3) S/CNT-CeO prepared by the present invention2Composite material can improve the electric conductivity of sulphur, inhibit shuttle effect, improve sulphur Utilization rate, have and carry sulfur content high (being greater than 50%), first discharge specific capacity height (0.2CmAg-1Shi Shouci electric discharge is greater than 1200mAhg-1), (600 specific capacities of charge and discharge still have 500mAhg to cyclical stability when 0.2C-1)。
Detailed description of the invention
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.
Specific embodiment
Below with reference to specific embodiment, the present invention is made further to be described in detail.It should be understood that described in the invention Embodiment is only used 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 various corresponding changes and modification easily can be made 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 the appended claims Protection scope.
Embodiment 1
(1) carbon nanotube is added to the volume ratio of triethylene glycol and water for ultrasound 10min in 0.5 mixed solution, shape The suspension for being 1g/L at carbon nanotube concentration；
(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 heat in ptfe autoclave and is reacted, react 2h at 100 DEG C.
(4) above-mentioned reaction product is put into nitrogen protection gas, 400 DEG C of reaction 1h, it is cold go after take out product to get Product CNT-CeO2；
(5) by above-mentioned (4) product and sulphur powder with mass ratio be 0.5 mixing, 1h is reacted at 140 DEG C to get product S/ CNT-CeO2 composite material.
(6) the Integration Assembly And Checkout method of button cell: by S/CNT-CeO2Composite material, conductive carbon black, PVDF press 8 ︰, 1 ︰ 1 mass ratio is scattered in NMP, is uniformly mixed and made into slurry, is coated on aluminium foil, the anode of diameter 14mm is struck out after drying Piece makees cathode 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 cell.Battery carries out charge and discharge with the charge-discharge magnification of 0.2C and follows in the charge and discharge section of 1.5-3.0V Ring stability test.
Embodiment 2
(1) carbon nanotube is added to the volume ratio of triethylene glycol and water for ultrasound 20min in 0.8 mixed solution, shape The suspension for being 3g/L at carbon nanotube concentration；
(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 heat in ptfe autoclave and is reacted, react 3h at 120 DEG C.
(4) above-mentioned reaction product is put into argon gas protective gas, 600 DEG C of reaction 2h, it is cold go after take out product to get production Object CNT-CeO2；
(5) it is 1.2 mixing with mass ratio by above-mentioned product and sulphur powder, 2h is reacted at 160 DEG C to get product S/CNT- CeO2Composite material.
(6) the Integration Assembly And Checkout method of button cell: by S/CNT-CeO2Composite material, conductive carbon black, PVDF press 8 ︰, 1 ︰ 1 mass ratio is scattered in NMP, is uniformly mixed and made into slurry, is coated on aluminium foil, the anode of diameter 14mm is struck out after drying Piece makees cathode 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 cell.Battery carries out charge and discharge with the charge-discharge magnification of 0.2C and follows in the charge and discharge section of 1.5-3.0V Ring stability test.
Embodiment 3
(1) carbon nanotube is added to the volume ratio of triethylene glycol and water for ultrasound 30min in 1.5 mixed solution, shape The suspension for being 5g/L at carbon pipe concentration；
(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 heat in ptfe autoclave and is reacted, react 5h at 150 DEG C；
(4) above-mentioned reaction product is put into nitrogen protection gas, 700 DEG C of reaction 3h, it is cold go after take out product to get production Object CNT-CeO2；
(5) it is 3 mixing with mass ratio by above-mentioned product and sulphur powder, 3h is reacted at 180 DEG C to get product S/CNT-CeO2 Composite material.
(6) the Integration Assembly And Checkout method of button cell: by S/CNT-CeO2Composite material, conductive carbon black, PVDF press 8 ︰, 1 ︰ 1 mass ratio is scattered in NMP, is uniformly mixed and made into slurry, is coated on aluminium foil, the anode of diameter 14mm is struck out after drying Piece makees cathode with metal lithium sheet, and electrolyte is 1M LiTFSI/DME ︰ DOL (1 ︰ 1), is assembled in the glove box full of argon gas At CR2025 button cell.Battery in the charge and discharge section of 1.5-3.0V, with the charge-discharge magnification of 0.2C carry out charge and discharge and Cyclical stability test.
Embodiment 4
(1) carbon nanotube is added to the volume ratio of triethylene glycol and water for ultrasound 25min in 1.7 mixed solution, shape The suspension for being 7g/L at carbon nanotube concentration；
(2) cerous nitrate and hexa are added sequentially in above-mentioned (1) in suspension, and stirred, formation is hanged Nitric acid cerium concentration is 0.07mol/L in supernatant liquid, and the concentration of hexa is 0.1 mol/L；
(3) above-mentioned suspension is fitted into heat in ptfe autoclave and is reacted, react 7h at 170 DEG C；
(4) above-mentioned reaction product is put into nitrogen protection gas, 800 DEG C of reaction 3.5h, it is cold go after take out product to get Product CNT-CeO2；
(5) by among the above product and sulphur powder with mass ratio be 3.5 mixing, 3.5h is reacted at 170 DEG C to get product S/ CNT-CeO2Composite material.
(6) the Integration Assembly And Checkout method of button cell: by S/CNT-CeO2Composite material, conductive carbon black, PVDF press 8 ︰, 1 ︰ 1 mass ratio is scattered in NMP, is uniformly mixed and made into slurry, is coated on aluminium foil, the anode of diameter 14mm is struck out after drying Piece makees cathode with metal lithium sheet, and electrolyte is 1M LiTFSI/DME ︰ DOL (1 ︰ 1), is assembled in the glove box full of argon gas At CR2025 button cell.Battery in the charge and discharge section of 1.5-3.0V, with the charge-discharge magnification of 0.2C carry out charge and discharge and Cyclical stability test.
Case study on implementation 5:
(1) carbon nanotube is added to ultrasound 10-40min in the mixed solution that the volume ratio of triethylene glycol and water is 2, Form 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 heat in ptfe autoclave and is reacted, react 10h at 180 DEG C；
(4) above-mentioned reaction product is put into argon gas protective gas, 1000 DEG C of reaction 5h, it is cold go after take out product to get Product CNT-CeO2；
(5) it is 5 mixing with mass ratio by above-mentioned product and sulphur powder, 5h is reacted at 200 DEG C to get product S/CNT-CeO2 Composite material.
(6) the Integration Assembly And Checkout method of button cell: by S/CNT-CeO2Composite material, conductive carbon black, PVDF press 8 ︰, 1 ︰ 1 mass ratio is scattered in NMP, is uniformly mixed and made into slurry, is coated on aluminium foil, the anode of diameter 14mm is struck out after drying Piece makees cathode 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 cell.Battery carries out charge and discharge with the charge-discharge magnification of 0.2C and follows in the charge and discharge section of 1.5-3.0V 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 material, it is characterised in that include the following steps:
(1) volume ratio of triethylene glycol and water is added in carbon nanotube is ultrasound 10-40min in the mixed solution of 0.5-2, is formed Carbon nanotube concentration is the suspension of 1-10g/L；
(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) step (2) above-mentioned suspension is fitted into ptfe autoclave, reacts 1-10h at 100-200 DEG C；
(4) step (3) reaction product is put into inert atmosphere, 400-1000 DEG C of reaction 1-5h, it is cold go after take out product to get Product CNT-CeO2；
(5) step (4) product and sulphur powder are mixed with mass ratio for 0.5-5,1-5h is reacted at 100-200 DEG C to get product S/ CNT-CeO2Composite material.
2. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as described in claim 12The preparation method of composite material, feature exist The volume ratio of triethylene glycol and water is 1-1.5 in the step (1).
3. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as described in claim 12The preparation method of composite material, feature exist The ultrasonic time of mixed solution is 20-30min in the step (1).
4. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as described in claim 12The preparation method of composite material, feature exist The concentration of carbon nanotube is 3-5g/L in suspension in the step (1).
5. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as described in claim 12The preparation method of composite material, feature exist The concentration of cerous nitrate is 0.05-0.075 mol/L in the step (2).
6. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as described in claim 12The preparation method of composite material, feature exist The concentration that hexa is added in the step (2) is 0.01-0.20 mol/L.
7. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as described in claim 12The preparation method of composite material, feature exist Reaction temperature is 100-200 DEG C in ptfe autoclave in the step (3), reaction time 3-5h.
8. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as described in claim 12The preparation method of composite material, feature exist Inert atmosphere is nitrogen or argon gas in the step (4).
9. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as described in claim 12The preparation method of composite material, feature exist The reaction temperature of tube furnace is 500-1000 DEG C in the step (4), reaction time 2-3h.
10. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as described in claim 12The preparation method of composite material, feature It is sulphur and CNT-CeO in step (5)2Mass ratio is 3-5.
11. a kind of lithium-sulphur cell positive electrode S/CNT-CeO as described in claim 12The preparation method of composite material, feature It is in the step (5) that reaction temperature is 120-180 DEG C, reaction time 2-3h.
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CN108232164B (en) * 2018-01-15 2020-08-07 中南大学 Lithium-sulfur battery positive electrode material and preparation method thereof
KR102244910B1 (en) * 2018-03-16 2021-04-26 주식회사 엘지화학 Ceria-carbon-surfur complex, manufacturing method thereof, positive electrode and lithium-sulfur battery comprising the same
CN109461903A (en) * 2018-09-29 2019-03-12 昆明理工大学 A kind of preparation method of lithium-sulfur battery composite cathode material
CN110993928B (en) * 2019-11-19 2021-04-09 宁波大学 Method for manufacturing lithium-sulfur battery positive electrode material
CN111200125A (en) * 2020-01-10 2020-05-26 西京学院 With CeO2CeO with frame material as carrier2Preparation method of/S composite material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103840143A (en) * 2014-03-19 2014-06-04 中南大学 Preparation method of S/TiO2 composite material for anode of sodium-sulfur battery
CN104659338A (en) * 2015-03-17 2015-05-27 东莞市迈科科技有限公司 Preparation method of positive electrode material of lithium sulfur battery
CN105098137A (en) * 2014-05-09 2015-11-25 宁德时代新能源科技有限公司 Lithium ion battery, and anode 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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103840143A (en) * 2014-03-19 2014-06-04 中南大学 Preparation method of S/TiO2 composite material for anode of sodium-sulfur battery
CN105098137A (en) * 2014-05-09 2015-11-25 宁德时代新能源科技有限公司 Lithium ion battery, and anode material and preparation method thereof
CN104659338A (en) * 2015-03-17 2015-05-27 东莞市迈科科技有限公司 Preparation method of positive electrode material of lithium sulfur battery
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

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