CN102983312A - Preparation method of composite fiber anode material of lithium-sulfur battery - Google Patents
Preparation method of composite fiber anode material of lithium-sulfur battery Download PDFInfo
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- CN102983312A CN102983312A CN2012104935485A CN201210493548A CN102983312A CN 102983312 A CN102983312 A CN 102983312A CN 2012104935485 A CN2012104935485 A CN 2012104935485A CN 201210493548 A CN201210493548 A CN 201210493548A CN 102983312 A CN102983312 A CN 102983312A
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Abstract
The invention relates to a preparation method of a composite fiber anode material of a lithium-sulfur battery. The preparation method comprises the following steps of: using glass fiber as a precursor, and corroding glass fiber after the surface of the fiber is plated with nickel by using a chemical plating method, so as to prepare a micron-level hollow nickel fiber tube; secondly, growing dense noanometer carbon fiber on the inner surface and the outer surface of the end part of the nickel fiber tube by using a microwave plasma chemistry vapor deposition method; diffusing a mixture of uniformly mixing sulfur and powder carbon with a binder according to a certain ratio in an organic solvent, and stirring to obtain slurry; uniformly coating the slurry on a current collector thin sheet; and preparing an anode after being dried. According to the preparation method provided by the invention, the micron-level hollow nickel fiber tube is used as a main branch and a nanometer-level carbon fiber as a secondary branch, so as to form a space network structure; and the carbon fiber and a conductive agent have a large contact area, so as to form a good conductive channel. The preparation method is beneficial to the improvement on the battery circulation property.
Description
Technical field
The invention belongs to field of electrochemical batteries, particularly relate to a kind of preparation method of lithium-sulphur cell positive electrode complex fiber material.
Background technology
Elemental sulfur has the high theoretical specific capacity of 1675mAh/g, and the theoretical specific energy of the lithium-sulfur cell that forms with lithium metal is up to 2600Wh/kg, far above used positive electrode LiCoO in the existing lithium ion battery
2, LiMn
2O
4, LiFePO
4Capacity.And the sulphur source is abundant, with low cost, pollute environment is low, and be a kind of very widely green energy-storing material of application prospect that has.
Because the poorly conductive of sulphur own, it is receiving and losing electrons and stop further carrying out of reaction normally.In order to make sulphur participate in anodal reaction, usually add conductive agent and improve.Yet, easily form the multiple electrolytical many thiamers that are dissolved in the lithium-sulfur cell course of reaction, and the reaction ending phase generates non-conductive sulfide Li
2S and Li
2S
2Cover the conductive agent particle surface, cause the electric charge transmission channel to reduce, the reduction of the utilance of active material and the effect of shuttling back and forth are serious in the positive electrode, so that battery capacity and cycle charge-discharge degradation.
For the utilance that promotes sulphur and improve the battery charging and discharging performance, the researcher has carried out a large amount of trials.J.L. the people (J. Electrochemistry Communications, 2002,4 (6) 499-502) such as Wang adopts heat treatment that sublimed sulfur and activated carbon are made active composite material, and utilization efficiency can reach 90%.But the high-specific surface area activated carbon, pore volume is less than 0.4cm
3/ g, its maximum sulphur loading is superelevation 44% not, and the composite material population size is little, and practical value is low.People (the J.Materials Science Forum such as Suk Ryu Ho, 2007,534-536 (2): 1509-1512) with CNT (carbon nano-tube) (CNT) and acetylene black jointly as conductive agent, research different content carbon nano-tube is on the impact of sulphur positive discharge and cycle performance.Carbon fiber preferably adsorptivity can improve that polysulfide is dissolved in electrolyte and the capacity attenuation that causes.The people such as Choi (J. Journal of Alloys and Compounds, 2008,449 (1-2), 0925-8388) carbon nano-fiber (CNF) of adding diameter 150nm in positive pole, its conductivity and stable mechanical performance, the about 500mAh/g of specific capacity after 60 times circulates.But nanometer materials are owing to stronger agglomeration is difficult to Uniform Dispersion, cause performance effectively to improve.For avoiding scattering problem on the impact of battery performance, people (the J.Electrochimica Acta such as Sheng S.Zhang, 2012,211:169-172) utilize phase transfer method to prepare porous sulphur rete, be assembled into battery take carbon cloth as collector with absorption matrix adopting sandwich afterwards, prepare the positive electrode with high-sulfur load capacity and high capacity density.Although above method makes moderate progress to the lithium-sulfur cell performance to a certain extent, its energy density and cyclical stability still need constantly to improve from a practical in addition segment distance.
Summary of the invention
The objective of the invention is to be to provide a kind of preparation method of lithium-sulphur cell positive electrode carbon fiber composite positive pole, the good electronic transmission performance that utilizes carbon fiber/nickel fibre pipe itself to have makes sulphur can effectively participate in electrochemical reaction; Simultaneously, the strong adsorptivity that nickel fiber hollow structure and the formed spatial network of carbon fiber outer, that inner port covers have can limit the dissolving of polysulfide, reduce because the effect of shuttling back and forth causes the irreversible decay of capacity, further improve cycle efficieny, the cycle performance of lithium-sulfur cell integral body is improved.
The present invention is that the solution that the problem of the above-mentioned proposition of solution adopts is: a kind of preparation method of lithium-sulfur cell composite fibre positive electrode is characterized in that having the following steps:
(1) adopt electroless plating method to cover one deck nickel film at the glass fibre matrix, glass fibre with sour eating away centre obtains the hollow nickel fibre pipe, adopt the microwave plasma CVD method at the intensive carbon fiber of nickel fibre pipe superficial growth, obtain carbon fiber/nickel fibre pipe composite material;
(2) mixture of sublimed sulfur, powder carbon is carried out ball milling after, be uniformly dispersed with being added in the binder solution that contains organic solvent after carbon fiber/nickel fibre pipe composite material mixes with certain proportion of preparation, be prepared into slurry;
(3) slurry that modulates evenly is coated on the pretreated collector, obtains lithium-sulfur cell composite fibre positive electrode after the drying.
Press such scheme, the wall thickness of described nickel fibre pipe is 0.5-2 μ m; The mass ratio of the mixture of sublimed sulfur, powder carbon and carbon fiber/nickel fibre pipe composite material is 10-20:1.
Press such scheme, the employed glass fiber diameter of step (1) is 5-30 μ m, and the acid of etching glass fiber is hydrofluoric acid.
Press such scheme, described organic solvent is acetone or 1-METHYLPYRROLIDONE.
Beneficial effect of the present invention is: carbon fiber of the present invention/nickel fibre pipe composite material, micrometer nickel fibre tube outer surface and port inside are all coated by the nano-level conducting carbon fiber, form microporous spacial framework, not only have good conductivity and adsorptivity; And the micrometer nickel fibre pipe can effectively disperse, and avoids the generation of electric conducting material agglomeration; Mutually form intensive conductive structure between the carbon fiber, be net distribution, the carbon granule that carbon fiber and periphery are filled may further be reaction of Salmon-Saxl good conductive channel is provided, and reduces megohmite insulant Li
2S and Li
2S
2Accumulation phenomena; The stronger adsorptivity of carbon fiber/nickel fibre pipe self and good spatial network distribute and can the polysulfide that generate in the course of reaction be adsorbed, fix, inhibition is shuttled back and forth effect and is caused its dissolving in electrolyte, reduce the loss of active material, thereby promote circulating battery invertibity and discharge stability.
Description of drawings
Fig. 1 is that the nickel fibre pipe that the embodiment of the invention 1 obtains amplifies 400 times of apparent patterns;
Fig. 2 is that nickel fiber outer surface and the internal port coated carbon fiber that the embodiment of the invention 1 obtains amplifies 5000 times of apparent patterns;
Fig. 3 is that the netted structure of embodiment 1 nickel fibre pipe superficial growth carbon fiber is amplified 10000 times of apparent patterns;
Fig. 4 is the first discharge curve after the assembled battery among the embodiment 1.
Embodiment
The invention will be further described below in conjunction with embodiment, but can not be interpreted as limitation of the invention.
Embodiment 1:
One. the preparation method of carbon fiber/nickel fibre pipe:
A) oil removing-alligatoring: choose the glass fibre matrix that diameter is about 15 μ m and place the ultrasonic oil removing 10min of ethanolic solution, after put into concentration 80g/L NaOH solution matrix is carried out roughening treatment, then time 10min uses washed with de-ionized water;
B) sensitization-activation: will put into first the SnCl that concentration is 30g/L through pretreated glass fibre matrix
2In the HCl mixed liquor of 100ml/L, soak 3min, cleans a little with deionized water after taking out.Then be immersed in the PdCl of concentration 0.2g/L
2With activate in the HCl mixed liquor of 50ml/L, 35 ℃ of temperature are taken out behind the 15min, washed with de-ionized water is filtered dry;
C) chemical nickel plating: (main component is 20g/L NiSO will to put into the chemical plating fluid of pH 4.6 ~ 4.9 through the glass fibre matrix of processing, having catalytic center
46H
2O, 15g/L NaH
2PO
2H
2O, 25g/L NaAC and 15g/L complexing agent etc.) in, 84 ℃ of temperature, time 10min can cover one deck nickel film at the glass fibre matrix surface;
D) matrix is removed: the glass fibre matrix of surface coverage one deck nickel film of above-mentioned preparation is positioned over carries out ultrasonic processing in the HF solution, obtain the hollow nickel fibre pipe, as shown in Figure 1, shown in the wall thickness of nickel fibre pipe be about 1 μ m;
E) microwave plasma modification: the hollow nickel fibre pipe that step d) is obtained places microwave plasma device (MPCVD), and microwave power is 500W, passes into 55sccmH
2And 3.4sccmCH
4, under 5.0KPa, carrying out the growth of carbon fiber, time 5min finally obtains carbon fiber/nickel fibre pipe composite material, and as shown in Figure 2, fiber outer surface and internal port all are coated with carbon fiber, form microporous spacial framework; As shown in Figure 3, mutually form intensive conductive structure between the carbon fiber, be net distribution, the carbon fiber diameter is about 50nm;
Two. with sublimed sulfur: amorphous state acetylene black in mass ratio 6:3 is mixed, and puts into the ball grinder high speed ball milling 6h that is added with absolute ethyl alcohol.In that to obtain active material behind the dry 12h under 60 ℃ in air dry oven for subsequent use; With above-mentioned prepared active material and carbon fiber/nickel fibre pipe composite material in mass ratio 11:1 be scattered in the mixed solution of LA132 binding agent and acetone, stirring is coated in sand papering with the slurry that modulates and through 0.1mol/L NaOH and 0.1mol/L H afterwards with scraper
2C
2O
4On the pretreated metal aluminum foil substrate, thickness is greatly about about 80 μ m.Put it in the vacuum drying chamber behind 55 ℃ of oven dry 20h for subsequent usely, can obtain lithium-sulfur cell composite fibre positive electrode.
Take the active material of above-mentioned preparation as anodal, lithium metal is negative pole, and barrier film is Celgard2400, adopts the LiClO of 1mol/L
4/ (DOL+DME) (DOX (C
3H
6O
2)+glycol dimethyl ether (C
4H
10O
2), volume ratio 1:1) be electrolyte, CR2025 button cell shell is mould, assembled battery in CSX-1 type vacuum glove box.For characterizing out the chemical property of battery after the assembling, adopt the LAND battery test system to measure.Restriction charge-discharge test interval is 1.0 ~ 2.8V, and current density is 0.2mA.First discharge specific capacity is 1025.3mAh/g, and specific capacity is 720.8mAh/g after the charge and discharge cycles 20 times, embodies preferably cyclical stability, as shown in Figure 4.
Embodiment 2:
One. carbon/nickel fibre pipe preparation method:
A) oil removing-alligatoring: choose the glass fibre matrix that diameter is about 20 μ m and place the ultrasonic oil removing 10min of ethanolic solution, after put into concentration 80g/L NaoH solution matrix is carried out roughening treatment, then time 10min uses washed with de-ionized water;
B) sensitization-activation: will put into first the SnCl that concentration is 30g/L through pretreated glass fibre matrix
2In the HCl mixed liquor of 100ml/L, soak 3min, cleans a little with deionized water after taking out.Then be immersed in the PdCl of concentration 0.2g/L
2With activate in the HCl mixed liquor of 50ml/L, 35 ℃ of temperature are taken out behind the 15min, washed with de-ionized water is filtered dry;
C) chemical nickel plating: (main component is 20g/L NiSO will to put into the chemical plating fluid of pH4.6 ~ 4.9 through the glass fibre matrix of processing, having catalytic center
46H
2O, 15g/L NaH
2PO
2H2O, 25g/L NaAC and 15g/L complexing agent etc.) in, 84 ℃ of temperature, time 10min can cover one deck nickel film at the glass fibre matrix surface;
D) matrix is removed: the glass fibre matrix of surface coverage one deck nickel film of above-mentioned preparation is positioned over carries out ultrasonic processing in the HF solution, obtain the hollow nickel fibre pipe;
E) microwave plasma modification: the hollow nickel fibre pipe that step d) is obtained places microwave plasma device (MPCVD), and microwave power is 500W, passes into 55sccmH
2And 3.3sccmCH
4, carrying out the growth of carbon fiber at 4.7KPa, time 5min finally obtains carbon fiber/nickel fibre pipe composite material;
Two. with sublimed sulfur: amorphous graphite in mass ratio 7:2 mixes, and puts into the ball grinder high speed ball milling 6h that is added with absolute ethyl alcohol.It is for subsequent use to obtain active material behind the dry 12h in 70 ℃ of lower and air dry ovens; With above-mentioned prepared active material and carbon fiber/nickel fibre pipe composite material in mass ratio 15:1 in binding agent PVDF(Kynoar) mix dispersion, fully dissolve take NMP as solvent, stirring is coated in sand papering with the slurry that modulates and through 0.1mol/L NaOH and 0.1mol/L H afterwards with scraper
2C
2O
4On the pretreated metal aluminum foil substrate, thickness is greatly about about 80 μ m.Put it in the vacuum drying chamber behind 60 ℃ of oven dry 20h for subsequent usely, can obtain lithium-sulfur cell composite fibre positive electrode.
Take the active material of above-mentioned preparation as anodal, lithium metal is negative pole, and barrier film is Celgard2400, adopts the LiClO of 1mol/L
4/ (DOL+DME) (DOX (C
3H
6O
2)+glycol dimethyl ether (C
4H
10O
2), volume ratio 1:1) be electrolyte, CR2025 button cell shell is mould, assembled battery in CSX-1 type vacuum glove box.For characterizing out the chemical property of battery after the assembling, adopt the LAND battery test system to measure.Restriction charge-discharge test interval is 1.0 ~ 2.8V, and current density is 0.2mA.First discharge specific capacity is 920.7mAh/g, and specific capacity is 650.4mAh/g after the charge and discharge cycles 20 times, embodies preferably cyclical stability.
Embodiment 3:
One. carbon/nickel fibre pipe preparation method:
A) oil removing-alligatoring: choose the glass fibre matrix that diameter is about 25 μ m and place the ultrasonic oil removing 10min of ethanolic solution, after put into concentration 80g/L NaoH solution matrix is carried out roughening treatment, then time 10min uses washed with de-ionized water;
B) sensitization-activation: will put into first the SnCl that concentration is 30g/L through pretreated glass fibre matrix
2In the HCl mixed liquor of 100ml/L, soak 3min, cleans a little with deionized water after taking out.Then be immersed in the PdCl of concentration 0.2g/L
2With activate in the HCl mixed liquor of 50ml/L, 35 ℃ of temperature are taken out behind the 15min, washed with de-ionized water is filtered dry;
C) chemical nickel plating: will put into pH through the glass fibre matrix of processing, having catalytic center is that (main component is 20g/L NiSO for 4.6 ~ 4.9 chemical plating fluid
46H
2O, 15g/L NaH
2PO
2H
2O, 25g/L NaAC and 15g/L complexing agent etc.) in, 84 ℃ of temperature, time 10min can cover one deck nickel film at the glass fibre matrix surface;
D) matrix is removed: the glass fibre matrix of surface coverage one deck nickel film of above-mentioned preparation is positioned over carries out ultrasonic processing in the HF solution, obtain the hollow nickel fibre pipe;
E) microwave plasma modification: the hollow nickel fibre pipe that step d) is obtained places microwave plasma device (MPCVD), and microwave power is 500W, passes into 55sccmH
2And 3.5sccmCH
4, under 5.2KPa, carrying out the growth of carbon fiber, time 5min finally obtains carbon fiber/nickel fibre pipe composite material;
Two. with sublimed sulfur: superconduction carbon black in mass ratio 6:3 mixes, and puts into the ball grinder high speed ball milling 6h that is added with absolute ethyl alcohol.It is for subsequent use to obtain active material behind the dry 12h in 70 ℃ of lower and air dry ovens; With above-mentioned prepared active material and carbon fiber/nickel fibre pipe composite material in mass ratio 19:1 be scattered in the ptfe emulsion that contains organic solvent, stirring is coated in sand papering with the slurry that modulates and through 0.1mol/L NaOH and 0.1mol/L H afterwards with scraper
2C
2O
4On the pretreated metal aluminum foil substrate, thickness is greatly about about 80 μ m.Put it in the vacuum drying chamber behind 60 ℃ of oven dry 20h for subsequent usely, can obtain lithium-sulfur cell composite fibre positive electrode.
Take the active material of above-mentioned preparation as anodal, lithium metal is negative pole, and barrier film is Celgard2400, adopts the LiClO of 1mol/L
4/ (DOL+DME) (DOX (C
3H
6O
2)+glycol dimethyl ether (C
4H
10O
2), volume ratio 1:1) be electrolyte, CR2025 button cell shell is mould, assembled battery in CSX-1 type vacuum glove box.For characterizing out the chemical property of battery after the assembling, adopt the LAND battery test system to measure.Restriction charge-discharge test interval is 1.0 ~ 2.8V, and current density is 0.2mA.First discharge specific capacity is 1044.7mAh/g, and specific capacity is 730.1mAh/g after the charge and discharge cycles 20 times, embodies preferably cyclical stability.
Claims (4)
1. the preparation method of a lithium-sulfur cell composite fibre positive electrode is characterized in that having the following steps:
(1) adopt electroless plating method to cover one deck nickel film at the glass fibre matrix, glass fibre with sour eating away centre obtains the hollow nickel fibre pipe, adopt the microwave plasma CVD method at the intensive carbon fiber of nickel fibre pipe superficial growth, obtain carbon fiber/nickel fibre pipe composite material;
(2) mixture of sublimed sulfur, powder carbon is carried out ball milling after, be uniformly dispersed with being added in the binder solution that contains organic solvent after carbon fiber/nickel fibre pipe composite material mixes with certain proportion of preparation, be prepared into slurry;
(3) slurry that modulates evenly is coated on the pretreated collector, obtains lithium-sulfur cell composite fibre positive electrode after the drying.
2. by the preparation method of lithium-sulfur cell composite fibre positive electrode claimed in claim 1, the wall thickness that it is characterized in that described nickel fibre pipe is 0.5-2 μ m; The mass ratio of the mixture of sublimed sulfur, powder carbon and carbon fiber/nickel fibre pipe composite material is 10-20:1.
3. by the preparation method of claim 1 or 2 described lithium-sulfur cell composite fibre positive electrodes, it is characterized in that the employed glass fiber diameter of step (1) is 5-30 μ m, the acid of etching glass fiber is hydrofluoric acid.
4. by the preparation method of claim 1 or 2 described lithium-sulfur cell composite fibre positive electrodes, it is characterized in that described organic solvent is acetone or 1-METHYLPYRROLIDONE.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600266A (en) * | 2015-01-09 | 2015-05-06 | 上海大学 | Method for preparing carbon fibre cloth loaded sulphur composite material |
| CN104900830A (en) * | 2015-06-29 | 2015-09-09 | 北京理工大学 | Lithium-sulfur battery with carbon fiber cloth as barrier layer |
| CN108123167A (en) * | 2016-11-28 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of lithium-sulfur cell electrode and its preparation and the lithium-sulfur cell structure for including it |
| CN110690398A (en) * | 2019-09-30 | 2020-01-14 | 上海大学 | Multifunctional composite diaphragm for high-temperature lithium-sulfur battery, and preparation method and application thereof |
| US11590568B2 (en) | 2019-12-19 | 2023-02-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
| US11633785B2 (en) | 2019-04-30 | 2023-04-25 | 6K Inc. | Mechanically alloyed powder feedstock |
| US11717886B2 (en) | 2019-11-18 | 2023-08-08 | 6K Inc. | Unique feedstocks for spherical powders and methods of manufacturing |
| US11839919B2 (en) | 2015-12-16 | 2023-12-12 | 6K Inc. | Spheroidal dehydrogenated metals and metal alloy particles |
| US11855278B2 (en) | 2020-06-25 | 2023-12-26 | 6K, Inc. | Microcomposite alloy structure |
| US11919071B2 (en) | 2020-10-30 | 2024-03-05 | 6K Inc. | Systems and methods for synthesis of spheroidized metal powders |
| US11963287B2 (en) | 2020-09-24 | 2024-04-16 | 6K Inc. | Systems, devices, and methods for starting plasma |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600266A (en) * | 2015-01-09 | 2015-05-06 | 上海大学 | Method for preparing carbon fibre cloth loaded sulphur composite material |
| CN104900830A (en) * | 2015-06-29 | 2015-09-09 | 北京理工大学 | Lithium-sulfur battery with carbon fiber cloth as barrier layer |
| US11839919B2 (en) | 2015-12-16 | 2023-12-12 | 6K Inc. | Spheroidal dehydrogenated metals and metal alloy particles |
| CN108123167A (en) * | 2016-11-28 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of lithium-sulfur cell electrode and its preparation and the lithium-sulfur cell structure for including it |
| CN108123167B (en) * | 2016-11-28 | 2020-04-17 | 中国科学院大连化学物理研究所 | Electrode for lithium-sulfur battery, preparation method of electrode and lithium-sulfur battery structure comprising electrode |
| US11633785B2 (en) | 2019-04-30 | 2023-04-25 | 6K Inc. | Mechanically alloyed powder feedstock |
| CN110690398A (en) * | 2019-09-30 | 2020-01-14 | 上海大学 | Multifunctional composite diaphragm for high-temperature lithium-sulfur battery, and preparation method and application thereof |
| US11717886B2 (en) | 2019-11-18 | 2023-08-08 | 6K Inc. | Unique feedstocks for spherical powders and methods of manufacturing |
| US11590568B2 (en) | 2019-12-19 | 2023-02-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
| US11855278B2 (en) | 2020-06-25 | 2023-12-26 | 6K, Inc. | Microcomposite alloy structure |
| US11963287B2 (en) | 2020-09-24 | 2024-04-16 | 6K Inc. | Systems, devices, and methods for starting plasma |
| US11919071B2 (en) | 2020-10-30 | 2024-03-05 | 6K Inc. | Systems and methods for synthesis of spheroidized metal powders |
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