CN102867940B - Process for preparing lithium sulfur battery modified anode - Google Patents

Process for preparing lithium sulfur battery modified anode Download PDF

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CN102867940B
CN102867940B CN201210385899.4A CN201210385899A CN102867940B CN 102867940 B CN102867940 B CN 102867940B CN 201210385899 A CN201210385899 A CN 201210385899A CN 102867940 B CN102867940 B CN 102867940B
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fiber cloth
lithium
cloth matrix
hollow nickel
battery
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CN102867940A (en
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王传新
谢秋实
汪建华
王升高
谢海鸥
晏倩
王子行
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Wuhan Institute of Technology
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10Energy storage using batteries

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Abstract

The invention relates to a preparation for a lithium sulfur battery modified anode material. The preparation includes mixing sublimed sulfur and a conductive agent according to a mass ratio of 6:3, adding absolute ethyl alcohol, performing ball milling for 6 hours, drying in a vacuum drying box for 12 hours at the temperature of 50 DEG C to 80 DEG C to obtain a mixture, mixing the mixture and hollow nickel fiber tubes according to a mass ratio of (5-9):1, adding an adhesive, dispersing in a dispersing agent, stirring to obtain slurry, coating the slurry on a metal aluminum foil which is subjected to acetone ultrasonic cleaning, and drying in the vacuum drying box for 12 hours at the temperature of 60 DEG C to obtain the lithium sulfur battery anode material. The preparation for the lithium sulfur battery modified anode material has the advantages that electrochemistry performances of battery cyclicity and the like are improved, and the performances and cyclic service life of the battery can be improved.

Description

A kind of technique of lithium-sulfur cell modification positive pole
Technical field
The invention belongs to field of electrochemical batteries, particularly a kind of preparation of lithium battery modified anode material.
Background technology
Elemental sulfur has high specific capacity as positive electrode, at a low price, the advantage such as low toxicity.The theoretical specific capacity of elemental sulfur is 1675mAh/g, and theoretical specific energy is 2600Wh/kg, is the positive electrode (LiCoO understood at present 2, LiNiO 2, LiMn 2o 4theoretical specific capacity is respectively 275mAh/g, 274mAh/g, 148mAh/g) in specific capacity the highest, being far longer than present stage business-like lithium secondary battery, is a kind of positive electrode with broad prospect of application.
But electro-chemical activity and the cyclical stability of sulphur are poor, limit its business-like practical application.Sulphur is that (conductivity when 25 DEG C is 5 × 10 for electronics and ion insulator -30scm -1), cause its electro-chemical activity low.And the polysulfide that battery produces in charge and discharge process is soluble in electrolyte, thus cause a large amount of irreversible loss of positive active material, reduce the capacity of battery.Meanwhile, " effect of shuttling back and forth " of solubility polysulfide and insoluble lithium sulfide, in the attachment of electrode surface, stop the carrying out of electrochemical reaction, cause the cyclical stability of battery to be decayed.
In order to solve the problem, researcher has carried out a large amount of trial experiments.The people such as Nazar (J. Nature Material, 2009,8:500-506) sulphur is filled in the CMK-3 with regular nanometer central hole structure, the nano-contact that elemental sulfur is good with conduction charcoal wall, enhance the conductivity of elemental sulfur, thus improve the chemical properties such as the cyclicity of battery.On this basis, the people such as Yi (J.ACS, 2011,5 (11): 9187-9193) conducting polymer is used to carry out coated to CMK-3, preparation polymer overmold CMK-3/S composite electrode, utilize the good conductivity of conducting polymer and to the absorption of polysulfide to improve the performances such as the specific capacity of battery and cyclicity.Although above method can improve the chemical property of lithium-sulfur cell to a certain extent, its electrochemistry such as specific discharge capacity and cyclicity also has a segment distance from commercialization, improvement of still needing.
Summary of the invention
Technical problem to be solved by this invention is the technique providing a kind of lithium-sulfur cell modification positive pole for above-mentioned prior art, the conductivity utilizing hollow nickel fibre pipe excellent and it is to the good adsorption of the fixing of sulphur and polysulfide, reduce the irreversible loss of active material, improve its utilance, thus improve the cycle performance of lithium sulfur battery anode material, solve the problem of lithium-sulfur cell cyclical stability difference.
The solution that the problem that the present invention is the above-mentioned proposition of solution adopts is: a kind of technique of lithium-sulfur cell modification positive pole, it includes following steps: by sublimed sulfur: the mass ratio=6:3 mixing of conductive agent, add absolute ethyl alcohol, ball milling 6h, at 50 ~ 80 DEG C of dry 12h in vacuum drying chamber, mixture and the hollow nickel fibre pipe of gained are that 5 ~ 9:1 mixes in mass ratio, and add binding agent and be scattered in together in dispersant, stir, then slurry is obtained, be coated on the metal aluminum foil of acetone ultrasonic cleaning, 60 DEG C of dry 12h in vacuum drying chamber, obtain lithium sulfur battery anode material.
By such scheme, the preparation method of hollow nickel fibre pipe is:
A) preliminary treatment of fiber cloth matrix: fiber cloth matrix is placed in acetone ultrasonic process 5min, then with being the H of 1:4 by volume 2o 2and H 2sO 4mixed solution alligatoring 2min is carried out to fiber cloth matrix, then use washed with de-ionized water, obtain pretreated fiber cloth matrix;
B) no-palladium activating: it is the NiSO of 40 ~ 60g/L that above-mentioned pretreated fiber cloth matrix is immersed concentration 4with in mass percent concentration 6 ~ 8%HCl mixed solution, take out after 10min, be filtered dry a little, and then to put it into mass percent concentration be 3%NaOH and concentration is 20g/LKBH 4activate in mixed solution, take out after 20s, be filtered dry a little, obtain the fiber cloth matrix activated;
C) chemical nickel plating: the fiber cloth matrix through overactivation is put into chemical plating fluid and carries out chemical plating, temperature is 88 DEG C, time 15min, obtains Ni/ fiber cloth composite fibre;
D) heat treatment of composite fibre: Ni/ fiber cloth composite fibre is placed in tube furnace heat treatment, and its heat treatment temperature is: first 450 DEG C of process 2h, then 650 DEG C of process 3h, obtain hollow nickel oxide pipe;
E) microwave plasma H reduces: hollow nickel oxide pipe step d) obtained is placed in microwave plasma H and reduces, and microwave power is 400 ~ 500W, after recovery time 15 ~ 20min, obtains hollow nickel fibre pipe.
By such scheme, described conductive agent is amorphous carbon or crystalline state carbon.
By such scheme, described binding agent is aqueous binders LA132 or PEO or beta-schardinger dextrin-.
By such scheme, described dispersant is ethanol or DMF or water.
Beneficial effect of the present invention is: (when 20 DEG C, conductivity is 1.54 × 10 to the excellent conductivity of hollow nickel fibre pipe of the present invention 7s), good conducting matrix grain can be provided as positive electrode, the conductivity of sulfur-bearing positive pole can be strengthened; Its large specific area of hollow nickel fiber can suppress insulation product Li 2s and Li 2s 2gathering at electrode surface, is conducive to the improvement of electrode conductivuty; Hollow nickel fibre pipe is formed simultaneously " micro-container " can fix sulphur and absorption suppresses the polysulfide produced in charge and discharge process to be dissolved in electrolyte, weaken its diffusion with electrolyte, weaken " effect of shuttling back and forth ", reduce the irreversible loss of active material, improve the utilance of sulphur, thus improve the chemical properties such as the cyclicity of battery, improve performance and the cycle life of battery.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but can not be interpreted as limitation of the invention.
Embodiment 1:
By sublimed sulfur: the mass ratio=6:3 mixing of amorphous carbon acetylene black, adds absolute ethyl alcohol, ball milling 6h, at 60 DEG C of dry 12h in vacuum drying chamber, for subsequent use.By above-mentioned obtained mixture and hollow nickel fibre pipe in mass ratio for 5:1 is dispersed in the mixed solution of LA32 aqueous binder and absolute ethyl alcohol, stir, obtained slurry is also coated on the metal aluminum foil of acetone ultrasonic cleaning, in vacuum drying chamber, 60 DEG C of dry 12h, obtain lithium sulfur battery anode material.
The preparation method of described hollow nickel fibre pipe is:
A) preliminary treatment of fiber cloth matrix: fiber cloth matrix is placed in acetone ultrasonic process 5min, then with being the H of 1:4 by volume 2o 2and H 2sO 4mixed solution alligatoring 2min is carried out to fiber cloth matrix, then use washed with de-ionized water, obtain pretreated fiber cloth matrix;
B) no-palladium activating: to immerse concentration through pretreated fiber cloth matrix be the NiSO of 40g/L by above-mentioned 4be in 6%HCl mixed solution with mass percent concentration, take out after 10min, be filtered dry a little, and then to put it into mass percent concentration be 3%NaOH and concentration is 20g/LKBH 4activate in mixed solution, take out after 20s, be filtered dry a little, obtain the fiber cloth matrix after activating;
C) chemical nickel plating: (adopt conventional chemical plating fluid, main component is concentration 24g/LNiSO the fiber cloth matrix through overactivation to be put into chemical plating fluid 4, 30g/LNaH 2pO 2, 20g/LNa 3c 6h 5o 7and portions additive, complex compound) in carry out chemical plating, temperature is 88 DEG C, time 15min, obtains Ni/ fiber cloth composite fibre;
D) heat treatment of composite fibre: Ni/ fiber cloth composite fibre is placed in tube furnace heat treatment, and its heat treatment temperature is: first 450 DEG C of process 2h, then 650 DEG C of process 3h, obtain hollow nickel oxide pipe;
E) microwave plasma H reduces: hollow nickel oxide pipe step d) obtained is placed in microwave plasma H and reduces, and microwave power is 400W, after recovery time 20min, obtains hollow nickel fibre pipe.
With the electrode of above-mentioned preparation for positive pole, take metal lithium sheet as negative pole, electrolyte adopts the LiClO of 1mol/L 4/ (DOL+DME) (1,3-dioxolanes+glycol dimethyl ether, both volume ratios are 1:1), barrier film is Celgard2320 type polypropylene screen, in argon gas atmosphere glove box, being assembled into CR2025 type button cell, in order to characterize the chemical property of the lithium-sulphur cell positive electrode prepared, the battery assembled being carried out charge-discharge test on the electric battery test system of indigo plant, discharge and recharge interval is 1.5-3.0V, and charging and discharging currents density is 0.2mA/cm 2.First discharge specific capacity is 941.9mAh/g, and the specific capacity after charge and discharge cycles 20 times is 630mAh/g, demonstrates higher capacity and good circulation stability.
Embodiment 2:
By sublimed sulfur: the mass ratio=6:3 mixing of amorphous carbon activated carbon, adds absolute ethyl alcohol, ball milling 6h, at 70 DEG C of dry 12h in vacuum drying chamber, for subsequent use.By above-mentioned obtained mixture and nickel fibre pipe in mass ratio for 6:1 is dispersed in the mixed solution of PEO (Pluronic F-127) and DMF (dimethyl formamide), stir, obtained slurry is also coated on the metal aluminum foil of acetone ultrasonic cleaning, in vacuum drying chamber, dry 12h, obtains lithium sulfur battery anode material.
The preparation method of described hollow nickel fibre pipe is:
A) preliminary treatment of fiber cloth matrix: fiber cloth matrix is placed in acetone ultrasonic process 5min, then with being the H of 1:4 by volume 2o 2and H 2sO 4mixed solution alligatoring 2min is carried out to fiber cloth matrix, then use washed with de-ionized water, obtain pretreated fiber cloth matrix;
B) no-palladium activating: to immerse concentration through pretreated fiber cloth matrix be the NiSO of 55g/L by above-mentioned 4be in 7%HCl mixed solution with mass percent concentration, take out after 10min, be filtered dry a little, and then to put it into mass percent concentration be 3%NaOH and concentration is 20g/LKBH 4activate in mixed solution, take out after 20s, be filtered dry a little, obtain the fiber cloth matrix activated;
C) chemical nickel plating: (adopt conventional chemical plating fluid, main component is concentration 24g/LNiSO the fiber cloth matrix through overactivation to be put into chemical plating fluid 4, 30g/LNaH 2pO 2, 20g/LNa 3c 6h 5o 7and portions additive, complex compound) in carry out chemical plating, temperature is 88 DEG C, time 15min, obtains Ni/ fiber cloth composite fibre;
D) heat treatment of composite fibre: Ni/ fiber cloth composite fibre is placed in tube furnace heat treatment, and its heat treatment temperature is: first 450 DEG C of process 2h, then 650 DEG C of process 3h, obtain hollow nickel oxide pipe;
E) microwave plasma H reduces: hollow nickel oxide pipe step d) obtained is placed in microwave plasma H and reduces, and microwave power is 450W, after recovery time 15min, obtains hollow nickel fibre pipe.
With the electrode of above-mentioned preparation for positive pole, take metal lithium sheet as negative pole, electrolyte adopts the LiClO of 1mol/L 4/ (DOL+DME) (1,3-dioxolanes+glycol dimethyl ether, both volume ratios are 1:1), barrier film is Celgard2320 type polypropylene screen, in argon gas atmosphere glove box, being assembled into CR2025 type button cell, in order to characterize the chemical property of the lithium-sulphur cell positive electrode prepared, the battery assembled being carried out charge-discharge test on the electric battery test system of indigo plant, discharge and recharge interval is 1.5-3.0V, and charging and discharging currents density is 0.2mA/cm 2.First discharge specific capacity is 1093.7mAh/g, and the specific capacity after charge and discharge cycles 20 times is 801.5mAh/g, demonstrates higher capacity and good circulation stability.
Embodiment 3:
By sublimed sulfur: the mass ratio=6:3 mixing of crystalline state carbon graphite carbon, adds absolute ethyl alcohol, ball milling 6h, at 80 DEG C of dry 12h in vacuum drying chamber, for subsequent use.By above-mentioned obtained mixture and nickel fibre pipe in mass ratio for 9:1 is dispersed in the beta-schardinger dextrin-aqueous solution, stir, obtained slurry is also coated on the metal aluminum foil of acetone ultrasonic cleaning, and in vacuum drying chamber, dry 12h, obtains lithium sulfur battery anode material.
The preparation method of hollow nickel fibre pipe is:
A) preliminary treatment of fiber cloth matrix: fiber cloth matrix is placed in acetone ultrasonic process 5min, then with being the H of 1:4 by volume 2o 2and H 2sO 4mixed solution alligatoring 2min is carried out to fiber cloth matrix, then use washed with de-ionized water, obtain pretreated fiber cloth matrix;
B) no-palladium activating: to immerse concentration through pretreated fiber cloth matrix be the NiSO of 60g/L by above-mentioned 4be in 8%HCl mixed solution with mass percent concentration, take out after 10min, be filtered dry a little, and then to put it into mass percent concentration be 3%NaOH and concentration is 20g/LKBH 4activate in mixed solution, take out after 20s, be filtered dry a little, obtain the fiber cloth matrix activated;
C) chemical nickel plating: (adopt conventional chemical plating fluid, main component is concentration 24g/LNiSO the fiber cloth matrix through overactivation to be put into chemical plating fluid 4, 30g/LNaH 2pO 2, 20g/LNa 3c 6h 5o 7and portions additive, complex compound) in carry out chemical plating, temperature is 88 DEG C, time 15min, obtains Ni/ fiber cloth composite fibre;
D) heat treatment of composite fibre: Ni/ fiber cloth composite fibre is placed in tube furnace heat treatment, and its heat treatment temperature is: first 450 DEG C of process 2h, then 650 DEG C of process 3h, obtain hollow nickel oxide pipe;
E) microwave plasma H reduces: hollow nickel oxide pipe step d) obtained is placed in microwave plasma H and reduces, and microwave power is 500W, after recovery time 17min, obtains hollow nickel fibre pipe.
With the electrode of above-mentioned preparation for positive pole, take metal lithium sheet as negative pole, electrolyte adopts the LiClO of 1mol/L 4/ (DOL+DME) (1,3-dioxolanes+glycol dimethyl ether, both volume ratios are 1:1), barrier film is Celgard2320 type polypropylene screen, in argon gas atmosphere glove box, being assembled into CR2025 type button cell, in order to characterize the chemical property of the lithium-sulphur cell positive electrode prepared, the battery assembled being carried out charge-discharge test on the electric battery test system of indigo plant, discharge and recharge interval is 1.5-3.0V, and charging and discharging currents density is 0.2mA/cm 2.First discharge specific capacity is 1002.7mAh/g, and the specific capacity after charge and discharge cycles 20 times is 723.6mAh/g, demonstrates higher capacity and good circulation stability.

Claims (4)

1. the technique of a lithium-sulfur cell modification positive pole, it includes following steps: by sublimed sulfur: the mass ratio=6:3 mixing of conductive agent, add absolute ethyl alcohol, ball milling 6h, at 50 ~ 80 DEG C of dry 12h in vacuum drying chamber, mixture and the hollow nickel fibre pipe of gained are that 5 ~ 9:1 mixes in mass ratio, and add binding agent and be scattered in together in dispersant, stir, then slurry is obtained, be coated on the metal aluminum foil of acetone ultrasonic cleaning, 60 DEG C of dry 12h in vacuum drying chamber, obtain lithium sulfur battery anode material, the preparation method of described hollow nickel fibre pipe is:
A) preliminary treatment of fiber cloth matrix: fiber cloth matrix is placed in acetone ultrasonic process 5min, then with being the H of 1:4 by volume 2o 2and H 2sO 4mixed solution alligatoring 2min is carried out to fiber cloth matrix, then use washed with de-ionized water, obtain pretreated fiber cloth matrix;
B) no-palladium activating: it is the NiSO of 40 ~ 60g/L that above-mentioned pretreated fiber cloth matrix is immersed concentration 4with in mass percent concentration 6 ~ 8%HCl mixed solution, take out after 10min, be filtered dry a little, and then to put it into mass percent concentration be 3%NaOH and concentration is 20g/LKBH 4activate in mixed solution, take out after 20s, be filtered dry a little, obtain the fiber cloth matrix activated;
C) chemical nickel plating: the fiber cloth matrix through overactivation is put into chemical plating fluid and carries out chemical plating, temperature is 88 DEG C, time 15min, obtains Ni/ fiber cloth composite fibre;
D) heat treatment of composite fibre: Ni/ fiber cloth composite fibre is placed in tube furnace heat treatment, and its heat treatment temperature is: first 450 DEG C of process 2h, then 650 DEG C of process 3h, obtain hollow nickel oxide pipe;
E) microwave plasma H reduces: hollow nickel oxide pipe step d) obtained is placed in microwave plasma H and reduces, and microwave power is 400 ~ 500W, after recovery time 15 ~ 20min, obtains hollow nickel fibre pipe.
2., by the technique of lithium-sulfur cell modification positive pole according to claim 1, it is characterized in that described conductive agent is amorphous carbon or crystalline state carbon.
3., by the technique of lithium-sulfur cell modification positive pole according to claim 1, it is characterized in that described binding agent is aqueous binders LA132 or PEO or beta-schardinger dextrin-.
4., by the technique of lithium-sulfur cell modification positive pole according to claim 1, it is characterized in that described dispersant is ethanol or DMF or water.
CN201210385899.4A 2012-10-12 2012-10-12 Process for preparing lithium sulfur battery modified anode Expired - Fee Related CN102867940B (en)

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CN103326003A (en) * 2013-06-08 2013-09-25 苏州诺信创新能源有限公司 Preparation method of nickel fiber tube used in lithium-sulfur battery
CN103469562B (en) * 2013-09-22 2015-05-13 武汉纺织大学 Preparation method of fabric surface by employing atomizing chemical plating
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CN110931737B (en) * 2019-11-19 2021-04-09 宁波大学 Positive electrode material of lithium-sulfur battery
US11590568B2 (en) 2019-12-19 2023-02-28 6K Inc. Process for producing spheroidized powder from feedstock materials
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