CN1262041C - Secondary lithium cell using sulfurized crosslinking PVC as cathode material - Google Patents
Secondary lithium cell using sulfurized crosslinking PVC as cathode material Download PDFInfo
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- CN1262041C CN1262041C CNB2004100188017A CN200410018801A CN1262041C CN 1262041 C CN1262041 C CN 1262041C CN B2004100188017 A CNB2004100188017 A CN B2004100188017A CN 200410018801 A CN200410018801 A CN 200410018801A CN 1262041 C CN1262041 C CN 1262041C
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- polyvinyl chloride
- cathode material
- vulcanization crosslinking
- crosslinking polyvinyl
- lithium battery
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- 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
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Abstract
The present invention discloses a secondary lithium cell using sulfurized crosslinking polyvinyl chloride as a cathode material and a preparation method thereof, which belongs to a technique of a serondary lithium cell. A cathode material of the secondary lithium cell comprises 60 to 70 wt% of sulfurized crosslinking polyvinyl chloride, 10 to 15 wt% of adhesive and 15 to 30 wt% of conductive agent. A polymer has the preparation method that after anhydrous sodium sulfide and sublimed sulfur are mixed, the mixture is dissolved into N, N-dimethyl formamide solvent to obtain a sodium polysulfide solution under agitation; polyvinyl chloride is dissolved into the N, N-dimethyl formamide solvent to obtain a polyvinyl chloride solution; the sodium polysulfide solution is dropped into the polyvinyl chloride solution to be agitated to obtain a sulfurized crosslinking polyvinyl chloride product, and the sulfurized crosslinking polyvinyl chloride product is dried to obtain a powdery product. A multisulfur linkage structure is grafted on a chain-shaped polymer framework by the cathode material of the secondary lithium cell provided by the present invention, and an S-S structure is fixed. The polysulphide has the advantages of no pollution in a synthetic process and low preparation cost. The polysulphide is used as the cathode material of the secondary lithium cell, and therefore, the secondary lithium cell has high energy density and good charging and discharging circulation performance.
Description
Technical field
The present invention relates to a kind ofly, belong to the serondary lithium battery technology with the serondary lithium battery and the preparation method of vulcanization crosslinking polyvinyl chloride as cathode material.
Background technology
In recent years, lithium ion battery becomes an important component part of field of chemical power source gradually, and the application potential in electric automobile environment-protecting clean dynamical system also makes increasing researcher join in the research to lithium ion battery.In lithium-ion battery system, the polysulfide cathode material is because with low cost, and energy density is high and become one of replacement candidate of existing cathode material, and is therefore very extensive to the research of polysulfide electrode material.Two phenothiazine polymer cathode materials (J.Electrochem.Soc., 1997,144 (6): L173) and in the lithium battery system obtained 270mAhg have been synthesized first in 1997 as Naoi
-1Specific discharge capacity, but because the preparation expensive raw material price of this class material, therefore the synthesis technique complexity is difficult to obtain practical application; Skotheim will gather carbon disulfide (PCS) electrode and be applied to serondary lithium battery and obtained discharge capacity and cycle performance (US Patent, 5460905) preferably, but the pollution that in the building-up process environment is produced also can not be ignored; Hyun KyungSung is that parent has synthesized sulfuration polybutadiene (SPB) anode material of lithium battery and obtained 325mAhg with the polybutadiene
-1Discharge capacity (US Patent, 6335118); Wang Jiulin adopts the method for high temperature (300 ℃～400 ℃) dehydrogenation sulfuration to realize the branching crosslinked (CN1339839A) of S-S structure on polymeric matrixs such as polyethylene glycol oxide, Kynoar, owing to constantly produce corrosive gas in the building-up process, to creating a great impression of environment and equipment, thereby make this route of synthesis have certain defective.In view of the existence of above problem, it is very necessary can finding the route of synthesis of environmental protection when realizing the polysulfide high-energy-density.
Summary of the invention
The object of the present invention is to provide that a kind of this serondary lithium battery has the energy density height with the serondary lithium battery and the preparation method of vulcanization crosslinking polyvinyl chloride as cathode material, the characteristics that cyclicity is good, the preparation process of battery cathode material is simply pollution-free.
The present invention is realized by following technical proposals: comprise the serondary lithium battery that is made of anode material, cathode material and electrolyte, described anode material is lithium metal, LiC
6Or lithium alloy.Described electrolyte is made of electrolyte and solvent, and wherein electrolyte is LiCF
3SO
3, LiN (CF
3SO
2)
2, LiBF
4, LiAsF
6Or LiClO
4Solvent is glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dioxolane, dioxane, oxolane, toluene or ortho-xylene, concentration is 1mol electrolyte/L solution, it is characterized in that the composition of cathode material and weight content percentage are:
Vulcanization crosslinking polyvinyl chloride: 60%～70%; The vulcanization crosslinking polyvinyl chloride is made of the repetitive shown in the following formula:
S in the formula
nBe the polysulfide bond structure, n=2～7; R
1, R
2Be hydrogen atom, any selection and the combination of alkyl or alkoxyl;
Adhesive: 10%～15%;
Electron conduction agent: 15%～30%.
Above-mentioned vulcanization crosslinking polyvinyl chloride is the tetrathio cross-linked polrvinyl chloride.
Above-mentioned adhesive is Kynoar, polytetrafluoroethylene, PVP, vinylidene fluoride-hexafluoropropylene copolymer, polyethylene glycol oxide or polyvinyl alcohol.
Described adhesive is polyethylene glycol oxide or polyvinyl alcohol.
Above-mentioned conductive agent is acetylene black, super carbon black, electrically conductive graphite, polyaniline or acetylene black-electrically conductive graphite mixture.
Described conductive agent is acetylene black-electrically conductive graphite mixture.
The preparation of above-mentioned serondary lithium battery comprises the preparation process and the assembling of anode material, cathode material, electrolyte, it is characterized in that the preparation of cathode material vulcanization crosslinking polyvinyl chloride comprises following process:
1. under inert gas shielding; with anhydrous sodium sulfide and sublimed sulfur according to 1: 1～1: 6 mixed in molar ratio after; standard according to the 230ml/mol sublimed sulfur adds quantitative N; dinethylformamide (DMF) solvent; then 20～30 ℃ stir 1～2 hour after elevated temperature to 60～70 ℃ and continue to stir 8～12 hours, obtain sodium polysulfide solution.
2. under inert gas shielding, with molecular weight M
wBe 2 * 10
4～2 * 10
6Polyvinyl chloride be dissolved in according to the standard of 1500ml/mol chlorine and obtain polyvinyl chloride solution among the DMF.
3. under inert gas shielding; under 80～100 ℃; according to Na: Cl=1: 1 ratio; sodium polysulfide solution is dripped in polyvinyl chloride solution; after stirring makes reaction carry out 16～24 hours; obtain the vulcanization crosslinking polyvinyl chloride product through washing, suction filtration, obtain powder product through 70～80 ℃ of vacuumizes after 24～48 hours again.
The invention has the advantages that: the cathode material of the serondary lithium battery that provides is that the polysulfide bond structure is grafted on the chain polymer skeleton, and the S-S structure is fixed.This polysulfides building-up process is pollution-free, and preparation cost is low, and with its serondary lithium battery energy density height as cathode material, charge-discharge performance is good.
Description of drawings
Fig. 1 is the first charge-discharge curve of the serondary lithium battery of cathode material for the vulcanization crosslinking polyvinyl chloride that is synthesized with embodiment 1.
Embodiment
Embodiment 1 is the serondary lithium battery preparation of cathode material with the tetrathio cross-linked polrvinyl chloride:
1. cathode material is synthetic
Take by weighing the mixing of 7.88g anhydrous sodium sulfide (99%) and 9.70g sublimed sulfur (99%) and be placed on 70mlN, in the dinethylformamide solvent, at room temperature stir after 1 hour rising reaction temperature to 62 ℃ and continue to stir 12 hours, stop to stir the back and keep temperature standby.
Take by weighing 12.51g polyvinyl chloride (Mw=2 * 10
5) and be dissolved in 300mlN, in the dinethylformamide solvent, obtain transparent settled solution, after this under 80 ℃, this solution is stirred and drips above-mentioned standby sodium polysulfide solution, the dropping process continues 1 hour, finish dripping the back 96 ℃ of lasting stirrings 18 hours, reddish brown precipitation appears in system, and reaction finishes.
Above-mentioned course of reaction is all finished under inert gas shielding.
The gained reactant system successively with acetone and deionized water wash and carry out decompress filter, is obtained the tetrathio polyvinyl chloride product, obtain the powdered electrode material after 24 hours through 80 ℃ of vacuumizes.
With the 350r/min rotating speed in stainless steel jar mill to polymeric material ball milling 12 hours, obtain average grain diameter at 10 other polymer powders of μ m level.
2. negative electrode preparation
Take by weighing polyethylene glycol oxide (Mw=2 * 10 according to 15: 25: 60 ratios
6), acetylene black～electrically conductive graphite mixture (mass ratio 1: 4) and synthetic polysulfide, after fully mixing under the deionized water peptizaiton, be coated on the Al collector, in 60 ℃ of vacuumizes 12 hours, obtain stand-by negative electrode pole piece.
3. battery testing
Selecting concentration for use is the LiN (CF of 1M
3SO
2)
2Glycol dimethyl ether～dioxolane～ortho-xylene (mass ratio 45: 50: 5) mixed solvent electrolyte as the electrolyte solution system of test battery.
As work electrode, lithium metal is as anode with prepared negative electrode pole piece, and above-mentioned solution is as electrolyte, and to carrying out charge-discharge test by tetrathio polyvinyl chloride cathode material as the serondary lithium battery of negative electrode, current density is 30mAg
-1, voltage range 1.6V～3.0V.Test battery obtains 301.3mAhg respectively
-1And 281.1mAhg
-1Discharge first and charging capacity, efficiency for charge-discharge is 93.3%.
Claims (7)
1. one kind is the serondary lithium battery of cathode material with the vulcanization crosslinking polyvinyl chloride, comprises by anode material, cathode material and electrolyte constituting, and described anode material is lithium metal, LiC
6Or lithium alloy; Described electrolyte is made of electrolyte and solvent, and wherein electrolyte is LiCF
3SO
3, LiN (CF
3SO
2)
2, LiBF
4, LiAsF
6Or LiClO
4Solvent is glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dioxolane, dioxane, oxolane, toluene or ortho-xylene, and concentration is 1mol electrolyte/L solution; It is characterized in that the composition of cathode material and weight content percentage are:
Vulcanization crosslinking polyvinyl chloride: 60%～70%; The vulcanization crosslinking polyvinyl chloride is made of the repetitive shown in the following formula:
S in the formula
nBe the polysulfide bond structure, n=2～7; R
1, R
2Be hydrogen atom, any selection and the combination of alkyl or alkoxyl;
Adhesive: 10%～15%;
Electron conduction agent: 15%～30%.
2. described by claim 1 is the serondary lithium battery of cathode material with the vulcanization crosslinking polyvinyl chloride, it is characterized in that the vulcanization crosslinking polyvinyl chloride is the tetrathio cross-linked polrvinyl chloride.
3. described by claim 1 is the serondary lithium battery of cathode material with the vulcanization crosslinking polyvinyl chloride, it is characterized in that adhesive is Kynoar, polytetrafluoroethylene, PVP, vinylidene fluoride-hexafluoropropylene copolymer, polyethylene glycol oxide or polyvinyl alcohol.
4. described by claim 3 is the serondary lithium battery of cathode material with the vulcanization crosslinking polyvinyl chloride, it is characterized in that adhesive is polyethylene glycol oxide or polyvinyl alcohol.
5. described by claim 1 is the serondary lithium battery of cathode material with the vulcanization crosslinking polyvinyl chloride, it is characterized in that, conductive agent is acetylene black, super carbon black, electrically conductive graphite, polyaniline or acetylene black-electrically conductive graphite mixture.
6. described by claim 5 is the serondary lithium battery of cathode material with the vulcanization crosslinking polyvinyl chloride, it is characterized in that, conductive agent is acetylene black-electrically conductive graphite mixture.
One kind to prepare described by claim 1 be the serondary lithium battery method of cathode material with the vulcanization crosslinking polyvinyl chloride, comprise the preparation process and the assembling of anode material, cathode material, electrolyte, it is characterized in that the preparation of cathode material vulcanization crosslinking polyvinyl chloride comprises following process:
(1) under inert gas shielding, with anhydrous sodium sulfide and sublimed sulfur according to 1: 1～1: 6 mixed in molar ratio after, standard according to the 230ml/mol sublimed sulfur adds quantitative N, the dinethylformamide solvent, then 20～30 ℃ stir 1～2 hour after elevated temperature to 60～70 ℃ and continue to stir 8～12 hours, obtain sodium polysulfide solution;
(2) under inert gas shielding, with molecular weight M
wBe 2 * 10
4～2 * 10
6Polyvinyl chloride be dissolved in N according to the standard of 1500ml/mol chlorine, obtain polyvinyl chloride solution in the dinethylformamide;
(3) under inert gas shielding; under 80～100 ℃; according to Na: Cl=1: 1 ratio; sodium polysulfide solution is dripped in polyvinyl chloride solution; after stirring makes reaction carry out 16～24 hours; obtain the vulcanization crosslinking polyvinyl chloride product through washing, suction filtration, obtain powder product through 70～80 ℃ of vacuumizes after 24～48 hours again.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100188017A CN1262041C (en) | 2004-03-29 | 2004-03-29 | Secondary lithium cell using sulfurized crosslinking PVC as cathode material |
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|---|---|---|---|
| CNB2004100188017A CN1262041C (en) | 2004-03-29 | 2004-03-29 | Secondary lithium cell using sulfurized crosslinking PVC as cathode material |
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|---|---|
| CN1564369A CN1564369A (en) | 2005-01-12 |
| CN1262041C true CN1262041C (en) | 2006-06-28 |
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| CN100376608C (en) * | 2005-12-13 | 2008-03-26 | 西北核技术研究所 | Production of positive material of lithium battery |
| CN103413976B (en) * | 2013-08-23 | 2015-04-15 | 天能集团江苏科技有限公司 | High-performance power accumulator and preparation method thereof |
| CN109251512A (en) * | 2018-09-17 | 2019-01-22 | 佛山市禅城区诺高环保科技有限公司 | A kind of long-acting weather-proof flame retarded rigid polyurethane foams |
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