CN1564348A - Secondary lithium cell using aminobenzene-benzoquinone composite polymer as cathode materal and prepn. thereof - Google Patents
Secondary lithium cell using aminobenzene-benzoquinone composite polymer as cathode materal and prepn. thereof Download PDFInfo
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- CN1564348A CN1564348A CNA2004100188002A CN200410018800A CN1564348A CN 1564348 A CN1564348 A CN 1564348A CN A2004100188002 A CNA2004100188002 A CN A2004100188002A CN 200410018800 A CN200410018800 A CN 200410018800A CN 1564348 A CN1564348 A CN 1564348A
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- aniline
- benzoquinones
- cathode material
- lithium battery
- composition polymer
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
Weight percent of components of cathode material is as following: anilin-benzoquinone composite polymer 65-75%, adhesive 5-15% and conduction agent 15-25%; Steps for preparing anilin-benzoquinone composite polymer are as following: according to mol ratio, dissolving benzoquinone, H+, H2O2, (NH4)2S2O8 into acetonitrile; reaction is carried out under protection of inert gases; deposited matter in brownish black color is obtained after washing reactant by using acetonitrile and deionized water; drying deposited matter obtains composite polymer needed. Advantages are: there is composite structure of electronic conduction framework + electrochemical oxidation-reduction functional group in same molecule. Thus the invention ensures both of energy density and cycle performance. Features are simple composite procedure, no pollution, and good cycle 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 aniline-benzoquinones composition polymer as cathode material.
Background technology
Step into 21 century, mobile electronic equipment is more and more important to people's routine work and life, thereby increased in the worldwide demand to secondary cell, extra small in order to adapt to, ultra-thin, ultralight equipment is to the specific (special) requirements of energy source, and the serondary lithium battery that has powerful advantages aspect energy density is subjected to extensive attention.
In the research field of serondary lithium battery, the polymer electrode material has crucial status, and since the nineties, people attempt electronic conductive polymer, sulphur, organic sulfur compound and polysulfide gradually as the serondary lithium battery cathode material.S A Chen obtains having 221WhKg by admixture lithium salts in polyaniline electrode in United States Patent (USP) 5849045 and 5863454
-1Serondary lithium battery with 91% average coulombic efficiency; DMarmortein use polymer dielectric has obtained the lithium-sulfur cell (J.Power Sources 2000,89:219～226) of discharge capacity near theoretical value 90～100 ℃ temperature range; People such as Skotheim also describe the synthetic method and the serviceability of the polysulfide cathode material of multiple different structure in detail in United States Patent (USP) 5460905,5441831,5601947 and 5690702.But the electronic conductive polymer energy density is lower, compare with other inorganic electrode materials not have clear superiority, and the cycle performance of sulphur and (gathering) sulfide electrode material haves much room for improvement, and therefore presses for polymer electrode is optimized.
Similar with the sulfur electrode performance, benzoquinones also is that a class has the electrochemical redox activity but the relatively poor organic compound of electric conductivity, consider the performance characteristics of itself, polyaniline powder and benzoquinones blend that T Nishihiyama mixes the p-type in United States Patent (USP) 6248474, use as the serondary lithium battery cathode active material, make the benzoquinones performance obtain to a certain degree improvement.But because the two is difficult to reach the even mixing of molecular level, therefore compare with above-mentioned electrode material on the battery serviceability, advantage is also not obvious.
Summary of the invention
The object of the present invention is to provide a kind ofly with serondary lithium battery and the preparation method of aniline-benzoquinones composition polymer as cathode material, this serondary lithium battery has the characteristics of the high and good cycle of energy density, and its preparation process 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), LiPF
6, LiBF
4, LiAsF
6Or LiClO
4, solvent is ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate or 1, the 4-butyrolactone, and the concentration of electrolyte is 1 mole of solute/L solution.It is characterized in that the component of cathode material and weight content percentage thereof are:
Aniline-benzoquinones composition polymer: 65%～75%
Adhesive: 5%～15%
Electron conduction agent: 15%～25%
Described aniline-benzoquinones composition polymer is made of constitutional repeating unit shown in formula 1, formula 2 or the formula 3:
R is a hydrogen atom in the formula, any selection and the combination of alkyl or alkoxyl.
Described adhesive is polytetrafluoroethylene, polyethylene glycol oxide, Kynoar, polyvinyl alcohol or hexafluoropropylene-vinylidene fluoride copolymers;
Above-mentioned adhesive is a polytetrafluoroethylene.
Described electron conduction agent is acetylene black, electrically conductive graphite, super carbon black or polyaniline;
Above-mentioned electron conduction agent is an acetylene black.
The preparation of above-mentioned serondary lithium battery comprises the preparation and the assembling of anode material, cathode material and electrolyte, it is characterized in that, the preparation of aniline in the cathode material-benzoquinones composition polymer comprises following process:
1 according to aniline unit: H
+: H
2O
2: (NH
4)
2S
2O
8=1: 1: 1: 1 molar ratio takes by weighing aniline-benzoquinones complex chemical compound, Bronsted acid, H respectively
2O
2And (NH
4)
2S
2O
8After, above-mentioned substance is mixed in acetonitrile.
2 under nitrogen or argon shield condition in-5 ℃～5 ℃ stirring reactions 18～36 hours.
Use acetonitrile and deionized water wash gained brownish black sediment successively after 3 reactions finish, obtain the serondary lithium battery cathode material of aniline-benzoquinones composition polymer again through 60～70 ℃ of forced air dryings 1～2 hour and 70～80 ℃ of vacuumize after 12～18 hours.
The invention has the advantages that, the serondary lithium battery cathode material that is provided, has structural advantage, the composite construction that in same molecule, has electron conduction skeleton+electrochemical redox functional group, effectively improved the inner conductive performance of material molecule, thereby guaranteed that when guaranteeing metric density electrode has excellent cycle performance.Its building-up process is simply pollution-free, the energy density height; The serondary lithium battery that is provided, cost is low, the efficiency for charge-discharge height, circulation ability is strong, has good actual application prospect.
Description of drawings
Fig. 1 is the discharge curve first of the serondary lithium battery of the cathode material manufacturing of synthesize with embodiment 1.
Fig. 2 is the cycle performance schematic diagram with the serondary lithium battery of 1 composite cathode made of embodiment.
Fig. 3 is the discharge curve first of the serondary lithium battery of the cathode material manufacturing of synthesize with embodiment 2.
Fig. 4 is the cycle performance schematic diagram of the serondary lithium battery of the cathode material manufacturing of synthesize with embodiment 2.
Embodiment
1. the poly-1-aminoanthraquinone cathode material is synthetic
Take by weighing the HClO of 1.435g concentration 70%
4The aqueous solution, 2.280g (NH
4)
2S
2O
8, 1.133g concentration 30% H
2O
2Saturated aqueous solution and 2.230g1-amino anthraquinones; after above-mentioned material mixed in acetonitrile; in argon shield; react 24h under the magnetic agitation condition; control reaction temperature is 0 ℃; after finishing, reaction, behind 60 ℃ of forced air drying 2h, 80 ℃ of vacuumize 12h, obtains the poly-1-aminoanthraquinone cathode material successively with acetonitrile and deionized water wash gained brownish black precipitation.
2. negative electrode is made
Take by weighing poly-1-aminoanthraquinone, acetylene black and polytetrafluoroethylene (60% water serial emulsion) according to 70: 20: 10 mass percents, above-mentioned substance is mixed in the alcohol dispersant, through ultrasonic, on tablet press machine, be pressed on aluminum foil current collector after stirring with 2MPa pressure, behind 80 ℃ of vacuumize 12h, obtain stand-by negative electrode pole piece.
3. battery testing
As reference electrode with to electrode, above-mentioned pole piece is a work electrode with lithium metal, selects for use the Celgard2400 barrier film at 1MoLL
-1LiPF
6In/ethylene carbonate-divinyl carbonate (volume ratio 1: the 1) electrolyte with 30mAg
-1Current density is carried out charge-discharge test, and charging/discharging voltage scope 1.5～3.5V circulates 25 times.The discharge capacity first that experiment showed, 1-amino anthraquinones polymer cathode material reaches 249mAhg
-1, through after 25 charge and discharge cycles, coulombic efficiency still remains on more than 80%.
Embodiment 2
1. poly-1,5-two-amino anthraquinones cathode material synthetic
Composition polymer monomer in the present embodiment is selected 1 of 1.190g for use, the 5-diamino-anthraquinone, and the building-up process of its polymer is identical with embodiment 1 with other amounts of components.
2. negative electrode is made and battery testing
The negative electrode manufacture craft is identical with embodiment 1 with the battery testing condition.Experiment showed, and gather 1, the discharge capacity first of 5-diamino-anthraquinone cathode material reaches 210.3mAhg
-1,, still can keep the initial discharge capacity more than 75% through after 30 charge and discharge cycles.
Claims (7)
1. one kind with the serondary lithium battery of aniline-benzoquinones composition polymer as cathode material, 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), LiPF
6, LiBF
4, LiAsF
6Or LiClO
4Solvent is ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate or 1, the 4-butyrolactone, and the concentration of electrolyte is 1 mole of solute/L solution, it is characterized in that: the component of cathode material and weight content percentage thereof are:
Aniline-benzoquinones composition polymer: 65%～75%
Adhesive: 5%～15%
Electron conduction agent: 15%～25%
2. described with the serondary lithium battery of aniline-benzoquinones composition polymer as cathode material by claim 1, it is characterized in that: aniline-benzoquinones composition polymer is made of constitutional repeating unit shown in formula 1, formula 2 or the formula 3:
R is a hydrogen atom in the formula, any selection and the combination of alkyl or alkoxyl.
3. described with the serondary lithium battery of aniline-benzoquinones composition polymer as cathode material by claim 1, it is characterized in that: adhesive is polytetrafluoroethylene, polyethylene glycol oxide, Kynoar, polyvinyl alcohol or hexafluoropropylene-vinylidene fluoride copolymers.
4. described with the serondary lithium battery of aniline-benzoquinones composition polymer as cathode material by claim 1, it is characterized in that: the electron conduction agent is acetylene black, electrically conductive graphite, super carbon black or polyaniline.
5. described with the serondary lithium battery of aniline-benzoquinones composition polymer as cathode material by claim 3, it is characterized in that: adhesive is a polytetrafluoroethylene.
6. described with the serondary lithium battery of aniline-benzoquinones composition polymer as cathode material by claim 4, it is characterized in that: the electron conduction agent is an acetylene black.
7. one kind prepares by claim 1 described with the serondary lithium battery method of aniline-benzoquinones composition polymer as cathode material, comprise the preparation and the assembling of anode material, cathode material and electrolyte, it is characterized in that: the preparation of aniline in the cathode material-benzoquinones composition polymer comprises following process:
(1) according to aniline unit: H
+: H
2O
2: (NH
4)
2S
2O
8=1: 1: 1: 1 molar ratio takes by weighing aniline-benzoquinones complex chemical compound, Bronsted acid, H respectively
2O
2And (NH
4)
2S
2O
8After, above-mentioned substance is mixed in acetonitrile;
(2) under nitrogen or argon shield condition in-5 ℃～5 ℃ stirring reactions 18～36 hours;
(3) use acetonitrile and deionized water wash gained brownish black sediment successively after reaction finishes, obtain the serondary lithium battery cathode material of aniline-benzoquinones composition polymer again through 60～70 ℃ of forced air dryings 1～2 hour and 70～80 ℃ of vacuumize after 12～18 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100188002A CN1564348A (en) | 2004-03-29 | 2004-03-29 | Secondary lithium cell using aminobenzene-benzoquinone composite polymer as cathode materal and prepn. thereof |
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|---|---|---|---|
| CNA2004100188002A CN1564348A (en) | 2004-03-29 | 2004-03-29 | Secondary lithium cell using aminobenzene-benzoquinone composite polymer as cathode materal and prepn. thereof |
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|---|---|
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|---|---|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411231C (en) * | 2006-07-20 | 2008-08-13 | 复旦大学 | Lithium ion battery with pyridyl quinone derivative as negative pole material |
| CN102598374A (en) * | 2009-11-12 | 2012-07-18 | 独立行政法人产业技术综合研究所 | Positive electrode active material for nonaqueous secondary battery |
| CN102751501A (en) * | 2012-06-14 | 2012-10-24 | 浙江工业大学 | Application of triphenylamine derivative polymer as lithium ion batteries cathode material |
| CN104752727A (en) * | 2013-12-31 | 2015-07-01 | 华为技术有限公司 | Quinone compound-graphene composite material and preparation method thereof as well as flexible lithium secondary battery |
| CN105308778A (en) * | 2013-07-09 | 2016-02-03 | 日东电工株式会社 | Electricity-storage-device electrode, manufacturing method therefor, and electricity-storage device using said electrode |
| CN106910895A (en) * | 2017-04-06 | 2017-06-30 | 广东工业大学 | A kind of organic electrode materials and its preparation method and application |
| CN110556549A (en) * | 2019-08-21 | 2019-12-10 | 天津大学 | Lithium primary battery |
| CN114181375A (en) * | 2021-11-25 | 2022-03-15 | 五邑大学 | Cross-linked quinone polymer and preparation method and application thereof |
| CN117843951A (en) * | 2024-01-08 | 2024-04-09 | 江苏科技大学 | Conjugated amine-containing polymer and preparation method and application thereof |
-
2004
- 2004-03-29 CN CNA2004100188002A patent/CN1564348A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411231C (en) * | 2006-07-20 | 2008-08-13 | 复旦大学 | Lithium ion battery with pyridyl quinone derivative as negative pole material |
| CN102598374A (en) * | 2009-11-12 | 2012-07-18 | 独立行政法人产业技术综合研究所 | Positive electrode active material for nonaqueous secondary battery |
| CN102598374B (en) * | 2009-11-12 | 2016-10-19 | 独立行政法人产业技术综合研究所 | Positive electrode active material for nonaqueous secondary battery |
| CN102751501A (en) * | 2012-06-14 | 2012-10-24 | 浙江工业大学 | Application of triphenylamine derivative polymer as lithium ion batteries cathode material |
| CN105308778A (en) * | 2013-07-09 | 2016-02-03 | 日东电工株式会社 | Electricity-storage-device electrode, manufacturing method therefor, and electricity-storage device using said electrode |
| CN104752727A (en) * | 2013-12-31 | 2015-07-01 | 华为技术有限公司 | Quinone compound-graphene composite material and preparation method thereof as well as flexible lithium secondary battery |
| CN106910895A (en) * | 2017-04-06 | 2017-06-30 | 广东工业大学 | A kind of organic electrode materials and its preparation method and application |
| CN106910895B (en) * | 2017-04-06 | 2020-02-21 | 广东工业大学 | Organic electrode material and preparation method and application thereof |
| CN110556549A (en) * | 2019-08-21 | 2019-12-10 | 天津大学 | Lithium primary battery |
| CN110556549B (en) * | 2019-08-21 | 2022-07-08 | 天津大学 | Lithium primary battery |
| CN114181375A (en) * | 2021-11-25 | 2022-03-15 | 五邑大学 | Cross-linked quinone polymer and preparation method and application thereof |
| CN114181375B (en) * | 2021-11-25 | 2023-10-13 | 五邑大学 | Crosslinked quinone polymer and preparation method and application thereof |
| CN117843951A (en) * | 2024-01-08 | 2024-04-09 | 江苏科技大学 | Conjugated amine-containing polymer and preparation method and application thereof |
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