CN103177882A - Negative plate for lithium ion capacitor and preparation method thereof - Google Patents
Negative plate for lithium ion capacitor and preparation method thereof Download PDFInfo
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- CN103177882A CN103177882A CN201310091486XA CN201310091486A CN103177882A CN 103177882 A CN103177882 A CN 103177882A CN 201310091486X A CN201310091486X A CN 201310091486XA CN 201310091486 A CN201310091486 A CN 201310091486A CN 103177882 A CN103177882 A CN 103177882A
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- lithium
- pole piece
- cathode pole
- negative plate
- lithium titanate
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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
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- Y02E60/13—Energy storage using capacitors
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Abstract
The invention relates to a negative plate for a lithium ion capacitor and a preparation method of the negative plate. The negative plate comprises an aluminum foil substrate, and is characterized in that coating straps are respectively distributed on front and back surfaces of the aluminum foil substrate; and admixture comprising lithium titanate, conductive agent and bonding agent is arranged in the coating strap. When the negative plate is prepared, firstly negative pole paste is mixed, and then screening is performed, so that coating admixture is formed. The coating admixture is uniformly coated on the front and back surfaces of an aluminum foil, and the aluminum foil is subjected to drying and rolling and then is shorn into the negative plate. The preparation process is simple, and large-scale operation is easy to realize. Meanwhile, the lithium titanate negative plate shows excellent electrochemical property, and is easily used for performing energy matching with an active carbon positive plate of the lithium ion capacitor, so that the negative plate has an extensive application prospect in the lithium ion capacitor.
Description
Technical field
The present invention relates to a kind of pole piece and preparation method thereof, relate in particular to a kind of lithium-ion capacitance cathode pole piece and preparation method thereof.
Background technology
The continuous increase of the development of modern civilization and world population makes the whole world grow with each passing day to the demand of the energy.And along with the worsening shortages of the traditional primary energy such as coal, oil supply, and the problems such as the global warming that causes of fuel energy and the deterioration of the ecological environment constantly aggravate, and make energy problem receive increasing concern.Exploring the reproducible new forms of energy of cleaning has become one of vital task of current Scientific World, becomes the key subjects that relation mankind's human future survival state.And wherein super capacitor and lithium ion battery with excellent separately performance, obtain people and pay close attention to widely.Since coming out, be widely used in numerous areas such as electronics, communication, automobile and other industries.
Spinel type lithium titanate (Li
4Ti
5O
12) because it has good security performance and unique structural stability (" zero strain " material), can overcome some shortcomings of conventional carbon material, become the emphasis of Recent study.From the angle of structure, Li
4Ti
5O
12Be desirable embedded type electrode, it can be ignored due to the embedding of lithium ion and the crystal structure of deviating to cause and change in volume in charge and discharge process, and crystal structure can hold a large amount of lithiums.By the degree of depth that restriction discharges and recharges, can keep the integrality of electrode structure, and can obtain cycle life preferably.So spinel type lithium titanate is the energy storage material that has application prospect.
Because the conductance of lithium titanate is extremely low, this has limited to a certain extent this material large-scale commercial applications and has used.Thereby how to improve the lithium titanate material electric conductivity be that many researchers make great efforts a difficult problem of capturing always.Improve at present the electric conductivity of lithium titanate mainly by three approach: the one, the lithium titanate of preparation nano particle; The 2nd, conducting metal mixes, and carbon coats; Three add other yuan usually improves the electric conductivity of too sour lithium, as zirconium (Zr), strontium (Sr) or the oxygen in the lithium titanate structure is changed into nitrogen etc.
Summary of the invention
Purpose of the present invention is exactly in order to solve the above-mentioned problems in the prior art, and a kind of lithium-ion capacitance cathode pole piece and preparation method thereof is provided
Purpose of the present invention is achieved through the following technical solutions:
A kind of lithium-ion capacitance cathode pole piece includes the aluminium foil base material, and wherein: the tow sides of described aluminium foil base material are distributed with coating zone, is provided with the mixture that lithium titanate, conductive agent and binding agent form in described coating zone.
Above-mentioned a kind of lithium-ion capacitance cathode pole piece, wherein: described lithium titanate mass percent is 30%-65%, and described conductive agent mass percent is 30%-60%, and described binding agent electricity agent mass percent is 5%-10%.
Further, above-mentioned a kind of lithium-ion capacitance cathode pole piece, wherein: described lithium titanate is business nanoscale metatitanic acid lithium, and described lithium titanate has spinel structure, and the granularity of described spinel structure is less than 1um.
Further, above-mentioned a kind of lithium-ion capacitance cathode pole piece, wherein: described conductive agent is the mixture of conductive carbon black and electrically conductive graphite.
Again further, above-mentioned a kind of lithium-ion capacitance cathode pole piece, wherein: described binding agent is one or more mixtures in Kynoar, polytetrafluoroethylene, butadiene-styrene rubber, carboxymethyl cellulose.
a kind of lithium-ion capacitance preparation method of cathode pole piece, it comprises the following steps: step 1., the binding agent of mass ratio 5%-10% is dissolved in deionized water solution or 1-METHYLPYRROLIDONE, step 2., the conductive agent that is 30%-60% with mass ratio adds in the binder solution that stirs, step 3., adding mass ratio after the vacuum high-speed stirred is even is the lithium titanate of 30%-65%, step 4., again the vacuum high-speed stirred evenly after, become cathode size, step 5., cathode size is crossed 150 mesh sieve screenings, consist of coating mixture, step 6., coating mixture is uniformly coated on the positive and negative of aluminium foil, step 7., drying, cut into cathode pole piece after roll-in.
The advantage of technical solution of the present invention is mainly reflected in: the pole piece preparation process is simple, easily scale operation.Simultaneously, this lithium titanate anode pole piece shows good chemical property, is easy to that to carry out energy flux matched with lithium-ion capacitor active carbon positive plate.Therefore this cathode pole piece is with a wide range of applications in lithium-ion capacitor.
Description of drawings
Purpose of the present invention, advantage and disadvantage will be for illustration and explanation by the non-limitative illustration of following preferred embodiment.These embodiment are only the prominent examples of using technical solution of the present invention, and all technical schemes of taking to be equal to replacement or equivalent transformation and forming are within all dropping on the scope of protection of present invention.In the middle of these accompanying drawings,
Fig. 1 is the organigram that lithium-ion capacitance is used cathode pole piece.
In figure, the implication of each Reference numeral is as follows:
1 aluminium foil base material 2 mixtures
Embodiment
A kind of lithium-ion capacitance cathode pole piece as shown in Figure 1 includes aluminium foil base material 1, and its special feature is: the tow sides of aluminium foil base material 1 of the present invention are distributed with coating zone.Simultaneously, be provided with the mixture 2 that lithium titanate, conductive agent and binding agent form in coating zone.
With regard to the better execution mode of the present invention one, the lithium titanate mass percent of employing is 30%-65%, and the conductive agent mass percent is 30%-60%, and binding agent electricity agent mass percent is 5%-10%.Simultaneously, for the ease of applying, lithium titanate is business nanoscale metatitanic acid lithium, and lithium titanate has spinel structure, and the granularity of spinel structure is less than 1um.
Further, the conductive agent of employing is the mixture 2 of conductive carbon black (Super P-Li) and electrically conductive graphite (KS6).Specifically, its quality of conductive agent is 30%～60% of mixture 2 gross masses.Wherein the conductive carbon black mass ratio is 8%～15%, take into account pole piece conductivity and preparation pole piece control aspect, be preferably 10%, as too lowly in conductive carbon black content can't effectively improve the conductivity of pole piece, conductive carbon black too high levels slurry when stirring slurry easily foams, can't accurately, effectively prepare even, stable pole piece, the film-making process can't be controlled well.Simultaneously, the electrically conductive graphite mass ratio is 20%～50%, is preferably 30%～45%, if this is because electrically conductive graphite content is too low, does not just have the electrically conductive graphite particle of sufficient amount to contact with active material particle, thereby affects the electric conductivity of pole piece.And electrically conductive graphite content is too low, certainly will cause in pole piece lithium titanate content high, and for can effectively to carry out energy flux matched with anode activated charcoal, too sour cathode of lithium pole piece must prepare low surface density pole piece.Thus, all higher to precision, operating personnel and the operative skill requirement of equipment, cause the film-making process wayward.If the electrically conductive graphite too high levels easily causes the cathode pole piece surface that large granular convex points is arranged, affect the pole piece surface topography, affect on the contrary cathode pole piece chemical property and security performance.
And binding agent is one or more mixtures in Kynoar, polytetrafluoroethylene, butadiene-styrene rubber, carboxymethyl cellulose.
Again further, the invention provides a kind of lithium-ion capacitance with the preparation method of cathode pole piece, it is characterized in that comprising the following steps: at first, the binding agent of mass ratio 5%-10% is dissolved in deionized water solution or 1-METHYLPYRROLIDONE.Afterwards, be that the conductive agent of 30%-60% adds in the binder solution that stirs with mass ratio.Subsequently, to add mass ratio after evenly be the lithium titanate of 30%-65% to the vacuum high-speed stirred.
In order to improve the fusion degree of each material, again the vacuum high-speed stirred evenly after, become cathode size.Afterwards, cathode size is crossed 150 mesh sieve screenings, consists of coating mixture.After completing above-mentioned steps, coating mixture is uniformly coated on the positive and negative of aluminium foil, cuts into cathode pole piece after drying, roll-in.
" embodiment one "
the CMC of mass ratio 1.6% is dissolved in deionized water, after the vacuum high-speed stirred is even, static approximately 6 hours, electrically conductive graphite with mass ratio 35% adds in the binder solution that stirs again, the vacuum high-speed stirred adds mass ratio after evenly again in slurry be 10% conductive carbon black, the vacuum high-speed stirred is the rear 150 purpose sieves of crossing evenly, add again 50% lithium titanate in the slurry of crossing good sieve, the vacuum high-speed stirred is even in de-airing mixer, then be that 3.4% SBR adds with mass ratio, rear one-tenth cathode size stirs, slurry evenly is coated with slurry on the positive and negative of aluminium foil after 150 mesh sieve, through cutting into cathode pole piece after roll-in after dry 36 hours dryings of 120 ℃ of vacuum cycle.
Take the active carbon pole piece as anodal, the lithium titanate pole piece is negative pole.Employing NKK company model is that the fibre diaphragm of TF4035 is the barrier film of lithium ion super electric capacity.Electrolyte adopts with 1.2M LiClO
4, solvent is dimethyl carbonate (DMC), Methylethyl carbonic ester (EMC).The anode and cathode active materials mass ratio is 3.5: 1, the positive and negative electrode pole piece separated in the lamination mode with barrier film be combined into battery core, and then battery core positive and negative electrode soldering polar ear, rubberizing, battery core is through the overheated shaping of colding pressing.Reinstall in the aluminum plastic film shell, closedtop, side seal mouth, put into 85 ℃ of dryings of vacuum drying chamber 48 hours, then annotate electrolyte and sealing in glove box.Secondary sealing again after changing into, the cutting edge shaping gets final product.
" embodiment two "
The PVDF of quality 6% is dissolved in NMP, after the vacuum high-speed stirred is even, static approximately 6 hours, electrically conductive graphite with mass ratio 35% adds in the binder solution that stirs again, the vacuum high-speed stirred adds mass ratio after evenly again in slurry be 10% conductive carbon black, and the vacuum high-speed stirred is crossed 150 purpose sieves after evenly.Afterwards, add again 49% lithium titanate in the slurry of crossing good sieve, the vacuum high-speed stirred is even in de-airing mixer, slurry is uniformly coated on slurry on the positive and negative of aluminium foil after 150 mesh sieve, the cathode pole piece that makes cuts into cathode pole piece through after dry 36 hours dryings of 120 ℃ of vacuum cycle after roll-in.Take the active carbon pole piece as anodal, the lithium titanate pole piece is negative pole.Employing NKK company model is that the fibre diaphragm of TF4035 is the barrier film of lithium ion super electric capacity.Electrolyte adopts with 1.25M LiPF
6, solvent is vinyl carbonate (EC), dimethyl carbonate (DMC).Controlling the positive, negative electrode plate surface density, is 3.0: 1 with the anode and cathode active materials mass ratio, the positive and negative electrode pole piece is separated in the lamination mode with barrier film be combined into battery core, and then battery core positive and negative electrode soldering polar ear, rubberizing, battery core is through the overheated shaping of colding pressing.Reinstall in the aluminum plastic film shell, closedtop, side seal mouth, put into 85 ℃ of dryings of vacuum drying chamber 48 hours, then annotate electrolyte and sealing in glove box; Secondary sealing again after changing into; The cutting edge shaping gets final product.
" embodiment three "
the PVDF of quality 6% is dissolved in NMP, after the vacuum high-speed stirred is even, static approximately 6 hours, electrically conductive graphite with mass ratio 35% adds in the binder solution that stirs again, the vacuum high-speed stirred adds mass ratio after evenly again in slurry be 10% conductive carbon black, the vacuum high-speed stirred is the rear 150 purpose sieves of crossing evenly, add again 49% lithium titanate in the slurry of crossing good sieve, the vacuum high-speed stirred is even in de-airing mixer, slurry is uniformly coated on slurry on the positive and negative of aluminium foil after 150 mesh sieve, the cathode pole piece that makes is through after dry 36 hours dryings of 120 ℃ of vacuum cycle, cut into cathode pole piece after roll-in.Take the active carbon pole piece as anodal, the lithium titanate pole piece is negative pole.
Afterwards, adopting NKK company model is that the fibre diaphragm of TF4035 is the barrier film of lithium ion super electric capacity.Electrolyte adopts with 1.25M LiPF
6, solvent is vinyl carbonate (EC), dimethyl carbonate (DMC).Controlling the positive, negative electrode plate surface density, is 2.8: 1 with the anode and cathode active materials mass ratio, the positive and negative electrode pole piece is separated in the lamination mode with barrier film be combined into battery core, and then battery core positive and negative electrode soldering polar ear, rubberizing, battery core is through the overheated shaping of colding pressing.Then, reinstall in the aluminum plastic film shell, closedtop, side seal mouth, put into 85 ℃ of dryings of vacuum drying chamber 48 hours, then annotate electrolyte and sealing in glove box.Afterwards, change into after again secondary sealing cutting edge shaping get final product.
Can find out by above-mentioned character express, after adopting the present invention, the pole piece preparation process is simple, easily scale operation.Simultaneously, this lithium titanate anode pole piece shows good chemical property, is easy to that to carry out energy flux matched with lithium-ion capacitor active carbon positive plate.Therefore this cathode pole piece is with a wide range of applications in lithium-ion capacitor.
Claims (6)
1. a lithium-ion capacitance cathode pole piece, include the aluminium foil base material, it is characterized in that: the tow sides of described aluminium foil base material are distributed with coating zone, are provided with the mixture that lithium titanate, conductive agent and binding agent form in described coating zone.
2. a kind of lithium-ion capacitance cathode pole piece according to claim 1, it is characterized in that: described lithium titanate mass percent is 30%-65%, described conductive agent mass percent is 30%-60%, and described binding agent electricity agent mass percent is 5%-10%.
3. a kind of lithium-ion capacitance cathode pole piece according to claim 1, it is characterized in that: described lithium titanate is business nanoscale metatitanic acid lithium, and described lithium titanate has spinel structure, and the granularity of described spinel structure is less than 1um.
4. a kind of lithium-ion capacitance cathode pole piece according to claim 1, it is characterized in that: described conductive agent is the mixture of conductive carbon black and electrically conductive graphite.
5. a kind of lithium-ion capacitance cathode pole piece according to claim 1, it is characterized in that: described binding agent is one or more mixtures in Kynoar, polytetrafluoroethylene, butadiene-styrene rubber, carboxymethyl cellulose.
6. a lithium-ion capacitance with the preparation method of cathode pole piece, is characterized in that comprising the following steps:
1. step is dissolved in the binding agent of mass ratio 5%-10% in deionized water solution or 1-METHYLPYRROLIDONE,
Step 2., the conductive agent that is 30%-60% with mass ratio adds in the binder solution that stirs,
Step 3., it is the lithium titanate of 30%-65% that the vacuum high-speed stirred adds mass ratio after evenly,
Step 4., again the vacuum high-speed stirred evenly after, become cathode size,
Step 5., cathode size is crossed 150 mesh sieves screenings, consists of coating mixture,
6. step is uniformly coated on coating mixture on the positive and negative of aluminium foil,
7. step cuts into cathode pole piece after drying, roll-in.
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| CN201310091486XA CN103177882A (en) | 2013-03-21 | 2013-03-21 | Negative plate for lithium ion capacitor and preparation method thereof |
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| CN201310091486XA CN103177882A (en) | 2013-03-21 | 2013-03-21 | Negative plate for lithium ion capacitor and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104658762A (en) * | 2015-02-04 | 2015-05-27 | 清华大学 | Asymmetric micro lithium ion capacitor and manufacturing method thereof |
| CN104681306A (en) * | 2014-12-12 | 2015-06-03 | 宁波南车新能源科技有限公司 | Preparation method for mixed capacitor cathode pulp |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6517972B1 (en) * | 2000-09-29 | 2003-02-11 | Telcordia Technologies, Inc. | High energy density hybrid battery/supercapacitor system |
| CN101699590A (en) * | 2009-11-03 | 2010-04-28 | 朝阳立塬新能源有限公司 | Hybrid supercapacitor |
| CN101789315A (en) * | 2010-03-19 | 2010-07-28 | 常州康维电子科技有限公司 | Hybrid super capacitor and preparation method thereof |
-
2013
- 2013-03-21 CN CN201310091486XA patent/CN103177882A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6517972B1 (en) * | 2000-09-29 | 2003-02-11 | Telcordia Technologies, Inc. | High energy density hybrid battery/supercapacitor system |
| CN101699590A (en) * | 2009-11-03 | 2010-04-28 | 朝阳立塬新能源有限公司 | Hybrid supercapacitor |
| CN101789315A (en) * | 2010-03-19 | 2010-07-28 | 常州康维电子科技有限公司 | Hybrid super capacitor and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104681306A (en) * | 2014-12-12 | 2015-06-03 | 宁波南车新能源科技有限公司 | Preparation method for mixed capacitor cathode pulp |
| WO2016090958A1 (en) * | 2014-12-12 | 2016-06-16 | 宁波南车新能源科技有限公司 | Preparation method for mixed capacitor negative electrode slurry |
| CN104658762A (en) * | 2015-02-04 | 2015-05-27 | 清华大学 | Asymmetric micro lithium ion capacitor and manufacturing method thereof |
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Application publication date: 20130626 |