CN105390297B - A kind of lithium titanate base hybrid super capacitor and preparation method thereof - Google Patents

A kind of lithium titanate base hybrid super capacitor and preparation method thereof Download PDF

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CN105390297B
CN105390297B CN201511008955.2A CN201511008955A CN105390297B CN 105390297 B CN105390297 B CN 105390297B CN 201511008955 A CN201511008955 A CN 201511008955A CN 105390297 B CN105390297 B CN 105390297B
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super capacitor
cathode
lithium titanate
hybrid super
electrolyte
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CN105390297A (en
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安仲勋
吴明霞
黄廷立
颜亮亮
范羚羚
夏恒恒
刘永环
虞嘉菲
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Shanghai Aowei Technology Development Co Ltd
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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
    • Y02E60/13—Energy storage using capacitors

Abstract

The present invention discloses a kind of lithium titanate base hybrid super capacitor and preparation method thereof, is made of anode, cathode, the diaphragm to fall between and organic electrolyte, anode：It using electric double layer energy storage material as active material, and is mixed with conductive agent and binder, coating is on a current collector；Cathode：Using Li4Ti5O12And Li7Ti5O12Mixture, and mixed with conductive agent and binder, coating is on a current collector；Electrolyte：It is made of solute and solvent, solvent CH3CN, solute LiPF6.Hybrid super capacitor prepared by the present invention compared with the super electric appliance of electric double layer have higher energy density (15~25Wh/Kg can be reached), identical high power density (>Characteristic 12000W/Kg) can be widely applied to the fields such as hybrid electric vehicle, Caddy, automobile starting and pure electric bus and tramcar.

Description

A kind of lithium titanate base hybrid super capacitor and preparation method thereof
[technical field]
The present invention relates to a kind of field of chemical power source, more particularly to the hybrid super capacitor of a kind of lithium titanate base is led Domain.
[background technology]
Lithium titanate (Li4Ti5O12) it is a kind of novel lithium ion battery negative material, its maximum feature is exactly that " zero answers Denaturation ".So-called " zero strain " refers to its crystal lattice constant and volume change all very littles in embedded or abjection lithium ion. In charge and discharge cycles, this " zero strain " can avoid leading to structural damage due to stretching back and forth for electrode material, from And the cycle life of electrode is improved, reduce the special capacity fade of tape loop, it may have extraordinary overcharging resisting is crossed and puts spy Sign, so lithium titanate is a kind of negative material of the negative material and hybrid super capacitor of excellent battery material.From reason Lower DOD cycles can be at 30,000 times or more service life, if design lithium titanate anode is excessive by upper lithium titanate, Service life is up to 10~1,000,000 service life.
Electrochemical capacitor in double electrode layer (EDLC) refers to having considerably beyond traditional capacitor capacity, utilizing electric double layer charge and discharge The device of electric principle, general positive and negative anodes all use same active material (such as activated carbon, carbon fiber, carbon cloth, carbon aerogels, carbon Nanotube, carbon black, graphene) it is used as electrode active material, one electric double layer of each self-forming to attract electrically opposite equivalent respectively Charge.Its main feature is that specific capacitance is big, specific power is high, have extended cycle life, use temperature range is wide and environmentally friendly.The disadvantage is that More relatively low than energy, in order to overcome the disadvantage, people to invent hybrid super capacitor, hybrid super capacitor is that a pole is adopted With unpolarized electrode (such as nickel hydroxide, Li of battery4Ti5O12Deng), another pole uses the polarizing electrode of double layer capacitor (such as Activated carbon), the design of this mixed type can increase substantially the energy density of ultracapacitor.
Just extremely activated carbon, cathode Li4Ti5O12Hybrid super capacitor be hybrid super capacitor typical generation Table, but since the capacitance section of the capacitor relatively narrow (2.0~2.7V) ratio energy for limiting the type ultracapacitor plays.
In addition, the electrolyte used in lithium ion battery and lithium-ion capacitor at present, solvent be mostly ethylene carbonate and Linear carbonates form, solute LiPF6Or LiAsF6, this kind of electrolyte feature is technology maturation, is highly suitable for carbon-based lithium Ion battery and carbon-based lithium ion capacitor, but such electrolytic conductivity is relatively low, generally in 10mS/cm or so；CH3CN is strong The conductivity of electrolyte, CH can be improved in polar solvent compared with carbonate-based solvent3CN, which has been employed successfully in, does not generate SEI films System, lithium titanate do not generate as negative material, SEI films, and electrolyte can use CH3CN makees solvent；And LiAsF6With CH3CN There is complex reaction, CH cannot be used3CN makees solvent, LiBF4CH can be used3CN makees solvent, but its electrical conductivity of solution is up to 1910mS/ Cm, the Et with the 1M used in electric double layer4NBF4/CH3CN conductivity 56mS/cm is compared, and conductivity is relatively low, is unfavorable for capacitor ratio The performance of power.And LiPF6CH3When CN is between concentration 0.8~1.2, the conductivity with 50~56mS/cm, with electric double layer The comparable conductivity of capacitor electrolyte.Its power characteristic can be played with the electrolyte.
[invention content]
To overcome Li4Ti5O12Hybrid super capacitor capacitance section relatively narrow (2.0~2.7V) deficiency, it is of the invention Purpose is to provide a kind of hybrid super capacitor of lithium titanate base, and anode uses electric double layer material；Cathode uses Li4Ti5O12 And Li7Ti5O12Mixture, its ratio be 3:7~7:Between 3；Electrolyte uses LiPF6/CH3CN systems, hybrid super electricity Container has higher capacitance section and higher compares energy.
To achieve the above object, a kind of lithium titanate base hybrid super capacitor is designed, by anode, cathode, between the two Between diaphragm and electrolyte composition, which is characterized in that
A anodes：It using electric double layer energy storage material as active material, and is mixed with conductive agent and binder, is coated on collection On fluid；
B cathode：Using Li4Ti5O12And Li7Ti5O12Mixture, and mixed with conductive agent and binder, be coated on afflux On body；
C electrolyte：It is made of solute and solvent, solvent is one-component solvent acetonitrile (CH3CN), solute is one-component solute LiPF6, concentration of electrolyte is in 0.8~1.2M.
The electric double layer energy storage material is the one or more of activated carbon, graphene, carbon nanotube and carbon aerogels.
Cathode is Li4Ti5O12And Li7Ti5O12Mixture, its ratio be 3:7~7:Between 3.
Concentration of electrolyte is 0.8~1.2M, and conductivity is 50~56mS/cm.
The diaphragm includes polyethene microporous membrane, microporous polypropylene membrane, composite membrane, inorganic ceramic membrane, paper diaphragm.
The method for preparing above-mentioned lithium titanate base hybrid super capacitor, which is characterized in that
The making of a positive plates：It is mixed with conductive agent and binder in proportion using electric double layer energy storage material as active material Close, be tuned into slurry, be then coated on a current collector, drying, roll, cut-parts, for 24 hours vacuum drying be fabricated to positive plate；
The making of b negative plates：By Li4Ti5O12And Li7Ti5O12Mixture ground and mixed uniformly be used as active material, press Ratio and conductive agent are tuned into slurry with binder, are then coated on a current collector, drying is rolled, cut-parts, is dried in vacuo for 24 hours It is fabricated to negative plate.
C injects LiPF in diaphragm6/CH3CN electrolyte is assembled into the ultracapacitor of 3Ah.
The cathode is excessive, positive electrode and negative electrode capacity ratio：1:2~1:Between 4.
Hybrid super capacitor is made by the present invention, capacitance section uses merely between 1.5~2.7V, with cathode Li4Ti5O12It compares, there is wider capacitance section.High rate charge-discharge performance with double layer capacitor comparable compares work( Rate and comparable cycle life characteristics, it is more simple than double layer capacitor and cathode to use Li4Ti5O12Capacitor compare have more High ratio energy, application range are wider.
[specific implementation mode]
Exemplary embodiment of the present invention will be more fully described below, but this field is should be appreciated that before being described herein Those of ordinary skill can change invention described herein, while obtain the technique effect of the present invention.Thus, it should be understood that following Description be for those of ordinary skill in the art one it is extensive disclose, and not lie in limitation described in the invention for its content Exemplary embodiment.
1. the production method of the embodiment in table 1 is as follows：
The making of positive plate：Using electric double layer material as active material, conductive agent and binder, mix according to a certain percentage It closes, which can be selected conventional ratio, be clear for a person skilled in the art, after being tuned into slurry, then be coated on collection On fluid, drying (110~120 DEG C), roll, cut-parts, for 24 hours vacuum drying (120~130 DEG C) be fabricated to positive plate.
The making of negative plate：By Li4Ti5O12And Li7Ti5O12Mixture ground and mixed uniformly be used as active material, by one Certainty ratio (ratio as shown in the Examples) and conductive agent are tuned into slurry with binder, are then coated on a current collector, drying (110~120 DEG C), roll, cut-parts, for 24 hours vacuum drying (120~130 DEG C) be fabricated to negative plate.
Selection cellulose paper is diaphragm, finally injects certain density LiPF6/CH3CN is assembled into the super capacitor of 3Ah Then device carries out chemical conversion and performance test to the ultracapacitor.
2. work system
Life test：Power supply charges to 2.7V with the electric current of 30A, and 30A is discharged to 1.5V, after recycling 100000 times, calculates Capacity retention ratio.
Embodiment 1
Anode：Activated carbon, positive face amount are 5Ah/m2
Cathode：Li4Ti5O12And Li7Ti5O12, ratio 7:3 cathode face amounts are 10Ah/m2。
Positive electrode and negative electrode capacity ratio：1:2.
Electrolyte is：1M LiPF6/CH3CN。
Embodiment 2
Anode：Activated carbon, positive face amount are 5Ah/m2
Cathode：Li4Ti5O12And Li7Ti5O12, ratio 6:4 cathode face amounts are 10Ah/m2。
Positive electrode and negative electrode capacity ratio：1:2.
Electrolyte is：1M LiPF6/CH3CN。
Embodiment 3
Anode：Activated carbon, positive face amount are 5Ah/m2
Cathode：Li4Ti5O12And Li7Ti5O12, ratio 5:5 cathode face amounts are 10Ah/m2。
Positive electrode and negative electrode capacity ratio：1:2.
Electrolyte is：1M LiPF6/CH3CN。
Embodiment 4
Anode：Activated carbon, positive face amount are 5Ah/m2
Cathode：Li4Ti5O12And Li7Ti5O12, ratio 4:6 cathode face amounts are 10Ah/m2。
Positive electrode and negative electrode capacity ratio：1:2.
Electrolyte is：1M LiPF6/CH3CN。
Embodiment 5
Anode：Activated carbon, positive face amount are 5Ah/m2
Cathode：Li4Ti5O12And Li7Ti5O12, ratio 3:7 cathode face amounts are 10Ah/m2。
Positive electrode and negative electrode capacity ratio：1:2.
Electrolyte is：1M LiPF6/CH3CN。
Embodiment 6
Anode：Activated carbon, positive face amount are 5Ah/m2
Cathode：Li4Ti5O12And Li7Ti5O12, ratio 2:8 cathode face amounts are 10Ah/m2。
Positive electrode and negative electrode capacity ratio：1:2.
Electrolyte is：1M LiPF6/CH3CN。
Embodiment 7
Anode：Activated carbon, positive face amount are 5Ah/m2
Cathode：Li4Ti5O12And Li7Ti5O12, ratio 8:2 cathode face amounts are 10Ah/m2。
Positive electrode and negative electrode capacity ratio：1:2.
Electrolyte is：1M LiPF6/CH3CN。
Embodiment 8
Anode：Activated carbon, positive face amount are 5Ah/m2
Cathode：Li4Ti5O12And Li7Ti5O12, ratio 7:3 cathode face amounts are 15Ah/m2。
Positive electrode and negative electrode capacity ratio：1:3.
Electrolyte is：1M LiPF6/CH3CN。
Embodiment 9
Anode：Activated carbon, positive face amount are 5Ah/m2
Cathode：Li4Ti5O12And Li7Ti5O12, ratio 7:3 cathode face amounts are 20Ah/m2。
Positive electrode and negative electrode capacity ratio：1:4.
Electrolyte is：1M LiPF6/CH3CN。
Embodiment 10
Anode：Activated carbon, positive face amount are 5Ah/m2
Cathode：Li4Ti5O12And Li7Ti5O12, ratio 7:3 cathode face amounts are 25Ah/m2。
Positive electrode and negative electrode capacity ratio：1:5.
Electrolyte is 1M LiPF6/CH3CN。
Embodiment 11
Anode：Activated carbon, positive face amount are 5Ah/m2
Cathode：Li4Ti5O12And Li7Ti5O12, ratio 7:3 cathode face amounts are 5Ah/m2。
Positive electrode and negative electrode capacity ratio：1:1.
Electrolyte is 1M LiPF6/CH3CN。
Embodiment 12
Anode：Activated carbon, positive face amount are 5Ah/m2
Cathode：Li4Ti5O12And Li7Ti5O12, ratio 7:3 cathode face amounts are 15Ah/m2。
Positive electrode and negative electrode capacity ratio：1:3.
Electrolyte is：1M LiBF4/CH3CN。
Embodiment 13
Anode：Activated carbon, positive face amount are 5Ah/m2
Cathode：Li4Ti5O12Cathode face amount is 15Ah/m2。
Positive electrode and negative electrode capacity ratio：1:3.
Electrolyte is 1M LiPF6/CH3CN。
Embodiment 14
Anode：Activated carbon, positive face amount are 5Ah/m2
Cathode：Activated carbon, cathode face amount are 5Ah/m2。
Positive electrode and negative electrode capacity ratio：1:1.
Electrolyte is 1M Et4NBF4/CH3CN。
The electrical property table of comparisons of the different embodiments of table 1
As can be seen from Table 1, Li 1) is used4Ti5O12And Li7Ti5O12Mixture be cathode ultracapacitor fluid injection after not Due to higher open-circuit voltage before chemical conversion, and there is wider capacitance section, to higher than energy, while from Embodiment can also obtain Li4Ti5O12And Li7Ti5O12Proper ratio is 3:7~7:Between 3；2) cathode is excessively conducive to super The performance of capacitor life-span, but the performance of the excessive more unfavorable specific power of cathode, suitable ratio are 1:2~1:Between 4；3) electric It solves liquid and uses 1M LiPF6/CH3CN and 1M LiBF4/CH3CN, which is compared, has higher specific power；4) mixed type of the invention is super Grade capacitor has comparable specific power and cycle life with higher compared with double electric layers supercapacitor than energy, has There is broader purposes.
Above said content is only the basic explanation under present inventive concept, and is appointed made by technical solution according to the present invention What equivalent transformation, is within the scope of protection of the invention.

Claims (8)

1. a kind of lithium titanate base hybrid super capacitor, by anode, cathode, the diaphragm to fall between and electrolyte group At, which is characterized in that
A anodes：It using electric double layer energy storage material as active material, and is mixed with conductive agent and binder, is coated on collector On；
B cathode：Cathode is Li4Ti5O12And Li7Ti5O12Mixture, its ratio be 3:7~7:Between 3, and with conductive agent and viscous Agent mixing is tied, coating is on a current collector；
C electrolyte：It is made of solute and solvent, solvent CH3CN, solute LiPF6。
2. a kind of lithium titanate base hybrid super capacitor as described in claim 1, which is characterized in that the electric double layer energy storage Material is the one or more of activated carbon, graphene, carbon nanotube and carbon aerogels.
3. a kind of lithium titanate base hybrid super capacitor as described in claim 1, which is characterized in that concentration of electrolyte is 0.8~1.2M, conductivity are 50 ~ 56mS/cm.
4. a kind of lithium titanate base hybrid super capacitor as described in claim 1, which is characterized in that the diaphragm includes Polyethene microporous membrane, microporous polypropylene membrane, composite membrane, inorganic ceramic membrane, paper diaphragm.
5. a kind of method preparing lithium titanate base hybrid super capacitor as described in claim 1, which is characterized in that
The making of a positive plates：It using electric double layer energy storage material as active material, mixes, adjusts with conductive agent and binder in proportion At slurry, be then coated on a current collector, drying, roll, cut-parts, for 24 hours vacuum drying be fabricated to positive plate；
The making of b negative plates：By Li4Ti5O12And Li7Ti5O12Mixture ground and mixed uniformly be used as active material, in proportion It is tuned into slurry with conductive agent and binder, is then coated on a current collector, drying rolls, cut-parts, for 24 hours vacuum drying making At negative plate,
C injects LiPF in diaphragm6/ CH3CN electrolyte is assembled into the ultracapacitor of 3Ah.
6. the method for preparing lithium titanate base hybrid super capacitor as claimed in claim 5, which is characterized in that the cathode It is excessive, positive electrode and negative electrode capacity ratio：1:2~1:Between 4.
7. the method for preparing lithium titanate base hybrid super capacitor as claimed in claim 5, which is characterized in that positive face amount For 5Ah/m2。
8. the method for preparing lithium titanate base hybrid super capacitor as claimed in claim 5, which is characterized in that cathode face amount For 10-20Ah/m2 。
CN201511008955.2A 2015-12-29 2015-12-29 A kind of lithium titanate base hybrid super capacitor and preparation method thereof Active CN105390297B (en)

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CN111029158B (en) * 2019-12-22 2021-12-17 北京蒙京石墨新材料科技研究院有限公司 Lithium ion supercapacitor lithium pre-embedding method

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CN103545120A (en) * 2013-10-30 2014-01-29 中国第一汽车股份有限公司 Organic system hybrid capacitor with rice-hull-based activated carbon serving as electrode material

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Publication number Priority date Publication date Assignee Title
CN101958428A (en) * 2010-09-15 2011-01-26 东莞新能源科技有限公司 Lithium ion secondary battery
CN103069620A (en) * 2010-10-01 2013-04-24 株式会社东芝 Nonaqueous electrolyte secondary battery and method for manufacturing same
CN102938328A (en) * 2011-08-15 2013-02-20 海洋王照明科技股份有限公司 Electrochemical capacitor and preparation method thereof
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