CN109872879A - A kind of lithium-ion capacitor electrode and its application - Google Patents
A kind of lithium-ion capacitor electrode and its application Download PDFInfo
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- CN109872879A CN109872879A CN201711249067.9A CN201711249067A CN109872879A CN 109872879 A CN109872879 A CN 109872879A CN 201711249067 A CN201711249067 A CN 201711249067A CN 109872879 A CN109872879 A CN 109872879A
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- ion capacitor
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- kynoar
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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 relates to a kind of lithium-ion capacitor electrode, including by the anode and cathode of diaphragm separately, by following preparation methods by three's " seamless " in combination together；Prepared by the method integrated electrode, effectively reduces electrode polarization, reduces the falling off of active material in electrode charge and discharge process, inactivate, makes lithium-ion capacitor with lower internal resistance and cyclical stability.
Description
Technical field
The present invention relates to electrochemical energy storage fields, and in particular to a kind of lithium-ion capacitor electrode.
Technical background
Lithium ion super capacitor is as a kind of energy storage device, and with high security, long service life, power height etc. is excellent
Point, it combines the advantage of common double layer capacitor and lithium ion battery, so in mobile communication, startup power supply, spare
There is better application prospect in the fields such as power supply.
Lithium ion super capacitor has the following characteristics that (1) for lithium ion battery, it is close to possess higher power
Degree, in high current application especially high energy pulse environment, can better meet power requirement.(2) when charge and discharge cycles
Between very short, far smaller than charge-discharge cycle time of battery.(3) battery is long, all the life need not maintenance.(4) operation temperature
Spend wide can work normally in the range of -45~85 DEG C.
Easily there is the power density and energy of device in lithium-ion capacitor, the lithium-ion capacitor especially after longtime running
Metric density decaying is rapid, one reason for this is that the contact resistance increase between electrode active material and diaphragm, collector etc. is led
It causes.
Summary of the invention
In order to solve the above technical problems, the present invention prepares a kind of lithium-ion capacitor electrode, including separately by diaphragm
Anode and cathode, by following preparation methods by three's " seamless " in combination together；
The preparation method includes deposition, heat-press step:
1) deposition step are as follows: by positive electrode, adhesive, solvent be uniformly mixed to obtain mixed material, using spraying, spin coating or
Knife coating procedure is deposited directly to one side surface of diaphragm；After to be dried, negative electrode material, adhesive, solvent are uniformly mixed to obtain mixing
Material is deposited directly to another side surface of diaphragm also with spraying, spin coating or knife coating procedure, sufficiently dry；Obtain integrated electricity
Pole；
Or, separately or concurrently carrying out the deposition of mixed material in diaphragm both side surface, then dry；Obtain integrated electrode；
2) heat-press step described in are as follows: the integrated electrode deposited is subjected to hot pressing.
The positive electrode includes one of absorbent charcoal material, conducting polymer, oxide or two or more；
The negative electrode material include absorbent charcoal material, graphite, hard charcoal, lithium titanate it is one or two kinds of more than；
The diaphragm include Kynoar, Kynoar-hexafluoropropylene copolymer, polytetrafluoroethylene (PTFE), polypropylene,
Polyethylene, cellulose acetate, glass fibre it is one or two kinds of more than.
The adhesive is Kynoar, Kynoar-hexafluoropropylene copolymer is one or two kinds of；
The solvent is N-Methyl pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetone, different
Fu Er ketone it is one or two kinds of more than；
The positive active material and negative electrode active material respectively with the mass ratio of adhesive are as follows: 100:1~1:2,
It is preferred that 50:1~20:1；The mass ratio of the adhesive and solvent is 1:200~1:1, preferably 1:50~1:2；
The face load amount of the positive active material and negative electrode active material is respectively 0.1mg/cm2~30mg/cm2, preferably
1~15mg/cm2。
50 DEG C~200 DEG C of drying temperature.
The temperature of the hot pressing are as follows: 30 DEG C~400 DEG C, preferably 50~180 DEG C；After the hot pressing degree refers to hot pressing
The ratio of electrode active material thickness and original electrode active material thickness, reasonable range are 90%~10%, preferably 80%
~20%.
The compacting equipment can are as follows: hot press or roll squeezer or both of which use.
Application of the electrode in lithium-ion capacitor.
The beneficial effects of the present invention are:
Prepared by the method integrated electrode effectively reduces electrode polarization, reduces living in electrode charge and discharge process
Property the falling off of substance, inactivate, make the lithium-ion capacitor there is lower internal resistance and cyclical stability.
Detailed description of the invention
Fig. 1 is the stable circulation linearity curve of lithium-ion capacitor in embodiment 1.
Fig. 2 is the stable circulation linearity curve of lithium-ion capacitor in comparative example.
Specific embodiment
Embodiment 1
By lithium titanate, Kynoar (PVDF), conductive black, N-Methyl pyrrolidone (NMP) according to 8:1:1:5 ratio
Example after mixing, is scratched onto polypropylene diaphragm, after 70 DEG C of drying, by active carbon, PVDF, conductive black, NMP according to 8:1:
After mixing, blade coating arrives two sides of above-mentioned electrode septation, 70 DEG C of drying to the ratio of 1:10.100 are carried out using hot press
DEG C hot pressing, hot pressing degree are 60%.Lithium titanate load amount is 3mg/cm2, and active carbon load amount is 9mg/cm2.
After the integrated electrode positive and negative anodes prepared are connected by conducting resinl with tab, it is wound into inner core of capacitor, is added
Enter the LiPF of 1mol/L6Inner core is sealed with aluminum plastic film after electrolyte (propene carbonate is solvent).Battery core is prepared and is completed.It is living
Property substance total amount be 15g.Charge-discharge test, blanking voltage 1.5- are carried out according to 0.5A/g (being based on active material quality)
2.9V.Record the cyclical stability of battery core internal resistance and 1000,2000,3000,4000,5000 circles.Battery core Equivalent DC internal resistance is
0.01mΩ。
Comparative example 1
By lithium titanate, Kynoar (PVDF), conductive black, N-Methyl pyrrolidone (NMP) P according to 8:1:1:5's
After mixing, on blade coating to aluminium foil, lithium titanate load amount is 3mg/cm to ratio2；Active carbon, PVDF, conductive black, NMP are pressed
It is scratched on aluminium foil after mixing according to the ratio of 8:1:1:10, active carbon load amount is 9mg/cm2.By metatitanic acid lithium electrode, poly- third
After alkene diaphragm, activated carbon electrodes are successively put well, it is wound into inner core of capacitor, the LiPF of 1mol/L is added6Electrolyte (propylene carbonate
Ester is solvent) after inner core is sealed with aluminum plastic film.Battery core is prepared and is completed.Active material total amount is 15g.According to 0.5A/g (base
In active material quality) carry out charge-discharge test, blanking voltage 1.5-2.9V.Record battery core internal resistance and 1000,2000,
3000, the cyclical stability of 4000,5000 circles.Battery core Equivalent DC internal resistance is 0.03m Ω, under the same terms, capacitor it is interior
Resistance is 3 times of the internal resistance in embodiment.Illustrate that integration can effectively improve ion transmission, reduces capacitor internal resistance.Fig. 1 and figure
2 comparisons are it can be seen that the lithium-ion capacitor capacity after 5000 circulations in embodiment 1 is still able to maintain 95%, and in comparative example
Lithium-ion capacitor can only be maintained at 86%, and illustrating can be substantially using the lithium-ion capacitor of the integrated electrode in embodiment
Improve the cyclical stability of capacitor.
Embodiment 2
By graphite, Kynoar (PVDF), conductive black, N-Methyl pyrrolidone (NMP) according to 8:1:1:5 ratio
After mixing, on blade coating to polypropylene diaphragm, after 70 DEG C of drying.By active carbon, PVDF, conductive black, NMP according to 8:1:1:
After mixing, blade coating arrives two sides of above-mentioned electrode septation, 70 DEG C of drying to 10 ratio.100 DEG C are carried out using hot press
Hot pressing, hot pressing degree are 60%.Lithium titanate load amount is 2mg/cm2, and active carbon load amount is 9mg/cm2.
After the integrated electrode positive and negative anodes prepared are connected by conducting resinl with tab, it is wound into inner core of capacitor, is added
Enter the LiPF of 1mol/L6Inner core is sealed with aluminum plastic film after electrolyte (propene carbonate is solvent).Battery core is prepared and is completed.It presses
Charge-discharge test, blanking voltage 3.0-4.3V are carried out according to 0.5A/g (being based on active material quality).Record battery core internal resistance and
1000, the cyclical stability of 2000,3000,4000,5000 circles.
Embodiment 3
By graphite, hard charcoal, Kynoar (PVDF), conductive black, N-Methyl pyrrolidone (NMP) according to 6:2:1:1:
5 ratio after mixing, is scratched onto polypropylene diaphragm, after 70 DEG C of drying.Active carbon, PVDF, conductive black, NMP are pressed
According to 8:1:1:10 ratio after mixing, blade coating arrive above-mentioned electrode septation two sides, 70 DEG C drying.Using hot press into
100 DEG C of hot pressing of row, hot pressing degree are 70%.Lithium titanate load amount is 2mg/cm2, and active carbon load amount is 9mg/cm2.
After the integrated electrode positive and negative anodes prepared are connected by conducting resinl with tab, it is wound into inner core of capacitor, is added
Enter the LiPF of 1mol/L6Inner core is sealed with aluminum plastic film after electrolyte (propene carbonate is solvent).Battery core is prepared and is completed.It presses
Charge-discharge test, blanking voltage 3.0-4.3V are carried out according to 0.5A/g (being based on active material quality).Record battery core internal resistance and
1000, the cyclical stability of 2000,3000,4000,5000 circles.
Embodiment 4
By lithium titanate, Kynoar (PVDF), conductive black, N-Methyl pyrrolidone (NMP) according to 8:1:1:5 ratio
Example after mixing, is scratched onto polypropylene diaphragm, after 70 DEG C of drying.By active carbon, PVDF, conductive black, NMP according to 8:1:
After mixing, blade coating arrives two sides of above-mentioned electrode septation, 70 DEG C of drying to the ratio of 1:10.100 are carried out using hot press
DEG C hot pressing, hot pressing degree are 60%.Lithium titanate load amount is 4mg/cm2, and active carbon load amount is 10mg/cm2.
After the integrated electrode positive and negative anodes prepared are connected by conducting resinl with tab, it is wound into inner core of capacitor, is added
Enter the LiPF of 1mol/L6Inner core is sealed with aluminum plastic film after electrolyte (propene carbonate is solvent).Battery core is prepared and is completed.It presses
Charge-discharge test, blanking voltage 3.0-4.3V are carried out according to 0.5A/g (being based on active material quality).Record battery core internal resistance and
1000, the cyclical stability of 2000,3000,4000,5000 circles.
Embodiment 5
By graphite, Kynoar (PVDF), conductive black, N-Methyl pyrrolidone (NMP) according to 8:1:1:6 ratio
After mixing, on blade coating to cellulose acetate membrane paper, after 80 DEG C of drying.By active carbon, PVDF, conductive black, NMP according to
After mixing, blade coating arrives two sides of above-mentioned electrode septation, 70 DEG C of drying to the ratio of 8:1:1:10.It is carried out using hot press
100 DEG C of hot pressing, hot pressing degree are 60%.Lithium titanate load amount is 2mg/cm2, and active carbon load amount is 9mg/cm2.
After the integrated electrode positive and negative anodes prepared are connected by conducting resinl with tab, it is wound into inner core of capacitor, is added
Enter the LiPF of 1mol/L6Inner core is sealed with aluminum plastic film after electrolyte (propene carbonate is solvent).Battery core is prepared and is completed.It presses
Charge-discharge test, blanking voltage 3.0-4.3V are carried out according to 0.5A/g (being based on active material quality).Record battery core internal resistance and
1000, the cyclical stability of 2000,3000,4000,5000 circles.
Embodiment 6
By graphite, Kynoar (PVDF), conductive black, N-Methyl pyrrolidone (NMP) according to 8:1:1:5 ratio
After mixing, on blade coating to fibreglass diaphragm, after 70 DEG C of drying.By active carbon, PVDF, conductive black, NMP according to 8:1:
After mixing, blade coating arrives two sides of above-mentioned electrode septation, 70 DEG C of drying to the ratio of 1:10.100 are carried out using hot press
DEG C hot pressing, hot pressing degree are 60%.Lithium titanate load amount is 3mg/cm2, and active carbon load amount is 9mg/cm2.
After the integrated electrode positive and negative anodes prepared are connected by conducting resinl with tab, it is wound into inner core of capacitor, is added
Enter the LiPF of 1mol/L6Inner core is sealed with aluminum plastic film after electrolyte (propene carbonate is solvent).Battery core is prepared and is completed.It presses
Charge-discharge test, blanking voltage 3.0-4.3V are carried out according to 0.5A/g (being based on active material quality).Record battery core internal resistance and
1000, the cyclical stability of 2000,3000,4000,5000 circles.
Embodiment 7
By lithium titanate, Kynoar (PVDF), conductive black, N-Methyl pyrrolidone (NMP) according to 8:1:1:5 ratio
Example after mixing, is scratched onto polyethylene diagrams, after 70 DEG C of drying.By active carbon, PVDF, conductive black, NMP according to 8:1:
After mixing, blade coating arrives two sides of above-mentioned electrode septation, 70 DEG C of drying to the ratio of 1:10.100 are carried out using hot press
DEG C hot pressing, hot pressing degree are 60%.Lithium titanate load amount is 3mg/cm2, and active carbon load amount is 9mg/cm2.
After the integrated electrode positive and negative anodes prepared are connected by conducting resinl with tab, it is wound into inner core of capacitor, is added
Enter the LiPF of 1mol/L6Inner core is sealed with aluminum plastic film after electrolyte (propene carbonate is solvent).Battery core is prepared and is completed.It presses
Charge-discharge test, blanking voltage 3.0-4.3V are carried out according to 0.5A/g (being based on active material quality).Record battery core internal resistance and
1000, the cyclical stability of 2000,3000,4000,5000 circles.
Claims (7)
1. a kind of lithium-ion capacitor electrode will by following preparation methods including passing through the anode and cathode of diaphragm separately
Three's " seamless " is in combination together；
The preparation method includes deposition, heat-press step:
1) deposition step are as follows: positive electrode, adhesive, solvent are uniformly mixed to obtain mixed material, utilize spraying, spin coating or blade coating
Method is deposited directly to one side surface of diaphragm；After to be dried, negative electrode material, adhesive, solvent are uniformly mixed to obtain mixed material,
It is deposited directly to another side surface of diaphragm also with spraying, spin coating or knife coating procedure, it is sufficiently dry；Obtain integrated electrode；
Or, separately or concurrently carrying out the deposition of the mixed material of anode and cathode in diaphragm both side surface, then dry；Obtain one
Polarizing electrode；
2) heat-press step described in are as follows: the integrated electrode deposited is subjected to hot pressing.
2. according to lithium-ion capacitor electrode described in claim 1, it is characterised in that:
The positive electrode includes one of absorbent charcoal material, conducting polymer, oxide or two or more；
The negative electrode material include absorbent charcoal material, graphite, hard charcoal, lithium titanate it is one or two kinds of more than；
The diaphragm includes Kynoar, Kynoar-hexafluoropropylene copolymer, polytetrafluoroethylene (PTFE), polypropylene, poly- second
Alkene, cellulose acetate, glass fibre it is one or two kinds of more than；It is preferred that Kynoar, Kynoar-hexafluoropropene are total
Polymers.
3. according to lithium-ion capacitor electrode as claimed in claim 1 or 2, it is characterised in that:
The adhesive is Kynoar, Kynoar-hexafluoropropylene copolymer is one or two kinds of；It is preferred that diaphragm
It is identical with adhesive component；
The solvent is N-Methyl pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetone, different Fu Er
Ketone it is one or two kinds of more than；It is preferred that N-Methyl pyrrolidone, acetone；
The positive active material and negative electrode active material respectively with the mass ratio of adhesive are as follows: 100:1~1:2, preferably
50:1~20:1；The mass ratio of the adhesive and solvent is 1:200~1:2, preferably 1:50~1:1；
The face load amount of the positive active material and negative electrode active material is respectively 0.1mg/cm on electrode2~30mg/cm2, excellent
Select 1~15mg/cm2.
4. according to lithium-ion capacitor electrode described in claim 1, it is characterised in that: 50 DEG C~200 DEG C of drying temperature.
5. according to lithium-ion capacitor electrode described in claim 1, it is characterised in that: the temperature of the hot pressing are as follows: 30 DEG C~
400 DEG C, preferably 50~180 DEG C；The hot pressing degree refers to electrode active material thickness and original electrode before hot pressing after hot pressing
The ratio of active material thickness, reasonable range are 90%~10%, preferably 80%~20%.
6. according to the lithium-ion capacitor electrode of claim 1 or 5, it is characterised in that: the compacting equipment of the hot pressing can are as follows:
One or both of hot press or roll squeezer use.
7. it is a kind of claim 1-6 arbitrarily as described in application of the electrode in lithium-ion capacitor.
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| CN106159197A (en) * | 2016-09-30 | 2016-11-23 | 上海空间电源研究所 | A kind of integrated flexible membrane electrode and preparation method thereof |
| CN106252659A (en) * | 2016-09-30 | 2016-12-21 | 上海空间电源研究所 | Integrated flexible thin film lithium sulfur or lithium ion battery cell, battery and preparation method |
| JP2017073350A (en) * | 2015-10-09 | 2017-04-13 | トヨタ自動車株式会社 | Method for manufacturing electrode body |
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2017
- 2017-12-01 CN CN201711249067.9A patent/CN109872879A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003132951A (en) * | 2001-10-25 | 2003-05-09 | Matsushita Electric Ind Co Ltd | Manufacturing method of lithium polymer secondary battery |
| CN104300128A (en) * | 2013-07-18 | 2015-01-21 | 中国科学院大连化学物理研究所 | Integrated membrane electrode structure for lithium sulfur battery and preparation method thereof |
| CN104518224A (en) * | 2013-09-29 | 2015-04-15 | 中国科学院大连化学物理研究所 | Lithium air battery integrated air electrode preparation method |
| JP2017073350A (en) * | 2015-10-09 | 2017-04-13 | トヨタ自動車株式会社 | Method for manufacturing electrode body |
| CN106159197A (en) * | 2016-09-30 | 2016-11-23 | 上海空间电源研究所 | A kind of integrated flexible membrane electrode and preparation method thereof |
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