CN106158412A - A kind of lithium-ion capacitor and preparation method thereof - Google Patents
A kind of lithium-ion capacitor and preparation method thereof Download PDFInfo
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- CN106158412A CN106158412A CN201510134757.4A CN201510134757A CN106158412A CN 106158412 A CN106158412 A CN 106158412A CN 201510134757 A CN201510134757 A CN 201510134757A CN 106158412 A CN106158412 A CN 106158412A
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- lithium
- ion capacitor
- positive pole
- activated carbon
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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 embodiment of the present invention provides a kind of lithium-ion capacitor, including shell, positive pole, negative pole, barrier film and electrolyte, described positive pole includes lithium metal oxide, activated carbon, conductive agent and binding agent.The embodiment of the present invention also provides a kind of method making lithium-ion capacitor, including sequentially stack negative pole, barrier film and positive pole, builds up square electric cell；Square electric cell is carried out heat treatment, obtains battery core of shaping；Setting battery core is put in the plastic-aluminum combined film package bag of pre-punching forming；Inject electrolyte at drying room；Seal under vacuo.The energy density of the lithium-ion capacitor of the present invention is 25Wh/kg, operating voltage range 4V～2.5V, significantly improves energy density and the operating voltage of present stage lithium-ion capacitor.And lithium-ion capacitor preparation method technique of the present invention is simple, yield rate is high, Product Safety is good, stable performance, it is easy to large-scale production.
Description
Technical field
The present invention relates to a kind of electrochemical energy storing device, particularly relate to a kind of lithium-ion capacitor and making thereof
Method.
Background technology
High power, charge/discharge rates be fast, low self-discharge, high electricity owing to having for lithium-ion capacitor (LIC)
Pressure and the feature of high-energy-density, in CAPACITY IN ELECTRICITY cities such as moment compensation device and uninterrupted power sources (UPS)
?；The electric regenerative such as electric car, hybrid electric vehicle market；The load such as solar electrical energy generation and wind-power electricity generation is put down
Homogenizing market；The electric power such as hybrid electric vehicle and duplicator Auxiliary market is with a wide range of applications.Wherein,
Electric regenerative market scale is maximum.
At present, there is a kind of inorganic mixed type lithium ion super capacitor in prior art, this lithium ion surpasses
The feature of level capacitor is to use the inorganic lithium intercalation compound such as series LiMn2O4, cobalt acid lithium to make positive pole, activated carbon
Make negative pole.The energy density of this lithium ion super capacitor is 13～18Wh/Kg, and operating voltage is
, there is energy density and operating voltage defect on the low side in 0.8V～1.8V.
Content of the invention
The purpose of the embodiment of the present invention is to provide a kind of lithium-ion capacitor and preparation method thereof, to improve lithium
The energy density of ionistor and operating voltage.
For reaching above-mentioned purpose, the embodiment of the invention discloses a kind of lithium-ion capacitor, technical scheme is as follows:
A kind of lithium-ion capacitor, including shell, positive pole, negative pole, barrier film and electrolyte；Wherein, described
Positive pole includes: lithium metal oxide, activated carbon, conductive agent and binding agent.
In the preferred embodiment of the present invention, described lithium metal oxide is LiNi(1-a-b)CoaAlbO2,
Wherein 0.1 < a < 0.3,0.01 <b < 0.2,0 < 1-a-b < 1.
In the preferred embodiment of the present invention, described LiNi(1-a-b)CoaAlbO2For
LiNi0.8Co0.15Al0.05O2。
In the preferred embodiment of the present invention, in described positive pole, the weight portion of lithium metal oxide is
40～80, the weight portion of activated carbon is 10～40, and the weight portion of conductive agent is 5～10, the weight portion of binding agent
It is 10～20.
One in the present invention is more highly preferred in embodiment, the weight portion of lithium metal oxide in described positive pole
Being 50～70, the weight portion of activated carbon is 10～30, and the weight portion of conductive agent is 5～8, the weight of binding agent
Part is 12～20.
In the preferred embodiment of the present invention, described negative pole includes: activated carbon, conductive agent and bonding
Agent；Described electrolyte is the organic system containing lithium hexafluoro phosphate and triethyl methyl tetrafluoro boric acid ammonia.
In the preferred embodiment of the present invention, the specific surface area of described activated carbon is not less than 1500m2/g。
In the preferred embodiment of the present invention, lithium metal oxide, activated carbon and lead in described positive pole
The weight sum of electricity agent is 0.5～1.55 with the ratio of activated carbon in described negative pole and the weight sum of conductive agent.
In the preferred embodiment of the present invention, described conductive agent is nano-carbon powder, conductive black, leads
One or more of electro-graphitic, Ketjen black, CNT and Graphene；Described binding agent be polytetrafluoroethylene (PTFE),
Kynoar, sodium carboxymethylcellulose, carboxymethyl cellulose ammonium, hydroxyethyl cellulose, hydroxy propyl cellulose
Element, hydroxypropyl methyl cellulose, methyl methacrylate-styrene-butadiene rubber, acrylonitrile-butadiene
Rubber, LA132, LA133 and LA135 one or more.
For reaching above-mentioned purpose, the embodiment of the invention discloses a kind of method making above-mentioned lithium-ion capacitor,
Comprise the following steps:
Negative pole, barrier film and positive pole are sequentially stacked, builds up square electric cell；
Square electric cell is carried out heat treatment, obtains battery core of shaping；
Setting battery core is put in the plastic-aluminum combined film package bag of pre-punching forming；
Inject electrolyte at drying room；
Seal under vacuo.
The operating voltage range of the lithium-ion capacitor that the embodiment of the present invention provides rises to 4V～2.5V, energy
Density reaches 25Wh/kg, significantly improves operating voltage and the energy density of present stage lithium-ion capacitor.And
And the lithium-ion capacitor preparation method technique of embodiment of the present invention offer is simple, yield rate is high, product safety
Good, the stable performance of property, it is easy to large-scale production.Certainly, implement arbitrary product of the present invention or method must not
Necessarily need to reach all the above advantage simultaneously.
Brief description
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to enforcement
In example or description of the prior art, the accompanying drawing of required use is briefly described, it should be apparent that, describe below
In accompanying drawing be only some embodiments of the present invention, for those of ordinary skill in the art, do not paying
On the premise of going out creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the product schematic diagram of the lithium-ion capacitor completing.
Detailed description of the invention
Inventor is in the R&D process carrying out lithium-ion capacitor, it has unexpectedly been found that, by lithium-ion capacitor
Positive pole in add appropriate activated carbon can improve the performance of lithium-ion capacitor, such as lithium-ion capacitor energy
Metric density and operating voltage etc..
Therefore, first aspect present invention provides a kind of lithium-ion capacitor, including shell, positive pole, negative pole,
Barrier film and electrolyte, wherein, the positive pole of lithium-ion capacitor includes lithium metal oxide, activated carbon, conduction
Agent and binding agent.
In the preferred embodiment of first aspect present invention, inventor finds, works as employing
LiNi(1-a-b)CoaAlbO2During the lithium metal oxide of type, compared with other type of lithium metal oxide,
The performance of obtained lithium-ion capacitor is more preferable, wherein, and 0.1 < a < 0.3,0.01 <b < 0.2,0 < 1-a-b < 1.
Specifically, above-mentioned LiNi(1-a-b)CoaAlbO2The lithium metal oxide of type can be LiNi0.8Co0.15Al0.05O2。
It should be noted that above-mentioned lithium metal oxide is all commercially, for example, LiNi0.8Co0.15Al0.05O2
Can choose from Shenzhen Bei Terui company, the product of NCA-1 type.
The addition of activated carbon is also influential for the performance of whole lithium-ion capacitor, adding of activated carbon
Enter amount too much, the addition of lithium metal oxide will certainly be reduced, so can largely effect on lithium-ion capacitor
Performance, but if the addition of activated carbon is very few, then the performance boost for whole lithium-ion capacitor
DeGrain.
Therefore, in some detailed description of the invention of first aspect present invention, it is preferable that lithium metal in positive pole
The weight portion of oxide is 40～80, and the weight portion of activated carbon is 10～40, and the weight portion of conductive agent is 5～10,
The weight portion of binding agent is 10～20；It is highly preferred that the weight portion of lithium metal oxide is 50～70 in positive pole,
The weight portion of activated carbon is 10～30, and the weight portion of conductive agent is 5～8, and the weight portion of binding agent is 12～20.
Choosing for activated carbon, inventor finds, when the specific surface area of activated carbon is not less than 1500m2/g
When, the performance of obtained lithium-ion capacitor is more.
For the conductive agent in positive pole and binding agent, the state of the art can be used to realize, this
Bright be not especially limited at this, for example, conductive agent in positive pole can selected from nano-carbon powder, conductive black,
One or more of electrically conductive graphite, Ketjen black, CNT and Graphene；Lead based on reduction cost and raising
The consideration of electrical property, preferably with electrically conductive graphite as conductive agent.
Binding agent in positive pole can be selected from polytetrafluoroethylene (PTFE), Kynoar, sodium carboxymethylcellulose, carboxylic
Methylcellulose ammonium, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, metering system
Acid methyl esters-SBR styrene butadiene rubbers, acrylonitrile-butadiene rubber, the aqueous binders (LA of LA series
132nd, LA133 and LA135) one or more, preferably with Kynoar (PVDF) as bonding
Agent, it is so that the performance of lithium-ion capacitor is more preferable.
The negative pole of the lithium-ion capacitor that the present invention provides may include that activated carbon, conductive agent and binding agent.
It is understood that the activated carbon in negative pole can select specific surface area to be not less than 1500m2The activated carbon of/g；
Conductive agent in negative pole can be selected from as nano-carbon powder, conductive black, electrically conductive graphite, Ketjen black, carbon
One or more of nanotube and Graphene；
Binding agent in negative pole can be selected from polytetrafluoroethylene (PTFE), Kynoar, sodium carboxymethylcellulose, carboxylic
Methylcellulose ammonium, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, metering system
Acid methyl esters-SBR styrene butadiene rubbers, acrylonitrile-butadiene rubber, the aqueous binders (LA of LA series
132nd, LA133 and LA135) one or more.
The electrolyte of the lithium-ion capacitor that the present invention provides can be containing lithium ion salt and triethyl methyl
The organic system of tetrafluoro boric acid ammonia salt.Specifically, electrolyte includes that solute is lithium hexafluoro phosphate (LiPF6) and three
Ethyl-methyl tetrafluoro boric acid ammonia (Et3MeNBF4) salt-mixture, solvent be selected from propylene carbonate ester (PC), ethyl
Carbonic ester (EC), dimethyl carbonate (DMC), acrylonitrile (AN), vinylene carbonate (VC), acetic acid
One or more in vinyl acetate (VA), ethylene sulfite (ES).Preferably solute LiPF6With
Et3MeNBF4Mol ratio be 2:1, solvent is the organic system of EC and DMC, the body of solute and solvent
Long-pending ratio is 1:1, and inventor finds, electrolyte conductivity and the wellability of such proportioning are more preferable.
The barrier film of lithium-ion capacitor that the present invention provides can be polyethylene porous membrane, polypropylene porous film,
Polyethylene and the one in polypropylene composite materials perforated membrane, vinylon non-woven fabrics, glass fibre porous membrane, tool
Which kind of barrier film body uses, and can be determined according to actual needs by those skilled in the art, sends out the present invention and exists
This is not especially limited.
In a kind of preferred embodiment of first aspect present invention, lithium metal oxide, activated carbon in positive pole
It is 0.5～1.55 with the weight sum of conductive agent with the ratio of activated carbon in described negative pole and the weight sum of conductive agent.
It when positive pole and negative pole are in this weight range, is more beneficial for improving the energy density of lithium-ion capacitor, increases
Add its life-span.
It should be noted that each component used by above-mentioned negative or positive electrode is generally pressed powder, at actual fabrication lithium
During ionistor, need to use 1-Methyl-2-Pyrrolidone (NMP) as solvent by used by negative or positive electrode
Each component be adjusted dilution, reach to be prepared again during suitable state.
A second aspect of the present invention provides a kind of making lithium-ion capacitor method, comprising:
Negative pole, barrier film and positive pole are sequentially stacked, builds up square electric cell；
Square electric cell is carried out heat treatment, obtains battery core of shaping；
Setting battery core is put in the plastic-aluminum combined film package bag of pre-punching forming；
Inject electrolyte at drying room；
Seal under vacuo.
Above-mentioned square electric cell heat treatment, can be to carry out crystallization operation on hot press, the technique ginseng of sizing
Number is 45 DEG C～60 DEG C, and pressure is 0.3Mba-0.5Mba, shapes 3～5 minutes.
In some detailed description of the invention of second aspect present invention, the manufacture craft of positive pole is: by lithium metal
Oxide, activated carbon, conductive agent and binding agent mixing, be made into by 1-Methyl-2-Pyrrolidone (NMP)
Slurry, is then coated on aluminium foil, puts in vacuum drying chamber 120 DEG C, is dried 24h, through roll-in, cut-parts
Become certain size.
In the present invention, the manufacture craft of negative pole is: mixes activated carbon, conductive agent and binding agent, uses 1-
N-methyl-2-2-pyrrolidone N (NMP) is made into slurry, is then coated on aluminium foil, puts in vacuum drying chamber 120 DEG C,
It is dried 24h, become certain size through roll-in, cut-parts.
Describe technical scheme below in conjunction with specific embodiment in detail.
Embodiment 1:
Positive plate makes: by LiNi0.8Co0.15Al0.05O2(being called for short NCA) (Shenzhen Bei Terui, NCA-1
Model) 80g, activated carbon (Kuraray, YP-50F model) 20g, (Switzerland spy is close for electrically conductive graphite
Height, SFG15 model) 10g, PVDF (France A Kema, HSV900 model) 10g mixing, use 1-
N-methyl-2-2-pyrrolidone N (NMP) is made into slurry, is then coated on aluminium foil, puts in vacuum drying chamber 120 DEG C,
It is dried 24h, be fabricated to the positive plate of a size of 52*82*0.08mm through roll-in, cut-parts, and put pole of burn-oning
Ear, i.e. obtains positive pole ear.
Negative plate makes: by activated carbon 80g, electrically conductive graphite 10g, PVDF 10g, be made into slurry with NMP
Material, is then coated on aluminium foil, puts in vacuum drying chamber 120 DEG C, is dried 24h, through roll-in, cut-parts system
It is made the negative plate of a size of 52*82*0.20mm, and lug of burn-oning, i.e. obtain negative plate.
Negative pole, barrier film, positive pole are stacked successively, is wound into square electric cell, then by 45 DEG C on hot press,
0.5Mba, shapes 5 minutes, puts in the aluminum plastic film of shaping, injects (1M LiPF in drying room6+0.5M
Et3MeNBF4)/(EC+DMC) (volume ratio 1:1) electrolyte, seal into lithium-ion capacitance under vacuum
Device, is shown in Fig. 1.
Embodiment 2～5
The method making lithium-ion capacitor in embodiment 2～5 is basically identical with embodiment 1, simply in positive pole
Included lithium metal oxide, activated carbon, conductive agent are different with consumption with the species of binding agent；Embodiment
In 2～5, species and the consumption of the lithium metal oxide included by positive pole, activated carbon, conductive agent and binding agent can
To see table 1.
The species of the material included by table 1 embodiment 2～5 positive pole and consumption
| Embodiment 2 | NCA:70g | Activated carbon: 10g | Conductive black: 10g | PTFE:10g |
| Embodiment 3 | NCA:60g | Activated carbon: 20g | Ketjen black: 5g | PTFE:12g |
| Embodiment 4 | NCA:50g | Activated carbon: 30g | Conductive black: 8g | PVDF:15g |
| Embodiment 5 | NCA:40g | Activated carbon: 40g | Electrically conductive graphite: 5g | PVDF:20g |
Wherein, conductive black is purchased from: Switzerland Te Migao, model SFG15；PVDF (polytetrafluoroethylene (PTFE)) purchases
From in: France A Kema, model HSV900.
The lithium-ion capacitor making in embodiment 1～5 is carried out voltage tester, and energy density is tested, and with
400mA/g (positive pole) current density discharge and recharge, circulates 50000 cycles, tests the electricity prepared by each embodiment
The retention value of the ratio electric capacity of container, and calculate specific capacity conservation rate.The results are shown in Table shown in 2.
The performance of the lithium-ion capacitor making in table 2 embodiment 1～5
| Operating voltage (V) | Energy density (Wh/kg) | Specific capacity conservation rate (%) | |
| Embodiment 1 | 2.5～4 | 26.5 | 88 |
| Embodiment 2 | 2.5～4 | 25.2 | 89 |
| Embodiment 3 | 2.5～4 | 24.1 | 86 |
| Embodiment 4 | 2.5～4 | 24.8 | 87 |
| Embodiment 5 | 2.5～4 | 25.5 | 88 |
From Table 2, it can be seen that technical scheme, after adding absorbent charcoal material in positive pole, with
Prior art is compared, and can significantly improve energy density and the operating voltage of lithium-ion capacitor, meanwhile, lithium
The cycle life of ionistor is also higher.
Above lithium-ion capacitor provided by the present invention and preparation method thereof is described in detail.Herein
In apply principle and embodiment to the present invention for the specific embodiment and be set forth, saying of above example
Bright method and the central idea thereof being only intended to help to understand the present invention.It should be pointed out that, for this area is general
For logical technical staff, under the premise without departing from the principles of the invention, some changing can also be carried out to the present invention
Entering and modifying, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (10)
1. a lithium-ion capacitor, including shell, positive pole, negative pole, barrier film and electrolyte, its feature
Being, described positive pole includes: lithium metal oxide, activated carbon, conductive agent and binding agent.
2. lithium-ion capacitor as claimed in claim 1, it is characterised in that described lithium metal oxide
For LiNi(1-a-b)CoaAlbO2, wherein 0.1 < a < 0.3,0.01 <b < 0.2,0 < 1-a-b < 1.
3. lithium-ion capacitor as claimed in claim 2, it is characterised in that described LiNi(1-a-b)CoaAlbO2
For LiNi0.8Co0.15Al0.05O2。
4. lithium-ion capacitor as claimed in claim 1 or 2, it is characterised in that lithium in described positive pole
The weight portion of metal oxide is 40～80, and the weight portion of activated carbon is 10～40, and the weight portion of conductive agent is
5～10, the weight portion of binding agent is 10～20.
5. lithium-ion capacitor as claimed in claim 4, it is characterised in that lithium metal in described positive pole
The weight portion of oxide is 50～70, and the weight portion of activated carbon is 10～30, and the weight portion of conductive agent is 5～8,
The weight portion of binding agent is 12～20.
6. lithium-ion capacitor as claimed in claim 1, it is characterised in that described negative pole includes: live
Property charcoal, conductive agent and binding agent；Described electrolyte is for containing lithium hexafluoro phosphate and triethyl methyl tetrafluoro boric acid
The organic system of ammonia.
7. lithium-ion capacitor as claimed in claim 1, it is characterised in that the ratio table of described activated carbon
Area is not less than 1500m2/g。
8. lithium-ion capacitor as claimed in claim 1, it is characterised in that lithium metal in described positive pole
The weight sum of activated carbon and conductive agent in the weight sum of oxide, activated carbon and conductive agent and described negative pole
Ratio be 0.5～1.55.
9. the lithium-ion capacitor as described in claim 1 or 6, it is characterised in that described conductive agent is for receiving
One or more of rice carbon dust, conductive black, electrically conductive graphite, Ketjen black, CNT and Graphene；Institute
Stating binding agent is polytetrafluoroethylene (PTFE), Kynoar, sodium carboxymethylcellulose, carboxymethyl cellulose ammonium, hydroxyl
Ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, Methyl Methacrylate-Styrene-fourth
Diene rubber, acrylonitrile-butadiene rubber, LA132, LA133 and LA135 one or more.
10. the method making lithium-ion capacitor as claimed in claim 1, it is characterised in that bag
Include following steps:
Negative pole, barrier film and positive pole are sequentially stacked, builds up square electric cell；
Square electric cell is carried out heat treatment, obtains battery core of shaping；
Setting battery core is put in the plastic-aluminum combined film package bag of pre-punching forming；
Inject electrolyte at drying room；
Seal under vacuo.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108493005A (en) * | 2018-01-22 | 2018-09-04 | 江苏集盛星泰新能源科技有限公司 | A kind of preparation method of lithium-ion capacitor |
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Application publication date: 20161123 |