CN108155027B - A kind of method of the pre- embedding lithium of lithium ion super capacitor cathode - Google Patents
A kind of method of the pre- embedding lithium of lithium ion super capacitor cathode Download PDFInfo
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- CN108155027B CN108155027B CN201611098898.6A CN201611098898A CN108155027B CN 108155027 B CN108155027 B CN 108155027B CN 201611098898 A CN201611098898 A CN 201611098898A CN 108155027 B CN108155027 B CN 108155027B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 69
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003990 capacitor Substances 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000011149 active material Substances 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 239000007773 negative electrode material Substances 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 239000003610 charcoal Substances 0.000 claims description 15
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims description 10
- 229910021382 natural graphite Inorganic materials 0.000 claims description 8
- -1 polypyridine Polymers 0.000 claims description 8
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 6
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 239000002322 conducting polymer Substances 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000004966 Carbon aerogel Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000010586 diagram Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000011325 microbead Substances 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims 1
- 230000002687 intercalation Effects 0.000 claims 1
- 238000009830 intercalation Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 12
- 239000006258 conductive agent Substances 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 230000004087 circulation Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000005030 aluminium foil Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 241000238557 Decapoda Species 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of methods of the pre- embedding lithium of lithium ion super capacitor cathode, including anode, diaphragm, cathode, and the electrolyte between positive electrode and negative electrode；The positive electrode includes active material and pre- embedding lithium additive；Wherein, pre- embedding lithium additive and the mass ratio of negative electrode material are 1:100~10:1；Anode, diaphragm, cathode are assembled into lithium ion super capacitor, are added after electrolyte to the pre- embedding lithium of battery charging.The cyclical stability of the lithium-ion capacitor of less pre- embedding lithium is more preferable, safe and reliable, at low cost.
Description
Technical field
The present invention relates to electrochemical energy storage fields.
Background technique
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.
It is cathode that most of lithium ion super capacitor, which is all made of carbonaceous material,.In order to improve the cyclicity of capacitor, all
It needs using pre- embedding lithium technology.
Early in a kind of lithium ion super capacitor that Fuji Heavy in 2006 announces, specific energy up to 12-30Wh/kg,
For capacity retention ratio still 96% or more, excellent cyclicity has benefited from pre-embedding lithium processes after 300000 circulations.
Pre- embedding lithium technology is a vital ring in lithium ion super capacitor manufacturing technology, manufacturing cost height and technique
Complexity is generally acknowledged technological difficulties.Available data has been discovered that a variety of manufacturing technologies of lithium ion super capacitor, lithium source
The factors such as selection, tax lithium process implementations, lithium doping amount decide device performance, manufacturing cost, reliability.
Fuji Heavy uses multicellular metal foil as collector, places a piece of lithium foil in the opposite position of outermost layer cathode,
Accordingly even when being the monomer containing multi-layered electrode, Li+ can also pass freely through the coating being attached on collector and be laminated in electrode
It is moved in unit, so that Li+ is doped in cathode.This pre-embedding lithium method needs to use lithium metal as lithium source, to being made
Environmental requirement is harsh, and has great security risk.
Professor Zheng Jianping of Tongji University is the stable metal lithium powder of 10~200nm, surface with passivating film using partial size
(SLMP) it is lithium source, cathode is made with dry process after mixing with hard charcoal, active carbon is that anode is assembled into LIC monomer, test knot
Fruit shows that monomer specific energy is about 25Wh/kg, 60% when the electric discharge specific energy of 44C multiplying power is about 2.4C, after 600 times recycle
The capacitor reduction amount of monomer is lower than 3%.Compared to the structure that Fuji Heavy uses lithium metal foil, the LIC of the structure can be in drying shed
In manufactured, without the harsh environment of glove box, considerably increase operability.
Rich lithium compound of the use such as Wu Feng of Beijing Institute of Technology with certain irreversible de- lithium property, such as cobalt acid lithium,
LiMn2O4 etc. is greatly improved the packaging technology of lithium ion super capacitor, the manufacturing cost and safety of capacitor
While having clear improvement, it also can increase a part of unnecessary quality to battery, reduce the energy density of battery, especially
In the case where needing pre- embedding lithium degree very big.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of sides of the pre- embedding lithium of lithium ion super capacitor and cathode
Method will not increase while this method can prepare electrode and safety in normal lithium battery coating environment
It is powered on the quality in pond, cost can greatly be reduced.
In order to achieve the above objectives, the specific technical solution of use is as follows,
A kind of method of the pre- embedding lithium of lithium ion super capacitor cathode, including anode, diaphragm, cathode, and it is located at anode
Electrolyte between cathode；
The positive electrode includes active material and pre- embedding lithium additive；
The negative electrode material includes natural graphite, hard charcoal, mesophase microbeads charcoal, amorphous carbon, silicon, silica, charcoal
One of silicon compound, lithium titanate are two or more；
Wherein, pre- embedding lithium additive and the mass ratio of negative electrode material are 1:100~10:1；
Anode, diaphragm, cathode are assembled into lithium ion super capacitor, are added after electrolyte to the pre- embedding lithium of battery charging.
Battery charging pre-embedding lithium method includes the pre- embedding lithium of constant current or the pre- embedding lithium of constant pressure；
The pre- embedding lithium of battery constant current, electric current are the pre- embedding lithium additive of the every g of 0.01mA-10A/, charge cutoff voltage 0.42V-
5V；
The pre- embedding lithium of battery constant pressure, voltage 0.42V-5V, cut-off current are 0.001m A-1m A.
The pre- embedding lithium additive is one of lithia, lithium peroxide, lithium nitride, charing lithium or two or more.
The pre- embedding lithium additive be preferred lithia, lithium peroxide, lithium nitride it is one or two kinds of more than；Pre- embedding lithium
Additive and the mass ratio of negative electrode material are 1:5~5:1.
The active material includes one of absorbent charcoal material, conducting polymer, oxide or two or more.
The absorbent charcoal material includes active carbon powder, activated carbon fibre, carbon aerogels, carbon nanotube, graphene, charcoal
It is one of black etc. or two or more；The conducting polymer includes polyaniline, polythiophene, polypyrrole, polypyridine, polyphenyl
And its one of derivative or two or more；
The oxide includes one of manganese dioxide, ruthenium-oxide, titanium dioxide or two or more.
The diaphragm is polyethylene diagrams, polypropylene diaphragm, polyethylene, polypropylene composite materials diaphragm, cellulosic separator, glass
Glass cellulosic separator or ceramic membrane.
The invention has the advantages that:
Provided by the present invention for the cathode pre-embedding lithium method of lithium-ion capacitor, the lithium-ion capacitance of less pre- embedding lithium
The good cycling stability of device, this method can prepare electrode and safety in normal lithium battery coating environment
While, the quality of battery will not be increased, cost can greatly be reduced.
Specific embodiment
Below with reference to embodiment, the content of invention is more specifically illustrated.Implementation of the invention is not limited to what dried shrimp was held high
Embodiment.
Embodiment 1
Prepare lithium-ion capacitor cathode.Natural graphite, conductive agent, PVDF are mixed according to mass ratio for 80:15:5
After even, NMP (additional amount of NMP account for entire slurry 50%) is added, stirs 12 hours, is coated on copper foil, it is natural after drying
The surface density of graphite is 5mgcm-2。
Prepare lithium-ion capacitor anode.By active carbon, conductive agent, PVDF, lithium nitride according to mass ratio be 60:10:5:
25 after mixing, and NMP (additional amount of NMP account for entire slurry 55%) stirring 12 hours is added, is coated on aluminium foil, dries
The surface density of active carbon is 15mgcm afterwards-2。
Above-mentioned positive and negative anodes are sliced into 7.7cm*5cm size, thoroughly after drying, anode, cathode, diaphragm are assembled into lamination
The aluminum-plastic packaged interior of corresponding size, fluid injection are packed into after battery.
Under inert conditions, to the pre- embedding lithium of battery charging, the electric current of pre- embedding lithium is 0.01Ag-1(based on lithium nitride matter in battery
Amount), charge cutoff voltage 1V.In charging process, guarantee that battery is in open state, to be conducive to nitrogen discharge.
After charging, battery seal test, 1A.g-1After 10000 circulations of (being calculated based on cell active materials) test
Capacity retention ratio and capacitance pool energy density (being based on active material), and be reported in Table 1 below.
Comparative example 1
Prepare lithium-ion capacitor cathode.Natural graphite, conductive agent, PVDF are mixed according to mass ratio for 80:15:5
After even, NMP (additional amount of NMP account for entire slurry 50%) is added, stirs 12 hours, is coated on copper foil, it is natural after drying
The surface density of graphite is 5mgcm-2。
Prepare lithium-ion capacitor anode.Active carbon, conductive agent, PVDF are uniformly mixed according to mass ratio for 85:10:5
Afterwards, NMP (additional amount of NMP account for entire slurry 50%) stirring 12 hours is added, is coated on aluminium foil, active carbon after drying
Surface density is 15mgcm-2。
Above-mentioned positive and negative anodes are sliced into 7.7cm*5cm size, thoroughly after drying, anode, cathode, diaphragm are assembled into lamination
The aluminum-plastic packaged interior of corresponding size, fluid injection are packed into after battery.
Under inert conditions, to the pre- embedding lithium of battery charging, the electric current of pre- embedding lithium is 0.01Ag-1(being based on active material), charging
Blanking voltage is 1V.In charging process, guarantee that battery is in open state, to be conducive to nitrogen discharge.
After charging, battery seal test, 1A.g-1After 10000 circulations of (being calculated based on cell active materials) test
Capacity retention ratio and capacitive energy density (being based on active material), and be reported in Table 1 below.
By result as can be seen that stable circulation is much better than the capacitor of not embedding lithium, and the energy density of capacitor is basic
Do not influence.
Embodiment 2
Prepare lithium-ion capacitor cathode.Natural graphite, conductive agent, PVDF are mixed according to mass ratio for 80:15:5
After even, NMP (additional amount of NMP account for entire slurry 50%) is added, stirs 12 hours, is coated on copper foil, it is natural after drying
The surface density of graphite is 3mgcm-2。
Prepare lithium-ion capacitor anode.By active carbon, conductive agent, PVDF, lithia according to mass ratio be 50:10:5:
35 after mixing, and NMP (additional amount of NMP account for entire slurry 55%) stirring 12 hours is added, is coated on aluminium foil, dries
The surface density of active carbon is 15mgcm afterwards-2。
Under inert conditions, to the pre- embedding lithium of battery charging, the electric current of pre- embedding lithium is 0.01Ag-1(based on lithia matter in battery
Amount), charge cutoff voltage 3.5V.In charging process, guarantee that battery is in open state, to be conducive to nitrogen discharge.
After charging, battery seal test, 1A.g-1After 10000 circulations of (being calculated based on cell active materials) test
Capacity retention ratio and capacitive energy density (being based on active material), and be reported in Table 1 below.Embodiment 3
Prepare lithium-ion capacitor cathode.By hard charcoal, conductive agent, PVDF according to mass ratio be 80:15:5 after mixing,
NMP (additional amount of NMP account for entire slurry 50%) is added, stirs 12 hours, is coated on copper foil, natural graphite after drying
Surface density is 5mgcm-2。
Prepare lithium-ion capacitor anode.By active carbon, conductive agent, PVDF, lithium nitride according to mass ratio be 60:10:5:
25 after mixing, and NMP (additional amount of NMP account for entire slurry 55%) stirring 12 hours is added, is coated on aluminium foil, dries
The surface density of active carbon is 12mgcm afterwards-2。
Above-mentioned positive and negative anodes are sliced into 7.7cm*5cm size, thoroughly after drying, anode, cathode, diaphragm are assembled into lamination
The aluminum-plastic packaged interior of corresponding size, fluid injection are packed into after battery.
Under inert conditions, to the pre- embedding lithium of battery charging, the electric current of pre- embedding lithium is 0.001Ag-1(based on lithium nitride matter in battery
Amount), charge cutoff voltage 1V.In charging process, guarantee that battery is in open state, to be conducive to nitrogen discharge.
After charging, battery seal test, 1A.g-1After 10000 circulations of (being calculated based on cell active materials) test
Capacity retention ratio and capacitive energy density (being based on active material), and be reported in Table 1 below.Embodiment 4
Prepare lithium-ion capacitor cathode.By hard charcoal, conductive agent, PVDF according to mass ratio be 80:15:5 after mixing,
NMP (additional amount of NMP account for entire slurry 50%) is added, stirs 12 hours, is coated on copper foil, natural graphite after drying
Surface density is 5mgcm-2。
Prepare lithium-ion capacitor anode.By active carbon, conductive agent, PVDF, lithium nitride according to mass ratio be 55:10:5:
30 after mixing, and NMP (additional amount of NMP account for entire slurry 53%) stirring 12 hours is added, is coated on aluminium foil, dries
The surface density of active carbon is 18mgcm afterwards-2。
Above-mentioned positive and negative anodes are sliced into 7.7cm*5cm size, thoroughly after drying, anode, cathode, diaphragm are assembled into lamination
The aluminum-plastic packaged interior of corresponding size, fluid injection are packed into after battery.
Under inert conditions, to the pre- embedding lithium of battery charging, the electric current of pre- embedding lithium is 0.02Ag-1(based on lithium nitride matter in battery
Amount), charge cutoff voltage 1V.In charging process, guarantee that battery is in open state, to be conducive to nitrogen discharge.
After charging, battery seal test, 1A.g-1After 10000 circulations of (being calculated based on cell active materials) test
Capacity retention ratio and capacitive energy density (being based on active material), and be reported in Table 1 below.Embodiment 5
Prepare lithium-ion capacitor cathode.By hard charcoal, conductive agent, PVDF according to mass ratio be 80:15:5 after mixing,
NMP (additional amount of NMP account for entire slurry 50%) is added, stirs 12 hours, is coated on copper foil, natural graphite after drying
Surface density is 5mgcm-2。
Prepare lithium-ion capacitor anode.By active carbon, conductive agent, PVDF, lithium peroxide according to mass ratio be 40:10:
5:45 after mixing, is added NMP (additional amount of NMP account for entire slurry 53%) stirring 12 hours, is coated on aluminium foil, dry
The surface density of active carbon is 15mgcm after dry-2。
Above-mentioned positive and negative anodes are sliced into 7.7cm*5cm size, thoroughly after drying, anode, cathode, diaphragm are assembled into lamination
The aluminum-plastic packaged interior of corresponding size, fluid injection are packed into after battery.
Under inert conditions, to the pre- embedding lithium of battery charging, the electric current of pre- embedding lithium is 0.02Ag-1(based on lithium peroxide in battery
Quality), charge cutoff voltage 4V.In charging process, guarantee that battery is in open state, to be conducive to nitrogen discharge.
After charging, battery seal test, 1A.g-1After 10000 circulations of (being calculated based on cell active materials) test
Capacity retention ratio and capacitive energy density (being based on active material), and be reported in Table 1 below.
Table 1
| Capacity retention ratio after 10000 circulations | Energy density (is based on active material) | |
| Embodiment 1 | 93% | 125Wh/kg |
| Comparative example 1 | 60% | 126Wh/kg |
| Embodiment 2 | 92% | 127Wh/kg |
| Embodiment 3 | 90% | 124Wh/kg |
| Embodiment 4 | 87% | 128Wh/kg |
| Embodiment 5 | 88% | 130Wh/kg |
Claims (5)
1. a kind of method of the pre- embedding lithium of lithium ion super capacitor cathode, lithium ion super capacitor includes anode, diaphragm, bears
Pole, and the electrolyte between positive electrode and negative electrode；It is characterized by:
The positive electrode of the anode includes active material and pre- embedding lithium additive；
The negative electrode material of the cathode includes natural graphite, hard charcoal, mesophase microbeads charcoal, amorphous carbon, silicon, silica, charcoal
One of silicon compound, lithium titanate are two or more；
Wherein, pre- embedding lithium additive and the mass ratio of negative electrode material are 1:100 ~ 10:1；
Anode, diaphragm, cathode are assembled into lithium ion super capacitor, are added after electrolyte to the pre- embedding lithium of battery charging;
Battery charges pre-embedding lithium method as the pre- embedding lithium of constant current；
The pre- embedding lithium of battery constant current, electric current are the pre- embedding lithium additive of 0.01 mA-0.02A/every g, and charge cutoff voltage is 0.42 V-
5 V；
The pre- embedding lithium additive is one of lithia, lithium peroxide, lithium nitride, charing lithium or two or more；
In the pre- process of intercalation that charges, guarantee that battery is in open state, to be conducive to gas discharge.
2. according to the method for claim 1, it is characterised in that:
The pre- embedding lithium additive be lithia, lithium peroxide, lithium nitride it is one or two kinds of more than；Pre- embedding lithium additive with
The mass ratio of negative electrode material is 1:5 ~ 5:1.
3. according to the method for claim 1, it is characterised in that:
The active material includes one of absorbent charcoal material, conducting polymer, oxide or two or more.
4. according to the method for claim 3, it is characterised in that:
The absorbent charcoal material include active carbon powder, activated carbon fibre, carbon aerogels, carbon nanotube, graphene, in carbon black
It is one or two kinds of more than；The conducting polymer includes polyaniline, polythiophene, polypyrrole, polypyridine, polyphenyl and its spreads out
One of biology is two or more；
The oxide includes one of manganese dioxide, ruthenium-oxide, titanium dioxide or two or more.
5. according to the method for claim 1, it is characterised in that:
The diaphragm is polyethylene diagrams, polypropylene diaphragm, polyethylene-polypropylene composite diaphragm, cellulosic separator or ceramics
Film.
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|---|---|---|---|---|
| CN111105938A (en) * | 2018-10-26 | 2020-05-05 | 中国科学院大连化学物理研究所 | Lithium pre-embedding method for negative electrode of lithium ion super capacitor |
| CN109686923B (en) * | 2018-12-17 | 2020-07-17 | 深圳先进技术研究院 | Preparation method of pre-lithium-intercalated negative electrode, pre-lithium-intercalated negative electrode prepared by preparation method, energy storage device, energy storage system and electric equipment |
| CN110246699A (en) * | 2019-05-17 | 2019-09-17 | 中国科学院电工研究所 | A kind of anode electrode piece of lithium-ion capacitor, lithium-ion capacitor and its cathode pre-embedding lithium method |
| EP3848949A1 (en) * | 2020-01-08 | 2021-07-14 | Fundación Centro de Investigación Cooperativa de Energías Alternativas, CIC Energigune Fundazioa | Metal ion capacitor based on hard carbon as negative electrode and a mixture of activated carbon and sacrificial salt as the positive electrode |
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| CN101252043A (en) * | 2007-04-25 | 2008-08-27 | 北京理工大学 | Pre-embedding method of lithium ion super capacitor cathode |
| CN101847516A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Capacitor battery of high-specific-energy organic system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101252043A (en) * | 2007-04-25 | 2008-08-27 | 北京理工大学 | Pre-embedding method of lithium ion super capacitor cathode |
| CN101847516A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Capacitor battery of high-specific-energy organic system |
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