CN104835652A - Lithium-intercalation negative pole piece used for lithium super-capacitor battery, method for preparing same, and lithium super-capacitor battery - Google Patents
Lithium-intercalation negative pole piece used for lithium super-capacitor battery, method for preparing same, and lithium super-capacitor battery Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 209
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 238000000034 method Methods 0.000 title abstract description 19
- 239000003990 capacitor Substances 0.000 title abstract description 15
- 238000009830 intercalation Methods 0.000 title abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 18
- 238000003892 spreading Methods 0.000 claims description 7
- 230000007480 spreading Effects 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011883 electrode binding agent Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 230000003204 osmotic effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910014127 LiMn2 O4 -LiMn2 O4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a lithium-intercalation negative pole piece used for a lithium super-capacitor battery, a method for preparing the same, and the lithium super-capacitor battery, belonging to the lithium super-capacitor battery technology field. The lithium-intercalation negative pole piece used for the lithium super-capacitor battery comprises a negative pole current collector and a negative pole material coating coated on the surface of the negative pole current collector and containing a carbon material, and the lithium powders are intercalated in the surface of the negative pole material coating evenly. The lithium-intercalation negative pole piece used for the lithium super-capacitor battery is high in lithium-intercalation efficiency, enables the lithium absorption in the negative pole material coating and the effective utilization rate to be improved, and saves the lithium usage amount while improving the energy density of the whole lithium super-capacitor battery, and saves the cost.
Description
Technical field
The present invention relates to the embedding lithium cathode sheet of a kind of lithium super capacitance cell and preparation method, lithium super capacitance cell, belong to lithium super capacitance cell technical field.
Background technology
At present, using energy source strengthens to trend that is small-sized, discrete and removableization future development, and therefore various energy storage device particularly secondary cell also obtains great development opportunity.And along with the rapid expansion of electric automobile application market, except the energy density of energy storage device be there are certain requirements, more and more higher to the requirement of power density, what have has exceeded the standard design ability of current secondary cell, therefore, have again high-octane energy storage device in the urgent need to the existing high power of one, lithium super capacitance cell is exactly a kind of energy storage device that can meet this demand.Lithium super capacitance cell have employed the principle of double electric layer capacitor in design, constructively have employed the combination of the negative material of Li-Ion rechargeable battery and the positive electrode of double electric layer capacitor, under the prerequisite retaining ultracapacitor power density, substantially increase the energy density of capacitor.
Lithium super capacitance cell system is roughly divided into two classes by the difference of negative material: carbonaceous material negative pole and lithium titanate anode.The intercalation potential platform of lithium titanate anode is at about 1.5V, and material with carbon element is at 0.2V and following, and the gram volume of carbonaceous material is higher than lithium titanate material, so consider from energy density angle, carbonaceous material is more suitable for the negative pole being chosen as lithium super capacitance cell.Lithium super capacitance cell positive electrode has continued super capacitor material, i.e. porous active carbon resistance rod, relies on interfacial electric double layer to store electric charge, produces electric capacity.
The battery capacity C of lithium super capacitance cell calculates the formulae discovery (in formula, Cp and Cn is respectively the capacity of positive and negative pole material) that can adopt below:
Adopting porous active carbon resistance rod as positive pole, carbonaceous material as in the lithium super capacitance cell of negative pole, because the capacitance (if graphite electrode theoretical amount is 372mAh/g) of carbonaceous negative material electrode much larger than the electric double layer storage power of porous active carbon resistance rod, will can be similar to and regard C ≈ C as
p, therefore lithium super capacitance cell energy density calculate formula can approximate conversion as follows:
In formula, C
sfor lithium super capacitance cell specific capacity.V
aand V
bbe respectively minimum value and the maximum in condenser voltage interval.
Conventional porous carbon resistance rod surface is containing " active site " in a large number with electrocatalysis, the irreversible electrochemical reaction at their easy initiating activity charcoal-electrolyte interface places, this true upper limit has determined the safe operating voltage of active carbon, after active carbon specific area brings up to certain value, specific discharge capacity is tending towards reaching capacity, the capacity of commercially available oil system active carbon is greatly about about 100F, and this has had a strong impact on the performance of lithium super capacitance cell energy density.And after the rich lithium compound that adulterates in porous activated carbon, just can utilize the specific capacity characteristic of chemical combination object height, such as cobalt acid lithium LiCoO
2about 130-150mAh/g, nickel cobalt mangaic acid LiCo
xni
ymn
zo
2150-180mAh/g, LiMn2O4 LiMn
2o
4130-150mAh/g, nickel cobalt lithium aluminate LiNi
xco
yal
zo
2160-210mAh/g, LiFePO4 LiFePO
4130-150mAh/g etc., great Fu degree improves the overall specific capacity of blended anode material.According to formula 2, do not changing on the basis of ceiling voltage, by increasing C
pimprove the energy density of lithium super capacitance cell.
The open circuit voltage of porous active Carbon Materials opposing metallic lithium is about 3.0V, in the lithium super capacitance cell that active carbon/carbonaceous material is formed, the interval interval of effective electromotive force of anode activated charcoal only has within 3.0-4.5V (opposing metallic lithium), and 1.0V (optimize 1.5V) cannot play a role to the energy storage capacity in the electromotive force interval of 3.0V, the energy density of lithium super capacitance cell is restricted.
By cathode pole piece being carried out pre-embedding lithium process, negative pole current potential can be reduced on the one hand, improving the effect of lithium super capacitance cell maximum operating voltage, achieve the effect of whole system being supplemented to lithium ion on the other hand.After the pre-embedding lithium of cathode pole piece, lithium super capacitance cell is assembled into porous active Carbon Materials, effect is just reduction of the potential of carbon material used as anode the most intuitively, under the operating voltage that lithium super capacitance cell is same, the potential of anode activated charcoal will reduce accordingly, add the stability of anode in the use procedure of lithium super capacitance cell, improve cycle characteristics.Moreover, lithium super capacitance cell after pre-embedding lithium, pass through charge/discharge process, enable lithium ion lower than the energy storage producing electrostatic adsorption desorption form in the electromotive force interval of active carbon open circuit voltage with anode activated charcoal storeroom, the effective electromotive force interval of anode activated charcoal increases between 1.5-4.5V.According to formula 2, by the pre-embedding lithium process of negative pole, C can be increased simultaneously
pand V
b, reduce V
a, play the effect increasing lithium super capacitance cell energy density.
At present, on Japan and Korea S market, the pre-embedding lithium of lithium super capacitance cell (also known as lithium-ion capacitor) is realized by the mode of increase lithium sheet third electrode mostly, lithium sheet point of addition can only be fixed on several position, cannot realize the direct embedding lithium to per unit area negative plate.In order to reach better pre-embedding lithium effect, realize the even embedding lithium of anticathode sheet, both positive and negative polarity collector must have loose structure, and hole size needs to control within the specific limits, processes and meet the conveyance capacity of collector to facilitate the coating of active material.This kind of collector production and processing difficulty is large, and cost is high, and product cost is increased.Based on above reason, in order to reach good pre-embedding lithium effect, avoid potential safety hazard when using, the lithium super capacitance cell finished product formation process length consuming time assembled, about several days time, the production efficiency of product is low, is unfavorable for large-scale industrial production.
The people such as the Osamu Hatozaki of Fuji Heavy report a kind of lithium super capacitance cell in the 16 International Electrochemical capacitor seminar in 2006, the negative pole of this lithium super capacitance cell is with the embedding lithium Carbon Materials through metal lithium sheet process, positive pole is active carbon, its operating voltage reaches 3.8V, specific energy reaches 12-30Wh/kg, and specific power is up to 6kW/kg.But the electrode manufacturing process of this method is very complicated, and assembling environmental requirement is very harsh.
Samsung Electro-Mechanics Co., Ltd is disclose a kind of lithium-ion capacitor in the Chinese invention patent of 201110321951.5 at application number, its negative pole comprises the material with carbon element that pre-doping has lithium ion, pre-doping mode be by metallic lithium foil and negative plate staggered relatively, therebetween use polypropylene non-woven fabric as barrier film, continue to make doped lithium ion in negative pole in 2 hours.This method is by using lithium paper tinsel to doped lithium ion in negative pole, owing to it using metallic lithium foil, and use barrier film negative pole and lithium paper tinsel to be separated, lithium ion is lower to the doping osmotic efficiency in negative pole, osmotic effect is poor, to reach the time of penetration that higher lithium ion permeability needs to grow very much.And use metallic lithium foil and barrier film, correspondingly increase production cost.
Summary of the invention
The object of the present invention is to provide and a kind ofly process easy, the cost-saving embedding lithium cathode sheet of lithium super capacitance cell.
Second object of the present invention is the preparation method providing the embedding lithium cathode sheet of a kind of lithium super capacitance cell.
3rd object of the present invention is to provide a kind of lithium super capacitance cell.
In order to realize above object, lithium super capacitance cell of the present invention is as follows by the technical scheme of embedding lithium cathode sheet:
The embedding lithium cathode sheet of a kind of lithium super capacitance cell, comprise negative current collector and be coated in the negative material coating comprising material with carbon element of negative pole currect collecting surface, described negative material coating surface is evenly embedded with lithium powder.
" being embedded with " involved by technique scheme refers to that lithium powder is some or all of to be imbedded in negative material coating, fully contacts and have certain adhesion with negative material.
The embedding lithium cathode sheet of lithium super capacitance cell of the present invention carries out pre-embedding lithium by the mode adding lithium powder in the negative material coating of negative plate, lithium powder is evenly distributed on the surface that negative plate is coated with negative material, good contact is realized with negative material, the absorption of lithium in negative material coating can be increased substantially, improve the effective rate of utilization of lithium, not needing, barrier film is set and just can realize good contact, its lithium raw material dosage reduces greatly, use the mode of the 3rd pole lithium sheet in hinge structure, reduce production cost.Because lithium metal Nature comparison is active, very easily chemical reaction occurs when running into air or water, lithium powder comparatively disperses relative to lithium sheet, and violent or lasting chemical reaction is less likely to occur, comparatively safe in the production and use procedure of negative plate.
Lithium super capacitance cell of the present invention is as follows by the technical scheme of the preparation method of embedding lithium cathode sheet:
A lithium super capacitance cell preparation method for embedding lithium cathode sheet, comprises the steps:
(1) negative material comprising material with carbon element is coated in negative pole currect collecting surface, oven dry, first time roll-in, vacuumize, obtain the not embedding lithium cathode sheet being coated with negative material coating;
(2) the negative material coating surface of the not embedding lithium cathode sheet obtained in step (1) by lithium powder spreading, then has the negative plate of lithium powder to carry out second time roll-in to spreading, obtains embedding lithium cathode sheet.
In described step (2), spreading carries out in the following manner: make not embedding lithium cathode sheet be in below, lithium powder is in top, utilizes the free gravity of lithium powder to drop to negative plate on the surface.
The pressure of the second time roll-in in described step (2) is 2-20Mpa.
The technical scheme of lithium super capacitance cell of the present invention is as follows:
A kind of lithium super capacitance cell, comprise positive plate, negative plate and electrolyte, described negative plate is embedding lithium cathode sheet, described embedding lithium cathode sheet comprises negative current collector and is coated in the negative material coating comprising material with carbon element of negative pole currect collecting surface, and described negative material coating surface is distributed with lithium powder.
The capacity of described positive plate is 1:2-1:5 with the ratio of the capacity of negative plate.
Described positive plate comprises positive active material, and described positive active material comprises rich lithium metal oxide and active carbon.
Described electrolyte comprises electrolytic salt, electrolyte solvent, film for additive and the agent of high pressure over-charge protective, and described electrolytic salt is the LiPF of 1mol/L
6, described electrolyte solvent is the mass ratio of ethylene carbonate EC and methyl ethyl carbonate EMC, described EC and EMC is 1:1, and described film for additive is PS, and the agent of described high pressure over-charge protective is FEC.
Different operating environments is adapted in order to make the processing of embedding lithium cathode sheet, the lithium powder of lithium super capacitance cell of the present invention in embedding lithium cathode sheet and preparation method thereof and lithium super capacitance cell can select stabilized lithium powder, can carry out processed safely operation to make embedding lithium cathode sheet in moisture and the higher environment of oxygen content.
Lithium super capacitance cell of the present invention is Copper Foil with negative current collector described in embedding lithium cathode sheet and preparation method thereof and lithium super capacitance cell.
Lithium super capacitance cell of the present invention is 20-100 μm with the particle diameter D50 of lithium powder described in embedding lithium cathode sheet and preparation method thereof and lithium super capacitance cell, makes the easier ionization of lithium powder, improves the chemical property of embedding lithium cathode sheet.
Lithium super capacitance cell of the present invention is the 30-100% of the charged capacity of material with carbon element with the charged capacity of lithium powder described in embedding lithium cathode sheet and preparation method thereof and lithium super capacitance cell, further, preferably spread the amount of lithium powder with the 30%-75% making the charged capacity of lithium powder account for the initial charged capacity of carbon material used as anode, while the energy density improving lithium super capacitance cell and fail safe, also reduce and negative plate analyses lithium phenomenon.
Lithium super capacitance cell of the present invention is 120-130 μm with the thickness of embedding lithium cathode sheet described in embedding lithium cathode sheet and preparation method thereof and lithium super capacitance cell.
Lithium super capacitance cell of the present invention material with carbon element described in embedding lithium cathode sheet and preparation method thereof and lithium super capacitance cell is selected from the conventional material with carbon element in this area, such as, in hard carbon, soft carbon and graphite one or more.
Lithium super capacitance cell of the present invention negative material coating described in embedding lithium cathode sheet and preparation method thereof and lithium super capacitance cell comprises conductive agent and negative electrode binder, described conductive agent is the conductive agent that this area is commonly used, as one or more in graphene conductive agent, carbon black and carbon nano-tube, described negative electrode binder is the negative electrode binder that this area is commonly used, as one or more in carboxymethyl cellulose binding agent, Kynoar.
The lithium super capacitance cell of the present invention preparation method of embedding lithium cathode sheet adopts the method to not embedding lithium cathode sheet surface spreading lithium powder, and lithium powder directly adds in negative plate by dispersion, roll-in mode, realizes perfect even embedding lithium, operates simpler.
Further, in the preparation method of lithium super capacitance cell of the present invention, utilize the gravity of lithium powder self to drop on negative plate surface, avoid between lithium powder particles and influence each other, make lithium powder become easy in a large amount of dispersions on negative plate surface.
In the pre-embedding lithium cathode sheet that lithium super capacitance cell of the present invention uses, the osmotic efficiency of lithium powder is high, lithium powder is uniformly dispersed in negative active core-shell material, improve specific energy and the specific power of lithium super capacitance cell, the operating voltage of final obtained lithium super capacitance cell is between 2.0V-4.4V, specific energy can reach 50-75Wh/kg, and specific power reaches 9000W/kg.It is simple that lithium super capacitance cell of the present invention also has assembling, fail safe high.
Embodiment
Technical scheme of the present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
The making of positive plate: get LiFePO4 that mass ratio is 12:72:7:9, active carbon, graphene conductive agent and carboxymethyl cellulose binding agent, take deionized water as solvent, anode sizing agent is made in mixing, then by anode sizing agent dual coating on aluminium foil, 120 DEG C of oven dry, pole piece thickness is 220 μm, roll-in, cut-parts, 115 DEG C of vacuumize 24h, obtain positive plate.
The making of negative plate: get hard carbon that mass ratio is 92:4:4, graphene conductive agent and Kynoar binding agent, take 1-METHYLPYRROLIDONE as solvent, cathode size is made in mixing, then by cathode size dual coating on Copper Foil, 120 DEG C of oven dry, pole piece thickness is 120 μm, roll-in, cut-parts, 115 DEG C of vacuumize 24h, obtain negative plate.
In the negative electrode material layer of above-mentioned negative plate, pre-engaged column lithium powder can obtain pre-embedding lithium cathode sheet, and its manufacturing process is:
In the drying shed of dew point temperature≤-40 DEG C, get the inertia lithium powder that particle diameter D50 is 20 μm, what calculate corresponding inertia lithium powder using 65% of total for described hard carbon charged capacity as the total capacity of the inertia lithium powder that should add takes quality, get the inertia lithium powder of above-mentioned quality, half is wherein placed in above negative plate, utilize the gravity even drop down of lithium powder self and be dispersed on negative plate upper surface, then twin rollers is used, under the pressure of 2-20Mpa, roll-in is carried out to the negative plate sprinkled with inertia lithium powder, then used by second half inertia lithium powder identical method to be sprinkling upon negative plate another on the surface, twin rollers is used to carry out roll-in to the negative plate sprinkled with inertia lithium powder under the pressure of 2-20Mpa, obtain pre-embedding lithium cathode sheet.
Arrange barrier film by between obtained positive plate, embedding lithium cathode sheet, and add electrolyte and can assemble and obtain lithium super capacitance cell, its assembling process is:
In the drying shed of dew point temperature≤-40 DEG C, select cellulosic separator as barrier film, place according to a graded with positive plate, pre-embedding lithium cathode sheet, in positive plate, in the total charged capacity of active material and negative plate, the total charged capacity of active material is 1:2, adopt Z-shaped lamination process to reel and make battery core, then battery core is loaded aluminum plastic film power brick, inject electrolyte, the electrolytic salt that this electrolyte uses is LiPF
6, electrolyte solvent is EC and EMC, wherein LiPF
6concentration is in the electrolytic solution 1mol/L; shared by EC and EMC, the mass fraction of electrolyte solvent is 50%, is also added with into membrane stabilizer PS and high pressure over-charge protective agent FEC, encapsulates after fluid injection completes in this electrolyte; 24h is left standstill, i.e. obtained lithium super capacitance cell under 45 DEG C of conditions.
The positive plate of embodiment 2-8 makes, negative plate makes, the assembling process of lithium super capacitance cell in table 1, the content do not addressed in table 1 is all identical with embodiment 1.
The manufacturing process of the positive plate of table 1 embodiment 2-8, negative plate, pre-embedding lithium cathode sheet
Obtained lithium super capacitance cell is carried out performance test according to following work system:
Under normal temperature, adopt 10C to charge to 4.4V the lithium super capacitance cell prepared, constant voltage 30min, 10C are discharged to 2.0V, and so circulation three times, calculates energy density each time, and calculating mean value.
According to above-mentioned work system, the chemical property obtained is tested to the lithium super capacitance cell prepared in embodiment 1-8 as shown in table 2.
The chemical property of the lithium super capacitance cell that table 2 embodiment 2-8 obtains
As can be seen from the test result of table 2, the energy density of the lithium super capacitance cell that embodiment 1-8 obtains can reach 50-80Wh/kg, and power density can reach 8341-9943W/kg.Circulate after 10000 times, embodiment 1-6 capability retention is all more than 95%, embodiment 7,8 conservation rate is then lower than 95%, the lithium super capacitance cell of embodiment 7,8 is disassembled, find negative plate occurs analysing lithium phenomenon, illustrate that the amount of the pre-embedding lithium of negative pole can cause negative pole to analyse lithium too much, in order to take into account useful life and high security, the pre-lithium-inserting amount of negative plate is preferably 30%-75%.
Claims (10)
1. the embedding lithium cathode sheet of lithium super capacitance cell, comprise negative current collector and be coated in the negative material coating comprising material with carbon element of negative pole currect collecting surface, it is characterized in that, described negative material coating surface is evenly embedded with lithium powder.
2. the embedding lithium cathode sheet of lithium super capacitance cell according to claim 1, is characterized in that, the particle diameter D50 of described lithium powder is 20-100 μm.
3. the embedding lithium cathode sheet of lithium super capacitance cell according to claim 1, is characterized in that, the charged capacity of described lithium powder is the 30-100% of the charged capacity of material with carbon element.
4. the embedding lithium cathode sheet of lithium super capacitance cell according to claim 1, is characterized in that, the thickness of described embedding lithium cathode sheet is 120-130 μm.
5. a lithium super capacitance cell preparation method for embedding lithium cathode sheet as claimed in claim 1, is characterized in that, comprise the steps:
(1) negative material comprising material with carbon element is coated in negative pole currect collecting surface, oven dry, first time roll-in, vacuumize, obtain not embedding lithium cathode sheet;
(2) the not embedding lithium cathode sheet surface obtained in step (1) by lithium powder spreading, then has the negative plate of lithium powder to carry out second time roll-in to spreading, obtains embedding lithium cathode sheet.
6. preparation method according to claim 5, is characterized in that, in described step (2), spreading carries out in the following manner: make not embedding lithium cathode sheet be in below, lithium powder is in top, utilizes the free gravity of lithium powder to drop to negative plate on the surface.
7. preparation method according to claim 5, is characterized in that, the charged capacity of described lithium powder is the 30-100% of the charged capacity of material with carbon element.
8. preparation method according to claim 5, is characterized in that, the thickness of described embedding lithium cathode sheet is 120-130 μm, and the particle diameter D50 of described lithium powder is 20-100 μm.
9. a lithium super capacitance cell, comprises positive plate and negative plate, it is characterized in that, described negative plate is embedding lithium cathode sheet as claimed in claim 1.
10. lithium super capacitance cell according to claim 9, is characterized in that, the capacity of described positive plate is 1:2-1:5 with the ratio of the capacity of negative plate.
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| CN106409529A (en) * | 2016-11-09 | 2017-02-15 | 清华大学 | Lithium-ion capacitor lithium intercalation method |
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Application publication date: 20150812 |