CN104332323A - Porous electrode, preparation method thereof and application of porous electrode in aspect of preparing lithium ion capacitor and supercapacitor - Google Patents
Porous electrode, preparation method thereof and application of porous electrode in aspect of preparing lithium ion capacitor and supercapacitor Download PDFInfo
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- CN104332323A CN104332323A CN201410372788.9A CN201410372788A CN104332323A CN 104332323 A CN104332323 A CN 104332323A CN 201410372788 A CN201410372788 A CN 201410372788A CN 104332323 A CN104332323 A CN 104332323A
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- 239000003990 capacitor Substances 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011149 active material Substances 0.000 claims abstract description 30
- 239000011267 electrode slurry Substances 0.000 claims abstract description 27
- 239000002798 polar solvent Substances 0.000 claims abstract description 23
- 238000000605 extraction Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims description 65
- 239000011148 porous material Substances 0.000 claims description 44
- 239000011230 binding agent Substances 0.000 claims description 27
- 239000006258 conductive agent Substances 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000011268 mixed slurry Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000004966 Carbon aerogel Substances 0.000 claims description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000007581 slurry coating method Methods 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 238000004146 energy storage Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 description 26
- 239000000853 adhesive Substances 0.000 description 25
- 230000001070 adhesive effect Effects 0.000 description 25
- 238000002156 mixing Methods 0.000 description 23
- 238000012360 testing method Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000005030 aluminium foil Substances 0.000 description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 229910021385 hard carbon Inorganic materials 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- -1 phthalic acid ester Chemical class 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- VJHCJDRQFCCTHL-UHFFFAOYSA-N acetic acid 2,3,4,5,6-pentahydroxyhexanal Chemical compound CC(O)=O.OCC(O)C(O)C(O)C(O)C=O VJHCJDRQFCCTHL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011800 void material 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a porous electrode, a preparation method thereof and an application of the porous electrode in the aspect of preparing a lithium ion capacitor and a supercapacitor. The porous electrode is formed by adding a pore-forming agent to electrode slurry, and after the electrode is formed, carrying out extraction on the electrode to remove the pore-forming agent by utilizing a polar solvent. According to the porous electrode in the invention, gaps in the surface are many and uniform, and porosity is relatively high, so that the electrode has a relatively-large electrochemical reaction interface; the mechanical strength is large, and the gaps are not easy to collapse, so that electrode performance is high and stable; when electrolyte enters and leaves out of the inner portion of the electrode, the electrolyte can spread quickly to enable electrochemical active materials to reach the surface of the electrode so as to carry out corresponding physical and chemical reactions; the electrode has relatively-high power output capability, and can meet the demand of high power density output of the lithium ion capacitor and the supercapacitor and the like; and the electrode is suitable for energy-storage equipment with high charge-discharge multiplying power, and especially suitable for the preparation of the supercapacitor and the lithium ion capacitor.
Description
Technical field
The invention belongs to technical field of electrode production, be specifically related to a kind of porous electrode, also relate to a kind of preparation scheme of porous electrode simultaneously and preparing the application in lithium-ion capacitor, ultracapacitor.
Background technology
The development building of human society is on a large amount of basis consuming the energy, and the urgency of research and development new forms of energy impels the whole world all finding more senior clean energy resource, and the pursuit for the wind energy of technology maturation, solar energy and water-energy generating electricity is more and more stronger.But these energy are all discontinuous, need high efficiency energy reserves system, can both effectively store as lithium-ion capacitor and ultracapacitor and export energy, the load of electrical network can be made in electric power system more balanced simultaneously.
Ultracapacitor (Supercapacitors) is applied to stand-by power supply, starts the fields such as power supply, the pulse power, grid balance owing to having the features such as high-specific-power, long-life, comparatively safe and environmental friendliness.Lithium-ion capacitor (Lithium ion capacitor, LIC) have employed the principle of ultracapacitor 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, thus substantially increase the energy density of capacitor.LIC is by a kind of asymmetric capacitor of two kinds of different energy storage mode combinations of materials.LIC energy storage mechnism is two kinds of modes and deposits, and is a kind ofly Electrostatic Absorption based on the solution side electric charge at electrode/electrolyte interface and produces electric double layer capacitance, is the operation principle of double electric layer capacitor; Be an embedding off-square formula for lithium ion, belong to the operation principle of lithium ion battery.
The power density of ultracapacitor and lithium-ion capacitor is all higher than lithium ion battery, wherein electrolyte enter and leave ultracapacitor with the inside of the electrode of lithium-ion capacitor, and can spread rapidly corresponding physics and chemical reaction occur, the demand of ultracapacitor and the output of lithium-ion capacitor high power density can be met.The porosity of electrode determines the power-performance of ultracapacitor and lithium-ion capacitor.But existing electrode is the porosity comparatively end often, and space skewness, or the mechanical strength of pore-creating success rear electrode is low, and gap easily subsides, and has a strong impact on the quality of electrode, can't meet the requirement of use.
Summary of the invention
The object of this invention is to provide a kind of porous electrode, solve that existing electrode porosity is low, space skewness and hold givey problem.
Second object of the present invention is to provide a kind of preparation method of porous electrode.
3rd object of the present invention is to provide a kind of porous electrode and is preparing the application in lithium-ion capacitor.
4th object of the present invention is to provide a kind of porous electrode and is preparing the application in ultracapacitor.
In order to realize above object, the technical solution adopted in the present invention is: a kind of porous electrode, is add pore creating material by electrode slurry, and after electrode moulding, and adopting polar solvent to carry out extracting to electrode, the method for removing pore creating material makes.
Described electrode moulding refers to by electrode slurry coating on a current collector, drying, roll-in aftershaping.
Described pore creating material dissolves in polar solvent.
Described pore creating material is phthalic acid ester.
Described pore creating material is any one in dibutyl phthalate, di-n-octyl phthalate, BBP(Butyl Benzyl Phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate, dibutyl phthalate.
Described polar solvent is any one in methyl alcohol, ethanol, acetone.
Described electrode slurry comprises active material, conductive agent and binding agent.
The addition of described pore creating material is: the mass ratio of pore creating material and active material is 1 ~ 10:90 ~ 99.
Described active material is any one or two kinds in active carbon, carbon aerogels, carbon nano-tube, grapheme material.
Described conductive agent is carbon black conductive agent (SP).
Described binding agent is any one or two kinds in carboxymethyl cellulose, butadiene-styrene rubber, polymethylacrylic acid, polymethyl methacrylate, polytetrafluoroethylene, Kynoar.
Further, when binding agent contains polymethyl methacrylate, the preferred acetone of polar solvent; When binding agent contains polymethylacrylic acid, polar solvent particular methanol or ethanol; When binding agent contains carboxymethyl cellulose, polar solvent preferred alcohol or acetone.
During use, binding agent is dispersed in water or organic solvent and forms adhesive dispersions system.
In described adhesive dispersions system, the mass percentage of binding agent is 3% ~ 20%.
Preferably, in described adhesive dispersions system, the mass percentage of binding agent is 5% ~ 15%.
Described organic solvent is 1-METHYLPYRROLIDONE (NMP).
The mass ratio of described active material and conductive agent is 90 ~ 99:1 ~ 10.
The gross mass of described active material and conductive agent and the mass ratio of binding agent are 70 ~ 99:1 ~ 30.
A preparation method for above-mentioned porous electrode, comprises the following steps:
1) close slurry, in electrode slurry, add pore creating material, mix to obtain mixed slurry;
2) by mixed slurry coating on a current collector, electrode plates is obtained after drying, roll-in;
3) electrode plates is placed in polar solvent and carries out extraction removing pore creating material, dry, to obtain final product.
Step 1) described in close slurry and comprise the following steps:
A) get powder active material to mix with powder conductive agent, obtain powder body material;
B) powder body material is mixed with adhesive dispersions system, obtain electrode slurry.
Wherein, step a) described in mixing be adopt planetary mixer be uniformly mixed, speed of agitator is 200 ~ 1200r/min, and mixing time is 30 ~ 120min.
Binding agent is dispersed in water or organic solvent by described adhesive dispersions system to be made.Described dispersion adopts planetary mixer to be uniformly mixed, and speed of agitator is 100 ~ 1200r/min, and mixing time is 60 ~ 240min.
Step b) described in mixing be adopt planetary mixer be uniformly mixed, speed of agitator is 1000 ~ 1200r/min, and mixing time is 60 ~ 120min.
Step 1) described in mixing be adopt planetary mixer be uniformly mixed under 38 ~ 42 DEG C of conditions, speed of agitator is 1000 ~ 2000r/min, and mixing time is 60 ~ 120min.
Step 2) in, described collector is the aluminium foil with conductive coating.Described conductive coating makes to be coated in by conducting resinl aluminium foil is formed.
Step 2) in, the temperature of described oven dry is 80 DEG C, and the time is 60 ~ 120min.
Step 2) in, the speed of described roll-in is 15m/min.The pressure of roll-in is 10 ~ 100MPa.
Step 2) thickness of gained pole piece is 220 μm.
Step 3) in, the temperature of described extraction is 25 ~ 50 DEG C, and the time is 60 ~ 5000s.
Step 3) described extraction be by electrode plates with the speed of 0.5 ~ 2m/min by the airtight casing filling polar solvent.
Step 3) in, the temperature of described oven dry is 60 DEG C, and the time is 10min.
The application in lithium-ion capacitor prepared by a kind of above-mentioned porous electrode.
The application in ultracapacitor prepared by a kind of above-mentioned porous electrode.
Porous electrode of the present invention adds pore creating material by electrode slurry, and after electrode moulding, and adopting polar solvent to carry out extracting to electrode, the method for removing pore creating material makes; Electrode surface space is many and even, higher porosity, thus has larger electrochemical reaction interface; Mechanical strength is high, and space is not easy to subside, the high and stable performance of electrode performance; When electrolyte enters and leaves electrode interior, can spread rapidly and make electroactive substance reach electrode surface there is corresponding physics and chemical reaction, there is higher power output capacity, meet the demand that the high power density such as ultracapacitor and lithium-ion capacitor exports, be applicable to the energy storage device of high charge-discharge magnification, especially the preparation of ultracapacitor and lithium-ion capacitor.
The preparation method of porous electrode of the present invention, adds pore creating material in electrode slurry, and after electrode plates is made in coating, oven dry, roll-in, then adopt polar solvent to extract electrode, pore creating material is dissolved in polar solvent, thus obtains porous electrode; The electrode obtained surface void is many and even, higher porosity, thus has larger electrochemical reaction interface; Mechanical strength is high, and space is not easy to subside, the high and stable performance of electrode performance; Raw materials used wide material sources, with low cost, preparation process non-environmental-pollution; Technique is simple, and easy to operate, easily be automated continuous seepage, production efficiency is high; Without the need to the equipment of complexity, cost is low, is applicable to large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the testing result schematic diagram of embodiment 5 gained ultracapacitor;
Fig. 2 is the charge-discharge test curve chart of embodiment 6 gained lithium-ion capacitor;
Fig. 3 is electrochemical impedance test result schematic diagram in experimental example; Wherein, A is the electrochemical impedance test result of embodiment 1 gained porous electrode; B is the electrochemical impedance test result of the active carbon pole piece in traditional ultracapacitor.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
The porous electrode of the present embodiment adds pore creating material by electrode slurry, and after electrode moulding, and adopting polar solvent to carry out extracting to electrode, the method for removing pore creating material makes.
Described pore creating material is dibutyl phthalate, and polar solvent is ethanol.Described electrode slurry comprises active material, conductive agent and adhesive dispersions system.Described active material is absorbent charcoal material, and conductive agent is SP, and binding agent is carboxymethyl cellulose and butadiene-styrene rubber.Carboxymethyl cellulose and butadiene-styrene rubber are dispersed in water by described adhesive dispersions system to be made; In described adhesive dispersions system, the mass percentage of binding agent is 9%.
The mass ratio of described active material and conductive agent is 90:4.5; The gross mass of active material and conductive agent and the mass ratio of binding agent are 84:4; The mass ratio of pore creating material and active material is 9:90.
The preparation method of the porous electrode of the present embodiment, comprises the following steps:
1) slurry is closed:
Take 5000g absorbent charcoal material, 250g SP, add in the planetary mixer of 15L and be uniformly mixed, speed of agitator is 1200r/min, and mixing time is 30min, obtains powder body material;
Get carboxymethyl cellulose 100g, butadiene-styrene rubber 150g, be added to the water, the planetary mixer being placed in 15L stirs, and speed of agitator is 600r/min, and mixing time is 150min, obtains the adhesive dispersions system that binding agent mass percentage is 9%;
Added by powder body material in adhesive dispersions system, the planetary mixer being placed in 15L stirs, and speed of agitator is 1000r/min, and mixing time is 120min, obtains electrode slurry;
2) add pore creating material: add in electrode slurry by 500g dibutyl phthalate, be placed in planetary mixer and stir under 40 DEG C of conditions, speed of agitator is 2000r/min, and mixing time is 60min, obtains mixed slurry;
3) pole piece is shaping: utilize transfer coater to be coated on by mixed slurry and have on the aluminium foil of conductive coating, dry 90min under 80 DEG C of conditions after, automatic roll machine is used to carry out roll-in (pressure is 20MPa), roll-in speed is 15m/min, obtains the electrode plates that thickness is 220 μm after roll-in.
4) pole piece extraction: (time of staying is for 1200s through being equipped with the containment housing of ethanol with the speed of 0.5m/min by electrode plates, extraction temperature is 35 DEG C), ethanol carries out extraction removing pore creating material to pole piece, and then dry 10min under 60 DEG C of conditions, obtains described porous electrode.
Embodiment 2
The porous electrode of the present embodiment adds pore creating material by electrode slurry, and after electrode moulding, and adopting polar solvent to carry out extracting to electrode, the method for removing pore creating material makes.
Described pore creating material is BBP(Butyl Benzyl Phthalate, and polar solvent is methyl alcohol.Described electrode slurry comprises active material, conductive agent and adhesive dispersions system.Described active material is grapheme material, and conductive agent is SP, and binding agent is polytetrafluoroethylene.Polytetrafluoroethylene is dispersed in water by described adhesive dispersions system to be made; In described adhesive dispersions system, the mass percentage of binding agent is 10%.
The mass ratio of described active material and conductive agent is 95:10; The gross mass of active material and conductive agent and the mass ratio of binding agent are 70:30; The mass ratio of pore creating material and active material is 5:95.
The preparation method of the porous electrode of the present embodiment, comprises the following steps:
1) slurry is closed:
Take 950g grapheme material, 100g SP, add in planetary mixer and be uniformly mixed, speed of agitator is 200r/min, and mixing time is 120min, obtains powder body material;
Get polytetrafluoroethylene 450g, be added to the water, be placed in planetary mixer and stir, speed of agitator is 1200r/min, and mixing time is 60min, obtains the adhesive dispersions system that binding agent mass percentage is 10%;
Added by powder body material in adhesive dispersions system, be placed in planetary mixer and stir, speed of agitator is 2000r/min, and mixing time is 60min, obtains electrode slurry;
2) add pore creating material: add in electrode slurry by 50g BBP(Butyl Benzyl Phthalate, be placed in planetary mixer and stir under 38 DEG C of conditions, speed of agitator is 1000r/min, and mixing time is 120min, obtains mixed slurry;
3) pole piece is shaping: utilize transfer coater to be coated on by mixed slurry and have on the aluminium foil of conductive coating, dry 60min under 80 DEG C of conditions after, automatic roll machine is used to carry out roll-in (pressure is 100MPa), roll-in speed is 15m/min, obtains the electrode plates that thickness is 220 μm after roll-in.
4) pole piece extraction: (time of staying is for 300s through being equipped with the containment housing of methyl alcohol with the speed of 2m/min by electrode plates, extraction temperature is 45 DEG C), methyl alcohol carries out extraction removing pore creating material to pole piece, and then dry 10min under 60 DEG C of conditions, obtains described porous electrode.
Embodiment 3
The porous electrode of the present embodiment adds pore creating material by electrode slurry, and after electrode moulding, and adopting polar solvent to carry out extracting to electrode, the method for removing pore creating material makes.
Described pore creating material is dicyclohexyl phthalate, and polar solvent is acetone.Described electrode slurry comprises active material, conductive agent and adhesive dispersions system.Described active material is absorbent charcoal material, and conductive agent is SP, and binding agent is Kynoar.Kynoar is dispersed in 1-METHYLPYRROLIDONE (NMP) by described adhesive dispersions system to be made; In described adhesive dispersions system, the mass percentage of binding agent is 7%.
The mass ratio of described active material and conductive agent is 98:1; The gross mass of active material and conductive agent and the mass ratio of binding agent are 99:3; The mass ratio of pore creating material and active material is 3:98.
The preparation method of the porous electrode of the present embodiment, comprises the following steps:
1) slurry is closed:
Take 980g absorbent charcoal material, 10g SP, add in planetary mixer and be uniformly mixed, speed of agitator is 600r/min, and mixing time is 90min, obtains powder body material;
Get Kynoar 30g, add in 1-METHYLPYRROLIDONE (NMP), be placed in planetary mixer and stir, speed of agitator is 100r/min, and mixing time is 240min, obtains the adhesive dispersions system that binding agent mass percentage is 7%;
Added by powder body material in adhesive dispersions system, be placed in planetary mixer and stir, speed of agitator is 1500r/min, and mixing time is 90min, obtains electrode slurry;
2) add pore creating material: add in electrode slurry by 30g dicyclohexyl phthalate, be placed in planetary mixer and stir under 42 DEG C of conditions, speed of agitator is 1500r/min, and mixing time is 90min, obtains mixed slurry;
3) pole piece is shaping: utilize transfer coater to be coated on by mixed slurry and have on the aluminium foil of conductive coating, dry 120min under 80 DEG C of conditions after, automatic roll machine is used to carry out roll-in (pressure is 40MPa), roll-in speed is 15m/min, obtains the electrode plates that thickness is 220 μm after roll-in.
4) pole piece extraction: (time of staying is for 600s through being equipped with the containment housing of acetone with the speed of 1m/min by electrode plates, extraction temperature is 25 DEG C), acetone carries out extraction removing pore creating material to pole piece, and then dry 10min under 60 DEG C of conditions, obtains described porous electrode.
Embodiment 4
The porous electrode of the present embodiment adds pore creating material by electrode slurry, and after electrode moulding, and adopting polar solvent to carry out extracting to electrode, the method for removing pore creating material makes.
Described pore creating material is di-sec-octyl phthalate, and polar solvent is acetone.Described electrode slurry comprises active material, conductive agent and adhesive dispersions system.Described active material is carbon aerogels, and conductive agent is SP, and binding agent is polymethyl methacrylate.Polymethyl methacrylate is dispersed in water by described adhesive dispersions system to be made; In described adhesive dispersions, the mass percentage of binding agent is 5%.
The mass ratio of described active material and conductive agent is 93:2; The gross mass of active material and conductive agent and the mass ratio of binding agent are 95:10; The mass ratio of pore creating material and active material is 2:93.
The preparation method of the porous electrode of the present embodiment, comprises the following steps:
1) slurry is closed:
Take 930g carbon aerogels, 20g SP, add in planetary mixer and be uniformly mixed, speed of agitator is 600r/min, and mixing time is 60min, obtains powder body material;
Get polymethyl methacrylate 100g, be added to the water, be placed in planetary mixer and stir, speed of agitator is 1000r/min, and mixing time is 80min, obtains the adhesive dispersions system that binding agent mass percentage is 5%;
Added by powder body material in adhesive dispersions system, be placed in planetary mixer and stir, speed of agitator is 1500r/min, and mixing time is 90min, obtains electrode slurry;
2) add pore creating material: add in electrode slurry by 20g di-sec-octyl phthalate, be placed in planetary mixer and stir under 42 DEG C of conditions, speed of agitator is 1500r/min, and mixing time is 90min, obtains mixed slurry;
3) pole piece is shaping: utilize transfer coater to be coated on by mixed slurry and have on the aluminium foil of conductive coating, dry 100min under 80 DEG C of conditions after, automatic roll machine is used to carry out roll-in (pressure is 50MPa), roll-in speed is 15m/min, obtains the electrode plates that thickness is 220 μm after roll-in.
4) pole piece extraction: (time of staying is for 600s through being equipped with the containment housing of acetone with the speed of 1m/min by electrode plates, extraction temperature is 25 DEG C), acetone carries out extraction removing pore creating material to pole piece, and then dry 10min under 60 DEG C of conditions, obtains described porous electrode.
Embodiment 5
The present embodiment is that the application in ultracapacitor prepared by embodiment 1 gained porous electrode.
By embodiment 1 gained porous electrode, be cut into the electrode slice that width is 40mm, wherein, the length of positive pole is 960mm, and the length of negative pole is 910mm; By the cellulosic separator (TF4035 of two-layer positive and negative electrode pole piece and 2 layers 35 μm, NKK company of Japan) be wound into the battery core that diameter is 18mm, by aluminium pole ears thick to 6mm width, 0.4mm by ultrasonic bonding (power is 800W) on positive pole and negative plate; And be positioned in aluminum hull that diameter is 22mm, tetraethyl boron fluoric acid ammonium salt/acetonitrile solution that after vacuumize 48h (120 DEG C), injected slurry volume is 100ml, concentration is 1.2mol/L, seals, obtains ultracapacitor.
Detect gained ultracapacitor, its capacity is 300F; Its test data as shown in Figure 1.
As can be seen from Figure 1, voltage be 2.7V start to discharge time, there is not obvious voltage drop phenomenon, the ultracapacitor using porous electrode of the present invention to prepare is described, compared with the ultracapacitor prepared with conventional method, in the space that in discharge process, electrolyte ion can be formed fast on pole piece, carry out charge migration motion.
Embodiment 6
The present embodiment is that the application in lithium-ion capacitor prepared by embodiment 1 gained porous electrode.
The preparation method of lithium-ion capacitor negative pole is as follows: get carboxymethyl cellulose 10g (Japan, Daicel), be dispersed in 990g water, forming mass fraction is the cmc soln of 1%; Get cmc soln 180g, add the hard carbon material (Japan of 94.5g, Sumitomo Bakelite), after stirring 2h (rotating speed is 25r/min), add styrene butadiene rubber sbr (Japanese JSR) 2.2g, after continuing to stir 2h (rotating speed is 2000r/min), obtain mixed slurry; Utilizing transfer coater to be coated on by mixed slurry has on the aluminium foil of conductive coating, dry 120min under 80 DEG C of conditions after, use automatic roll machine to carry out roll-in (pressure 40MPa), roll-in speed is 15m/min, obtains the hard carbon electrode plates that thickness is 110 μm after roll-in; Hard carbon electrode plates is cut to the round-shaped of diameter 14mm, is positioned in glove box, the lithium powder of 1mg is sprinkling upon on this electrode slice, adopt the pressure of 5MPa to carry out lithium powder shaping process by baby press, prepare the hard carbon electrode of lithium powder doping.
The preparation method of lithium-ion capacitor: embodiment 1 gained porous electrode is cut to the circle that diameter is 18mm; Using porous electrode as positive pole, cover cellulosic separator successively, the hard carbon electrode of lithium powder doping is as negative pole, add pad, drip lithium hexafluoro phosphate/ethylene carbonate, the dimethyl carbonate (ethylene carbonate: dimethyl carbonate=1:1 of the 1.2M of 2ml, mass ratio) electrolyte, be packaged into buckle type lithium-ion capacitor.
Detect gained lithium-ion capacitor, it carries out charge-discharge test result as shown in Figure 2 between voltage range 2.0V-3.8V.
As can be seen from Figure 2, adopt lithium-ion capacitor prepared by embodiment 1 gained porous electrode, carry out in the process of discharge test at 3.8V, there is no obvious voltage drop phenomenon, electrolyte ion in the lithium-ion capacitor adopting porous electrode of the present invention to prepare is described, migration velocity is in the electrodes rapid, and the power benefits of this porous electrode is obvious.
Experimental example
The porosity of the pole piece of embodiment 1 gained porous electrode and other traditional wet method ultracapacitor is compared, the porosity of embodiment 1 gained porous electrode is 48%, and the porosity of traditional activated carbon for super capacitors pole piece (Kai Maijiahua, Luoyang) is 43%.The raising of porosity, can improve the ability that pole piece stores electrolyte, and can accelerate diffusion and the migration rate of electrolyte.
Carry out electrochemical impedance test to embodiment 1 gained porous electrode and traditional super capacitor electrode slice (commercial goods, Kai Maijiahua, Luoyang), result as shown in Figure 3.Wherein, what Fig. 3-A showed is the electrochemical impedance test result of embodiment 1 gained porous electrode; The electrochemical impedance test result of the active carbon pole piece that what Fig. 3-B showed is in traditional ultracapacitor.
As can be seen from the contrast of Fig. 3-A and Fig. 3-B, the test curve of embodiment 1 gained porous electrode and the intersection point of real axis are 0.16 ohm, and the test curve of traditional active carbon pole piece and the intersection point of real axis are 0.25 ohm; And the test curve of embodiment 1 gained porous electrode is less than the diffusion zone of test curve in intermediate frequency zone of traditional active carbon pole piece at the diffusion zone of intermediate frequency zone.
Adopting uses the same method detects embodiment 2-4 gained porous electrode, and result is as shown in table 1.Wherein, comparative example is traditional super capacitor electrode slice (commercial goods, Kai Maijiahua, Luoyang).
The porosity of table 1 embodiment 1-4 gained porous electrode and electrochemical impedance test result
| Object | Porosity | Electrochemical impedance test curve and real axis intersection point | Test curve is at the diffusion zone of intermediate frequency zone |
| Embodiment 1 | 48％ | 0.16 ohm | Less |
| Embodiment 2 | 47％ | 0.16 ohm | Less |
| Embodiment 3 | 48％ | 0.17 ohm | Less |
| Embodiment 4 | 49％ | 0.16 ohm | Less |
| Comparative example | 43％ | 0.25 ohm | Larger |
Experimental result shows: porous electrode of the present invention is all better than the active carbon pole piece of traditional ultracapacitor in porosity and electrolyte ion migration rate.
Claims (10)
1. a porous electrode, is characterized in that: be add pore creating material by electrode slurry, and after electrode moulding, and adopting polar solvent to carry out extracting to electrode, the method for removing pore creating material makes.
2. porous electrode according to claim 1, is characterized in that: described pore creating material is any one in dibutyl phthalate, di-n-octyl phthalate, BBP(Butyl Benzyl Phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate, dibutyl phthalate.
3. porous electrode according to claim 1, is characterized in that: described polar solvent is any one in methyl alcohol, ethanol, acetone.
4. porous electrode according to claim 1, is characterized in that: described electrode slurry comprises active material, conductive agent and binding agent.
5. porous electrode according to claim 4, is characterized in that: the addition of described pore creating material is: the mass ratio of pore creating material and active material is 1 ~ 10:90 ~ 99.
6. the porous electrode according to claim 4 or 5, is characterized in that: described active material is any one or two kinds in active carbon, carbon aerogels, carbon nano-tube, grapheme material.
7. a preparation method for porous electrode as claimed in claim 1, is characterized in that: comprise the following steps:
1) close slurry, in electrode slurry, add pore creating material, mix to obtain mixed slurry;
2) by mixed slurry coating on a current collector, electrode plates is obtained after drying, roll-in;
3) electrode plates is placed in polar solvent and carries out extraction removing pore creating material, dry, to obtain final product.
8. the preparation method of porous electrode according to claim 7, is characterized in that: step 3) in, the temperature of described extraction is 25 ~ 50 DEG C, and the time is 60 ~ 5000s.
9. the application in lithium-ion capacitor prepared by a porous electrode as claimed in claim 1.
10. the application in ultracapacitor prepared by a porous electrode as claimed in claim 1.
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