CN104616906A - Cathode embedded magnesium ion supercapacitor and preparing method thereof - Google Patents
Cathode embedded magnesium ion supercapacitor and preparing method thereof Download PDFInfo
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- CN104616906A CN104616906A CN201510040094.XA CN201510040094A CN104616906A CN 104616906 A CN104616906 A CN 104616906A CN 201510040094 A CN201510040094 A CN 201510040094A CN 104616906 A CN104616906 A CN 104616906A
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- Prior art keywords
- magnesium ion
- negative pole
- negative
- embedding
- carbon
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- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001425 magnesium ion Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 7
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011149 active material Substances 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- 239000011777 magnesium Substances 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 14
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 13
- 230000004888 barrier function Effects 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000003610 charcoal Substances 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 10
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 10
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 10
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000005030 aluminium foil Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 238000011160 research Methods 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical group [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000005486 organic electrolyte Substances 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 2
- 239000008151 electrolyte solution Substances 0.000 abstract 2
- 239000012528 membrane Substances 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 abstract 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 22
- 238000002347 injection Methods 0.000 description 18
- 239000007924 injection Substances 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 239000006245 Carbon black Super-P Substances 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 230000004087 circulation Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 229910021385 hard carbon Inorganic materials 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- 229920006255 plastic film Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- 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)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a cathode embedded magnesium ion supercapacitor and a preparing method thereof. Magnesium ions in the negative electrode embedded supercapacitor a positive electrode, a negative electrode, in between the membrane and an electrolyte, a positive charge can be absorbed by a porous electric double layer formed of carbon materials as the active material, negative use can be embedded / Escape magnesium ions as the active material carbon materials; electrolytic solution using an organic electrolytic solution may be available to provide the magnesium ions and the formation of the desired double layer charge. The supercapacitor can be embedded Mg2 + introduced into the carbon material as the negative electrode supercapacitor, to be able to form a porous carbon adsorption charge the electric double layer as a cathode, anode and cathode materials by optimizing the use of the ratio, the more compatible use with the electrolyte good membrane, so that all the capacity to play an active material, resistance characteristics and other aspects of life to achieve a good balance, with high power characteristics and high energy density, and low cost without pollution.
Description
Technical field
The present invention relates to a kind of ultracapacitor, specifically, relate to the negative pole of ultracapacitor.
Background technology
In recent years, along with the development of new energy technology, be developed novel lithium ion super capacitor, make the voltage of ultracapacitor, energy density has and significantly improve.In the periodic table of elements, Mg and Li is in cornerwise position, and both have many similar character (as table 1), Mg/Mg as can be seen from the table
2+though electromotive force without Li/Li
+negative, but also considerable, Mg
2+there is Li
+similar ionic radius, magnesium resource is very abundant simultaneously, therefore develops magnesium cell and has cost advantage.
The Nature comparison of table 1 Mg and Li
| Metal | Atomic weight/gmol -1 | Valence charge | Theoretical specific capacity/mAhg -1 | Electrode potential/V | Ionic radius/nm | Earth resource/% | Fail safe |
| Li | 6.94 | 1 | 3862 | -3.03 | 0.068 | 0.006 | Low |
| Mg | 24.31 | 2 | 2205 | -2.37 (acid) | 0.062 | 1.94 | High |
At present, less to the research of magnesium ion ultracapacitor, by Mg
2+and associated materials is incorporated in ultracapacitor and goes, main or use for reference the correlative study present situation of Mg secondary cell, its key is also to locate and suitable reversiblely can takes off/positive and negative the material of embedding magnesium, and the electrolyte that compatibility is good.At present, magnesium secondary battery anode material generally adopts pure magnesium, about the report of other negative material is relatively less.Similar to the applicable cases of lithium, magnesium metal is as negative material, and possible Problems existing is: in long-term cyclic process, easily forms magnesium dendrite at electrode surface, causes deterioration of cell properties, even cause short circuit.Chusid etc. (Adv.Mater., 2003,15:627-630) propose to adopt AZ31 alloy (Al and Zn be respectively 3% and l%) as negative material, at Mg (AlCl
2etBt)
2test in/THF, confirm that these alloys can be used as the negative material of magnesium second electrode.The Yuan Huatang (CN1411083A) of Nankai University have studied a kind of magnesium alloy negative material, and its component is MgM
xm
ythe above alloy of (0<x, y≤0.5) binary (M is Ni, Cu, Ti, Si, B etc.), and obtain good opening voltage.Except Magnesium and magnesium alloys, also there is similar magnesium being deposited on carbon or other material.Novak attempts the Mg (ClO at 1mol/L
4in)/acetonitrile, magnesium ion is inserted in KS-6 graphite.Maeda and Touzain (Synthetic Metals, 24 (3): 267-270) describes at MgCl
2in/methyl-sulfoxide, magnesium ion reversible electrochemical is inserted in the RESEARCH OF PYROCARBON of highly crystallized.
Summary of the invention
The object of the invention is to propose a kind of magnesium ion ultracapacitor and manufacture method, to meet the needs of association area development.
Described magnesium ion ultracapacitor, is made up of positive pole, negative pole, marginal barrier film and electrolyte;
Described positive pole adopts and can form the porous carbon material of electric double layer as active material by adsorption charge; Negative pole adopts the Carbon Materials that can embed/deviate from magnesium ion as active material; Electrolyte adopts the organic electrolyte solution that can provide magnesium ion and can provide the required electric charge forming electric double layer.
Described positive pole is made up of plus plate current-collecting body and the positive pole composite material be coated on plus plate current-collecting body, and positive pole composite material comprises the component of following percentage by weight:
Positive active material 88% ~ 96%
Conductive agent 2% ~ 7%
Binding agent 2% ~ 5%
Described positive active material is the porous carbon material energy that enough adsorption charges form electric double layer, is selected from one or more in active carbon, carbon nano-tube or carbon fiber etc.;
Described conductive agent is selected from carbon black, graphite or its mixture;
Described binding agent is selected from one or more in polytetrafluoroethylene (PTFE), Kynoar (PVDF), sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR);
Described negative pole is made up of negative current collector and the negative pole composite material be coated on negative current collector, and negative pole composite material comprises the component of following percentage by weight:
Can embed/deviate from the Carbon Materials 75% ~ 95% of magnesium ion
Conductive agent 3% ~ 15%
Binding agent 2% ~ 10%
The described Carbon Materials embedding/deviate from magnesium ion comprises one or more in hard charcoal, KS-6 graphite or high crystallization RESEARCH OF PYROCARBON (HOPG) etc.;
Described conductive agent is selected from carbon black, graphite or its mixture;
Described binding agent is selected from one or more in polytetrafluoroethylene (PTFE), Kynoar (PVDF), sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR);
Described negative or positive electrode collector is holey metal material or metal foil material, comprises the one in nickel foam, aluminium foil, Copper Foil or titanium foil material;
Described electrolyte is selected from magnesium perchlorate (Mg (ClO
4)
2)/acetonitrile, Mg (ClO
4)
2+ tetraethylammonium tetrafluoroborate (Et
4nBF
4)/acetonitrile, MgCl
2/ methyl-sulfoxide or MgCl
2+ Et
4nBF
4one in/methyl-sulfoxide;
Described barrier film is the porous film material with certain porosity, and porosity is generally 30 ~ 70%, preferred glass fibers paper, PP or PE microporous barrier, nylon cloth, polyvinyl alcohol film or asbestos paper;
Described magnesium ion ultracapacitor making step is:
The making of positive pole:
After described porous carbon material, conductive agent and binding agent being mixed, be stirred to paste, then adopt film applicator slurry to be coated on plus plate current-collecting body, through 100 ~ 130 DEG C of oven dry, then after roll-in, obtain positive pole;
The making of negative plate:
After can embedding/deviate from the mixing of the Carbon Materials of magnesium ion, conductive agent and binding agent, be stirred to paste, then adopt the coating of film applicator slurry on a current collector, through 100 ~ 130 DEG C of oven dry, then after roll-in, obtain positive pole;
Then adopt method well known in the art (similar patent CN 101252043A), be assembled into magnesium ion ultracapacitor.
The present invention proposes Mg
2+carbon Materials can be embedded be incorporated in ultracapacitor as negative pole, so that the porous charcoal of electric double layer can be formed as positive pole by adsorption charge, the magnesium ion ultracapacitor that this method makes, by optimizing the proportioning of the material that both positive and negative polarity uses, adopt and the good barrier film of compatibility of electrolyte, make that each active material plays at capacity, obtain good balance in inner resistance and life-span etc., there is high power characteristic and higher energy density, and low cost, the feature such as pollution-free.
Embodiment
Below by specific embodiment, the present invention is further illustrated, but the scope that these embodiments do not limit the present invention in any way.
Embodiment 1
First be the making of positive plate, by active carbon (AC), conductive black (Super-P), sodium carboxymethylcellulose, butadiene-styrene rubber in mass ratio 95 ︰ 2.5 ︰ 2 ︰ 0.5 mix, slurry is stirred into deionized water, then be coated on aluminium foil with film applicator, in an oven through 130 DEG C of oven dry, then roll-in, cut-parts, pole piece is of a size of 150 × 90 × 0.25mm
3.
The making step of negative plate is, by hard charcoal, conductive black (Super-P), PVDF in mass ratio 85 ︰ 10 ︰ 5 mix, with 1-Methyl-2-Pyrrolidone furnishing slurry, then be coated on Copper Foil with film applicator, in an oven through 100 DEG C of oven dry, then roll-in, cut-parts, pole piece is of a size of 150 × 90 × 0.3mm
3.
Select 4535 barrier films of NKK company, by 12 positive poles and 12 negative poles, battery core is formed in the mode that handover is stacked, aluminum plastic film is adopted to pack, and draw from both sides with aluminium matter lug, reserved liquid injection port, through 120 DEG C, after vacuumize in 48 hours, in vacuum glove box, inject 0.5mol/L Mg (ClO
4)
2/ acetonitrile solution.After fluid injection, from liquid injection port introducing one very magnesium sheet metal.Before changing into, be first a very positive pole of hard carbon material with active material, magnesium sheet metal is negative pole, and adopt the constant current electric discharge 60min of 0.2A, carry out magnesium ion and embed in advance, pre-embedding lithium doping amount is about theoretical 50%.Then change into, after changing into, operating voltage is between 1.0 ~ 3.6V, and capacitor electrostatic capacity reaches 1200F, and energy density reaches 10Wh/Kg, and after 500 circulations, capability retention is more than 87%.
Embodiment 2
First be the making of positive plate, by active carbon (AC), conductive black (Super-P), sodium carboxymethylcellulose, butadiene-styrene rubber in mass ratio 95 ︰ 2.5 ︰ 2 ︰ 0.5 mix, slurry is stirred into deionized water, then be coated on aluminium foil with film applicator, in an oven through 100 DEG C of oven dry, then roll-in, cut-parts, pole piece is of a size of 150 × 90 × 0.25mm
3.
The making step of negative plate is, by hard charcoal, conductive black (Super-P), PVDF in mass ratio 85 ︰ 10 ︰ 5 mix, with 1-Methyl-2-Pyrrolidone furnishing slurry, then be coated on Copper Foil with film applicator, in an oven through 100 DEG C of oven dry, then roll-in, cut-parts, pole piece is of a size of 150 × 90 × 0.3mm
3.
Select 4535 barrier films of NKK company, by 12 positive poles and 12 negative poles, battery core is formed in the mode that handover is stacked, aluminum plastic film is adopted to pack, and draw from both sides with aluminium matter lug, reserved liquid injection port, through 120 DEG C, after vacuumize in 48 hours, in vacuum glove box, inject 0.5mol/L Mg (ClO
4)
2+ 1mol/L Et
4nBF
4/ acetonitrile solution.After fluid injection, from liquid injection port introducing one very magnesium sheet metal.Before changing into, be first a very positive pole of hard carbon material with active material, magnesium sheet metal is negative pole, adopts the constant current electric discharge 10min of 0.2A, carries out magnesium ion and embeds pre-embedding lithium doping amount in advance and be about theoretical 30%.After changing into, operating voltage is between 2.5 ~ 3.6V, and capacitor electrostatic capacity reaches 1500F, and energy density reaches 7.5Wh/Kg, and after 500 circulations, capability retention is more than 85%.
Embodiment 3
First be the making of positive plate, by active carbon, conductive black, sodium carboxymethylcellulose, butadiene-styrene rubber in mass ratio 95 ︰ 2.5 ︰ 2 ︰ 0.5 mix, slurry is stirred into deionized water, then be coated on aluminium foil with film applicator, in an oven through 120 DEG C of oven dry, then roll-in, cut-parts, pole piece is of a size of 150 × 90 × 0.25mm
3.
The making step of negative plate is: by hard charcoal, conductive black (Super-P), PVDF in mass ratio 85 ︰ 10 ︰ 5 mix, with 1-Methyl-2-Pyrrolidone furnishing slurry, then be coated on Copper Foil with film applicator, in an oven through 130 DEG C of oven dry, then roll-in, cut-parts, pole piece is of a size of 150 × 90 × 0.3mm
3.
Select 4535 barrier films of NKK company, by 12 positive poles and 12 negative poles, battery core is formed in the mode that handover is stacked, aluminum plastic film is adopted to pack, and draw from both sides with aluminium matter lug, reserved liquid injection port, through 120 DEG C, after vacuumize in 48 hours, in vacuum glove box, inject 0.5mol/L Mg (ClO
4)
2+ 1mol/L Et
4nBF
4/ acetonitrile solution.After fluid injection, from liquid injection port introducing one very magnesium sheet metal.Before changing into, be first a very positive pole of hard carbon material with active material, magnesium sheet metal is negative pole, and adopt the constant current electric discharge 30min of 0.2A, carry out magnesium ion and embed in advance, pre-embedding lithium doping amount is about theoretical 60%.After changing into, operating voltage is between 2.0 ~ 3.6V, and capacitor electrostatic capacity reaches 1500F, and energy density reaches 10Wh/Kg, and after 500 circulations, capability retention is more than 90%.
Embodiment 4
First be the making of positive plate, by active carbon, conductive black, sodium carboxymethylcellulose, butadiene-styrene rubber in mass ratio 95 ︰ 2.5 ︰ 2 ︰ 0.5 mix, slurry is stirred into deionized water, then be coated on aluminium foil with film applicator, in an oven through 130 DEG C of oven dry, then roll-in, cut-parts, pole piece is of a size of 150 × 90 × 0.25mm
3.
The making step of negative plate is: by hard charcoal, conductive black (Super-P), PVDF in mass ratio 85 ︰ 10 ︰ 5 mix, with 1-Methyl-2-Pyrrolidone furnishing slurry, then be coated on Copper Foil with film applicator, in an oven through 130 DEG C of oven dry, then roll-in, cut-parts, pole piece is of a size of 150 × 90 × 0.3mm
3.
Select 4535 barrier films of NKK company, by 12 positive poles and 12 negative poles, battery core is formed in the mode that handover is stacked, aluminum plastic film is adopted to pack, and draw from both sides with aluminium matter lug, reserved liquid injection port, through 120 DEG C, after vacuumize in 48 hours, in vacuum glove box, inject 0.5mol/L Mg (ClO
4)
2+ 1mol/L Et
4nBF
4/ acetonitrile solution.After fluid injection, from liquid injection port introducing one very magnesium sheet metal.Before changing into, be first a very positive pole of hard carbon material with active material, magnesium sheet metal is negative pole, adopts the constant current electric discharge 60min of 0.2A, carries out magnesium ion and embeds pre-embedding lithium doping amount in advance and be about theoretical 70%.After changing into, operating voltage is between 1.0 ~ 3.6V, and capacitor electrostatic capacity reaches 1500F, and energy density reaches 12Wh/Kg, and after 500 circulations, capability retention is more than 90%.
The magnesium ion ultracapacitor Performance comparision of the different Magnesium-doped amount of table 1
| Numbering | Electrode material | Electrolyte | Preparatory doping time/min | Operating voltage/V | Doping/% | Capacity/F | Energy density/WhKg -1 | Capability retention (500 times) |
| 1 | The hard charcoal of AC/ | 0.5mol/L Mg(ClO 4) 2/ acetonitrile | 60 | 1.0~3.6 | 50 | 1200 | 10 | 87 |
| 2 | The hard charcoal of AC/ | 0.5mol/L Mg(ClO 4) 2+1mol/L Et 4NBF 4/ acetonitrile | 10 | 2.5~3.6 | 30 | 1500 | 7.5 | 85 |
| 3 | The hard charcoal of AC/ | 0.5mol/L Mg(ClO 4) 2+1mol/L Et 4NBF 4/ acetonitrile | 30 | 2.0~3.6 | 60 | 1500 | 10 | 90 |
| 4 | The hard charcoal of AC/ | 0.5mol/L Mg(ClO 4) 2+1mol/L Et 4NBF 4/ acetonitrile | 60 | 1.0~3.6 | 70 | 1500 | 12 | 90 |
Embodiment 5
First be the making of positive plate, by active carbon, conductive black (Super-P), sodium carboxymethylcellulose, butadiene-styrene rubber in mass ratio 95 ︰ 2.5 ︰ 2 ︰ 0.5 mix, slurry is stirred into deionized water, then be coated on aluminium foil with film applicator, in an oven through 130 DEG C of oven dry, then roll-in, cut-parts, pole piece is of a size of 150 × 90 × 0.25mm
3.
The making step of negative plate is: by hard charcoal, conductive black (Super-P), PVDF in mass ratio 85 ︰ 10 ︰ 5 mix, with 1-Methyl-2-Pyrrolidone furnishing slurry, then be coated on Copper Foil with film applicator, in an oven through 130 DEG C of oven dry, then roll-in, cut-parts, pole piece is of a size of 150 × 90 × 0.3mm
3.
Select 4535 barrier films of NKK company, by 12 positive poles and 12 negative poles, form battery core in the mode that handover is stacked, adopt aluminum plastic film to pack, and draw from both sides with aluminium matter lug, reserved liquid injection port, through 120 DEG C, after vacuumize in 48 hours, in vacuum glove box, inject 0.5mol/L MgCl
2+ 1mol/L Et
4nBF
4/ dimethyl sulfoxide solution.After fluid injection, from liquid injection port introducing one very magnesium sheet metal.Before changing into, be first a very positive pole of hard carbon material with active material, magnesium sheet metal is negative pole, and adopt the constant current electric discharge 60min of 0.2A, carry out magnesium ion and embed in advance, pre-embedding lithium doping amount is about theoretical 50%.After changing into, operating voltage is between 1.0 ~ 3.6V, and capacitor electrostatic capacity reaches 1000F, and energy density reaches 7.5Wh/Kg, and after 500 circulations, capability retention is more than 80%.
Embodiment 6
First be the making of positive plate, by active carbon, conductive black (Super-P), sodium carboxymethylcellulose, butadiene-styrene rubber in mass ratio 95 ︰ 2.5 ︰ 2 ︰ 0.5 mix, slurry is stirred into deionized water, then be coated on aluminium foil with film applicator, in an oven through 100 DEG C of oven dry, then roll-in, cut-parts, pole piece is of a size of 150 × 90 × 0.25mm
3.
The making step of negative plate is: by high crystallization RESEARCH OF PYROCARBON (HOPG), conductive black (Super-P), PVDF in mass ratio 85 ︰ 10 ︰ 5 mix, with 1-Methyl-2-Pyrrolidone furnishing slurry, then be coated on Copper Foil with film applicator, in an oven through 100 DEG C of oven dry, then roll-in, cut-parts, pole piece is of a size of 150 × 90 × 0.3mm
3.
Select 4535 barrier films of NKK company, by 12 positive poles and 12 negative poles, battery core is formed in the mode that handover is stacked, aluminum plastic film is adopted to pack, and draw from both sides with aluminium matter lug, reserved liquid injection port, through 120 DEG C, after vacuumize in 48 hours, in vacuum glove box, inject 0.5mol/L Mg (ClO
4)
2+ 1mol/L Et
4nBF
4/ acetonitrile solution.After fluid injection, from liquid injection port introducing one very magnesium sheet metal.Before changing into, be first a very positive pole of hard carbon material with active material, magnesium sheet metal is negative pole, adopts the constant current electric discharge 60min of 0.2A, carries out magnesium ion and embed in advance.After changing into, operating voltage is between 1.0 ~ 3.6V, and capacitor electrostatic capacity reaches 1600F, and energy density reaches 13Wh/Kg, and after 500 circulations, capability retention is more than 85%.
Just several preferred embodiment of the present invention described in this specification, above embodiment is only in order to illustrate technical scheme of the present invention but not limitation of the present invention.All those skilled in the art, all should be within the scope of the present invention under this invention's idea by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. the embedding magnesium ion ultracapacitor of negative pole, is made up of positive pole, negative pole, marginal barrier film and electrolyte; It is characterized in that: described positive pole adopts and can form the porous carbon material of electric double layer as active material by adsorption charge; Negative pole adopts the Carbon Materials that can embed/deviate from magnesium ion as active material; Electrolyte adopts the organic electrolyte solution that can provide magnesium ion and can provide the required electric charge forming electric double layer.
2. the embedding magnesium ion ultracapacitor of negative pole according to claim 1, is characterized in that: described positive pole is made up of plus plate current-collecting body and the positive pole composite material be coated on plus plate current-collecting body, and positive pole composite material comprises the component of following percentage by weight:
Positive active material 88% ~ 96%
Conductive agent 2% ~ 7%
Binding agent 2% ~ 5%
Described positive active material is can form the porous carbon material of electric double layer by adsorption charge.
3. the embedding magnesium ion ultracapacitor of negative pole according to claim 2, is characterized in that: described positive active material is selected from one or more in active carbon, carbon nano-tube or carbon fiber.
4. the embedding magnesium ion ultracapacitor of negative pole according to claim 2, is characterized in that: described conductive agent is selected from carbon black, graphite or its mixture;
Described binding agent is selected from one or more in polytetrafluoroethylene (PTFE), Kynoar (PVDF), sodium carboxymethylcellulose (CMC) or butadiene-styrene rubber (SBR).
5. the embedding magnesium ion ultracapacitor of negative pole according to claim 1, is characterized in that: described negative pole is made up of negative current collector and the negative pole composite material be coated on negative current collector, and negative pole composite material comprises the component of following percentage by weight:
Can embed/deviate from the Carbon Materials 75% ~ 95% of magnesium ion
Conductive agent 3% ~ 15%
Binding agent 2% ~ 10%.
6. the embedding magnesium ion ultracapacitor of the negative pole according to any one of claim 1 ~ 5, is characterized in that: the described Carbon Materials embedding/deviate from magnesium ion comprises one or more in hard charcoal, KS-6 graphite or high crystallization RESEARCH OF PYROCARBON (HOPG).
7. the embedding magnesium ion ultracapacitor of negative pole according to claim 6, is characterized in that: described conductive agent is selected from carbon black, graphite or its mixture;
Described binding agent is selected from one or more in polytetrafluoroethylene (PTFE), Kynoar (PVDF), sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR);
Described negative or positive electrode collector is holey metal material or metal foil material, comprises the one in nickel foam, aluminium foil, Copper Foil or titanium foil material.
8. the embedding magnesium ion ultracapacitor of the negative pole according to any one of claim 1 ~ 5, is characterized in that: described electrolyte is selected from magnesium perchlorate (Mg (ClO
4)
2)/acetonitrile, Mg (ClO
4)
2+ tetraethylammonium tetrafluoroborate (Et
4nBF
4)/acetonitrile, MgCl
2/ methyl-sulfoxide or MgCl
2+ Et
4nBF
4one in/methyl-sulfoxide.
9. the embedding magnesium ion ultracapacitor of the negative pole according to any one of claim 1 ~ 5, is characterized in that: described barrier film is for having porous film material.
10. the manufacture method of the embedding magnesium ion ultracapacitor of the negative pole according to any one of claim 1 ~ 9, is characterized in that, comprise the steps:
The making of positive pole:
After described porous carbon material, conductive agent and binding agent being mixed, be stirred to paste, then adopt film applicator slurry to be coated on plus plate current-collecting body, through 100 ~ 130 DEG C of oven dry, then after roll-in, obtain positive pole;
The making of negative plate:
After can embedding/deviate from the mixing of the Carbon Materials of magnesium ion, conductive agent and binding agent, be stirred to paste, then adopt the coating of film applicator slurry on a current collector, through 100 ~ 130 DEG C of oven dry, then after roll-in, obtain positive pole;
Then magnesium ion ultracapacitor is assembled into.
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| CN106848307A (en) * | 2016-12-27 | 2017-06-13 | 重庆大学 | Magnesium transition metal phosphate class compound chargeable battery positive electrode and preparation method |
| CN107221443A (en) * | 2017-07-17 | 2017-09-29 | 深圳中科瑞能实业有限公司 | Sodium ion hybrid super capacitor and preparation method thereof |
| CN107369565A (en) * | 2017-07-17 | 2017-11-21 | 深圳中科瑞能实业有限公司 | Magnesium ion hybrid super capacitor and preparation method thereof |
| CN107369564A (en) * | 2017-07-17 | 2017-11-21 | 深圳中科瑞能实业有限公司 | Conductive metal material is used as magnesium ion hybrid super capacitor negative pole and magnesium ion hybrid super capacitor and preparation method thereof |
| CN109961961A (en) * | 2017-12-26 | 2019-07-02 | 深圳中科瑞能实业有限公司 | Ruthenium ion double layer capacitor and preparation method thereof |
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Application publication date: 20150513 |