CN101699590B - Hybrid supercapacitor - Google Patents
Hybrid supercapacitor Download PDFInfo
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- CN101699590B CN101699590B CN 200910219706 CN200910219706A CN101699590B CN 101699590 B CN101699590 B CN 101699590B CN 200910219706 CN200910219706 CN 200910219706 CN 200910219706 A CN200910219706 A CN 200910219706A CN 101699590 B CN101699590 B CN 101699590B
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- lithium
- electrolyte
- containing compound
- hybrid
- super capacitor
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- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 29
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 239000003990 capacitor Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 20
- 229920005596 polymer binder Polymers 0.000 claims description 10
- 239000002491 polymer binding agent Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- -1 ethylene isopropyl ester Chemical class 0.000 claims description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- 239000005030 aluminium foil Substances 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 4
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 3
- 229910013188 LiBOB Inorganic materials 0.000 claims description 3
- DISYGAAFCMVRKW-UHFFFAOYSA-N butyl ethyl carbonate Chemical compound CCCCOC(=O)OCC DISYGAAFCMVRKW-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- YYSONLHJONEUMT-UHFFFAOYSA-N pentan-3-yl hydrogen carbonate Chemical compound CCC(CC)OC(O)=O YYSONLHJONEUMT-UHFFFAOYSA-N 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- MPDDTAJMJCESGV-CTUHWIOQSA-M (3r,5r)-7-[2-(4-fluorophenyl)-5-[methyl-[(1r)-1-phenylethyl]carbamoyl]-4-propan-2-ylpyrazol-3-yl]-3,5-dihydroxyheptanoate Chemical compound C1([C@@H](C)N(C)C(=O)C2=NN(C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C2C(C)C)C=2C=CC(F)=CC=2)=CC=CC=C1 MPDDTAJMJCESGV-CTUHWIOQSA-M 0.000 claims description 2
- WYFCZWSWFGJODV-MIANJLSGSA-N 4-[[(1s)-2-[(e)-3-[3-chloro-2-fluoro-6-(tetrazol-1-yl)phenyl]prop-2-enoyl]-5-(4-methyl-2-oxopiperazin-1-yl)-3,4-dihydro-1h-isoquinoline-1-carbonyl]amino]benzoic acid Chemical compound O=C1CN(C)CCN1C1=CC=CC2=C1CCN(C(=O)\C=C\C=1C(=CC=C(Cl)C=1F)N1N=NN=C1)[C@@H]2C(=O)NC1=CC=C(C(O)=O)C=C1 WYFCZWSWFGJODV-MIANJLSGSA-N 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims 2
- 229910052749 magnesium Inorganic materials 0.000 claims 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 239000011888 foil Substances 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 2
- AGFJBJZWQNDDPA-UHFFFAOYSA-K [O-2].[V+5].[Li+].P(=O)([O-])([O-])[O-] Chemical compound [O-2].[V+5].[Li+].P(=O)([O-])([O-])[O-] AGFJBJZWQNDDPA-UHFFFAOYSA-K 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 238000002347 injection Methods 0.000 description 16
- 239000007924 injection Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 239000002002 slurry Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000004513 sizing Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000007581 slurry coating method Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- CXDRFZUNPAAQKC-UHFFFAOYSA-N [Li].[V].[O].P(O)(O)(O)=O Chemical compound [Li].[V].[O].P(O)(O)(O)=O CXDRFZUNPAAQKC-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 229910018095 Ni-MH Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910018477 Ni—MH Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- 229910014127 LiMn2 O4 -LiMn2 O4 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a hybrid supercapacitor, which is composed of a shell, an anode, a cathode, an organic membrane and organic electrolyte which are sandwiched between the anode and the cathode. The anode is made of a lithium-containing compound such as lithium vanadium oxide phosphate and the like, active carbon, conductive carbon black, a macromolecular adhesive and an aluminum foil, the cathode is made of a lithium-containing compound, conductive carbon black, an adhesive and an aluminum foil, and the organic electrolyte is composed of an electrolyte salt containing lithium ions and a hybrid organic solvent. The invention combines the advantages of a lithium ion battery with the advantages of a hybrid supercapacitor, and produces a hybrid supercapacitor with high energy density of a lithium ion battery as well as long service life and high power density of a supercapacitor; furthermore, the hybrid supercapacitor has a longer service life and a safer property because the cathode is composed of a lithium titanate material and the electrolyte is improved. Compared with the supercapacitor, the hybrid supercapacitor has a higher energy density, and can substantially expand the application area thereof, particularly is applicable to electric bicycles, electric cars and other fields, and can substitute lead-acid batteries in many occasions.
Description
Technical field
The present invention relates to a kind of electrochemical energy storing device field, be specifically related to a kind of novel hybrid super capacitor.
Background technology
Power supply is all indispensable piths of various circuit.Do not having under the situation of civil power, only take the mode of power storage could be satisfied the circuit use, therefore various energy storage devices are important component parts of mobile using electricity system, and its performance is directly connected to important indicators such as the useful life, power characteristic of mobile electrical appliance.
Present energy storage device is battery, secondary cell, ultracapacitor etc. once.Primary cell is not chargeable, can't use repeatedly, comprehensive use cost height.But the secondary cell repeated charge is the first-selected energy storage device of present many mobile electrical appliances; At present, common secondary cell has: lead-acid battery, nickel-cadmium cell, Ni-MH battery, lithium ion battery, ultracapacitor etc.Lead-acid battery, nickel-cadmium cell have the pollution of lead, cadmium heavy metal, are just progressively used by the countries in the world restriction; Because the price of nickel rises steadily, the cost performance of Ni-MH battery is also in continuous decline.Lithium ion battery and ultracapacitor are the novel energy-storing devices that occurs in recent years, have tangible performance advantage.Lithium ion battery energy density height, but power density is lower, and the life-span is lacked (about 1000 times); In the ultracapacitor life-span long (can reach more than 100,000 times), power density is big, but energy density is lower.
Lithium ion battery is combined with the advantage of ultracapacitor, produce a kind of lithium ion battery high-energy-density that has, the device of ultracapacitor long-life, high power density is the target of industry expectation.Application number is that 200710035205.3 patent has proposed a kind of super capacitance cell, and lithium ion is embedded compound and porous carbon mixture as positive pole, and porous carbon and graphite mixture have proposed a kind of super capacitance cell as negative pole.
Summary of the invention
The objective of the invention is: lithium ion battery is combined with the advantage of ultracapacitor, produce a kind of lithium ion battery high-energy-density that has, the hybrid super capacitor of ultracapacitor long-life, high power density.
The anodal phosphoric acid vanadium oxygen lithium (LiVOPO that adopts of the present invention
4) waiting lithium-containing compound, active carbon, conductive black, negative pole adopts lithium titanate (Li
4Ti
5O
12), conductive black, and the employing electrolyte system different with 200710035205.3, produce well behaved hybrid super capacitor, characteristics such as have that energy density height, power density are big, long-life, fail safe are good, use in the fields such as electric bicycle, electric automobile that are particularly suitable for, and at the alternative lead-acid battery of many occasions.
The present invention takes following technical scheme for achieving the above object: a kind of hybrid super capacitor that the present invention proposes, form by shell, positive pole, negative pole, organic barrier film and organic electrolyte between both positive and negative polarity, it is characterized in that described positive pole mainly contains lithium-containing compound, active carbon, conductive black, high polymer binder and aluminium foil; Described negative pole mainly contains lithium-containing compound, conductive black, high polymer binder and Copper Foil; Described organic electrolyte is made up of electrolytic salt that contains lithium ion and mixed organic solvents.
Described mixed organic solvents is dipropyl carbonate, methyl ethyl carbonate, vinylene carbonate, ethyl propyl carbonic acid ester, ethylene isopropyl ester, carbonic acid first butyl ester, dibutyl carbonate, ethyl butyl carbonate, gamma-valerolactone, oxolane, dimethyl-tetrahydrofuran, glycol dimethyl ether, dimethoxymethane, 1, in the 2-dimethoxy ethane at least two kinds, every kind of weight of solvent accounts for mixed organic solvents gross weight≤70%.
The lithium-containing compound of described composition hybrid super capacitor positive pole is phosphoric acid vanadium oxygen lithium LiVOPO
4, LiFePO 4 LiFePO
4, LiMn2O4 LiMn
2O
4And at least a in the material of other doped chemical X of above-mentioned lithium-containing compound.Described doped chemical X is at least a among S, Si, P, B, Al, Cr, V, Ti, Mn, Fe, Zn, Ni, Li, Mg, La, Ce, the Nd.Wherein the weight content of positive electrode is: lithium-containing compound 50～95%, active carbon 0.5～45%, conductive black 0.5～10%, high polymer binder 3～15%; Aluminium foil plays the collector effect, and its thickness is 12～30 μ m.
The lithium-containing compound of described composition negative pole is lithium titanate Li
4Ti
5O
12Or contain the lithium titanate Li of other doped chemical X
4Ti
5O
12Material.Doped chemical X is at least a among S, Si, P, B, Al, Cr, V, Ti, Mn, Fe, Zn, Ni, Li, Mg, La, Ce, the Nd.Wherein the weight content of negative material is: lithium-containing compound 55～95%, conductive black 0.5～10%, high polymer binder 2～15%, active carbon 0～20%; Copper Foil plays the collector effect, and its thickness is 9～25 μ m.
The negative pole of described hybrid super capacitor can also be made up of active carbon and Copper Foil that graphite, conductive black, high polymer binder, choosing add, wherein the weight content of negative material is: graphite 55～95%, conductive black 0.5～10%, binding agent 2～15%, active carbon 0～20%; Copper Foil plays the collector effect, and its thickness is 9～25 μ m; The used graphite of negative pole comprises at least a in native graphite, Delanium, the carbonaceous mesophase spherules.
The described electrolytic salt that contains lithium ion is Li (C
2H
5) PF
3, LiN (CF
3SO
2)
2, LiBOB, LiBMB, LBPFPB, LiBF
4, LiPF
6, LiClO
4, LiSCN, LiAsF
6In at least a, its weight content in organic electrolyte is 5～20%; (by weight) every kind of solvent is not more than 70% in the described organic solvent.
High polymer binder mainly adopts Kynoar (PVDF), carboxylic styrene butadiene latex (SBR)+sodium carboxymethylcellulose (CMC), carboxylic styrene butadiene latex (SBR)+hydroxypropyl methylcellulose (HPMC), polyvinyl alcohol (PVA) etc.
Hybrid super capacitor manufacturing process of the present invention is: weighing and burden → slurry stirring → slurry coat make on aluminium foil or the Copper Foil collector pole piece → pole piece rolling → minute be cut to suitable size → soldering polar ear → be wound as core bag → dress shell → drying → notes electrolyte → seasoned → seal → detect.
That hybrid super capacitor of the present invention can be made as required is cylindrical, cuboid or coin shape etc.Its shell can adopt stainless steel case, aluminum hull, plastic housing or aluminum plastic film.
Hybrid super capacitor proposed by the invention is compared with existing lithium-ion electric pool technology, and product has higher power density, and in the longer life-span, security performance is better; The negative pole that is particularly proposed adopts lithium titanate Li
4Ti
5O
12The product safety performance of material improves a lot.Compare with ultracapacitor, the technology of the present invention product has higher energy density, can expand its application significantly.Compare with the super capacitance cell that patent 200710035205.3 proposes, because negative pole adopts lithium titanate Li
4Ti
5O
12Therefore material and improved the electrolyte composition has higher life-span and security performance.
Embodiment
The present invention is described in detail below by embodiment, following Example just meets several examples of the technology of the present invention content, do not illustrate that the present invention only limits to the described content of following example, the technical staff in the industry all belongs to content of the present invention according to the product of claim item of the present invention manufacturing.
Embodiment 1
1. anode sizing agent preparation (by weight): with commercial phosphoric acid vanadium oxygen lithium 50%, active carbon 25%, conductive black 10%, binding agent PVDF (15%) and total amount are 2.5 times of above-mentioned solid-like total amounts (N-methyl pyrrolidone) nmp solvent, mix to form uniform slurry in 8 hours in the vacuum planetary mixer.
2. cathode size preparation (by weight): with business-like lithium ion battery native graphite 95%, conductive black 2%, binding agent SBR (2%), CMC (1%) and total amount are times deionized water of above-mentioned solid-like total amount 3.5, mix to form uniform slurry in 8 hours in the vacuum planetary mixer.
3. slurry coating: with coating machine be coated in the above-mentioned anode sizing agent for preparing on the aluminum foil current collector equably respectively, cathode size is coated on the Copper Foil collector.
4. pole piece is rolling: use to coat to roller mill that the positive and negative electrode sheet is respectively rolling to be more closely knit pole piece, with further increase bond strength, reduce resistance.
5. pole piece is cut with lug and is welded: will go up rolling good pole piece of step with cutting machine and cut into suitable size, and lug is welded on the electrode slice.
6. be wound as core bag, dress shell, drying: the pole piece that will weld lug is wound into circle or flat core bag with the commercial li-ion battery diaphragm, and the core bag is put into the length and width height be respectively: the shell of 70mm, 27mm, 120mm, and the both positive and negative polarity lug of core bag and the positive and negative terminal of shell welded together; With laser-beam welding machine the cover plate of shell is carried out seal welding, only stay the liquid injection hole about next Φ 1mm; Connect shell then and put into vacuum drying chamber oven dry 10 hours together.
7. annotate electrolyte: inject electrolyte in adorning shell and dry good core bag, electrolyte is formed: solvent is dipropyl carbonate content 45%, methyl ethyl carbonate ester content 50%, vinylene carbonate content 5%; Solute Li (C
2H
5) PF
3(its weight be solvent gross weight 20%); After electrolyte is annotated, the liquid injection hole on the shell is temporarily sealed up with adhesive tape.
8. seasoned, seal: the hybrid super capacitor of fluid injection is put on the seasoned machine, and its both positive and negative polarity links to each other with the both positive and negative polarity of seasoned machine respectively, starts seasoned machine and carries out seasonedly, with the stainless steel steel ball liquid injection hole is sealed after seasoned 8 hours.
9. detect: with battery charge-discharge test instrument the hybrid super capacitor of making is tested, discharged and recharged with 1C, its discharge capacity is 8.6Ah, and circulating, capacity is 90.5% of an initial capacity after 2000 times; The 1C charging, the 10C discharge test, discharge capacity is 7.8Ah.
Embodiment 2
1. anode sizing agent preparation (by weight): with business-like lithium ion battery LiMn2O4 95%, active carbon 1%, conductive black 1%, commercial li-ion battery binding agent L135 (3%) and total amount are the water of 5 times of above-mentioned solid-like total amounts, mix to form uniform slurry in 8 hours in the vacuum planetary mixer.
2. cathode size preparation (by weight): with commercialization lithium ion battery Delanium 55%, conductive black 10%, commercial organic ultracapacitor active carbon 20%, polyvinyl alcohol 15%, and total amount is the deionized water of 4 times of above-mentioned solid-like total amounts, mixes forming uniform slurry in 8 hours in the vacuum planetary mixer.
3. slurry coating: with embodiment 1.
4. pole piece is rolling: with embodiment 1.
5. pole piece is cut with lug and is welded: with embodiment 1.
6. be wound as core bag, dress shell, drying: with embodiment 1.
7. annotate electrolyte: inject electrolyte in adorning shell and dry good core bag, electrolyte is formed: solvent is ethyl propyl carbonic acid ester content 30%, gamma-valerolactone content 70%; Solute LiPF
6(its weight be solvent gross weight 15%); After electrolyte is annotated, the liquid injection hole on the shell is temporarily sealed up with adhesive tape.
8. seasoned, seal: the hybrid super capacitor of fluid injection is put on the seasoned machine, and its both positive and negative polarity links to each other with the both positive and negative polarity of seasoned machine respectively, starts seasoned machine and carries out seasonedly, with the stainless steel steel ball liquid injection hole is sealed after seasoned 8 hours.
9. detect: with battery charge-discharge test instrument the hybrid super capacitor of making is tested, discharged and recharged with 1C, its discharge capacity is 9.2Ah, and circulating, capacity is 91.4% of an initial capacity after 2000 times; The 1C charging, the 10C discharge test, discharge capacity is 7.5Ah.
Embodiment 3
1. anode sizing agent preparation (by weight): with business-like lithium ion battery LiFePO 4 85%, active carbon 7.5%, conductive black 0.5%, binding agent SBR (5%), CMC (2%) and total amount are the deionized water of 3.8 times of above-mentioned solid-like total amounts, mix to form uniform slurry in 8 hours in the vacuum planetary mixer.
2. cathode size preparation (by weight): with business-like lithium ion battery carbonaceous mesophase spherules 85%, conductive black 10%, commercial organic ultracapacitor active carbon 0.5%, commercial li-ion battery binding agent L135 (4.5%) and total amount are the water of 5 times of above-mentioned solid-like total amounts, mix to form uniform slurry in 8 hours in the vacuum planetary mixer.
3. slurry coating: with embodiment 1.
4. pole piece is rolling: with embodiment 1.
5. pole piece is cut with lug and is welded: with embodiment 1.
6. be wound as core bag, dress shell, drying: with embodiment 1.
7. annotate electrolyte: inject electrolyte in adorning shell and dry good core bag, electrolyte is formed: solvent is ethylene isopropyl ester content 30%, carbonic acid first butyl ester content 40%, dimethoxymethane 20%, oxolane 10%; Solute LiPF
6(its weight be solvent gross weight 10%), LiBF4 (for the solvent gross weight 5%); After electrolyte is annotated, the liquid injection hole on the shell is temporarily sealed up with adhesive tape.
8. seasoned, seal: the hybrid super capacitor of fluid injection is put on the seasoned machine, and its both positive and negative polarity links to each other with the both positive and negative polarity of seasoned machine respectively, starts seasoned machine and carries out seasonedly, with the stainless steel steel ball liquid injection hole is sealed after seasoned 8 hours.
9. detect: with battery charge-discharge test instrument the hybrid super capacitor of making is tested, discharged and recharged with 1C, its discharge capacity is 12.2Ah, and circulating, capacity is 96.4% of an initial capacity after 2000 times; The 1C charging, the 10C discharge test, discharge capacity is 11.3Ah.
Embodiment 4
1. anode sizing agent preparation (by weight): with business-like lithium ion battery LiFePO 4 30%, commercial li-ion battery LiMn2O4 15%, active carbon 45%, conductive black 3%, PVDF (7%) and total amount are the nmp solvent of 2.5 times of above-mentioned solid-like total amounts, mix to form uniform slurry in 8 hours in the vacuum planetary mixer.
2. cathode size preparation (by weight): with commercialization lithium ion battery Delanium 80%, conductive black 0.5%, commercial organic ultracapacitor active carbon 10%, PVDF (9.5%) and total amount are the deionized water of 5 times of above-mentioned solid-like total amounts, mix to form uniform slurry in 8 hours in the vacuum planetary mixer.
3. slurry coating: with embodiment 1.
4. pole piece is rolling: with embodiment 1.
5. pole piece is cut with lug and is welded: with embodiment 1.
6. be wound as core bag, dress shell, drying: with embodiment 1.
7. annotate electrolyte: inject electrolyte in adorning shell and dry good core bag, electrolyte is formed: solvent is dibutyl carbonate content 30%, ethyl butyl carbonate content 40%, dimethoxymethane 15%, glycol dimethyl ether 10%, dimethyl-tetrahydrofuran 5%; Solute LiN (CF
3SO
2)
2(its weight be solvent gross weight 10%), LiBOB (for the solvent gross weight 2%), LiSCN (for the solvent gross weight 3%); After electrolyte is annotated, the liquid injection hole on the shell is temporarily sealed up with adhesive tape.
8. seasoned, seal: the hybrid super capacitor of fluid injection is put on the seasoned machine, and its both positive and negative polarity links to each other with the both positive and negative polarity of seasoned machine respectively, starts seasoned machine and carries out seasonedly, with the stainless steel steel ball liquid injection hole is sealed after seasoned 8 hours.
9. detect: with battery charge-discharge test instrument the hybrid super capacitor of making is tested, discharged and recharged with 1C, its discharge capacity is 7.8Ah, and circulating, capacity is 97.1% of an initial capacity after 2000 times; The 1C charging, the 10C discharge test, discharge capacity is 7.1Ah.
Embodiment 5
1. anode sizing agent preparation (by weight): with business-like lithium ion battery LiFePO 4 81%, commercial organic ultracapacitor active carbon 10%, conductive black 3%, commercial li-ion battery binding agent L133 (6%) and total amount are the deionized water of 3.8 times of above-mentioned solid-like total amounts, mix to form uniform slurry in 8 hours in the vacuum planetary mixer.
2. cathode size preparation (by weight): with lithium titanate (Li
4Ti
5O
12) 80%, conductive black 5%, commercial organic ultracapacitor active carbon 10%, PVDF binding agent 10% and total amount are the deionized water of 5 times of above-mentioned solid-like total amounts, mix to form uniform slurry in 8 hours in the vacuum planetary mixer.
3. slurry coating: with embodiment 1.
4. pole piece is rolling: with embodiment 1.
5. pole piece is cut with lug and is welded: with embodiment 1.
6. be wound as core bag, dress shell, drying: with embodiment 1.
7. annotate electrolyte: inject electrolyte in adorning shell and dry good core bag, electrolyte is formed: solvent is methyl ethyl carbonate ester content 70%, vinylene carbonate content 5%, 1,2-dimethoxy ethane 10%, dibutyl carbonate 15%; Solute LiBMB (its weight be solvent gross weight 6%), LiAsF
6(be solvent gross weight 4%), LiBPFPB (for the solvent gross weight 5%); After electrolyte is annotated, the liquid injection hole on the shell is temporarily sealed up with adhesive tape.
8. seasoned, seal: the hybrid super capacitor of fluid injection is put on the seasoned machine, and its both positive and negative polarity links to each other with the both positive and negative polarity of seasoned machine respectively, starts seasoned machine and carries out seasonedly, with the stainless steel steel ball liquid injection hole is sealed after seasoned 8 hours.
9. detect: with battery charge-discharge test instrument the hybrid super capacitor of making is tested, discharged and recharged with 1C, its discharge capacity is 14.3Ah, and circulating, capacity is 96.8% of an initial capacity after 2000 times; The 1C charging, the 10C discharge test, discharge capacity is 13.1Ah.
Claims (1)
1. hybrid super capacitor is made up of shell, positive pole, negative pole, organic barrier film and organic electrolyte between both positive and negative polarity, and described positive pole mainly contains lithium-containing compound, active carbon, conductive black, high polymer binder and aluminium foil; Described negative pole mainly contains lithium-containing compound, conductive black, high polymer binder and Copper Foil; Described organic electrolyte is made up of electrolytic salt that contains lithium ion and mixed organic solvents; It is characterized in that described mixed organic solvents is at least two kinds in dipropyl carbonate, vinylene carbonate, ethyl propyl carbonic acid ester, ethylene isopropyl ester, carbonic acid first butyl ester, dibutyl carbonate, ethyl butyl carbonate, gamma-valerolactone, glycol dimethyl ether, the dimethoxymethane, every kind of weight of solvent accounts for mixed organic solvents gross weight≤70%;
Forming anodal lithium-containing compound is to contain at least a LiVOPO among other doped chemical S, Si, P, B, Al, Cr, V, Ti, Mn, Fe, Zn, Ni, Mg, La, Ce, the Nd
4Material;
The lithium-containing compound of forming negative pole is to contain at least a Li among other doped chemical S, Si, P, B, Al, Cr, V, Ti, Mn, Fe, Zn, Ni, Mg, La, Ce, the Nd
4Ti
5O
12Material.
2, hybrid super capacitor according to claim 1 is characterized in that: wherein the weight content of positive electrode is: lithium-containing compound 50～95%, active carbon 0.5～45%, conductive black 0.5～10%, high polymer binder 3～15%; The thickness of aluminium foil is 12～30 μ m.
3, hybrid super capacitor according to claim 1 is characterized in that: wherein the weight content of negative material is: lithium-containing compound 55～95%, conductive black 0.5～10%, high polymer binder 2～15%, active carbon 0～20%; The thickness of Copper Foil is 9～25 μ m.
4, hybrid super capacitor according to claim 1 is characterized in that: the lithium-ion electrolyte salt that contains in the described organic electrolyte is Li (C
2H
5) PF
3, LiN (CF
3SO
2)
2, LiBOB, LiBMB, LBPFPB, LiBF
4, LiPF
6, LiClO
4, at least a among LiSCN, the LiAsF6, its weight content in organic electrolyte is 5～20%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103000383A (en) * | 2011-09-15 | 2013-03-27 | 海洋王照明科技股份有限公司 | Super capacitance battery and preparation method thereof |
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| CN104157467A (en) * | 2014-08-22 | 2014-11-19 | 东莞市迈科新能源有限公司 | Carbon-based lithium ion supercapacitor |
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