CN100590761C - Process for manufacturing super capacitor battery - Google Patents
Process for manufacturing super capacitor battery Download PDFInfo
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- CN100590761C CN100590761C CN200810031490A CN200810031490A CN100590761C CN 100590761 C CN100590761 C CN 100590761C CN 200810031490 A CN200810031490 A CN 200810031490A CN 200810031490 A CN200810031490 A CN 200810031490A CN 100590761 C CN100590761 C CN 100590761C
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- lithium ion
- ion battery
- super capacitor
- electrode material
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- 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
Abstract
The invention discloses a novel energy storage device synchronously provided with characteristics of a super capacitor and a lithium ion battery, and a method for producing the same. The invention hasthe following steps that: a lithium ion battery material and a super capacitor electrode material are separately prepared into pastes, and are alternatively coated to produce a super capacitor battery electrode plate; or a lithium ion battery electrode plate and a super capacitor electrode plate are respectively produced and are wound, then a lithium ion battery roll core and a super capacitor roll core are connected in parallel to form a super capacitor battery roll core cluster, then the super capacitor battery roll core cluster is placed into a battery case and welded, the drying and dehydration are performed, electrolyte is injected, and the novel energy storage device with high energy density and high power density, namely a super capacitor battery is obtained through charge and discharge activation.
Description
Technical field
The present invention relates to a kind of manufacture method that has the energy storage device of ultracapacitor and lithium ion battery characteristics concurrently, belong to electrochemical field.
Background technology
Energy crisis, shortage of resources, environmental pollution be human survival face sternly complete challenge, seeking secondary energy sources clean, renewable, resource-conserving is the task of realizing that human social needs to be resolved hurrily.
Lithium ion battery have operating voltage height, energy density big, have extended cycle life, advantages such as self-discharge rate is little, environmental protection, become the trend of secondary cell development.The power supply that has been widely used in portable electricity consuming productses such as wireless telecommunications, digital camera, notebook computer, and aspect the electrodynamic source of vehicle using motor, electric bicycle, battery-operated motor cycle, mine lamp, electric tool, hybrid vehicle, pure electric vehicle, having broad application prospects.But since in the lithium ion battery supply of energy storage and energy be by lithium ion in the positive and negative electrode material embedding or take off embedding and realize, relate to the solid-state diffusion process of lithium ion in the particle of positive and negative electrode material, and be accompanied by the expansion and the contraction of material volume in the charge and discharge process, thus limited lithium ion battery under the ultra-high magnifications (as 100C, 1000C etc.) discharge and recharge and high magnification under cyclical stability.
The ultracapacitor power density is big, have extended cycle life, and can reach 100000 times, and has environmental friendliness and advantage such as non-maintaining, all has broad application prospects in fields such as Aero-Space, defence and military, electric automobile, electronic information and instrument and meters.Although but the ultracapacitor energy density is little, far below the energy density of chemical power sources such as lithium ion battery, hangs down 2,3 orders of magnitude, thereby limited the range of application of ultracapacitor widely than lithium ion battery.
Making a kind of energy storage device (super capacitance cell) that has the characteristics of lithium ion battery and ultracapacitor concurrently, can absorb the advantage of lithium ion battery and ultracapacitor, and overcome the shortcoming of the two, is a kind of energy storage device that development potentiality is relatively arranged.
But, the physicochemical properties difference of lithium ion battery electrode material such as cobalt acid lithium, LiFePO4, LiMn2O4, graphite and super capacitance electrode material such as active carbon, pyrolytic carbon, carbon aerogels etc. is big, electrode material preparation slurry to solvent, binding agent, solid content require widely different, be difficult to mix, easy layering during coating, be difficult to even coating, and the requirement to technological parameters such as bake out temperature and coating speeds is also different, thereby makes the electrode slurry preparation of super capacitance cell and electrode evenly apply very difficulty.
Therefore, how to adopt explained hereafter simple, control easily to produce the energy storage device that has lithium ion battery and ultracapacitor characteristic concurrently, significant for the development of super capacitance cell with application.
Summary of the invention
Physicochemical properties difference at lithium ion battery electrode material in the super capacitance cell and super capacitance electrode material is big, when electrode material preparation slurry and coating to solvent, binding agent, solid content, or even bake out temperature and speed require different, thereby the problem of preparation of the electrode slurry of super capacitance cell and electrode coating difficulty, the invention provides the manufacture method of a kind of super capacitance cell electrode and super capacitance cell, concrete steps are as follows:
(1) with in LiFePO4, lithium nickel cobalt manganese oxygen, cobalt acid lithium, LiMn2O4, Li-Ni-Mn-O, lithium-nickel-cobalt-oxygen, lithium vanadium oxygen, ferric metasilicate lithium and their doped compound one or more as active substance of lithium ion battery anode; With raw material of wood-charcoal material and material modified such as native graphite, Delanium, MCMB, charcoal fiber, carbon nanotube, coke, pyrolytic carbons as lithium ion battery negative pole active materials, carbon materialses such as active carbon, carbon aerogels, carbon nano-tube, pyrolytic carbon, and oxide such as ruthenium-oxide, manganese oxide, cobalt oxide, nickel oxide, vanadium oxide, and in their doped compound one or more are as ultracapacitor negative or positive electrode material.
(2) according to the pulp of lithium ion battery compounding and production process of routine, active substance of lithium ion battery anode, negative electrode active material are hybridly prepared into lithium ion battery anode glue size and cathode size with binding agent, conductive agent, additive, solvent etc. respectively.
(3) according to the ultracapacitor slurry compounding and production process of routine, be hybridly prepared into super capacitor electrode paste with binding agent, conductive agent, additive, solvent etc.
(4) when electrode material applies, on collector, alternately coat lithium ion battery electrode material and electrode material for super capacitor, the mass ratio of control lithium ion battery electrode material and electrode material for super capacitor is between 0.05～20, then drying, roll film, cut the positive plate and the negative plate that are made into super capacitance cell.Then with super capacitance cell positive plate, negative plate and barrier film assembling super capacitance cell core, and adopt multicore to reel and assembling in parallel, be that positive and negative plate and barrier film adopt the mode of reeling to be assembled into the rouleau core, by with the parallel connection of a plurality of volume core, obtain the volume core cluster of big capacity super capacitance cell.
(5) or according to the lithium ion cell electrode production technology, lithium ion battery electrode sizing agent is coated, dry, roll film, cut, and is made into positive plate, the negative plate of lithium ion battery, is assembled into core of lithium ion cell with barrier film.According to the electrode of super capacitor production technology, super capacitor electrode paste is coated, dry, roll film, cut, and is made into positive plate, the negative plate of ultracapacitor, is assembled into the ultracapacitor core with barrier film.Adopt a plurality of lithium ion battery coil cores and ultracapacitor volume core to carry out the parallel connection assembling, the mass ratio of control lithium ion battery electrode material and electrode material for super capacitor is between 0.05～20, is not only had lithium ion battery coil core but also have the volume core cluster that ultracapacitor is rolled up the big capacity super capacitance cell of core.
In the manner described above the volume core cluster of super capacitance cell is packed into and weld behind the battery case, drying and dehydrating injects electrolyte, obtains super capacitance cell of the present invention after discharging and recharging activation.
The present invention has the characteristics of ultracapacitor and lithium ion battery concurrently, compares with conventional art, has the following advantages:
(1) has excellent ultra-high magnifications charging and discharging capabilities.
Contain in the super capacitance cell of the present invention and have electrode material for super capacitor in a large number, thereby realize utilizing the capacitance characteristic of super capacitance cell to carry out discharging and recharging under the ultra-high magnifications, and have good cyclical stability.
(2) energy density is higher than ultracapacitor more than 10 times.
Contain in the super capacitance cell of the present invention and can store up the lithium ion battery electrode material of lithium in a large number, thereby have energy density suitable on the order of magnitude, apparently higher than the respective value of ultracapacitor with lithium ion battery.
(3) adopt lithium ion battery electrode material and electrode material for super capacitor separately to prepare slurry, can avoid causing the difference that binding agent, solvent are required owing to the physical and chemical performance difference of two class electrode materials, and problems such as the electrode material mixing is inhomogeneous, layering.
Owing to both comprised lithium ion battery electrode material in the super capacitance cell electrode material, comprise electrode material for super capacitor again, and the difference of the physical and chemical performance of this two classes electrode material is very big, compare with lithium ion battery electrode material, electrode material for super capacitor generally has much higher specific area, very little grain diameter, loose surface texture and very low density, and also differ widely with the affinity of different solvents, therefore when the preparation slurry, often require higher binder content, lower solid content, in addition also different at binding agent with the requirement of dicyandiamide solution.And when two kinds of electrode materials mix preparation, the binding agent consumption that needs is more and bond effect is undesirable, and because the nature difference of two kinds of electrode materials, prepared slurry is easy to occur lamination, is difficult to guarantee in the subsequent production process two kinds of materials of ratio coating as requested.
(4) employing alternately applies lithium ion battery electrode material and super capacitance electrode material on collector, can realize adopting simple technology to apply lithium ion battery electrode material and super capacitance electrode material simultaneously at same collector.
This technology can be adjusted binding agent and consumption thereof, suitable solid content, the viscosity of employing respectively according to the character of two class electrode materials, and controls the ratio of two class electrode materials accurately, easily by the spreading area of control different materials.Compare with applying after the electrode material mixed preparing form slurry with lithium ion battery, ultracapacitor, avoided in the coating process because the ratio of two class electrode material layerings causing, two class electrode materials is forbidden and owing to two class electrode materials require difference to cause the big problem of cohesive force difference of two class electrode materials and collector to adhesive properties and consumption.And owing to have lithium ion battery electrode material and electrode material for super capacitor simultaneously concurrently on the collector, when battery energy storage and capacitor discharge, all collectors can both be fully used, and therefore have excellent high-rate discharge capacity.
(5) by being made into lithium ion cell electrode sheet and super capacitor electrode slice earlier, with lithium ion battery coil core and ultracapacitor volume core formation in parallel super capacitance cell volume core cluster, simplified the production technology of super capacitance cell greatly behind the coiling.
This technology can adopt the production technology of traditional lithium ion battery and ultracapacitor to manufacture corresponding electrode sheet and volume core respectively, thereby adopt different binding agents and dicyandiamide solution respectively according to the character of two class electrode materials, adjust binding agent consumption, solid content, viscosity etc.Compare with (4), in the selection of binding agent and dicyandiamide solution and the preparation of slurry, aspects such as the speed in the coating process, surface density, bake out temperature can be convenient, and the volume core quantity that the control of ratio can be advanced by the parallel connection of multireel core between the two class electrode materials and the collocation of weight realize, thereby electrode manufacturing process control can be simpler.
Table 1 the present invention compares with the performance of typical lithium-ion-power cell and ultracapacitor
| Project | Energy density (Wh/kg) | Power density (W/kg) | Cycle life is inferior |
| Lithium-ion-power cell | 120 | 300 | 500-1000 |
| Ultracapacitor | 0.1-3 | 1000-10000 | ＞10000 |
| Super capacitance cell of the present invention | 30-80 | 2000-10000 | 3000-30000 |
Description of drawings
Fig. 1 alternately applies lithium ion battery electrode material and electrode material for super capacitor schematic diagram.
Fig. 2 super capacitance cell typical case of the present invention discharge curve (50C)
Fig. 3 super capacitance cell typical recycling of the present invention performance curve (50C)
Embodiment
With LiFePO
4As active substance of lithium ion battery anode, be hybridly prepared into LiFePO with binding agent, conductive agent, additive, solvent etc.
4Anode sizing agent.As lithium ion battery negative pole active materials, be hybridly prepared into the graphite cathode slurry with graphite with binding agent, conductive agent, additive, solvent etc.With the active carbon is the electrode of super capacitor active material, is hybridly prepared into the active carbon slurry with binding agent, conductive agent, additive, solvent etc.
With the aluminium foil is collector, alternately coats LiFePO by accompanying drawing 1 mode
4Anode sizing agent and active carbon slurry, the quality ratio of control lithium ion battery electrode material and electrode material for super capacitor is 1, then drying, roll film, cut the positive plate that is made into super capacitance cell.
With the Copper Foil is collector, by accompanying drawing 1 mode alternately graphite utmost point slurry and active carbon slurry, the mass ratio of control lithium ion battery electrode material and electrode material for super capacitor is 1, then drying, roll film, cut the negative plate that is made into super capacitance cell.
With super capacitance cell positive plate, negative plate and barrier film assembling super capacitance cell core, and adopt multicore to reel and assembling in parallel, be that positive and negative plate and barrier film adopt the mode of reeling to be assembled into the rouleau core,, obtain the volume core cluster of big capacity super capacitance cell by with the parallel connection of 16 volume cores.
With the volume core cluster of super capacitance cell pack into thickness, width, highly weld after being respectively 34mm, 70mm, 65mm battery case, drying and dehydrating injects electrolyte, obtains super capacitance cell of the present invention after discharging and recharging activation.
After tested, be 4.12Ah by the gained 347065 type superbattery average sizes of above-mentioned explained hereafter, energy density is 50Wh/kg, maximum power density is 5000W/kg, capability retention＞85% after the 50C circulation 5000 times.
Embodiment 2
With LiFePO
4As active substance of lithium ion battery anode, be hybridly prepared into LiFePO with binding agent, conductive agent, additive, solvent etc.
4Anode sizing agent.As lithium ion battery negative pole active materials, be hybridly prepared into the graphite cathode slurry with graphite with binding agent, conductive agent, additive, solvent etc.With the active carbon is the electrode of super capacitor active material, is hybridly prepared into the active carbon slurry with binding agent, conductive agent, additive, solvent etc.
With lithium ion cell electrode LiFePO
4Anode sizing agent, graphite cathode slurry are coated to respectively on aluminium foil, the Copper Foil, drying, roll film, cut, and are made into positive plate, the negative plate of lithium ion battery respectively, are assembled into lithium ion battery coil core with barrier film.
The activated carbon for super capacitors slurry is coated to respectively on aluminium foil, the Copper Foil, drying, rolls film, cut, be made into positive plate, the negative plate of ultracapacitor, be assembled into ultracapacitor volume core with barrier film.
Adopt 4 lithium ion battery coil cores to carry out assembling in parallel with 8 ultracapacitor volume cores, the mass ratio of control lithium ion battery electrode material and electrode material for super capacitor is 1, is not only had lithium ion battery coil core but also have the volume core cluster that ultracapacitor is rolled up the big capacity super capacitance cell of core.
With the volume core cluster of super capacitance cell pack into thickness, width, highly weld after being respectively 34mm, 70mm, 65mm battery case, drying and dehydrating injects electrolyte, obtains super capacitance cell of the present invention after discharging and recharging activation.
After tested, be 4.26Ah by the gained 347065 type superbattery average sizes of above-mentioned explained hereafter, energy density is 50Wh/kg, maximum power density is 5000W/kg, capability retention＞88% after the 50C circulation 5000 times.
Embodiment 3
With LiFePO
4As active substance of lithium ion battery anode, be hybridly prepared into LiFePO with binding agent, conductive agent, additive, solvent etc.
4Anode sizing agent.As lithium ion battery negative pole active materials, be hybridly prepared into the graphite cathode slurry with graphite with binding agent, conductive agent, additive, solvent etc.With the active carbon is the electrode of super capacitor active material, is hybridly prepared into the active carbon slurry with binding agent, conductive agent, additive, solvent etc.
With the aluminium foil is collector, alternately coats LiFePO by accompanying drawing 1 mode
4Anode sizing agent and active carbon slurry, the quality ratio of control lithium ion battery electrode material and electrode material for super capacitor is 20, then drying, roll film, cut the positive plate that is made into super capacitance cell.
With the Copper Foil is collector, by accompanying drawing 1 mode alternately graphite utmost point slurry and active carbon slurry, the mass ratio of control lithium ion battery electrode material and electrode material for super capacitor is 20, then drying, roll film, cut the negative plate that is made into super capacitance cell.
With super capacitance cell positive plate, negative plate and barrier film assembling super capacitance cell core, and adopt multicore to reel and assembling in parallel, be that positive and negative plate and barrier film adopt the mode of reeling to be assembled into the rouleau core,, obtain the volume core cluster of big capacity super capacitance cell by with the parallel connection of 16 volume cores.
With the volume core cluster of super capacitance cell pack into thickness, width, highly weld after being respectively 34mm, 70mm, 65mm battery case, drying and dehydrating injects electrolyte, obtains super capacitance cell of the present invention after discharging and recharging activation.
After tested, be 6.25Ah by the gained 347065 type superbattery average sizes of above-mentioned explained hereafter, energy density is 70Wh/kg, maximum power density is 5000W/kg, capability retention＞87% after the 50C circulation 5000 times.
Embodiment 4
With LiNi
1/3Co
1/3Mn
1/3O
2As active substance of lithium ion battery anode, be hybridly prepared into LiNi with binding agent, conductive agent, additive, solvent etc.
1/3Co
1/3Mn
1/3O
2Anode sizing agent.As lithium ion battery negative pole active materials, be hybridly prepared into the graphite cathode slurry with graphite with binding agent, conductive agent, additive, solvent etc.With the active carbon is the electrode of super capacitor active material, is hybridly prepared into the active carbon slurry with binding agent, conductive agent, additive, solvent etc.
With lithium ion cell electrode LiNi
1/3Co
1/3Mn
1/3O
2Anode sizing agent, graphite cathode slurry are coated to respectively on aluminium foil, the Copper Foil, drying, roll film, cut, and are made into positive plate, the negative plate of lithium ion battery respectively, are assembled into lithium ion battery coil core with barrier film.
The activated carbon for super capacitors slurry is coated to respectively on aluminium foil, the Copper Foil, drying, rolls film, cut, be made into positive plate, the negative plate of ultracapacitor, be assembled into ultracapacitor volume core with barrier film.
Adopt 1 lithium ion battery coil core to carry out assembling in parallel with 15 ultracapacitor volume cores, the mass ratio of control lithium ion battery electrode material and electrode material for super capacitor is 0.1, is not only had lithium ion battery coil core but also have the volume core cluster that ultracapacitor is rolled up the big capacity super capacitance cell of core.
With the volume core cluster of super capacitance cell pack into thickness, width, highly weld after being respectively 34mm, 70mm, 65mm battery case, drying and dehydrating injects electrolyte, obtains super capacitance cell of the present invention after discharging and recharging activation.
After tested, be 1.12Ah by the gained 347065 type superbattery average sizes of above-mentioned explained hereafter, energy density is 10Wh/kg, maximum power density is 2000W/kg, capability retention＞80% after the 50C circulation 5000 times.
Claims (1)
1. the manufacture method of a super capacitance cell, with anode material for lithium-ion batteries, negative material and super capacitor material through the batching, coating, film-making, assembling, activation, be made into super capacitance cell, it is characterized in that: lithium ion battery anode glue size, cathode size are separated preparation with the ultracapacitor slurry, during the anode sizing agent coating, on collector, alternately coat anode material for lithium-ion batteries and electrode material for super capacitor; During the cathode size coating, on collector, alternately coat lithium ion battery negative material and electrode material for super capacitor, not only had lithium ion battery coil core but also have the volume core cluster that ultracapacitor is rolled up the big capacity super capacitance cell of core.
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| CN200810031490A CN100590761C (en) | 2008-06-16 | 2008-06-16 | Process for manufacturing super capacitor battery |
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| CN200810031490A CN100590761C (en) | 2008-06-16 | 2008-06-16 | Process for manufacturing super capacitor battery |
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| CN100590761C true CN100590761C (en) | 2010-02-17 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101814379A (en) * | 2010-04-28 | 2010-08-25 | 复旦大学 | Super capacitor |
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| CN101847764A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | High-specific-energy/high-specific-power type super battery |
| CN102290245B (en) * | 2011-04-29 | 2012-11-21 | 深圳市惠程电气股份有限公司 | Polyimide capacitor battery and manufacturing method thereof |
| CN102593555B (en) * | 2012-02-29 | 2014-03-12 | 中国科学院长春应用化学研究所 | Method for arranging bar code type capacitive electrode plate in electrode of alkaline cell as well as mixed negative electrode |
| CN102983381A (en) * | 2012-11-06 | 2013-03-20 | 中国科学院大连化学物理研究所 | Energy storage device with interleaved distributed inner parallel structure |
| CN103117374B (en) * | 2013-02-19 | 2016-02-10 | 宁德新能源科技有限公司 | Anode pole piece of lithium rechargeable battery and preparation method thereof |
| CN103138030B (en) * | 2013-02-26 | 2015-06-10 | 淄博君行电源技术有限公司 | Preparation method of asymmetric rare earth capacitor battery |
| CN104599852A (en) * | 2013-10-30 | 2015-05-06 | 张彩欣 | Super capacitor battery and manufacturing method thereof |
| CN105097289B (en) * | 2014-05-19 | 2020-12-04 | 清华大学 | Hybrid energy storage device |
| CN105098293A (en) * | 2014-05-19 | 2015-11-25 | 清华大学 | Hybrid energy storage device |
| CN105070516A (en) * | 2015-09-08 | 2015-11-18 | 上海空间电源研究所 | High-specific-energy super capacitor positive pole sheet and preparation method thereof |
| CN105513827B (en) * | 2015-12-15 | 2017-06-13 | 宁波中车新能源科技有限公司 | A kind of (LMO NCM AC)/(LTO AC) hybrid battery capacitance electrode material and electrode slice |
| CN105551816A (en) * | 2015-12-21 | 2016-05-04 | 中航锂电（洛阳）有限公司 | Positive plate of hybrid super capacitor and preparation method of positive plate and hybrid super capacitor |
| WO2017206095A1 (en) * | 2016-06-01 | 2017-12-07 | GM Global Technology Operations LLC | Lithium ion battery and capacitor hybridization in material and electrode level |
| CN107331528A (en) * | 2017-06-29 | 2017-11-07 | 中国科学院电工研究所 | Multi-layer composite electrode and the lithium ion battery electric capacity using the electrode |
| JP7163902B2 (en) * | 2019-12-09 | 2022-11-01 | トヨタ自動車株式会社 | Manufacturing method of lithium ion battery |
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| Power-ion battery:bridging the gap between Li-ion andsupercapacitor chemistries. A.Du Pasquier,et al.Journal of Power Sources,Vol.136 . 2004 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101814379A (en) * | 2010-04-28 | 2010-08-25 | 复旦大学 | Super capacitor |
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| CN101290833A (en) | 2008-10-22 |
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