CN104795532A - Electrode, electrical storage device comprising electrode and preparation method of electrical storage device - Google Patents
Electrode, electrical storage device comprising electrode and preparation method of electrical storage device Download PDFInfo
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- CN104795532A CN104795532A CN201510209623.4A CN201510209623A CN104795532A CN 104795532 A CN104795532 A CN 104795532A CN 201510209623 A CN201510209623 A CN 201510209623A CN 104795532 A CN104795532 A CN 104795532A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an electrode, an electrical storage device comprising the electrode and a preparation method of the electrical storage device. The electrode comprises a conductive base material, wherein active material layers coat the conductive base material, and are discontinuously arranged pattern blocks or are in continuously arranged net and lattice structures; and the thicknesses of the active material layers in the nets and lattices in the continuously arranged net and lattice structures are greater than those of the connected parts of the adjacent nets and lattices. According to the electrode, through coating of discontinuously arranged patterned active material layers or continuously arranged net and lattice active material layers on the conductive material layer according to different battery shapes, the target of improving the flexibility of the electrode is reached. The electrode can be fabricated into a strip, a chain or a block and the like; and the battery is not formed by series-parallel connection of a plurality of single bodies, and is one battery, so that the manufacturing cost is low; and the safety is good. An external control management circuit does not need to be added; the thickness of the battery can be 0.5-50mm; the relative available capacity is high; the internal resistance is small; the pulse performance is good; and the actual application range can be expanded.
Description
Technical field
The invention belongs to electrical storage device field, especially relate to a kind of electrode, comprise the electrical storage device of this electrode and electrical storage device preparation method.
Background technology
The electrode adopting conventional art to manufacture, generally do not have flexibility or flexible poor, along with cell thickness increases, battery can lose flexibility completely.
The method of current solution cell flexible probably has:
Many baby battery connection in series-parallel, this technology is with the watchband type batterypatent of APPLE company for representative, and its shortcoming is, baby battery manufactures difficulty, and production cost is high, is difficult to industrialization and realizes; Many battery series-parallel connections can produce battery capacity and voltage uneven and cause the problem wanting additional control circuit and produce potential safety hazard;
Flexible material and flexible electrode.Lower with the cell thickness of flexible material and flexible electrode manufacture at present, general maximum ga(u)ge at about 1mm, thus causes cell integrated capacity on the low side;
In recent years, the raising that development and people along with smart mobile phone technology require portable type electronic product, the wearable electronic such as intelligent watch, bracelet product becomes the emphasis of exploitation gradually.And these products are faced with low, the inflexible shortcoming of battery capacity, govern the development of electronic product.Therefore battery slimming, flexibility is required.
Battery is through method manufactures such as winding or laminations by positive electrode, negative electrode, barrier film etc.Wherein positive electrode and negative electrode are made up of active positive electrode material, negative electrode active material and conductive base etc. respectively.So the flexibility of inside battery assembly must be improved in order to develop flexible battery product.Therefore the problem that a kind of flexible electrode becomes those skilled in the art's research how is designed.
Summary of the invention
In view of this, the present invention is intended to propose a kind of flexible electrode, comprises the electrical storage device of this electrode and electrical storage device preparation method, to solve the problem of cell flexible.
For achieving the above object, technical scheme of the present invention is achieved in that
A kind of flexible electrode, comprise conductive base, described conductive base is coated with active material layer, described active material layer is be interrupted the pattern block arranged or the net, the grating texture that arrange continuously, and the thickness of the active material layer in the net of described continuous setting, grating texture in net, lattice is greater than the thickness of junction of adjacent two nets, compartment.
Further, the thickness of the active material layer in the net of described continuous setting, lattice is 10 μm of-10mm, and the thickness of the junction of described adjacent two nets, compartment is less than or equal to 5mm for being greater than 0.
Further, the width of the junction of the width of the discontinuities of described pattern block or adjacent net, compartment is 1mm-20mm.
Further, the thickness of described conductive base is 5 μm of-5mm.
Further, described conductive base is the conducting film material containing one or more in metallic copper, titanium, aluminium, nickel or silver.
Further, described active material layer is active layers of one or more compositions in fluorocarbons, lithium-contained composite oxide, metal sulfide, organosulfur compound, graphite and metallic zinc, nickel, manganese and oxide thereof, compound.
Further, described active layer adopts the one in extruding, spraying, nick, deposition or printing to prepare.
Comprise the electrical storage device of above-mentioned electrode.
A preparation method for electrical storage device, comprises the steps:
S1, batching;
S2, coating:
S21. positive and negative electrode chooses the thick conductive base of 5 μm of-5mm;
S22. on positive and negative electrode conductive base, apply active material layer, as required active material layer is applied into the pattern block that interruption is arranged or the net, the grating texture that arrange continuously;
S3, film-making:
S31. the gap between pattern block positive and negative electrode not being applied active material or apply adjacent two nets of a small amount of active material, the junction alignment of compartment, and negative electrode do not apply active material pattern block between gap or apply adjacent two nets of a small amount of active material, junction center line and the positive electrode of compartment does not apply the gap between the pattern block of active material or apply adjacent two nets of a small amount of active material, the junction center line of compartment aligns.According to different battery, negative electrode do not apply the width in the gap between the pattern block of active material or apply adjacent two nets of a small amount of active material, the width of the junction of compartment does not apply the gap between the pattern block of active material width than positive electrode or to apply adjacent two nets of a small amount of active material, the narrow at least 0.5mm of width of the junction of compartment or width the same;
S32. clean out certain region respectively at the two ends of positive and negative electrode, welding can the lug of extracted current on the area;
S4 assembles:
S41. negative electrode occupy barrier film middle, and positive electrode occupy negative electrode middle, and barrier film separates positive and negative electrode, adopts up-coiler to carry out reeling or lamination; Winding or lamination after core corrosion-resistant and high-temperature resistant termination gummed paper ending stickup shaping, core positive and negative electrode lug alignment;
S42. by the core that the aluminum plastic film encapsulation steps s41 cut out completes, then carry out banding limit, top side with top side seal machine, retain a side open-ended.
S43. the core completed step s42 at the temperature of 70 DEG C vacuumizes baking 12-16h, then in glove box, carries out injections electrolyte, at room temperature still aging 8-24h behind the limit of side seal step s42 reservation.
Further, the thickness of positive and negative electrode that described step s2 has been coated with is 15 μm of-15mm.
Relative to prior art, electrode of the present invention has following advantage:
(1) electrode of the present invention is according to the active material layer conductive base that do not coexist of cell shapes being interrupted the patterning arranged by coating or the net, the trellis active material layer that arrange continuously, reaches the object increasing electrode flexibility;
(2) above-mentioned electrode can do become band, chain or bulk etc.Battery is not many monomer connection in series-parallel, but a battery, and such low cost of manufacture, fail safe are good, need not add extra control and management circuit;
(3) cell thickness can accomplish 0.5-50mm, and relative usage capacity is large, and internal resistance is little, and pulse behaviors is good, can widen actual range of application.
Accompanying drawing explanation
The accompanying drawing forming a part of the present invention is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is the electrode structure of the Li-ion rechargeable table ring battery described in the embodiment of the present invention;
Fig. 2 is the electrode structure of the wearable battery of the Li-ion rechargeable described in the embodiment of the present invention;
Fig. 3 is other various patterning shapes of electrode of the present invention.
Description of reference numerals:
1-conductive base, 2-active material layer.
Embodiment
It should be noted that, when not conflicting, the embodiment in the present invention and the feature in embodiment can combine mutually.
Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
The raw material of this invention is the raw material that any rechargeable battery uses;
Positive and negative electrode base material is the base material that any rechargeable battery uses;
External structure has certain flexibility;
Basic similar to conventional batteries in proportioning process, in formula, containing electrode active material, (such as positive electricity very: the ternary lithium ion active material of cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, different ratio or hickelous nydroxide etc.; Negative electricity is very: artificial or native graphite, Graphene, hydrogen bearing alloy, cadmium metal or zinc etc.); Conductive agent SP, VGCF, SFG-6, carbon nano-tube etc.; Binder PVDF, CMC, SBR etc.; Solvent NMP, water etc. with auxiliary reagent as oxalic acid etc.
Coating process uses the coating process of extruding, spraying, nick, deposition or printing etc. to be coated on conductive base by active material, positive electrode chooses 5 μm of thick metals of-5mm or radio frequency base material, negative electrode chooses 5 μm of-5mm metals or radio frequency base material, and makes it can reach the structure of setting.This structure has netted or other structure, is coated with the active material of design thickness in grid, and size is between 2mm-100mm.For not apply active material or to apply a small amount of active material between grid, size is between 1mm-20mm.Distance between negative electrode grid is greater than distance between positive electrode grid at least more than 0.5mm or equal.The positive and negative electrode structure applied has certain thickness, and thickness is generally between 15 μm of-15mm.Such positive, negative electrode plate is after superposition or winding, and the base part branch not applying active material or apply a small amount of active material has certain flexibility, can arbitrarily bend this place, make battery be provided with certain flexibility.Make, with the battery that this electrode manufactures, there is higher thickness and better flexibility.According to the bending degree of battery request, the adjustable gap length not covering material or cover material on a small quantity.
Will align in the position not applying active material between positive and negative electrode grid when film-making and assembling or apply a small amount of active material, and the position that negative electrode does not apply active material or applies a small amount of active material falls within the centre at position that positive electrode does not apply active material or applies a small amount of active material.The width of negative electrode electrodes can equal the width that positive electrode also can be greater than positive electrode, during winding, ending can be that positive electrode is longer than negative electrode ending or negative electrode is longer than positive electrode ending, also can equal negative electrode or finish up with the base material of positive electrode or negative electrode by positive electrode.
Embodiment 1:
Li-ion rechargeable table ring battery (specification 0420100)
This battery can be loaded in the space of watchband, becomes to be integrated with watchband, has both saved space and has added aesthetics, again for table provides electricity.For better improving capacity and the high rate performance of this battery, the present invention chooses carbon nano-tube and adds in positive electrode slurry as conductive agent, and the making that good lithium ion battery material carries out showing ring battery also chosen by other material.
Batching: the percentage by weight of each component is as follows:
Positive electrode: cobalt acid lithium (97.95%), carbon nano-tube (1%), PVDF (1%), oxalic acid (0.05%);
Negative electrode: Delanium (95.98%), SP (1%), PVDF (3%), oxalic acid (0.02%);
Add the solvent NMP of concentration 95%-105% respectively, adopt double-planet de-airing mixer, positive and negative electrode separately at two double planetary mixer after fully stirring and disperse and lower the temperature, adjusting viscosity makes the viscosity of positive and negative electrode slurry be issued between 1000-3000cp at 25-30 degree environment; It is stand-by that positive and negative electrode slurry all uses 150 eye mesh screens to carry out filtration;
Coating:
Positive electrode chooses 15 μm of thick aluminum foils; Negative electrode chooses 10 μm of thick Copper Foils.The mode of employing batch (-type) automatic coating machine, extrusion coated is coated with positive and negative electrode slurry.In coating process, make to roll up greatly electrode occur a 3mm gap not applying active material or apply a small amount of active material in lateral attitude every 13mm; Coated face density is set to 32mg/cm2, and baking temperature is 90 DEG C, regulates coating speed to be out drying to electrode from baking oven.Pole piece adopts hydraulic pressure roller to roll positive electrode to design thickness 90-93 μm after drying, and rolls negative electrode to 120-123 μm.Painting effect as shown in Figure 1;
Film-making:
Positive electrode is of a size of 150mm (length) * 92mm (wide);
Negative electrode is of a size of 170mm (length) * 93mm (wide);
Make positive and negative electrode gap align during film-making, and ensure that each gap of positive electrode all falls within the middle of negative electrode gap.Clean out the region of 4*4mm at the two ends of electrode, welding can the lug of extracted current on the area, and lug is positive electrode aluminium pole ears and the negative electrode nickel lug of 2mm*0.1mm;
Assembling:
Employing basement membrane is the barrier film of even spread pottery alundum (Al2O3) and glue PVDF on individual layer polyolefin, and membrane thicknesses is 18 μm, the wide 95mm of long 400mm*;
External packing is the Imported Aluminium plastic film of 210mm*50mm*86 μm;
Negative electrode occupy barrier film middle, and positive electrode occupy negative electrode middle, and barrier film separates positive and negative electrode, adopts mutual-inserting type up-coiler to reel; Core after winding is with stopping gummed paper ending stickup shaping, and the positive and negative electrode lug of core aligns.By the aluminum plastic film cut out this core coated, then carry out banding limit, top side with top side seal machine, retain a side open-ended.
Baking 16h is vacuumized at the temperature of 70 DEG C to the battery core sealed, in glove box, then injects 5g LiPF6 electrolyte, at room temperature still aging 20h behind the limit that side seal retains.
Preliminary filling partial volume
Namely the table ring battery of flexible is obtained after preliminary filling partial volume is carried out to the battery core after ageing.
Embodiment 2: the wearable battery of Li-ion rechargeable (specification 04100100)
This battery can be contained on clothes or on cap or other place needed, as the power supply of wearable device flexible.For better improving capacity and the high rate performance of this battery, the present invention chooses carbon nano-tube and adds in positive electrode slurry as conductive agent, and the making that good lithium ion battery material carries out wearable battery also chosen by other material.
Batching: the percentage by weight of each component is as follows:
Positive electrode: cobalt acid lithium (97.95%), carbon nano-tube (1%), PVDF (1%), oxalic acid (0.05%);
Negative electrode: Delanium (95.98%), SP (1%), PVDF (3%), oxalic acid (0.02%);
Add the solvent NMP that concentration is 95%-105% respectively, adopt double-planet de-airing mixer, positive and negative electrode separately at two double planetary mixer after fully stirring and disperse and lower the temperature, adjusting viscosity makes the viscosity of positive and negative electrode slurry be issued between 1000-3000cp at 25-30 degree environment; It is stand-by that positive and negative electrode slurry all uses 150 eye mesh screens to carry out filtration;
Coating:
Positive electrode chooses 15 μm of thick aluminum foils; Negative electrode chooses 10 μm of thick Copper Foils.The mode of employing batch (-type) automatic coating machine, extrusion coated is coated with positive and negative electrode slurry.In coating process, make to roll up greatly electrode occur a 3mm gap not applying active material or apply a small amount of active material in lateral attitude every 15mm; The snap ring that a width is the quality of rubber materials of 3mm is installed every 15mm in the position that the scraper of coating machine is connected with applicator roll, like this in the process of coating large volume longitudinal direction on there will be a gap of 3mm not applying active material or apply a small amount of active material every 15mm.Coated face density is set to 32mg/cm2, and baking temperature is 90 DEG C, regulates coating speed to be out drying to electrode from baking oven.Pole piece adopts hydraulic pressure roller to roll positive electrode to design thickness 90-93 μm after drying, and rolls negative electrode to 120-123 μm.
Painting effect as shown in Figure 2;
Film-making:
Positive electrode is of a size of 1000mm (length) * 92mm (wide);
Negative electrode is of a size of 1100mm (length) * 93mm (wide);
Make positive and negative electrode gap align during film-making, and ensure that each gap of negative electrode all falls within the middle of positive electrode gap.Clean out the region of 4*4mm at the two ends of electrode, welding can the lug of extracted current on the area, and lug is positive electrode aluminium pole ears and the negative electrode nickel lug of 5mm*0.08mm;
Assembling:
Employing basement membrane is the barrier film of even spread pottery alundum (Al2O3) and glue PVDF on individual layer polyolefin, and membrane thicknesses is 18 μm, the wide 95mm of long 2200mm*;
External packing is the Imported Aluminium plastic film of 210mm*150mm*86 μm;
Negative electrode occupy barrier film middle, and positive electrode occupy negative electrode middle, and barrier film separates positive and negative electrode, adopts mutual-inserting type up-coiler to reel; Core high tempreture tape after winding finishes up stickup shaping, the positive and negative electrode ear alignment of core.By the aluminum plastic film cut out this core coated, then carry out banding limit, top side with top side seal machine, retain a side open-ended.
Baking 16h is vacuumized at the temperature of 70 DEG C to the battery core sealed, in glove box, then injects 12g LiPF6 electrolyte, at room temperature still aging 20h after the side that heat-sealing retains.
Preliminary filling partial volume
Both the wearable battery of flexible had been obtained after preliminary filling partial volume is carried out to the battery core after ageing.
The battery of this size that traditional handicraft makes and shape, not bent;
The battery of this size that the present invention makes and shape, maximumly can be bent to 90 DEG C.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. an electrode, comprise conductive base, it is characterized in that: described conductive base is coated with active material layer, described active material layer is be interrupted the pattern block arranged or the net, the grating texture that arrange continuously, and the thickness of the active material layer in the net of described continuous setting, grating texture in net, lattice is greater than the thickness of junction of adjacent two nets, compartment.
2. electrode according to claim 1, is characterized in that: the thickness of the active material layer in the net of described continuous setting, lattice is 10 μm of-10mm, and the thickness of the junction of described adjacent two nets, compartment is less than or equal to 5mm for being greater than 0.
3. electrode according to claim 1, is characterized in that: the width of the junction of the width of the discontinuities of described pattern block or adjacent net, compartment is 1mm-20mm.
4. electrode according to claim 1, is characterized in that: the thickness of described conductive base is 5 μm of-5mm.
5. electrode according to claim 1, is characterized in that: described conductive base is the conducting film material containing one or more in metallic copper, titanium, aluminium, nickel or silver.
6. electrode according to claim 1, is characterized in that: described active material layer is active layers of one or more compositions in fluorocarbons, lithium-contained composite oxide, metal sulfide, organosulfur compound, graphite and metallic zinc, nickel, manganese and oxide thereof, compound.
7. electrode according to claim 1, is characterized in that: described active layer adopts the one in extruding, spraying, nick, deposition or printing to prepare.
8. comprise the electrical storage device of the electrode as described in any one of claim 1-7.
9. a preparation method for electrical storage device, is characterized in that: comprise the steps:
S1, batching;
S2, coating:
S21. positive and negative electrode chooses the thick conductive base of 5 μm of-5mm;
S22. on positive and negative electrode conductive base, apply active material layer, as required active material layer is applied into the pattern block that interruption is arranged or the net, the grating texture that arrange continuously;
S3, film-making:
S31. the gap between pattern block positive and negative electrode not being applied active material or apply adjacent two nets of a small amount of active material, the junction alignment of compartment, and negative electrode do not apply active material pattern block between gap or apply adjacent two nets of a small amount of active material, junction center line and the positive electrode of compartment does not apply the gap between the pattern block of active material or apply adjacent two nets of a small amount of active material, the junction center line of compartment aligns.According to different battery, negative electrode do not apply the width in the gap between the pattern block of active material or apply adjacent two nets of a small amount of active material, the width of the junction of compartment does not apply the gap between the pattern block of active material width than positive electrode or to apply adjacent two nets of a small amount of active material, the narrow at least 0.5mm of width of the junction of compartment or width the same;
S32. clean out certain region respectively at the two ends of positive and negative electrode, welding can the lug of extracted current on the area;
S4 assembles:
S41. negative electrode occupy barrier film middle, and positive electrode occupy negative electrode middle, and barrier film separates positive and negative electrode, adopts up-coiler to carry out reeling or lamination; Winding or lamination after core corrosion-resistant and high-temperature resistant termination gummed paper ending stickup shaping, core positive and negative electrode lug alignment;
S42. by the core that the aluminum plastic film encapsulation steps s41 cut out completes, then carry out banding limit, top side with top side seal machine, retain a side open-ended.
S43. the core completed step s42 at the temperature of 70 DEG C vacuumizes baking 12-16h, then in glove box, carries out injections electrolyte, at room temperature still aging 8-24h behind the limit of side seal step s42 reservation.
10. the preparation method of electrical storage device according to claim 9, is characterized in that: the thickness of the positive and negative electrode that described step s2 has been coated with is 15 μm of-15mm.
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| CN1274955A (en) * | 1999-05-19 | 2000-11-29 | 日本电气株式会社 | Non-aqueous electrolyte secondary cell |
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| CN203225307U (en) * | 2013-05-14 | 2013-10-02 | 东莞新能源科技有限公司 | Flexible lithium ion battery |
| CN104143655A (en) * | 2014-07-31 | 2014-11-12 | 天津力神电池股份有限公司 | Flexible and pliable lithium ion secondary battery and manufacturing method thereof |
| CN104466229A (en) * | 2013-09-25 | 2015-03-25 | 华为技术有限公司 | Flexible lithium secondary battery and preparation method thereof |
| CN204732472U (en) * | 2015-04-27 | 2015-10-28 | 刘强 | Flexible electrode and comprise the battery of this flexible electrode |
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2015
- 2015-04-27 CN CN201510209623.4A patent/CN104795532A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1274955A (en) * | 1999-05-19 | 2000-11-29 | 日本电气株式会社 | Non-aqueous electrolyte secondary cell |
| CN101507014A (en) * | 2006-08-25 | 2009-08-12 | 丰田自动车株式会社 | Electrode for a power storing apparatus and power storing apparatus provided with that electrode |
| CN203225307U (en) * | 2013-05-14 | 2013-10-02 | 东莞新能源科技有限公司 | Flexible lithium ion battery |
| CN104466229A (en) * | 2013-09-25 | 2015-03-25 | 华为技术有限公司 | Flexible lithium secondary battery and preparation method thereof |
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Application publication date: 20150722 |
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