CN101414671A - Nonaqueous secondary electrolytic battery - Google Patents
Nonaqueous secondary electrolytic battery Download PDFInfo
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- CN101414671A CN101414671A CNA200810213497XA CN200810213497A CN101414671A CN 101414671 A CN101414671 A CN 101414671A CN A200810213497X A CNA200810213497X A CN A200810213497XA CN 200810213497 A CN200810213497 A CN 200810213497A CN 101414671 A CN101414671 A CN 101414671A
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- battery case
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A nonaqueous secondary electrolytic battery comprises an electricity-generating element formed by spirally winding a laminate of a positive electrode plate, a separating material and a negative electrode plate, and an electrolytic solution with which the separating material, if it is a separator, is impregnated. The electricity-generating element is sealed in a battery case formed by a resin-laminated sheet comprising a metal layer as a barrier layer. Only a pair of lead terminals is drawn to the exterior of the battery case. The resin sheet comprises an oriented resin layer laminated on both surfaces of the metal layer. The inner heat-fused layers are opposed and heat-fused to each other. A molten and solidified resin mass is formed protruding from the inner end of the welded portion toward the inner space of the battery by 0.1 mm or more. Alternatively, the welded portion is formed thinner at the outer end thereof than at the inner end thereof.
Description
The application is to be on November 4th, 1999 applying date, and application number is 200610094163.6, and denomination of invention is divided an application for the patent application of " non-aqueous electrolytic secondary cell ".
Technical field
The present invention relates to comprise the battery of the shell that forms by resin plate.
Background technology
In recent years, developed for example electronic equipment of portable cordless telephone, pocket pc and field camera.Various electronic equipments have been reduced to a certain degree dimensionally, make that they can be portable.This need use energy density height and lightweight battery to be installed in these electronic equipments.The representative cells that satisfies these requirements is the nonaqueous electrolyte secondary cell, this battery comprises: as the lithiated intercalation compound of negative material, this lithiated intercalation compound has lithium metal, lithium alloy and the lithium ion that is absorbed in as in the host material carbon group compound of (term " host material " refers to absorb and to discharge the material of lithium ion as used herein); The compound that carries out reversible electrochemical reaction as positive electrode, with lithium ion, for example lithium cobalt composite oxide; And as LiClO
4And LiPF
6Lithium salts be dissolved in wherein proton-organic solvent as electrolyte solution.
This nonaqueous electrolyte battery comprises: negative plate, this negative plate have the negative polarization compound that comprises above-mentioned negative material, and negative material remains on the negative electrode collector as supporter; Positive plate, this positive plate have the positive polarization compound that comprises above-mentioned positive electrode, and positive electrode remains on the positive electrode collector as supporter; Be located at the isolated material between negative plate and the positive plate.This isolated material is often referred to dividing plate, be used to keep electrolyte solution and be inserted in negative plate and positive plate between in case two electric pole short circuits.Yet, for preventing short circuit and can being also referred to as isolated material by the solid electrolyte of conducting ion between negative plate and positive plate.
Each is the above-mentioned positive plate of flakiness shape and negative plate stacked or common screw winding and form generating element mutually all, and isolated material is inserted between positive plate and the negative plate.This generating element is contained in the metal battery case of the iron of for example stainless steel, nickel plating or aluminium, electrolyte solution is injected wherein again.Use cover plate hermetic seal battery case then, be assembled into battery.
The mechanical strength of using this metal battery shell to provide high-air-tightness to become reconciled, but be very limited aspect reduction battery weight and the selection cell shapes.
Propose a kind of structure as a method that addresses the above problem: generating element is contained in the battery case that resin plate makes.The advantage of this structure is: the selectance that can reduce battery weight and increase cell shapes.On the other hand, this structure has following defective and the problem that will solve.
(a) this structure comprises that the stacked resin plate that constitutes by metal forming and thermoplastic resin layer is used as above-mentioned resin plate, and its special benefits is a high-air-tightness.Yet metal forming cracks when welding resin plate under tension, reduces the sealing property of resin plate.Therefore, water enters battery, reduces battery life.
(b) this structure of this resin plate formation battery case is along with inner pressure of battery raises, and the welding portion of overlapped resin plate end is peeled off easily.The metal-resin plate has enough strong air-tightness on the direction perpendicular to metal forming.Yet the outside of battery case is not owing to metal forming with inner the separation, but owing to is clipped in the resin bed that is positioned at the weld part office of its overlapped end between two metal formings.Therefore, power and water is separated matter and is become branch to pass through resin bed easily.
(c) manufacturing of such battery is finished by following technology usually: the generating element of leaded end is put into the open cell shell that resin plate is made, inject electrolyte solution to battery case, be put in lead end between the opening portion both sides then and weld the battery case peristome and assign to seal this battery case.Yet,, therefore under electrolyte solution is attached to the situation in the resin plate zone that will weld, weld sometimes because electrolyte solution drips on the generating element during injecting battery case and spills or be attached to lead end.This also causes sealing property to worsen.
(d) if use the screw winding generating element, then be different from the time of in being contained in the battery case that resin plate makes and be contained in the metal-back, can be lax easily.As a result, the interval between each battery lead plate can not keep constant for a long time.Therefore, this structure discharge capacity occurs and descends after charge-discharge cycles repeatedly.
(e) made by resin plate under the first step of battery case, two parallel sides of resin plate are welded to each other the formation cylinder.Yet when assembled battery, this welding portion is outstanding from battery case.Therefore, this protuberance hinders a plurality of batteries to pile up.Therefore, pile up these batteries and be easy to generate unnecessary space, or spended time compresses these accumulation batteries so that this protuberance does not have obstruction.
(f) in this structure, generating element bears less pressure than the conventional enclosure that metal-back constitutes.Therefore, be used at the battery that shell is made by resin plate under the situation of vibration environment, generating element moves in battery case easily, makes sometimes in the fixed area of thermal weld part and the lead end of the position between the generating element to disconnect.And, because generating element bears little pressure, can cause that distance between electrodes is inhomogeneous in the generating element, cause charging-discharge performance to worsen.
In view of the foregoing produced the present invention.The purpose of this invention is to provide long-life battery, this battery has enough strong air-tightness, reduces the weight of the battery case that resin plate makes simultaneously.Another object of the present invention is that the welding portion that prevents the resin plate two ends hinders battery to pile up, and increases the volume energy density of entire cell.A further object of the present invention is the lead end fracture that prevents in the battery case.
Summary of the invention
Comprise following element according to battery of the present invention: generating element, comprise be arranged opposite to each other, insert the positive plate and the negative plate of isolated material therebetween; The lead end that links to each other with each battery lead plate; The battery case (forming) that constitutes by resin plate by stacked bearing tree fat layer on the two sides of metal level, shell is at one or two direction opening before the sealing, put into above-mentioned generating element then therein and insert above-mentioned lead end at an opening, weld at opening part again, thus can.
Metal level for constituting resin plate can use aluminium foil, alloy foil, titanium foil etc.It is one that the resin bed of formation resin plate and the quantity of metal level do not limit.Can use two or more resin beds and metal level, to form resin plate.Resin bed can be the form that comprises the sandwich construction of identical or different material layer.It is resin bed-metal level-resin bed structure that the structure of resin plate does not limit, but can be resin bed-resin bed-metal level-resin bed structure or resin bed-metal level-resin bed-metal level-resin bed structure.In a word, oriented resin bed is added on two surfaces of metal level, metal level is easy fracture not, makes sealing property be improved.Term used herein " is added on two surfaces of metal level " may not mean resin bed and metal layer contacting.For example, resin plate can have directed resin bed-non-directional resin bed-metal level-non-directional resin bed-directed resin bed structure.Therefore, the structure with thin non-directional resin bed comprises in the present invention in essence.
Be the opening of welding resin plate, for example the thermoplastic macromolecule material of polyethylene, polypropylene and polyethylene terephthalate must be present in the superficial layer of resin plate.
In the preferred embodiment of the generating element of Shi Yonging, positive plate and negative plate and intercalary isolated material are wound on together in the present invention, form oval cross section almost perpendicular to the elliptical coil of axis.Yet the present invention is not defined in this shape.According to generating element of the present invention can be coil, the isolated material intercalary plane electrode plate group that for example has circle or noncircular cross section and with the superimposed plate electrode group of intercalary isolated material.Term used herein " ellipse " mean by approximate half-circular part and near linear part in conjunction with and the shape that forms, such structure is that relative a pair of semi-circular portion is partly interconnected endways by two parallel lines.
Under the situation in ellipse coiling generating element is contained in battery case that be made of resin plate, one or two direction upper shed, the plane of the opening of the vertical unsealing battery case of the wireline reel of preferred oval coiling generating element.Terminology used here " vertically " not only means " vertical fully " but also shows " almost vertical ".
Comprise positive pole, negative pole and the isolated material of combining according to generating element of the present invention.Active anode compartment material, adhesive and the conductive agent described are later mixed, prepare the positive polarization compound, the positive polarization compound is coated on one or two surface of the tabular of conduction or paper tinsel shape collector body again, prepare positive plate.Active cathode material and the adhesive described are later mixed, prepare the negative polarization compound, the negative polarization compound is coated on one or two surface of the tabular of conduction or paper tinsel shape collector body again, the dry then material that had applied is prepared negative plate.
Prevent from isolated material before the sealed cell shell, electrolyte solution to be injected in the battery case usually under the situation of two electric pole short circuits.Yet generating element can comprise positive pole, negative pole of combining and the solid electrolyte that also serves as isolated material.Above-mentioned solid electrolyte can be organic material, inorganic material or their combination, perhaps can be polyelectrolyte or the porous material that is impregnated with electrolyte solution.
As for as electrolytical non-aqueous electrolytic solution, can use material known.The example of non-aqueous electrolytic solution comprises polar solvent for example ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, sulfolane, dimethyl sulfoxide (DMSO), acetonitrile, dimethyl formamide, dimethylacetylamide, 1,2-dimethoxy ethane, 1,2-diethoxy ethane, oxolane, 2-methyltetrahydrofuran, dioxolanes and methyl acetate with and composition thereof.
The example that is dissolved in the lithium salts of organic solvent comprises for example LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiCF
3CO
2, LiCF
3SO
3, LiN (SO
2CF
3), LiN (SO
2CF
2CF
3), LiN (COCF
3) and LiN (COCF
2CF
3)
2Salt with its mixture.
In addition, the dielectric substrate that mainly is made of organic material, inorganic material or its mixture can be formed on the upper surface of positive polarization compound layer and/or negative polarization compound layer.Dielectric substrate is necessary chemistry or electrochemical stability in battery, and has high mechanical strength.Preferred electrolyte is made of solid electrolyte.Yet dielectric substrate need not be made of single component generally.Further, dielectric substrate need not made by electrolyte generally.For example, can use impregnated and have the solid electrolyte of conductance of enhancing or a known isolated material of being crossed by electrolyte-impregnated by electrolyte solution.In other words, lithium ion can transmit through electrolyte solution on the interface of dielectric substrate and battery lead plate or on electrolyte panel smoothly.Yet, being contained in the dielectric substrate as organic electrolyte solution, charging voltage can not be elevated to outside the decomposition voltage scope of organic electrolyte solution, and this has limited the range of choice of the active material that uses.Therefore, the preferred dielectric substrate that does not have organic electrolyte solution that uses makes and selects the degree of freedom of material to be improved.
When using organic solid material for example poly(ethylene oxide), polyacrylonitrile, polyethylene glycol and modified product thereof serve as the component of solid electrolyte,, seldom rupture because this organic solid material is lighter and more soft than solid inorganic material.On the other hand, when the component of solid electrolyte is a lithium ion conducting solid inorganic material for example when lithium-lanthanum perovskite and lithium ion conducting glass, the solid electrolyte that obtains has high thermal endurance, thereby at high temperature has good reliability.
In addition, when electrolytical component was the mixture of organic material and inorganic material, the dielectric substrate that obtains can make two kinds of compositions supply a gap mutually, and realized the advantage of two kinds of compositions.In other words, even the fusing of the organic material in the mixture, inorganic material also can keep it motionless, thereby can not flow away.Even when comprising a large amount of inorganic material, this organic material plays adhesive, can prevent fracture.Component at dielectric substrate is under the situation of mixture, if a kind of composition of mixture is an electrolyte, another kind of composition is for example calcium salt of magnesium oxide, silicon dioxide and silicon dioxide or the non-electrolyte of its mixture of inorganic material (inorganic filler).Mixture can comprise the inorganic material of content 70-85%, solid inorganic material and other composition (for example, adhesive such as Kynoar) of content 10-15%.Can or not use electrolytic salt according to forming.
For the isolated material that constitutes according to generating element of the present invention, can use insulation polyethene microporous membrane, the polyelectrolyte that is impregnated with electrolyte solution or contain colloidal electrolyte with the polyelectrolyte of electrolyte solution impregnation.On the other hand, can unite use insulation microporous barrier, polymer solid electrolyte etc.When the porous polymer solid electrolyte layer was used as polymer solid electrolyte, the electrolyte of dipping macromolecular material can be different with the electrolyte that enters pore.
Do not limit positive electrode active materials especially.The inorganic compound example that can be used as this positive electrode active materials comprises by constituent structure formula Li
xMO
2Or Li
yM
2O
4Composite oxides, oxide and the laminated metal chalcogenide of (wherein M represents transition metal, and x represents a numeral among the 0-1, and y represents a numeral among the 0-2) expression with tunnel-like pore.The object lesson of these inorganic compounds comprises LiCoO
2, LiNiO
2, LiMn
2O
4, Li
2Mn
2O
4, MnO
2, FeO
2, V
2O
5, V
6O
13, TiO
2And TiS
2The example that can be used as the organic compound of positive electrode active materials comprises for example polyaniline of conducting polymer.Above-mentioned various active material can mix and uses and no matter be inorganic or organic.
Do not limit negative active core-shell material especially.Here the example of the negative active core-shell material of Ying Yonging alloy, the transition metal oxide LiFe for example that comprises oxide, these metals and the lithium of Al, Si, Pb, Sn, Zn and Cd
2O
3, WO
2And MoO
2, carbon-based material graphite and carbon, lithium nitride Li for example for example
5(Li
3N), metallic lithium foil and their mixture.
Under the opening two ends of resin plate are welded to each other situation with the sealed cell shell, can and solidify this resin by fusing, just can further strengthen the sealing property of battery case so that form piece in weld part office than more close battery case inside, the inner of welding portion.
The battery case of making at this spendable resin plate can be the Any shape that can hold generating element, for example the cup-shaped lamination shell that obtains of the shell that obtains of three limits of the shell that obtains of four limits of the film formed cylinder lamination of fuse metal lamination resin shell, two metal laminated resin plates of hot melt, folding resin plate and this folded sheet of hot melt and stamped metal Laminated resin board.
Be to strengthen the sealing property of battery, the welding portion thickness at two edges of the resin plate opening that is welded to each other for the sealed cell shell is predetermined to be the place, the inner less than battery case at the place, outer end of battery case.Can think that reduction outer end thickness can reduce and the contact area of atmosphere, strengthen sealing property.
Make by resin plate in preparation, above-mentioned generating element holds under the situation of the shell of sealed cell of its inside, two parallel edges of preferred rectangle resin plate relatively and be welded to each other together are formed on the cylinder (after this this welding portion is called " welding portion X ") of both direction opening.The lead end of above-mentioned generating element is placed among in two openings one, then two of opening edges relatively and be welded to each other to form can, the surface that forms welding portion X thus is fixed to the structure on battery case surface.By welding portion X is fixed to the battery case surface, can prevent that welding portion X is outstanding from battery case.Therefore, when a plurality of battery stack, there is not unnecessary space to produce.And this structure makes battery stack simple.
Similarly, make by resin plate in preparation, generating element holds under the situation of the shape of sealing bag battery case of its inside, by two parallel edges of relative mutually rectangle resin plate are welded together, be formed on the cylinder (after this this welding portion is called " welding portion X ") of both direction opening.The lead end of above-mentioned generating element is placed among in two openings one, two of opening edges relatively and be welded to each other that (after this lead end welding portion that is placed on wherein is called " welding portion Y " to form can then, after this another welding portion is called " welding portion Z "), the surface that forms welding portion X thus is fixed to the structure on the surface of welding portion Y and/or welding portion Z.Arrange with this, can prevent that also welding portion X is outstanding from battery case.Therefore, when a plurality of battery stack, there is not unnecessary space to produce.And this structure makes battery stack simple.
For welding portion X being fixed to battery case surface or welding portion Y and/or welding portion Z, can use suitable adhesive according to the material of resin plate.On the other hand, they hot melt is together mutually.
Fixed band is wound on situation on the coiling generating element along wireline reel under, the welding portion X preferred orientation of battery case this fixed band that becomes to overlap.Coiling shape generating element always is pressed on the overlapped part of welding portion X and fixed band, is keeping constant distance between the electrode during the charge-discharge cycles, makes thus along with cycle-index increases the capacity that produces to reduce and reduce to minimum.
Be provided with at battery under the situation of bending lead end, the bending radius of lead end is preferably in 0.5mm-4mm.When radius of curvature during less than 0.5mm, the lead-in wire easy fracture.Otherwise when radius of curvature surpassed 4mm, space availability ratio reduced.
In generating element is contained in structure in the sealed cell shell that resin plate constitutes, be preferably arranged for: generating element has linear extension, and to force down in normal atmosphere (An) in the lead end of battery case outside and the sealed cell shell be 760mmHg.This is because the difference of interior pressure and normal atmosphere (An) causes generating element clamped, is keeping constant distance between the electrode during the charge-discharge cycles, makes thus along with cycle-index increases the capacity reduction that produces and reduces to minimum.
For electrolyte solution is injected the battery case that resin plate constitutes, preferred situation is that the anti-expanded material that is made of insulation net, nonwoven fabrics, felt or porous material contact with generating element along the arranging so that generating element is contained in the battery case around axle of generating element, then from preventing expanded material side injection electrolyte solution.In more detail, the generating element that is fixed with the anti-expanded material of insulation is contained in the battery case of both direction opening.Then, weld and seal this battery case at the opening part that anti-expanded material is not set.After this, electrolyte injects battery case by another opening that is provided with anti-expanded material.After this battery case is vacuumized.Then two opposite edges of another opening are welded to each other together to seal this battery case.Because injection period electrolyte infiltrate anti-expanded material and flow in the generating element simultaneously, drip on the generating element and spill so can prevent electrolyte, can prevent that therefore electrolyte is attached to the battery case interior zone near opening.And, because the upper end of generating element is covered by anti-expanded material, even when bubble occurs in electrolyte when vacuumizing during, there is not electrolyte to spill from generating element yet, can prevent that electrolyte is attached to hermetic unit, prevent the sealing property deterioration thus.
The example of above-mentioned anti-expanded material comprises net, nonwoven fabrics, felt and the porous material that for example polypropylene and poly polyolefin are made.Prevent that for fixing expanded material to generating element, can adopt for example hot melt and bonding method.Preferably use the jointing material that in adhesive tape, has used so far as for adhesive.The example of this jointing material comprises silicon-based adhesive, rubber-based adhesive and acryloid cement.
Description of drawings
Fig. 1 is the perspective view of the rechargeable nonaqueous electrolytic battery of first embodiment that comprises of the present invention.
Fig. 2 is the perspective view of the generating element of first embodiment.
Fig. 3 is the amplification profile of the resin plate of first embodiment.
Fig. 4 is the perspective view of the rechargeable nonaqueous electrolytic battery of second embodiment that comprises of the present invention.
Fig. 5 is the amplification profile of the welding portion of the lead-in wire electrode cut open of the line A-A ' along Fig. 4.
Fig. 6 is the amplification profile of the welding portion cut open of the line B-B ' along Fig. 4.
Fig. 7 is the amplification profile of the welding portion of the dissimilar battery of second embodiment of expression and Fig. 6.
Fig. 8 is the amplification profile of welding portion of the rechargeable nonaqueous electrolytic battery of the 3rd embodiment that comprises of the present invention.
Fig. 9 is the amplification profile of welding portion of the another kind of battery of third embodiment of the invention.
Figure 10 is the perspective view of the rechargeable nonaqueous electrolytic battery of the 4th embodiment that comprises of the present invention.
Figure 11 is the perspective view that generating element is not contained in battery case wherein.
Figure 12 is the perspective view that generating element is contained in battery case wherein.
Figure 13 is the perspective view of sealed cell shell.
Figure 14 is the amplification profile of the welding portion cut open of the line A-A ' along Figure 10.
Figure 15 is the perspective view of generating element of the rechargeable nonaqueous electrolytic battery of the 6th embodiment that comprises of the present invention.
Figure 16 is the perspective view that generating element is contained in battery case wherein.
Figure 17 is the perspective view of sealed cell shell.
Figure 18 is the end view of the battery of the 7th embodiment that comprises of the present invention.
Figure 19 is the amplification profile of welding portion.
Figure 20 is the end view of the battery of the 8th embodiment that comprises of the present invention.
Figure 21 is the end view of the battery of the 9th embodiment that comprises of the present invention.
Figure 22 is the end view of the battery of the 11 embodiment that comprises of the present invention.
Figure 23 is the perspective view of positive plate end.
Figure 24 is the profile of positive plate end.
Figure 25 is the profile of the part of generating element coiling beginning.
Figure 26 is the plane graph of the battery of the 12 embodiment that comprises of illustrative the present invention.
Figure 27 is the profile that the line X-X along Figure 26 cuts open.
Figure 28 is the front elevation of illustrative manufacturing step.
Embodiment
＜the first embodiment 〉
After this in conjunction with Fig. 1-3 first embodiment that the present invention comprises will be described.
Rechargeable nonaqueous electrolytic battery 10 according to present embodiment comprises electrode body 11 (see figure 2)s, and electrode body 11 is made of with the nonaqueous electrolytic solution (not shown) the positive plate, negative plate and the isolated material (not shown) that are contained in the battery case 13 that resin plate 12 (see figure 3)s constitute.Parameter 14 expression positive wire ends, parameter 15 expression negative pole end lead-in wires.Parameter 16 expressions will be welded on the edge on the battery case end, above the diagram of lead end 14,15 partly is placed on.Parameter 17 expression will be welded on the edge on the battery case end relative with edge 16.
Positive plate comprises the lithium cobalt composite oxide that remains on the collector body as active material.As for collector body, use the aluminium foil of thick 20 μ m.The preparation technology of positive plate is: mix 8 parts of Kynoar as adhesive, 5 parts of acetylene black and 87 parts of active materials as conductive agent, suitably add the N-methyl pyrrolidone in this mixture, this mixture is stirred pulping to form the positive polarization compound, apply this positive polarization compound to the two sides of current collector material, then drying coating material.
As for the collector body of negative plate, use the plate-like paper tinsel of thick 14 μ m.The preparation technology of negative plate is: mix 86 parts of graphite and 14 parts of Kynoar as adhesive as active material, this mixture is stirred pulping to form the negative polarization compound, apply the two sides of this negative polarization compound to collector body, then drying coating material.
Dividing plate as isolated material is the polyethylene porous septum.Electrolyte is to contain 1mol/l LiPF
6Ethylene carbonate and diethyl carbonate be the mixture of 1:1 (volume).
About the size of each assembly, the thickness of positive plate and width are respectively 180 μ m and 62mm, and the thickness of dividing plate and width are respectively 25 μ m and 67mm, and the thickness of negative plate and width are respectively 170 μ m and 64mm.
Then, rectangle aluminum lead end is welded to positive plate and negative plate.The polyimide resin band adheres to welding portion to strengthen battery case by the urethanes based adhesive of electrolyte resistance then.Then, stack gradually positive pole, dividing plate, negative pole and dividing plate.The mode around axle that is parallel to generating element with the longer sides of rectangle is wound on this lamination on the rectangle polyvinyl plastic core, forms non-circular generating element.The fixed band 18 made of polyimides is parallel to around axle in the end of electrode and adheres to the coiling of generating element wall with the stationary power generation element then, and its length is corresponding to electrode width (length of electrode is parallel to around axle).(see figure 2)
Then, generating element 11 is placed on the core of flat resin plate 12.In the mode of sealing generating element 11 from two ends coiling resin plate 12.The opposed facing mode of PE layer with modification is in contact with one another the end of resin plate 12, pushes in by the heating plate heating then, makes their mutual hot melts.(welding portion of gained is the edge 19 that will weld.) then, there be not a side thermoplastic resin plate of lead end 14,15.Then, electrolyte vacuum is injected in the battery case, and its quantity makes each electrode and dividing plate complete wetting and do not have free electrolyte to exist in the electrode group outside.Then, thermoplastic resin plate 12 on a side that is provided with lead end 14,15 similarly.As a result, form the battery case 13 that only welds three positions.
10 samples that prepare the battery 1A of the present invention of design capacity 800mAh, long 80mm, wide 35mm and thick 4mm according to above-mentioned formation and step.And, except the structure of the resin plate 12 that constitutes battery case 13 is following, every kind of 10 samples of battery 1B of the present invention, 1C, 1D that prepare design capacity 800mAh, long 80mm, wide 35mm and thick 4mm according to above-mentioned identical formation and step.In other words, the resin plate 12 of battery 1B comprises by the aluminium lamination of the pet layer of the thick 12 μ m of biaxial orientation prepared, thick 9 μ m, by the PP layer (oriented polypropylene (OPP)) of the thick 15 μ m of directional process preparation and the MODIFIED PP layer of thick 50 μ m with downward order.In this structure, the MODIFIED PP layer is welded to each other and forms battery case 13.
The resin plate 12 of battery 1C comprises by the aluminium lamination of the pet layer of the thick 12 μ m of biaxial orientation prepared, thick 9 μ m, by the nylon layer (oriented nylon) of the thick 12 μ m of directional process preparation and the MODIFIED PP layer of thick 50 μ m with downward order.
The resin plate 12 of battery 1D comprises by the aluminium lamination of the nylon layer (oriented nylon) of the thick 12 μ m of directional process preparation, thick 9 μ m, by the pet layer of the thick 12 μ m of directional process preparation and the MODIFIED PP layer of thick 50 μ m with downward order.
And, except the structure of the resin plate 12 that constitutes battery case 13 is following, prepare 10 samples of the comparison battery R1 of design capacity 800mAh, long 80mm, wide 35mm and thick 4mm according to formation identical and step with battery 1A.In other words, the resin plate 12 of battery R1 comprises by the aluminium lamination of the pet layer of the thick 12 μ m of biaxial orientation prepared, thick 9 μ m and the modified PE layer of thick 70 μ m with downward order.
Each resin plate (the wide x 50mm of 20mm is long) that is used for preparing the battery case 13 of these batteries 1A-1D and R1 repeatedly therein the heart sentence the angle bucklings of 180 degree, launch (this moves and constitutes a circulation) then.Cycle-index when measuring the aluminium lamination fracture thus.The result is shown in the table 1.
Table 1
| Battery | The structure of resin plate | Bend cycles number of times when fracture takes place |
| 1A | The biaxially oriented PET/PE/ modified PE of biaxial orientation PET/A1/ | 10 |
| 1B | The directed PP/ MODIFIED PP of biaxial orientation PET/A1/ | 8 |
| 1C | Biaxial orientation PET/A1/ oriented nylon/modified PE | 11 |
| 1D | The directed PP/ modified PE of oriented nylon/A1/ | 9 |
| R1 | Biaxial orientation PET/A1/ modified |
1 |
Table 1 shows that the resin plate of comparison battery R1 ruptures in first bend cycles.On the other hand, show comprise be located at as above the aluminium lamination of metal level and the resin plate of battery 1A, 1B, 1C and the 1D of following directed resin bed more than the relatively more difficult fracture of resin plate of battery R1.
10 samples of every kind of battery 1A-1D and R1 constant current and constant voltage under 800mA, 4.1V and 3h are full of.It is distolateral that the edge 17 that will weld then bends towards lead-in wire, makes it by twofold.Make thus the battery of processing remain on 60 ℃ of temperature and 90% RH following 30 days then.Detect aluminium corrosion (perusal), the vertical expansion of battery and the leakage of electrolyte of battery then in the office, folding part.The result lists in table 2.
Table 2
| Battery | The aluminium corrosion | Cell expansion (vertically) | Electrolyte leakage |
| 1A | 0/10 sample | 0.1mm-0.2mm | 0/10 |
| 1B | 0/10 sample | 0.1mm-0.2mm | 0/10 |
| 1C | 0/10 sample | 0.1mm-0.2mm | 0/10 |
| 1D | 0/10 sample | 0.1mm-0.2mm | 0/10 |
| R1 | 6/10 sample | 0.3mm-1.5 |
3/10 |
Table 2 shows, compares with comparing battery R1, and battery 1A-1D of the present invention does not have aluminium corrosion and electrolyte leakage, does not almost expand yet.
Directed resin plate is not limited in the present embodiment employed.
According to the invention provides a kind of rechargeable nonaqueous electrolytic battery, this battery comprises the battery case that the resin plate made by metal and resin forms, and this battery case does not have defective to produce in manufacturing step and assembling easily.
＜the second embodiment 〉
Rechargeable nonaqueous electrolytic battery according to present embodiment comprises oval generating element of reeling, and generating element is made of with the nonaqueous electrolytic solution (not shown) the positive plate, isolated material and the negative plate that are contained in by in the film formed bag of the fuse metal lamination resin shape battery case.The outward appearance of this rechargeable nonaqueous electrolytic battery as shown in Figure 4.Parameter 20 expression bag shape battery cases, parameter 21 expression generating elements, generating element comprises the positive plate and the negative plate of reeling by as polyethene microporous membrane (dividing plate) ellipse of isolated material.Parameter 22 expression generating elements around axle, parameter 23 expressions are connected to the positive wire end of positive plate, parameter 24 expressions are connected to the negative wire end of negative plate.
As for positive electrode active materials, use the lithium cobalt composite oxide.Positive plate comprises on the aluminium foil collector body that remains on thick 20 μ m the above-mentioned lithium cobalt composite oxide as active material.The preparation technology of positive plate is: mix 6 parts of Kynoar as adhesive, 3 parts of acetylene black and 91 parts of active materials as conductive agent, suitably add the N-methyl pyrrolidone in this mixture, this mixture is stirred pulping to form the positive polarization compound, apply the two sides of this positive polarization compound, then drying coating material to collector body.
The preparation technology of negative plate is: mix 92 parts of graphite and 8 parts of Kynoar as adhesive as main material, suitably add the N-methyl pyrrolidone in this mixture, this mixture is stirred pulping with preparation negative polarization compound, apply this negative polarization compound to the Copper Foil collector body of thick 14 μ m, then drying coating material.As for electrolyte, use to contain 1mol/l LiPF
6Ethylene carbonate and diethyl carbonate be the mixture of 3:7 (volume).
About the size of battery lead plate, the thickness of positive plate is that 185 μ m, width are 42mm, and the thickness of dividing plate is that 25 μ m, width are 45mm, and the thickness of negative plate is that 160 μ m, width are 43.5mm. Lead end 23,24 is welded to positive plate and negative plate respectively.Positive plate, dividing plate and negative plate stack gradually, and are parallel to mode ellipse around axle 22 with the long limit of rectangle then and are wound on the rectangle polyvinyl plastic core generating element with preparation size 48mm x 27.3mm x 3.23mm.
Then, the fixed band that unshowned polypropylene is made (application of adhesive on one surface) is parallel to the coiling that the wall part that adheres to generating element 30 around axle 22 fixes generating element 30 in the insulation division office of battery lead plate, its length is corresponding to the width of electrode (length of generating element 30 be parallel to generating element around axle).
Be placed in the generating element that thus form by metal laminated resin in film formed cylindrical battery shell 20 at both direction opening around axle 22 perpendicular to the mode of plane of the opening with generating element 30.Two opposite edges that are provided with the opening of lead end 23,24 are welded to each other to seal this battery case, and lead end 23,24 is placed on wherein.Then, by another opening electrolyte vacuum is injected in the battery case, its quantity makes each electrode and dividing plate complete wetting and does not have free electrolyte to exist in the generating element outside.After this, two of another opening opposite edges are welded to each other with sealed cell shell 20.
The cross section (the line A-A ' along Fig. 4 cuts open) of the welding portion of the diagram of the lead end of battery shown in Fig. 5 illustrative Fig. 4 part.In the figure; parameter 25 expressions constitute the sealer (the PET films of thick 12 μ m) of the resin plate of battery case 20; parameter 26 expression metallic spacers (aluminium foils of thick 9 μ m), and parameter 27 expression hot melt layers (the sour modified low-density polyethylene layers of thick 150 μ m).As outermost surface protection PET film 25 and bonding mutually by the urethanes based adhesive as the aluminium foil 26 of separator.
Resin plate for welding formation battery case 20 makes two resin plates overlapped in hot melt layer 27 modes respect to one another.Be heat fused to together mutually at 250 ℃ of following resin plates of temperature then.Then, it is thick heat-fused portion to be expressed to 250 μ m.In this way, the resin of fusion pushes out the sealed cell shell from welding portion the inner of battery case 20, forms resin mass 28 simultaneously.By with the resin mass 28 of fusion and curing from welding portion the inner towards battery case 20 the outstanding mode thermoplastic resin plate that forms in inner space, and the outer end thickness X of predetermined welding portion equals the inner thickness Y of welding portion, thus preparation battery 2A (see figure 6).The rated capacity of battery A is 420mAh.
And, by in the same way as described above, that is: with the resin mass 28 of fusion and curing towards the outstanding mode thermoplastic resin plate that forms in the inner space of battery case 20, and the outer end thickness X of predetermined welding portion is less than the inner thickness Y of welding portion, thus preparation battery 2B (see figure 7).For making the thickness difference at welding portion two ends, use bevelled press to come the thermoplastic resin plate.Under the situation of battery B, the thickness X of outer end is 100 μ m, and inner thickness Y is 250 μ m, and rated capacity is similar to battery A, is 420mAh.
And preparation battery R2 is example as a comparison.Except the outstanding mode that forms equals to prepare this battery in the mode identical with 2B with above-mentioned battery 2A the inner thickness Y of welding portion in the outer end thickness X of the weld part office of battery case 20 thermoplastic resin plate and welding portion towards the battery case inner space there not to be resin mass.
The resistance to pressure measurement result of battery 2A, 2B and R2 is listed in table 3.For measuring resistance to pressure, apply hydraulic pressure in the inside of battery case 20.Hydraulic pressure when the measurement welding portion is peeled off.
Table 3
| Is there there resin mass 28 in the battery? | Pressure during the welding portion opening | |
| Battery R2 | No | 15atm. |
| Battery 2A | Have | 28atm. |
| Battery 2B | Have | 28atm |
For making the welding portion opening, comprise that the pressure of the battery 2A of resin mass 28 and 2B needs is about the twice of the battery R2 that does not contain resin mass, resin mass 28 is positioned at the inner of the welding portion of battery case 20.The chances are because stress is distributed on the two ends of the inner bent resin piece 28 of adhesive interface does not directly act on the adhesive interface of battery 2A and 2B for this, although stress only acts on the adhesive interface of welding portion.As a result, improved the resistance to pressure of battery.
Can find out from The above results,, can obviously improve the resistance to pressure of battery case 20 by on the inner of the welding portion of battery case 20, forming resin mass 28.And even when voltage rise is high in the heat that causes owing to overcharge or internal short-circuit or high-temperature storage makes, the rechargeable nonaqueous electrolytic battery that is provided can not produce at the welding portion of battery case and peel off, thereby shows good sealing.
, also work towards the resin mass of the inner space projection of battery case from the inner of welding portion even its size is quite little.As long as the part projection 0.1mm that part that it is welded to each other from the inner surface of resin and battery case or resin and lead end are welded to each other or more will play enough effects.
For the influence of the difference between the inner thickness Y of checking outer end thickness X of welding portion and welding portion, prepare following battery 2C-2G.
The welding portion of the battery case 20 of battery 2C-2G has identical section structure, as shown in Figure 7, the inner thickness Y of the welding portion of battery 2C-2G is 250 μ m, and the thickness of the outer end of welding portion is respectively 245 μ m, 240 μ m, 200 μ m, 150 μ m and 50 μ m, the difference between the inner thickness Y of welding portion and the outer end thickness X of welding portion (=Y-X) be respectively 5 μ m, 10 μ m, 50 μ m100 μ m and 200 μ m.
Battery 2C-2G and above-mentioned battery 2A constant current-constant voltage charging under 400mA and 4.1V was deposited 1 month under 60 ℃ of temperature to fully loaded in 4 hours then.The Capacity Ratio of the capacity of the battery that will deposit and the battery deposited afterwards.The increase of the water content of the battery that measurement has been deposited and the evaporation loss of electrolyte solution.60 ℃-January, aging result of experiment was listed at table 4.
Table 4
| The thickness difference | The increase of water content | The evaporation loss of electrolyte solution | Capacity retention rate % | |
| Battery 2A | 0μm | 310ppm | 21mg | 82.0 |
| Battery 2C | 5μm | 57ppm | 7mg | 85.2 |
| Battery 2D | 10μm | 34ppm | 5mg | 90.3 |
| Battery 2E | 50μm | 30ppm | 5mg | 92.2 |
| Battery 2F | 100μm | 23ppm | 4mg | 93.5 |
| Battery 2G | 200μm | 20ppm | 3mg | 94.0 |
These result of experiment show with the inner thickness Y of welding portion to be compared, and the outer end thickness X of welding portion is more little, can stop moisture to enter battery and electrolyte solution more and be evaporated to the battery outside, can improve the storge quality of battery more.This is because the welding portion of resin plate does not serve as the metal part 26 on barrier layer, it has prevented that moisture from entering in the battery case and electrolyte solution is evaporated to the battery outside, so the process hot melt layer causes moisture to enter in the battery easily and electrolyte solution is evaporated to the battery outside.
In addition, when moisture enters inside battery, the LiPF of it and electrolyte solution
6Reaction produces HF, and HF corrosion afterwards constitutes the aluminium of positive electrode collector, has increased the interior resistance of battery, or reacts with electrolyte solution on electrode surface, forms film, causes battery capacity to descend.Therefore, top thickness by making welding portion is less than the root thickness of welding portion, can reduce welding portion and extraneous contact area, shorten the path of moisture and electrolyte solution operation, can prevent that moisture from entering inside battery and electrolyte solution is evaporated to the battery outside, thereby prevent the deterioration of battery performance.Therefore, can prepare long battery of storage time.
The 3rd embodiment
Present embodiment only is different from above-mentioned second embodiment on the structure of electrolyte solution and welding portion.Other structure of present embodiment is identical with second embodiment shown in Fig. 4-6.As for the battery of the 3rd embodiment, prepare following 6 battery 3A-3F.As for electrolyte solution, these batteries use and contain 1.2mol/l LiPF
6Ethylene carbonate and diethyl carbonate be the mixture of 3:8 (volume).
Battery 3A
The structure of welding portion as shown in Figure 8.The inner thickness Y of welding portion is 300 μ m, and the outer end thickness X of welding portion is 250 μ m.
Battery 3B
The structure of welding portion as shown in Figure 8.The inner thickness Y of welding portion is 300 μ m, and the outer end thickness X of welding portion is 200 μ m.
Battery 3C
The structure of welding portion as shown in Figure 8.The inner thickness Y of welding portion is 300 μ m, and the outer end thickness X of welding portion is 150 μ m.
Battery 3D
The structure of welding portion as shown in Figure 8.The inner thickness Y of welding portion is 300 μ m, and the outer end thickness X of welding portion is 100 μ m.
Battery 3E
The structure of welding portion as shown in Figure 8.The inner thickness Y of welding portion is 300 μ m, and the outer end thickness X of welding portion is 75 μ m.
Battery 3F
The structure of welding portion as shown in Figure 8.The inner thickness Y of welding portion is 300 μ m, and the outer end thickness X of welding portion is 50 μ m.
Battery 3G
The structure of welding portion as shown in Figure 9.The inner thickness Y of welding portion is 300 μ m, and the outer end thickness X of welding portion is 250 μ m.
Battery 3H
The structure of welding portion as shown in Figure 9.The inner thickness Y of welding portion is 300 μ m, and the outer end thickness X of welding portion is 200 μ m.
Battery 3I
The structure of welding portion as shown in Figure 9.The inner thickness Y of welding portion is 300 μ m, and the outer end thickness X of welding portion is 150 μ m.
Battery 3J
The structure of welding portion as shown in Figure 9.The inner thickness Y of welding portion is 300 μ m, and the outer end thickness X of welding portion is 100 μ m.
Battery 3K
The structure of welding portion as shown in Figure 9.The inner thickness Y of welding portion is 300 μ m, and the outer end thickness X of welding portion is 75 μ m.
Battery 3L
The structure of welding portion as shown in Figure 9.The inner thickness Y of welding portion is 300 μ m, and the outer end thickness X of welding portion is 50 μ m.
Compare battery R3
The same resin plate of the battery 3A-3F of use and the foregoing description.Yet the structure of arranging welding portion makes the i.e. 300 μ m of outer end thickness X that the inner thickness Y of welding portion equals welding portion.
Compare battery R4
The same resin plate of the battery 3A-3F of use and the foregoing description.Yet the structure of arranging welding portion makes the i.e. 250 μ m of outer end thickness X that the inner thickness Y of welding portion equals welding portion.
Compare battery R5
The same resin plate of the battery 3A-3F of use and the foregoing description.Yet the structure of arranging welding portion makes the i.e. 200 μ m of outer end thickness X that the inner thickness Y of welding portion equals welding portion.
Compare battery R6
The same resin plate of the battery 3A-3F of use and the foregoing description.Yet the structure of arranging welding portion makes the i.e. 150 μ m of outer end thickness X that the inner thickness Y of welding portion equals welding portion.
Compare battery R7
The same resin plate of the battery 3A-3F of use and the foregoing description.Yet the structure of arranging welding portion makes the i.e. 100 μ m of outer end thickness X that the inner thickness Y of welding portion equals welding portion.
Compare battery R8
The same resin plate of the battery 3A-3F of use and the foregoing description.Yet the structure of arranging welding portion makes the i.e. 75 μ m of outer end thickness X that the inner thickness Y of welding portion equals welding portion.
Compare battery R9
The same resin plate of the battery 3A-3F of use and the foregoing description.Yet the structure of arranging welding portion makes the i.e. 50 μ m of outer end thickness X that the inner thickness Y of welding portion equals welding portion.
Table 5 expression 420mAh is the performance of battery R3-R9 relatively, and fold takes place in the side of promptly inner thickness, battery case, the aluminium lamination in the fold district breaks and the leakage of electrolyte solution takes place.
Table 5
| Compare battery | Throat thickness (μ m) | Does the side of battery case fold? | Does aluminium lamination break? | Does electrolyte solution leak? |
| R3 | 300 | No | No | No |
| R4 | 250 | Be | Be | Be |
| R5 | 200 | Be | Be | Be |
| R6 | 150 | Be | Be | Be |
| |
100 | Be | Be | Be |
| R8 | 75 | Be | Be | Be |
| |
50 | Be | Be | Be |
Table 6 expression is the ratio of 1CmA discharge capacity and the initial value of 1CmA discharge capacity of the battery 3A-3L of battery R3-R9 and the foregoing description relatively, and battery charged 3 hours under 1CmA/4.2V, deposits 1 year under 25 ℃ then.
Table 6
| The outer end thickness of welding portion (μ m) | Battery | Discharge capacity is than (%) | Battery | Discharge capacity is than (%) | Battery | Discharge capacity is than (%) |
| 300 | R3 | 60.0 | -- | -- | -- | -- |
| 250 | R4 | 47.2 | 3A | 83.4 | 3G | 84.2 |
| 200 | R5 | 45.3 | 3B | 85.5 | 3H | 85.1 |
| 150 | R6 | 43.3 | 3C | 92.2 | 3I | 92.4 |
| 100 | R7 | 43.2 | 3D | 92.3 | 3J | 92.9 |
| 75 | R8 | 43.1 | 3E | 92.4 | 3K | 92.9 |
| 50 | R9 | 40.5 | 3F | 93.5 | 3L | 93.6 |
Can find out that from table 5 welding portion thickness is that 250 μ m or all littler comparison battery table reveal the electrolyte solution leakage.As a result, observe battery in the side of battery case and fold, the aluminium lamination of metal stacking resin plate breaks.Therefore, think that moisture enters the position of generating element through hermetic unit and the evaporation of electrolyte solution causes the long term storage performance of battery greatly to worsen.Simultaneously, the battery of not observing welding portion thickness 300 μ m folds, but because moisture enters the deterioration that shows the long term storage performance of battery with the evaporation of electrolyte solution.
On the other hand, show high discharge ratio, greatly improved the long term storage performance according to the battery 3A-3L of the foregoing description.The chances are for this because guaranteed the inner thickness of welding portion, prevented to break owing to the aluminium lamination that the fold on the side of shell causes.Think simultaneously because the outer end thickness of welding portion is little, reduced welding portion and extraneous contact area, can stop moisture to enter in the battery and the evaporation of electrolyte solution.
In addition, compare battery group 3A-3F and battery group 3G-3L, the outer end thickness of the welding portion of battery group 3G-3L is identical with the outer end thickness of the welding portion of battery group 3A-3F, but external surface shape difference, thereby the storge quality of battery (discharge capacity ratio) is irrelevant with the external surface shape of welding portion, and only relevant with extraneous contact area with the outer end face of welding portion.Therefore, think that the external surface shape of welding portion can be arbitrarily, as long as the outer end thickness of welding portion is less than the inner thickness of welding portion.
Difference between the outer end thickness of welding portion and the inner thickness of welding portion does not limit especially.Yet,, can obtain better storge quality when the difference between the inner thickness of the outer end of welding portion thickness and welding portion is 50 μ m or when bigger.
The 4th embodiment
In conjunction with Figure 10-14, the fourth embodiment of the present invention is described.
Comprise according to rechargeable nonaqueous electrolytic battery of the present invention being placed on ellipse coiling generating element 30 and the non-aqueous electrolytic solution (not shown) that constitutes by positive plate, isolated material and negative plate in bag shape battery case 31 that battery case 31 is made up of fuse metal-Laminated resin board.Figure 10 represents the outward appearance of the battery case 31 that sealed.
The preparation of generating element 30: positive plate and negative plate are wound into ellipse with the polyethene microporous membrane that serves as isolated material (dividing plate), as shown in figure 11.The positive wire end that parameter 32 expression is connected with positive plate, parameter 33 are represented the negative wire end that is connected with negative plate, and for example make by copper, al and ni by the metallic conductor of thickness range 50 μ m-100 μ m for negative plate.
The structure of positive plate and negative plate is same as the previously described embodiments.The electrolyte solution that is adopted is to contain 1mol/l LiPF
6Ethylene carbonate and diethyl carbonate be the mixture of 4:6 (volume).The size of reference electrode plate, the thickness of positive plate are 180 μ m, and width is 51mm, and the thickness of dividing plate is 25 μ m, and width is 53mm, and the thickness of negative plate is 170 μ m, and width is 51mm. Lead end 32 and 33 is welded to respectively on positive plate and the negative plate.Positive plate, dividing plate and negative plate be with this sequential cascade, and the mode ellipse that is parallel to the wireline reel of generating element 30 with the long limit of rectangle is wound on the rectangle polyvinyl plastic core generating element with preparation size 53mm x 35mm x 4mm then.
On the other hand, battery case 31 is formed by metal-Laminated resin board.Resin plate comprises the surface protection PET film 34 of the outer field thickness 12 μ m of the conduct of sequential cascade, as the aluminium foil 35 of the thickness 20 μ m on barrier layer with as the sour modified poly ethylene layer 36 of the thickness 100 μ m of hot melt layer, as shown in figure 14.Utilize mutual gluing of surfaces protection PET film 34 of urethane groups adhesive and aluminium foil 35.
Generating element 30 is sealed in the battery case 31 prepares battery, battery case 31 is prepared by resin plate according to following steps.
At first, in the first step, heating is the opposite face of mutual extrusion rectangle resin plate down, and similar face (sour modified poly ethylene layer 36) is in contact with one another, thereby fusing is to form welding portion 37 (=welding portion X), as shown in figure 11 mutually.In this arrangement, resin plate forms cylinder-shaped bag, has opening 30a at two ends.
Then, in second step, generating element 30 is contained in the battery case 31, the plane of the opening 30a of the wireline reel vertical cylindrical battery case of generating element 30, as shown in figure 12.
In addition, in the third step, the wireline reel of the parallel generating element of welding portion 37 (=welding portion X) of bag shape battery case, crooked welding portion 37 is so that contact with the outer surface of battery case 31, as shown in figure 13.Then, metal-lamination resin molding 2 is being pulled out the position hot melt of lead end, forms welding portion 38 (=welding portion Y), and lead end is pulled out from welding portion 38.
Therefore, except with the opening opening opposing place that pulls out lead end, the sealed cell shell.Then electrolyte solution is injected in the battery case through this opening vacuum, its quantity makes each electrode and dividing plate thoroughly wetting, and there is not electrolyte solution in the generating element outside.
Afterwards, in the 4th step, mutually the opposite edges of hot melt and the opening of welding portion 38 relative sides form welding portion 39 (=welding portion Z), thus complete sealed cell shell 31.And lead end is pulled out from welding portion 38.
At last, welding portion 37 (welding portion X) is fixed on the side of battery case 31 by adhesive or hot melt.For welding portion being bonded to the side of battery case, can use any adhesive that is suitable for the outermost material of resin plate.
Close position between welding portion 37 under these conditions (welding portion X) and the welding portion 38 (welding portion Y) is welding portion 37 (welding portion X) and welding portion 38 (welding portion Y) handing-over mutually on the surface of battery case 31, and the position that welding portion X and welding portion Y join mutually is between positive wire end 32 and negative wire end 33.
The prepared rechargeable nonaqueous electrolytic battery note of present embodiment is made battery 4A, and relatively the rechargeable nonaqueous electrolytic battery note is made battery R10, the structure of this comparison electrolytic secondary cell is that welding portion (=welding portion X) is outstanding from the surface of battery case, it forms by two opposite flank welding with rectangular slab, the side is relative each other, thereby similar face is in contact with one another.10 samples of preparation battery 4A and R10, rated capacity is 500mAh.These batteries all carry out the charge-discharge cycles test under the following conditions.
Charging: 500mA constant current+4.1V constant voltage, 3hr altogether
Discharge: 500mA constant current, end voltage: 2.75V
The result, average discharge capacity at 10 samples of the 100th circulation time battery 4A is 490mAh, and be 465mAh in the average discharge capacity of 10 samples of the 100th circulation time battery R10, show that the battery 4A of present embodiment is little with the decline that cycle-index increases capacity.The chances are for this because welding portion 37 (=welding portion X) is fixed on the surface of battery case 31, makes shell at the fixing regional thickening of welding portion 37.In this structure, generating element 30 heart therein keeps pressurized, makes distance between electrodes keep constant during charge-discharge cycles, thereby can make the capacity reduced minimum with cycle-index.And when a plurality of rechargeable nonaqueous electrolytic batteries of present embodiment made up mutually with serial or parallel connection, the welding portion 37 of battery case 31 can not produce obstruction, thereby the battery of high-energy-density is provided and need not to increase any space.Therefore, the rechargeable nonaqueous electrolytic battery of present embodiment is fit to combination.
The 5th embodiment
Present embodiment is different from above-mentioned the 4th embodiment, in the 5th embodiment, the end of welding portion 37 is fixed on other welding portion 38 (welding portion Y) or welding portion 39 (welding portion Z), and in above-mentioned the 4th embodiment, welding portion 37 (welding portion X) utilizes adhesive etc. to be fixed on the surface of battery case 31.Other structure of present embodiment is identical with above-mentioned the 4th embodiment.Therefore, utilize figure and the description of the 4th embodiment, can ignore and be repeated in this description.
Battery for the 5th embodiment, prepare three kinds of batteries, be 10 samples, rated capacity is 500mAh, be that the lead-in wire of the welding portion 37 of battery 5A is pulled out end and utilized adhesive on welding portion 38 (welding portion Y), welding portion 37 and the lead-in wire of battery 5B pulled out the end opposing ends and utilized adhesive on welding portion 39 (welding portion Z), and the two ends of the welding portion 37 of battery 5C utilize adhesive on welding portion 38 (welding portion Y) and welding portion 39 (welding portion Z).The comparison battery R10 of above-mentioned then the 4th embodiment and above-mentioned battery 5A, 5B and 5C all carry out the charge-discharge cycles test under the following conditions.
Charging: 500mA constant current+4.1V constant voltage, 3hr altogether
Discharge: 500mA constant current, end voltage: 2.75V
As a result, list in the average discharge capacity of 10 samples of the 100th circulation time as following table 7.
Table 7
Can find out that from table 7 battery 5A, the 5B of present embodiment compares with comparing battery R10 with 5C, smaller with the capacity decline of cycle-index.This chances are because welding portion 37 (=welding portion X) is fixed at least that lead-in wire pulls out that the welding portion 38 (=welding portion Y) of side is gone up or the welding portion 39 (=welding portion Z) relative with welding portion 38 on, as above-mentioned the 4th embodiment, cause welding portion X to be pressed on the surface of battery case 31, make shell 31 at the fixing regional thickening of welding portion 37.In this structure, generating element 30 heart therein keeps pressurized, makes distance between electrodes keep constant during charge-discharge cycles.And when a plurality of battery 5A, the 5B of present embodiment and 5C made up mutually with serial or parallel connection, the welding portion 37 of battery case 31 can not produce obstruction, thereby the battery of high-energy-density is provided and need not to increase any space.Therefore, the rechargeable nonaqueous electrolytic battery of present embodiment is fit to combination.
The 6th embodiment
Present embodiment is different from above-mentioned the 4th embodiment, and fixed band is reeled along the generating element 30 of the 4th embodiment.Other structure of present embodiment is identical with the 4th embodiment.Same label is used for same parts, is repeated in this description to ignore.
Said fixing band 40 along wireline reel 41 at generating element 30 coiling one or many, as shown in figure 15.Therefore, fixed band 40 is pulled out at the lead-in wire of generating element 30 on the end surface of side by between two lead ends 32 and 33.When generating element 30 holds and is sealed in the battery case 31, the welding portion 37 of battery case 31 is overlapping along wireline reel and fixed band 40.Welding portion 37 closely contacts with the surface of battery case 31 by adhesive and is bonding.Yet two parts also can interconnect by hot melt.On the other hand, welding portion 37 also can be bonding or be welded to welding portion 38 and/or welding portion 39.
The battery 6A of the 6th embodiment and comparison battery R11 (welding portion 37 is in outside the position of fixed band 40) carry out the charge-discharge cycles test under the following conditions.Average discharge capacity at 10 samples of the 100th circulation time measurement.As a result, the battery 6A of present embodiment is 496mAh, and relatively battery R11 is 465mAh.Therefore the battery 6A that confirms present embodiment is little with the capacity decline of cycle-index.
Charging: 500mA constant current+4.1V constant voltage, 3hr altogether
Discharge: 500mA constant current, end voltage: 2.75V
Therefore, the structure of the rechargeable nonaqueous electrolytic battery of present embodiment is that to be parallel to the welding portion 37 of wireline reel 41 of generating element 30 overlapping with fixed band 40, makes generating element 30 at the overlay region pressurized, thereby keep distance between electrodes between charge period.Therefore, can make capacity reduced minimum with cycle-index.
The 7th embodiment
In conjunction with Figure 18 and 19, the seventh embodiment of the present invention is described.
The battery 50 of present embodiment comprises battery case 51, generating element 52 and lead end 53.Battery 50 is contained among the outer container K.
The preparation of generating element 52: the screw winding positive plate, serve as the isolated material of dividing plate and the lamination of negative plate, positive plate has the positive polarization compound that contains the positive electrode active materials that is coated on the collector body, and negative plate has the negative polarization compound that contains the negative active core-shell material that is coated on the collector body.Generating element 51 is contained in the battery case, and electrolyte solution injects battery case then.As for the collector body of positive plate, use aluminium foil.As for active material, use lithium-cobalt composite oxide.For negative plate, use Copper Foil.For host material, use graphite.As for dividing plate, use polyethene microporous membrane.As for electrolyte solution, use to contain 1mol/l LiPF
6Ethylene carbonate and methyl ethyl carbonate be the mixture of 4:6 (volume).
Lead end 53 is flat.Lead end 53 links to each other with negative plate with positive plate, and exposes to the open air in the outside of battery case 51, and between the resin plate of the welding portion 57 of battery case 51.The zone that lead end 53 passes the terminal surface of resin is being inserted and is being managed 58, pipe 58 by the insulating resin of thickness 100 μ m for example acid-modified poly ethylene make.In this structure, battery case can keep air-tightness.Simultaneously, the barrier layer 55 that can prevent lead end 53 and battery case 51 is in contact with one another caused short circuit.
Lead end 53 is in the bending of the outside of battery case 51, and links to each other with the protective circuit P that is positioned at outer container K the inner.Use jig bending lead end 53, range of curvature radius is 0.5mm-4mm.Therefore, lead end 53 can not rupture.Yet, can reduce the whole dimension of battery 50.In this structure, battery 50 can be contained in size than among the in the past little outer container K.As a result, can further make electronics miniaturization.The width range of preferred lead end is 2mm-7mm, and thickness range is 0.05mm-2.0mm.The material that is suitable for lead end 53 is aluminium, nickel or copper.
Except that last bending lead end 53, finish the preparation of the battery 50 of present embodiment in the identical mode of traditional preparation process technology.
Preparation lead end 53 is not crooked, checks then and utilizes the flexible how many times of jig just can rupture.As for jig, radius can be 0.2mm, 0.3mm, 0.4mm, 0.5mm and 1.0mm.Therefore, prepare the battery 8A and the 8B of comparison battery R12, R13 and R14 and present embodiment.About the size of lead end 53, the width of lead end 53 is 3mm, and thickness is 0.1mm.About the material of lead end 53, aluminium is used for positive pole, and nickel is used for negative pole.The result lists in table 8.
Table 8
Can find out from table 8, confirm with 0.4mm or more the lead end of minor radius bending battery and with 0.5mm or more have significant difference between the battery of the lead end of long radius bending.Therefore, with the battery 8A of the lead end of 0.5mm or more long radius bending and 8B easy fracture lead end 53 not.
Therefore, be bending lead end 53, the angular bend of bent position with 180 degree wanted in the jig contact of preferred lead end 53 usefulness radius 0.5mm-4mm.
Preparation battery 8A and 8B respectively have 20 samples, and battery 8A has the lead end 53 with the 0.5mm radius bend, and battery 8B has the lead end 53 with the 1.0mm bending.Then, these samples all are contained among the outer container K.Lead end 53 links to each other with protective circuit P then.Battery 50 is fixed on the inwall of outer container K by two-sided tape.Then vertically, laterally, battery carried out on the vertical direction 1 hour vibration (amplitude; 4mm; Frequency: 1000cpm).Afterwards, check the crack conditions of lead end 53.Relatively battery R12-R14 has the lead end with radius 0.2mm, 0.3mm and 0.4mm bending respectively, and preparation and similar inspection be each 20 sample of battery R12-R14 relatively.The result lists at table 9.Other situation of lead end 53 is identical with battery 8A and 8B.
Table 9
From table, can find out that wire breaking does not appear in the battery 8A and the 8B sample of present embodiment, and relatively wire breaking appears in all samples of battery.Therefore, confirm the battery 8A of present embodiment and 8B even applying the fracture that does not occur lead end under the vibration.
The 8th embodiment
Figure 20 represents the front elevation according to the battery of the eighth embodiment of the present invention.
Except that lead end 62 is covered the sweep by pipe 63, identical with the battery 50 of above-mentioned the 7th embodiment according to the battery 60 of present embodiment of the present invention.Pipe 63 covers the sweep of lead end 62.In this structure, can prevent the short circuit on the barrier layer of lead end 62 and battery case 61.
The structure of pipe 63 can keep battery air tightness, and is similar with first embodiment.
About managing 63 material, preferably manage 63 by making, because it is inserted between the crucible zone and lead end 62 of battery case 61 with the crucible zone identical materials of battery case 61.Even be positioned at when 63 of pipes on the sweep of lead end 62, can prevent the fracture of lead end 62.In this case, manage 63 unnecessary by making with the crucible zone same material.Be bending lead end 62, preferably utilize the jig bending lead end 62 of radius 0.5mm-4mm.Yet the necessary thickness of considering pipe 63 is selected suitable jig.For example, when the thickness of managing 63 is 100 μ m, preferably select the jig of radius 0.4mm-3.9mm.
In the present embodiment, check short circuit during the preparation of battery 60 shown in Figure 20.Utilize the jig of radius 0.4mm, check 1000 samples of battery 60.Pipe 63 is made up of acid-modified poly ethylene of thickness 100 μ m.Other situation is with identical shown in the 7th embodiment.As for comparative example, except that lead end 62 is covered by pipe 63, similar inspection with the battery of having of the same way as preparation of the battery 60 of the 8th embodiment with the lead end of radius 0.5mm bending.
As a result, 1000 relatively have 10 to show lead-in wire and barrier layer short circuit in the battery.On the other hand, all not short circuits of 1000 batteries that have the lead end that is covered by pipe 63.Therefore, short circuit minimum during confirmation lead end 62 can be made battery trial-production make by pipe 63 coverings.
The 9th embodiment
In conjunction with Figure 21, the battery according to the ninth embodiment of the present invention is described.
In the battery 70 of present embodiment, the length of the battery 50 of welding portion 72 to the seven embodiment of battery case 71, and extend to lead-in wire 73 sweep.Other situation is identical with the battery 50 of the 7th embodiment.Therefore, the sweep of lead-in wire 73 closely contacts with the resin plate of forming battery case 71, has improved the performance of the 73 counter-bending loads that go between, thereby more is difficult to make lead-in wire 73 fractures.Be bending lead 73, must as the 8th embodiment, consider the thickness of resin plate.Must be noted that, not only will prevent wire breaking, and will prevent resin plate fracture or wrinkling.
In the present embodiment, carry out following test.Prepare the battery 70 of the unbent lead-in wire 73 of having of 2 samples.Then, utilize in crooked two samples of jig of radius 0.3mm, and utilize in crooked two samples of jig of radius 0.4mm another.All observe the sweep of these batteries under micro-.The thickness of resin plate is 100 μ m.
As a result, lead-in wire 73 fractures all do not appear in these samples.Yet having battery with the jig bending lead 73 of radius 0.3mm, to can be observed the stack membrane fracture and the inner stack membrane of sweep of sweep outside wrinkling.Therefore, preferably utilize radius 0.4mm or bigger jig with the 0.5mm or the lead-in wire 73 of the battery 70 of the crooked present embodiment of long radius more.
The tenth embodiment
Battery according to the tenth embodiment of the present invention is identical with the structure of above-mentioned the 4th embodiment, comprise oval generating element 31 and non-aqueous electrolytic solution (not shown) of reeling, generating element 30 is contained in the bag shape battery case 31 that forms by fuse metal-Laminated resin board, shown in Figure 10-14.What pulled out by generating element 30 is flat rubber belting lead end 32 and 33, and they directly are connected with negative plate with positive plate respectively by ultrasonic bonding or riveted joint.Lead end 32 and 33 is pulled out from battery case 31 linearities through welding portion 38.Terminology used here " linearity " means that flat rubber belting collector body lead-in wire does not have bending and curved portion, and is vertically forming straight line.
In the present embodiment, the battery hermetic seal is in the chamber, and this chamber has been evacuated to the pressure that is lower than conventional atmospheric pressure (760mmHg).Therefore, under the pressure of 720mmHg, 700mmHg, 600mmHg, 300mmHg and 170mmHg, prepare 5 battery 10A-10E respectively.As for comparing battery R15, the tentative battery of preparing comprises the aluminum lead that serves as the positive wire end, and nickel down-lead is ultrasonically bonded on it, directly is connected with positive plate current collector.Except that positive wire, relatively the structure of battery R15 is identical with the battery 10A of present embodiment.
To all there be the battery 10A-10E and the comparison battery R15 of the present embodiment of 50 samples to carry out following experiment.More detailed, these batteries charged 3 hours at 1CmA (500mA)/4.1V, and carried out vibration experiment, and Oscillation Amplitude is 0.8mm, frequency is 10Hz, 100Hz, 10Hz, 300Hz and 10Hz, and speed is that 1Hz/min is with this order swing on three crisscross X, Y and Z.The temperature of the battery surface during the measuring vibrations and open circuit voltage (hereinafter referred to as " OCV ") then.Measure the OCV and the internal resistance of the battery of having tested afterwards.The result lists in table 10.
Table 10
For the result of above-mentioned vibration experiment, abnormality do not occur according to the battery 10A-10E of embodiments of the invention and for example catch fire and smolder, and relatively some samples of battery R15 occur smoldering and the leakage of electrolyte solution.
The battery 10A sample of OCV or battery surface variation of temperature appears in dismounting.Observe the generating element 30 of these samples then.The following is observed situation.More detailed, observe positive wire end 32 distortion or crooked, form bending part.This hole that also confirms really about 0.5mm diameter of drawing by the fusing bending part forms.Think that the EDGE CONTACT by crooked positive wire end 32 and negative plate forms these holes during vibrating.
Similarly, dismounting shows the sample of the comparison battery R15 that smolders.Observe the generating element 30 of the sample of these dismountings then.As a result, observe following situation.More detailed, observe positive wire end 32 in certain zone (ultrasonic bonding part) break, the nickel down-lead that is positioned at the outside of battery case 30 in this zone interconnects with the aluminum lead that is connected with positive plate, observes the end surface that nickel down-lead partly penetrates generating element.Think to be short-circuited penetrating the district, cause temperature to raise fast and smolder.
Then, will all there be the battery 10A-10E and the comparison battery R15 of the present embodiment of 50 samples to carry out following experiment.More detailed, these batteries charged 3 hours at 1CmA (500mA)/4.2V, deposited 30 days under 60 ℃ of temperature afterwards.In table 11, list 50 samples of these batteries and deposit the average internal resistance and the discharge capacity of front and back.
Table 11
Be to measure discharge capacity, at 1CmA (500mA), 4.2V and 25 ℃ of following chargings 3 hours discharge into 2.75V afterwards under 1CmA with battery.Utilize 1kHz ac to measure internal resistance.
Deposit the measured internal resistance of experiment after-30 days to 60 ℃ and raise and deposit measured comparing before the experiment, find that battery 10A-10E internal resistance is elevated to 25m Ω from 13m Ω, and relatively the internal resistance of battery is elevated to 76m Ω.
Dismantle the battery 10E of the present embodiment of having deposited and compare battery.Observe the generating element 30 of battery then.As a result, observe following situation.In other words, the cosmetic variation of positive wire end 32 does not appear in the battery 10E of present embodiment, and the positive wire end of observing comparison battery R15 corrodes on aluminium and the interconnective position of nickel.This chances are one of internal resistance rising cause of increased.
Therefore, can guarantee battery 10A-10E safe handling under vibration of present embodiment, and can prevent the decline of discharge capacity in the use at high temperature or the increase of internal resistance.And because the interior pressure of battery 10A-10E is positioned at (preferred 600mmHg or littler) under the atmospheric pressure, the difference of atmospheric pressure and inner pressure of battery causes the generating element pressurized.In this structure, can keep the distance between electrodes of generating element constant, the battery of excellent charge-discharge performance can be provided.
The 11 embodiment
In conjunction with Figure 22-25, the 11st embodiment of the present invention is described.Rechargeable nonaqueous electrolytic battery according to present embodiment comprises oval generating element 80 and non-aqueous electrolytic solution (not shown) of reeling, generating element 80 has positive plate, isolated material and negative plate, be contained in the bag shape battery case of forming by resin plate 81, in this structure, the wireline reel of generating element 80 is perpendicular to the plane of the opening of battery case 81.Fig. 1 represents the outward appearance of this rechargeable nonaqueous electrolytic battery.
For positive electrode active materials, use lithium-cobalt composite oxide.Positive plate 82 is included in 83 liang of lip-deep above-mentioned lithium-cobalt composite oxides that serve as active material layer of collector body.Collector body 83 is aluminium foils of thickness 20 μ m.The preparation technology of positive plate 82: with 8 parts of Kynoar and 5 parts of acetylene blacks of serving as conductive agent and 87 parts of active materials mixing of serving as adhesive, suitably add the N-methyl pyrrolidone in this mixture, this mixture is stirred pulping to form the positive polarization compound, apply the two sides of this positive polarization compound, then drying coating material to collector body 83.In this case, collector body 83 has the exposure plot that is formed on end, does not have the positive polarization compound.Positive plate 82 thickness are 180 μ m, and width W is 49mm.Positive wire end 86 is welded on the exposure plot of collector body.Then dielectric polyimide adhesive tape 87 is bonded to positive plate 82 on the position away from lead end.The width W of insulating tape 87 is 55mm and length is 25mm.Bonding width is 35mm.10mm edge extent on two vertical ends of insulating tape does not exist bonding.Therefore, there is W
2＜W＜W
1Relation, as shown in figure 23.
On the other hand, go out negative plate with similar prepared, preparation technology is: mix 92 parts of graphite and 8 parts of Kynoar as adhesive as active material, suitably add the N-methyl pyrrolidone in this mixture, this mixture is stirred pulping to form the negative polarization compound, apply the two sides of this negative polarization compound, then drying coating material to collector body.As for the collector body 92 of negative plate 90, the Copper Foil of used thickness 14 μ m.The thickness of negative plate 90 is 170 μ m, and width is 51mm.Negative plate 90 also has the collector body that does not have the negative polarization compound, and exposes to the open air endways.Negative wire end 92 is welded to the exposure plot on the collector body.Be similar to positive plate then, dielectric polyimide adhesive tape 87 is bonded to negative plate 90 on the position away from lead end 92.Isolated material (dividing plate) is the polyethene microporous membrane of thickness 25 μ m and width 53mm.
With this sequential cascade positive plate 82, negative plate 90 and dividing plate 95, along oval this lamination of reeling of rectangular core, the long limit of rectangle is parallel to the wireline reel of generating element 80 to form generating element 80 then.Figure 25 illustrates the core cross section of generating element 80.The insulating tape 87 of negative plate 90 is positioned on the exposure plot of collector body 83 of positive plate 82, and the insulating tape of positive plate 82 is positioned on the exposure plot of collector body of negative plate 90.
The fixed band of being made by polyethylene (simultaneously being coated with adhesive at it) is parallel on wireline reel bonds to generating element 80 along the sidewall of generating element the insulated part of electrode, its length is corresponding to electrode width (length of generating element is parallel to the wireline reel of generating element), the coiling of stationary power generation element.
Generating element 80 is contained in the battery case 81 that is formed by metal-Laminated resin board then, and the wireline reel of generating element 80 is perpendicular to the open surfaces of battery case 81.At this opening sealed cell shell 81, lead end 86 and 92 is fixed thereon afterwards.Then the electrolyte solution vacuum is injected battery case 81, its quantity makes that various electrodes and isolated material can be thoroughly wetting, does not have electrolyte solution in the outside of generating element.The electrolyte solution that uses is to contain 1mol/l LiPF
6Ethylene carbonate and diethyl carbonate be the mixture of 3:7 (volume).At last, according to the present embodiment experiment basis, sealing is also welded battery case 81, prepares the battery 11A of rated capacity 500mAh.
Then, for comparatively speaking, prepare comparison battery R16 and battery R17 relatively, relatively battery R16 is included in the insulating tape 87 that uses among the preparation battery 11A, and adhesive is coated in (W=W on the whole surface of insulating tape
2), and compare the identical (W of width that battery R17 removes insulating tape with electrode width
2=W=W
1) outside, structure is identical with R16, and adhesive is coated on the whole surface of insulating tape.
In table 12, list the defects count that the battery 11A of present embodiment and comparison battery R16 and R17 occur during reeling.
Table 12
Relatively battery R16 has the insulating tape that exposes to the open air at the adhesive coating area, and adhesive is bonded in undesirable zone during therefore causing reeling.According to experimental basis, resulting bad coiling can not be prepared good battery product.
Then battery 11A and comparison battery R17 according to present embodiment are carried out following experiment.Prepare 200 samples of these batteries.These batteries all charge under 500mA constant current-4.1V, charging (5 hours altogether) under constant voltage then.Afterwards, experimentize 1, the end surface of 10 samples of hammering is until being short-circuited from 20 samples.Other 10 samples pressurized under the spreader bar of 200kg pressure experimentizes 2.
For experiment 1, the maximum temperature of battery surface after table 13 is listed short circuit.For experiment 2, table 13 list pressurized after 1 minute battery exist or do not have a short-circuit conditions.In table 13, label ※ represents that violent smoldering appears in the battery experimental session.
Table 13
Compare with comparing battery R17, confirm that the battery 11a of present embodiment in any of these experiment is good in the fail safe during Short Circuit withstand and the short circuit.
The 12 embodiment
In conjunction with Figure 26-28, the 12nd embodiment of the present invention is described.
Figure 26 represents the front elevation of the battery that the preparation technology according to present embodiment prepares.
Positive plate is included in the lithium-cobalt composite oxide that serves as active material on the collector body.Collector body is the aluminium foil of thickness 20 μ m.The preparation technology of positive plate: with 8 parts of Kynoar and 5 parts of acetylene blacks of serving as conductive agent and 87 parts of active materials mixing of serving as adhesive, suitably add the N-methyl pyrrolidone in this mixture, this mixture is stirred pulping to form the positive polarization compound, apply the two sides of this positive polarization compound, then drying coating material to collector body.
As for the collector body of negative plate, the Copper Foil of used thickness 14 μ m.Preparation technology is: mix 92 parts of graphite and 8 parts of Kynoar as adhesive as host material, suitably add the N-methyl pyrrolidone in this mixture, this mixture is stirred pulping to form the negative polarization compound, apply the two sides of this negative polarization compound, then drying coating material to collector body.
Dividing plate is a polyethene microporous membrane.Electrolyte solution is to contain 1mol/l LiPF
6Ethylene carbonate and diethyl carbonate be the mixture of 1:1 (volume).
As for the size of each parts, the thickness of positive plate is 180 μ m, and width is 49mm, and block board thickness is 25 μ m, and width is 53mm, and the thickness of negative plate is 170 μ m, and width is 51mm.Reel along the rectangle polyvinyl plastic core is oval with these parts that this order is stacked, form generating element.
The resin plate of forming battery case 100 is made of stack membrane; stack membrane comprises the aluminium foil 102 of the thickness that the serves as the barrier layer 9 μ m that the surface protection pet layer 101 that serves as outermost thickness 12 μ m, the basal surface that utilizes urea groups adhesive and pet layer 101 are bonding and is positioned at the acid-modified poly ethylene layer 103 of the thickness 100 μ m below the aluminium foil 102, shown in the profile of Figure 27.For acid-modified poly ethylene layer, can use the sort of polyethylene of 100 ℃ of softening points as hot melt layer.
Provide anti-expanded material 110 on the part opposing ends pulling out of generating element 107 with lead-in wire.Anti-expanded material 110 is nonwoven fabric of long fibers that polypropylene (ASAHI CHEMICAL INDUSTRY CO., LTD. produces) is made, thickness 0.23mm, the tearing strength 0.40kg of transverse and longitudinal, weight 22g/m
2Anti-expanded material 110 utilize adhesive generating element 107 with lead end 104 opposing ends on, thereby cover terminal fully.Anti-expanded material can only be placed on the terminus inner of generating element 107.Yet, when anti-expanded material 110 utilizes on the generating element 107 of adhesive at this battery, even not sealing fully of battery case 100 can prevent the leakage of electrolyte solution.In this battery, lead end 104 and anti-expanded material 110 are positioned on the opposing end surface of generating element 107.Yet two parts can be positioned on the identical end face.
Can prepare this battery by technology shown in Figure 28.
At first, with lead end 104 mode stationary power generation element 107 (step a) down.Anti-expanded material 110 covers the other end of generating element 107 fully, utilizes adhesive (step b) on it then.Then, these parts are twined by Laminated resin board and form battery case 100, have only outside lead end 104 is exposed to.The edge of thermoplastic resin plate then, sealed open (step c).Yet battery case 100 also has an opening 111 in anti-expanded material 110 1 sides.Then, electrolyte solution is annotated (step d) on anti-expanded material 110 by opening 111.Then, electrolyte solution is absorbed by anti-expanded material 110, infiltrates afterwards in the dividing plate between positive plate and negative plate.Then air is removed (step e) by vacuum pump from the inside of battery case 100.At last, hot melt opening 111, sealed cell shell.Therefore, obtain the battery 1 (step f) that design capacity is 500mAh.
In the present embodiment, electrolyte solution injects battery cases through anti-expanded material 110, prevents that electrolyte solution from dripping on the generating element 107 and spill, thereby prevents that electrolyte solution is attached to the inner area near the battery case 100 of opening 111.And, even bubble breaks during the finding time of battery case 100,, can from generating element, not spill drop because the upper end of generating element 107 is covered by anti-expanded material 110 in electrolyte solution.In addition, because battery case 100 is sealed in lead end 104 1 sides before electrolyte solution injects, the battery table of preparing according to present embodiment reveals good air-tightness.
Battery according to present embodiment preparation technology is carried out following experiment.
At first, prepare 10 samples according to the battery 12A of present embodiment.As for comparative example, electrolyte solution injects the battery case in collector body lead-in wire side except that preventing expanded material 110, prepares 10 samples of battery R18 with the identical method of present embodiment.Then, these batteries all with constant current 500mA charging and charging (3 hours altogether) under constant voltage 4.10V, discharge into 2.75V under the constant current 500mA afterwards.All to these battery measurement capacity (capacity before the experiment).These batteries all store 30 days under 60 ℃ of temperature and 90% RH, discharge under condition same as described above then.All to these battery measurement capacity (residual capacity).And, under condition same as described above, these batteries are charged once more and discharge.Then all to these battery measurement capacity (recovery capacity).In addition, all these batteries are observed, whether the aluminium of looking at stack membrane corrodes and whether electrolyte solution leaks from battery case.
In table 14, list the result.In this table, label * represents to observe battery the aluminium corrosion.Label
*Expression battery except that observing the aluminium corrosion has electrolyte solution to leak from battery case.According to the capacity before the experiment, represent the value of residual capacity and recovery capacity with percentage (%).
Table 14
Can find out that from table 14 relatively battery R18 compares with the battery 12A of present embodiment, residual capacity and recovery capacity are low.This is that moisture enters in the battery case from the outside because relatively battery R18 has carried out the cell reaction that caused by airborne moisture.Observe all samples that compare battery R18 and the aluminium corrosion occurs.Observing corrosion 8 in the sample electrolyte solution occurs and leaks out battery case from the collector body lead-in wire.This defective also is owing to the air that enters battery case from the outside is caused.
On the other hand, the battery 12A that observes present embodiment electrolyte leakage neither occurs and the aluminium corrosion also do not occur.Therefore, the air-tightness of the battery 12A that clearly prepares according to present embodiment is better than conventional batteries.
And even the electrolyte solution that uses is the non-aqueous electrolytic solution that contains lithium salts, the battery of preparing according to the present invention is not easy to occur the decline of battery capacity, the leakage and the corrosion of metals of electrolyte solution.In addition,, do not need slowly and carry out the injection of electrolyte solution and finding time of battery case subtly according to preparation technology of the present invention, but the efficient production battery.And, by preventing that expanded material is fixed on the generating element pulling out on the relative side of side in advance with collector body lead-in wire, can prevent during each step process or electrolyte solution injection period electrolyte solution be attached to lead-in wire and find time during the skew of position, make the percentage of defective minimize.
Preferably on relative plane, the plane of pulling out with lead end 104, anti-expanded material 110 is fixed on the generating element 107.Terminology used here " the relative plane, plane of pulling out with lead end 104 " means under the situation of ellipse coiling generating element the plane perpendicular to wireline reel, do not pull out lead-in wire from this plane, or meaning the plane of under the situation of approximate rectangular generating element, not pulling out lead-in wire, this plane is relative with the plane of pulling out lead-in wire.Generating element comprises stacked ordinary telegram pole plate mutually, and isolated material is between electrode.
In the present embodiment, polypropylene non-woven fabric is as anti-expanded material.Anti-expanded material with similar effect is not defined in polypropylene non-woven fabric.These examples of material comprise net, nonwoven fabrics, felt and the porous material that for example polypropylene and poly polyolefin are made.
Claims (25)
1. rechargeable nonaqueous electrolytic battery comprises as lower member;
Generating element comprises that each other the lead end of settling relatively that the therebetween positive plate of isolated material and negative plate is arranged and be electrically connected with described battery lead plate respectively is positive wire end and negative wire end; With
Battery case is made up of resin plate, and at one or two direction openings, described generating element is contained in wherein before the sealing, and described lead end inserts in the described opening, welds described opening with the sealed cell shell,
Above-mentioned resin plate comprises the directed resin bed on the two sides that is positioned at metal level.
2. rechargeable nonaqueous electrolytic battery comprises as lower member:
Generating element comprises that each other the lead end of settling relatively that the therebetween positive plate of isolated material and negative plate is arranged and be electrically connected with described battery lead plate respectively is positive wire end and negative wire end; With
Battery case is made up of resin plate, and at one or two direction openings, described generating element is contained in wherein before the sealing, and described lead end inserts in the described opening, welds described opening with the sealed cell shell,
The welding portion thickness at the opening pressurized edge of described battery case is held bigger than its outer end within it.
3. rechargeable nonaqueous electrolytic battery as claimed in claim 2, wherein said generating element forms by reel along wireline reel described positive plate and negative plate, cross section perpendicular to wireline reel in this structure is oval, generating element is contained in the described battery case, and its wireline reel is perpendicular to the plane of the opening of battery case.
4. rechargeable nonaqueous electrolytic battery as claimed in claim 2, the resin plate of wherein forming described battery case are the mutual stacked metal-stack membranes of metal forming and resin bed.
5. rechargeable nonaqueous electrolytic battery as claimed in claim 3, the resin plate of wherein forming described battery case are the mutual stacked metal-stack membranes of metal forming and resin bed.
6. rechargeable nonaqueous electrolytic battery comprises as lower member:
Generating element comprises that each other the lead end of settling relatively that the therebetween positive plate of isolated material and negative plate is arranged and be electrically connected with described battery lead plate respectively is positive wire end and negative wire end; With
Bag shape battery case is made up of resin plate, and described generating element is contained in wherein back sealing,
For forming this battery case, two parallel side relatively also welding each other with the rectangle resin plate forms the cylindrical of both direction upper shed, and this welding portion is " welding portion X " hereinafter referred to as,
The lead end of above-mentioned generating element is put into of two openings, two edges with opening relatively also weld each other then, form sealing bag, thereby the surface that forms welding portion X is fixed on the lip-deep structure of battery case, the welding portion that lead end is put into wherein is called " welding portion Y " hereinafter, and another welding portion is called " welding portion Z " hereinafter
The surface of welding portion X is fixed on the surface of welding portion Y and/or welding portion Z.
7. rechargeable nonaqueous electrolytic battery as claimed in claim 6, the end of wherein said welding portion X is between described positive wire end and described negative wire end.
8. rechargeable nonaqueous electrolytic battery as claimed in claim 6, wherein said generating element forms by reel along wireline reel described positive plate and negative plate, cross section perpendicular to wireline reel in this structure is oval, generating element is contained in the described battery case, and its wireline reel is perpendicular to the plane of the opening of battery case.
9. rechargeable nonaqueous electrolytic battery as claimed in claim 7, wherein said generating element forms by reel along wireline reel described positive plate and negative plate, cross section perpendicular to wireline reel in this structure is oval, generating element is contained in the described battery case, and its wireline reel is perpendicular to the plane of the opening of battery case.
10. rechargeable nonaqueous electrolytic battery as claimed in claim 6, the resin plate of wherein forming described battery case are the mutual stacked metal-stack membranes of metal forming and resin bed.
11. rechargeable nonaqueous electrolytic battery as claimed in claim 7, the resin plate of wherein forming described battery case are the mutual stacked metal-stack membranes of metal forming and resin bed.
12. rechargeable nonaqueous electrolytic battery as claimed in claim 8, the resin plate of wherein forming described battery case are the mutual stacked metal-stack membranes of metal forming and resin bed.
13. rechargeable nonaqueous electrolytic battery as claimed in claim 9, the resin plate of wherein forming described battery case are the mutual stacked metal-stack membranes of metal forming and resin bed.
14. rechargeable nonaqueous electrolytic battery comprises as lower member:
Generating element comprises: with positive plate and negative plate that isolated material is reeled, wherein isolated material is between described positive and negative electrode plate, and the cross section perpendicular to wireline reel in this structure is oval; And the lead end that is electrically connected with described positive plate and described negative plate respectively and pulls out from the end surface of wireline reel, i.e. positive wire end and negative wire end;
Fixed band, this fixed band is reeled on described generating element along wireline reel, extends to described end surface from the edge surface of described generating element, and passes the space between described positive wire end and the negative wire end; With
Bag shape battery case is made up of resin plate, and described generating element is contained in wherein back sealing,
For forming this battery case, two parallel side relatively also welding each other with the rectangle resin plate forms the cylindrical of both direction upper shed, and this welding portion is " welding portion X " hereinafter referred to as,
The lead end of above-mentioned generating element is put into of two openings, with two edges relatively also welding each other of opening, form sealing bag, thereby the surface of formation welding portion X is fixed on the lip-deep structure of battery case then,
Form and the partly overlapping welding portion X of fixed band.
15. rechargeable nonaqueous electrolytic battery as claimed in claim 14, wherein said generating element are contained in the described battery case, its wireline reel is perpendicular to described plane of the opening.
16. rechargeable nonaqueous electrolytic battery as claimed in claim 14, the resin plate of wherein forming described battery case are the mutual stacked metal-stack membranes of metal forming and resin bed.
17. rechargeable nonaqueous electrolytic battery as claimed in claim 15, the resin plate of wherein forming described battery case are the mutual stacked metal-stack membranes of metal forming and resin bed.
18. rechargeable nonaqueous electrolytic battery comprises as lower member;
Generating element comprises: with banded positive plate and banded negative plate that isolated material is reeled, wherein isolated material is between described positive and negative electrode plate; And the lead end from pulling out perpendicular to the terminal surface of wireline reel and being electrically connected with described positive plate and described negative plate respectively, i.e. positive wire end and negative wire end; With
Bag shape battery case is made up of resin plate, and described generating element is contained in wherein back sealing, wherein,
Above-mentioned positive plate comprises the positive polarization compound that is coated on the banded collector body, and has in a vertically terminal current collection tagma of exposing to the open air, and above-mentioned positive wire end is connected with the exposure plot,
Above-mentioned negative plate comprises the negative polarization compound that is coated on the banded collector body, and has in a vertically terminal current collection tagma of exposing to the open air, and above-mentioned negative wire end is connected with the exposure plot,
Insulating tape, its length be greater than the width of described battery lead plate, utilizes the adhesive layer that is coated between them to bond on described at least positive plate and negative plate one, and the length that forms adhesive layer is littler than the width of described battery lead plate, and is outstanding from described battery lead plate.
19. rechargeable nonaqueous electrolytic battery as claimed in claim 18, wherein when described positive plate and negative plate isolated material in the middle of being positioned at their is reeled, described insulating tape is positioned on the position of the exposure plot of described collector body of corresponding another battery lead plate and described lead end.
20. rechargeable nonaqueous electrolytic battery as claimed in claim 18, wherein said generating element forms by reel along wireline reel described positive plate and negative plate, cross section perpendicular to wireline reel in this structure is oval, generating element is contained in the described battery case, and its wireline reel is perpendicular to the plane of the opening of battery case.
21. rechargeable nonaqueous electrolytic battery as claimed in claim 19, wherein said generating element forms by reel along wireline reel described positive plate and negative plate, cross section perpendicular to wireline reel in this structure is oval, generating element is contained in the described battery case, and its wireline reel is perpendicular to the plane of the opening of battery case.
22. rechargeable nonaqueous electrolytic battery as claimed in claim 18, the resin plate of wherein forming described battery case are the mutual stacked metal-stack membranes of metal forming and resin bed.
23. rechargeable nonaqueous electrolytic battery as claimed in claim 19, the resin plate of wherein forming described battery case are the mutual stacked metal-stack membranes of metal forming and resin bed.
24. rechargeable nonaqueous electrolytic battery as claimed in claim 20, the resin plate of wherein forming described battery case are the mutual stacked metal-stack membranes of metal forming and resin bed.
25. rechargeable nonaqueous electrolytic battery as claimed in claim 21, the resin plate of wherein forming described battery case are the mutual stacked metal-stack membranes of metal forming and resin bed.
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31596798A JP4433506B2 (en) | 1998-11-06 | 1998-11-06 | battery |
| JP315967/1998 | 1998-11-06 | ||
| JP344976/1998 | 1998-12-04 | ||
| JP085270/1999 | 1999-03-29 | ||
| JP085155/1999 | 1999-03-29 | ||
| JP085171/1999 | 1999-03-29 | ||
| JP086977/1999 | 1999-03-29 | ||
| JP085208/1999 | 1999-03-29 | ||
| JP088599/1999 | 1999-03-30 | ||
| JP088251/1999 | 1999-03-30 | ||
| JP088072/1999 | 1999-03-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100978326A Division CN1330019C (en) | 1998-11-06 | 1999-11-04 | Nonaqueous secondary electrolytic battery |
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| CN101414671A true CN101414671A (en) | 2009-04-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA200810213497XA Pending CN101414671A (en) | 1998-11-06 | 1999-11-04 | Nonaqueous secondary electrolytic battery |
| CNB2006100941636A Expired - Fee Related CN100464444C (en) | 1998-11-06 | 1999-11-04 | Non-aqueous electrolytic secondary cell |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2006100941636A Expired - Fee Related CN100464444C (en) | 1998-11-06 | 1999-11-04 | Non-aqueous electrolytic secondary cell |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104412407A (en) * | 2012-06-18 | 2015-03-11 | Nec能源元器件株式会社 | Film pack battery |
Families Citing this family (12)
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| KR100601534B1 (en) * | 2004-07-28 | 2006-07-19 | 삼성에스디아이 주식회사 | Battery outer body and lithium polymer battery using it |
| CN101841012B (en) * | 2010-02-24 | 2012-10-24 | 北汽福田汽车股份有限公司 | Preparation method of car storage battery box body and box body prepared by using same |
| JP5531977B2 (en) * | 2011-02-07 | 2014-06-25 | 大日本印刷株式会社 | Battery case sheet and battery device |
| KR101381706B1 (en) * | 2011-10-31 | 2014-04-14 | 에스케이이노베이션 주식회사 | Jelly roll of Pouch cell for Secondary Battery |
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| JP2021157882A (en) * | 2020-03-25 | 2021-10-07 | 株式会社パワーフォー | Secondary battery |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3512551B2 (en) * | 1996-01-30 | 2004-03-29 | 株式会社リコー | Rechargeable battery |
| JP3452172B2 (en) * | 1997-01-28 | 2003-09-29 | 株式会社ユアサコーポレーション | Flat battery |
| JPH10294097A (en) * | 1997-02-24 | 1998-11-04 | Mitsubishi Electric Corp | Thin type cell |
| JP3767151B2 (en) * | 1997-02-26 | 2006-04-19 | ソニー株式会社 | Thin battery |
-
1998
- 1998-11-06 JP JP31596798A patent/JP4433506B2/en not_active Expired - Fee Related
-
1999
- 1999-11-04 CN CNA200810213497XA patent/CN101414671A/en active Pending
- 1999-11-04 CN CNB2006100941636A patent/CN100464444C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104412407A (en) * | 2012-06-18 | 2015-03-11 | Nec能源元器件株式会社 | Film pack battery |
| US9871231B2 (en) | 2012-06-18 | 2018-01-16 | Nec Energy Devices, Ltd. | Film-covered battery |
| CN104412407B (en) * | 2012-06-18 | 2018-04-10 | Nec能源元器件株式会社 | film-covered battery |
| US10510997B2 (en) | 2012-06-18 | 2019-12-17 | Envision Aesc Energy Devices Ltd. | Film-covered battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1967902A (en) | 2007-05-23 |
| CN100464444C (en) | 2009-02-25 |
| JP2000149885A (en) | 2000-05-30 |
| JP4433506B2 (en) | 2010-03-17 |
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| ASS | Succession or assignment of patent right |
Owner name: GS YUASA INTERNATIONAL LTD. Free format text: FORMER OWNER: YUASA BATTERY CO LTD Effective date: 20110504 |
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| C41 | Transfer of patent application or patent right or utility model | ||
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Effective date of registration: 20110504 Address after: Kyoto Japan Applicant after: GS Yuasa International Corporation Co-applicant after: Sanyo GS Battery Co., Ltd. Address before: Kyoto Japan Applicant before: Yuasa Battery Co., Ltd. Co-applicant before: Sanyo GS Battery Co., Ltd. |
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| ASS | Succession or assignment of patent right |
Free format text: FORMER OWNER: SANYO GS BATTERY CO., LTD. |
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| C41 | Transfer of patent application or patent right or utility model | ||
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Effective date of registration: 20110830 Address after: Kyoto Japan Applicant after: GS Yuasa International Corporation Co-applicant after: Sanyo Electric Co., Ltd. Address before: Kyoto Japan Applicant before: GS Yuasa International Corporation Co-applicant before: Sanyo GS Battery Co., Ltd. |
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| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20090422 |