CN1214480C - Lithium ion secondary battery and its manufacture - Google Patents
Lithium ion secondary battery and its manufacture Download PDFInfo
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- CN1214480C CN1214480C CNB971817111A CN97181711A CN1214480C CN 1214480 C CN1214480 C CN 1214480C CN B971817111 A CNB971817111 A CN B971817111A CN 97181711 A CN97181711 A CN 97181711A CN 1214480 C CN1214480 C CN 1214480C
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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
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Abstract
The present invention aims to provide a secondary lithium ion battery which ensures ionic conductance and adhesion strength and has the advantages of small size, compactness, no use of a firm external can, thinness, arbitrary shape, high charge and discharge efficiency, stabilization and practicality, and a manufacture method thereof. The battery of the present invention has a multilayer lamination body (12), and the multilayer lamination body (12) is formed by that an adhesive resin layer (8) which is composed of an electrolyte phase (9), a macromolecular gel phase (10)containing an electrolyte and a macromolecular solid phase (11) joints a positive electrode (1) and a negative electrode (3) to a separator (3) containing a Li-iron non-aqueous electrolyte.
Description
Technical field
The present invention relates to make anodal and the opposed lithium rechargeable battery of negative pole, particularly relate to lithium rechargeable battery slim and that charge-discharge characteristic is good keeping electrolytical spacer to be clipped in the middle.
Background technology
Very strong to the requirement that the miniaturization of portable electronic machine is lightweight, it realizes then requiring guaranteeing etc. of Towards Higher Voltage, high-energy-densityization, anti-high load capacityization and fail safe, is just carrying out all battery exploitation and improvement now.Lithium ion battery is the secondary cell that can realize high voltage, high-energy-density, high withstand load in existing battery, is the battery that is hopeful to satisfy above-mentioned requirements most.
Lithium rechargeable battery as its main formation, has positive pole, negative pole and is clipped in two interelectrode ion conductive layers.In the lithium rechargeable battery of present practicability, it is anodal that what use is the active material powder that makes lithium-cobalt composite oxide etc. and be coated onto that work becomes tabular positive pole on the aluminium collector body after electronic conductance body powder and adhering resin mix, what negative pole used is that the active material powder of carbon element system is mixed with adhering resin, and is coated onto that work becomes tabular negative pole on the copper collector.In addition, ion conductive layer uses is to make the porous film of polyethylene or polypropylene etc. be full of the conductive layer of the solvent of the non-water system that contains lithium ion.
Now practicability lithium rechargeable battery, adopt the firm outer tinning of using stainless steel etc., and the way of pressurizeing is kept the electrical connection between positive pole-ion conductive layer-negative pole.As making method anodal and that negative pole closely contacts, the method for the firm housing that the employing use is made with metal etc.But above-mentioned outer tinning has increased the weight of lithium rechargeable battery, makes miniaturization, when the lightweight difficulty that becomes is got up, because the outspoken nature of outer tinning, it is difficult that arbitrary shapeization has also become.
Want to make lithium rechargeable battery miniaturization and lightweight and arbitrary shapeization, just must make anodal and ion conductive layer, negative pole and ion conductive layer engage, and keep this state and needn't be from external pressurized.
About the method for this respect, in United States Patent (USP) 5437692, disclose a kind of polymer and be used as ion conductive layer lithium ion conductive, with the adhesive linkage of lithium-containing compound, positive pole and negative pole are joined to method on the above-mentioned conductive layer.In addition, in WO95/15589, disclose a kind of plastic ion conductive layer that forms earlier, engaged the method for anodal and negative pole again with this plasticity ion conductive layer.
But, if with disclosed method in the above-mentioned United States Patent (USP) 5437692, then can not obtain enough intensity, can not do battery to such an extent that enough must approach, in addition, the battery behavior of also high, charge-discharge characteristic of the ionic conduction resistance between ion conductive layer and positive pole and the negative pole etc. also has problem in practicality.In addition,,, can not obtain enough intensity, can not make battery to such an extent that enough must approach such problem so exist owing to engage plastic ion conductive layer if according to above-mentioned WO95/15589.
Summary of the invention
The present invention makes in order to eliminate problem as described above, purpose provides a kind of battery structure, this battery structure makes anodal with adhesive resin and negative pole and ion conductive layer (below, be called spacer) be adjacent to, in the enough bond strengths that can guarantee between electrode and the spacer, can also guarantee to make between positive pole and negative pole and the spacer ionic conduction resistance and the battery that uses existing outer tinning roughly the same.
The invention provides a kind of lithium rechargeable battery, it is characterized in that: possess multilayer laminate, this laminated body use by the electrolysis liquid phase, contain electrolyte high-molecular gel mutually and the adhesive resin layer that constitutes of the mixed phase of macromolecule solid phase, anodal and negative pole are joined on the barrier film that maintains electrolyte, wherein, described high-molecular gel is not dissolved in electrolyte mutually, does not react in lithium rechargeable battery, becomes gel phase under the situation that electrolyte exists;
Described macromolecule solid phase is not dissolved in electrolyte, does not react in lithium rechargeable battery, becomes solid phase under the situation that electrolyte exists.
In the above-mentioned lithium rechargeable battery of the present invention, described positive pole and negative pole alternatively are configured in and cut off between a plurality of barrier films that come.
In the above-mentioned lithium rechargeable battery of the present invention, described positive pole and negative pole alternatively are configured between the barrier film that winds up.
In the above-mentioned lithium rechargeable battery of the present invention, described positive pole and negative pole alternatively are configured between the barrier film of folding up.
In the above-mentioned lithium rechargeable battery of the present invention, high-molecular gel mutually and the macromolecule solid phase contain the macromolecular material of of the same race or xenogenesis, the mean molecule quantity of the macromolecular material that the mean molecule quantity of the macromolecular material that above-mentioned high-molecular gel is mutually contained and above-mentioned macromolecule solid phase are contained is different.
In the above-mentioned lithium rechargeable battery of the present invention, also can be high-molecular gel mutually and the macromolecule solid phase contain Kynoar, the mean molecule quantity of the Kynoar that the mean molecule quantity of the Kynoar that above-mentioned high-molecular gel is mutually contained and above-mentioned macromolecule solid phase are contained is different.
In the above-mentioned lithium rechargeable battery of the present invention, can also be high-molecular gel mutually and the macromolecule solid phase contain polyvinyl alcohol, the mean molecule quantity of the polyvinyl alcohol that the mean molecule quantity of the polyvinyl alcohol that above-mentioned high-molecular gel is mutually contained and above-mentioned macromolecule solid phase are contained is different.
According to lithium rechargeable battery of the present invention, the mean molecule quantity of the macromolecular material that above-mentioned high-molecular gel is mutually contained is less than the mean molecule quantity of the contained macromolecular material of above-mentioned macromolecule solid phase.
According to lithium rechargeable battery of the present invention, above-mentioned high-molecular gel phase and above-mentioned macromolecule solid phase comprise the macromolecular material of identical type.
According to lithium rechargeable battery of the present invention, high-molecular gel phase and macromolecule solid phase contain Kynoar, and the mean molecule quantity of the Kynoar that above-mentioned high-molecular gel is mutually contained is less than the mean molecule quantity of the contained Kynoar of above-mentioned macromolecule solid phase.
According to lithium rechargeable battery of the present invention, employing uses the zygosity resin bed that is made of the mixed phase between the high-molecular gel phase that contains electrolyte, macromolecule solid phase, the macromolecule liquid phase to engage, bond strength and ionic conductivity between positive pole and negative pole and the barrier film can be guaranteed, and adhesive strength and macroion conductance can be guaranteed.Even if so make the laminated cell of laminated body, do not need firm outer tinning yet, can obtain small compact and high-performance, battery capacity lithium rechargeable battery big, practicality with multilayer.
The invention provides a kind of manufacture method of lithium rechargeable battery, described lithium rechargeable battery has the laminated body that makes positive pole and negative pole join the multilayer on the barrier film that maintains electrolyte to, it is characterized in that comprising the following steps: that coating is dissolved into the bonding agent that constitutes in the solvent by the different multiple macromolecular material of mean molecule quantity on the relative face of barrier film, having formed by the adhesive resin layer makes positive pole and negative pole alternatively join cell body between the barrier film of multilayer to, this cell body be impregnated in the electrolyte, above-mentioned adhesive resin layer is become to containing the high-molecular gel phase of electrolyte, the mixed phase of macromolecule solid phase and electrolyte layer.As mentioned above, employing makes floods electrolyte and makes it to become way for the mixed phase of the high-molecular gel phase, macromolecule solid phase and the electrolyte layer that contain electrolyte in the adhesive resin layer, just can guarantee bond strength and ionic conductivity between positive pole and negative pole and barrier film, and adopt the way that single laminated body is overlapped, just can make small compact and do not need firm outer tinning, high and the stable and lithium rechargeable battery of practicality of slim, arbitrary shape and efficiency for charge-discharge.
Description of drawings
The major part profile schema diagram of Fig. 1, Fig. 2 and Fig. 3 shows an embodiment of lithium rechargeable battery of the present invention, is a kind of structure with single laminated body of multilayer.The structure of the single laminated body of profile schema diagram key diagram 1, Fig. 2 and Fig. 3 of Fig. 4.Fig. 5 shows the example of (200% charging) result of the test that overcharges.Fig. 6 shows the example of over-discharge test results.In Fig. 5 and Fig. 6, what (A) illustrate is charge characteristic, and what (B) illustrate is flash-over characteristic.
Embodiment
Below, with reference to description of drawings the preferred embodiments of the present invention.
The major part profile schema diagram of Fig. 1, Fig. 2 and Fig. 3 shows an embodiment of lithium rechargeable battery of the present invention, Fig. 4 (a) and (b) be the profile schema diagram of the structure of the laminated body among key diagram 1, Fig. 2 and Fig. 3, Fig. 4 (b) is the local expanded view of the adhesive resin layer of Fig. 4 (a).
At Fig. 1 in Fig. 4, laminated body 12 is made of following part: the positive pole 1 that edge forming is made of positive electrode active material layer 3 on positive electrode collector 2 that the metal by aluminium foil etc. constitutes, the negative pole 4 that edge forming is made of negative electrode active material layer 6 on negative electrode collector 5 that the metal by copper etc. constitutes, the adhesive resin layer 8 that maintains the spacer 7 of the electrolyte that contains lithium ion and spacer 7 and positive pole 1 and spacer 7 are engaged with negative pole 4.
Fig. 1 is 7 of a kind of a plurality of spacers that come in cut-out, the structure of configuration anodal 1 and negative pole 4 alternatively, and Fig. 2 and Fig. 3 are a kind of 7 of the spacers that winds up, alternatively the structure of configuration anodal 1 and negative pole 4.Do not come though draw among the figure,, also can do to become 7 of the spacers of folding up, alternatively the structure of configuration anodal 1 and negative pole 4.
Shown in Fig. 4 (b), adhesive resin layer 8 is made of macromolecule solid phase 11, the high-molecular gel phase 10 that contains electrolyte, the mixed phase that remains on by the electrolysis liquid phase 9 in macromolecule solid phase 11 or high-molecular gel phase 10 minute apertures that form.
Macromolecule solid phase 11 with adhesive resin layer 8, make a side and anodal 1 of the forward surface of spacer 7, engage (bonding) with the opposing party's of spacer 7 forward surface securely with negative pole 4, can obtain the macroion conductance with electrolysis liquid phase 9,10 control mutually with high-molecular gel because of the reduction of melting joint (bonding) intensity that is produced mutually between macromolecule solid phase 11 and the electrolysis liquid phase 9, also keep the macroion conductance simultaneously, make the ionic conductivity height extremely between spacer 7 and positive pole 1 and the negative pole 4.
In order to form macromolecule solid phase 11 and high-molecular gel mutually 10 on adhesive resin 8, use is dissolved into bonding agent in the solvent to the different macromolecular material of mean molecule quantity.
In other words, as bonding agent, use will be by the macromolecular material of electrolyte swelling (low-molecular-weight macromolecule) and can be dissolved into the bonding agent in the The suitable solvent equably by the macromolecular material of swelling (HMW macromolecule), with this bonding agent anodal 1 with negative pole 4 joins on the spacer 7 and after making the bonding agent intensive drying, under the temperature of regulation, in this bonding agent, flood electrolyte, just can form by containing the high molecular macromolecule solid phase 11 of HMW and containing adhesive resin that the high molecular gel phase 10 of low-molecular-weight and electrolysis liquid phase 9 constitute mutually 8.
The macromolecular material that above-mentioned mean molecule quantity is different, same kind or different types of macromolecular material are all right.Under the situation of different types of macromolecular material, though even if be identical also can form gel phase and solid phase by means of this combination mean molecule quantity, in this case, ideal situation is the mean molecule quantity difference.Its reason is: even if different types of macromolecular material is similar as molecular weight, then owing to the generation of the what is called ' topological complexing (entanglement) ' in solution system, gel state has the time of origin variation, and battery behavior also has the possibility that changes.
Form adhesive resin 8 macromolecular material mutually as being used for, must in electrolyte, not dissolve at least, in lithium rechargeable battery, do not react.And, when having electrolyte, must become gel phase and solid phase, can use so long as satisfy the macromolecular material of this condition.In addition, even if the macromolecular material of same kind, temperature history in the time of also can depending on the solvent types of electrolyte or make lithium rechargeable battery can obtain two kinds of forms of gel phase or solid phase, but, for example can use the acrylic ester macromolecule of poly-(methyl methacrylate) etc. as the macromolecular material that under condition of the present invention, can become gel phase, poly-(acrylonitrile), copolymer between low-molecular-weight Kynoar and they and other macromolecular compound, copolymer between low molecular weight polyethylene pure and mild they and other macromolecular compound, or with low molecular weight polyethylene alcohol mixture of main component etc.In addition, as the macromolecular material that under condition of the present invention, can become solid phase, can use the copolymer between copolymer between HMW Kynoar, poly-(tetrafluoroethene) or they and other macromolecular compound, high molecular weight polyvinyl alcohol and they and other macromolecular compound, or be the mixture etc. of main component with the high molecular weight polyvinyl alcohol.
As the positive active material that in positive electrode active material layer 3, uses, for example can use the composite oxides between the transition metal of lithium and cobalt, manganese, nickel etc., contain lithium chalcogenide or their complex chemical compound, can be used in the complex chemical compound that has various interpolation elements in above-mentioned composite oxides, the chalcogenide that contains lithium or their complex chemical compound in addition.In addition, as the negative electrode active material that uses in negative electrode active material layer 6, carbon materials etc. are so long as the material that lithium ion can be come in and gone out can use.
As positive electrode collector 2 and negative electrode collector 5, so long as stable metal can use in lithium rechargeable battery, it is desirable to use aluminium as positive electrode collector 2, it is desirable to use copper as negative electrode collector.The shape of collector body 2,5, any can using such as paper tinsel, netted, wire netting, but, for obtain with active material between bond strength and for the dipping of the electrolyte after being easy to engage, be desirable as the big shape of surface area of netted, wire netting and so on.
The material that uses in spacer is so long as with dipping electrolyte such as the multiple aperture plasma membrane of insulating properties, net, nonwoven fabrics and can obtain the film of enough intensity, no matter which type of film can use.The multiple aperture plasma membrane that use is made of polypropylene, polyethylene etc. is desirable from the viewpoint of guaranteeing fail safe.Under the situation of using fluorine resin system, sometimes must carry out surface treatment to guarantee cementability with plasma etc.
As electrolyte, can use separately or in the mixture of ester series solvent of ether series solvent to dimethoxy-ethane, diethoxyethane, dimethyl ether, diethyl ether etc., propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate etc., be dissolved with LiPF
6, LiClO
4, LiBF
4, LiCF
3SO
3, LiN (CF
3SO
2)
2, LiC (CF
3SO
2)
3, LiN (C
2F
5SO
2)
2Deng electrolyte solution.
Below, the embodiment of lithium rechargeable battery of the present invention is at length described, but self-evident, the present invention is not subjected to the restriction of these embodiment.
(anodal making)
Employing is made 87 weight portion LiCoO
28 weight portion graphite powders, 5 weight portion Kynoar are distributed to the positive active material cream that the way in the N-methyl pyrrolidone (below, be called NMP) is modulated into, with about 300 microns of doctor blade (doctor Blade) method applied thickness, form the positive active material film.Mounting becomes the aluminium net of 30 microns of the thickness of positive electrode collector 2 at an upper portion thereof, is adjusted into the positive active material cream of 300 microns of thickness more at an upper portion thereof once more with the coating of doctor blade method.It is placed to become after 60 minutes in 60 ℃ drying machine be leather hard, form the laminated body of positive electrode collector 2 and positive active material.Employing makes this laminated body roll into 400 microns way, is made into the positive pole 1 that has formed positive electrode active material layer 3.After being dipped into this positive pole 1 in the electrolyte, measure the peel strength between positive electrode active material layer and the positive electrode collector, the value of this intensity is 20～25gf/cm.
(making of negative pole)
90 weight portion mesocarbon particulates (Mesophase Microbead Carbon) (ProductName MCMB, Osaka gas production), 5 weight portion Kynoar are distributed to the negative electrode active material cream that is modulated among the NMP, be 300 microns of thickness with the coating of doctor blade (doctor Blade) method, form the negative electrode active material film.Mounting becomes the copper mesh of 20 microns of the thickness of negative electrode collector at an upper portion thereof, is adjusted into the negative electrode active material cream of 300 microns of thickness more at an upper portion thereof once more with the coating of doctor blade method.It is placed to become after 60 minutes in 60 ℃ drying machine be leather hard, form the laminated body of negative electrode collector 5 and negative electrode active material.Employing makes this laminated body roll into 400 microns way, is made into the negative pole 4 that has formed negative electrode active material layer 6.
After being dipped into this negative pole 4 in the electrolyte, measure the peel strength between negative electrode active material layer 6 and the negative electrode collector 5, the value of this intensity is 5～10gf/cm.
(adjustment of bonding agent)
With mean molecule quantity (Mw) poly-(methyl methacrylate) (production of Aldric company) 3.0 weight portions of 350000, mean molecule quantity (Ww) is 534000 Kynoar (production of Aldric company) 2.0 weight portions, make it to mix with the proportion of composing of the NMP of 95 weight portions, stir fully to make it to become and be uniform solution, make sticking bonding agent.
(making of battery)
On a face separately of 2 porous acrylic sheets that use as spacer 7 (ヘ キ ス ト セ ラ ニ-ズ produces セ Le ガ-De #2400), coat adjusted bonding agent.Then, before the bonding agent drying, the above-mentioned positive pole of having made 1 be clipped between the spacer 7 make it to be adjacent to, make it to paste and 60 ℃ dry 2 hours down.By the way that NMP is evaporated, become film for porous matter with continuous hole from bonding agent.
The current collection joint on the end separately that is connected respectively to this tabular stromatolithic structure cell body, adopt to positive pole to each other, the negative pole way of carrying out spot welding to each other, above-mentioned tabular stromatolithic structure cell body is electrically connected in parallel.
At room temperature, should be dipped into 1.0mol/dm by flat board folding layer structure cell body
3Concentration in the mixed solvent (mol ratio is 1: 1) of ethylene carbonate and dimethyl carbonate, dissolved LiPF
6Solution in inject electrolyte.
Secondly, measure the peel strength (using the assay method by JIS K6854 regulation) of positive electrode active material layer 3 and spacer 7, negative electrode active material layer 6 and spacer 7, this intensity is respectively 25～30gf/cm, 15～20gf/cm.
Adopt with the encapsulation of aluminium lamination press mold and inject tabular stromatolithic structure cell body behind the electrolyte, it is bonding and carry out the way of sealing part reason to make it thermosol, finishes lithium rechargeable battery.
Only as follows the adjustment of the bonding agent of the foregoing description 1 change, making has tabular stromatolithic structure cell body shown in Figure 1.
(adjustment of bonding agent)
With mean molecule quantity (Mw) poly-(acrylonitrile) (production of Aldric company) 3.0 weight portions of 86200, mean molecule quantity (Ww) is 534000 Kynoar (production of Aldric company) 2.0 weight portions, make it to mix with the proportion of composing of the NMP of 95 weight portions, stir fully to make it to become and be uniform solution, make sticking bonding agent.
Only as follows the adjustment of the bonding agent of the foregoing description 1 change, making has tabular stromatolithic structure cell body shown in Figure 1.
(adjustment of bonding agent)
With mean molecule quantity (Mw) 180000 Kynoar (production of Aldric company) 2.5 weight portions, mean molecule quantity (Ww) is 534000 Kynoar (production of Aldric company) 2.5 weight portions, make it to mix with the proportion of composing of the NMP of 95 weight portions, stir fully to make it to become and be uniform solution, make sticking bonding agent.
Only as follows the adjustment of the bonding agent of the foregoing description 1 change, making has tabular stromatolithic structure cell body shown in Figure 1.
(adjustment of bonding agent)
With mean molecule quantity (Mw) 180000 Kynoar (production of Aldric company) 3.5 weight portions, mean molecule quantity (Ww) is 534000 Kynoar (production of Aldric company) 3.5 weight portions, make it to mix with the proportion of composing of the NMP of 93 weight portions, stir fully to make it to become and be uniform solution, make sticking bonding agent.
Only as follows the adjustment of the bonding agent of the foregoing description 1 change, making has tabular stromatolithic structure cell body shown in Figure 1.
(adjustment of bonding agent)
With mean molecule quantity (Mw) 180000 Kynoar (production of Aldric company) 5.0 weight portions, mean molecule quantity (Ww) is 534000 Kynoar (production of Aldric company) 5.0 weight portions, make it to mix with the proportion of composing of the NMP of 90 weight portions, stir fully to make it to become and be uniform solution, make sticking bonding agent.
As follows the change of the electrolyte in the manufacturing of the adjustment of the bonding agent of the foregoing description 1 and battery, all the other handle with embodiment 1 the samely, make to have tabular stromatolithic structure cell body shown in Figure 1.
(adjustment of bonding agent)
With mean molecule quantity (Mw) 180000 Kynoar (production of Aldric company) 2.5 weight portions, mean molecule quantity (Ww) is 534000 Kynoar (production of Aldric company) 2.5 weight portions, make it to mix with the proportion of composing of the NMP of 95 weight portions, stir fully to make it to become and be uniform solution, make sticking bonding agent.
(electrolyte)
With 1.0mol/dm
3Concentration in the mixed solvent (mol ratio is 1: 1) of ethylene carbonate (production of Northeast chemical company) and dimethyl carbonate (producing), dissolve LiPF with the pure medicine of light society
6(Tokyo changes into company and produces).
Only as follows the adjustment of the bonding agent of the foregoing description 6 change, making has tabular stromatolithic structure cell body shown in Figure 1.
(adjustment of bonding agent)
With mean molecule quantity (Mw) 180000 Kynoar (production of Aldric company) 3.5 weight portions, mean molecule quantity (Ww) is 534000 Kynoar (production of Aldric company) 3.5 weight portions, make it to mix with the proportion of composing of the NMP of 93 weight portions, stir fully to make it to become and be uniform solution, make sticking bonding agent.
Only as follows the adjustment of the bonding agent of the foregoing description 6 change, making has tabular stromatolithic structure cell body shown in Figure 1.
(adjustment of bonding agent)
With mean molecule quantity (Mw) 180000 Kynoar (production of Aldric company) 5.0 weight portions, mean molecule quantity (Ww) is 534000 Kynoar (production of Aldric company) 5.0 weight portions, make it to mix with the proportion of composing of the NMP of 90 weight portions, stir fully to make it to become and be uniform solution, make sticking bonding agent.
As follows the adjustment of the bonding agent of the foregoing description 1 change, the implantation temperature of the electrolyte in the manufacturing of battery is changed to 70 ℃, all the other handle with embodiment 1 the samely, make to have tabular stromatolithic structure cell body shown in Figure 1.
(adjustment of bonding agent)
With mean molecule quantity (Mw) 180000 Kynoar (production of Aldric company) 2.5 weight portions, mean molecule quantity (Ww) is 534000 Kynoar (production of Aldric company) 2.5 weight portions, make it to mix with the proportion of composing of the NMP of 95 weight portions, stir fully to make it to become and be uniform solution, make sticking bonding agent.
Only as follows the adjustment of the bonding agent of the foregoing description 1 change, all the other handle with embodiment 1 the samely, make to have tabular stromatolithic structure cell body shown in Figure 1.
(adjustment of bonding agent)
With mean molecule quantity (Mw) 22000 polyvinyl alcohol (production of Na カ ラ イ chemical company) 2.5 weight portions, mean molecule quantity (Ww) is 186000 polyvinyl alcohol (production of Aldric company) 2.5 weight portions, make it to mix with the proportion of composing of the NMP of 95 weight portions, stir fully to make it to become and be uniform solution, make sticking bonding agent.
Only as follows the adjustment of the bonding agent of the foregoing description 1 change, all the other handle with embodiment 1 the samely, make to have tabular stromatolithic structure cell body shown in Figure 1.
(adjustment of bonding agent)
With mean molecule quantity (Mw) 180000 Kynoar 1.5 weight portions, mean molecule quantity (Mw) is 22000 polyvinyl alcohol, 1.5 weight portions, mean molecule quantity (Ww) is 534000 Kynoar 2.5 weight portions, make it to mix with the proportion of composing of the NMP of 94.5 weight portions, stir fully to make it to become and be uniform solution, make sticking bonding agent.
With positive pole and the negative pole shown in the foregoing description 1,, make the lithium rechargeable battery with tabular stromatolithic structure cell body shown in Figure 2 with the bonding agent shown in the foregoing description 1～11.
(making of battery)
To (ヘ キ ス ト produces by acrylic sheet, trade name セ Le ガ-De #2400) adhesive-applying on the single face of each of 2 spacers 7 of the band shape of Gou Chenging, between the face after banded negative pole 4 (or anodal) is clipped in this coating and after being adjacent to stickup, put into 60 ℃ drying machine 2 hours, make the NMP evaporation.
On face with a side of the spacer 7 of negative pole 4 (or anodal) the articulate band shape that is clipped in the middle, coat bonding agent, make the amount of the end bending regulation of this spacer 7, anodal 1 (or negative pole) is clipped in crease in the middle of coincidence get up to feed in the laminating machine.Then, on the opposing party's of the spacer of above-mentioned band shape face, coat bonding agent, pasting other positive pole 1 (or negative pole) with the opposed position of the positive pole 1 (or negative pole) that before was clipped in the crease place, spacer 7 is rolled into oval shape, carry out the limit repeatedly and paste the operation of other positive pole 1 (or negative pole) limit coiling spacer 7, formation has the cell body of the battery stack body of multilayer, and the limit adds flanging to this cell body and carries out drying, is made into the such tabular volume type stromatolithic structure cell body of Fig. 2.
The way that employing connects the current collection joint spot welding on the end separately that is connected respectively to this tabular stromatolithic structure cell body is electrically connected above-mentioned tabular stromatolithic structure cell body in parallel.
This tabular stromatolithic structure cell body is being dipped into 1.0mol/dm
3Concentration in the mixed solvent (mol ratio is 1: 1) of ethylene carbonate and dimethyl carbonate, dissolved LiPF
6Electrolyte in after, enclose in the bag of making of the aluminium lamination press mold with the thermosol bonding method, make battery.
In the present embodiment, though what illustrate is the example of coiling spacer 7, but also can be to fold the negative pole 4 of band shape (or anodal 1) is joined to the spacer between the spacer 7, carry out pasting the operation of anodal 1 (or negative pole) edge contraction spacer repeatedly on one side.
Embodiment 13
With positive pole and the negative pole shown in the foregoing description 1,, make the lithium rechargeable battery with tabular stromatolithic structure cell body shown in Figure 3 with the bonding agent shown in the foregoing description 1～11.With the difference of the foregoing description 2 be reel simultaneously spacer, positive pole and negative pole this point.
(making of battery)
Banded negative pole 4 (or anodal) is configured in by acrylic sheet (ヘ キ ス ト production, trade name セ Le ガ-De #2400) between 2 spacers 7 of the band shape of Gou Chenging, and the outside that strip-shaped positive electrode 1 (or negative pole) is made it to give prominence to the spacer 7 that is configured in a side a certain amount ofly.On the lateral surface of the face of the inboard of each spacer 7 and anodal 1 (or negative pole) spacer 7 of configuration, coat bonding agent, make anodal 1 (or negative pole) and 2 spacers 7 and negative pole 4 (or anodal) coincidence get up to feed laminating machine, then, on the face in the outside of the opposing party's spacer 7, adhesive-applying, paste on this applicator surface after making positive pole 1 (or negative pole) bending that highlights, be wound into oval shape the positive pole after this bending 1 (or negative pole) bag being advanced inboard stacked like that spacer 7, formation has the cell body of the electrode laminate of multilayer, heating edge dry this cell body in limit is made tabular volume type stromatolithic structure cell body.
The way that employing connects the current collection joint spot welding on the end separately that is connected respectively to this tabular stromatolithic structure cell body is electrically connected above-mentioned tabular stromatolithic structure cell body in parallel.
This tabular stromatolithic structure cell body is being dipped into 1.0mol/dm
3Concentration in the mixed solvent (mol ratio is 1: 1) of ethylene carbonate and dimethyl carbonate, dissolved LiPF
6Electrolyte in after, enclose in the bag of making of the aluminium lamination press mold with the thermosol bonding method, make battery.
Comparative example 1
Only following change is carried out in the adjustment of the bonding agent of the foregoing description 1, made lithium rechargeable battery.
(adjustment of bonding agent)
With poly-(methyl methacrylate) (production of ALdrich company) 5.0 weight portions of mean molecule quantity (Mw) 350000, the composition ratio of NMP95 weight portion is mixed, and stirs feasible becoming fully and is uniform solution, makes sticking bonding agent.
Comparative example 2
Only following change is carried out in the adjustment of the bonding agent of the foregoing description 1, made lithium rechargeable battery.
(adjustment of bonding agent)
With poly-(acrylonitrile) (production of ALdrich company) 5.0 weight portions of mean molecule quantity (Mw) 86200, the composition ratio of NMP95 weight portion is mixed, and stirs feasible becoming fully and is uniform solution, makes sticking bonding agent.
Comparative example 3
Only following change is carried out in the adjustment of the bonding agent of the foregoing description 1, made lithium rechargeable battery.
(adjustment of bonding agent)
With Kynoar (production of ALdrich company) 5.0 weight portions of mean molecule quantity (Mw) 180000, the composition ratio of NMP95 weight portion is mixed, and stirs feasible becoming fully and is uniform solution, makes sticking bonding agent.
Comparative example 4
Only following change is carried out in the adjustment of the bonding agent of the foregoing description 1, made lithium rechargeable battery with tabular stromatolithic structure cell body shown in Figure 1.
(adjustment of bonding agent)
With Kynoar (production of ALdrich company) 7.0 weight portions of mean molecule quantity (Mw) 534000, the composition ratio of NMP93 weight portion is mixed, and stirs feasible becoming fully and is uniform solution, makes sticking bonding agent.
Comparative example 5
Use and the foregoing description 6 and 9 are with a kind of bonding agent, electrolyte implantation temperature in the making of the battery of embodiment 1 is changed to 100 ℃, all the other handle with embodiment 1 the samely, make the lithium rechargeable battery with tabular stromatolithic structure cell body shown in Figure 1.
Characteristic to the lithium rechargeable battery that obtains in embodiment 1～11 and comparative example 1～5 is estimated.Table 1 is with the adhesive strength (peel strength) of positive active material and spacer and negative electrode active material and spacer, shows the measurement result of resistance of element cell of the various batteries of the foregoing description 1～11 and comparative example 1～5.Fig. 5 shows (200% charging) result of the test of overcharging, and Fig. 6 shows over-discharge test results, (A) expression charge characteristic, (B) expression flash-over characteristic among the figure.No matter though which illustrated all is the lithium rechargeable battery of the foregoing description 6～8, even if in other embodiment, also can obtain same result.
Table 1
| Peel strength (gf/cm) | Cell resistance (Ω) | ||
| Positive pole/spacer | Negative pole/ | ||
| Embodiment | |||
| 1 | 17 | 12 | 24 |
| | 15 | 14 | 23 |
| | 20 | 13 | 21 |
| | 22 | 33 | 25 |
| | 21 | 52 | 30 |
| | 25 | 15 | 20 |
| | 24 | 29 | 22 |
| | 28 | 44 | 28 |
| | 26 | 16 | 20 |
| | 20 | 12 | 21 |
| | 23 | 14 | 27 |
| Comparative example 1 | 0 (can not measure) | 0 (can not measure) | Can not measure |
| Comparative example 2 | 0 (can not measure) | 0 (can not measure) | Can not measure |
| Comparative example 3 | 0 (can not measure) | 0 (can not measure) | Can not measure |
| Comparative example 4 | 52 | 61 | 150 |
| Comparative example 5 | 0 (can not measure) | 0 (can not measure) | Can not measure |
By the result of above-mentioned table 1 as can be known, the lithium rechargeable battery of comparative example 1～3, peel strength is bordering on 0, and its value can not be measured.No matter which all is by means of the electrolyte swelling owing to the bonding agent that uses in comparative example 1～3, the bonding agent that constitutes mutually by electrolyte and the high-molecular gel that contains this electrolyte, though so be considered to the ionic conductivity height, but can not guarantee adhesive strength, and owing to peel off so resistance is big between electrode, it is difficult measuring.
In addition, the lithium rechargeable battery of comparative example 4, although demonstrate big peel strength value,, because ionic conductivity is low, element cell resistance uprises.
The lithium rechargeable battery of comparative example 5, peel strength is bordering on 0, is not measurable value, and the resistance of battery is also big, can not measure.Though the composition of the bonding agent that uses in this comparative example 5 is identical with embodiment 6 and 9, but because the implantation temperature of electrolyte is up to 100 ℃, so at the macromolecule of not swelling of low temperature also with swelling, the same with comparative example 1～3 finally, though think that ionic conductivity can uprise, and can not guarantee adhesive strength.
On the other hand, the lithium rechargeable battery of embodiment 1～11, cell resistance are 20～30 Ω, and peel strength is 12～52gf/cm, and ionic conductivity and adhesive strength two sides are guaranteed.In embodiment 1～11, become contain electrolyte high-molecular gel mutually and the mixed phase of macromolecule solid phase, guarantee ionic conductivity mutually by means of the high-molecular gel that contains electrolyte, guarantee adhesive strength by means of the macromolecule solid phase.
In addition, in the use of battery, taken place unusual for a certain reason and under the situation about heating up, swelling will take place because of electrolyte in the macromolecule solid phase, and the result cuts off electric current because of peeling off between electrode and the spacer, is desirable from guaranteeing the fail safe this point.
Have, the flash-over characteristic (curve (B)) after as shown in Figure 5, overcharge (curve (A)) demonstrates good characteristic again, and in addition, as shown in Figure 6, the charge characteristic (curve (A)) after the overdischarge (curve (B)) also demonstrates good characteristic.
The possibility of industrial utilization
The secondary cell of the portable electronic machine of portable personal computer, cell-phone etc. can be used as, when improving the performance of battery, miniaturization, lightweight and arbitrary shape can also be realized.
Claims (12)
1. lithium rechargeable battery is characterized in that:
Possess multilayer laminate, this laminated body use by the electrolysis liquid phase, contain electrolyte high-molecular gel mutually and the adhesive resin layer that constitutes of the mixed phase of macromolecule solid phase, positive pole and negative pole are joined on the barrier film that maintains electrolyte,
Wherein, described high-molecular gel is not dissolved in electrolyte mutually, does not react in lithium rechargeable battery, becomes gel phase under the situation that electrolyte exists;
Described macromolecule solid phase is not dissolved in electrolyte, does not react in lithium rechargeable battery, becomes solid phase under the situation that electrolyte exists.
2. the described lithium rechargeable battery of claim 1 is characterized in that: described positive pole and negative pole alternatively are configured in and cut off between a plurality of barrier films that come.
3. the described lithium rechargeable battery of claim 1, it is characterized in that: described positive pole and negative pole alternatively are configured between the barrier film that winds up.
4. the described lithium rechargeable battery of claim 1, it is characterized in that: described positive pole and negative pole alternatively are configured between the barrier film of folding up.
5. the described lithium rechargeable battery of claim 1, it is characterized in that: high-molecular gel mutually and the macromolecule solid phase contain the macromolecular material of of the same race or xenogenesis, the mean molecule quantity of the macromolecular material that the mean molecule quantity of the macromolecular material that above-mentioned high-molecular gel is mutually contained and above-mentioned macromolecule solid phase are contained is different.
6. the described lithium rechargeable battery of claim 1, it is characterized in that: high-molecular gel mutually and the macromolecule solid phase contain Kynoar, the mean molecule quantity of the Kynoar that the mean molecule quantity of the Kynoar that above-mentioned high-molecular gel is mutually contained and above-mentioned macromolecule solid phase are contained is different.
7. the described lithium rechargeable battery of claim 1, it is characterized in that: high-molecular gel mutually and the macromolecule solid phase contain polyvinyl alcohol, the mean molecule quantity of the polyvinyl alcohol that the mean molecule quantity of the polyvinyl alcohol that above-mentioned high-molecular gel is mutually contained and above-mentioned macromolecule solid phase are contained is different.
8. the described lithium rechargeable battery of claim 1, it is characterized in that: the mean molecule quantity of the macromolecular material that above-mentioned high-molecular gel is mutually contained is less than the mean molecule quantity of the contained macromolecular material of above-mentioned macromolecule solid phase.
9. the described lithium rechargeable battery of claim 8 is characterized in that: above-mentioned high-molecular gel mutually and above-mentioned macromolecule solid phase comprise the macromolecular material of identical type.
10. the described lithium rechargeable battery of claim 1, it is characterized in that: high-molecular gel phase and macromolecule solid phase contain Kynoar, and the mean molecule quantity of the Kynoar that above-mentioned high-molecular gel is mutually contained is less than the mean molecule quantity of the contained Kynoar of above-mentioned macromolecule solid phase.
11. the manufacture method of a lithium rechargeable battery, described lithium rechargeable battery has the laminated body that makes positive pole and negative pole join the multilayer on the barrier film that maintains electrolyte to, it is characterized in that comprising the following steps: that coating is dissolved into the bonding agent that constitutes in the solvent by the different multiple macromolecular material of mean molecule quantity on the relative face of barrier film, having formed by the adhesive resin layer makes positive pole and negative pole alternatively join cell body between the barrier film of multilayer to, this cell body be impregnated in the electrolyte, above-mentioned adhesive resin layer is become to containing the high-molecular gel phase of electrolyte, the mixed phase of macromolecule solid phase and electrolyte layer.
12. the manufacture method of the described lithium rechargeable battery of claim 11, it is characterized in that: described dipping operation comprises the step of a heating battery body, so that in described adhesive resin layer, make macromolecular material form the high-molecular gel phase, and make macromolecular material form the macromolecule solid phase with big mean molecule quantity with less mean molecule quantity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB971817111A CN1214480C (en) | 1997-12-22 | 1997-12-22 | Lithium ion secondary battery and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB971817111A CN1214480C (en) | 1997-12-22 | 1997-12-22 | Lithium ion secondary battery and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1245592A CN1245592A (en) | 2000-02-23 |
| CN1214480C true CN1214480C (en) | 2005-08-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB971817111A Expired - Fee Related CN1214480C (en) | 1997-12-22 | 1997-12-22 | Lithium ion secondary battery and its manufacture |
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|---|---|
| CN (1) | CN1214480C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320682C (en) * | 2002-03-08 | 2007-06-06 | 居永明 | Repeatedly chargeable-dischargeable lithium ion power cell and its production method |
| JP4087343B2 (en) * | 2004-02-25 | 2008-05-21 | Ｔｄｋ株式会社 | Lithium ion secondary battery and method for charging lithium ion secondary battery |
| JP6044083B2 (en) * | 2011-06-21 | 2016-12-14 | 日産自動車株式会社 | Multilayer battery and manufacturing method thereof |
| DE112015003717T5 (en) * | 2014-08-11 | 2017-05-04 | Gs Yuasa International Ltd. | Positive electrode plate for nonaqueous electrolyte energy storage device, and nonaqueous electrolyte energy storage device |
| CN108461820B (en) * | 2018-02-08 | 2024-01-19 | 宜昌力佳科技有限公司 | High-current lithium-manganese button cell and preparation method thereof |
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1997
- 1997-12-22 CN CNB971817111A patent/CN1214480C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1245592A (en) | 2000-02-23 |
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