CN101252209A - Lithium secondary battery with a laminate housing material - Google Patents
Lithium secondary battery with a laminate housing material Download PDFInfo
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- CN101252209A CN101252209A CNA2008100810624A CN200810081062A CN101252209A CN 101252209 A CN101252209 A CN 101252209A CN A2008100810624 A CNA2008100810624 A CN A2008100810624A CN 200810081062 A CN200810081062 A CN 200810081062A CN 101252209 A CN101252209 A CN 101252209A
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- inorganic particulate
- absorbing sheet
- absorption function
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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
The invention provides a lithium secondary battery with excellent productivity, wherein deterioration of the housing material due to penetration of moisture into the inside of the battery and hydrogen fluoride generating inside the battery are prevented. A lithium secondary battery wherein a power generating element comprising a positive electrode material layer, a negative electrode material layer and a layer having a lithium salt electrolyte is sealed in a housing composed of a laminate housing material comprising a metallic layer and a synthetic resin layer, characterized in that an absorption sheet is sealed along with the power generating element in the housing, wherein the absorption sheet comprises an absorption layer composed of at least one resin layer containing inorganic particles having an acid absorption function and inorganic particles having a water absorption function, said absorption layer containing at least 5 parts by weight of a total of the inorganic particles having acid absorption function and the inorganic particles having water absorption function relative to 100 parts by weight of the resin.
Description
Technical field
The present invention relates to a kind of power supply that is applied to e-machine, be equipped on power supply on the electric automobile, utilize the lithium rechargeable batteries of the electric power storage purposes that fuel cell or solar cell etc. discharge.In more detail, the present invention relates to a kind of lithium rechargeable batteries that uses durability, fail safe and the excellent in workability of laminate housing material.
Background technology
As the case material of enclosed-type battery, be to use metallic plates such as corrosion resistant plate in the past.But, so metallic plates such as corrosion resistant plate because rigidity is not suitable for being processed into thin flat by force, so in addition because its than great when being used in thin battery, the energy density of the per unit weight of battery decline.
Therefore, use the laminate housing material that metal forming and resin molding are fitted to make thin battery in recent years.Laminate housing material is compared lighter more soft with corrosion resistant plate, therefore be fit to be processed into thin flat, and then can seal, so have easy feature with the battery closure.But it is higher that lamination outsourcing material and corrosion resistant plate are compared poisture-penetrability, and in addition, heat seal lands has the high problem of poisture-penetrability.
If the poisture-penetrability height, then being present in airborne moisture can invade inside battery lentamente, and the lithium salts electrolyte can react and hydrolysis with moisture in lithium rechargeable batteries, and produces hydrogen fluoride.Deterioration takes place on the heat seal lands of laminate housing material or the metal film in its result.More easily invade inside battery owing to this deterioration causes airborne moisture, thereby promote above-mentioned deterioration, finally leakage takes place and battery life is exhausted.
For extending battery life, must prevent the water intrusion inside battery as much as possible.Therefore, known have a kind ofly simultaneously cell device and hygroscopic material are contained in the shell of synthetic resin, again that shell is airtight fully, invade from the outside to prevent air or moisture, even and have moisture to invade also the lithium rechargeable batteries (for example, patent documentation 1) that can be absorbed by hygroscopic material.In this battery, the material that can remove only limits to moisture, does not remove hydrogen fluoride.Therefore, do not existed by the moisture of moisture absorption, then produce hydrogen fluoride, cause the deterioration of housing material with the reaction of lithium salts electrolyte if having.In addition, above-mentioned hygroscopic material is to be the sheet that the hygroscopic agent powder-stuck is formed with binding agent, therefore exist the hygroscopic agent powder inside battery from the hygroscopic material surface or end face come off and produce the possibility of defective at arresting elements such as electrode, barrier films.In addition, because the moisture pick-up properties of hygroscopic material is high, so the unusual problem of difficulty of the operation that also is present in hygroscopic material in the manufacturing step of hygroscopic material or lithium rechargeable batteries.
In addition, the known plastic layer that has a kind of inclosure that electrolyte side electrolyte etc., that make the outer packaging bag that comprises metal level and plastic layer is arranged has anti-sealing and sees through function and prevent that acid from seeing through the lithium rechargeable batteries (for example, patent documentation 2) of function.In the case, if form outer packaging bag, then can produce and prevent to see through the more weak part of ability by mold pressing processing.In addition, see through function and prevent that acid from seeing through function in order to make it have the moisture of preventing, and in plastic layer, be mixed into particles of absorbent materials, so on outer packaging bag, can produce defective.Therefore, can't be applied to purposes with the battery of above-mentioned mold pressing processing.
In addition, known have a kind of in the laminate housing body that is constituted by metallic film and heat sealability resin molding, interlayer at its sealing sandwiches hygroscopic agent, utilizes heat-sealing again and with the lithium rechargeable batteries (for example, patent documentation 3) that seals around the above-mentioned hygroscopic agent.In the case, the processing that hygroscopic agent is sandwiched laminating seal portion is comparatively difficult, in addition the then weakened of sealing.In order to keep the then intensity of sealing, must strengthen the area of sealing, thereby cause the use amount increase of laminate housing material or the problem on the battery size.In addition, this battery does not have sour absorbability, therefore can't suppress because the deterioration of the external packing body that hydrofluoric generation caused.
[patent documentation 1] Japan Patent spy opens the 2000-243357 communique
No. 3137061 specification of [patent documentation 2] Japan Patent
[patent documentation 3] Japan Patent spy opens the 2003-187762 communique
Summary of the invention
The present invention forms in order to address the above problem, and its objective is that providing a kind of prevents that moisture from invading inside battery or because the housing material deterioration that hydrogen fluoride caused that can produce in inside battery, and the lithium rechargeable batteries of excellent in workability.
Present inventors find, in the lithium rechargeable batteries of arresting element being enclosed in the laminate housing body, absorbing sheet and arresting element are enclosed in addition in the package body simultaneously, and this absorbing sheet has the absorbed layer by resin bed constituted more than 1 layer, the inorganic particulate that contains the inorganic particulate with sour absorption function and have the water absorption function in this resin bed can be realized above-mentioned purpose thus.
That is, the present invention relates to a kind of lithium rechargeable batteries, it is in by the external packing body that laminate housing material constituted that comprises metal level and synthetic resin layer, and enclosing has the arresting element that contains positive electrode material layer and negative electrode material layer and have the electrolytical layer of lithium salts; It is characterized in that: this arresting element and absorbing sheet are enclosed in addition in the package body simultaneously, this absorbing sheet has the absorbed layer by resin bed constituted more than 1 layer, contain inorganic particulate in this resin bed and have the inorganic particulate of water absorption function with sour absorption function, this absorbed layer adds up to the above-mentioned inorganic particulate that has the inorganic particulate of sour absorption function and have the water absorption function that contains at least 5 weight portions with respect to resin 100 weight portions.
Among the present invention, because absorbing sheet has sour absorption function and water absorption function, so by it being contained in lithium rechargeable batteries inside, can absorb effectively the moisture of being sneaked into when making lithium rechargeable batteries, because hydrogen fluoride that the moisture of sneaking into produces and the moisture of invading from the sealing of external packing body, because the hydrogen fluoride that the moisture of invading produces, and avoid moisture and hydrogen fluoride to the influence of arresting element, reach the adherence reduction in the sealing of external packing body.Therefore, can suppress the heating of the deterioration of external packing body or battery and on fire, thereby the lithium rechargeable batteries of durability and excellent in safety can be provided.In addition, because housing material does not contain the particle with sour absorption function and has the particle of water absorption function, so can suitably be shaped by mold pressing processing yet.Therefore, the processability of lithium rechargeable batteries of the present invention is also excellent.
Description of drawings
Fig. 1 is the profile of an example of just (bearing) pole plate of expression lithium rechargeable batteries of the present invention.
Fig. 2 is the profile of an example of the arresting element of expression lithium rechargeable batteries of the present invention.
Fig. 3 is the plane graph of an example of expression lithium rechargeable batteries of the present invention.
Fig. 4 is the plane graph of an example of expression lithium rechargeable batteries of the present invention.
Fig. 5 is the profile of an example of expression absorbing sheet of the present invention.
Fig. 6 is the oblique view of an example of expression absorbing sheet of the present invention.
Fig. 7 is the oblique view of an example of the application of expression absorbing sheet of the present invention.
Fig. 8 is the oblique view of an example of the application of expression absorbing sheet of the present invention.
Fig. 9 is the profile of an example of expression lithium rechargeable batteries of the present invention.
Figure 10 is the profile of an example of expression lithium rechargeable batteries of the present invention.
Figure 11 is the profile of an example of expression lithium rechargeable batteries of the present invention.
Figure 12 is the profile of an example of expression lithium rechargeable batteries of the present invention.
Figure 13 is the profile of an example of expression lithium rechargeable batteries of the present invention.
Figure 14 is test film is made in expression according to the making 1 of the test film that does not have the resin bed that does not contain inorganic particulate a oblique view.
Figure 15 is test film is made in expression according to the making 2 of the test film that does not have the resin bed that does not contain inorganic particulate a oblique view.
Figure 16 is test film is made in expression according to the making 1 of the test film with the resin bed that does not contain inorganic particulate a oblique view.
Figure 17 is test film is made in expression according to the making 2 of the test film with the resin bed that does not contain inorganic particulate a oblique view.
[explanation of symbol]
1 positive electrode
2 negative materials
3 positive electrode collectors
4 negative electrode collectors
5 positive plates
6 negative plates
7 contain electrolytical layer
8 arresting elements
9 laminate housing materials
9a is through the laminate housing material of mold pressing processing
10 mouth-sealed portions
11 follow film
12 positive terminals
13 negative terminals
14 absorbing sheets
15 do not contain the resin bed of inorganic particulate
16 absorbed layers
The laminate of 17 absorbing sheets and barrier film
Embodiment
Below, according to diagram lithium rechargeable batteries of the present invention is elaborated.Lithium rechargeable batteries of the present invention is arresting element is enclosed in addition in the package body and to be formed, and the external packing body is made of the laminate housing material that comprises metal level and synthetic resin layer.An example of the plane graph of expression lithium rechargeable batteries of the present invention among Fig. 3 and 4.Among Fig. 3 and 4,9 is laminate housing material, and mouth-sealed portion 10 places around it carry out welding and form the external packing body.Laminate housing material 9 comprises metal level and synthetic resin layer, for example, laminate housing material 9 can have the structure of successively nylon membrane, aluminium foil and polyolefin film being fitted, and polyolefin film is fused to the inboard of external packing body or utilizes solid to seal and forms the external packing body.As polyolefin film, for example can use: polypropylene screen, polyethylene film, modified poly ethylene film etc.
Between laminate housing material and positive terminal and negative terminal, can insert the then film 11 that is used to prevent the extraneous gas intrusion.Then film can the material of property constitutes by having then to positive terminal and negative terminal, for example polyolefin such as polyethylene, polypropylene, modified poly ethylene or modified polypropene.
As shape, for example can suitably adopt bag type and mold pressing type by the formed external packing body of laminate housing material.The bag type is that laminate housing material is formed a bag shape, arresting element is contained in the above-mentioned bag again and forms.As the manufacture method of bag type, following several mode is arranged then: 4 limits of 2 lamination housing materials are sealed and make the mode of pouch; The laminate housing material of rectangle is overlapped relative limit along the center line doubling again, only will 2 limits vertical seal or above-mentioned 2 limits and center line sealed and make pouch with center line, insert arresting element, the mode that peristome is sealed again from peristome then; And, the laminate housing material with rectangle does not fold and this 1 group of relative edge is sealed, in the above-mentioned hot compact part mode relative with the center line of above-mentioned housing material, above-mentioned housing material is folded, one in 2 peristomes is sealed, make pouch thus, insert arresting element from peristome then, and the mode that peristome is sealed etc.In addition, the mold pressing type is to obtain in the following manner: utilize forcing press and mould that the sealant layer side of laminate housing material is processed into concavity (mold pressing processing), arresting element is contained in this recess, and the laminate housing material with other superposes in the above again.Above-mentioned other laminate housing material can form recess and also can not form recess.In addition, also has following mode: use the laminate housing material of 1 rectangle, form recess at one-sided demifacet, perhaps form recess respectively and carry out using after the doubling along center line in the both sides of center line from its center line.
Arresting element among the present invention is a common employed arresting element in the lithium rechargeable batteries, wherein comprises positive electrode material layer, negative electrode material layer and has the electrolytical layer of lithium salts.Positive electrode material layer and negative electrode material layer, for example shown in Figure 1, be formed at respectively on collector body 3 and 4, constitute positive plate 5 and negative plate 6 respectively.Positive plate 5 and negative plate 6, for example shown in Figure 2, be to serve as to be situated between every carrying out lamination, thereby constitute arresting element 8 to contain the electrolytical layer of lithium salts 7.
Positive electrode and negative material can contain electrode active material and conductive auxiliary agent or resin etc. separately simultaneously.As conductive auxiliary agent, for example can enumerate: graphite, carbon black, carbon fiber, and metal such as nickel, aluminium, copper, silver.In addition, as resin, for example can enumerate: fluororesin, fluorubber etc.
As positive active material, can use: cobalt acid lithium (LiCoO
2), lithium nickelate (LiNiO
2) and LiMn2O4 (LiMnO
2) the lithium transition metal composite oxides that wait.In addition, in order to improve the conductivity of these positive active materials, be preferably the carbon dust that further is mixed into acetylene black or powdered graphite etc.As negative electrode active material, can use: the noncrystalline of soft carbon or hard carbon etc. is the carbonaceous powder of carbonaceous material or native graphite etc.
On positive plate 5 and the negative plate 6, coating positive electrode 1 and negative material 2 and form lamellar on positive electrode collector 3 and negative electrode collector 4 respectively.As the material that is fit to be used in each collector body, for example, can enumerate aluminium foil as positive electrode collector, can enumerate steel foil as negative electrode collector.
The mode that does not directly contact with positive plate and negative plate, with contain electrolytical layer 7 serve as be situated between every and arresting element is reeled or lamination.As containing electrolytical layer 7, typically use: make the layer that the aqueous or gelatinous lithium salts electrolyte of impregnation forms in the barrier film that is made of the porous resin film.As barrier film, for example use: porous matter and have the polyethylene system barrier film of lithium ion permeability or porous matter polypropylene and the porous matter polyethylene lamination structure barrier film that forms of lamination in addition.Under the situation that electrode material or battery lead plate reach a high temperature, barrier film can take place softening and lose porousness, has therefore that can to suppress the mobile of lithium ion be the security mechanism of cell reaction concurrently.
Aqueous electrolyte (electrolyte) is by the lithium salts electrolyte dissolution is obtained in non-water solvent.Gelatinous electrolyte is to obtain by above-mentioned aqueous electrolyte is remained in the macromolecular compound.
As above-mentioned non-water solvent, for example can use: carbonates such as ethylene carbonate ester (ethylene carbonate), propylene glycol carbonate (propylene carbonate), carbonic acid butanediol ester, dimethyl carbonate, diethyl carbonate, carbonic acid ethyl methyl esters; Cyclic ethers such as oxolane, 2-methyltetrahydrofuran; 1, cyclic ethers such as 3-dioxolanes, 4-methyl dioxolanes; Lactones such as gamma-butyrolacton; Sulfolane etc.Also can use: 3-methyl sulfolane, dimethoxy-ethane, diethoxyethane, ethyoxyl methoxy base ethane, diethylene glycol diethyl ether (ethyldiglyme) etc.
As electrolyte, if be dissolved in the non-water solvent and generate the electrolyte of lithium ion, then can use electrolyte arbitrarily, both can use a kind separately, also can mix more than 2 kinds and use.For example: lithium hexafluoro phosphate (LiPF
6), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), lithium perchlorate (LiClO
4), trifluoromethanesulfonic acid lithium (LiCF
3SO
3), two (trifyl) imines lithium (LiN (SO
2CF
3)
2), three (trifyl) lithium methide (LiC (SO
2CF
3)
3), tetrachloro-lithium aluminate (LiAlCl
4) or hexafluorosilicic acid lithium (LiSiF
6) etc.
As the macromolecular compound that can be used for gel-like electrolyte, for example can enumerate: the fluorine such as copolymer of Kynoar or vinylidene and hexafluoropropylene are macromolecular compound; Poly(ethylene oxide) or the ethers such as crosslinked body that contain poly(ethylene oxide) are macromolecular compound; Perhaps polyacrylonitrile etc.
In the lithium rechargeable batteries of the present invention, arresting element and absorbing sheet are enclosed in the external packing body simultaneously.Above-mentioned absorbing sheet has by the absorbed layer that resin bed constituted more than 1 layer, contains the inorganic particulate with sour absorption function in the resin bed and has the inorganic particulate of water absorption function.Above-mentioned absorbed layer, can be constituted by the single resin bed that contains inorganic particulate and have an inorganic particulate of water absorption function, perhaps also can be constituted by resin bed that contains inorganic particulate and the laminate that the resin bed that contains the inorganic particulate with water absorption function forms with sour absorption function with sour absorption function.In addition, above-mentioned absorbed layer with respect to resin 100 weight portions, adds up to the above-mentioned inorganic particulate that has the inorganic particulate of sour absorption function and have the water absorption function that contains at least 5 weight portions.The total amount of above-mentioned inorganic particulate with respect to resin 100 weight portions, is preferably smaller or equal to 200 weight portions, more preferably 10～150 weight portions.If the total amount of above-mentioned inorganic particulate then can't obtain sufficient absorption function less than above-mentioned lower limit; If the total amount of above-mentioned inorganic particulate is too much, the situation that then exists the film formability to descend.In addition, the above-mentioned inorganic particulate that has the inorganic particulate of sour absorption function and have the water absorbability, as described below, can there be the situation of the inorganic particulate that is respectively different and has the situation of the same inorganic particulate of two kinds of absorption functions.In the previous case, have the inorganic particulate of sour absorption function and have the amount separately of the inorganic particulate of water absorption function, with respect to resin 100 weight portions, be preferably more than and equal 2.5 weight portions, more preferably more than or equal to 5 weight portions.
As inorganic particulate with water absorption function, if having the material of moisture-absorption characteristics, then can use material arbitrarily, preferably cause less material such as change in volume and state variation owing to moisture absorption; For example can enumerate: metal oxide, zeolite, calcined hydrotalcite, hydrotalcite oxide, magnesium sulfate (0～3 hydrate), phosphorus pentoxide, calcium chloride etc.Preferable alloy oxide, zeolite, calcined hydrotalcite, hydrotalcite oxide and magnesium sulfate (0～3 hydrate), more preferably zeolite, calcined hydrotalcite, hydrotalcite oxide and magnesium sulfate (0～3 hydrate).Inorganic particulate with water absorbability can use a kind separately, also multiple mixing can be used in addition.
As above-mentioned material, be preferably and using through under the state that dehydrates below the decomposition temperature of each material with moisture-absorption characteristics.In addition, the moisture absorption of hydrotalcite is lower, but with its in calcine the calcined hydrotalcite that forms below 300 ℃, in calcining the hydrotalcite oxide that forms more than 300 ℃, be dewatering state, moisture absorption increases, and therefore is suitable as drier.
As inorganic particulate, can enumerate: metal carbonated, zeolite, hydrotalcite, calcined hydrotalcite, hydrotalcite oxide with sour absorption function; Preferred zeolite, hydrotalcite, calcined hydrotalcite, hydrotalcite oxide.Inorganic particulate with sour absorbability can use a kind separately, also multiple mixing can be used in addition.
As employed resin in the absorbed layer, if the resin of being invaded by electrolyte then can use resin arbitrarily easily, but the copolymer of the copolymer of preferably polyethylene, polypropylene, polymethylpentene, ethene and butylene, ethene and propylene, ionomer, modified poly ethylene, modified polypropene, vinyl-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer.Above-mentioned resin can use a kind of resin separately, also various kinds of resin can be mixed in addition and use.
In the absorbing sheet, be preferably on the two sides of absorbed layer and have the resin bed that does not contain inorganic particulate.In addition, in the manufacturing of resin, use a spot of inorganic particulate usually as additives such as nertralizer, stabilizer, anticaking agent, nucleators.Therefore, the inorganic particulate in above-mentioned " resin bed that does not contain inorganic particulate " is with except the inorganic particulate of the additive that can unavoidably contain.As the use amount of the inorganic particulate of above-mentioned additive,, be about 0.01～0.5 weight portion usually with respect to resin 100 weight portions.But, in preferred implementation of the present invention,, be to use the resin that does not contain or contain hardly inorganic particulate fully as the resin that does not contain above-mentioned inorganic particulate.
By having the resin bed that does not contain above-mentioned inorganic particulate, can suppress because the inorganic particulate in the absorbed layer and have the disengaging of the inorganic particulate of water absorption function, the pollution of the lithium rechargeable batteries inside that is caused or the breakage of arresting element with sour absorption function.In addition, because the infiltration rate of acid and water is suppressed, so when making absorbing sheet and when making lithium rechargeable batteries, the operation of absorbing sheet is more or less freely.For example shown in Figure 5, absorbing sheet has and will not contain the structure of resin bed 15 laminations on the two sides of absorbed layer 16 of inorganic particulate.Perhaps, as shown in Figure 6, the also available resin bed 15 that does not contain inorganic particulate is coated the integral body of absorbed layer 16.By coating, can further suppress the pollution in the above-mentioned lithium rechargeable batteries, the operation of absorbing sheet is become be more prone to.
As the resin in the resin bed that does not contain above-mentioned inorganic particulate, if be difficult to the resin of being invaded by electrolyte, then can use resin arbitrarily, but preferred thermoplastic resin, the especially copolymer of the copolymer of preferably polyethylene, polypropylene, polymethylpentene, ethene and butylene, ethene and propylene, ionomer, modified poly ethylene, modified polypropene, vinyl-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer.Above-mentioned resin can use a kind of resin separately, also various kinds of resin can be mixed in addition and use.
The thickness of absorbing sheet, be according to the inorganic particulate with sour absorption function and have the water absorption function inorganic particulate mixed volume and wish to keep time of absorbing sheet function and suitably decision.If it is blocked up not contain the thickness of resin bed of inorganic particulate, then the infiltration rate of absorbed layer can become extremely slow, if thickness is thin excessively, then the infiltration rate of absorbed layer can become too fast, makes the operation of absorbing sheet become difficulty.In addition, also must consider the influence of absorber thickness to the thickness of lithium rechargeable batteries.The thickness of absorbed layer is preferably 10～1000 μ m, and the thickness that does not contain the resin bed of inorganic particulate is preferably 1～100 μ m respectively.Thick 20～100 μ m more preferably of absorbed layer do not contain thickness 2～20 μ m more preferably of the resin bed of inorganic particulate.
Inorganic particulate and the particle diameter with inorganic particulate of water absorption function with sour absorption function are if for reaching the particle diameter of expectation thickness, then can adopt particle diameter arbitrarily, but be preferably 0.01～100 μ m, more preferably 0.1～30 μ m.
The allocation position of the absorbing sheet in the lithium rechargeable batteries of the present invention is not if the inside of package body then has special restriction outside.For example, as shown in Figure 7, be preferably the mode of clamping arresting element 8 and dispose 2 absorbing sheets 14, but also can only dispose 1 absorbing sheet 14 in any side with absorbing sheet 14.In addition, as shown in Figure 8, also absorbing sheet 14 can be processed into tubular, and use in the mode of interior bag arresting element 8.The profile of the example of the allocation position of absorbing sheet when the inside of external packing bodies is enclosed with absorbing sheet 14 in Fig. 9～11st, expression.Fig. 9 is the example that is configured in the mode of clamping arresting element 8.As shown in figure 10, also absorbing sheet 14 can be disposed at positive terminal 12 or negative terminal 13 export to the laminate housing external body part near.In addition, as shown in figure 11, also can be the configuration among Fig. 9 and the combination of the configuration among Figure 10.
When absorbing sheet 14 is disposed at external packing body inside, be preferably the mouth-sealed portion 10 that also absorbing sheet 14 is disposed at the laminate housing body.In the case, absorbing sheet is disposed at least a portion of mouth-sealed portion, is more preferably and is disposed at mouth-sealed portion on the whole.Its example of expression among Figure 12 and 13.As shown in figure 12, can on 1 mouth-sealed portion, use 1 absorbing sheet, as shown in figure 13, also can on 1 mouth-sealed portion, use 2 absorbing sheets.Also dispose absorbing sheet by the mouth-sealed portion of package body outside, can reduce the amount of moisture of invading efficiently, can avoid hydrogen fluoride for a long time the influence of arresting element, and the then decline of property of mouth-sealed portion from mouth-sealed portion.
Absorbing sheet among the present invention also utilizes radioactive ray to make the resin of absorbed layer produce crosslinked and absorbing sheet that form.As radioactive ray, preferably use electron beam, gamma-rays.By making resin crosslinks, and improve thermal endurance,, also can keep the inorganic particulate that has the inorganic particulate of sour absorption function and have the water absorption function safely even when the temperature of lithium rechargeable batteries reaches a high temperature.
In addition, absorbing sheet of the present invention also can carry out the embossing processing to its two sides or any one side.Utilizing embossing to handle increases surface area, can accelerate the infiltration rate to hydrogen fluoride and moisture of inside battery thus.In addition, absorbing sheet is being disposed under the situation of mouth-sealed portion, is utilizing embossing to handle and the convex-concave structure of formation, when carrying out thermal welding with housing material, bring into play the outlet effect of existing air or electrolyte etc. in the thermal welding portion, therefore can reduce the bad generation of following of weld portion.
Absorbing sheet among the present invention also can have adhering agent layer or adhesion agent layer on its two sides or any one side.By having adhering agent layer or adhesion agent layer, can utilize sticker that absorbing sheet is attached on the laminate housing material and make lithium rechargeable batteries, so the allocation position of absorbing sheet can be fixed, therefore, can prevent departing from of in the manufacturing step of lithium rechargeable batteries absorbing sheet position.
Absorbing sheet of the present invention, can make by the following method: use the extruder of single shaft, two, four etc. or pressurization kneader, class clap in mixer well-known mixers such as (Banbury Mixer), to have the inorganic particulate of sour absorption function, inorganic particulate and resin and carry out melting mixing and make particle again with water absorption function, with the gained pellet supply to membrane formation devices such as T mould extrusion forming device or expansion-molded device.In addition, by employed extruder in the granulating directly is connected with membrane formation device or connects through gear pump, then also can not carry out forming absorbing sheet under the granular situation.
On the two sides of the absorbed layer of absorbing sheet, have under the situation of the resin bed that does not contain inorganic particulate, the above-mentioned resin that obtains particle and the resin bed that is used for not containing inorganic particulate is supplied to multilayer membrane formation devices such as multilayer T mould extrusion forming device or the expansion-molded device of multilayer simultaneously, the resin bed lamination that do not contain inorganic particulate on the two sides of absorbed layer, can be made absorbing sheet thus.In addition, by employed extruder or mixing roll in the granulating directly are connected or connect through gear pump with the multilayer membrane formation device, can not carry out forming absorbing sheet under the granular situation.In addition, if the absorbing sheet that will obtain in such a manner is cut into desired size, add hot compression then, the integral body that then can obtain absorbed layer is not contained the absorbing sheet of the resin bed coating of inorganic particulate.
The absorbing sheet that obtains in such a manner and arresting element are packed in the laminate housing body simultaneously, also absorbing sheet is clipped in the mouth-sealed portion of external packing body as required, utilize heat-sealing so that positive terminal and negative terminal outstanding mode from the external packing body seals, can make lithium rechargeable batteries thus.
Absorbing sheet of the present invention except that can be used for lithium rechargeable batteries, also can be used for double layer capacitor.
[embodiment]
By the following examples the present invention is specifically described, but the present invention is not limited to following examples.
The situation that does not have the resin bed that does not contain inorganic particulate in the A absorbing sheet
(1) making of absorbing sheet
With being equipped with two extruders (two extruders of PCM-46 that pond shellfish limited company makes) of quantitatively giving feeder, the resin and the inorganic particulate of mixed volume shown in the table 1 are carried out melting mixing, use T mould (manufacturing of toshiba machine limited company) to obtain the film of thickness shown in the table 1 then.The film that is obtained is placed on dew point temperature to be preserved in the hothouse below-50 ℃.
(2) making 1 of test film (absorbing sheet only is disposed at the making of the test film of test film inside)
Make test film as follows with formation shown in Figure 14.Operation shown below is to carry out in the hothouse below-50 ℃ in dew point temperature.At first, use recess to be of a size of mould and forcing press (the laminated film forming test machine of wide 30mm, long 50mm, dark 3.5mm, treasured spring limited company makes), become the mode of recess with sealant layer side (polyolefin film side), under the condition of the 5MPa that exerts pressure, pressing speed 1s/100mm, to laminate housing material (lithium ion battery aluminium lamination blocking, clear and electrician packs limited company and makes, and has the laminate of aluminium foil between nylon membrane and polyolefin film) carry out mold pressing processing.In the recess of the laminate housing material (9a) of mold pressing processing, accommodate that the barrier film (manufacturing of CELGARD limited company) that will be folded into wide 28mm, long 48mm is clipped between 2 absorbing sheets of wide 28mm, long 48mm and (17) of formation.Be cut to wide 40mm, long 60mm without the laminate housing material (9) of mold pressing processing with through the laminate housing material (9a) of above-mentioned mold pressing processing, overlap in separately the relative mode of sealant layer, under 200 ℃, 1MPa, 5 seconds condition, process pouch with wide any 3 limits are sealed of 5mm.Ethylene carbonate ester, dimethyl carbonate and diethyl carbonate are mixed with 1: 1: 1 volume ratio, in the mode that becomes 1mol/L lithium hexafluoro phosphate is dissolved in and wherein makes electrolyte (Kishida chemistry limited company makes), from the peristome injection electrolyte decompression is contained the above-mentioned electrolyte of 3ml and be dipped in barrier film, then under 200 ℃, 1MPa, 5 seconds condition, so that 5mm is wide peristome is sealed, make test film.
(3) making 2 of test film (absorbing sheet being disposed at the making of the test film of test film inside and mouth-sealed portion)
Make test film as follows with formation shown in Figure 15.Operation shown below is to carry out in the hothouse below-50 ℃ in dew point temperature.At first, be of a size of mould and forcing press (the laminated film forming test machine of wide 30mm, long 50mm, dark 3.5mm with recess, treasured spring limited company makes), become the mode of recess with sealant layer side (polyolefin film side), under the condition of the 5MPa that exerts pressure, pressing speed 1s/100mm, laminate housing material (lithium ion battery is packed limited company's manufacturing with aluminium lamination paper tinsel, clear and electrician, has the laminate of aluminium foil between nylon membrane and polyolefin film) is carried out mold pressing processing.In the recess of the laminate housing material (9a) of mold pressing processing, accommodate that the barrier film (manufacturing of CELGARD limited company) that will be folded into wide 28mm, long 48mm is clipped between 2 absorbing sheets of wide 28mm, long 48mm and (17) of formation.The laminate housing material (9) and the laminate housing material of processing through above-mentioned mold pressing (9a) without mold pressing processing of wide 40mm, long 60mm will be cut to, carry out overlapping in the relative mode of sealant layer separately, along any 3 limits, between overlapping laminate housing material, sandwich the absorbing sheet (14) that is cut to wide 5mm, long 55mm, under 200 ℃, 1MPa, 5 seconds condition, so that 5mm is wide above-mentioned 3 limits are sealed, be configured as a bag shape.With 1: 1: 1 volume ratio ethylene carbonate ester, dimethyl carbonate and diethyl carbonate are mixed, in the mode that becomes 1mol/L lithium hexafluoro phosphate is dissolved in and wherein makes electrolyte (Kishida chemistry limited company makes), from the peristome injection electrolyte decompression is contained the above-mentioned electrolyte of 3ml and be dipped in barrier film, absorbing sheet with wide 5mm, long 55mm is clipped in (14) peristome then, under 200 ℃, 1MPa, 5 seconds condition, so that 5mm is wide peristome is sealed, make test film.
Use the hydrotalcite (DHT-4A of 15 weight portions, consonance chemical industry limited company makes) as inorganic particulate with sour absorption function, use the electromagnetic shock to be provided with aperture 20 μ m stainless steel sifts (manufacturing of ASONE limited company) of 15 weight portions to sieve (AS200DIGIT, the manufacturing of AS ONE limited company) the magnesium sulfate 0 hydrate (MG-0K-100 that carries out classification, Ako Kasei Co., Ltd. makes) as inorganic particulate with water absorption function, use the polypropylene (PP of 100 weight portions, Prime PolyproF-744NP, Prime Polymer limited company makes) as resin, obtain the absorbing sheet of thickness 50 μ m according to the manufacture method of above-mentioned absorbing sheet.Use the absorbing sheet obtained, make test film according to the method for the making 1 of test film.
Except the amount of hydrotalcite and magnesium sulfate being changed into 30 weight portions respectively, all the other make test film in mode similarly to Example 1.
As having beyond the inorganic particulate of water absorption function, all the other make test film in mode similarly to Example 1 except using zeolite (Molecular Sieves 4A powder, crust Industries, Inc makes).
Except using calcined hydrotalcite (DTH-4C, the manufacturing of consonance chemical industry limited company) conduct simultaneously has the inorganic particulate of sour absorption function and has the inorganic particulate of water absorption function, and its mixed volume is adjusted into beyond 30 weight portions, all the other make test film in mode similarly to Example 1.
Except using hydrotalcite oxide (KW-2200, the manufacturing of consonance chemical industry limited company) conduct simultaneously has the inorganic particulate of sour absorption function and has the inorganic particulate of water absorption function, and its mixed volume is adjusted into beyond 30 weight portions, all the other make test film in mode similarly to Example 1.
As beyond the resin, all the other make test film in mode similarly to Example 1 except using modified polypropene (ADMER QF551, Mitsui Chemicals Inc. makes).
As beyond the resin, all the other make test film in mode similarly to Example 1 except using vinyl-vinyl acetate copolymer (EVAFLEX P1007, Mitsui/chemistry limited company of Du Pont makes).
As beyond the resin, all the other make test film in mode similarly to Example 1 except using ethylene-vinyl alcohol copolymer (EVAL F101B, Kuraray limited company makes).
As beyond the resin, all the other make test film in mode similarly to Example 1 except using low density polyethylene (LDPE) (Prime Polymer limited company makes for LDPE, NEO-ZEX 0234CL).
As beyond the resin, all the other make test film in mode similarly to Example 1 except using polymethylpentene (TPX DX845, Mitsui Chemicals Inc. makes).
Use the hydrotalcite (DHT-4A of 30 weight portions, consonance chemical industry limited company makes) as having the inorganic particulate of sour absorption function and the polypropylene (PP of 100 weight portions, Prime PolyproF-744NP, Prime Polymer limited company makes) as resin, according to the manufacture method of above-mentioned absorbing sheet, the hydrotalcite of making thickness 25 μ m disperses polypropylene foil.In addition, use the electromagnetic shock to be provided with aperture 20 μ m stainless steel sifts (manufacturing of AS ONE limited company) of 30 weight portions to sieve (AS200DIGIT, the manufacturing of AS ONE limited company) the magnesium sulfate 0 hydrate (MG-0K-100 that carries out classification, Ako Kasei Co., Ltd. makes) as inorganic particulate with water absorption function, the above-mentioned polypropylene that uses 100 weight portions is as resin, according to the manufacture method of above-mentioned absorbing sheet, the magnesium sulfate of making thickness 25 μ m disperses polypropylene foil.(great achievement laminating machine limited company makes, and FL750), under 0.5MPa, 180 ℃, the condition of 1m/min, disperses polypropylene foils to carry out heated lamination in 2 magnesium sulfate that obtained, and makes the absorbing sheet of thickness 50 μ m to utilize laminating machine.Use this absorbing sheet, make test film according to making 1 method of test film.
Use the absorbing sheet identical, according to the method making test film of the making 2 of test film with embodiment 1.
Use the absorbing sheet identical, according to the method making test film of the making 2 of test film with embodiment 2.
Use the absorbing sheet identical, according to the method making test film of the making 2 of test film with embodiment 3.
Use the absorbing sheet identical, according to the method making test film of the making 2 of test film with embodiment 4.
Use the absorbing sheet identical, according to the method making test film of the making 2 of test film with embodiment 5.
Comparative example 1
Except not using the inorganic particulate with sour absorption function and having the inorganic particulate of water absorption function, all the other make test film in mode similarly to Example 1.
Comparative example 2
Except not being mixed into the inorganic particulate with sour absorption function, and the magnesium sulfate that uses 30 weight portions is as having beyond the inorganic particulate of water absorption function, and all the other make test film in mode similarly to Example 1.
Comparative example 3
Except not being mixed into the inorganic particulate with water absorption function, the hydrotalcite that uses 30 weight portions is as having beyond the inorganic particulate of sour absorption function, and all the other make test film in mode similarly to Example 1.
Comparative example 4
Do not use absorbing sheet, make test film according to the method for the making 1 of test film.
Comparative example 5
(great achievement laminating machine limited company makes to utilize laminating machine, FL760), under 0.5MPa, 180 ℃, the condition of 1m/min, the hydrotalcite of the absorbing sheet of making among the embodiment 11 is disperseed the polypropylene foil side, on the sealant layer side of the lithium ion battery of heated lamination in the making 1 of test film with the aluminium lamination blocking, and acquisition has the aluminium lamination blocking of acid/water absorption function.Except using the aluminium lamination blocking that is obtained as laminate housing material, not use beyond the absorbing sheet, all the other make test film according to the method for the making 1 of test film.
Comparative example 6
(great achievement laminating machine limited company makes to utilize laminating machine, FL760), under 0.5MPa, 180 ℃, the condition of 1m/min, the hydrotalcite of the absorbing sheet of making among the embodiment 1 is disperseed the polypropylene foil side, on the sealant layer side of the lithium ion battery of heated lamination in the making 1 of test film with the aluminium lamination blocking, and acquisition has the aluminium lamination blocking of acid/water absorption function.Except using the aluminium lamination blocking that is obtained as laminate housing material, not use beyond the absorbing sheet, all the other make test film according to the method for the making 1 of test film.
Comparative example 7
The hydrotalcite of making among the embodiment 11 is disperseed polypropylene foil and the polypropylene foil that is dispersed with magnesium sulfate, under the situation of not carrying out heat lamination, carry out overlappingly, use it, make test film according to the method for the making 1 of test film as absorbing sheet.
Comparative example 8
Except the amount of the hydrotalcite of embodiment 1 and magnesium sulfate being changed into 0.5 weight portion respectively, all the other make test film in mode similarly to Example 1.
Comparative example 9
Use the absorbing sheet identical, make test film according to the method for the making 2 of test film, but do not dispose absorbing sheet in the inside of test film with embodiment 1, only at mouth-sealed portion configuration absorbing sheet, and the making test film.
[table 1-1]
The formation of absorbing sheet and allocation position
| Absorbing sheet | The allocation position of absorbing sheet | ||||
| Sneak into agent | Mixed volume (weight portion) | Thickness [μ m] | Test film | Mouth-sealed | |
| Embodiment | |||||
| 1 | Polypropylene | 100 | 50 | Configuration | - |
| |
15 | ||||
| |
15 | ||||
| |
Polypropylene | 100 | 50 | Configuration | - |
| Hydrotalcite | 30 | ||||
| Magnesium sulfate | 30 | ||||
| |
Polypropylene | 100 | 50 | Configuration | - |
| |
15 | ||||
| |
15 | ||||
| |
Polypropylene | 100 | 50 | Configuration | - |
| Calcined hydrotalcite | 30 | ||||
| |
Polypropylene | 100 | 50 | Configuration | - |
| The hydrotalcite oxide | 30 | ||||
| |
Modified polypropene | 100 | 50 | Configuration | - |
| |
15 | ||||
| |
15 | ||||
| |
Vinyl-vinyl acetate copolymer | 100 | 50 | Configuration | - |
| |
15 | ||||
| |
15 | ||||
| |
Ethylene-vinyl alcohol copolymer | 100 | 50 | Configuration | - |
| |
15 | ||||
| |
15 | ||||
| |
Low density polyethylene (LDPE) | 100 | 50 | Configuration | - |
| |
15 | ||||
| |
15 | ||||
| |
Polymethylpentene | 100 | 50 | Configuration | - |
| |
15 | ||||
| |
15 | ||||
| |
Polypropylene | 100 | 25 | 50 | Configuration | - |
| Hydrotalcite | 30 | |||||
| Polypropylene | 100 | 25 | ||||
| Magnesium sulfate | 30 |
[table 1-2]
| |
Polypropylene | 100 | 50 | | Configuration | |
| Hydrotalcite | ||||||
| 15 | ||||||
| |
15 | |||||
| |
Polypropylene | 100 | 50 | Configuration | Configuration | |
| Hydrotalcite | 30 | |||||
| Magnesium sulfate | 30 | |||||
| |
Polypropylene | 100 | 50 | | Configuration | |
| Hydrotalcite | ||||||
| 15 | ||||||
| |
15 | |||||
| |
Polypropylene | 100 | 50 | Configuration | Configuration | |
| Calcined hydrotalcite | 30 | |||||
| |
Polypropylene | 100 | 50 | Configuration | Configuration | |
| The hydrotalcite oxide | 30 | |||||
| Comparative example 1 | Polypropylene | 100 | 50 | Configuration | - | |
| Comparative example 2 | Polypropylene | 100 | 50 | Configuration | - | |
| Magnesium sulfate | 30 | |||||
| Comparative example 3 | Polypropylene | 100 | 50 | Configuration | - | |
| Hydrotalcite | 30 | |||||
| Comparative example 4 | - | - | - | - | - | |
| Comparative example 5 | Polypropylene | 100 | 25 | 50 | The absorbing sheet thermosphere is pressed on the laminate housing material and fits | |
| Hydrotalcite | 30 | |||||
| Polypropylene | 100 | 25 | ||||
| Magnesium sulfate | 30 | |||||
| Comparative example 6 | Polypropylene | 100 | 50 | The absorbing sheet thermosphere is pressed on the laminate housing material and fits | ||
| |
15 | |||||
| |
15 | |||||
| Comparative example 7 | Polypropylene | 100 | 25 | Configuration | - | |
| Hydrotalcite | 30 | |||||
| Polypropylene | 100 | 25 | ||||
| Magnesium sulfate | 30 | |||||
| Comparative example 8 | Polypropylene | 100 | 50 | Configuration | - | |
| Hydrotalcite | 0.5 | |||||
| Magnesium sulfate | 0.5 | |||||
| Comparative example 9 | Polypropylene | 100 | 50 | - | | |
| Hydrotalcite | ||||||
| 15 | ||||||
| |
15 | |||||
Reliability test
The test film of above-mentioned making placed 30 days in 60 ℃, the constant temperature and humidity cabinet of 95%RH after, its outward appearance of visual observations, the hydrogen fluoride concentration and the water content of the electrolyte solution in the determination test sheet simultaneously.In addition, as follows, water content is to measure according to karl-Fischer method (Karl Fischer Method), and hydrogen fluoride content is to measure according to the chromatography of ions.Result of the test is shown in table 2～4.
The mensuration of moisture
The dew point temperature through argon replaces be below-50 ℃ gas displacement type glove box (AS ONE limited company makes, SG-1000) in, (flat natural pond industry limited company makes, and AQV-300) measures to utilize Ka Er-Fei Xiu capacity titration outfit.
The mensuration of hydrogen fluoride content
If lithium hexafluoro phosphate (TiPF as the electrolyte use
6) be the state of salt, then a little less than the stability to moisture, can generate hydrogen fluoride with the water reaction, but the hexafluorophosphoric acid anion (PF through dissociating
6 -) can not react with water.Therefore, utilize lithium hexafluoro phosphate (LiPF
6) stable properties in rare aqueous solution, the pure water of impurity is removed in use with Water Purifiers (Elix-UV3 that Japanese Millipore limited company makes), the 1ml electrolyte dilution is become the solution of 100ml, (eastern Cao limited company makes to utilize the ion chromatograph of suppressor mode, IC-2001), use anion organic acid analysis column (the super IC-AZ that eastern Cao limited company makes), use the NaHCO of 2.0mmol/L
3Na with 3.0mmol/L
2CO
3The aqueous solution that mixes is measured above-mentioned solution with the flow of 1.5ml/min as dissolution fluid.
[table 2]
Reliability test result
| | Embodiment | 1 | |
|
|
|
|
|
|
|
|
| Outward appearance | No change | No change | No change | No change | No change | No change | No change | No change | No change | ||
| Hydrogen fluoride concentration [ppm] | Initial stage | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | |
| After the test | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | ||
| Water content [ppm] | Initial stage | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | |
| After the test | 20 | 20 | 30 | 20 | 20 | 20 | 20 | 20 | 20 | ||
[table 3]
Reliability test result
| | Embodiment | 10 | |
Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| Outward appearance | No change | No change | Leakage | Expand | Leakage | Leakage | Leakage | Leakage | No change | Leakage | ||
| Hydrogen fluoride concentration [ppm] | Initial stage | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | |
| After the test | 20 | 20 | 250 | 80 | 150 | 270 | 270 | 260 | 40 | 240 | ||
| Water content [ppm] | Initial stage | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | |
| After the test | 20 | 20 | 500 | 60 | 450 | 480 | 500 | 490 | 40 | 470 | ||
[table 4]
Reliability test result
| | Embodiment | 12 | |
|
|
|
Comparative example 9 | |
| Outward appearance | No change | No change | No change | No change | No change | Expand | ||
| Hydrogen fluoride concentration [ppm] | Initial stage | 30 | 30 | 30 | 30 | 30 | 30 | |
| After the |
10 | 10 | 20 | 10 | 10 | 60 | ||
| Water content [ppm] | Initial stage | 40 | 40 | 40 | 40 | 40 | 40 | |
| After the |
10 | 10 | 20 | 10 | 10 | 60 | ||
Shown in table 2 and table 3, all do not have cosmetic variation in the test film that in test film, disposes absorbing sheet of embodiment 1～11, and then hydrogen fluoride concentration and water content are lower than initial value.This result shows: if absorbing sheet of the present invention is placed the inside of the external packing body that is made of laminate housing material, then can improve the characteristic of battery effectively, therefore the lithium rechargeable batteries of durability and excellent in safety can be provided.
On the other hand, in test film, do not dispose in the comparative example 1 and 4 of absorbing sheet, the corrosion of aluminium foil and the peeling off of mouth-sealed portion of housing material take place, leak thereby liquid takes place.In the comparative example 2 of unmixed inorganic particulate of going into to have sour absorption function, find to have and suppress the effect that water content increases, but when outward appearance is observed, find expansion.Infer that its reason is owing to being hydrofluoric influence that lithium hexafluoro phosphate effect produce with electrolyte from the outside moisture that immerses of test film before being absorbed the sheet moisture absorption.In addition, in the comparative example 3 of unmixed inorganic particulate of going into to have the water absorption function, compare, find to have and suppress the effect that hydrogen fluoride concentration increases, but the corrosion of aluminium foil and peeling off of mouth-sealed portion take place, leak thereby liquid takes place with comparative example 1 and 4.
Absorbing sheet fitted in the sealant layer side of laminate housing material and be not disposed in the comparative example 5 and 6 in the test film, find that the corrosion and the liquid of aluminium foil leaks from mouth-sealed portion.Its reason can be enumerated: add man-hour in mold pressing, and the interface of the aluminium foil of laminate housing material and aluminium foil and the resin bed above it, the magnesium sulfate particle and the hydrotalcite particle that are fitted in the absorbing sheet on the laminate housing material are damaged, and produce defective.
In addition, hydrotalcite is not disperseed polypropylene foil and magnesium sulfate to disperse polypropylene foil to fit and in the comparative example 7 that uses, do not find that liquid leaks or expands, but have hydrogen fluoride concentration and water content to equate or the result of rising to some extent with initial value.When use embodiment 11 hydrotalcite is disperseed absorbing sheet that polypropylene foil and magnesium sulfate dispersion polypropylene foil fitted the time, hydrogen fluoride concentration and water content are lower than initial value.Infer its former because: have the acid and the absorption function of water concurrently by making same absorbing sheet, and raising hydrogen fluoride and the diffuser efficiency of steam in absorbing sheet.Can judge according to these results: in same absorbing sheet, have the absorbing sheet of the absorption function of acid and water concurrently by use, and improve the absorption efficiency of acid and water, and effectively improve battery behavior.
Comparative example 8 is the amount of inorganic particulate with sour absorption function in the absorbed layer and the inorganic particulate with water absorption function situations less than scope of the present invention.Its absorbability is insufficient, and the liquid leakage takes place.
On the other hand, only in the comparative example 9 of the absorbing sheet of the mouth-sealed portion of package body configuration outside, discovery has the effect of the increase of inhibition hydrogen fluoride concentration partly and water content, but finds to expand when outward appearance is observed.It is generally acknowledged that its reason is:, can be subjected to because the initial stage hydrofluoric influence that contains moisture or grade and produced through the minor amount of water that absorbing sheet immerses though find to have at mouth-sealed portion to moisture that immerses from the outside or the hydrofluoric assimilation effect that inside is produced.
B. the situation that has the resin bed that does not contain inorganic particulate in the absorbing sheet
(1) making 1 of absorbing sheet
Use is equipped with two extruders (two extruders of PCM-46 that pond shellfish limited company makes) of quantitative feeder; with the mixed volume shown in the table 5; melting mixing is carried out in the agent of sneaking in the absorbed layer shown in the table 5, be configured as graininess with cold cut formula comminutor then.The particle of formed thereby is stored in dew point temperature in the hothouse below-50 ℃.The particle of formed thereby is dropped in the single shaft extruder (FS40 that pond shellfish limited company makes), as shown in table 5, the resin that does not contain the resin bed of inorganic particulate is dropped in 2 single shaft extruders (FS30 that pond shellfish limited company makes), use 3 layers of T mould (manufacturing of toshiba machine limited company) of the branch manifold mode that will above-mentioned 3 extruders connects into, acquisition have thickness shown in the table 5, by the resin bed/absorbed layer that does not contain inorganic particulate/the do not contain co-extruded films that resin bed constituted of inorganic particulate.The co-extruded films that is obtained is stored in dew point temperature in the hothouse below-50 ℃.In dew point temperature is hothouse below-50 ℃, this co-extruded films is cut to wide 60mm, long 110mm, as shown in Figure 5, obtain to have on the two sides of absorbed layer the absorbing sheet of the resin bed that does not contain inorganic particulate.
(2) making 2 of absorbing sheet
Use is equipped with two extruders (two extruders of PCM-46 that pond shellfish limited company makes) of quantitative feeder; with the mixed volume shown in the table 5; compounding ingredient in the absorbed layer shown in the table 5 is carried out melting mixing, be configured as graininess with cold cut formula comminutor then.The particle of formed thereby is stored in dew point temperature in the hothouse below-50 ℃.The particle of formed thereby is dropped in the single shaft extruder (FS40 that pond shellfish limited company makes), as shown in table 5, the resin that does not contain the resin bed of inorganic particulate is dropped in 2 single shaft extruders (FS30 that pond shellfish limited company makes), use 3 layers of T mould (manufacturing of toshiba machine limited company) of the branch manifold mode that will above-mentioned 3 extruders be formed by connecting, acquisition have the thickness shown in the table 5, by the resin bed/absorbed layer that does not contain inorganic particulate/the do not contain co-extruded films that resin bed constituted of inorganic particulate.The co-extruded films that is obtained is stored in dew point temperature in the hothouse below-50 ℃.In dew point temperature is hothouse below-50 ℃, this co-extruded films is cut to wide 60mm, long 110mm, under 120 ℃, 0.5MPa, carry out adding hot compression in 1 minute then, as shown in Figure 6, obtain the absorbing sheet that is wrapped in the absorbed layer in the resin bed that does not contain inorganic particulate.
(3) making 1 of test film (absorbing sheet only is disposed at the making of the test film of test film inside)
Make test film as follows with formation shown in Figure 16.Operation as follows is to carry out in the hothouse below-50 ℃ in dew point temperature.At first, (clear and electrician packs limited company and makes with the aluminium lamination blocking with lithium ion battery, the laminate that has aluminium foil between nylon membrane and the polyolefin film) is cut into wide 75mm, long 250mm, become inboard mode with sealant layer (layer of polyolefin film) and carry out doubling, 2 minor faces are overlapped.Shown in Figure 16 (b), under 200 ℃, 5 seconds condition, other 2 limits (parts shown in 10) are sealed so that 5mm is wide, make the bag shape that short brink has peristome.Clamp the barrier film (manufacturing of CELGARD limited company) that is folded into wide 110mm, long 60mm with 2 absorbing sheets (14), with 1: 1: 1 volume ratio ethylene carbonate, dimethyl carbonate and diethyl carbonate are mixed, in the mode that becomes 1mol/L lithium hexafluoro phosphate is dissolved in and wherein makes electrolyte (Kishida chemistry limited company makes), the above-mentioned electrolyte of 25ml injected and the electrolyte decompression is contained from peristome be dipped in barrier film, then under 200 ℃, 5 seconds condition, so that 10mm is wide peristome is sealed, make test film.
(4) making 2 of test film (absorbing sheet being disposed at the making of the test film of test film inside and mouth-sealed portion)
Make test film as follows with formation shown in Figure 17.Operation shown below is to carry out in the hothouse below-50 ℃ in dew point temperature.At first, (clear and electrician packs limited company and makes with the aluminium lamination blocking with lithium ion battery, the laminate that has aluminium foil between nylon membrane and the polyolefin film) being cut into wide 75mm, long 250mm, be that the mode of inboard is carried out doubling with sealant layer (polyolefin film layer), with 2 minor faces coincidences.Along other 2 limits (minor face), the absorbing sheet (14) of wide 5mm, long 120mm is clipped between the overlapping laminating foil, under 200 ℃, 5 seconds condition, so that 5mm is wide above-mentioned 2 limits (parts shown in 10) are sealed, be formed in the bag shape that short brink has peristome.Clamp the barrier film (manufacturing of CELGARD limited company) that is folded into wide 110mm, long 60mm with 2 absorbing sheets (14), its peristome from the made bag is inserted.With 1: 1: 1 volume ratio ethylene carbonate ester, dimethyl carbonate and diethyl carbonate are mixed, in the mode that becomes 1mol/L lithium hexafluoro phosphate is dissolved in and wherein makes electrolyte (Kishida chemistry limited company makes), the above-mentioned electrolyte of 25ml is injected from peristome the electrolyte decompression is contained be dipped in barrier film.Then, shown in Figure 17 (b), the absorbing sheet (14) of wide 10mm, long 60mm is clipped in the peristome, under 200 ℃, 5 seconds condition, peristome is sealed, make test film so that 10mm is wide.
Method according to the making 1 of absorbing sheet is carried out the making of absorbing sheet.In order to make absorbed layer, and use the hydrotalcite (DHT-4A of 15 weight portions, consonance chemical industry limited company makes) as inorganic particulate with sour absorption function, use the electromagnetic shock to be provided with aperture 20 μ m stainless steel sifts (manufacturing of AS ONE limited company) of 15 weight portions to sieve (AS200DIGIT, the manufacturing of AS ONE limited company) magnesium sulfate (MG-0K-100 that carries out classification, anhydrous magnesium sulfate, red fringe changes into) as inorganic particulate with water absorbability, use the polypropylene (PP of 100 weight portions, Prime Polypro F-744NP, Prime Polymer limited company makes) as resin.Use the resin of low density polyethylene (LDPE) (PrimePolymer limited company makes for LDPE, NEO-ZEX 0234CL) as the resin bed that is used for not containing inorganic particulate.Do not contain with the resin bed 10 μ m/ absorbed layers 50 μ m/ that do not contain inorganic particulate inorganic particulate resin bed 10 μ m mode system film and make absorbing sheet, use this absorbing sheet and make test film according to the method for the making 1 of test film.
Embodiment 18
Except the amount of hydrotalcite and magnesium sulfate being changed into 30 weight portions respectively, all the other make test film in mode similarly to Example 17.
Embodiment 19
As having beyond the inorganic particulate of water absorption function, all the other make test film in mode similarly to Example 17 except using zeolite (Molecular Sieves 4A powder, crust Industries, Inc makes).
Embodiment 20
Except using calcined hydrotalcite (DTH-4C, the manufacturing of consonance chemical industry limited company) conduct simultaneously has the inorganic particulate of sour absorption function and has the inorganic particulate of water absorption function, and its mixed volume is adjusted into beyond 30 weight portions, all the other make test film in mode similarly to Example 17.
Embodiment 21
Except using hydrotalcite oxide (KW-2200, the manufacturing of consonance chemical industry limited company) conduct simultaneously has the inorganic particulate of sour absorption function and has the inorganic particulate of water absorption function, and its mixed volume is adjusted into beyond 30 weight portions, all the other make test film in mode similarly to Example 17.
Embodiment 22
In addition, all the other make test film in mode similarly to Example 17 except the resin of absorbed layer being changed into modified polypropene (ADMER QF551, Mitsui Chemicals Inc. makes).
Embodiment 23
In addition, all the other make test film in mode similarly to Example 17 except the resin of absorbed layer being changed into vinyl-vinyl acetate copolymer (EVAFLEX P1007, Mitsui-chemistry limited company of Du Pont makes).
Embodiment 24
Except the resin of absorbed layer being changed into ethylene-vinyl alcohol copolymer (EVAL F101B, Kuraray limited company make) in addition, all the other are to make test film with the same mode of embodiment 17.
Embodiment 25
In addition, all the other make test film in mode similarly to Example 17 except the resin of absorbed layer being changed into low density polyethylene (LDPE) (PrimePolymer limited company makes for LDPE, NEO-ZEX 0234CL).
Embodiment 26
In addition, all the other make test film in mode similarly to Example 17 except the resin of absorbed layer being changed into polymethylpentene (TPX DX845, Mitsui Chemicals Inc. makes).
Embodiment 27
In addition, all the other make test film in mode similarly to Example 17 except the resin that will be used for not containing the inorganic particulate resin bed is changed into modified polypropene (ADMER QF551, Mitsui Chemicals Inc. makes).
Embodiment 28
In addition, all the other make test film in mode similarly to Example 17 except the resin that will be used for not containing the inorganic particulate resin is changed into vinyl-vinyl acetate copolymer (EVAFLEX P1007, Mitsui-chemistry limited company of Du Pont makes).
Embodiment 29
In addition, all the other make test film in mode similarly to Example 17 except the resin that will be used for not containing the inorganic particulate resin bed is changed into ethylene-vinyl alcohol copolymer (EVALF101B, Kuraray limited company makes).
Embodiment 30
In addition, all the other make test film in mode similarly to Example 17 except the resin that will be used for not containing the inorganic particulate resin bed is changed into polypropylene (Prime Polymer limited company makes for PP, Prime PolyproF-744NP).
Embodiment 31
In addition, all the other make test film in mode similarly to Example 17 except the resin that will be used for not containing the inorganic particulate resin bed is changed into polymethylpentene (TPX DX845, Mitsui Chemicals Inc. makes).
Embodiment 32
Use the absorbing sheet identical, according to the method making test film of the making 2 of test film with embodiment 17.
Embodiment 33
Use the absorbing sheet identical, according to the method making test film of the making 2 of test film with embodiment 18.
Embodiment 34
Use the absorbing sheet identical, according to the method making test film of the making 2 of test film with embodiment 19.
Embodiment 35
Use the absorbing sheet identical, according to the method making test film of the making 2 of test film with embodiment 20.
Embodiment 36
Use the absorbing sheet identical, according to the method making test film of the making 2 of test film with embodiment 21.
Embodiment 37
Use and embodiment 17 identical materials, carry out the making of absorbing sheet, make test film according to the method for the making 2 of test film according to the method for the making 2 of absorbing sheet.
Embodiment 38
The absorbing sheet of made among the embodiment 17 after placing for 1 week under 25 ℃, the environment of 60%RH, is made test film according to the method for the making 2 of test film.
Comparative example 10
Except not using the inorganic particulate with sour absorption function and having the inorganic particulate of water absorption function, all the other make test film in mode similarly to Example 17.
Comparative example 11
Except not using the inorganic particulate with sour absorption function, the magnesium sulfate that uses 30 weight portions is as having beyond the inorganic particulate of water absorption function, and all the other make test film in mode similarly to Example 17.
Comparative example 12
Except not being mixed into the inorganic particulate with water absorption function, the hydrotalcite that uses 30 weight portions is as having beyond the inorganic particulate of sour absorption function, and all the other make test film in mode similarly to Example 17.
Comparative example 13
Do not use absorbing sheet, make test film according to the method for the making 1 of test film.
Comparative example 14
Except absorbing sheet did not have the resin bed that does not contain inorganic particulate, all the other made test film in mode similarly to Example 17.
Comparative example 15
Use the absorbing sheet identical, carry out the making of test film, do not dispose absorbing sheet in test film inside according to the method for the making 2 of test film with embodiment 17, only at mouth-sealed portion configuration absorbing sheet, and the making test film.
Comparative example 16
The absorbing sheet made in the comparative example 14 after placing for 1 week under 25 ℃, the environment of 60%RH, is made test film according to the method for the making 2 of test film.
[table 5-1]
The formation of absorbing sheet and allocation position
| The resin bed that does not contain inorganic particulate | Absorbed layer | The allocation position of absorbing sheet | |||||
| Resin | Thickness [μ m] | Sneak into agent | Mixed volume [weight portion] | Thickness [μ m] | In the test film | Mouth-sealed | |
| Embodiment | |||||||
| 17 | |
10 | PP | 100 | 50 | Configuration | - |
| |
15 | ||||||
| |
15 | ||||||
| Embodiment 18 | |
10 | PP | 100 | 50 | Configuration | - |
| Hydrotalcite | 30 | ||||||
| Magnesium sulfate | 30 | ||||||
| Embodiment 19 | |
10 | PP | 100 | 50 | Configuration | - |
| |
15 | ||||||
| |
15 | ||||||
| Embodiment 20 | |
10 | PP | 100 | 50 | Configuration | - |
| Calcined hydrotalcite | 30 | ||||||
| Embodiment 21 | |
10 | PP | 100 | 50 | Configuration | - |
| The hydrotalcite oxide | 30 | ||||||
| Embodiment 22 | |
10 | Modified polypropene | 100 | 50 | Configuration | - |
| |
15 | ||||||
| |
15 | ||||||
| Embodiment 23 | |
10 | Vinyl-vinyl acetate copolymer | 100 | 50 | Configuration | - |
| |
15 | ||||||
| |
15 | ||||||
| Embodiment 24 | |
10 | Ethylene-vinyl alcohol copolymer | 100 | 50 | Configuration | - |
| |
15 | ||||||
| |
15 | ||||||
| Embodiment 25 | |
10 | LDPE | 100 | 50 | Configuration | - |
| |
15 | ||||||
| |
15 | ||||||
| Embodiment 26 | |
10 | Polymethylpentene | 100 | 50 | Configuration | - |
| |
15 | ||||||
| |
15 | ||||||
| Embodiment 27 | |
10 | PP | 100 | 50 | Configuration | - |
| |
15 | ||||||
| |
15 | ||||||
| Embodiment 28 | Vinyl- |
10 | PP | 100 | 50 | Configuration | - |
| |
15 | ||||||
| |
15 | ||||||
[table 5-2]
| Embodiment 29 | Ethylene- |
10 | PP | 100 | 50 | Configuration | - |
| |
15 | ||||||
| |
15 | ||||||
| Embodiment 30 | |
10 | PP | 100 | 50 | Configuration | - |
| |
15 | ||||||
| |
15 | ||||||
| Embodiment 31 | |
10 | PP | 100 | 50 | Configuration | - |
| |
15 | ||||||
| |
15 | ||||||
| Embodiment 32 | |
10 | PP | 100 | 50 | | Configuration |
| Hydrotalcite | |||||||
| 15 | |||||||
| |
15 | ||||||
| Embodiment 33 | |
10 | PP | 100 | 50 | Configuration | Configuration |
| Hydrotalcite | 30 | ||||||
| Magnesium sulfate | 30 | ||||||
| Embodiment 34 | |
10 | PP | 100 | 50 | | Configuration |
| Hydrotalcite | |||||||
| 15 | |||||||
| |
15 | ||||||
| Embodiment 35 | |
10 | PP | 100 | 50 | Configuration | Configuration |
| Calcined hydrotalcite | 30 | ||||||
| Embodiment 36 | |
10 | PP | 100 | 50 | Configuration | Configuration |
| The hydrotalcite oxide | 30 | ||||||
| Embodiment 37 | |
10 | PP | 100 | 50 | | Configuration |
| Hydrotalcite | |||||||
| 15 | |||||||
| |
15 | ||||||
| Comparative example 10 | |
10 | PP | 100 | 50 | Configuration | - |
| Comparative example 11 | |
10 | PP | 100 | 50 | Configuration | - |
| Magnesium sulfate | 30 | ||||||
| Comparative example 12 | |
10 | PP | 100 | 50 | Configuration | - |
| Hydrotalcite | 30 | ||||||
| Comparative example 13 | Do not have | Do not have | Do not have | Do not have | Do not have | - | - |
| Comparative example 14 | - | - | PP | 100 | 50 | Configuration | - |
| |
15 | ||||||
| |
15 | ||||||
| Comparative example 15 | |
10 | PP | 100 | 50 | - | |
| Hydrotalcite | |||||||
| 15 | |||||||
| |
15 |
(1) reliability test 1
The test film of above-mentioned making placed 30 days in 60 ℃, the constant temperature and humidity cabinet of 95%RH after, visual observations outward appearance, hydrogen fluoride concentration and the water content in the electrolyte solution in the determination test sheet simultaneously.In addition, as follows, water content is to measure according to karl-Fischer method, and hydrogen fluoride content is to measure according to the chromatography of ions.Result of the test is shown in table 6～8.
The mensuration of water content
The dew point temperature through argon replaces be below-50 ℃ gas displacement type glove box (AS ONE limited company makes, SG-1000) in, (flat natural pond industry limited company makes, and AQV-300) measures to utilize Ka Er-Fei Xiu capacity titration outfit.
The mensuration of hydrogen fluoride content
Lithium hexafluoro phosphate (TiPF as the electrolyte use
6If) be the state of salt, then a little less than the stability for moisture, can generate hydrogen fluoride with the water reaction, but the hexafluorophosphoric acid anion (PF through dissociating
6 -) but can not react with water.Therefore, utilize lithium hexafluoro phosphate (LiPF
6) stable properties in rare aqueous solution, the pure water of impurity is removed in use with Water Purifiers (Elix-UV3 that Japanese Millipore limited company makes), the 1ml electrolyte dilution is become the solution of 100ml, (eastern Cao limited company makes to utilize the ion chromatograph of suppressor mode, IC-2001), use anion organic acid analysis column (superIC-AZ that eastern Cao limited company makes), use NaHCO 2.0mmol/L
3Na with 3.0mmol/L
2CO
3The aqueous solution that mixes is measured above-mentioned solution with the flow of 1.5ml/min as dissolution fluid.
[table 6]
The result of reliability test 1
| | Embodiment | 17 | Embodiment 18 | Embodiment 19 | Embodiment 20 | Embodiment 21 | Embodiment 22 | Embodiment 23 | Embodiment 24 | Embodiment 25 | Embodiment 26 | |
| Outward appearance | No change | No change | No change | No change | No change | No change | No change | No change | No change | No change | ||
| Hydrogen fluoride concentration [ppm] | Initial stage | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | |
| After the test | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | ||
| Water content [ppm] | Initial stage | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | |
| After the test | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | ||
[table 7]
The result of reliability test 1
| Assessment item | Embodiment 27 | Embodiment 28 | Embodiment 29 | Embodiment 30 | Embodiment 31 | Comparative example 10 | Comparative example 11 | Comparative example 12 | Comparative example 13 | Comparative example 14 | |
| Outward appearance | No change | No change | No change | No change | No change | Liquid leaks | Expand | Liquid leaks | Liquid leaks | No change | |
| Hydrogen fluoride concentration [ppm] | Initial stage | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| After the test | 20 | 20 | 20 | 20 | 20 | 250 | 60 | 150 | 270 | 20 | |
| Water content [ppm] | Initial stage | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
| After the test | 20 | 20 | 20 | 20 | 20 | 500 | 30 | 450 | 480 | 20 | |
[table 8]
The result of reliability test 1
| Assessment item | Embodiment 32 | Embodiment 33 | Embodiment 34 | Embodiment 35 | Embodiment 36 | Embodiment 37 | Comparative example 15 | |
| Outward appearance | No change | No change | No change | No change | No change | No change | Expand | |
| Hydrogen fluoride concentration [ppm] | Initial stage | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| After the |
10 | 10 | 20 | 10 | 10 | 10 | 60 | |
| Water content [ppm] | Initial stage | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
| After the |
10 | 10 | 10 | 10 | 10 | 10 | 60 | |
Show, in test film, dispose among the embodiment 17～31 of absorbing sheet all do not have cosmetic variation according to table 6 and 7, and then hydrogen fluoride concentration and water content are lower than initial value.In addition, show, also dispose among the embodiment 32～37 of absorbing sheet, can confirm the reduction effect of stronger hydrogen fluoride concentration and water content at mouth-sealed portion according to table 8.This result represents, if absorbing sheet of the present invention is placed the inside (be preferably and also further place mouth-sealed portion) of the external packing body that constitutes by laminate housing material, then can improve the characteristic of battery effectively, therefore the lithium rechargeable batteries of durability and excellent in safety can be provided.
On the other hand, in test film, do not dispose in the comparative example 10 and comparative example 13 of absorbing sheet, the corrosion of aluminium foil and the peeling off of mouth-sealed portion of housing material take place, leak thereby liquid takes place.In the comparative example 11 of unmixed inorganic particulate of going into to have sour absorption function, find to have and suppress the effect that water content increases, but when outward appearance is observed, find expansion.Infer that its reason is: since from the outside moisture that immerses of test film before being absorbed the sheet moisture absorption, with electrolyte be that the lithium hexafluoro phosphate effect produces hydrofluoric influence.In addition, unmixed comparative example 12 of going into to have the inorganic particulate of water absorption function is compared with comparative example 10 and comparative example 13, finds to have and suppresses the effect that hydrogen fluoride concentration increases, but the corrosion of aluminium foil and peeling off of mouth-sealed portion take place, and leaks thereby liquid takes place.In addition, only the comparative example 15 of the absorbing sheet of the mouth-sealed portion of package body configuration is outside compared with comparative example 10 and comparative example 13, and finding has the effect that can effectively suppress the increase of hydrogen fluoride concentration and water content, but finds to expand when outward appearance is observed.It is generally acknowledged that its reason is:, can be subjected to because the initial stage is contained moisture or through the minor amount of water that absorbing sheet the immerses hydrofluoric influence that produces that grades though find to have to moisture that immerses from the outside or the hydrofluoric assimilation effect that inside is produced at mouth-sealed portion.Comparative example 14 similarly to Example 17 because in dew point temperature for carrying out the making of absorbing sheet in the hothouse below-50 ℃, so the evaluation of outward appearance, hydrogen fluoride concentration and water content is compared equal no change with embodiment 17.But, then as described below if the absorbing sheet of comparative example 14 is carried out reliability test (comparative example 16) after placing for 1 week under 25 ℃, the moisture absorption environment of 60%RH, expand in appearance, confirm that in addition hydrogen fluoride concentration and water content increase.
(2) reliability test 2
In order to estimate the operability of absorbing sheet, shown in embodiment 38 and comparative example 16, the absorbing sheet of made after placing for 1 week under 25 ℃, the environment of 60%RH, is made test film, to estimate with the same mode of reliability test 1.Result of the test is shown in table 9.
[table 9]
The result of reliability test 2
| Assessment item | Embodiment 38 | Comparative example 16 | |
| Outward appearance | No change | Expand | |
| Hydrogen fluoride concentration [ppm] | Initial stage | 30 | 30 |
| After the |
10 | 60 | |
| Water content [ppm] | Initial stage | 40 | 40 |
| After the |
10 | 60 |
Show according to table 9, absorbing sheet has among the embodiment 38 of the resin bed that does not contain inorganic particulate, even it is positioned in the moisture absorption environment, hydrogen fluoride concentration and water content are from the initial value minimizing, obtain the same result of result with reliability test 1, but absorbing sheet does not have in the comparative example 16 of the resin bed that does not contain inorganic particulate, expands in appearance, confirms that hydrogen fluoride concentration and water content increase.This result represents that absorbing sheet of the present invention has the effect that reduces the humidity effect in absorbing sheet manufacturing environment and the battery production environment, and therefore the lithium rechargeable batteries of productivity excellence can be provided.
(3) SEM observes
Have on the absorbing sheet of having no way of and come off in order to investigate inorganic particulate, then with SEM (scanning electron microscopy) observe with embodiment 17 and 37 and comparative example 14 in end face after the absorbing sheet cutting made.
Absorbing sheet does not have in the comparative example 14 of the resin bed that does not contain inorganic particulate, takes place damagedly on the end face after absorbing sheet is cut off, and then finds to infer to be adhering to of the particle that comes off from end face.But, among the embodiment 17 and 37, but do not find so damaged and adhere to.This result represents to have the absorbing sheet of the present invention of the resin bed that does not contain inorganic particulate, does not produce the cast that can pollute inside battery, and therefore the lithium rechargeable batteries of fail safe and excellent in te pins of durability can be provided.
Claims (12)
1. lithium rechargeable batteries, it is in by the external packing body that laminate housing material constituted that comprises metal level and synthetic resin layer, and enclosing has the arresting element that contains positive electrode material layer and negative electrode material layer and have the electrolytical layer of lithium salts, it is characterized in that:
In above-mentioned external packing body, enclose simultaneously above-mentioned arresting element and absorbing sheet are arranged; Above-mentioned absorbing sheet has the absorbed layer by resin bed constituted more than 1 layer, and contain inorganic particulate with sour absorption function and inorganic particulate in the above-mentioned resin bed with water absorption function, and above-mentioned absorbed layer, with respect to resin 100 weight portions, add up to above-mentioned inorganic particulate and the above-mentioned inorganic particulate that contains at least 5 weight portions with water absorption function with sour absorption function.
2. lithium rechargeable batteries according to claim 1 is characterized in that: above-mentioned absorbing sheet is laminated on the two sides of above-mentioned absorbed layer, and further has the resin bed that does not contain inorganic particulate.
3. lithium rechargeable batteries according to claim 1 and 2 is characterized in that: above-mentioned external packing body has mouth-sealed portion, and utilizes above-mentioned absorbing sheet that at least a portion of above-mentioned mouth-sealed portion is sealed.
4. lithium rechargeable batteries according to claim 1 and 2 is characterized in that: above-mentioned have an electrolytical layer of lithium salts, is to contain to be soaked with to make the electrolyte of lithium salts electrolyte dissolution in non-water solvent or the porous resin film of gel-like electrolyte.
5. lithium rechargeable batteries according to claim 1 and 2, it is characterized in that: above-mentioned absorbed layer is constituted by containing above-mentioned inorganic particulate and above-mentioned single resin bed with inorganic particulate of water absorption function with sour absorption function, or by the resin bed that contains above-mentioned inorganic particulate with sour absorption function with contain the above-mentioned formed layered product of resin bed and constituted with inorganic particulate of water absorption function.
6. lithium rechargeable batteries according to claim 1 and 2, it is characterized in that: above-mentioned inorganic particulate with sour absorption function be selected from zeolite, hydrotalcite, calcined hydrotalcite and hydrotalcite oxide formed in the group more than 1 or 1, the inorganic particulate with water absorption function be selected from 0 to 3 hydrate of zeolite, calcined hydrotalcite, hydrotalcite oxide and magnesium sulfate formed in the group more than 1 or 1.
7. lithium rechargeable batteries according to claim 1 and 2 is characterized in that: the resin in the above-mentioned absorbed layer contain be selected from copolymer, ionomer, modified poly ethylene and the modified polypropene of copolymer, ethene and the vinyl alcohol of copolymer, polymethylpentene, ethene and the vinyl acetate of copolymer, ethene and the propylene of polyethylene, polypropylene, ethene and butylene formed in the group more than 1 or 1.
8. lithium rechargeable batteries according to claim 1 and 2 is characterized in that: above-mentioned absorbed layer is carried out the radioactive ray crosslinking Treatment.
9. lithium rechargeable batteries according to claim 2, it is characterized in that: the resin in the above-mentioned resin bed that does not contain inorganic particulate, contain be selected from copolymer, ionomer, modified poly ethylene and the modified polypropene of copolymer, ethene and the vinyl alcohol of copolymer, polymethylpentene, ethene and the vinyl acetate of copolymer, propylene and the ethene of polyethylene, polypropylene, ethene and butylene formed in the group more than 1 or 1.
10. lithium rechargeable batteries according to claim 2 is characterized in that: the integral body of above-mentioned absorbed layer is coated by the above-mentioned resin bed that does not contain inorganic particulate.
11. lithium rechargeable batteries according to claim 1 and 2 is characterized in that: two sides or any one side to above-mentioned absorbing sheet are carried out the embossing processing.
12. lithium rechargeable batteries according to claim 1 and 2 is characterized in that: on the two sides of above-mentioned absorbing sheet or form adhering agent layer or adhesion agent layer on the one side arbitrarily.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007040538 | 2007-02-21 | ||
| JP2007040539 | 2007-02-21 | ||
| JP2007040538 | 2007-02-21 | ||
| JP2008025119 | 2008-02-05 | ||
| JP2008025118 | 2008-02-05 |
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| Publication Number | Publication Date |
|---|---|
| CN101252209A true CN101252209A (en) | 2008-08-27 |
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ID=39907796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100810624A Pending CN101252209A (en) | 2007-02-21 | 2008-02-20 | Lithium secondary battery with a laminate housing material |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5226332B2 (en) |
| CN (1) | CN101252209A (en) |
Cited By (4)
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| CN102656734A (en) * | 2009-12-17 | 2012-09-05 | 安格斯公司 | Purifier for removing hydrogen fluoride from electrolytic solution |
| CN105874640A (en) * | 2014-01-13 | 2016-08-17 | 株式会社Lg化学 | Battery cell having improved battery safety by using inert particles |
| CN105940521A (en) * | 2014-01-29 | 2016-09-14 | 凸版印刷株式会社 | Terminal film for electricity storage devices, and electricity storage device |
| CN112993451A (en) * | 2019-12-17 | 2021-06-18 | 双叶电子工业株式会社 | Tab lead, lithium ion battery, and nonaqueous electrolyte device |
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| JP5387062B2 (en) * | 2009-03-06 | 2014-01-15 | 日産自動車株式会社 | Secondary battery |
| JP5327020B2 (en) * | 2009-11-26 | 2013-10-30 | トヨタ自動車株式会社 | All solid battery |
| US8771866B2 (en) * | 2010-03-30 | 2014-07-08 | Samsung Sdi Co., Ltd. | Pouch type secondary battery and the fabrication method thereof |
| JP5733915B2 (en) * | 2010-06-24 | 2015-06-10 | Fdk株式会社 | Lithium ion secondary battery |
| JP5660619B2 (en) * | 2011-04-28 | 2015-01-28 | Ｎｅｃエナジーデバイス株式会社 | Film-clad battery and manufacturing method thereof |
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| KR102033746B1 (en) * | 2015-09-15 | 2019-10-17 | 주식회사 엘지화학 | Case for Secondary Battery Comprising Inner Sealant Layer Including Nanaporous Material and Lithium Secondary Battery Comprising the Same |
| JP6865051B2 (en) * | 2017-02-02 | 2021-04-28 | 三洋化成工業株式会社 | Lithium ion battery |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4239253B2 (en) * | 1997-09-30 | 2009-03-18 | 東洋製罐株式会社 | Non-aqueous electrolyte battery container |
| JP3858689B2 (en) * | 2001-12-21 | 2006-12-20 | 日本電気株式会社 | BATTERY USING LAMINATE PACKAGE AND METHOD FOR MANUFACTURING THE SAME |
-
2008
- 2008-02-05 JP JP2008025118A patent/JP5226332B2/en not_active Expired - Fee Related
- 2008-02-20 CN CNA2008100810624A patent/CN101252209A/en active Pending
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| CN102656734A (en) * | 2009-12-17 | 2012-09-05 | 安格斯公司 | Purifier for removing hydrogen fluoride from electrolytic solution |
| US9023204B2 (en) | 2009-12-17 | 2015-05-05 | Entegris, Inc. | Purifier for removing hydrogen fluoride from electrolytic solution |
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| CN105874640A (en) * | 2014-01-13 | 2016-08-17 | 株式会社Lg化学 | Battery cell having improved battery safety by using inert particles |
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| JP2008235255A (en) | 2008-10-02 |
| JP5226332B2 (en) | 2013-07-03 |
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