CN103229330A

CN103229330A - Separator for electrochemical element, method for manufacturing same, electrode for electrochemical element, electrochemical element

Info

Publication number: CN103229330A
Application number: CN2011800505053A
Authority: CN
Inventors: 中村祐介; 儿岛映理; 片山秀昭
Original assignee: Hitachi Maxell Ltd
Current assignee: Maxell Ltd
Priority date: 2010-10-21
Filing date: 2011-09-02
Publication date: 2013-07-31
Also published as: WO2012053286A1; JPWO2012053286A1

Abstract

A separator for an electrochemical element is characterized in comprising a resin (A) formed by photopolymerization and provided with a bridge structure, and an electrically insulating inorganic fine particles (B), the ratio a/b of the volume (a) of the resin (A) and the volume (b) of the inorganic particles (B), excluding the pore volume, being 0.6-9. A method for manufacturing a separator for an electrochemical element is characterized in comprising a step for forming pores by vaporizing a volatile substance from a sheet for forming a separator for an electrochemical element containing the volatile substance, or a step for forming pores by extracting a material with a specific solvent from a sheet for forming a separator for an electrochemical element containing the material soluble in the solvent.

Description

Electro chemical elements use distance piece and manufacture method thereof, electrode for electrochemical device and electrochemical element

Technical field

The electro chemical elements use distance piece of the anti-short-circuit excellence when dimensional stability when the present invention relates to high temperature and warpage and manufacture method thereof, with above-mentioned distance piece after integrated electrode for electrochemical device and have above-mentioned electro chemical elements use distance piece and also very safe electrochemical element under hot environment.

Background technology

With rechargeable nonaqueous electrolytic battery such as lithium secondary battery or ultracapacitor be representative use the electrochemical element of nonaqueous electrolyte because the high such feature of energy density, thereby the power supply that is used as portable machines such as mobile phone or subnotebook PC uses widely, high performance along with portable machine, the high capacity of electrochemical element has the trend of further propelling, guarantees that further fail safe becomes important problem.

In the existing lithium secondary battery, as the distance piece that is located between positive pole and the negative pole, for example used thickness is the porous membrane of the polyolefin about 20～30 μ m.But, when making the porous membrane of this kind polyolefin, in order to offer fine and uniform hole, and use the complicated step such as extraction of biaxial stretch-formed or pore-creating agent, the cost height, thereby realistic situation is that the distance piece price uprises.

In addition, raw material as distance piece, turn-off (shutdown) effect in order to ensure following what is called, having used fusing point is polyethylene about 120～140 ℃, wherein, above-mentioned shutoff effect is: make the formation resin fusion of distance piece and the hole is stopped up below the abnormal heating temperature of battery, the internal resistance of battery is raise, thereby improve the fail safe of battery when short circuit etc.But the temperature of the battery of having no progeny in the pass is further under the situation such as risings, fusion polyethylene flow easily, thereby have the fuse situation of (meltdown) of the what is called that produces the distance piece rupture of membranes.In such cases, both positive and negative polarity directly contacts, and temperature has the danger of further rising.

For anti-short circuit of planting here due to fusing, proposed to have used the micro-porous film of stable on heating resin or the method that nonwoven fabrics uses as distance piece.For example, disclose the distance piece of the micro-porous film that has used fully aromatic polyamide in the patent documentation 1, disclosed the distance piece that has used polyimide porous membrane in the patent documentation 2.In addition, disclose the distance piece that has used the polyamide nonwoven fabrics in the patent documentation 3, disclosed the relevant technology that will use the nonwoven fabrics of aramid fibre as the distance piece of base material in the patent documentation 4.But when using heat-resisting micro-porous film of this kind or nonwoven fabrics, the cost of material or the difficulty of manufacturing etc. becomes problem.

On the other hand, in the patent documentation 5, disclosed relevant on the non woven cloth in polymer base material and the technology that wherein has the distance piece of porous inorganic lining.Yet this kind distance piece has been owing to adopted excellent heat resistance to lack the inorganic lining of flexibility, in the time of therefore in being applied to use the electrochemical element of coiling body, might produce the crackle that caused by warpage and short circuit.Particularly, in the electrochemical element of the coiling body of the use flat of rectangular cell and so on,, therefore be very difficult to use this kind distance piece owing to produce strong warpage.

The prior art document

Patent documentation

Patent documentation 1: Japanese kokai publication hei 5-335005 communique

Patent documentation 2: No. 2000306568 communiques of TOHKEMY

Patent documentation 3: Japanese kokai publication hei 9-259856 communique

Patent documentation 4: Japanese kokai publication hei 11-40130 communique

Patent documentation 5: Japanese Unexamined Patent Application Publication 2006-504228 communique

Summary of the invention

Invent problem to be solved

Based on this kind situation, require to develop and do not damaging productivity ratio aspect cost or the manufacturing process, the anti-short-circuit when making the dimensional stability of distance piece or warpage improves, and improves the fail safe or the technology of dependability of the electrochemical element that has used above-mentioned distance piece.

The present invention finishes in view of above-mentioned thing, and it provides the electrochemical element of the excellent in safety under reliability and the high temperature, the distance piece that can constitute this electrochemical element and manufacture method thereof.

The means that are used to deal with problems

Electro chemical elements use distance piece of the present invention is characterised in that, be to comprise the electro chemical elements use distance piece that utilizes photopolymerization and form and have the inorganic particles B of the Resin A of cross-linked structure and electrical insulating property, wherein, remove cavity volume, the volume a of above-mentioned Resin A and the ratio a/b of the volume b of above-mentioned inorganic particles B are 0.6～9.

In addition, the manufacture method of electro chemical elements use distance piece of the present invention is characterised in that, be the manufacture method of the electro chemical elements use distance piece of the invention described above, it comprises: make above-mentioned volatile substances and form the operation in hole from the electro chemical elements use distance piece that contains volatile materials forms the sheet material of usefulness; Perhaps, utilize above-mentioned solvent extraction above-mentioned material, thereby form the operation in hole by forming in the sheet material of usefulness from the electro chemical elements use distance piece that contains the material that can be dissolved in the specific solvent.

In addition, electrode for electrochemical device of the present invention is characterised in that, and is integrated with the electro chemical elements use distance piece of the invention described above.

In addition, electrochemical element of the present invention is characterised in that, is the electrochemical element that comprises positive pole, negative pole, distance piece and nonaqueous electrolyte, and wherein, above-mentioned distance piece is the electro chemical elements use distance piece of the invention described above.

The effect of invention

According to the present invention, can improve the reliability of electrochemical element and the fail safe under the high temperature.

Description of drawings

Figure 1A is the vertical view of an example of expression electrochemical element of the present invention (rechargeable nonaqueous electrolytic battery), and Figure 1B is the profile of Figure 1A.

Fig. 2 is the stereogram of an example of expression electrochemical element of the present invention.

Embodiment

Electro chemical elements use distance piece of the present invention (is designated hereinafter simply as " distance piece ".) be the employed distance piece of distance piece with electrochemical element of nonaqueous electrolyte, contain and utilize photopolymerization and form and in a part, have the Resin A of cross-linked structure and the inorganic particles B of electrical insulating property at least.

In addition, in the distance piece of the present invention, the ratio a/b of the volume b of the volume a of Resin A (remove cavity volume after volume) and inorganic particles B (remove cavity volume after volume) is more than 0.6 below 9.Like this, with regard to distance piece of the present invention, by the ratio of components optimization with Resin A and inorganic particles B, thereby flexibility, mechanical strength or the heat-resisting shrinkage of having guaranteed distance piece are good, can constitute the electrochemical element of the excellent in safety under reliability and the high temperature.

Promptly, in the distance piece of the present invention, by above-mentioned a/b value is made as more than 0.6, preferably be made as more than 3, thereby utilize the effect of the Resin A that is imbued with flexibility, even for example when constituting coiling body electrode group (particularly the cross section that uses in the rectangular cell etc. is the coiling body electrode group of flat), carry out under the situation of warpage, also can suppress generation of defects such as crackle, form the distance piece of anti-short-circuit excellence.

In addition, in the distance piece of the present invention, owing to used the resin that is imbued with flexibility, the distance piece of the form that forms even therefore be coated on the electrode, do not have the contraction that causes by distance piece yet, in addition, in manufacture process by the distance piece of volume to volume (roll-to-roll), also do not have defectives such as crackle, productivity ratio is very excellent.

In addition, in the distance piece of the present invention, by above-mentioned a/b value is made as below 9, preferably be made as below 8, thereby can bring into play the effect of inorganic particles B effectively, the dimensional stability when improving high temperature and make heat-resisting shrinkage excellence, in addition, can also guarantee high strength (mechanical strength) etc., thereby form the distance piece of anti-short-circuit excellence.

Thus, use the reliability and the fail safe under the high temperature of the electrochemical element of the present invention that has the distance piece of the present invention of above-mentioned effect and constitute good.

And among the present invention, the volume a of Resin A is the value of calculating according to the quality of the density of Resin A and the Resin A in the distance piece, and the volume b of inorganic particles B is the value of calculating according to the quality of the density of inorganic particles B and the inorganic particles B in the distance piece.

Resin A in the distance piece of the present invention is to utilize photopolymerization and the resin that forms.If this kind Resin A then can make the manufacturing of distance piece easy, and can shorten manufacturing time, therefore can improve the productivity ratio of distance piece.

And, with regard to Resin A,, use fusion temperature that differential scanning calorimetry (DSC) (DSC) records and glass transition temperature preferably outside the scope of the common serviceability temperature of electrochemical element according to the regulation of the K7121 of Japanese Industrial Standards (JIS).More particularly, the glass transition temperature of Resin A is preferably below 0 ℃, more preferably-10 ℃ below.In addition, the fusion temperature of Resin A is preferably more than 80 ℃, more preferably more than 100 ℃.

As this kind Resin A, can enumerate the resin that makes known monomer or oligomer carry out photopolymerization and form.Specifically, for example can enumerate the acrylic resin that forms by acrylic resin monomer [alkyl (methyl) acrylate and derivatives thereof such as methyl methacrylate, methyl acrylate] and their oligomer and crosslinking agent; The crosslinked resin that forms by urethane acrylate and crosslinking agent; Crosslinked resin that forms by epoxy acrylate and crosslinking agent etc.And, in any one above-mentioned resin, as crosslinking agent, all can use binary or polynary acrylic monomerss such as dioxane glycol diacrylate (Dioxane Glycol Diacrylate), tristane dimethanol diacrylate, oxirane modification trimethylolpropane triacrylate, dipentaerythritol five acrylate, caprolactone modification dipentaerythritol acrylate, 6-caprolactone modification dipentaerythritol acrylate.

In addition, in Resin A, also can use the crosslinked resin that derives from unsaturated polyester resin, above-mentioned unsaturated polyester resin is by the ester composition that binary or polynary pure and mild dicarboxylic acids are got by the polycondensation manufacturing, forms by photopolymerization with the mixture of styrene monomer; Utilize photopolymerization and the resin that forms by multi-functional epoxy compound, multifunctional oxetanes or their mixture; The various polyurethane resins that utilize the photopolymerization reaction of PIC and polyalcohol and generate etc.

And, as above-mentioned multi-functional epoxy compound, for example can enumerate ethylene glycol diglycidylether, 1,6-hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, glycerol polyglycidyl ether, sorbierite glycidol ether, 3,4-epoxy radicals cyclohexenyl group methyl-3 ', 4 '-epoxy radicals cyclohexene carboxylate ester, 1,2:8,9 diepoxy Ji limonenes etc.In addition, as above-mentioned multifunctional oxetanes, for example can enumerate 3-ethyl-3{[(3-ethyl oxetanes-3-yl) methoxyl group] methyl } oxetanes, dimethylbenzene dioxygen heterocycle butane etc.

In addition, as above-mentioned PIC, for example can enumerate hexamethylene diisocyanate, phenylene diisocyanate, toluene di-isocyanate(TDI) (TDI), 4,4 '-methyl diphenylene diisocyanate (MDI), IPDI (IPDI) or two (4-isocyanato-cyclohexyl) methane etc.In addition, as above-mentioned polyalcohol, for example can enumerate PPG, polycarbonate polyol, PEPA etc.

And, when the formation (photopolymerization) of each above-mentioned resin, also can and use monofunctional monomers such as isobornyl acrylate, methoxy poly (ethylene glycol) acrylate, phenoxy group polyethylene glycol acrylate.Particularly, and used under the situation of isobornyl acrylate, can form the more good Resin A of flexibility and intensity balance, therefore preferred.

Inorganic particles B in the distance piece of the present invention is the intensity that improves distance piece, dimensional stability etc. and help to improve the composition of anti-short-circuit.In addition, utilize inorganic particles B, can be so that the control in the hole rate of distance piece, aperture be very easy.As inorganic particles B, so long as following above-mentioned material, just be not particularly limited, above-mentioned material has electrical insulating property and does not react under the temperature more than 150 ℃ and indeformable thermal endurance, solvent (aftermentioned) speech that uses when nonaqueous electrolyte that electrochemical element had or distance piece are made is stable, and the electrochemistry aspect that is difficult for oxidized reduction in the operating voltage range of this external electrochemical element is stablized.

As the concrete example of inorganic particles B, can enumerate iron oxide, silicon dioxide (SiO ₂), aluminium oxide (Al ₂O ₃), TiO ₂(titanium dioxide), BaTiO ₃Deng inorganic oxide particle; Inorganic nitride such as aluminium nitride, silicon nitride particulate; The ionic crystals particulate of slightly solubilities such as calcirm-fluoride, barium fluoride, barium sulfate; Covalent bond such as silicon, diamond crystal fine particle; Small bits of clay such as montmorillonite etc.Here, above-mentioned inorganic oxide particle also can be to come from the material of mineral resources such as boehmite, zeolite, apatite, kaolin, mullite, spinelle, olivine, mica or their particulates such as artificiality.In addition, also can be by with metal, SnO ₂, the surface of illustrated conductive material covers with the material (for example above-mentioned inorganic oxide etc.) with electrical insulating property and makes it to have the particle of electrical insulating property in indium tin oxide electroconductive oxides such as (ITO) or the carbonaceous materials such as carbon black, graphite etc.Inorganic particles B both can use independent a kind of above-mentioned illustrative material, and also two or more kinds may be used.In the middle of the above-mentioned illustrative inorganic particles B, more preferably inorganic oxide particle, further preferred aluminium oxide, titanium dioxide, silicon dioxide, boehmite.

The particle diameter of inorganic particles B is preferably more than the 0.001 μ m in average grain diameter, more preferably more than the 0.1 μ m, in addition, is preferably below the 15 μ m, more preferably below the 1 μ m.And the average grain diameter of inorganic particles B for example may be prescribed as: use laser light scattering particle size distribution meter (for example, HORIBA corporate system " LA-920 "), make inorganic particles B be dispersed in number average bead diameter measured in the medium that does not dissolve it.

In addition, form as inorganic particles B, for example both can have near spherical shape, also can have tabular or fibrous shape, yet consider from the viewpoint of the anti-short-circuit that improves distance piece, be preferably tabular particle or the particle of offspring structure that the primary particle cohesion is formed.Particularly, consider from the aspect of the hole rate that improves distance piece, more preferably the particle of the offspring structure that the primary particle cohesion is formed.As the above-mentioned tabular particle or the representational example of offspring, can enumerate tabular aluminium oxide or tabular boehmite, the aluminium oxide of offspring shape or the boehmite of offspring shape etc.

In the distance piece of the present invention, Resin A and inorganic particles B are under the situation of not using the porous substrate that is made of fibrous material described later, preferably form the main body of distance piece by them, specifically, the cumulative volume of Resin A and inorganic particles B is in the cumulative volume (volume after removing the hole part) of the composition that constitutes distance piece, being preferably more than the 50 volume %, more than the 70 volume %, also can be 100 volume % more preferably.On the other hand, in distance piece of the present invention, under the situation of using the porous substrate that constitutes by fibrous material described later, the cumulative volume of Resin A and inorganic particles B is in the cumulative volume (volume after removing the hole part) of the composition that constitutes distance piece, be preferably more than the 20 volume %, more preferably more than the 40 volume %.

In addition, in order to ensure the intensity or the shape stability of distance piece, also can make fibrous material and Resin A or be mixed together existence with inorganic particles B.As fibrous material, so long as heat resisting temperature (can't see the temperature of distortion during visualization) is more than 150 ℃, has electrical insulating property, stable on the electrochemistry, and stable in the solvent that when nonaqueous electrolyte that electrochemical element had or distance piece are made, uses, with regard to material, just be not particularly limited.And said among the present invention " fibrous material " is meant that aspect ratio [length of length direction/with the width (diameter) of the direction of length direction quadrature] is the material more than 4, and aspect ratio is preferably more than 10.

As the concrete constituent material of fibrous material, for example can enumerate resins such as cellulose and modification body thereof (carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC) etc.), polyolefin (copolymer of polypropylene (PP), propylene etc.), polyester (PETG (PET), PEN (PEN), polybutylene terephthalate (PBT) (PBT) etc.), polyacrylonitrile (PAN), aromatic polyamides, polyamidoimide, polyimides; Inorganic oxides such as glass, aluminium oxide, zirconia, silicon dioxide etc., these constituent materials also can contain more than 2 kinds.In addition, fibrous material also can contain known various additive (for example being antioxidant etc.) as required under the situation of resin.

In addition, it is below the thickness of distance piece that the diameter of fibrous material needs only, yet for example is preferably 0.01～5 μ m.If diameter is excessive, the winding deficiency between the fibrous material then constitutes making the sheet thing under the situation of base material of distance piece, and its intensity diminishes, thereby has the situation that is difficult to dispose.In addition, if diameter is too small, then the hole of distance piece becomes too small, and ion permeability has the trend of reduction, thereby has the situation of the load characteristic that reduces electrochemical element.

The content of the fibrous material in the distance piece all for example is being preferably more than the 10 volume % in the constituent, more preferably more than the 20 volume %.And the content of the fibrous material in the distance piece is preferably below the 70 volume %, more preferably below the 60 volume %, yet under situation about using as porous substrate described later, is preferably below the 90 volume %, more preferably below the 80 volume %.

For the existence of the fibrous material in the distance piece, for example the angle for the distance piece face of major axis (axle of length direction) on average is preferably below 30 °, more preferably below 20 °.

Distance piece of the present invention considers preferably have turn-off function from the viewpoint of the fail safe of further its electrochemical element of raising use.When giving turn-off function to distance piece, for example can enumerate make it to contain fusing point be the thermoplastic resin below 140 ℃ more than 80 ℃ (below be called " hot melt property resin C ".), perhaps make it to contain by heating and absorb aqueous nonaqueous electrolyte (nonaqueous electrolytic solution.Below economize sometimes slightly " electrolyte ".) and swelling takes place and the resin that also increases along with temperature rising swelling (below be called " hot swelling resin D ".)。Have with regard to utilizing above-mentioned method for the distance piece of turn-off function, in electrochemical element during heat release, hot melt property resin C fusion and stop up the hole of distance piece, or the nonaqueous electrolytic solution in the hot swelling resin D absorption electrochemical element, thereby the shutoff that produces the carrying out that suppresses electrochemical reaction.

As hot melt property resin C, the material that is preferably as follows, promptly, it is the resin below 140 ℃ more than 80 ℃ that fusing point promptly uses the measured fusion temperature of DSC according to the regulation of JIS K7121, and more preferably fusion temperature is more than 120 ℃, has electrical insulating property, stable the solvent that uses when nonaqueous electrolyte that electrochemical element had or distance piece are made, in addition, in the operating voltage range of electrochemical element, be difficult for oxidized reduction, stable on electrochemistry.Specifically, can enumerate polyethylene (PE), polypropylene (PP), copolymerization polyolefin, polyolefin derivative thing (haloflex etc.), polyolefin-wax, pertroleum wax, palm wax etc.As above-mentioned copolymerization polyolefin, can the vinyl-vinyl monomer copolymer be shown example, more particularly, can ethylene-acrylic acid copolymers such as ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer or ethylene-ethyl acrylate copolymer be shown example.The construction unit that derives from ethene in the above-mentioned copolymerization polyolefin is preferably 85 moles more than the %.In addition, also can use poly-cycloolefin etc.In hot melt property resin C, both can use above-mentioned illustrative resin independent a kind, also can use more than 2 kinds.

As hot melt property resin C, in the middle of above-mentioned illustrative material, the construction unit that is fit to use PE, polyolefin-wax, PP or derive from ethene is the above EVA of 85 moles of %.In addition, hot melt property resin C also can contain the known various additives (for example antioxidant etc.) that can add in the resin as required.

As hot swelling resin D, usually use resin with following character, that is, at the temperature province (about below 70 ℃) that battery was used, not Electolyte-absorptive, or uptake is restricted, so the degree of swelling is-below the Ding, yet when being heated to essential temperature (Tc), can Electolyte-absorptive and swelling significantly, and along with temperature rises, swelling also increases.In the electrochemical element that has used the distance piece that contains hot swelling resin D, in a side than Tc low temperature, owing in the hole of distance piece, there is the electrolyte that can flow that is not absorbed by hot swelling resin D, therefore the conductibility of Li (lithium) ion of distance piece inside uprises, become electrochemical element with good load characteristic, yet present along with the temperature of character that temperature rising swelling also increases (following be called sometimes " hot swelling ") when above being heated to, hot swelling resin D absorbs the interior electrolyte of electrochemical element and swelling significantly, hot swelling resin D after the swelling stops up the hole of distance piece, and reduce the electrolyte that can flow and make electrochemical element become the withered state of liquid, thereby the reactivity that can suppress electrolyte and active material, the fail safe that further improves electrochemical element.And when the high temperature that reaches above Tc, because of hot swelling makes the withered further aggravation of aforesaid liquid, the reaction of battery is subjected to further inhibition, therefore can also further improve the fail safe under the high temperature.

The temperature that hot swelling resin D begins to demonstrate hot swelling is preferably more than 75 ℃.This be because, be made as more than 75 ℃ by the temperature that hot swelling resin D is begun demonstrate hot swelling, thereby the conductibility of Li ion is reduced significantly and make the temperature that internal resistance rose (Tc) of electrochemical element be set at about more than 80 ℃.On the other hand, the lower limit of temperature that demonstrates hot swelling is high more, and then the Tc of distance piece becomes high more, and is therefore about below 130 ℃ for Tc is set at, and preferably the temperature that begins to demonstrate hot swelling of hot swelling resin D is made as below 125 ℃, more preferably be made as below 115 ℃.If it is too high to demonstrate the temperature of hot swelling, then can't suppress the unusual exothermic reaction of the active material in the electrochemical element fully, thereby have a situation of the effect of the fail safe that can't guarantee to improve electrochemical element fully, in addition, if it is low excessively to demonstrate the temperature of hot swelling, then have the situation that the conductibility of the Li ion in the serviceability temperature zone (about below 70 ℃) at common electrochemical element became low.

In addition, under than the low temperature of the temperature that demonstrates hot swelling, hot swelling resin D is Electolyte-absorptive not as much as possible preferably, and swelling is few more good more.This be because, serviceability temperature zone at electrochemical element, for example under the room temperature, if electrolyte is not included in by hot swelling resin D but is held with the state that can flow in the hole of distance piece, then the characteristics such as load characteristic of electrochemical element can become good.

Normal temperature (25 ℃) down the electrolyte content that absorbed of hot swelling resin D can utilize the hot swelling resin D of expression change in volume by the defined swelling B of following formula (1) _REstimate.

B _R＝(V ₀/V _i)-1 (1)

In the above-mentioned formula (1), V ₀Be illustrated in the volume (cm of the hot swelling resin D after flooding 24 hours under 25 ℃ in the electrolyte ³), V _iBe illustrated in the volume (cm of the hot swelling resin D before the dipping in the electrolyte ³).

In distance piece of the present invention, use under the situation of hot swelling resin D the swelling B of the hot swelling resin D under the normal temperature (25 ℃) _RBe preferably below 1, can expect by the swelling that absorption caused of electrolyte little, that is, and B _R, then good more near 0 little value.In addition, in temperature one side lower than the temperature that demonstrates hot swelling, the variations in temperature of expectation swelling becomes as far as possible little.

On the other hand, as hot swelling resin D, use following resin, that is, when the lower limit that is heated to the temperature that demonstrates hot swelling was above, the absorption quantitative change of electrolyte was big, in demonstrating the temperature range of hot swelling, along with temperature rising swelling also increases.For example, preferably use 120 ℃ that measure down, with the swelling B of following formula (2) definition _TIt is the resin more than 1.

B _T＝(V ₁/V ₀)-1 (2)

In the above-mentioned formula (2), V ₀Be illustrated in the volume (cm of the hot swelling resin D after flooding 24 hours under 25 ℃ in the electrolyte ³), V ₁Be illustrated in the electrolyte 25 ℃ down dipping make electrolyte be warmed up to 120 ℃ and after 24 hours at the volume (Gm of the hot swelling resin D after through 1 hour under 120 ℃ ³).

On the other hand,, then also have the situation of the distortion that produces electrochemical element, therefore be preferably below 10 if excessive with the swelling of the hot swelling resin D of above-mentioned formula (2) definition.

Can be with the swelling of above-mentioned formula (2) definition by using light scattering method or utilizing the such method of graphical analysis of the image that CCD camera etc. shoots, directly measure the variation of the size of hot swelling resin D, thereby estimate, yet for example can use following method to measure more exactly.

Use the known adhesive resins of swelling that define in the same manner with above-mentioned formula (1) and formula (2), under 25 ℃ and 120 ℃, in its solution or emulsion, heat of mixing swelling resin D and prepare slurry is coated on it on base materials such as PET sheet material or glass plate and makes film, measures its quality.Then, this film was flooded 24 hours in 25 ℃ electrolyte and quality measurement then, heats to 120 ℃ with electrolyte, be determined at 120 ℃ of quality that keep down after 1 hour, utilize following formula (3)～(9) to calculate swelling B _TAnd in following formula (3)～(9), the volume increase of composition when 25 ℃ are warmed up to 120 ℃, beyond the electrolyte can be ignored.

V _i＝M _i×W/P _A (3)

V _B＝(M ₀-M _i)/P _B (4)

V _C＝M ₁/P _C-M ₀/P _B (5)

V _V＝M _i×(1W)/P _V (6)

V ₀＝V _i+V _B-V _V×(B _B+1) (7)

V _D＝V _V×(B _B+1) (8)

B _T＝{V ₀+V _C-V _D×(B _C+1)}/V ₀-1 (9)

Here, in above-mentioned formula (3)～(9),

V _i: the volume (cm of the hot swelling resin D in electrolyte before the dipping ³),

V ₀: the volume (cm that in electrolyte, floods the hot swelling resin D after 24 hours at normal temperatures ³),

V _B: in electrolyte, flood after 24 hours volume (cm at normal temperatures by the electrolyte that film absorbed ³),

V _C: begin from the time point that electrolyte, has flooded at normal temperatures 24 hours, to electrolyte is warmed up to after 120 ℃ again under 120 ℃ through 1 hour during, by the volume (cm of the electrolyte that film absorbed ³),

V _V: the volume (cm of the adhesive resin in electrolyte before the dipping ³),

V _D: the volume (cm that in electrolyte, floods the adhesive resin after 24 hours at normal temperatures ³),

M _i: the quality (g) of the film in electrolyte before the dipping,

M ₀: in electrolyte, flood at normal temperatures the film after 24 hours quality (g),

M ₁: in electrolyte, flood at normal temperatures after 24 hours, with electrolyte be warmed up to after 120 ℃ again quality (g) at the film after through 1 hour under 120 ℃,

W: the quality ratio of the hot swelling resin D in the film in electrolyte before the dipping,

P _A: the proportion (g/cm of the hot swelling resin D in electrolyte before the dipping ³),

P _B: the proportion (g/cm of the electrolyte under the normal temperature ³),

P _C: the proportion (g/cm of the electrolyte under the set point of temperature ³),

P _V: the proportion (g/cm of the adhesive resin in electrolyte before the dipping ³),

B _B: in electrolyte, flood at normal temperatures the adhesive resin after 24 hours swelling,

B _C: the swelling of the adhesive resin during with the intensification of above-mentioned formula (2) definition.

In addition, can be according to the V that utilizes above-mentioned method to obtain by above-mentioned formula (3) and above-mentioned formula (7) _iAnd V ₀, use above-mentioned formula (1) to obtain swelling B under the normal temperature _R

And electrochemical element of the present invention is identical with known in the past electrochemical element, and the solution that for example will be dissolved with lithium salts in organic solvent uses as nonaqueous electrolyte that (details of the kind of lithium salts and organic solvent, lithium salt etc. is narrated in the back.)。Thus,, recommend following resin, that is, in the organic solvent solution of lithium salts, when any one temperature that arrives 75～125 ℃, begin to demonstrate above-mentioned hot swelling as hot swelling resin D, preferably can be in this solution so that swelling B _RAnd B _TSatisfy the mode of above-mentioned value and carry out swelling.

As hot swelling resin D, the material that is preferably as follows promptly, has thermal endurance and electrical insulating property, stable with respect to electrolyte, in addition, in the operating voltage range of battery, be difficult for oxidized reduction, stable on electrochemistry, as this kind material, for example can enumerate the resin crosslinks body.More particularly, can the crosslinked body that be selected from least a kind of resin in styrene resin (polystyrene (PS) etc.), styrene butadiene ribber (SBR), acrylic resin (polymethyl methacrylate (PMMA) etc.), polyalkylene oxide (poly(ethylene oxide) (PEO) etc.), fluororesin (Kynoar (PVDF) etc.) and their derivative be shown example; Urea resin; Polyurethane etc.In hot swelling resin D, can use above-mentioned illustrative resin independent a kind, also two or more kinds may be used.In addition, hot swelling resin D also can contain the known various additives that can add in the resin as required, for example antioxidant etc.

In the middle of above-mentioned constituent material, optimization styrene resin crosslinks body, the crosslinked body of acrylic resin and the crosslinked body of fluororesin, the crosslinked PMMA of preferred especially use.

Come Electolyte-absorptive that the mechanism of swelling and unclear takes place though rise by temperature, yet can think relevant with glass transition temperature (Tg) for these resin crosslinks bodies.That is, it is soft that in general resin becomes when being heated to its Tg, and therefore can infer: foregoing resin can absorb a large amount of electrolyte and swelling takes place under the temperature more than the Tg.Thereby as hot swelling resin D, that considers in the reality temperature specific heat swelling resin D that produces the shutoff effect begins that to demonstrate the temperature of hot swelling slightly high, then can think preferably use big about 75～125 ℃ of resin crosslinks bodies with Tg.And the Tg of said resin crosslinks body as hot swelling resin D uses the measured value of DSC according to the regulation of JIS K7121 in this specification.

In the above-mentioned resin crosslinks body, can select following material, promptly, under the so-called drying regime before containing electrolyte, even Yin Wendu rises and swelling, also can shrink once more by reducing temperature, be accompanied by the invertibity that has aspect the change in volume of variations in temperature to a certain degree like this, in addition, owing to have the heat resisting temperature more much higher than the temperature that demonstrates hot swelling, therefore be limited to about 100 ℃ even demonstrate the following of temperature of hot swelling, also can be heated to 200 ℃ or more than it.Thus, even heat, also do not have the impaired situation of hot swelling of resin fusing or resin in the production process of distance piece etc., it is easy that the disposal in the manufacturing process that comprises general heating process becomes.

Hot melt property resin C or hot swelling resin D (followingly are called " shutoff resin " with hot melt property resin C and hot swelling resin D sometimes in the lump.) form be not particularly limited, yet preferably use the resin of the shape of particulate, its size preferably has 1/100～1/3 average grain diameter of the thickness of distance piece so long as the particle diameter when dry gets final product less than the thickness of distance piece, specifically, average grain diameter is preferably 0.1～20 μ m.Under the too small situation of the particle diameter that turn-offs resin particle, the gap smaller between the particle, the conducting path of ion is elongated and the characteristic of electrochemical element is reduced.In addition, if it is excessive to turn-off the particle diameter of resin particle, then the gap becomes big and raising is diminished for the effect of the patience of the short circuit that is caused by lithium arborescence etc.And, the average grain diameter of turn-offing resin particle for example may be prescribed as: use laser light scattering particle size distribution meter (for example HORIBA corporate system " LA-920 "), make this microparticulate in not making the medium (for example water) that turn-offs resin generation swelling and the number average bead diameter that records.

In addition, turn-offing resin also can be above-mentioned form in addition, can also exist under the state after integrated on the surface that is layered in other inscape, for example inorganic particles or fibrous material.Specifically, also can be used as with inorganic particles and exist as the particle of the core shell structure of shell to turn-off resin as core, in addition, can also be the fiber that has the sandwich construction that turn-offs resin on the surface of core.In addition, also can by form at the one or both sides of distance piece contain the layer that turn-offs resin (only by turn-off the layer that resin forms or contain turn-off resin and adhesive layer etc.), have the shutoff resin in the distance piece thereby make.

For the content of the shutoff resin in the distance piece, the effect in order more easily to obtain to turn-off for example is preferably as follows.The volume of the shutoff resin in whole constituents of distance piece is preferably more than the 10 volume %, more preferably more than the 20 volume %.On the other hand, the aspect of the shape stability when guaranteeing the high temperature of distance piece considers that the volume of the shutoff resin in whole constituents of distance piece is preferably below the 50 volume %, more preferably below the 40 volume %.

Distance piece of the present invention for example can utilize the method for following (1)～(4) to make.The manufacture method of distance piece (1) is following method, promptly, preparation contains monomer or the oligomer that is used to form Resin A, Photoepolymerizationinitiater initiater, and inorganic particles B, also has the particle of employed as required hot melt property resin C or hot swelling resin D etc., and they are scattered in the volatile materials (volatile solvent) and liquid composition (slurry etc.) (monomer or oligomer, Photoepolymerizationinitiater initiater also can be dissolved in the volatile materials), with the coating of this liquid composition or infiltrate in porous substrate, carry out rayed and make the sheet material that distance piece forms usefulness, then by with volatile materials dry removing under the temperature of regulation, thereby form the hole.As the porous substrate under this situation, specifically, can enumerate at least a kind of porous sheet such as nonwoven fabrics of weaving cotton cloth, having the structure that to be entwined between these fibrous materials that constitutes by the fibrous material that in constituent, contains above-mentioned illustrative each material etc.More particularly, can the illustration paper delivery, nonwoven fabrics such as PP nonwoven fabrics, polyester non-woven fabric (PET nonwoven fabrics, PEN nonwoven fabrics, PBT nonwoven fabrics etc.), PAN nonwoven fabrics.

As the volatile materials that uses in the above-mentioned liquid composition, preferably the material that monomer or oligomer, Photoepolymerizationinitiater initiater, inorganic particles B etc. can be dispersed or dissolved equably for example is fit to use common organic solvents such as ketone such as furans such as aromatic hydrocarbon, oxolane, methylethylketone, methyl iso-butyl ketone (MIBK) such as toluene.And, in these solvents, also can be for the purpose of control surface tension force, suitably adding various expoxy propane such as alcohol (ethylene glycol, propylene glycol etc.) or acetate mono-methyl is glycol ethers etc.In addition, also water can be used for volatile materials, also can suitably add alcohols (methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol etc.) and come control surface tension force this moment.

In addition,, for example can use 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,2-dimethoxy-2 phenyl acetophenone, 2-hydroxy-2-methyl propiophenone etc. as Photoepolymerizationinitiater initiater.The use amount of Photoepolymerizationinitiater initiater is preferably with respect to amount 100 mass parts of monomer and oligomer and be made as 1～10 mass parts.

In the above-mentioned liquid composition, will comprise that preferably the solid component content of monomer or oligomer, Photoepolymerizationinitiater initiater, inorganic particles etc. is made as for example 10～50 quality %.

The manufacture method of distance piece of the present invention (2) is following method, promptly, preparation comprises monomer or the oligomer that is used to form Resin A, Photoepolymerizationinitiater initiater, inorganic particles B, and can be dissolved in material M among the specific solvent X (being not dissolved in the material among the employed solvent Y in the preparation of liquid composition), also have the particle etc. of employed as required hot melt property resin C or hot swelling resin D and they are scattered in liquid composition (slurry etc.) (monomer or the oligomer that forms among the solvent Y, Photoepolymerizationinitiater initiaters etc. also can be dissolved among the solvent Y), with the coating of this liquid composition or infiltrate in porous substrate, carry out rayed and make the sheet material that distance piece forms usefulness, then above-mentioned material M is extracted and the formation hole with above-mentioned specific solvent X.

As solvent X, for example can use methyl ethyl carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, oxolane, 6-caprolactone etc.

As the above-mentioned material M that can be dissolved among the specific solvent X, for example can use vistanex, polyurethane resin, acrylic resin etc.These materials for example preferably use emboliform resin, and its size or use amount can be adjusted according to desired hole rate of distance piece or aperture.As a rule, the average grain diameter of above-mentioned material (average grain diameter of utilizing the method identical with the average grain diameter of inorganic particles B to record) is preferably 0.1～20 μ m, in addition, use amount preferably in the middle of all solids composition of above-mentioned liquid composition, is made as 1～10 quality %.

For for the solvent Y in the above-mentioned liquid composition in the manufacture method (2), can use with manufacture method (1) in liquid composition in the identical material of operable volatile materials.In addition, the solid component content of the above-mentioned liquid composition of manufacture method (2) is identical with the situation of manufacture method (1), for example preferably is made as 10～50 quality %.In addition, for the above-mentioned liquid composition in the manufacture method (2), also can use with the situation identical materials of manufacture method (1) and come control surface tension force.

The manufacture method of distance piece of the present invention (3) is following method, promptly, the material identical with the above-mentioned liquid composition in the manufacture method (1) is coated on the base materials such as film or metal forming, carry out rayed and make the sheet material that distance piece forms usefulness, then volatile materials is utilized drying to remove and forms the hole under the temperature of regulation, from base material, peel off thereafter.And the liquid composition in the manufacture method (3) also can contain fibrous material, comprises that also the solid constituent amount of this fibrous material for example is preferably 10～50 quality %.

The manufacture method of distance piece of the present invention (4) is following method, promptly, the material identical with the above-mentioned liquid composition in the manufacture method (2) is coated on the base materials such as film or metal forming, carry out rayed and make the sheet material that distance piece forms usefulness, then above-mentioned material M is extracted with above-mentioned specific solvent X, thereby peel off from base material thereafter in the formation hole.And the liquid composition in the manufacture method (4) also can contain fibrous material, comprises that also the solid constituent amount of this fibrous material for example is preferably 10～50 quality %.

In addition, utilizing manufacture method (3) or manufacture method (4) to make under the situation of distance piece, also can be by the positive pole of electrochemical element and any one party in the negative pole be made as base material, thus form distance piece and the integrated structure that forms of electrode.Under this situation, distance piece is not peeled off from the electrode as base material.

With regard to distance piece and electrode integrated and structure for because the mixture layer of electrode and the adaptation height of distance piece, so can distance piece not peeled off from electrode, just electrode is reeled each other or stacked.In addition, owing to used the high Resin A of flexibility, therefore under the situation of the rechargeable nonaqueous electrolytic battery that uses coiling body, can prevent the short circuit in the bight in interior week of coiling body.

In manufacture method (1)～(4), as long as light-struck condition is made as the condition that adopts in the general photopolymerization.Specifically, for example as the light source of ultraviolet light and use the high-pressure mercury-vapor lamp of wavelength 365nm, with 60mW/cm ²Exposure intensity, rayed of carrying out 10 seconds etc. gets final product.And the light wavelength of using in the rayed, exposure intensity and irradiation time etc. can suitably change.

As the hole rate of distance piece, make ion permeability good for guarantor's liquid measure of under dry status, guaranteeing electrolyte, be preferably more than 10%.On the other hand, from guaranteeing distance piece intensity and the viewpoint consideration that prevents internal short-circuit, the hole rate of distance piece is preferably below 70% under dried state.And the hole rate of the distance piece under the dried state: P (%) can be by by the thickness of distance piece, the quality of unit are, the density of constituent, uses following formula (10) and obtain at the summation of each component i and calculate.

P＝100-(∑a _i/ρ _i)×(m/t) (10)

Here, in the above-mentioned formula, a _iBe the ratio of the component i represented with quality %, ρ _iBe the density (g/cm of component i ³), m is the quality (g/cm of the per unit area of distance piece ²), t is the thickness (cm) of the distance piece that records under the dried state.

In addition, with regard to distance piece of the present invention, the preferred utilization according to the method for JIS P8117 carried out and with at 0.879g/mm ²Pressure under the air of 100mL to see through the Gurley value that the second numerical table of film shows be 10～300sec.If the Gurley value is excessive, then ion permeability will diminish, and on the other hand, if too small, then has the situation that the intensity of distance piece diminishes.In addition, as the intensity of distance piece, be preferably more than the 50g with the perverse intensitometer of bundle of the pin that uses diameter 1mm.If it is too small to prick perverse intensity, then under the situation of the arborescence crystal that produces lithium, have the situation that stab out the short circuit that caused of generation by distance piece.By adopting above-mentioned formation, can form distance piece with above-mentioned Gurley value or thorn intensity.

Independent and have the thickness of the distance piece of the present invention under the situation of distance piece with respect to anodal and negative pole, from the anodal viewpoint consideration of isolating more reliably with negative pole, be preferably more than the 5 μ m, more preferably more than the 6 μ m, more preferably more than the 10 μ m.On the other hand,, then have the situation that the energy density made behind the battery reduces, so its thickness is preferably below the 70 μ m, more preferably below the 50 μ m, more preferably below the 30 μ m if the thickness of distance piece is excessive.And under the situation with distance piece and the integrated structure that forms of electrode, the thickness of so-called distance piece is meant the thickness of the distance piece of a face coating electrode.

As long as electrochemical element of the present invention has nonaqueous electrolyte and has the distance piece of the invention described above, for other formation and structure for be not particularly limited, can use the various formations and the structure that were adopted in the known in the past electrochemical element.

And electrochemical element of the present invention also comprises nonaqueous electrolyte primary cell or ultracapacitor etc. except that the nonaqueous electrolyte secondary cell, can be applied to ideally in the purposes of the fail safe under the special requirement high temperature.Below, be that the situation of rechargeable nonaqueous electrolytic battery is that the center is described in detail with electrochemical element of the present invention.

As the form of rechargeable nonaqueous electrolytic battery, can enumerate tubular (square tube shape or cylindrical shape etc.) that cylinder of steel or aluminium pot etc. are used as the outsourcing tinning etc.In addition, also can be made as with evaporation the flexible-packed battery of the laminated film of metal as the external packing body arranged.

In positive pole, for example can use the positive pole that has this structure of anode mixture layer that comprises positive active material, adhesive and conductive auxiliary agent etc. at the one or both sides of collector body.

As positive active material, can use used in the known in the past rechargeable nonaqueous electrolytic battery can occlusion, discharge the material of Li ion.For example can use with Li _1+xMO ₂The transition metal oxide that contains lithium, the LiMn of the layer structure of (0.1＜x＜0.1, M:Co, Ni, Mn, Al, Mg etc.) expression ₂O ₄Or with the part of its element with other element substitutions the lithium manganese oxide of spinel structure, with LiMPO ₄The olivine compounds of (M:Co, Ni, Mn, Fe etc.) expression etc.As the concrete example of the transition metal oxide that contains lithium of above-mentioned layer structure, except LiCoO ₂Or LiNi _1-xCo _X-yAl _yO ₂Beyond (0.1≤x≤0.3,0.01≤y≤0.2) etc., can also the oxide (LiMn that contain Co, Ni and Mn at least be shown example _1/3Ni _1/3Co _1/3O ₂, LiMn _5/12Ni _5/12Co _1/6O ₂, LiMn _3/5Ni _1/5Co _1/5O ₂Deng) etc.

As conductive auxiliary agent, can use carbon feedstocks such as carbon black, as adhesive, can use fluororesin such as PVDF, utilize mixed above-mentioned material and positive active material and anode mixture, can on collector body, form the anode mixture layer.

In addition, as the collector body of positive pole, can use the paper tinsel, stamped metal, net, expansion alloy of metal such as aluminium etc., be the aluminium foil of 10～30 μ m yet be fit to used thickness usually.

The leading part of side of the positive electrode is not normally by forming the anode mixture layer and the exposed division of residual collector body is provided with it as leading part in the part of collector body when positive pole is made.But, leading part not necessarily require be from from the beginning of just with collector body integrated part, also can by after make collector body be connected to wait to be provided with the paper tinsel of aluminum.

As negative pole, so long as used negative pole in the known in the past rechargeable nonaqueous electrolytic battery, promptly containing can occlusion, discharge the negative pole of the negative electrode active material of Li ion, just is not particularly limited.For example, as negative electrode active material, can use the sintered body, MCMB (MCMB), carbon fiber etc. of graphite, RESEARCH OF PYROCARBON class, coke class, vitreous carbon class, organic high molecular compound can occlusion, discharge the mixture more than a kind or 2 kinds of the carbon-based material of lithium.In addition, element and alloys thereof such as Si, Sn, Ge, Bi, Sb, In contain the compound that lithium nitride or otide containing lighium thing etc. can discharge and recharge under the low-voltage near the lithium metal, and perhaps lithium metal or lithium/aluminium alloy also can be used as the negative electrode active material use.As negative pole, the negative pole that can use the cathode agent that will suitably add conductive auxiliary agent raw material of wood-charcoal material such as (etc.) carbon blacks or adhesive (PVDF etc.) etc. and form in these negative electrode active materials to be processed as formed body (anode mixture layer) as core with collector body and make perhaps uses a kind of separately in the paper tinsel of above-mentioned various alloys or lithium metal or is laminated in the negative pole that forms on the collector body etc.

In negative pole, use under the situation of collector body,, can use the paper tinsel, stamped metal, net, expansion alloy of copper or nickel system etc., yet use Copper Foil usually as collector body.This negative electrode collector is under the situation of the thickness of attenuate negative pole integral body for the battery that obtains high-energy-density, and the upper limit of thickness is preferably 30 μ m, and lower limit is preferably 5 μ m.In addition, the leading part of negative side needs only and the leading part of side of the positive electrode is identically formed.

Electrode can use with the form of coiling body electrode group that above-mentioned positive pole and above-mentioned negative pole folder are formed across the electrode group of the stacked cascade type that forms of distance piece of the present invention and with its coiling.And, in the electrochemical element of the present invention, because the distance piece of the present invention of the anti-short-circuit excellence when having used warpage, therefore under the situation of having used the coiling body electrode group that distance piece is applied distortion, its effect is more obvious, under the situation of having used the coiling body electrode group (cross section is the coiling body electrode group of flat) that makes the flat that distance piece bends strongly, its effect is particularly evident.

As nonaqueous electrolyte, can use lithium salts is dissolved in the organic solvent and solution (nonaqueous electrolytic solution).As lithium salts, form Li so long as in solvent, dissociate ⁺Ion and be difficult for causing the material of side reactions such as decomposition in the employed voltage range as battery just is not particularly limited.For example can use LiClO ₄, LiPF ₆, LiBF ₄, LiAsF ₆, LiSbF ₆Deng inorganic lithium salt, LiCF ₃SO ₃, LiCF ₃CO ₂, Li ₂C ₂F ₄(SO ₃) ₂, LiN (CF ₃SO ₂) ₂, LiC (CF ₃SO ₂) ₃, LiC _nF _2n _{+ 1}SO ₃(2≤n≤7), LiN (R _fOSO ₂) ₂(R here, _fThe expression fluoroalkyl) organic lithium salt etc. such as.

As organic solvent used in the nonaqueous electrolyte,, just be not particularly limited so long as dissolve above-mentioned lithium salts and in employed voltage range, can not cause the material of side reactions such as decomposition as battery.For example can enumerate cyclic carbonates such as ethylene carbonate ester, propylene glycol carbonate, carbonic acid butanediol ester, vinylene carbonate; Linear carbonate such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate; Chain esters such as methyl propionate; Cyclic esters such as gamma-butyrolacton; Dimethoxy-ethane, diethyl ether, 1, chain ethers such as 3-dioxolanes, diethylene glycol dimethyl ether, triglyme, tetraethylene glycol dimethyl ether; Cyclic ethers such as diox, oxolane, 2-methyltetrahydrofuran; Nitriles such as acetonitrile, propionitrile, methoxypropionitrile; Sulfurous esters such as sulfurous acid glycol ester etc.; They also can mix more than 2 kinds and use.And, in order to make the battery of more good characteristic, preferably use mixed solvent of ethylene carbonate ester and linear carbonate etc. with the combination that can obtain high conductivity.In addition, in these nonaqueous electrolytes, purpose for the characteristic that improves fail safe or charge-discharge cycle, high temperature storage and so on also can suitably add additives such as vinylene carbonate class, 1,3-N-morpholinopropanesulfonic acid lactone, diphenyl disulfide, cyclohexane, biphenyl, fluorobenzene, tert-butyl benzene.

As the concentration of this lithium salts in nonaqueous electrolyte, preferably be made as 0.5～1.5mol/L, more preferably be made as 0.9～1.3mol/L.

Electrochemical element of the present invention can be used for the purposes identical with known in the past electrochemical element.

Embodiment

Below, will be described in detail the present invention based on embodiment.But following embodiment does not limit the present invention.

(embodiment 1)

The making of＜distance piece 〉

Will be as urethane acrylate 3.5 mass parts of oligomer, as diamyl oxidation pentaerythritol diacrylate 3.5 mass parts of monomer (crosslinking agent), as 2 of Photoepolymerizationinitiater initiater; 4,6-trimethylbenzoyl diphenyl phosphine oxide 0.05 mass parts, mix equably and prepare the slurry that distance piece forms usefulness as boehmite (average grain diameter 0.6 μ m) 32.95 mass parts of inorganic particles B and as toluene 60 mass parts of volatile materials.In this slurry,,, between the gap at interval, pass through behind the coating sizing-agent by lifting coating, next with 60mW/cm with regulation by the PET system nonwoven fabrics of thick 12 μ m ²The ultraviolet ray of 10 seconds wavelength 365nm of illumination irradiation, dry thereafter and remove toluene, obtain the distance piece of thick 16 μ m.

＜anodal making 〉

Will be as the LiCoO of positive active material ₂90 mass parts, as acetylene black 7 mass parts of conductive auxiliary agent and as the PVDF3 mass parts of adhesive,, mix as solvent with N-N-methyl-2-2-pyrrolidone N-(NMP), prepare the thickener that contains anode mixture.As the two sides of the aluminium foil of the thick 15 μ m of collector body so that to be coated with cloth length be that the mode of surperficial 280mm, back side 210mm intermittently is coated with ground this thickener of cloth, after the drying, carry out calender process, so that gross thickness reaches the thickness that the mode of 150 μ m is adjusted the anode mixture layer, making width is that positive pole is produced in the cutting of 43mm ground.Thereafter, the exposed division to the aluminium foil in the positive pole has carried out the joint installation.

The making of＜negative pole 〉

Will be as graphite 95 mass parts and the PVDF5 mass parts of negative electrode active material,, mix and prepare the thickener that contains cathode agent as solvent with NMP.So that being the mode of surperficial 290mm, back side 230mm, coating length is coated with this thickener on the two sides of the collector body of the thick 10 μ m that make by Copper Foil off and on, after the drying, carry out calender process, adjust the thickness of anode mixture layer so that gross thickness is the mode of 142 μ m, making width is that negative pole is produced in the cutting of 45mm ground.Thereafter, the exposed division of the Copper Foil in the anticathode has carried out the joint installation.

The assembling of＜battery 〉

The positive pole that obtains as previously mentioned and negative pole are superposeed in above-mentioned distance piece at folder, be wound into helical form and produce coiling body electrode group.The coiling body electrode group of gained flattened and make flat, pack in the aluminum outsourcing tinning of thick 4mm, high 50mm, wide 34mm, inject electrolyte (in that ethylene carbonate ester and methyl ethyl carbonate are mixed with volume ratio 1 to 2 must solvent dissolved LiPF with concentration 1.2mol/L ₆The solution that forms) seal after,, produce the prismatic nonaqueous electrolyte secondary battery of the outward appearance shown in Fig. 2 with the structure shown in Figure 1A, the B.

Here, if the battery shown in Figure 1A, B and Fig. 2 is described, then Figure 1A is the vertical view of the rechargeable nonaqueous electrolytic battery of present embodiment, and Figure 1B is the profile of Figure 1A.Shown in Figure 1B, positive pole 1 and negative pole 2 made to press from both sides as previously mentioned across distance piece 3 be wound into spiral helicine coiling body electrode group 6, be housed in the square outsourcing tinning 4 with nonaqueous electrolytic solution.Wherein, in Fig. 1, for fear of miscellaneousization, not shown anodal 1 or use during the making of negative pole 2 as the metal forming of collector body or electrolyte etc.

Outsourcing tinning 4 is an aluminium alloy system, is the part that constitutes the housing material of battery, these outsourcing tinning 4 double as positive terminals.And, dispose the insulator of making by polythene strip 5 in the bottom of external packing jar 4, from the coiling body electrode group 6 that constitutes by positive pole 1, negative pole 2 and distance piece 3, draw the positive wire body 7 and the negative wire body 8 that are connected with an end separately of positive pole 1 and negative pole 2.In addition, cover plate 9 places of the aluminium alloy system of sealing at the peristome with outsourcing tinning 4 folder is equipped with the terminal 11 of stainless steel across the insulating cell 10 of polypropylene system, and the lead plate 13 of stainless steel is installed across insulator 12 at this terminal 11 places folder.

In addition, this cover plate 9 is inserted into the peristome of above-mentioned outsourcing tinning 4, by the junction surface welding with both, and the peristome of outsourcing tinning 4 is sealed, and inside battery is airtight.And, in cover plate 9, be provided with electrolyte inlet 14, when battery is assembled, in battery, inject electrolyte from this electrolyte inlet 14, thereafter, inject the electrolyte into mouthful 14 sealings.In addition, in cover plate 9, be provided with the safety valve 15 of explosion-proof usefulness.

In the battery of this embodiment 1, by positive wire body 7 directly is welded on outsourcing tinning 4 and cover plate 9 are played a role as positive terminal, by negative wire body 8 is welded on the lead plate 13, by this lead plate 13 with negative wire body 8 and terminal 11 conductings, thereby terminal 11 is played a role as negative terminal, yet, also there is its positive and negative opposite situation according to material of outsourcing tinning 4 etc.

Fig. 2 is the stereogram that schematically shows the outward appearance of the battery shown in Figure 1A, the B, this Fig. 2 is to represent that above-mentioned battery is that the situation of rectangular cell is purpose and illustrated figure, diagrammatically represent battery among this Fig. 2, only illustrated the central specific member of member of formation of battery.In addition, among Figure 1B, the part of interior all sides of coiling body electrode group 6 is not made as section yet, in distance piece 3, has omitted the hatching of expression section.

(embodiment 2)

Use will be as urethane acrylate 15 mass parts of oligomer, as diamyl oxidation pentaerythritol diacrylate 15 mass parts of monomer, as 2 of Photoepolymerizationinitiater initiater; 4; 6-trimethylbenzoyl diphenyl phosphine oxide 0.15 mass parts, as boehmite (average grain diameter 0.6 μ m) 10 mass parts of inorganic particles B and as toluene 59.85 mass parts of volatile materials mix equably and slurry that the distance piece prepared forms usefulness with; in addition, produce distance piece in the same manner with embodiment 1.After this, except using this distance piece, produce rechargeable nonaqueous electrolytic battery in the same manner with embodiment 1.

(embodiment 3)

Except inorganic particles B being changed into titanium dioxide (average grain diameter 0.6 μ m), prepare the slurry that distance piece forms usefulness in the same manner with embodiment 1, except using this slurry, produce distance piece in the same manner with embodiment 1.After this, except using this distance piece, produce rechargeable nonaqueous electrolytic battery in the same manner with embodiment 1.

(embodiment 4)

Except inorganic particles B being changed to aluminium oxide (average grain diameter 0.4 μ m), prepare the slurry that distance piece forms usefulness in the same manner with embodiment 1, except using this slurry, produce distance piece in the same manner with embodiment 1.After this, except using this distance piece, produce rechargeable nonaqueous electrolytic battery in the same manner with embodiment 1.

(embodiment 5)

Use mould to be coated with machine and the gap is made as 40 μ m ground will be coated on the substrate surface of polytetrafluoroethylene system, follow with 60mW/cm with the slurry that the slurry identical distance part prepared among the embodiment 1 forms usefulness ²10 seconds ultraviolet ray of illumination irradiation, after drying, from base material, peel off down, obtain the distance piece that thickness is 16 μ m.Except using this distance piece, produce rechargeable nonaqueous electrolytic battery in the same manner with embodiment 1.

(embodiment 6)

Will be as urethane acrylate 13 mass parts of oligomer, as diamyl oxidation pentaerythritol diacrylate 13 mass parts of monomer, as 2 of Photoepolymerizationinitiater initiater; 4,6-trimethylbenzoyl diphenyl phosphine oxide 0.13 mass parts, mix equably and prepare the slurry that distance piece forms usefulness as boehmite (average grain diameter 0.6 μ m) 12.87 mass parts of inorganic particles B and as toluene 61 mass parts of volatile materials.In this slurry, be the PET system nonwoven fabrics of 12 μ m, utilize to lift coating and behind the coating sizing-agent, between the gap at interval, pass through, then with 60mW/cm with regulation by thickness ²10 seconds ultraviolet ray of illumination irradiation, carry out drying thereafter, obtain the perforated membrane that thickness is 12 μ m., in the one side of above-mentioned perforated membrane utilize mould be coated with machine so that dried thickness reach the mode of 4 μ ms be coated with the emulsion (the average grain diameter 1.0 μ ms of PE particulate) that contain PE particulate, carry out drying and form the pass tomography, obtain distance piece thereafter.Except using this distance piece, produce rechargeable nonaqueous electrolytic battery in the same manner with embodiment 1.

(embodiment 7)

Use will be as urethane acrylate 15.7 mass parts of oligomer, as isobornyl acrylate 10.4 mass parts of monomer (crosslinking agent), as 2 of Photoepolymerizationinitiater initiater; 4; 6-trimethylbenzoyl diphenyl phosphine oxide 0.78 mass parts, mix equably and the distance piece prepared forms the slurry of usefulness as boehmite (average grain diameter 0.6 μ m) 23.5 mass parts of inorganic particles B and as toluene 49.62 mass parts of volatile materials; in addition, produce distance piece in the same manner with embodiment 1.After this, except using this distance piece, produce rechargeable nonaqueous electrolytic battery in the same manner with embodiment 1.

(embodiment 8)

The slurry that will form usefulness with the slurry identical distance part of preparation among the embodiment 1 similarly uses mould to be coated with machine the gap is coated on the negative pole of making among the embodiment 1 with being made as 40 μ m.The coating back is with 60mW/cm ²10 seconds ultraviolet ray of illumination irradiation, further dry, obtain on anode mixture layer, being formed with the electrode (negative pole) of distance piece.Above-mentioned distance piece is formed at the two sides of negative pole, and the thickness of the integrated layer that forms of anode mixture layer and distance piece reaches 70 μ m respectively on the two sides of the collector body of negative pole.

Will with above-mentioned distance piece integrated electrode (negative pole) and the positive pole of in embodiment 1, making, between them, do not press from both sides the distance piece ground of establishing other and superposeed, with helical coil around and produce coiling body electrode group.Below, produce rechargeable nonaqueous electrolytic battery in the same manner with embodiment 1.

(embodiment 9)

The slurry that will form usefulness with the slurry identical distance part of preparation among the embodiment 1 similarly uses mould to be coated with machine the gap is coated on the negative pole of making among the embodiment 1 with being made as 3 μ m.The coating back is with 60mW/cm ²10 seconds ultraviolet ray of illumination irradiation, further dry, obtain on anode mixture layer, being formed with the electrode (negative pole) of distance piece.Above-mentioned distance piece is formed at the two sides of negative pole, and the thickness of the integrated layer that forms of anode mixture layer and distance piece reaches 5 μ mm respectively on the two sides of the collector body of negative pole.

(comparative example 1)

Use will be as urethane acrylate 2 mass parts of oligomer, as diamyl oxidation pentaerythritol diacrylate 2 mass parts of monomer, as 2 of Photoepolymerizationinitiater initiater; 4; 6-trimethylbenzoyl diphenyl phosphine oxide 0.02 mass parts, mix equably and the distance piece prepared forms the slurry of usefulness as boehmite (average grain diameter 0.6 μ m) 35.98 mass parts of inorganic particles B and as toluene 60 mass parts of volatile materials; in addition, produce distance piece in the same manner with embodiment 1.After this, except using this distance piece, produce rechargeable nonaqueous electrolytic battery in the same manner with embodiment 1.

(comparative example 2)

Use will be as urethane acrylate 16 mass parts of oligomer, as diamyl oxidation pentaerythritol diacrylate 16 mass parts of monomer, as 2 of Photoepolymerizationinitiater initiater; 4; 6-trimethylbenzoyl diphenyl phosphine oxide 0.16 mass parts, mix equably and the distance piece prepared forms the slurry of usefulness as boehmite (average grain diameter 0.6 μ m) 7.84 mass parts of inorganic particles B and as toluene 60 mass parts of volatile materials; in addition, produce distance piece in the same manner with embodiment 1.After this, except using this distance piece, produce rechargeable nonaqueous electrolytic battery in the same manner with embodiment 1.

(comparative example 3)

Except being that the PE microporous film of 16 μ m is used for producing rechargeable nonaqueous electrolytic battery in the same manner with embodiment 1 distance piece with thickness.

(comparative example 4)

The urethane acrylate, the diamyl oxidation pentaerythritol diacrylate and 2 that replace embodiment 1; 4; 6-trimethylbenzoyl diphenyl phosphine oxide, and with polyacrylic acid 7.05 mass parts, mix equably and prepare the slurry that distance piece forms usefulness as boehmite (average grain diameter 0.6 μ m) 32.95 mass parts of inorganic particles B and as isopropyl alcohol 60 mass parts of volatile materials.

Using mould to be coated with machine is made as 9 μ m ground with the gap this slurry is coated on the negative pole of making among the embodiment 1.The coating back is with 60mW/cm ²10 seconds ultraviolet ray of illumination irradiation, further dry, obtain on anode mixture layer, being formed with the electrode (negative pole) of distance piece.Above-mentioned distance piece is formed at the two sides of negative pole, and the thickness of the integrated layer that forms of anode mixture layer and distance piece reaches 16 μ m respectively on the two sides of the collector body of negative pole.

The formation of the distance piece that uses in the rechargeable nonaqueous electrolytic battery with embodiment 1～9 and comparative example 1～4 is shown in Table 1.

[table 1]

In the table 1, so-called " a/b value " is meant the ratio a/b of the volume a (remove cavity volume after volume) of Resin A and the volume b of inorganic particles B (remove cavity volume after volume), and so-called " total amount of Resin A and inorganic particles B " is meant the ratio of the cumulative volume of the volume a (remove cavity volume after volume) of Resin A and the volume b of inorganic particles B (remove cavity volume after volume) with respect to the cumulative volume of the constituent of distance piece (remove cavity volume after volume).

At first, the distance piece that uses in the rechargeable nonaqueous electrolytic battery to embodiment 1～9 has been confirmed the dimensional stability under the high temperature.That is, each distance piece (being the integrated distance piece of negative pole among the embodiment 8 and 9) was kept 1 hour in 150 ℃ thermostat, compared size (width and length) before keeping and the size after the maintenance.Consequently, do not see change in size, can be confirmed to be the distance piece that can prevent by the fail safe reduction of the battery that contraction caused under the high temperature.

Then, to the rechargeable nonaqueous electrolytic battery of embodiment 1～9 and comparative example 1～4, carried out the following test that discharges and recharges.That is,, to 4.2V, carry out the constant voltage charging under the 4.2V thereafter with the electric current constant current charge of 0.2C to each battery.Total charging time was made as 8 hours.Do not reach battery below the 0.02C for the electric current finish time, be judged as micro-short circuit has taken place in constant voltage charging.In addition, for the battery that micro-short circuit does not take place, after measuring internal resistance, with the electric current constant current discharge of 0.2C to 3V.In addition, each battery to after the discharge charges under condition same as described above, thereafter with the electric current constant current discharge of 2C to 3V, confirm whether can obtain the favorable charge-discharge characteristic.Above result is shown in the table 2.

[table 2]

	Discharge and recharge result of the test
		Embodiment 1	Well
Embodiment
	2	Well
Embodiment 3			Well
	Embodiment
4		Well
	Embodiment
5		Well
	Embodiment 6		Well
Embodiment 7		Well
	Embodiment
8		Well
	Embodiment
9		Well
	Comparative example 1		Bad (micro-short circuit)
Comparative example 2		Bad (micro-short circuit)
	Comparative example 3		Well
Comparative example 4		Well

In addition, for the battery of embodiment 6 that has used distance piece and comparative example 3 with shutoff resin, in order to estimate turn-off characteristic, and with discharge and recharge identical condition of when test under put into thermostat after charging, heat from 30 ℃ to 150 ℃ with the ratio elevated temperature of 1 ℃ of per minute, obtain the variations in temperature of the internal resistance of battery.After this, resistance value is elevated to value under 30 ℃ more than 5 times the time temperature be made as the shutoff temperature of this distance piece.In addition, after the temperature of battery arrives 150 ℃, under this state, carry out temperature with thermostat at 150 ℃ of elevated temperature tests that keep 2 hours.In elevated temperature test, observe the appearance of battery, determine the Da Wendu that is up to of battery.In addition, determine the voltage of the battery behind the elevated temperature test.Above result is shown in the table 3.

[table 3]

From table 2, can be clear that, used to contain with appropriate ratio of components and utilized photopolymerization to form and have the Resin A of cross-linked structure at least and micro-short circuit does not take place the rechargeable nonaqueous electrolytic battery of the embodiment 1～9 of the distance piece of inorganic particles B in a part, charge-discharge characteristic is good.In addition, as preceding above-mentioned, because the distance piece excellent in dimensional stability of using in the battery of EXAMPLE l～9 at high temperature, therefore as shown in table 3, voltage behind the elevated temperature test of the rechargeable nonaqueous electrolytic battery of embodiment 6 reduces little, turn-off function is played a role effectively, so the temperature during elevated temperature test rises and be inhibited, have high reliability and fail safe.

Relative therewith, with regard to having used as the battery of the comparative example 1 of the too small distance piece of the volume of Resin A and the a/b value of the ratio of the volume of inorganic particles B and having used with regard to the battery of comparative example 2 of the excessive distance piece of a/b value, micro-short circuit has taken place when the charging that discharges and recharges test.Can infer it is that in addition, the inorganic particles B in the battery spacers of comparative example 2 is few, so lack the cause of the anti-short-circuit between both positive and negative polarity respectively because the battery spacers of comparative example 1 lacks flexibility for these.In addition, in the battery of the comparative example 3 that has used common PE microporous film distance piece, in elevated temperature test, being up to Da Wendu uprises, voltage after the test also is reduced near the 0V, can think that to this cause of short circuit has taken place the result because produced the thermal contraction and the rupture of membranes of distance piece between both positive and negative polarity.

In addition, the distance piece for

embodiment

8,9 and comparative example 4 has carried out flexible appraisal.Flexible appraisal is after respectively the positive pole of making among the distance piece integrated electrode of gained and the embodiment 1 being made coiling body, utilize 90 ℃ hot press with the pressure of 2t with coiling body extruding 1 hour, utilize the coiling body after the visualization punching press that flawless is arranged.Its result has used in the coiling body of distance piece of

embodiment

8 and 9, does not observe crackle, and has used in the coiling body of distance piece of comparative example 4, has observed crackle.In addition, each coiling body after the use punching press, make rechargeable nonaqueous electrolytic battery in the same manner with embodiment 1, discharge and recharge test as hereinbefore, its result is in the battery of the distance piece that has used

embodiment

8 and 9, do not see short circuit, and in the battery of the distance piece that has used comparative example 4,, obtained being judged as the result that micro-short circuit has taken place based on criterion as hereinbefore.

And, in the battery of embodiment 1～7 in the battery of used distance piece and

embodiment

8 and 9 used distance piece integrated electrode can only utilize simple operation to make, therefore, can improve the productivity ratio of distance piece and battery (electrochemical element).

The present invention is in the scope that does not break away from its aim, even also can implement as the form beyond above-mentioned.Disclosed execution mode is an example among the application, is not limited to them.For scope of the present invention, explained by the record of above-mentioned specification, not equal to be by the record of the scope of the technical scheme of being added and preferentially explained, with the scope of the scope equivalence of technical scheme in all changes be included in the scope of technical scheme.

Symbol description

1 positive pole

2 negative poles

3 distance pieces

4 outsourcing tinnings

5 insulators

6 coiling body electrode groups

7 positive wire bodies

8 negative wire bodies

9 cover plates

10 insulating cells

11 terminals

12 insulators

13 lead plates

14 electrolyte inlets

15 safety valves

Claims

1. an electro chemical elements use distance piece is characterized in that,

Be to comprise the electro chemical elements use distance piece that forms and have the inorganic particles B of the Resin A of cross-linked structure and electrical insulating property by photopolymerization,

Wherein, remove cavity volume, the volume a of described Resin A and the ratio a/b of the volume b of described inorganic particles B are 0.6～9.

2. electro chemical elements use distance piece according to claim 1, wherein,

Described inorganic particles B is selected from least a in aluminium oxide, titanium dioxide, silicon dioxide and the boehmite.

3. electro chemical elements use distance piece according to claim 1, it also comprises fibrous material.

4. electro chemical elements use distance piece according to claim 1, its also comprise be selected from fusing point be 80～140 ℃ hot melt property resin C and by heating absorb that swelling takes place aqueous nonaqueous electrolyte and the hot swelling resin D that also increases along with temperature rising swelling at least a.

5. an electrode for electrochemical device is characterized in that,

Integrated and make with the described electro chemical elements use distance piece of claim 1.

6. an electrochemical element is characterized in that, is the electrochemical element that comprises positive pole, negative pole, distance piece and nonaqueous electrolyte,

Wherein, described distance piece is the described electro chemical elements use distance piece of claim 1.

7. electrochemical element according to claim 6, wherein,

Described distance piece is with anodal or integrated with negative pole.

8. the manufacture method of an electro chemical elements use distance piece is characterized in that, is the manufacture method of the described electro chemical elements use distance piece of claim 1, comprising:

Form the sheet material of usefulness from the electro chemical elements use distance piece that contains volatile materials, make described volatile substances and form the operation in hole; Perhaps

Form in the sheet material of usefulness from the electro chemical elements use distance piece that contains the material that can be dissolved in the specific solvent, utilize the described material of described solvent extraction, thereby form the operation in hole.

9. the manufacture method of electro chemical elements use distance piece according to claim 8, wherein,

Described volatile materials is water or organic solvent.