CN104205427A - Electrode for non-aqueous electrolyte secondary cell and non-aqueous electrolyte secondary cell using same - Google Patents
Electrode for non-aqueous electrolyte secondary cell and non-aqueous electrolyte secondary cell using same Download PDFInfo
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- CN104205427A CN104205427A CN201380016471.5A CN201380016471A CN104205427A CN 104205427 A CN104205427 A CN 104205427A CN 201380016471 A CN201380016471 A CN 201380016471A CN 104205427 A CN104205427 A CN 104205427A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/808—Foamed, spongy materials
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Abstract
Provided are an electrode for a non-aqueous electrolyte secondary cell in which electroconductivity does not readily fall even when subjected to a press treatment, and a non-aqueous electrolyte secondary cell using same. An electrode for a non-aqueous electrolyte secondary cell containing an electrode composite material including an active material capable of absorbing and desorbing lithium, characterized in that porous aluminum having a porosity of 80 to 95% functions as the collector, the electrode composite material is charged in the pores, and the particle diameter (da) of the active material and the pore diameter (dp) of the porous aluminum satisfy da/dp<= 0.10.
Description
Technical field
Even if the present invention relates to implement pressurized treatments conductivity is also difficult to the electrode for nonaqueous electrolyte secondary battery declining and uses the rechargeable nonaqueous electrolytic battery of this electrode.
Background technology
In recent years, rechargeable nonaqueous electrolytic battery is because reasons such as having high-energy-density is widely used.In this rechargeable nonaqueous electrolytic battery, make lithium ion between positive pole-negative pole, move the principle discharging and recharging thereby utilize.In rechargeable nonaqueous electrolytic battery, as positive active material, practical or strive realizing commercialization as the cobalt acid lithium of lithium metal oxide, LiMn2O4, lithium nickelate, ferric phosphate lithium etc.As negative electrode active material, use the material with carbon elements such as graphite.And, there is the electrode of conductive agent and bonding agent composite material to hold on the collector body of aluminium foil or the such metal forming of Copper Foil by adding in these positive active materials and negative electrode active material, form positive pole or negative pole.
Because battery capacity depends on the amount of active material, therefore, by hold active material as much as possible on collector body, can realize the high capacity of battery.Use aluminium foil or the such metal forming of Copper Foil at collector body, metal forming is two-dimensional structure, and the active matter quality holding is few, poorer than porous body in this.Therefore,, in order to increase the active matter quality holding in electrode, also can consider three-dimensional porous bodies such as foaming body or nonwoven fabrics shapes for collector body.For example, in patent documentation 1, recorded a kind of collector body being made up of three-dimensional porous body, this three-dimensional porous body is by resinous nonwoven fabrics and be formed at the conductive layer of this nonwoven surface and use and in non-water solvent, be dissolved with the body lotion of aluminium salt and the aluminium electroloysis electrodeposited coating that forms on the surface of this conductive layer forms.In addition, in patent documentation 2, having recorded a kind of is nonwoven fabrics shape nickel chromium triangle porous collector bodies more than 25 quality % to the processing of nonwoven fabrics shape nickel enforcement chromaking, chromium containing ratio.
But, these collector bodies have oxidative resistance and electrolyte resistance, vesicularity is improved, even if thereby be suitable for industrial production and rolled electrode group also can not be short-circuited positive pole and the battery of fault for providing, utilize this fibrous tectosome that shows as three-dimensional netted body, in the time of repeated charge, firmly keeping repeatedly can not be satisfactory aspect the active material of dilation.
In addition, as the manufacture method of porous metals, known: in the metal of melting, to mix the blowing agents such as titantium hydride, under the state that comprises produced gas, make its liquation foaming solidifying (patent documentation 3); With by metal dust and sodium chloride uniformly-spaced material mix, carry out compression forming, by metal dust energising heating, remove the interval method (patent documentation 4) of interval insulant etc. afterwards.
But can utilize the porous aluminum that patent documentation 3 is made is hole obturator-type independent of each other, can not fill active material or immerse electrolyte, therefore, cannot use as electrode.In addition, the hole forming in the porous aluminum that can utilize the interval method of recording in patent documentation 4 to make, its metal dust being around sintered surrounds, therefore be the structure that is suitable for firmly keeping active material, but, in the time utilizing the method for passing through discharge plasma sintering (SPS), need large electric current, therefore, size is restricted, and is difficult to manufacture practical porous metals.In addition, in the porous aluminum in hole with this structure, exist while carrying out pressurized treatments under the state of the fillers such as active material in hole, hole wall is because filler sustains damage, the problem that exists the conductivity of porous aluminum to decline.In addition, in patent documentation 5, also record a kind of nonaqueous electrolyte battery collector body, employing vapor phase method etc. forms aluminium alloy layer on the resinite surface with intercommunicating pore, by resinite thermal decomposition, is filled with active material thus in the thread aluminium porous body of the hollow of having removed resinite.But, in this collector body, fill active material just taking the thread post of hollow as the mode of core is kept, the problem that exists active material easily to come off from aluminium porous body.In addition, this aluminium porous body as shown in Figure 4, the space segment of hollow beyond thread be not situated between by wall form the intercommunicating pore of three-dimensional integrated expansion.
Formerly technical literature
Patent documentation
Patent documentation 1: TOHKEMY 2010-9905 communique
Patent documentation 2: TOHKEMY 2009-176517 communique
Patent documentation 3: Japanese kokai publication hei 11-302765 communique
Patent documentation 4: TOHKEMY 2004-156092 communique
Patent documentation 5: TOHKEMY 2011-249260 communique
Summary of the invention
Invent problem to be solved
Invention In view of the foregoing completes, its object be to provide a kind of can be because of pressurized treatments time active material damage porous aluminum wall cause the electrode for nonaqueous electrolyte secondary battery that the conductivity of electrode declines and the rechargeable nonaqueous electrolytic battery that uses this electrode.
For solving the means of problem
In order to solve the problem of prior art, the present inventor conducts in-depth research, found that: electrode for nonaqueous electrolyte secondary battery is configured to from existing porous metals and constructs different porous aluminum collector bodies and be filled in the electrode composite material in its hole, in the hole of porous aluminum collector body, filling bag, containing the electrode composite material of active material, can hold thus active material and prevent from coming off in hole.And find to meet da/dp≤0.10 by the particle diameter da of active material and the aperture dp of porous aluminum, in the time of pressurized treatments, active material can not damage porous aluminum wall, thereby can prevent electrode conductivity decline, result, can realize by the increase of electrode capacity the raising of battery behavior.
; a first aspect of the present invention is a kind of rechargeable nonaqueous electrolytic battery; it contains and comprises the electrode composite material that can occlusion discharges the active material of lithium; above-mentioned electrode for nonaqueous electrolyte secondary battery is characterised in that: using the porous aluminum with 80～95% porosity as collector body; in this hole, be filled with above-mentioned electrode composite material, the particle diameter da of above-mentioned active material and the aperture dp of porous aluminum meet da/dp≤0.10.
A second aspect of the present invention is a kind of rechargeable nonaqueous electrolytic battery, in above-mentioned first aspect, above-mentioned electrode composite material, except comprising active material, also comprises conductive auxiliary agent and bonding agent, and active material is 85～95 quality % with respect to the ratio of whole electrode composite materials.
A third aspect of the present invention is a kind of rechargeable nonaqueous electrolytic battery, it is characterized in that, at least one using the electrode for nonaqueous electrolyte secondary battery described in above-mentioned first aspect or second aspect as anodal and negative pole, rechargeable nonaqueous electrolytic battery comprises the barrier film and the nonaqueous electrolyte that are disposed between both positive and negative polarity.
Invention effect
Rechargeable nonaqueous electrolytic battery of the present invention is made up of the porous aluminum that is filled with the electrode composite material that comprises active material in hole, and the particle diameter da of active material and the aperture dp of porous aluminum meet da/dp≤0.10, thereby active material can not damage porous aluminum wall in the time of pressurized treatments, can prevent that the conductivity of electrode from declining.As a result, can obtain the rechargeable nonaqueous electrolytic battery of the high power capacity that internal resistance is little.
Brief description of the drawings
Fig. 1 is the electron micrograph that represents the inside of the porous aluminum collector body using in the present invention.
Fig. 2 represents that the particle diameter da of active material and the aperture dp of porous aluminum collector body meet da/dp≤0.10 o'clock, is accommodated in the schematic diagram of the active material in the hole of porous aluminum collector body.
Fig. 3 is while representing that the particle diameter da of active material and the aperture dp of porous aluminum collector body meet da/dp > 0.10, is accommodated in the schematic diagram of the active material in the hole of porous aluminum collector body.
Fig. 4 is the microphotograph that represents the inside of existing aluminium porous body.
Embodiment
Below, porous aluminum collector body electrode for nonaqueous electrolyte secondary battery of the present invention being used is described in detail.Wherein, this porous aluminum can be applicable in anodal and negative pole collector body or two collector bodies of any.
(a) porous aluminum collector body
The porous aluminum collector body using in the present invention by aluminium powder that volume ratio is according to the rules mixed with support the mixed-powder extrusion forming of powder, this formed body is heat-treated under torpescence atmosphere and sintering, support powder the most at last and remove and obtain afterwards.In addition, also can be by compound to mixed-powder and metallic plate.As shown in Figure 1, porous aluminum collector body is made up of the hole after supporting powder and being removed and the combination metal dust wall that forms the aluminium powder through oversintering of the surrounding in this hole.On in conjunction with metal dust wall, be formed with a large amount of fine holes, the structure of the open cell type that formation hole links by these fine holes each other.
The porosity of porous aluminum collector body, the porosity before pressurized treatments described later is defined as 80～95%.When porosity is lower than 80% time, the hole that hole is linked is each other few, cannot in hole, fill the active material of ormal weight, is difficult to realize the high capacity of battery.In addition, fully do not fill active material and refer to that electrolyte is also difficult to infiltration, because pressurized treatments makes space compressed, more difficult thereby the immersion of electrolyte becomes, result, contributes to the active material of cell reaction to reduce, and the utilance of active material reduces.On the other hand, in the time that porosity exceedes 95%, the undercapacity of collector body self cannot be filled composite material and be made electrode in hole.The porosity of porous aluminum collector body more preferably 85%～90%.
At this, the porosity p (%) of the porous aluminum collector body before pressurized treatments calculates by following formula (1).
p＝[{hv－(hw/2.7)}/hv]×100 (1)
Wherein,
Hv: the cumulative volume (cm of the porous aluminum collector body before pressurized treatments
3)
Hw: the quality (g) of the porous aluminum collector body before pressurized treatments
2.7: the density (g/cm of aluminum
3)
(b) aluminium powder
The aluminium powder using in the present invention adopts fine aluminium powder, Al alloy powder or their mixture.Under environment for use, alloying component becomes the reason of corrosion resistance variation, preferably uses fine aluminium powder.Fine aluminium is that purity is aluminium more than 99.0mass%.
On the other hand, going in more high-intensity situation, preferably using the mixture of Al alloy powder or it and fine aluminium powder.As aluminium alloy, use the aluminium alloy of 1000 series, 2000 series, 3000 series, 4000 series, 5000 series, 6000 series, 7000 series.
The particle diameter of aluminium powder is 1～50 μ m preferably.In the manufacture of porous aluminum collector body, for the surface of supporting powder all being covered with aluminium powder, preferably the particle diameter of aluminium powder is less, more preferably 1～10 μ m.The particle diameter of aluminium powder specifies according to the median particle diameter that adopts laser diffraction and scattering method (Micro-track method) to record.
(c) add element powders
Also can use and in fine aluminium powder, add the mixture that adds element powders.This interpolation element is applicable to employing and is selected from the independent a kind of element in magnesium, silicon, titanium, iron, nickel, copper, zinc etc. or the multiple element being made up of two or more combination in any.This mixture by heat treatment forms aluminium and the alloy that adds element.In addition, according to the kind of adding element, can also form aluminium and the intermetallic compound that adds element.By containing this aluminium alloy or intermetallic compound, can obtain various effects.For example, add in the aluminium alloy of element and aluminium at silicon or copper etc., the melting point depression of aluminium powder, can reduce the required temperature of heat treatment, therefore can cut down and manufacture required energy, and by alloying, its intensity be improved.In addition, in the time forming the intermetallic compound of the interpolation elements such as aluminium and nickel, produce heat release and acceleration of sintering, and form the tissue that intermetallic compound disperses, thereby realize high strength.
Can in Al alloy powder, add interpolation element powders, also can in the mixture of Al alloy powder and fine aluminium powder, add interpolation element powders.In these cases, can form new alloy system or intermetallic compound.In addition, as adding element powders, can also use the multiple interpolation element powders interpolation mischmetal powder of alloying each other.
Add element powders or add the addition of mischmetal powder with respect to Al alloy powder or fine aluminium powder, suitably determine according to the formula weight of the alloy forming or intermetallic compound.
In addition, add preferably 1～50 μ m of particle diameter of element powders.In order to realize and fully the mixing of fine aluminium powder, Al alloy powder, support powder, preferable particle size is more fine, uses at least than supporting the thin powder of powder.The particle diameter that adds element powders is same with aluminium powder, specifies according to the median particle diameter that adopts laser diffraction and scattering method (Micro-track method) to record.
(d) support powder
In the present invention, as supporting powder, use the powder with the fusing point higher than the fusing point of aluminium powder.In addition, by mixed-powder and metallic plate Composite in the situation that, use the powder with the fusing point higher than the low melting point in aluminium powder and metallic plate.As this support powder, preferred water soluble, from easily obtaining aspect, is applicable to using sodium chloride or potassium chloride.Support the space that forms of powder and become the hole of porous aluminum by removing, thereby support the particle diameter reaction aperture of powder.The particle diameter of the support powder therefore, using in the present invention is 100～1000 μ m preferably.The particle diameter that supports powder is specified by screen cloth mesh.Therefore,, by utilizing classification to make to support the particle diameter of powder consistent, can obtain the consistent porous aluminum in aperture.
(e) metallic plate
In the present invention, can will under mixed-powder and the compound state of metallic plate, use.Metallic plate is the reticulate body of the plate of atret-or paper tinsel and porose wire netting, expanding metal, punch metal etc.Metallic plate is as supporter, and the intensity of porous aluminum collector body improves, and then conductivity improves.As metallic plate, be applicable to not occurring while using heat treatment the raw material of evaporation or decomposition, particularly, be applicable to using the material of the metals such as aluminium, titanium, iron, nickel, copper or its alloy system.
The Composite of mixed-powder and metallic plate refers to: for example use wire netting in the situation that at metallic plate, fill mixed-powder and cover the integrated form of whole net with mixed-powder in mesh.Be provided with in conjunction with for example catalyst filling or active material in the porous aluminum of metal dust wall in the both sides of metallic plate, if metallic plate is porose reticulate body, even fill from a side in the region cut apart by metallic plate, also can be filled to opposite side region, therefore preferable alloy plate is reticulate body.At this, mesh part, the fiber of metallic fiber and the gap portion of fiber of the mesh part of porose finger wire netting, the punching part of punch metal, expanding metal.
The porose aperture of reticulate body both can be larger than the aperture of removing the hole of supporting powder and obtain from the mixed-powder engaging, also can be less than it.
In order not damage the porosity of porous aluminum collector body, also preferably the porose aperture opening ratio of reticulate body is large.
(f) mixed method
Aluminium powder with support the mixed proportion of powder, volume is separately made as to Val, Vs, the volume fraction Val/ (Val+Vs) of aluminium powder preferably 5～20%, more preferably 10～15%.At this, volume Val, Vs are the values of obtaining according to quality separately and proportion.Exceed 20% at the volume fraction of aluminium powder, support the containing ratio of powder very few, therefore support that powder does not contact each other and independent existence can not be removed fully completely by supporting powder.The support powder not being completely removed becomes the reason of porous aluminum corrosion.On the other hand, at the volume fraction of aluminium powder, lower than 50%, the wall that forms porous aluminum became thin, thereby the undercapacity of porous aluminum, was difficult to process and keep shape.
In addition, in order to realize the state that fully covers support powder with aluminium powder, preferably the particle diameter (dal) of aluminium powder is enough little compared with supporting the particle diameter (ds) of powder, and for example dal/ds is below 0.10.
Wherein, as by aluminium and the mixed media that support powder mixes, can use oscillating mixer, container rotary blender etc., as long as can obtain sufficient admixture, be not particularly limited.
(g) Composite method
When mixed-powder is filled in mold for forming, can be by mixed-powder and metallic plate Composite.As the mode of Composite, both can between mixed-powder, sandwich metallic plate, also can clamp mixed-powder with metallic plate.Can also repeatedly carry out the Composite of mixed-powder and metallic plate and form multistage.In the time of Composite, also can combined aluminium powder and different mixed-powder and the diverse various metals plates of particle diameter, mixed proportion that supports powder.
(h) extrusion forming method
More than the preferred 200Mpa of pressure when extrusion forming.Carry out moulding by applying enough pressure, aluminium powder rubs each other, and the firmly oxidation overlay film on the aluminium powder surface of sintering is destroyed each other to hinder aluminium powder.This oxidation overlay film is in contact with one another aluminium sealing, the prevention of melting, and poor with the wettability of molten aluminum, possesses the effect of repelling liquid aluminium.Therefore, at the pressure of extrusion forming, lower than 200MPa, the destruction of the oxidation overlay film on aluminium powder surface is insufficient, and when heating, the aluminium of melting oozes out sometimes outside formed body, the glomerate aluminium block of shape.Because forming aluminium block, the porosity of porous aluminum becomes higher than desired value.Therefore,, aspect the porosity of uncontrollable porous aluminum, the formation of this aluminium block is drawback.In addition, cause shape destroyed because forming aluminium block, in this point, also become problem must be removed.As long as the device using and mould allow, the porous aluminum wall forming when briquetting pressure is large becomes firm and preferred.But, if exceed 400MPa, there is the tendency that effect is saturated.In order to improve the release property of extrusion forming body, preferably use the lubricant of the metal base such as aliphatic acid, zinc stearate such as stearic acid, various wax, synthetic resin, the synthetic hydrocarbon of olefines etc.
(i) heat treatment method
Heat treatment is above and carry out lower than the temperature of the fusing point that supports powder with the fusing point of the aluminium powder that used.The fusing point of aluminium powder refers to that the temperature of liquid phase appears in pure aluminum or aluminum alloy.By being heated to occur the temperature of liquid phase, liquid phase is oozed out from aluminium powder, and liquid phase contacts with each other, thus make aluminium powder each other metallicity combination.
In heat treatment temperature lower than above-mentioned fusing point in the situation that, due to not melting of aluminium, thereby aluminium powder each other, the combination of aluminium powder and metallic plate is insufficient.In addition, being heated to above-mentioned fusing point when above, the surperficial aluminium that covers the support powder that is positioned at sintered body most surface is removed, and forms and has the surperficial sintered body that aperture opening ratio is large.When the aperture opening ratio of sintered body is large, in the time being applied to collector body, be conducive to fill active material.
If heating-up temperature, more than supporting the fusing point of powder, will cause supporting powder melts, therefore heat with the temperature lower than the fusing point that supports powder and carry out.As support powder and use the water soluble salts such as sodium chloride or potassium chloride in the situation that, preferably with lower than 700 DEG C, heat-treat more preferably less than 680 DEG C.In the case of the temperature more than fusing point to support powder heats, follow the melting of supporting powder, cannot maintain the shape of hole body.In addition, temperature is higher, and the viscosity of the aluminium of melting is lower, and the aluminium of melting oozes out into the outside of extrusion forming body, forms the aluminium block of convex.Because forming aluminium block, the porosity of porous aluminum becomes higher than desired value.Aspect the porosity of uncontrollable porous aluminum, the formation of this aluminium block is drawback.In addition, cause shape destroyed because forming aluminium block, in this point, also become problem must be removed.The heating retention time in heat treatment is preferably about 1～60 minute.In addition, also can in the time of heat treatment, on extrusion forming body, apply load, carry out the compression of extrusion forming body, or repeatedly carry out repeatedly heating and cooling.
The torpescence atmosphere of heat-treating is to suppress the atmosphere of aluminum oxidation, is applicable to adopting vacuum, the atmosphere of nitrogen, argon gas, hydrogen, decomposition ammonia and their mist.Preferably vacuum atmosphere.Vacuum atmosphere preferably 2 × 10
-2below Pa, more preferably 1 × 10
-2below Pa.Exceeding 2 × 10
-2in the situation of Pa, be adsorbed on aluminium powder surface moisture remove insufficiently, in the time of heat treatment, aluminium surface is oxidized.As mentioned above, the oxidation overlay film on aluminium surface and the wettability of liquid aluminium are poor, and result causes the aluminium of melting to ooze out and glomerate of shape.The in the situation that of the torpescence atmosphere such as nitrogen, preferably oxygen concentration below 1000ppm, dew point is below-30 DEG C.
(j) remove the method that supports powder
Removing support powder in sintered body is applicable to adopting and makes to support powder stripping and method of carrying out in water.Bathe medium method by sintered body being immersed in to enough water-baths or flowing water, can easily will support powder stripping.The support powder of stripping in water is removed from sintered body by the fine holes that is formed at metal dust wall.In the situation that using water soluble salt as support powder, make the few water of impurity such as water preferred ion exchanged water or distilled water of its stripping, but running water do not have special problem yet.The dip time conventionally scope about a few hours～24 hour is suitably selected.By utilizing ultrasonic wave etc. to apply vibration, also can promote stripping in dipping.
(k) electrode
As electrode for nonaqueous electrolyte secondary battery of the present invention, anodal and negative pole all can be suitable for.Kind electrode contains electrode composite material, and this electrode composite material comprises the active material that can occlusion discharges lithium.Under the state of electrode composite material in the hole that is filled in above-mentioned porous aluminum current collection ladder, held.Electrode composite material, except active material, can also comprise conductive auxiliary agent and bonding agent.
, as long as the positive active material using can be used in rechargeable nonaqueous electrolytic battery, be not particularly limited be anodal in the situation that at electrode, for example, can use the lithium metal oxides such as the sour lithium of cobalt, LiMn2O4, lithium nickelate, LiFePO4.In the situation that electrode is negative pole, as long as the negative electrode active material using can be used in rechargeable nonaqueous electrolytic battery, be not particularly limited.
No matter be positive pole or negative pole, by add conductive auxiliary agent in electrode composite material, the conductivity of electrode integral improves.Be not particularly limited as conductive auxiliary agent, can use known or commercially available material.For example, can enumerate the carbon black such as acetylene black, Ketjen black, active carbon, graphite etc.
No matter be positive pole or negative pole, by add bonding agent in electrode composite material, the combination of the composition by bonding agent, active material each other, conductive auxiliary agent each other, the combination of active material and conductive auxiliary agent becomes firmly, is more difficult to occur active material coming off from collector body.Be not particularly limited as used bonding agent, can use known or commercially available material.For example, can enumerate Kynoar (PVDF), polytetrafluoroethylene (PTFE), polyvinylpyrrolidone (PVP), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, butadiene-styrene rubber (SBR), polyvinyl alcohol (PVA), carboxymethyl cellulose (CMS) etc.
In addition, conventionally in electrode composite material, add conductive auxiliary agent and bonding agent, in this case, no matter be positive pole or negative pole, active material is with respect to preferably 85～95 quality % of ratio of whole electrode composite materials (active material+conductive auxiliary agent+bonding agent).If this ratio is lower than 85 quality %, active material deficiency, cannot realize high battery capacity.On the other hand, if this ratio exceedes 95 quality %, the conductivity of electrode integral declines, and can not obtain each composition separately between or abundant combination between composition, can not realize high battery capacity.
For this electrode for nonaqueous electrolyte secondary battery, the particle diameter da of the active material before pressurized treatments and the aperture dp of porous aluminum must meet da/dp≤0.10.But in the situation that active material particle gathering becomes second particle, da is as the particle diameter processing of second particle.Fig. 2 schematically shows the situation that meets this ratio.In this case, da is enough little compared with dp, so active material 1 formation is accommodated in the state in hole 3 and can damage porous aluminum wall 2 when pressurized treatments.In contrast, as shown in the schematic diagram of Fig. 3, the in the situation that of da/dp > 0.1, da is enough not little compared with dp, so the strong extruding porous aluminum of active material 1 wall 2 when pressurized treatments in hole 3, is damaged (4 in figure is damaged portion).Result causes the conductivity of electrode to decline.In addition, for the not special regulation of lower limit of da/dp, by 1 × 10
-5as lower limit.In conductivity and the poor active material of ionic conductivity, particle diameter da is less, and the efficiency of electrode reaction is just larger, so from battery performance aspect, da is the smaller the better.But particle diameter da is less, the surface area of active material will increase, and just more needs to increase the ratio of the conductive auxiliary agent that is used for guaranteeing the conductivity between active material.The ratio of the active material in result composite material reduces, and may cause the energy density of battery to reduce.Therefore, preferably do not utilize the active material of particle diameter lower than tens of nm.From with the relation of particle diameter of making the support powder that porous aluminum collector body uses, da/dp preferably 1 × 10
-5.
The particle diameter da of active material refers to the diameter of a circle that is equivalent to of active material., refer to have and the sectional area diameter of a circle of the same area of active material.By the sectional area of microscopic examination numerical computations active material, calculate thus and be equivalent to diameter of a circle, obtain particle diameter da.10 above active material samples are carried out to microscopic examination, utilize arithmetic mean to determine particle diameter da.
Form and have the shape of major diameter and minor axis in the hole of porous aluminum, the major diameter of aperture dp finger-hole.In addition, in hole, be circular in the situation that, aperture dp refers to diameter.The microscopic examination in the cross section by the porous aluminum collector body before pressurized treatments, to 10 above mensuration aperture, hole dp, utilizes their arithmetic mean to determine aperture dp.
Below, the manufacture method of electrode for nonaqueous electrolyte secondary battery is described.Conventionally active material, conductive auxiliary agent and bonding agent, under the slurry form being scattered in solvent, are filled in porous aluminum collector body.Active material, conductive auxiliary agent and the bonding agent concentration in slurry does not limit, and suitably selects from the viewpoint of slurry viscosity etc.In addition, can in viscosity regulates, add tackifier, in order to form good dispersity, also can add dispersant.The solvent of slurry is also not particularly limited, for example, be applicable to using METHYLPYRROLIDONE, water etc.In the situation that using Kynoar as bonding agent, preferably METHYLPYRROLIDONE is used for to solvent.Use polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose etc. as bonding agent in the situation that, preferably by water for solvent.
The composition of active material, conductive auxiliary agent and bonding agent (tackifier as required and/or dispersant) is scattered in to the slurry in solvent, for example, is filled in porous aluminum collector body by known methods such as plunging.As plunging, using porous aluminum collector body as barrier film, at a side configuration slurry, opposite side sees through side as slurry.So, thereby slurry is seen through the side decompression that sees through of opposite side, thus, in the hole of porous aluminum collector body, fill above-mentioned each composition.Also can replace this method, to being disposed at the slurry pressurization of a side, thus, in the hole of porous aluminum collector body, fill above-mentioned each composition.
In addition, also can replace plunging, adopt porous aluminum collector body is immersed in the slurry that is dispersed with above-mentioned each composition in solvent, makes above-mentioned each composition be diffused into the method (hereinafter referred to as infusion process) in the hole of porous aluminum collector body.
In plunging and infusion process, the electrode composite material in slurry is filled in the hole of porous aluminum by being formed in conjunction with the fine holes on metal dust wall.
Operation is filled with the electrode of above-mentioned each composition as mentioned above, solvent is dispersed and be dried with 50～200 DEG C.
The electrode that operation obtains is like this by regulating electrode density by the pressurized treatments that roll-type pressuring machine or dull and stereotyped pressuring machine etc. pressurize.The thickness of the electrode after pressurized treatments is preferably 0.2～0.9 times of thickness before pressurized treatments.Particularly preferably utilize dull and stereotyped pressuring machine to carry out pressurized treatments.This is because in the pressurized treatments of use roll-type pressuring machine, porous aluminum collector body may deform and cause electrode to come off.
(l) rechargeable nonaqueous electrolytic battery
Rechargeable nonaqueous electrolytic battery of the present invention uses operation is manufactured as mentioned above electrode, is disposed at interelectrode barrier film and nonaqueous electrolyte, is assembled into rechargeable nonaqueous electrolytic battery.Wherein, the both sides of preferred positive pole and negative pole or only positive pole are made up of above-mentioned electrode, and still also only negative pole is made up of above-mentioned electrode.
As barrier film, can adopt the polymeric membrane such as normally used polyethylene (PE), polypropylene (PP).As nonaqueous electrolyte, can use the lithium hexafluoro phosphate (LiPF being dissolved in the organic solvent such as ethylene carbonate (EC), diethyl carbonate (DEC)
6), lithium perchlorate (LiClO
4).
Embodiment
Illustrate the present invention below by example and comparative example.But the present invention is not limited to following example and comparative example.
(example 1～5 and comparative example 6～8)
First, the porous aluminum collector body that electrode for nonaqueous electrolyte secondary battery of the present invention uses is made in operation as described below.
As aluminium powder, use the different following fine aluminium powder (A1, A3) of particle diameter.As supporting powder, using different sodium chloride powder (B1～B4) and the particle diameters of particle diameter is the potassium chloride (C1) of 605 μ m.As shown in table 1, volume ratio according to the rules mixes each powder, modulation mixed-powder.
[table 1]
This mixed-powder is filled in the mould with 10mm × 30mm hole, according to the exert pressure moulding shown in table 1.The loading of mixture is the weight that the thickness of extrusion forming body reaches 1mm.Arriving pressure in maximum is 1 × 10
-2under atmosphere below Pa, according to the temperature and time shown in table 1, this extrusion forming body is heat-treated, make sintered body, the sintered body obtaining is flooded 6 hours in the flowing water (running water) of 20 DEG C, make to support powder stripping, make porous aluminum sample 1～8 (width 12mm × length 30mm × thickness 1mm).Sample 1～8th, does not fill the sample before the pressurized treatments of electrode composite material, utilizes micrometer to measure thickness.
< fine aluminium powder, (more than aluminium purity 99.7mass%) >
A1: median particle diameter 3 μ m (fusing point: 660 DEG C)
A3: median particle diameter 17 μ m (fusing point: 660 DEG C)
< sodium chloride powder >
B1: particle diameter 925 μ m (screen cloth eye intermediate value) (fusing point: 800 DEG C)
B2: particle diameter 605 μ m (screen cloth eye intermediate value) (fusing point: 800 DEG C)
B3: particle diameter 400 μ m (screen cloth eye intermediate value) (fusing point: 800 DEG C)
B4: particle diameter 120 μ m (screen cloth eye intermediate value) (fusing point: 800 DEG C)
< potassium chloride powder >
C1: particle diameter 605 μ m (screen cloth eye intermediate value) (fusing point: 776 DEG C)
, mould is changed into the mould in the hole with Φ 13mm below, use the porous aluminum collector body sample of making according to above-mentioned identical method, electrode for nonaqueous electrolyte secondary battery of the present invention is made in operation as described below.
(making anodal)
According to the weight portion described in table 2, be used as the LiFePO4 that is coated with carbon of positive active material, as the acetylene black of conductive auxiliary agent with as the PVDF of bonding agent.And, using above-mentioned total as 100 weight portions, be scattered in NMP 200 weight portions as solvent modulation slurry.
Adopt above-mentioned infusion process, the porous aluminum collector body sample 1～7 of above-mentioned making is immersed in the slurry (1 liter) that is dispersed with positive active material, conductive auxiliary agent and bonding agent in solvent, and reduce pressure (0.1MPa).After dipping, wipe the unnecessary slurry that is attached to porous aluminum collector body positive and negative off with scraper.Porous aluminum collector body sample 8 is because porosity is too high, be difficult to keep shape, thus cannot be used for slurry dipping with and subsequent test.
Then, the porous aluminum collector body sample that is filled with slurry is disposed in drying device, is dried 2 hours, the example shown in making table 2 and the anodal sample of comparative example with 80 DEG C.Further utilize dull and stereotyped pressuring machine by their pressurized treatments the thickness to 0.7mm.
Resistance ratio before and after electrode composite material loading and pressurized treatments after the porosity of the porous aluminum collector body before the pressurized treatments recording described in table 2 is expressed as follows, da/dp, pressurized treatments.
[table 2]
(porosity)
The porosity of the porous aluminum collector body before pressurized treatments is obtained according to above-mentioned formula (1).
(da/dp)
Da/dp is as described below to be obtained.First,, for da, numerical computations is observed the cross-sectional image of the active material obtaining by SEM, calculated with respect to diameter of a circle, obtains particle diameter da.10 active material samples are carried out to same observation, utilize arithmetic mean to determine particle diameter da.For dp, SEM observation is carried out in the cross section of the porous aluminum sample of not filling electrode composite material, major diameter or diameter are measured in 10 above holes, utilize arithmetic mean to determine aperture dp.Obtain da/dp by the da determining as mentioned above and dp.
(electrode composite material loading)
As described below the obtaining of electrode composite material loading before pressurized treatments.First, use the quality of porous aluminum divided by the density of the raw material (aluminum) of formation porous aluminum, obtain the raw-material volume that forms porous aluminum collector body, deduct this volume by electrode volume, obtain spatial volume (cm
3).Then, deducted the quality of filling electrode composite material porous aluminum collector body sample before by the anodal quality after pressurized treatments, obtain the quality (g) of electrode composite material.Then, use the quality (g) of electrode composite material divided by spatial volume (cm
3), obtain the quality of the electrode composite material of space per unit volume, set it as electrode composite material loading.Electrode composite material loading is at 0.7g/cm
3being more than qualified, is defective lower than this value.
(resistance ratio)
As described below the obtaining of resistance ratio before and after pressurized treatments.Use the porous aluminum sample after filling anodal electrode composite material and before pressurized treatments and press anodal sample after treatment in fact applying, in each sample, alongst with the interval of 10mm, four electrode terminals being set.And measure the resistance of each sample according to four-terminal method.The ratio (Ra/Rb) of the resistance R b of the sample before the resistance R a of the sample after pressurized treatments and pressurized treatments is qualified below 1.5 time, exceedes this value for defective.
(make and evaluate battery)
Make above-mentioned anodal sample after pressurized treatments is evaluated to battery for the two plate of active electrode.Electrode is used to lithium metal.As electrolyte, use the LiPF that is dissolved with 1.3mol/L in the mixed solvent (volume ratio 3:7) of ethylene carbonate and methyl ethyl carbonate
6nonaqueous electrolytic solution.As barrier film, use micro-porous polyethylene membrane.Exterior body uses the resin container after polypropylene block is processed, and exposes outside mode by electrode group storage sealing to be arranged at the open end of active electrode and the each terminal to electrode.
(battery testing)
Use the evaluation battery of making as mentioned above to make a service test, as described below the obtaining of electrode capacity of the per unit mass of positive active material.
With 0.2C, the evaluation battery of made is charged to after 4V, with 0.2C electric discharge, during using electric discharge until the product of required time of the electric current that voltage circulates lower than 2V and electric discharge as electrode capacity.Using with this electrode capacity divided by the value of quality gained that is filled in the active material in anodal sample as the electrode capacity of the per unit mass of positive active material.At this, be filled in as described below the obtaining of quality of the active material in anodal sample: deducted the quality of filling electrode composite material porous aluminum collector body sample before by the anodal quality after pressurized treatments, obtain the quality (g) of electrode composite material, then the mass ratio of the positive active material in itself and anodal composite material is multiplied each other.
Table 2 represents the electrode capacity of the per unit mass (1g) of positive active material.100mAh/g is qualified above, is defective lower than this value.
In example 1～5, porosity and da/dp are in scope given to this invention, and the electrode capacity of the per unit mass of electrode composite material loading, resistance ratio and positive active material is qualified.
In contrast, in comparative example 6, because da/dp is excessive, therefore resistance ratio is defective.
In comparative example 7, because the porosity of porous aluminum collector body is too low, therefore electrode composite material loading is defective.In addition, electrolyte immerses difficulty to active material, and the electrode capacity of the per unit mass of positive active material is defective.
In comparative example 8, because the porosity of porous aluminum collector body is too high, therefore porous aluminum is difficult to keep shape, cannot be produced on the positive pole that is filled with electrode composite material in the hole of porous aluminum collector body.Therefore, electrode composite material loading and resistance ratio cannot be measured, battery performance cannot be evaluated.
Utilizability in industry
Electrode for nonaqueous electrolyte secondary battery of the present invention, in the time of pressurized treatments, active material can not damage porous aluminum wall, can prevent that the conductivity of electrode from declining.As a result, can improve by the increase of electrode capacity the battery behavior of rechargeable nonaqueous electrolytic battery.
Symbol description
1: active material; 2: porous aluminum wall; 3: the hole of porous aluminum; 4: the damaged portion of porous aluminum wall; Da: the particle diameter of active material; Dp: the aperture of porous aluminum.
Claims (3)
1. an electrode for nonaqueous electrolyte secondary battery, it is the electrode for nonaqueous electrolyte secondary battery that contains electrode composite material, described electrode composite material comprises the active material that can occlusion discharges lithium, and described electrode for nonaqueous electrolyte secondary battery is characterised in that:
Using the porous aluminum with 80～95% porosity as collector body, in this hole, be filled with described electrode composite material, the particle diameter da of described active material and the aperture dp of porous aluminum meet da/dp≤0.10.
2. electrode for nonaqueous electrolyte secondary battery as claimed in claim 1, is characterized in that:
Described electrode composite material, except comprising active material, also comprises conductive auxiliary agent and bonding agent, and active material is 85～95 quality % with respect to the ratio of whole electrode composite materials.
3. a rechargeable nonaqueous electrolytic battery, is characterized in that:
At least one using the electrode for nonaqueous electrolyte secondary battery described in claim 1 or 2 as anodal and negative pole,
Rechargeable nonaqueous electrolytic battery comprises the barrier film and the nonaqueous electrolyte that are disposed between both positive and negative polarity.
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| JP2012-082947 | 2012-03-30 | ||
| JP2012082947 | 2012-03-30 | ||
| PCT/JP2013/002118 WO2013145752A1 (en) | 2012-03-30 | 2013-03-28 | Electrode for non-aqueous electrolyte secondary cell and non-aqueous electrolyte secondary cell using same |
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|---|---|
| JP (1) | JP6149031B2 (en) |
| KR (1) | KR101630559B1 (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107078305A (en) * | 2015-01-19 | 2017-08-18 | 古河电气工业株式会社 | Lithium rechargeable battery surface-treated electro-deposited copper foil, electrode for lithium ion secondary battery and lithium rechargeable battery using the copper foil |
| CN108140839A (en) * | 2015-10-30 | 2018-06-08 | 东亚合成株式会社 | The agent of non-aqueous electrolyte secondary battery electrode binding and its manufacturing method, with and application thereof |
| CN114824265A (en) * | 2021-01-21 | 2022-07-29 | 本田技研工业株式会社 | Electrode and electricity storage device |
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| US9929408B2 (en) * | 2013-11-08 | 2018-03-27 | Semiconductor Energy Laboratory Co., Ltd. | Electrode member, secondary battery, and method for manufacturing electrode member |
| WO2017002234A1 (en) * | 2015-07-01 | 2017-01-05 | 株式会社日立製作所 | Underground resource searching device and underground resource searching system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011249260A (en) * | 2010-05-31 | 2011-12-08 | Sumitomo Electric Ind Ltd | Current collector for nonaqueous electrolyte battery, electrode for nonaqueous electrolyte battery, and nonaqueous electrolyte battery |
| JP2011253645A (en) * | 2010-05-31 | 2011-12-15 | Mitsubishi Materials Corp | Collector for nonaqueous electrolyte secondary battery and electrode using the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11302765A (en) | 1998-04-20 | 1999-11-02 | Shinko Kosen Kogyo Kk | Blowing metal excellent in impact absorption |
| JP2004156092A (en) | 2002-11-06 | 2004-06-03 | National Institute Of Advanced Industrial & Technology | Porous metal having excellent energy absorbability, and production method therefor |
| JP4635978B2 (en) * | 2006-08-02 | 2011-02-23 | ソニー株式会社 | Negative electrode and secondary battery |
| JP2009176517A (en) | 2008-01-23 | 2009-08-06 | Sumitomo Electric Ind Ltd | Nonwoven fabric-like nickel chromium current collector for nonaqueous electrolyte secondary battery and electrode using it |
| JP2010009905A (en) | 2008-06-26 | 2010-01-14 | Sumitomo Electric Ind Ltd | Collector of positive electrode for lithium based secondary battery, and positive electrode and battery equipped with it |
| JP5402380B2 (en) * | 2009-03-30 | 2014-01-29 | 三菱マテリアル株式会社 | Method for producing porous aluminum sintered body |
| WO2010116682A1 (en) * | 2009-03-30 | 2010-10-14 | 三菱マテリアル株式会社 | Process for producing porous sintered aluminum, and porous sintered aluminum |
| JP5509786B2 (en) * | 2009-10-28 | 2014-06-04 | 三菱マテリアル株式会社 | Positive electrode for non-aqueous electrolyte secondary battery |
-
2013
- 2013-03-28 JP JP2014507442A patent/JP6149031B2/en not_active Expired - Fee Related
- 2013-03-28 KR KR1020147027098A patent/KR101630559B1/en active IP Right Grant
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011249260A (en) * | 2010-05-31 | 2011-12-08 | Sumitomo Electric Ind Ltd | Current collector for nonaqueous electrolyte battery, electrode for nonaqueous electrolyte battery, and nonaqueous electrolyte battery |
| JP2011253645A (en) * | 2010-05-31 | 2011-12-15 | Mitsubishi Materials Corp | Collector for nonaqueous electrolyte secondary battery and electrode using the same |
Non-Patent Citations (1)
| Title |
|---|
| MASATAKA HAKAMADA等: ""Influence of Porosity and Pore Size on Electrical Resistivity of Porous Aluminum Produced by Spacer Method"", 《MATERIALS TRANSACTIONS》, vol. 48, no. 1, 25 December 2006 (2006-12-25), pages 32 - 36 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107078305A (en) * | 2015-01-19 | 2017-08-18 | 古河电气工业株式会社 | Lithium rechargeable battery surface-treated electro-deposited copper foil, electrode for lithium ion secondary battery and lithium rechargeable battery using the copper foil |
| CN107078305B (en) * | 2015-01-19 | 2020-06-12 | 古河电气工业株式会社 | Surface-treated electrolytic copper foil for lithium ion secondary battery, electrode for lithium ion secondary battery using same, and lithium ion secondary battery |
| CN108140839A (en) * | 2015-10-30 | 2018-06-08 | 东亚合成株式会社 | The agent of non-aqueous electrolyte secondary battery electrode binding and its manufacturing method, with and application thereof |
| CN108140839B (en) * | 2015-10-30 | 2021-06-29 | 东亚合成株式会社 | Binder for nonaqueous electrolyte secondary battery electrode, method for producing same, and use thereof |
| CN114824265A (en) * | 2021-01-21 | 2022-07-29 | 本田技研工业株式会社 | Electrode and electricity storage device |
| CN114824265B (en) * | 2021-01-21 | 2024-05-07 | 本田技研工业株式会社 | Electrode and power storage device |
Also Published As
| Publication number | Publication date |
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| CN104205427B (en) | 2017-10-03 |
| WO2013145752A1 (en) | 2013-10-03 |
| KR20150002631A (en) | 2015-01-07 |
| JPWO2013145752A1 (en) | 2015-12-10 |
| JP6149031B2 (en) | 2017-06-14 |
| KR101630559B1 (en) | 2016-06-14 |
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