WO2014010526A1 - Non-aqueous electrolyte secondary battery - Google Patents

Non-aqueous electrolyte secondary battery Download PDF

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Publication number
WO2014010526A1
WO2014010526A1 PCT/JP2013/068486 JP2013068486W WO2014010526A1 WO 2014010526 A1 WO2014010526 A1 WO 2014010526A1 JP 2013068486 W JP2013068486 W JP 2013068486W WO 2014010526 A1 WO2014010526 A1 WO 2014010526A1
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Prior art keywords
separator
battery
thickness
active
positive electrode
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PCT/JP2013/068486
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French (fr)
Japanese (ja)
Inventor
久幸 内海
西島 主明
西村 直人
貴洋 松山
功 浅子
俊平 西中
智史 有馬
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シャープ株式会社
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Priority to JP2012155419A priority Critical patent/JP2015167065A/en
Priority to JP2012-155419 priority
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Publication of WO2014010526A1 publication Critical patent/WO2014010526A1/en

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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

Provided is a non-aqueous electrolyte secondary battery that can cause an increase in rate characteristics even if the thickness of an applied film has been caused to be thick. The non-aqueous electrolyte secondary battery is such that a cathode and an anode having an active material layer at at least one surface of a collector are laminated with a separator therebetween, the thickness of the active material layer of the cathode is at least 80 μm, the thickness of the active material layer of the anode is at least 40 μm, the separator thickness is 25-75 μm and void ratio is 35-75%, and the void ratio of the separator is the same as the void ratio of the active material layers of the cathode and anode or is greater than the void ratio of the active material layers of the cathode and anode.

Description

Nonaqueous electrolyte secondary battery

The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to a non-aqueous electrolyte secondary battery having excellent rate characteristics.

As a non-aqueous electrolyte secondary battery, a lithium secondary battery has been put into practical use and is widely used. Furthermore, in recent years, lithium secondary batteries are attracting attention not only as small-sized batteries for portable electronic devices but also as large-capacity devices for power storage such as in-vehicle use, solar power generation systems and nighttime power storage. Yes.

The electrode (positive electrode and negative electrode) of the secondary battery forms a coating film by applying a paste containing an active material and a binder onto a current collector such as a long metal foil on one or both sides. Is dried, and then the dried coating film is pressed and wound, and then cut into a predetermined width or a predetermined length as necessary. The manufactured electrode is laminated via a separator to form a strip-like or wound laminate, and then inserted into the battery container. Moreover, the electrically conductive material is added to the paste as needed.

If this conventional manufacturing method is applied to a large-capacity secondary battery for power storage, it is necessary to increase the number of layers or the number of windings in order to ensure a large capacity. As a result, a current collector or separator There is a problem that the manufacturing cost increases.

On the other hand, if the thickness of the coating film is increased to increase the amount of active material, a laminate can be manufactured with a smaller number of stacks or turns, and the number of current collectors and separators can be reduced. Reduction can be achieved. However, this method has a problem that the rate characteristic is lowered as the thickness of the coating film is increased.

In order to improve rate characteristics, separators have also been studied. For example, in Patent Document 1, when a pressure of 2.5 kg / cm 2 is applied in the thickness direction of the separator, the thickness of the separator is 0.02 mm or more and 0.15 mm or less, and the porosity of the separator is 40% or more. A separator has been proposed. Further, in Patent Document 2, a polyolefin microporous film having communication holes in the film thickness direction, having a film thickness of 21 μm or more and a porosity of 42% or more, and the heat shrinkage rate in the width direction at 120 ° C. is 4% or less. A polyolefin microporous membrane having a polypropylene content of 5 to 20% by mass based on the whole polyolefin has been proposed.

JP 2009-9947 A JP 2011-225736 A

However, in the conventional method, when the thickness of the coating film is increased, the effect is not sufficient.

Therefore, an object of the present invention is to provide a nonaqueous electrolyte secondary battery capable of improving rate characteristics even when the thickness of the coating film is increased.

In order to solve the above problems, the nonaqueous electrolyte secondary battery of the present invention is a nonaqueous electrolyte secondary battery in which a positive electrode and a negative electrode having an active material layer on at least one surface of a current collector are laminated via a separator. The positive electrode active material layer thickness is 80 μm or more, the negative electrode active material layer thickness is 40 μm or more, the separator thickness is 25 to 75 μm, and the porosity is 35 to 75%. The rate is the same as the porosity of the active material layer of the positive electrode and the negative electrode or larger than the porosity of the active material layer of the positive electrode and the negative electrode.

According to the present invention, it is possible to provide a nonaqueous electrolyte secondary battery capable of improving rate characteristics even when the thickness of the coating film is increased.

Hereinafter, embodiments of the present invention will be described in detail.

The non-aqueous electrolyte secondary battery of the present invention is a non-aqueous electrolyte secondary battery in which a positive electrode and an negative electrode having an active material layer on at least one surface of a current collector are laminated via a separator, and the active material layer of the positive electrode The thickness of the negative electrode active material layer is 40 μm or more, the separator thickness is 25 to 75 μm, and the porosity is 35 to 75%. It is characterized by being equal to the porosity of the active material layer or larger than the porosity of the positive and negative electrode active material layers.

In the present invention, the thickness of the active material layer of the positive electrode is 80 μm or more, and the thickness of the active material layer of the negative electrode is 40 μm or more. Here, the thickness of the active material layer means the thickness of the active material layer on one side when applied to one side of the current collector, and the thickness of both sides when applied on both sides of the current collector. Means the combined thickness of the active material layers. The thickness of the active material layer of the positive electrode is 80 μm or more, preferably 90 to 150 μm, more preferably 100 to 140 μm. The thickness of the active material layer of the negative electrode is 40 μm or more, preferably 50 to 80 μm, more preferably 60 to 75 μm. If the thickness of the active material layer of the positive electrode is smaller than 80 μm and the thickness of the active material layer of the negative electrode is smaller than 40 μm, the number of electrodes used in the battery increases, and the number of separators and current collectors increases. This is not preferable because the cost increases.

When the thickness of the active material layer of the positive electrode is expressed using the coating amount of the positive electrode active material, the coating amount per unit area of one side of the current collector is 15 mg / cm 2 or more, more preferably 15 to 38 mg / cm 2. It is. In the case of double-sided coating, the coating amount is twice that of single-sided coating, and per unit area of both sides of the current collector is 30 mg / cm 2 or more, more preferably 30 to 76 mg / cm 2 . Further, the thickness of the active material layer of the negative electrode is expressed by using the coating amount of the negative electrode active material, and the coating amount per unit area of one side of the current collector is 7 mg / cm 2 or more, preferably 15 to 22 mg / cm 2. 2 . In the case of double-sided coating, the coating amount is twice that of single-sided coating, and is 14 mg / cm 2 or more, preferably 30 to 44 mg / cm 2 per unit area of both sides of the current collector.

In the present invention, the separator has a thickness of 25 to 75 μm and a porosity of 35 to 75%. As a separator, well-known materials, such as a porous material and a nonwoven fabric, can be used. As a material for the separator, a material that does not dissolve or swell in the organic solvent in the electrolytic solution is preferable. Specifically, a porous film or a nonwoven fabric made of a polyolefin resin such as polyethylene or polypropylene, an aramid resin, or a cellulose resin can be used. A material made of such a material can be used as a single layer or a plurality of layers. In the case of a plurality of layers, at least one non-woven fabric may be used from the viewpoint of cycle characteristics, low temperature performance, load characteristics, and the like. The thickness of the separator is 25 to 75 μm, preferably 30 to 60 μm. When the thickness of the separator is smaller than 25 μm, a short circuit between the electrodes tends to occur, and the charge / discharge cycle characteristics (discharge capacity retention ratio) are lowered. Further, when the thickness of the separator is larger than 75 μm, the membrane resistance of the separator is increased and the rate characteristics are deteriorated.

In the present invention, the porosity of the separator is 35 to 75%, preferably 40 to 70%. This is because if the porosity is less than 35%, the membrane resistance of the separator is increased and the rate characteristics are liable to be lowered, and if it exceeds 75%, the mechanical strength of the separator is lowered and the insulation is lowered. The porosity (%) of the separator is defined by the following formula (I).

Porosity = {1- (theoretical volume of separator / apparent volume of separator)} × 100 (I)

Here, the theoretical volume of the separator is defined by the following equation.
Theoretical volume of separator = (mass of separator) / (density of separator)

In the present invention, the porosity of the separator is the same as the porosity of the positive electrode and the negative electrode or larger than the porosity of the positive electrode and the negative electrode. Here, the porosity (%) between the positive electrode and the negative electrode is defined by the following formula (II).

Porosity = {1− (theoretical volume of electrode / apparent volume of electrode)} × 100 (II)

Here, the theoretical volume of the electrode is defined by the following equation.
Theoretical volume of electrode = (electrode mass) / (electrode density)

In the present invention, since the porosity of the separator is the same as that of the positive electrode or larger than that of the positive electrode, the separator can secure the amount of electrolyte solution to be held and the degree of freedom of movement of the electrolyte solution. The diffusion resistance of lithium ions between the separator and the positive electrode can be reduced. This facilitates the movement of lithium ions from the separator to the positive electrode even in a short time large current discharge. When the porosity of the separator is smaller than the porosity of the positive electrode, a sufficient amount of lithium ions cannot be supplied from the separator to the positive electrode during large current discharge, so that the rate characteristics are deteriorated. On the other hand, even in the case of the negative electrode, in the present invention, since the porosity of the separator is the same as that of the negative electrode or larger than that of the negative electrode, the separator can secure the amount of electrolyte solution to be held and the degree of freedom of movement of the electrolyte solution. / Diffusion resistance of lithium ions between negative electrodes can be reduced. Thereby, even if it is a high-current discharge for a short time, the lithium ion detach | desorbed from the negative electrode active material can move to a separator easily. On the other hand, when the porosity of the separator is smaller than the porosity of the negative electrode, the lithium ions desorbed from the negative electrode active material cannot be easily transferred to the separator during large current discharge, so that the rate characteristics are deteriorated. As described above, according to the present invention, lithium ions can be easily transferred from the separator to the positive electrode, and lithium ions desorbed from the negative electrode active material can be easily transferred to the separator even in a short-time high-current discharge. Since it can move, the fall of a rate characteristic can be suppressed.

(Positive electrode)
A lithium composite metal oxide is used for the positive electrode active material. Specific examples include LiCoO 2 , LiNiO 2 , LiFeO 2 , LiMnO 2 , LiMn 2 O 4 , Li 2 MnO 3 , LiCoPO 4 , LiNiPO 4 , LiMnPO 4 , LiFePO 4 (lithium iron phosphate). LiFePO 4 is preferable. This is because the safety is high and the cost is low. Note that the lithium iron phosphate includes a compound in which the iron site and the phosphorus site are substituted with different elements. Examples of the iron site substitution element include at least one metal element selected from the group consisting of Zr, Sn, Y, and Al, and examples of the phosphorus site substitution element include Si.

The positive electrode active material can be produced by using any combination of carbonates, hydroxides, chlorides, sulfates, acetates, oxides, oxalates, nitrates and the like of each element as a starting material. Among these, carbonates, hydroxides, acetates, oxides, and oxalates are preferable from the viewpoint of hardly generating a gas that can affect the synthesis during firing. More preferred are carbonates, hydroxides, acetates and oxalates, which can be synthesized.

In addition, weak acid salts (carbonates, acetates, oxalates) or strong acid salts (nitrates, chlorides) are preferred from the viewpoint of being easy to produce a uniform solution in the air atmosphere during the liquid phase method and inexpensive. Among these, acetate or nitrate is more preferable.

As a method for producing the positive electrode active material, methods such as a solid phase method, a sol-gel method, a melt quench method, a mechanochemical method, a coprecipitation method, a hydrothermal method, and a spray pyrolysis method can be used. For single-phase synthesis, it is important that the mixed state before firing is uniform and that the particle size is small, so the sol-gel method, coprecipitation method, hydrothermal method, spray pyrolysis, which are liquid phase methods The method is preferred. From the viewpoint of yield, a sol-gel method, a coprecipitation method, and a hydrothermal method are more preferable. The sol-gel method is more preferable.

(Production method of positive electrode)
The positive electrode is prepared by kneading and dispersing at least a positive electrode active material, a conductive material, a binder, and a thickener using a solvent to obtain a paste, applying the paste to one or both sides of a current collector, and drying the paste. To do. Examples of the organic solvent include N-methyl-2-pyrrolidone, toluene, cyclohexane, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl acetate, methyl acrylate, diethyltriamine, N, N-dimethylaminopropylamine, ethylene oxide, Tetrahydrofuran or the like can be used. When a water-soluble binder is used, water can be used as a solvent. When water is used as the solvent, the pH of the paste is 5 or higher, preferably 8 or higher. This is because when the pH is less than 5, the battery using the obtained positive electrode does not improve the cycle characteristics.

As the conductive material, acetylene black, carbon black, natural graphite, artificial graphite or the like can be used alone or in combination.

The ratio of the positive electrode active material and the conductive material contained in the coating film is 2 to 20 parts by weight, preferably 4 to 10 parts by weight of the conductive material with respect to 100 parts by weight of the positive electrode active material. If the conductive material is less than 2 parts by weight, the contact resistance between the positive electrode active material and the current collector is increased, which is not preferable. Further, even if the amount of the conductive material is more than 20 parts by weight, the effect of reducing contact resistance commensurate with the amount added cannot be obtained, and the cost increases.

The binder includes polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, ethylene propylene diene polymer, styrene-butadiene rubber, acrylonitrile-butadiene rubber, fluorine rubber, polyvinyl acetate, polymethyl methacrylate, polyethylene, nitrocellulose, Examples of the styrene-butadiene rubber or the water-based binder emulsion include a fluorine-modified styrene-butadiene rubber, an olefin copolymer, and an acid-modified olefin copolymer. When the aqueous binder emulsion is used, a thickener such as carboxymethyl cellulose (hereinafter abbreviated as CMC), polyvinyl alcohol, polyvinyl pyrrolidone and the like can be used as necessary.

The current collector used for the positive electrode is a current collector having a pair of opposing main surfaces, one main surface corresponding to one side, and both main surfaces corresponding to both sides, a thin plate-like and foil-like metal current collector. An electric body can be used, and as the material thereof, aluminum, nickel, chromium and alloys thereof can be used, but aluminum is preferable.

(Negative electrode)
A known material can be used as the negative electrode active material. In order to constitute a high energy density battery, it is preferable that the potential for lithium insertion / extraction is close to the deposition / dissolution potential of metallic lithium. A typical example is a carbon material such as natural or artificial graphite in the form of particles (scale-like, lump-like, fibrous, whisker-like, spherical, pulverized particles, etc.).

Examples of artificial graphite include graphite obtained by graphitizing mesocarbon microbeads, mesophase pitch powder, isotropic pitch powder, and the like. Also, graphite particles having amorphous carbon attached to the surface can be used. Among these, natural graphite is preferable because it is inexpensive and close to the redox potential of lithium and can constitute a high energy density battery.

Further, lithium transition metal oxide, lithium transition metal nitride, transition metal oxide, silicon oxide, and the like can be used as the negative electrode active material. Among these, Li 4 Ti 5 O 12 is preferable because it has high potential flatness and a small volume change due to charge and discharge.

(Method for producing negative electrode)
The negative electrode can be produced by a known method. For example, a negative electrode active material, a binder, and a conductive material are mixed, the obtained mixed powder is formed into a sheet shape, and the obtained molded body is pressure-bonded to a current collector, for example, a foil-shaped current collector made of stainless steel or copper. Can be produced. Further, as in the case of the positive electrode, it can be prepared using water as a solvent. In that case, at least the negative electrode active material, the conductive material, and the binder are kneaded and dispersed using water to obtain a paste. It can be produced by applying to a current collector. A conductive material may be added as necessary.

The current collector used for the negative electrode is a current collector having a pair of opposing main surfaces, one main surface corresponding to one surface, and both main surfaces corresponding to both surfaces, a thin plate-like, foil-shaped metal collector. An electric body can be used, and as the material thereof, aluminum, nickel or copper can be used, but copper is preferable.

(Nonaqueous electrolyte)
As the non-aqueous electrolyte, for example, an organic electrolyte, a gel electrolyte, a polymer solid electrolyte, an inorganic solid electrolyte, a molten salt, or the like can be used.

Examples of the organic solvent constituting the organic electrolyte include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), and butylene carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate, and dipropyl carbonate. Chain carbonates such as γ-butyrolactone (GBL), lactones such as γ-valerolactone, furans such as tetrahydrofuran and 2-methyltetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, 1,2-diethoxy Examples include ethers such as ethane, ethoxymethoxyethane, dioxane, dimethyl sulfoxide, sulfolane, methyl sulfolane, acetonitrile, methyl formate, methyl acetate, and the like. Can be.

Moreover, since cyclic carbonates such as PC, EC and butylene carbonate are high-boiling solvents, they are suitable as a solvent to be mixed with GBL.

Examples of the electrolyte salt constituting the organic electrolyte include lithium borofluoride (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium trifluoroacetate (LiCF 3 COO) ), Lithium salts such as lithium bis (trifluoromethanesulfone) imide (LiN (CF 3 SO 2 ) 2 ), and a mixture of one or more of these can be used. The salt concentration of the electrolytic solution is preferably 0.5 to 3 mol / L.

A dehydrating agent or a deoxidizing agent may be added to the electrolytic solution. Specifically, vinylene carbonate, fluoroethylene carbonate, trifluoropropylene carbonate, phenylethylene carbonate, succinic anhydride, glutaric anhydride, maleic anhydride, ethylene sulfite, 1,3-propane sultone, 1,4-butane sultone, Examples include methyl methanesulfonate, dibutyl sulfide, heptane, octane, and cycloheptane. These may be contained in the electrolytic solution at a concentration of 0.1 wt% or more and 5 wt% or less. Cycle characteristics can be further improved, and capacity retention characteristics after high temperature storage can be improved.

(Other parts)
Various other known materials can be used for other members such as a battery container, and there is no particular limitation.

(Method for manufacturing secondary battery)
The secondary battery includes, for example, a laminate including a positive electrode, a negative electrode, and a separator sandwiched between them. The laminate may have, for example, a strip-like planar shape. In the case of producing a cylindrical or flat battery, the laminate may be wound to form a wound body.

One or more of the laminates are inserted into the battery container. Usually, the positive electrode and the negative electrode are connected to the external conductive terminal of the battery. Thereafter, the battery container is sealed to block the positive electrode, the negative electrode, and the separator from the outside air.

In the case of a cylindrical battery, the sealing method is such that a lid having a resin packing is fitted into the opening of the battery container and the battery container and the lid are caulked, or the opening and lid of the battery container are laser welded or the like. A welding method is common. In the case of a square battery, a method of attaching a lid called a metallic sealing plate to the opening and performing welding can be used. In addition to these methods, a method of sealing with a binder and a method of fixing with a bolt via a gasket can also be used. Furthermore, a method of sealing with a laminate film in which a thermoplastic resin is attached to a metal foil can also be used. An opening for electrolyte injection may be provided at the time of sealing. When using an organic electrolyte, the organic electrolyte is injected from the opening, and then the opening is sealed. Gas generated by energization before sealing may be removed. When a large battery having a capacity per battery of 20 Ah or more and 500 Ah or less is manufactured, a plurality of openings for injecting electrolyte may be provided. For example, one opening is for injecting electrolyte. The other is preferably used for removing gas. When the capacity is less than 20 Ah, it is not preferable because it is difficult to reduce the cost as a storage battery system, and when the capacity exceeds 500 Ah, even if lithium iron phosphate is used as the positive electrode active material, safety is lowered, which is not preferable.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.


Examples 1-4 and Comparative Examples 1-2
(Preparation of positive electrode)
Fill positive electrode active material powder 100 (g), conductive material powder 6 (g), binder 8 (g), thickener aqueous solution 1.2 (g), and ion-exchanged water 78.8 (g). The mixture was stirred and mixed at room temperature using a mix 80-50 type (manufactured by Primex) to obtain an aqueous paste.

This aqueous paste was applied on both sides of a rolled aluminum foil (thickness: 20 μm) using a die coater, dried in air at 100 ° C. for 30 minutes, pressed and processed into a positive electrode plate (coating surface size: 30 cm (vertical) ) × 15 cm (horizontal)).

(Preparation of negative electrode)
Negative electrode active material powder 100 (g), binder 0.8 (g), thickener aqueous solution 1 (g), and ion-exchanged water 100 (g) using a biaxial planetary mixer (manufactured by Primex) An aqueous paste was obtained by stirring and kneading at room temperature.

This aqueous paste was applied onto both sides of a rolled copper foil (thickness: 10 μm) using a die coater, dried in air at 100 ° C. for 30 minutes, pressed and processed into a negative electrode plate (coating surface size: 30.4 cm). (Vertical) × 15.4 cm (Horizontal)) was obtained.

The porosity of the positive electrode and negative electrode used was changed by the following method.
By calculating the electrode thickness per unit area from the apparent volume of the electrode in the formula (II) of the porosity, and adjusting the clearance at the time of press processing in electrode production to press the porosity to a predetermined electrode thickness Adjusted.
In addition, the porosity of the positive electrode and the negative electrode was calculated using the above formula (II).

(Production of battery)
The produced positive electrode and negative electrode were dried under reduced pressure at 130 ° C. for 24 hours, and placed in a glove box under an Ar atmosphere. The following battery assembly was all performed in the glove box at room temperature.
A polyethylene microporous membrane (30.4 cm (vertical) × 15.4 cm (horizontal) × 25 μm (thickness)) is placed on the negative electrode as a separator, and the positive electrode is overlaid thereon, and the PE microporous membrane is overlaid thereon. The operation was repeated to produce a laminate in which 10 PE microporous films were sandwiched between 6 negative electrodes and 5 positive electrodes. Ni leads were ultrasonically welded to six negative electrodes, Al leads were ultrasonically welded from five positive electrodes, inserted into an Al laminated bag, and three sides were heat-sealed. An electrolyte solution in which LiPF 6 was dissolved in a solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed at a volume ratio of 1: 2 to 1 mol / L was poured into the cell, and each lead was taken out. Meanwhile, the last side of the Al laminate bag was heat-sealed to obtain a battery. Table 1 shows the electrolyte injection amount and the battery capacity. The injection amount of the electrolyte was appropriately determined according to the thickness of the electrode used in each battery, and was set to an amount that allowed the electrolyte to sufficiently permeate the positive and negative electrodes and the separator of the actually produced battery.

The separator was processed using a polyethylene microporous membrane (manufactured by Celgard or Sumitomo Chemical) and non-woven fabric (manufactured by Vilene) so as to have a predetermined thickness and porosity by roll pressing the separator. Table 1 shows values of thickness and porosity.

Figure JPOXMLDOC01-appb-T000001

Table 2 shows the thicknesses and void ratios of the positive electrode active material layers, the negative electrode active material layers, and the separators of Examples 1 to 4 and Comparative Examples 1 and 2.

(Battery capacity measurement)
The initial discharge capacity of the battery was determined by charging to 3.6 V at a constant current of 0.1 C and discharging to 2 V at a constant current of 0.1 C (hereinafter referred to as 0.1 C discharge capacity). Further, the rate characteristic was defined by (1.0 C discharge capacity / 0.1 C initial discharge capacity). The 1.0 C discharge capacity was obtained by charging to 3.6 V at a constant current of 0.1 C and discharging to 2 V at a constant current of 1.0 C. The results are shown in Table 3.

Then, after performing the charge / discharge cycle test of 0.1C charge / discharge once and 1C charge / discharge 99 times, 0.1C charge / discharge was performed once as the 100th time. The 100th discharge capacity retention rate was determined from the ratio of the 100th discharge capacity to the initial discharge capacity. The cycle characteristics were defined by the discharge capacity maintenance rate. The results are shown in Table 3.

(Good product rate)
The yield rate was defined by the following formula.

Non-defective product rate (%) = {(number of normally operating batteries) / (number of fabricated batteries)} × 100

Here, “the number of normally operating batteries” refers to the number of batteries in which the internal resistance of the manufactured battery is measured using a battery high tester 3561 (manufactured by Hioki Electric Co., Ltd.) and the resistance shows a normal value.

Examples 5 to 6 and Comparative Example 3
Batteries were prepared and evaluated in the same manner as in Examples 1 to 4 except that the porosity of the positive electrode and the negative electrode was changed by the following method.
By calculating the electrode thickness per unit area from the apparent volume of the electrode in the formula (II) of the porosity, and adjusting the clearance at the time of press processing in electrode production to press the porosity to a predetermined electrode thickness Adjusted.

Table 2 shows the thickness and porosity of the positive electrode active material layer, the negative electrode active material layer, and the separator, and Table 3 shows the evaluation results.

Example 7
Batteries were prepared and evaluated in the same manner as in Examples 1 to 4 except that the porosity of the positive electrode and negative electrode was changed by the same method as in Examples 5 to 6 and Comparative Example 3 above. did.

Table 2 shows the thickness and porosity of the positive electrode active material layer, the negative electrode active material layer, and the separator, and Table 3 shows the evaluation results.

Examples 8 to 11 and Comparative Example 4
Batteries were prepared and evaluated in the same manner as in Examples 1 to 4 except that the porosity of the positive electrode and negative electrode was changed by the same method as in Examples 5 to 6 and Comparative Example 3 above. did.

Table 2 shows the thickness and porosity of the positive electrode active material layer, the negative electrode active material layer, and the separator, and Table 3 shows the evaluation results.

Figure JPOXMLDOC01-appb-T000002

Figure JPOXMLDOC01-appb-T000003

(result)
Examples 1 to 4 had a discharge capacity retention rate and rate characteristics of the 100th time exceeding 90%, and the non-defective rate was 100%. On the other hand, in Comparative Example 1, the discharge capacity retention rate at the 100th time was less than 90%, and the rate characteristic was a low value of 86%. In Comparative Example 2, the separator thickness was 18 μm, the cycle characteristics were low, and the yield rate was also reduced.

Further, Comparative Example 3 is a case where the porosity of the separator is lower than the porosity of the active material layer of the positive electrode and the negative electrode.

In Comparative Example 4, the separator porosity was 79%, and the non-defective product rate was lowered.

From the results of Examples 5 to 7, a cycle characteristic of 97% or more and a rate characteristic of 96% or more can be obtained by making the porosity of the positive electrode active material layer larger than the porosity of the negative electrode active material layer. It was.

Claims (3)

  1. A non-aqueous electrolyte secondary battery in which a positive electrode and a negative electrode having an active material layer on at least one surface of a current collector are laminated via a separator,
    The thickness of the active material layer of the positive electrode is 80 μm or more, the thickness of the active material layer of the negative electrode is 40 μm or more,
    The separator has a thickness of 25 to 75 μm and a porosity of 35 to 75%.
    A non-aqueous electrolyte secondary battery in which the porosity of the separator is the same as the porosity of the active material layer of the positive electrode and the negative electrode or larger than the porosity of the active material layer of the positive electrode and the negative electrode.
  2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode has a porosity of 35 to 60%.
  3. The nonaqueous electrolyte secondary battery according to claim 1, wherein the porosity of the negative electrode is 35 to 60%.
PCT/JP2013/068486 2012-07-11 2013-07-05 Non-aqueous electrolyte secondary battery WO2014010526A1 (en)

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014175352A1 (en) * 2013-04-26 2014-10-30 シャープ株式会社 Positive electrode for lithium ion secondary batteries, and lithium ion secondary battery comprising same
WO2014175350A1 (en) * 2013-04-26 2014-10-30 シャープ株式会社 Lithium ion secondary battery
RU2628772C2 (en) * 2014-08-21 2017-08-22 Джонсон Энд Джонсон Вижн Кэа, Инк. Biocompatible recharged supply elements for biomedical devices
RU2670422C1 (en) * 2014-08-21 2018-10-23 Джонсон Энд Джонсон Вижн Кэа, Инк. Methods of manufacture of biocompatible energisation elements for biomedical devices containing multilayer composites and objected divisions
CN109314277A (en) * 2016-06-08 2019-02-05 日产自动车株式会社 Non-aqueous electrolyte secondary battery
CN109314268A (en) * 2016-06-08 2019-02-05 日产自动车株式会社 Non-aqueous electrolyte secondary battery
US10361405B2 (en) 2014-08-21 2019-07-23 Johnson & Johnson Vision Care, Inc. Biomedical energization elements with polymer electrolytes
US10361404B2 (en) 2014-08-21 2019-07-23 Johnson & Johnson Vision Care, Inc. Anodes for use in biocompatible energization elements
US10367233B2 (en) 2014-08-21 2019-07-30 Johnson & Johnson Vision Care, Inc. Biomedical energization elements with polymer electrolytes and cavity structures
US10374216B2 (en) 2014-08-21 2019-08-06 Johnson & Johnson Vision Care, Inc. Pellet form cathode for use in a biocompatible battery
US10381687B2 (en) 2014-08-21 2019-08-13 Johnson & Johnson Vision Care, Inc. Methods of forming biocompatible rechargable energization elements for biomedical devices
US10386656B2 (en) 2014-08-21 2019-08-20 Johnson & Johnson Vision Care, Inc. Methods and apparatus to form separators for biocompatible energization elements for biomedical devices
US10451897B2 (en) 2011-03-18 2019-10-22 Johnson & Johnson Vision Care, Inc. Components with multiple energization elements for biomedical devices
US10598958B2 (en) 2014-08-21 2020-03-24 Johnson & Johnson Vision Care, Inc. Device and methods for sealing and encapsulation for biocompatible energization elements
US10627651B2 (en) 2014-08-21 2020-04-21 Johnson & Johnson Vision Care, Inc. Methods and apparatus to form biocompatible energization primary elements for biomedical devices with electroless sealing layers
US10775644B2 (en) 2012-01-26 2020-09-15 Johnson & Johnson Vision Care, Inc. Ophthalmic lens assembly having an integrated antenna structure

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6585843B2 (en) * 2016-06-08 2019-10-02 株式会社エンビジョンAescジャパン Nonaqueous electrolyte secondary battery
JP2018113108A (en) * 2017-01-06 2018-07-19 学校法人早稲田大学 Secondary battery

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000260415A (en) * 1999-03-11 2000-09-22 Denso Corp Nonaqueous electrolyte secondary battery
JP2001223029A (en) * 2000-02-09 2001-08-17 Shin Kobe Electric Mach Co Ltd Nonaqueous electrolyte secondary battery
JP2003303625A (en) * 2002-04-08 2003-10-24 Japan Storage Battery Co Ltd Non-aqueous electrolyte secondary battery
JP2007042525A (en) * 2005-08-05 2007-02-15 Hitachi Vehicle Energy Ltd Lithium ion battery
JP2011175933A (en) * 2010-02-25 2011-09-08 Hitachi Vehicle Energy Ltd Lithium ion battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000260415A (en) * 1999-03-11 2000-09-22 Denso Corp Nonaqueous electrolyte secondary battery
JP2001223029A (en) * 2000-02-09 2001-08-17 Shin Kobe Electric Mach Co Ltd Nonaqueous electrolyte secondary battery
JP2003303625A (en) * 2002-04-08 2003-10-24 Japan Storage Battery Co Ltd Non-aqueous electrolyte secondary battery
JP2007042525A (en) * 2005-08-05 2007-02-15 Hitachi Vehicle Energy Ltd Lithium ion battery
JP2011175933A (en) * 2010-02-25 2011-09-08 Hitachi Vehicle Energy Ltd Lithium ion battery

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10451897B2 (en) 2011-03-18 2019-10-22 Johnson & Johnson Vision Care, Inc. Components with multiple energization elements for biomedical devices
US10775644B2 (en) 2012-01-26 2020-09-15 Johnson & Johnson Vision Care, Inc. Ophthalmic lens assembly having an integrated antenna structure
WO2014175350A1 (en) * 2013-04-26 2014-10-30 シャープ株式会社 Lithium ion secondary battery
JPWO2014175352A1 (en) * 2013-04-26 2017-02-23 シャープ株式会社 Positive electrode for lithium ion secondary battery and lithium ion secondary battery including the same
US9735420B2 (en) 2013-04-26 2017-08-15 Sharp Kabushiki Kaisha Positive electrode for lithium ion secondary batteries and lithium ion secondary battery including the same
WO2014175352A1 (en) * 2013-04-26 2014-10-30 シャープ株式会社 Positive electrode for lithium ion secondary batteries, and lithium ion secondary battery comprising same
US10367233B2 (en) 2014-08-21 2019-07-30 Johnson & Johnson Vision Care, Inc. Biomedical energization elements with polymer electrolytes and cavity structures
US10627651B2 (en) 2014-08-21 2020-04-21 Johnson & Johnson Vision Care, Inc. Methods and apparatus to form biocompatible energization primary elements for biomedical devices with electroless sealing layers
US10361405B2 (en) 2014-08-21 2019-07-23 Johnson & Johnson Vision Care, Inc. Biomedical energization elements with polymer electrolytes
US10361404B2 (en) 2014-08-21 2019-07-23 Johnson & Johnson Vision Care, Inc. Anodes for use in biocompatible energization elements
RU2670422C1 (en) * 2014-08-21 2018-10-23 Джонсон Энд Джонсон Вижн Кэа, Инк. Methods of manufacture of biocompatible energisation elements for biomedical devices containing multilayer composites and objected divisions
US10374216B2 (en) 2014-08-21 2019-08-06 Johnson & Johnson Vision Care, Inc. Pellet form cathode for use in a biocompatible battery
US10381687B2 (en) 2014-08-21 2019-08-13 Johnson & Johnson Vision Care, Inc. Methods of forming biocompatible rechargable energization elements for biomedical devices
US10386656B2 (en) 2014-08-21 2019-08-20 Johnson & Johnson Vision Care, Inc. Methods and apparatus to form separators for biocompatible energization elements for biomedical devices
RU2628772C2 (en) * 2014-08-21 2017-08-22 Джонсон Энд Джонсон Вижн Кэа, Инк. Biocompatible recharged supply elements for biomedical devices
US10598958B2 (en) 2014-08-21 2020-03-24 Johnson & Johnson Vision Care, Inc. Device and methods for sealing and encapsulation for biocompatible energization elements
US10558062B2 (en) 2014-08-21 2020-02-11 Johnson & Johnson Vision Care, Inc. Methods and apparatus to form biocompatible energization primary elements for biomedical device
CN109314268B (en) * 2016-06-08 2020-01-21 远景Aesc 日本有限公司 Nonaqueous electrolyte secondary battery
CN109314268A (en) * 2016-06-08 2019-02-05 日产自动车株式会社 Non-aqueous electrolyte secondary battery
CN109314277A (en) * 2016-06-08 2019-02-05 日产自动车株式会社 Non-aqueous electrolyte secondary battery

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