CN102190323B - Inorganic oxide powder, slurry containing inorganic oxide, lithium ion secondary battery having the slurry and preparation method thereof - Google Patents
Inorganic oxide powder, slurry containing inorganic oxide, lithium ion secondary battery having the slurry and preparation method thereof Download PDFInfo
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- CN102190323B CN102190323B CN201110046076.4A CN201110046076A CN102190323B CN 102190323 B CN102190323 B CN 102190323B CN 201110046076 A CN201110046076 A CN 201110046076A CN 102190323 B CN102190323 B CN 102190323B
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Abstract
The invention discloses inorganic oxide powder, which is applicable for forming an insulated inorganic oxide porous film on the surface of at least one of an anode, a cathode and a clapboard forming a lithium ion secondary battery. The invention discloses inorganic oxide powder, which forms the insulated inorganic oxide porous film on the surface of at least one of an anode, a cathode and a clapboard used in the lithium ion secondary battery, wherein (1) the purity of an oxide is 90 wt% or higher; (2) according to a mass ratio, the content of coarse particle whose grain diameter is 10 mum or lower is 10 ppm or lower; and (3) the porosity of pressure powder of the inorganic oxide powder obtained in a range of 29 MPa or higher and 147 MPa or lower is 40 percent by volume or higher and 80 percent by volume or lower; the average aperture of the pressure powder is 0.06 mum or higher; and the variable quantity of the porosity per 1 MPa pressure in the event of moulding the pressure powder is 0.020% or higher and 0.060% or lower.
Description
Technical field
The present invention relates to for forming the inorganic oxide powder of the inorganic oxide porous-film with insulating property at least one the surface in the middle of anodal, negative pole and dividing plate three, this dividing plate is for lithium-ion secondary cell.The invention still further relates to the slurry that contains this inorganic oxide powder, and further relate to the lithium-ion secondary cell that uses this what slurry, and the method for producing it.
Background technology
Because its high-energy-density, lithium-ion secondary cell is for portable digital instrument, as portable phone and PC, and except these digital implementations, recently and also accelerate development for the lithium-ion secondary cell of automobile.
Conventionally, lithium-ion secondary cell comprises positive pole and negative pole, and comprises dividing plate, and this dividing plate is placed so that the space electrical isolation between these electrode slices.The dividing plate of using as lithium-ion secondary cell, for example, used many micro pore sheet of being made by polyolefin resin.
When being short-circuited in battery, by the closing function of dividing plate, caused the obstruction of the hole of dividing plate, and make the lithium ion motion of this part of being short-circuited become impossible, so the battery functi on of short position can being lost.By this way, the dividing plate being comprised of many micro pore sheet plays the effect of the safety of maintaining lithium ion secondary cell.Yet when the temperature that makes battery due to the temporary transient heat producing is during for example higher than 150 ℃, this dividing plate occurs to shrink fast, therefore short position anodal and negative pole amplifies sometimes.In this case, the temperature of battery has reached the state that is extremely superheated to several Baidu or higher temperature sometimes, causes going wrong at secure context.
Therefore, JP H09-147916A advises that a kind of technology is as the means that overcome the above problems, in this technology, on electrode, (for example,, on the surface of positive pole, negative pole or dividing plate that forms lithium-ion secondary cell) forms the inorganic oxide porous-film that contains the inorganic oxide filler with insulating property.
In addition, JP 2005-327680A discloses the lithium-ion secondary cell that comprises porous-film, this porous-film has the porosity of thickness and the 35-75% (volume) of 2-10 μ m, this film is used alpha alumina particles as the inorganic oxide filler using in this inorganic oxide porous-film, and the primary granule that this particle has the median size of 0.2-1.5 μ m is therein connected under the state of (connected) has thermotolerance.Identical file has been described the purposes that this alpha alumina particles is suitable for controlling the pore texture of porous-film.
In addition, the open road of No. 2005/124899 brochure of international publication WO: by regulating the porosity of porous-film at 40-80%, likely prevent that charging and discharging characteristic and the charging and discharging characteristic in low temperature environment under the large electric current of battery from sharply becoming bad in the scope of preferred 45-80% and most preferably 50-70%; Also describe: there is 0.1-0.8 g/cm
3tap density and 5-20 m
2the alpha alumina particles of the BET specific surface area of/g is preferably used as the inorganic oxide filler that used here, and the polycrystalline particle obtaining by roasting and Mechanical Crushing α-aluminum oxide precursor is preferably used as this alpha alumina particles.
In addition; No. 2008/004430 brochure suggestion of international publication WO; although the inorganic oxide porous-film that contains this inorganic oxide filler by by inorganic oxide powder and additive as being dispersed in together with binding agent in solvent and forming as gravure processes with coating method; but the coarse aggregate of inorganic oxide is removed, because coarse particle (wherein the size of inorganic oxide filler grain is greater than the film thickness of target porous-film) is usually blended in wherein.
In addition, JP 2008-91192A discloses a kind of method, and the porous-film that wherein contains this inorganic oxide filler is the slurry that contains inorganic oxide filler, binding agent and solvent by coating, is then dried this slurry and is rolled into pre-determined thickness to obtain.
Yet, in use, meet when the inorganic oxide powder of the shape described in above-mentioned patent document, tap density, median size and BET specific surface area forms inorganic oxide porous-film, the porous-film that goal porosity can not be realized and obtain contains many coarse aggregate particles, the latter can cause problem in the production of porous-film, so this powder is not necessarily gratifying as the powder of inorganic porous membrane that is used to form lithium-ion secondary cell.
Summary of the invention
In these cases, the object of this invention is to provide for form the inorganic oxide powder of the inorganic oxide porous-film with excellent heat resistance and insulating property and the inorganic oxide slurry that contains this inorganic oxide powder on positive pole, negative pole and dividing plate three's at least one the surface that forms lithium-ion secondary cell.Another object of the present invention is to provide the lithium-ion secondary cell that comprises the inorganic oxide porous-film being comprised of inorganic oxide powder, and produces its method.
The inventor has conducted in-depth research to realize above-mentioned purpose, and finds that following invention has met above-mentioned purpose, so the present invention is accomplished.
The invention provides following invention.
<1> is for forming the inorganic oxide powder of the inorganic oxide porous-film with insulating property, wherein at least one the surface being placed in the middle of the positive pole of lithium-ion secondary cell, negative pole and dividing plate three
(1) oxide compound purity is 90wt% or higher,
(2), according to mass ratio, the coarse grained content with 10 μ m or higher particle diameter is 10 ppm or lower, and
(3) porosity of the powder compact (green formed body) (or compression moulding body) of the inorganic oxide powder obtaining under the pressure in 29 MPa or higher and 147 MPa or lower scope is 40% (volume) or more and 80% (volume) or lower, the mean pore size of powder compact is 0.06 μ m or higher, and when molded powder compact under every 1MPa pressure the variable quantity of porosity be 0.020% or higher and 0.060% or lower.
<2> is according to the inorganic oxide powder of <1>, and wherein this inorganic oxide is α-aluminum oxide.
<3> is according to the inorganic oxide powder of <2>, and the thermal expansivity of the powder compact of the inorganic oxide powder wherein obtaining under the pressure of 147 MPa at 40 ℃-600 ℃ is 7 * 10
-6/ ℃ or higher and 9 * 10
-6/ ℃ or lower.
<4> inorganic oxide slurry, it comprises according to any one inorganic oxide powder, binding agent and solvent in <1>-<3GreatT.Gre aT.GT.
<5> produces the method for lithium-ion secondary cell, and this battery comprises electrode group and the electrolytic solution by positive pole, negative pole and dividing plate lamination are also reeled and obtained, and the method comprises the following steps:
To according to the inorganic oxide slurry of <4>, be coated on the surface of the positive pole that formed by the electrode mixture layer that contains electrode active material and binding agent and/or negative pole, and dry this slurry forms inorganic oxide porous-film.
<6> produces the method for lithium-ion secondary cell, and this battery comprises electrode group and the electrolytic solution by positive pole, negative pole and dividing plate lamination are also reeled and obtained, and the method comprises the following steps:
Inorganic oxide slurry according to <4> is coated on the surface of dividing plate, and dry this slurry forms inorganic oxide porous-film.
<7> lithium-ion secondary cell, its method by <5> or <6> obtains.
By inorganic oxide powder of the present invention, heat-staple inorganic oxide porous-film can be provided, it has and is very suitable for the porosity relevant to lithium ion conductive of lithium-ion secondary cell application and has high uniformity.
Embodiment
The invention provides inorganic oxide powder and (be sometimes referred to as below " inorganic oxide powder of the present invention ", or sometimes referred to as " electrodeless oxide powder "), it is for form the inorganic oxide powder of the inorganic oxide porous-film with insulating property on anodal, negative pole and dividing plate (they are for constructing lithium-ion secondary cell) three's at least one surface, wherein
(1) oxide compound purity is 90wt% or higher,
(2), according to mass ratio, the coarse grained content with 10 μ m or higher particle diameter is 10 ppm or lower, and
(3) porosity of the powder compact of the inorganic oxide powder obtaining under the pressure in 29 MPa or higher and 147 MPa or lower scope is 40% (volume) or more and 80% (volume) or lower, the mean pore size of powder compact is 0.06 μ m or higher, and when molded powder compact under every 1MPa pressure the variable quantity of porosity be 0.020% or higher and 0.060% or lower.
In the present invention, the variation (according to % value) of porosity value during the porosity change of every 1 MPa pressure 1 MPa that referred to pressure change on putting on this powder compact when molded powder compact.
For example, porosity for the powder compact of preparing powder compact under the pressure at 73 MPa and obtaining is 55.8% (volume), and the porosity of preparing another powder compact and another powder compact of obtaining under the pressure of 147 MPa is the situation of 52.2% (volume), by the porosity change of every 1 MPa pressure when the molded powder compact of using that these results calculate, be the variation (73-147=-74) of absolute value (55.8%-52.2%=3.6%) this pressure when at molded powder compact of the variation of porosity value, it is 0.049% (3.6%/74) thus.
Inorganic oxide powder of the present invention is not particularly limited, as long as it is the material with electrical insulation capability, it can use aluminum oxide, titanium dioxide, magnesium oxide, silicon oxide etc., preferential oxidation aluminium (alumina).Especially, excellent in thermotolerance and be that chemically stable α-aluminum oxide is most preferred.
The purity of inorganic oxide powder of the present invention is 90wt% or higher preferably, more preferably 99wt% or higher, further preferably 99.9wt% or higher, most preferably 99.99wt% or higher.
Especially, for inorganic oxide powder of the present invention be alpha-alumina powder and purity lower than the situation of 90wt%, in alpha-alumina powder, impurity is as Si, the content of Na and Fe can increase.Therefore, not only cannot obtain gratifying electrical insulation capability, and the combined amount of the foreign matter that can cause short circuit consisting of metal adversely improves.
In addition, the porosity of the powder compact of being made by inorganic oxide powder of the present invention under the pressure in 29 MPa or higher and 147 MPa or lower scope is 40% (volume) or higher and 80% (volume) or lower, and mean pore size is 0.06 μ m or higher.In addition, when the powder compact of molded (or be shaped) inorganic oxide powder, the variable quantity of the porosity of every 1 MPa pressure is 0.020% or higher, preferably 0.025% or higher, and the variable quantity of porosity is 0.080% or lower, preferably 0.065% or lower, more preferably 0.060% or lower.
In inorganic oxide powder of the present invention, the pressure when at molded powder compact is 29 MPa or when lower, sometimes because low molding pressure can not be manufactured uniform powder compact.In addition, the pressure when at molded powder compact is 147 MPa or when higher, sometimes because produce cracking when molded, can not manufacture uniform powder compact.
In the situation that the porosity of the powder compact of inorganic oxide powder of the present invention is lower than 40% (volume), by the slurry of preparing from inorganic oxide powder being coated in the surface of the electrode mixture layer that contains electrode active material (positive electrode active materials or negative active core-shell material) and binding agent and the porosity of the inorganic oxide porous-film of the inorganic oxide powder of the present invention that dry this slurry obtains also can reduce, as a result, in above-mentioned inorganic oxide porous-film, the amount of contained electrolytic solution can adversely decline.
In the situation that the porosity of the powder compact of inorganic oxide powder of the present invention is higher than 80% (volume), by the slurry of preparing from inorganic oxide powder of the present invention being coated in the surface of the electrode (negative or positive electrode) being comprised of the electrode mixture layer that contains electrode active material and binding agent and the porosity of the inorganic oxide porous-film of the inorganic oxide powder of the present invention that dry this slurry obtains also can improve, and above-mentioned inorganic oxide porous film strength can adversely decline.In mean pore size, lower than 0.06 μ m in the situation that, phenomenon identical while having little porosity with above-mentioned powder compact can adversely occur.
When the powder compact of molded inorganic oxide powder of the present invention, the variable quantity of the porosity of every 1 MPa pressure is lower than 0.020% time, can not control-by the slurry of preparing from inorganic oxide powder of the present invention is coated in the surface of the electrode (negative or positive electrode) being formed by the electrode mixture layer that contains electrode active material and binding agent and dry this slurry obtains-porosity of the inorganic oxide porous-film of inorganic oxide powder of the present invention.On the other hand, when when the powder compact of molded inorganic oxide powder of the present invention, the variable quantity of the porosity of every 1 MPa pressure is greater than 0.060%, by the slurry of preparing from inorganic oxide powder of the present invention being coated in the surface of the electrode (negative or positive electrode) being formed by the electrode mixture layer that contains electrode active material and binding agent and the porosity of the inorganic oxide porous-film of the inorganic oxide powder of the present invention that dry this slurry obtains will adversely become inhomogeneous, therefore make to maintain equably electrolytic solution.
In addition, in inorganic oxide powder of the present invention, according to mass ratio, the coarse grained content with 10 μ m or higher particle diameter is 10 ppm or lower.In the situation that there is the coarse grained content of 10 μ m or higher particle diameter, be greater than 10 ppm, sometimes on filming, partly form due to the caused defect of aggregate particle, as lines or coarse porosity.
As mentioned above, α-aluminum oxide is preferably as inorganic oxide powder of the present invention.In the situation that inorganic oxide powder of the present invention is α-aluminum oxide, when alpha-alumina powder, binding agent and solvent are mixed, prepare α-aluminum oxide slurry and obtained α-aluminum oxide slurry is coated on the surface of the electrode mixture layer that contains electrode active material and film to form, then this is filmed while more preferably carrying out roller process, likely guarantee fully porosity and the pore diameter of the α-aluminum oxide porous-film relevant to lithium ion electric conductivity, and, likely advantageously arbitrarily porosity is controlled in preferred scope simultaneously.
In addition, in the situation that inorganic oxide powder of the present invention is α-aluminum oxide, the thermal expansivity of the powder compact of preparing under the pressure of 147 MPa of alpha-alumina powder at the temperature of 40 ℃-600 ℃ preferably 7 * 10
-6/ ℃ or higher and 9 * 10
-6/ ℃ or lower.
Although the inorganic oxide porous-film of lithium-ion secondary cell requires to have excellent thermotolerance, the thermal expansivity of known α-aluminum oxide itself is approximately 8 * 10
-6/ ℃ (referring to, for example " Introduction To Ceramics ", p595, Wiley Interscience).Need, even if the α-aluminum oxide in lithium-ion secondary cell is being short-circuited, cause also bringing into play the effect that maintains steady state in the situation of superheat state excessively.
Thermal expansivity for the powder compact of preparing under the pressure of 147 MPa of alpha-alumina powder at the temperature of 40 ℃-600 ℃ is lower than 7 * 10
-6/ ℃ situation because form the particle of powder compact, can cause and reset and easily carry out sintering, therefore, if this powder compact for inorganic oxide porous-film, the physical properties of film itself (porosity etc.) adversely changes sometimes.
At thermal expansivity, be greater than 9 * 10
-6/ ℃ situation under, not mating between anodal thermal expansivity and the thermal expansivity of negative pole can increase.If this powder compact, for inorganic oxide porous-film, adversely produces cracking sometimes in this inorganic oxide porous-film.
Preferably the alpha-alumina powder as inorganic oxide powder of the present invention has 1 μ m or lower median size (average aggregate particle diameter), has 1-20 m
2/ g, preferably 2-15 m
2the BET specific surface area of/g.
The method of producing alpha-alumina powder of the present invention is not particularly limited, and for example, this alpha-alumina powder can be produced by aluminium-alcohol salt method.
This aluminium-alcohol salt method refer to aluminium-alcohol salt through hydrolysis, obtain slurry-, colloidal sol-or gelatinous aluminium hydroxide, subsequent drying and obtain the method for dry powder aluminium hydroxide.
Particularly, this aluminium-alcohol salt comprises the compound being represented by following general formula (1):
Al(OR
1)(OR
2)(OR
3) (1)
R wherein
1, R
2and R
3represent independently of one another alkyl.
In general formula (1), the example of alkyl comprises the alkyl with 1-4 carbon atom, as methyl, and ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl.The object lesson of this aluminium-alcohol salt comprises aluminum isopropylate, aluminum ethylate, aluminium secondary butylate and trimethyl carbinol aluminium.
By water, be hydrolyzed the paste-like aluminium hydroxide that this aluminium-alcohol salt obtains and conventionally have within the scope of 0.01-1 μ m, preferably the average primary particle diameter within the scope of 0.02-0.05 μ m.
The pulverous aluminium hydroxide obtaining by dry paste-like aluminium hydroxide is for conventionally having about 0.1-0.8 g/cm
3the form of loose (bulky) powder of not compacted density.This is compacted density 0.4-0.8 g/cm preferably not
3.
This target α-aluminum oxide can obtain by the above-mentioned dry powder aluminium hydroxide of roasting.Roasting is normally carried out under the state in being filled in calcination vessel.This calcination vessel comprises, for example, and square crucible.Consider to pollute and control, this calcination vessel is preferably manufactured by the material such as aluminum oxide.
The example of the stoving oven using in roasting comprises the fixed stove of material, typically has tunnel furnace, flow box stoving oven, coflow box stoving oven etc. intermittently of ventilation type intermittently.The rotary kiln of can also giving an example.
Maturing temperature, until temperature reaches the heat-up rate of maturing temperature, and roasting time suitably selects, to obtain the α-aluminum oxide with above-described predetermined physical character.Maturing temperature is 1100-1450 ℃, preferred 1200-1350 ℃, until the heat-up rate that temperature reaches maturing temperature 30-500 ℃/h normally, roasting time is 0.5-24 hour normally, preferably 1-10 hour.
Calcination atmosphere, except atmospheric air, can be rare gas element, as nitrogen or argon gas.Roasting can be carried out in as gas furnace in the atmosphere with high steam partial pressure, and wherein roasting is used propane gas or analogue to be undertaken by burning.
The alpha-alumina powder obtaining is preferably broken, because it is greater than in median size under the state of 1 μ m and assembles in some cases.This breaking method is not particularly limited, and can be for example by the equipment with known, carries out as vibromill, ball mill and jet mill.Also likely use any in dry-type pulverizing method and wet type breaking method.Carry out broken method as maintaining purity in the situation that not comprising coarse aggregate particle when, can exemplify and use the breaking method of jet mill as preferred method.
Inorganic oxide slurry of the present invention is comprised of above-mentioned inorganic oxide powder of the present invention, binding agent and solvent.
Known binding agent can be used as this binding agent, specifically, can use fluoro-resin, as poly(vinylidene fluoride) (PVDF), and tetrafluoroethylene (PTFE) and tetrafluoraoethylene-hexafluoropropylene copolymer (FEP); Polyacrylic acid derivative, as polyacrylic acid, polymethyl acrylate, polyethyl acrylate, the own ester of polyacrylic acid polyhexamethylene and polyacrylic acid; Polymethacrylate derivative, as polymethyl acrylic acid, polymethylmethacrylate, the own ester of polyethyl methacrylate and polymethyl acrylic acid; Polymeric amide, polyimide, polyamidoimide, polyvinyl acetate, polyvinylpyrrolidone, polyethers, polyethersulfone, hexafluoro polypropylene, styrene butadiene rubbers, carboxymethyl cellulose, polyacrylonitrile and their derivative, polyethylene, polypropylene, aromatic polyamide resin etc.
Be selected from tetrafluoroethylene, hexafluoroethylene, R 1216, perfluoroalkyl vinyl ether, vinylidene fluoride, trifluorochloroethylene, ethene, propylene, five fluorine propylene, methyl fluoride vinyl ether, the multipolymer of two or more raw materials in vinylformic acid and hexadiene can be used.
Known solvent can be used as this solvent, specifically, can make water, acetone, tetrahydrofuran (THF), methylene dichloride, chloroform, dimethyl formamide, METHYLPYRROLIDONE (NMP), hexanaphthene, dimethylbenzene, pimelinketone or their mixed solvent.
Can add known thickening material, to obtain the inorganic oxide slurry of the viscosity with the coating of being best suited for.
Disperse the method for above-mentioned inorganic oxide slurry to be not particularly limited, the stirring means being undertaken by known epicyclic mixer (planetary mixer) and the method for disperseing with hyperacoustic radiation can both be used.Now, along with this slurry at 100 S
-1shearing rate under viscosity degradation, dispersion, mixing and transfer step can become satisfactory by workability.
In addition, above-mentioned inorganic oxide slurry is coated to positive pole or contain negative active core-shell material and the surface of the electrode mixture layer of binding agent on or the lip-deep method that is coated to dividing plate be not particularly limited, example as is known scraper coating method, photogravure method etc. can both be used.In addition, drying means is not particularly limited, known hot gas drying, and vacuum-drying etc. can both be used.The thickness of the inorganic oxide porous-film that obtained in this case is preferably set within the scope of 1-50 μ m, more preferably within the scope of about 2-10 μ m.
The inorganic oxide porous-film obtaining of producing from inorganic oxide slurry has high thermotolerance and insulating property.This inorganic oxide porous-film is to form at least one the surface in anodal, negative pole and dividing plate three, then with anodal, negative pole lamination and reel to form electrode group together with dividing plate.As a result, preferably use the lithium-ion secondary cell obtaining that comprises this electrode group and electrolytic solution.
The example of preferably producing the method for this lithium-ion secondary cell comprises the method with the following step: above-mentioned inorganic oxide slurry is coated on the surface of the positive pole that is comprised of the electrode mixture layer that contains electrode active material (positive electrode active materials or negative active core-shell material) and binding agent and/or negative pole to subsequent drying and form inorganic oxide porous-film.In addition, the method can be that above-mentioned inorganic oxide slurry is coated on the surface of dividing plate, is not on the surface of positive pole and/or negative pole, and subsequent drying forms the method for inorganic oxide porous-film.
Concrete method illustrates below.; one end of negative wire is connected to negative wire shank; wherein form from the teeth outwards inorganic oxide porous-film, and one end of negative pole is connected to positive wire shank, and anodal and negative pole carries out lamination and coiling and forms electrode group (electrode slice group) via dividing plate.This electrode group (electrode slice group) is installed in battery can with the state being inserted between upper and lower dead ring, and after injecting electrolytic solution, battery can is sealed by battery lid, produces thus the lithium-ion secondary cell with excellent security.
Producing above-mentioned lithium-ion secondary cell in the situation that of (comprising inorganic oxide porous-film), above-mentioned inorganic oxide porous-film can be by being coated in inorganic oxide slurry of the present invention on the surface of dividing plate and the step of dry this slurry is produced.
The lithium-ion secondary cell of being produced by aforesaid method comprises by the formed inorganic oxide porous-film of inorganic oxide powder of the present invention therefore having excellent thermotolerance and insulating property.
Embodiment
The present invention will utilize embodiment to describe in detail, but the present invention is not limited only to the following example.The evaluation method of physicals is as described below separately.
(aluminum oxide purity)
By solid-state emission spectrography measurement Si, Na, Mg, the content of Cu and Fe.
By deduct the total content (%) of the weight of Si contained in α-aluminum oxide, Na, Mg, Cu and Fe from 100, measure aluminum oxide purity.Calculation formula is as follows.
The total content (%) of purity (%)=100 – impurity weight
(BET specific surface area)
According to the method defining in JIS-Z-8830, by nitrogen absorption process, measure BET specific surface area.As the measuring apparatus of specific surface area, use " the FlowSorb II 2300 " that by Shimadzu Corporation, manufactured.
(average aggregate particle size)
Use utilizes laser scattering method as the particle size distribution analysis device (" Microtrack HRA X-100 ", is manufactured by Honeywell Inc) of ultimate principle, measures size distribution curve, and average aggregate particle size is measured as 50 wt% equivalent grain sizes.In the situation that measuring, by carrying out ultrasonic wave dispersion with 0.2wt% sodium hexametaphosphate solution.
(porosity of powder compact)
The alpha-alumina powder with mold filling 10 g of 30 mm diameters, then under the pressure of 29 MPa, carry out single shaft molded (single shaft compacting), under the pressure of 29,73 or 147 MPa, carry out subsequently CIP molded and obtain powder compact, then use mercury porosimeter (AutoPore III9430 is manufactured by Micromeritics Instrument Corporation) to measure void content and pore diameter.The porosity of each powder compact is obtained by following equation.
Porosity (volume %)=[void content (ml/g)/((1/3.98*)+void content (ml/g))] * 100
* theoretical density (the g/cm of 3.98=α-aluminum oxide
3)
In addition,, by using method of least squares, by the relation between pressure and porosity, calculated the porosity dependency of molding pressure.
(thermal expansivity)
The alpha-alumina powder with the mold filling 1.5g of 10 mm diameters, then under the pressure of 49 MPa, at room temperature carry out single shaft molded, under the pressure of 147 MPa, carry out subsequently CIP molded and obtain powder compact, then by Thermo Mechanical Analyzer (TMA/SS6300 is manufactured by SII NanoTechnology Inc), measure thermal expansivity.About this thermal expansivity, until the coefficient of expansion of 600 ℃ carries out linear-apporximation, be then defined as the gradient of near linear.
(content of 10 μ m or higher coarse aggregate particle)
Alpha-alumina powder (1.5-30 g) is by being dispersed in hyperacoustic radiation in 800 g pure water of the Sodium hexametaphosphate 99 (as dispersion agent) that contains 0.2% to prepare α-aluminum oxide slurry, then this slurry flow is crossed the screen cloth of the pore diameter with 10 μ m, and the alpha-alumina powder being then retained on this screen cloth is recovered and measures content.
(embodiment 1)
First, from being hydrolyzed as the raw-material standby aluminum isopropylate water of aluminum with 99.99% purity, obtain paste-like aluminium hydroxide, be then dried and obtain and there is 0.1 g/cm
3the dry powder aluminium hydroxide of not compacted density.
Then, this dry powder aluminium hydroxide is calcined by maintaining 3 hours in the gas furnace carrying out roasting by the burning of propane gas at 1200 ℃, then broken by jet mill, obtains alpha-alumina powder.
The alpha-alumina powder obtaining has 5.2 m
2the BET specific surface area of/g, the median size of 0.45 μ m, and 3 ppm or the lower coarse grained content with 10 μ m or higher particle diameter.About the content of impurity, Si content is 4 ppm, and Fe content is 7 ppm, and Cu content is 1 ppm, and Na content is 2 ppm, and Mg content is 1 ppm, and aluminum oxide purity is 99.99wt% or higher.
Then, the α-aluminum oxide powder obtaining carries out molded under the pressure of 29,73 and 147 MPa, obtains powder compact.The porosity of each powder compact is respectively 59.2,55.8 and 52.2% (volume), and mean pore size is within the scope of 0.08-0.11 μ m, and the porosity change of every 1MPa is 0.059%, and at 40 ℃-600 ℃, the thermal expansivity of powder compact is 8.5 * 10
-6/ ℃.
The alpha-alumina powder obtaining according to the above method, poly(vinylidene fluoride) (PVDF) as film adhesive,, stirring mixed with the METHYLPYRROLIDONE as solvent (NMP) of appropriate amount, with preparation porous coating (slurry), wherein the content of filler accounts for the 94wt% of the total amount of filler and film adhesive.The viscosity of slurry is measured by viscoelasticity analysis device (Physica MCR301 is manufactured by Anton Paar).As a result, when shearing rate is 100 S
-1time, this viscosity is 0.32 Pas.
By natural spherical plumbago being coated on the end face of the pellet electrode of manufacturing on copper sheet, by metering bar coater, apply this porous coating, then dry, acquisition has the even porous-film of the thickness of 3-5 μ m.
(embodiment 2)
From being hydrolyzed as the raw-material standby aluminum isopropylate water of aluminum with 99.99% purity, obtain paste-like aluminium hydroxide, be dried, obtain the first dry powder aluminium hydroxide.Then, with pure water, this first dry powder aluminium hydroxide is wetting, then dry, obtain and there is 0.6 g/cm
3the dry powder aluminium hydroxide of not compacted density.
Then, this dry powder aluminium hydroxide is calcined by maintain 4 hours at 1220 ℃, then broken by jet mill, obtains alpha-alumina powder.
The alpha-alumina powder obtaining has 4.13m
2the BET specific surface area of/g, the median size of 0.69 μ m, 3 ppm or the higher coarse grained content with 10 μ m or higher particle diameter.Yet coarse grained content is less than 10 ppm.About the content of impurity, Si content is 11 ppm, and Fe content is 10 ppm, and Cu content is 1 ppm or lower, and Na content is 5 ppm or lower, and Mg content is 1 ppm or lower, and aluminum oxide purity is 99.99wt% or higher.
Then the alpha-alumina powder, obtaining carries out molded and obtains powder compact under the pressure of 29,73 and 147 MPa.The porosity of each powder compact is respectively 53.7,52.0 and 50.5% (volume), and mean pore size is within the scope of 0.12-0.13 μ m, and the porosity change of every 1MPa is 0.027%, and at 40 ℃-600 ℃, the thermal expansivity of powder compact is 8.7 * 10
-6/ ℃.
According to method similarly to Example 1, except using from as the raw-material standby aluminium-alcohol salt of aluminum with 99.9% purity, obtain alpha-alumina powder.
The alpha-alumina powder obtaining according to the above method, poly(vinylidene fluoride) (PVDF) as film adhesive,, stirring mixed with the METHYLPYRROLIDONE as solvent (NMP) of appropriate amount, with preparation porous coating (slurry), wherein the content of filler accounts for the 94wt% of the total amount of filler and film adhesive.The viscosity of slurry is measured by viscoelasticity analysis device (Physica MCR301 is manufactured by Anton Paar).As a result, when shearing rate is 100 S
-1time, this viscosity is 0.19 Pas.
By natural spherical plumbago being coated on the end face of the pellet electrode of manufacturing on copper sheet, by metering bar coater, apply this porous coating, then dry, acquisition has the uniform micro film of the thickness of 3-5 μ m.
The pellet electrode being obtained by aforesaid method is cut into the ring with 1.45 cm diameters and manufactures electrode, the electrode obtaining vacuum-drying 8 hours at 120 ℃.After vacuum-drying, use respectively the electrode obtaining as negative pole, lithium paper tinsel is as positive pole, and the TF40-50 being manufactured by NIPPON KODOSHI CORPORATION, as dividing plate, has the LiPF of the concentration of 1 mol/ liter
6/ carbonic acid ethylidene ester: dimethyl carbonate: ethylmethyl carbonate (=20:30:30 v/v%)+3 wt% carbonic acid vinylidene ester is as electrolytic solution, with CR2032 type (IEC/JIS standard) coin battery, carry out Of Assembling A Bipolar Battery, then rated capacity retains and compares 1C/0.2C.As a result, it is 99%.
Here, the capacity retention in the present invention is than the following calculating of 1C/0.2.Use charging and discharging valuator device (" TOSCAT (registered trademark)-3100 ", by Toyo System Co., Ltd manufactures), under the current density of 60 mA/g, carry out constant current charge until bipolar cell reaches 5 mV.Reach after 5 mV, carry out constant voltage charge, until current value becomes 6 mA/g, then under the constant current of the current density of 60 mA/g, discharge, until reach 1.5 V.In second period, carry out identical charging and discharging, and the integrated amount (integrated quantity) of electric power (electricity) is got the capacity of doing when 0.2C while discharging in second period.Subsequently, carry out the 3rd cycle, under the current density of 60 mA/g, carry out constant current charge, until reach 5 mV.After reaching 5 mV, carry out constant voltage charge, until current value reaches 6 mA/g.Then, under the constant current of the current density of 360 mA/g, discharge, until reach 1.5 V.In the 4th cycle, carry out identical charging and discharging, and the integrated amount of electric power is got the capacity while doing at 1C while discharging in the 4th cycle.The value that is multiplied by 100 acquisitions by the value that the capacity when at 0.2C obtains by the institute's acquisition capacity when the 1C is got as capacity retention compares 1C/0.2C.
(comparative example 1)
First, according to method similarly to Example 1, obtain dry powder aluminium hydroxide.Then, this aluminium hydroxide is calcined by maintain 2 hours at 1250 ℃, then by vibratory milling crusher machine, obtains alpha-alumina powder.
The alpha-alumina powder obtaining has 11.0m
2the BET specific surface area of/g, the median size of 0.22 μ m, 7300 ppm or the higher coarse grained content with 10 μ m or higher particle diameter.About the content of impurity, Si content is 12 ppm, and Fe content is 3 ppm, and Cu content is 1 ppm, and Na content is 2 ppm, and Mg content is 1 ppm, and aluminum oxide purity is 99.99wt% or higher.
Then, the alpha-alumina powder obtaining carries out molded under the pressure of 29,73 and 147 MPa, obtains powder compact.The porosity of each powder compact is respectively 46.3,44.5 and 43.7% (volume), and mean pore size is about 0.04 μ m, and the porosity change of every 1MPa is 0.020%, and at 40 ℃-600 ℃, the thermal expansivity of powder compact is 6.1 * 10
-6/ ℃.
The alpha-alumina powder obtaining according to the above method, poly(vinylidene fluoride) (PVDF) as film adhesive,, stirring mixed with the METHYLPYRROLIDONE as solvent (NMP) of appropriate amount, with preparation porous coating (slurry), wherein the content of filler accounts for the 94wt% of the total amount of filler and film adhesive.The viscosity of slurry is measured by viscoelasticity analysis device (Physica MCR301 is manufactured by Anton Paar).As a result, when shearing rate is 100 S
-1time, this viscosity is 0.15 Pas.
By natural spherical plumbago being coated on the end face of the pellet electrode of manufacturing on copper sheet, by metering bar coater, apply this porous coating, then dry.As a result, be considered to, by the caused inhomogeneous generation of filming of aggregate particle, cannot obtain uniformly and film.
(comparative example 2)
First, according to method similarly to Example 1, obtain dry powder aluminium hydroxide.Then, this aluminium hydroxide is calcined by maintain 4 hours at 1270 ℃, then by vibratory milling crusher machine, obtains alpha-alumina powder.
The alpha-alumina powder obtaining has 5.1m
2the BET specific surface area of/g, the median size of 0.52 μ m, 800ppm or the higher coarse grained content with 10 μ m or higher particle diameter.About the content of impurity, Si content is 15 ppm, and Fe content is 7 ppm, and Cu content is 1 ppm, and Na content is 4 ppm, and Mg content is 3 ppm, and aluminum oxide purity is 99.99wt% or higher.
Then the alpha-alumina powder, obtaining carries out molded and obtains powder compact under the pressure of 29,73 and 147 MPa.The porosity of each powder compact is respectively 42.9,42.6 and 41.5% (volume), and mean pore size is approximately 0.09 μ m, and the porosity change of every 1MPa is 0.012%, and at 40 ℃-600 ℃, the thermal expansivity of powder compact is 8.1 * 10
-6/ ℃.
The alpha-alumina powder obtaining according to the above method, poly(vinylidene fluoride) (PVDF) as film adhesive,, stirring mixed with the METHYLPYRROLIDONE as solvent (NMP) of appropriate amount, with preparation porous coating (slurry), wherein the content of filler accounts for the 94wt% of the total amount of filler and film adhesive.The viscosity of slurry is measured by viscoelasticity analysis device (Physica MCR301 is manufactured by Anton Paar).As a result, when shearing rate is 100 S
-1time, this viscosity is 0.11 Pas.
By natural spherical plumbago being coated on the end face of the pellet electrode of manufacturing on copper sheet, by metering bar coater, apply this porous coating, then dry.As a result, be considered to, by the caused inhomogeneous generation of filming of aggregate particle, cannot obtain uniformly and film.
Inorganic oxide powder of the present invention can provide inorganic oxide porous-film, the latter has and is very suitable for the optimal porosity relevant to lithium ion conductive of lithium-ion secondary cell application and has high uniformity and be heat-staple, therefore industrial be useful.
Claims (6)
1. an inorganic oxide powder, it is for forming the inorganic oxide porous-film with insulating property at least one the surface in the middle of the positive pole, negative pole and the dividing plate three that use at lithium-ion secondary cell, wherein,
(1) oxide compound purity is 90wt% or higher,
(2), according to mass ratio, the coarse grained content with the particle diameter that is not less than 10 μ m is to be not more than 10 ppm,
(3) in the porosity that is not less than 29 MPa and is not more than the powder compact of the inorganic oxide powder obtaining under the pressure in the scope of 147 MPa, be to be not less than 40 volume % and to be not more than 80 volume %, the mean pore size of powder compact is 0.06 μ m or higher, and when molded powder compact under every 1MPa pressure the variable quantity of porosity be 0.020% or higher and 0.060% or lower, and
(4) this inorganic oxide is α-aluminum oxide.
2. according to the inorganic oxide powder of claim 1, the thermal expansivity of the powder compact of the inorganic oxide powder of wherein manufacturing under the pressure of 147 MPa at 40 ℃-600 ℃ is to be not less than 7 * 10
-6/ ℃ and be not more than 9 * 10
-6/ ℃.
3. an inorganic oxide slurry, it comprises according to the inorganic oxide powder of claim 1 or 2, binding agent and solvent.
4. produce the method for lithium-ion secondary cell, described battery comprises electrode group and the electrolytic solution by positive pole, negative pole and dividing plate lamination are also reeled and obtained, and the method comprises the following steps:
To according to the inorganic oxide slurry of claim 3, be coated on the surface of the positive pole that formed by the electrode mixture layer that contains electrode active material and binding agent and/or negative pole;
Then dry this slurry forms inorganic oxide porous-film.
5. produce the method for lithium-ion secondary cell, described battery comprises electrode group and the electrolytic solution by positive pole, negative pole and dividing plate lamination are also reeled and obtained, and the method comprises the following steps:
To be coated on the surface of dividing plate according to the inorganic oxide slurry of claim 3;
Then dry this slurry forms inorganic oxide porous-film.
6. a lithium-ion secondary cell, its method by claim 4 or 5 obtains.
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| JP5362132B2 (en) * | 2012-01-20 | 2013-12-11 | 住友化学株式会社 | Inorganic oxide powder, inorganic oxide-containing slurry, lithium ion secondary battery using the slurry, and manufacturing method thereof |
| CN104185651B (en) * | 2012-06-28 | 2016-01-20 | 株式会社吴羽 | Resin combination, the rechargeable nonaqueous electrolytic battery manufacture method of resin-filled film and rechargeable nonaqueous electrolytic battery resin-filled film |
| KR101535199B1 (en) | 2012-11-30 | 2015-07-09 | 주식회사 엘지화학 | Slurry with improved dispersibility and its use |
| TWI609518B (en) * | 2013-12-09 | 2017-12-21 | Ｌｇ化學股份有限公司 | Slurry with improved dispersibility and its use |
| CN104269507B (en) * | 2014-09-19 | 2017-04-05 | 国家电网公司 | A kind of lithium ion battery composite separation membrane and preparation method thereof |
| CN105185938A (en) * | 2015-07-21 | 2015-12-23 | 大连比克动力电池有限公司 | Anode of lithium-ion battery and lithium-ion battery prepared from same |
| CN105355813A (en) * | 2015-12-14 | 2016-02-24 | 苏州锂盾储能材料技术有限公司 | Lithium ion battery diaphragm material and preparation method thereof |
| JP6360531B2 (en) * | 2016-09-15 | 2018-07-18 | 住友化学株式会社 | Non-aqueous electrolyte secondary battery laminated separator, non-aqueous electrolyte secondary battery member, and non-aqueous electrolyte secondary battery |
| CN106374075A (en) * | 2016-09-26 | 2017-02-01 | 中材科技股份有限公司 | Reticular porous composite isolation film and preparation method thereof |
| KR101907363B1 (en) | 2016-11-14 | 2018-10-11 | 스미또모 가가꾸 가부시키가이샤 | Alumina, slurry containing the same, and porous alumina film, laminated separator, nonaqueous electrolyte secondary battery using the same, and method for manufacturing nonaqueous electrolyte secondary battery |
| JP6562147B2 (en) * | 2018-02-05 | 2019-08-21 | 三菱マテリアル株式会社 | Insulating film, insulated conductor, metal base substrate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09147916A (en) * | 1995-11-20 | 1997-06-06 | Fuji Photo Film Co Ltd | Nonaqueous electrolyte secondary battery |
| CN1468892A (en) * | 2002-06-11 | 2004-01-21 | ������������ʽ���� | Dielectric coated pole, plasma discharge processing apparatus and thin-film forming method |
| JP2005327680A (en) * | 2004-05-17 | 2005-11-24 | Matsushita Electric Ind Co Ltd | Lithium ion secondary battery |
| CN1806351A (en) * | 2004-06-22 | 2006-07-19 | 松下电器产业株式会社 | Secondary battery and method for producing the same |
| CN101212305A (en) * | 2006-12-30 | 2008-07-02 | 上海亿动信息技术有限公司 | Information publishing method and system |
| CN101558513A (en) * | 2006-11-20 | 2009-10-14 | 帝人株式会社 | Separator for nonaqueous secondary battery, process for producing the same, and nonaqueous secondary battery |
-
2011
- 2011-02-25 CN CN201110046076.4A patent/CN102190323B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09147916A (en) * | 1995-11-20 | 1997-06-06 | Fuji Photo Film Co Ltd | Nonaqueous electrolyte secondary battery |
| CN1468892A (en) * | 2002-06-11 | 2004-01-21 | ������������ʽ���� | Dielectric coated pole, plasma discharge processing apparatus and thin-film forming method |
| JP2005327680A (en) * | 2004-05-17 | 2005-11-24 | Matsushita Electric Ind Co Ltd | Lithium ion secondary battery |
| CN1806351A (en) * | 2004-06-22 | 2006-07-19 | 松下电器产业株式会社 | Secondary battery and method for producing the same |
| CN101558513A (en) * | 2006-11-20 | 2009-10-14 | 帝人株式会社 | Separator for nonaqueous secondary battery, process for producing the same, and nonaqueous secondary battery |
| CN101212305A (en) * | 2006-12-30 | 2008-07-02 | 上海亿动信息技术有限公司 | Information publishing method and system |
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