WO2018020908A1 - CORPS FRITTÉ COMPORTANT DU LiCoO2 ET CIBLE DE PULVÉRISATION TUBULAIRE - Google Patents

CORPS FRITTÉ COMPORTANT DU LiCoO2 ET CIBLE DE PULVÉRISATION TUBULAIRE Download PDF

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Publication number
WO2018020908A1
WO2018020908A1 PCT/JP2017/022660 JP2017022660W WO2018020908A1 WO 2018020908 A1 WO2018020908 A1 WO 2018020908A1 JP 2017022660 W JP2017022660 W JP 2017022660W WO 2018020908 A1 WO2018020908 A1 WO 2018020908A1
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sintered body
cylindrical
porosity
region
precursor
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PCT/JP2017/022660
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English (en)
Japanese (ja)
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雄一 武富
守賀 金丸
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株式会社コベルコ科研
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a sintered body containing LiCoO 2 and a cylindrical sputtering target.
  • Li-based thin-film secondary batteries are used in various devices such as thin-film solar cells, thin-film thermoelectric elements, and wireless charging elements, and their demand is rapidly increasing.
  • a Li-based thin film secondary battery is typically composed of a positive electrode composed of a LiCoO 2 containing thin film containing Li and Co as a transition metal, a solid electrolyte containing Li, and a negative electrode composed of a Li metal thin film. ing.
  • a sputtering target having the same composition as the film (hereinafter sometimes abbreviated as target.)
  • Sputtering of sputtering is preferably used.
  • the sputtering method has advantages such as easy adjustment of film forming conditions and easy film formation on a semiconductor substrate.
  • a magnetron sputtering method is employed in which sputtering is performed while applying a magnetic field to the cathode.
  • Patent Document 1 As such a cylindrical sputtering target, in Patent Document 1, a cylindrical molded body is mounted on a plate-shaped molded body having a sintering shrinkage rate equivalent to that of the cylindrical molded body. It is described that a cylindrical sintered body having a relative density of 95% or more is obtained by placing and firing, and a cylindrical sputtering target is produced using this.
  • a cylindrical molded body is sintered at normal pressure using a firing furnace including a pipe for supplying atmospheric gas and an outlet for discharging the atmospheric gas from above.
  • a method for producing a sintered body for a cylindrical sputtering target is described, which includes the step of obtaining a cylindrical sintered body.
  • JP 2005-281862 A Japanese Patent Application Laid-Open No. 2012-126587
  • the cylindrical sintered body when a sintered body is manufactured by firing metal powder, the cylindrical sintered body is more susceptible to cracking due to thermal shrinkage than the flat plate-type sintered body. Further, even if a cylindrical sintered body can be produced without cracking during sintering, the cylindrical sintered body may be broken by processing when producing a cylindrical sputtering target using the cylindrical sintered body. . In the manufacturing methods disclosed in Patent Documents 1 and 2, there is a lack of studies for manufacturing a cylindrical sintered body that is difficult to break during processing by controlling the structure of the cylindrical sintered body itself.
  • the embodiment of the present invention has been made paying attention to the above-mentioned problems, and its purpose is to provide a sintered body that is difficult to break during processing or the like. It is another object of the present invention to provide a cylindrical sputtering target provided with such a sintered body.
  • the sintered body according to the embodiment of the present invention A pore in the central region containing LiCoO 2 , having a cylindrical shape including a hollow portion defined by the inner peripheral surface, and having a range from 15% to 70% of the distance from the outer peripheral surface to the inner peripheral surface
  • the rate is 15% or more and 34% or less over 80% or more of the height of the cylindrical sintered body,
  • the following expression (1) is satisfied. 200 ⁇ (Do + Di) ⁇ ⁇ ⁇ L / 200 ⁇ 950 (1)
  • Do is the outer diameter [mm] of the sintered body
  • Di is the inner diameter [mm] of the sintered body
  • L is the height [mm] of the sintered body.
  • the sintered body according to the embodiment of the present invention may have a relative density of 90% or more.
  • the cylindrical sputtering target according to the present invention includes a backing tube and a sintered body according to the embodiment of the present invention.
  • the sintered body according to the embodiment of the present invention is not easily broken during processing.
  • FIG. 1 is a schematic view schematically showing a part of a sintered body according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram schematically showing cutting positions from the top surface and the bottom surface of the precursor sintered body.
  • the inventors of the present invention have a cylindrical shape including a hollow portion defined by an inner peripheral surface in a sintered body containing LiCoO 2 , and an outer peripheral surface.
  • a predetermined region located between the inner peripheral surface and the inner peripheral surface is controlled to have a predetermined porosity over a predetermined ratio of the height of the sintered body, and further, the outer diameter of the sintered body It was found that by controlling the inner diameter and the height so as to satisfy a predetermined relationship, a sintered body that is difficult to break during processing or the like can be obtained.
  • the “sintered body” means a single sintered body and does not include a combination of a plurality of sintered bodies.
  • the sintered body of the embodiment of the present invention consists of a single sintered body.
  • the sintered body according to the embodiment of the present invention may be referred to as a “cylindrical sintered body”.
  • the cylindrical sintered body As described later, the cylindrical sintered body, it a powder containing LiCoO 2 was filled in a graphite mold, to further heat treatment to thereby obtain a precursor sintered body, a precursor sintered by pressure sintering To obtain a cylindrical sintered body.
  • the production of a cylindrical sintered body is more susceptible to thermal shrinkage during pressure sintering or heat treatment than the production of a flat plate sintered body, and a precursor sintered body and / or a cylindrical sintered body.
  • the heat shrinkage in the outer diameter direction and the height direction is nonuniform, and the precursor sintered body and / or the cylindrical sintered body may be distorted and cracked.
  • powder containing LiCoO 2 is filled in a graphite mold and sintered under pressure, the precursor sintered body may crack due to thermal shrinkage, and even if the precursor sintered body does not crack during pressure sintering, Further, when the precursor sintered body is further heat-treated, the thermal shrinkage further proceeds and the cylindrical sintered body may be cracked.
  • the cylindrical sintered body may break.
  • the inventors of the present invention focused on controlling the structure of the precursor sintered body by appropriately controlling the pressure sintering conditions. And it discovered that the cylindrical sintered compact which is hard to be cracked in the case of heat processing is obtained by heat-processing to the precursor sintered compact which has the predetermined structure controlled appropriately.
  • the cylindrical sintered body thus obtained is structurally strong and difficult to crack.
  • FIG. 1 is a schematic view schematically showing a part of a cylindrical sintered body according to an embodiment of the present invention, and shows a cross-section in a plane defined by an outer diameter direction and a height direction of the cylindrical sintered body. Show.
  • the cylindrical sintered body has a cylindrical shape having an outer peripheral surface and an outer peripheral surface over 360 °.
  • the said figure is a schematic diagram for making an understanding of the cylindrical sintered compact concerning embodiment of this invention easy, and this invention is not limited to this.
  • the region inside the cylindrical sintered body has a first region 5, a second region 6 (central region), and a third region 7 from the outer peripheral surface 1 toward the inner peripheral surface 2. .
  • the cylindrical sintered body has a cylindrical shape including a hollow portion defined by an inner peripheral surface, and a central region (range 15% to 70% of the distance from the outer peripheral surface to the inner peripheral surface ( The porosity of the second region 6) is 15% or more and 34% or less over 80% or more of the height of the cylindrical sintered body. That is, when the distance from the outer peripheral surface to the inner peripheral surface is d, the central region is a range from a position of 0.15 ⁇ d to a position of 0.70 ⁇ d.
  • the cylindrical sintered body includes a step of obtaining a precursor sintered body by filling a graphite mold with a powder containing LiCoO 2 and performing pressure sintering, and further heat-treating the precursor sintered body.
  • a cylindrical sintered body When producing the precursor sintered body, the outer part (outer peripheral surface, inner peripheral surface, upper surface and bottom surface of the precursor sintered body) in contact with the graphite mold is in contact with the graphite mold because of the large heat transfer from the graphite mold.
  • sintering of the powder containing LiCoO 2 proceeds easily, and the porosity is lowered.
  • the porosity increases from the outer peripheral surface toward the intermediate portion between the outer peripheral surface and the inner peripheral surface, and the outer peripheral surface It is considered that the porosity decreases from the intermediate portion between the inner peripheral surface and the inner peripheral surface toward the inner peripheral surface. Further, it is considered that the porosity increases from the upper surface toward the intermediate portion between the upper surface and the bottom surface, and the porosity decreases from the intermediate portion between the upper surface and the bottom surface toward the bottom surface.
  • the cylindrical sintered body obtained by the heat treatment has a lower porosity value than the precursor sintered body by the heat treatment, but the porosity distribution is the same.
  • the outer first region 5 and the third region 7 have a low porosity, and the inner second region 6 has a high porosity.
  • the outer first region 5 and the third region 7 have a low porosity (high density), and the inner second region 6 has a high porosity (low density). ). Since the outer first region 5 and the third region 7 are dense and hard, they are strong against impacts from the outside, and the inner second region 6 is soft and low in density, so that it is made into a cylindrical sintered body. It is considered to have a function of relieving applied stress. Since the cylindrical sintered body has such a porosity over a predetermined proportion of the height of the cylindrical sintered body, the cylindrical sintered body is strong against external force and is not easily cracked.
  • the porosity is 15% or more and 34% or less over 80% or more of the height of the cylindrical sintered body.
  • the ratio of the length L * of the portion having the porosity that is, the value represented by L * / L ⁇ 100 means 80% or more.
  • the porosity increases from the upper surface 3 toward the intermediate portion between the upper surface 3 and the bottom surface 4 and decreases from the intermediate portion between the upper surface 3 and the bottom surface 4 toward the bottom surface 4. Therefore, when measuring the distribution of the porosity in the height direction of the cylindrical sintered body in the second region 6, for example, the porosity T of the top surface 3 and the porosity B of the bottom surface 4 of the cylindrical sintered body, and the cylinder The porosity M at a position half the height of the shaped sintered body is measured. From the result, the second region has a lower porosity of the porosity T or the porosity B, with the porosity M as the upper limit. It can be regarded as having a porosity distribution as a lower limit.
  • Examples of the method for measuring the porosity include the following methods. First, the cylindrical sintered body is obtained so as to obtain a cross section of the cylindrical sintered body (hereinafter, sometimes referred to as a vertical cross section) in a plane defined by the outer diameter direction and the height direction of the cylindrical sintered body. Disconnect. Then, a 10 mm (height direction) ⁇ 9 mm (outer diameter direction) sample is taken from the cross section, and after filling each sample with resin, the cross section is polished to expose the sample cross section. Next, the polished surface is observed at 450 times using an optical microscope, all the pores present in the observation field selected at random are specified, the total area of the pores is calculated, and the pore area relative to the area of the observation field is calculated. The ratio of the total area is defined as the porosity. The area of the pores may be calculated using commercially available image analysis software. For example, “ImageJ” manufactured by Wayne Rasband may be used.
  • the second region 6 (central region) is in the range of 15% or more and 70% or less of the distance from the outer peripheral surface to the inner peripheral surface, and over 80% or more of the height of the cylindrical sintered body. It has a porosity of 15% or more and 34% or less. If the distance from the outer peripheral surface to the inner peripheral surface is less than 15%, the first region 5 becomes too narrow, so that it is weak against impact from the outside, and the cylindrical sintered body is easily cracked. If it is larger than 70%, the third region 7 becomes too narrow, so that it is weak against an external impact and the cylindrical sintered body is easily cracked.
  • a range from 17% to 68% of the distance from the outer peripheral surface to the inner peripheral surface It is preferable that it is 20% or more and 65% or less of range.
  • the porosity of the second region is less than 15%, the second region 6 becomes too hard, so that the function of the second region 6 that relaxes stress cannot be sufficiently exerted, and the cylindrical sintered body is easily cracked.
  • it exceeds 34% the second region 6 becomes too soft, so that it cannot withstand the external impact applied to the first region 5 or the third region 7, and the cylindrical sintered body easily breaks.
  • the porosity of the second region 6 is preferably 16% or more, more preferably 17% or more, preferably 32% or less, more preferably 30. % Or less.
  • the ratio of the porosity in the height direction of the cylindrical sintered body is less than 80%, in the second region 6, a portion where the porosity is too low and too hard or a portion where the porosity is too high and too soft. The ratio increases, and the function of the second region 6 for relaxing the stress cannot be sufficiently exhibited, or it becomes weak against an external impact, and the cylindrical sintered body is easily cracked.
  • the porosity is preferably 85% or more, more preferably 90% or more, and most preferably 100% of the height of the cylindrical sintered body. It spans.
  • the first region 5 is a range from the outer peripheral surface to the second region 6. From the viewpoint of increasing the density of the first region 5 and obtaining a cylindrical sintered body that is more resistant to external force, the porosity of the first region 5 is preferably 2% or more and 15% or less, and the porosity is , Preferably over 90% of the height of the cylindrical sintered body, most preferably over 100%.
  • the third region 7 is a range from the second region 6 to the outer peripheral surface. From the viewpoint of increasing the density of the third region 7 and obtaining a cylindrical sintered body that is more resistant to external force, the porosity of the third region 7 is preferably 2% or more and 15% or less, and the porosity is , Preferably over 90% of the height of the cylindrical sintered body, most preferably over 100%.
  • the lower limit of the above formula (1) is preferably 210, more preferably 220, and the upper limit of the above formula (1) is preferably 940, more Preferably it is 930.
  • the cylindrical sintered body since the cylindrical sintered body has a predetermined structure, the cylindrical sintered body becomes strong against external force. For example, when the cylindrical sintered body is transported or processed into a sputtering target. It becomes difficult to break when the sputtering target is attached to the production line.
  • the cylindrical sintered body contains lithium cobalt oxide (LiCoO 2 ).
  • LiCoO 2 lithium cobalt oxide
  • the ratio of LiCoO 2 to the whole sintered body is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and most preferably 100% by mass. is there.
  • components other than LiCoO 2 include transition metals other than Co (Mn, Fe, or Ni), complex oxides of Li and other transition metals, and Co.
  • the resistance of the cylindrical sintered body is preferably 100 k ⁇ or less, more preferably 50 k ⁇ or less, from the viewpoint of improving the film formation rate.
  • the resistance may be measured by a two-terminal method in a region between the outer peripheral surface and the inner peripheral surface of the cylindrical sintered body.
  • the relative density of the entire cylindrical sintered body is preferably 85% or more, more preferably 90% or more.
  • the relative density may be calculated by setting the theoretical density of LiCoO 2 to 5.06 g / cm 3 and dividing the apparent density of the cylindrical sintered body measured by the Archimedes method by the theoretical density.
  • the cylindrical sintered body includes a step of obtaining a precursor sintered body by filling a powder containing LiCoO 2 into a graphite mold and performing pressure sintering, and a cylindrical sintering by further heat-treating the precursor sintered body. It is manufactured by performing the process of obtaining a body.
  • the sintering method examples include a normal pressure sintering method in which the raw materials are sintered in an air atmosphere, and a pressure sintering method in which the raw materials are filled in a mold such as a graphite mold.
  • pressure sintering by hot pressing sintering can be performed at a low temperature due to the sintering support effect by pressurization, compared to normal pressure sintering in which sintering is performed only by heating, so that a sintered body with a fine crystal structure can be obtained.
  • the pores are formed at the contact points between the crystal grains. Therefore, it is considered that a crystal structure in which pores are uniformly dispersed in a cylindrical sintered body can be obtained by forming a fine crystal structure by a hot press method.
  • the relative density of the cylindrical sintered body is increased.
  • the composite oxide such as LiCoO 2 targeted in the embodiment of the present invention has a property that it is difficult to increase the relative density, and therefore, a hot press method is effective.
  • the density can be controlled relatively easily even at a low sintering temperature due to the assist effect of the pressurization.
  • a ceramic mold may be used, but it is difficult to manufacture a ceramic mold having a large size, and therefore a graphite mold is preferably used.
  • a powder containing LiCoO 2 (hereinafter sometimes referred to as raw material powder) is used.
  • the powder may contain another composite oxide in accordance with the composition of the sintered body.
  • a commercially available LiCoO 2 powder may be used as it is.
  • the LiCoO 2 -containing powder is entirely (100% by mass) made of LiCoO 2 .
  • components other than LiCoO 2 include transition metals other than Co (Mn, Fe, or Ni), complex oxides of Li and other transition metals, and Co.
  • the filling amount of the raw material powder may be appropriately adjusted in consideration of the thermal shrinkage of the raw material powder and the size of the finally obtained cylindrical sintered body.
  • the powder containing LiCoO 2 was filled in a graphite mold, to obtain a precursor sintered body by pressure sintering.
  • the raw material powder may be filled directly without preforming, or once filled into another mold and pre-molded with a mold press, then filled into the graphite mold. Also good.
  • the latter preforming is performed for the purpose of improving the handleability when setting a predetermined mold in the pressure sintering process. For example, a pressure of about 0.5 to 1.0 tonf / cm 2 is applied.
  • a preform may be used.
  • the conditions of pressure sintering such as the atmosphere during hot pressing, the temperature, pressure and time during sintering, etc., the precursor sintered body obtained by pressure sintering has the structure described later and is finally obtained.
  • the cylindrical sintered body is not particularly limited as long as it has the structure defined in the embodiment of the present invention.
  • the pressure sintering is performed in an inert atmosphere such as nitrogen gas or argon gas.
  • an inert atmosphere such as nitrogen gas or argon gas.
  • the method for controlling the atmosphere is not particularly limited.
  • the atmosphere may be adjusted by introducing nitrogen gas or argon gas into the furnace.
  • the heating rate up to the sintering temperature is not particularly limited, and may be, for example, in the range of 1 to 20 ° C./min.
  • the pressure sintering is preferably performed at a temperature of 700 to 1000 ° C. and a pressure of 10 to 100 MPa for 0.5 to 4 hours, for example.
  • the relative density of the sintered body can be improved by setting the pressure sintering temperature to 700 ° C. or higher. By setting the pressure sintering temperature to 1000 ° C. or less, weight reduction due to sintering can be suppressed and the relative density of the sintered body can be improved. From the viewpoint of further improving the relative density, a more preferable lower limit of the pressure sintering temperature is 800 ° C., and a more preferable upper limit is 950 ° C. or less.
  • the relative density of the sintered body can be improved by setting the pressure of pressure sintering to 10 MPa or more. Moreover, damage of the graphite mold can be suppressed by setting the pressure of pressure sintering to 100 MPa or less. From the viewpoint of further improving the relative density, a more preferable lower limit of the pressure sintering pressure is 20 MPa, and from a viewpoint of further suppressing breakage of the graphite mold, a more preferable upper limit of the pressure sintering pressure is 50 MPa. is there.
  • the relative density of the sintered body can be improved by setting the pressure sintering time to 0.5 hours or longer. In addition, by reducing the pressure sintering time to 4 hours or less, weight reduction due to sintering can be suppressed, and the relative density of the sintered body can be improved. From the viewpoint of further improving the relative density, the more preferable lower limit of the pressure sintering time is 1 hour, and the more preferable upper limit is 3 hours.
  • the temperature may be maintained when the maximum temperature range is reached during pressure sintering.
  • the holding time at this time is preferably about 100 hours or less, although it depends on the temperature and pressure during sintering.
  • the holding time can be zero.
  • the precursor sintered body obtained by pressure sintering has first to third regions that change from the first region to the third region of the cylindrical sintered body by heat treatment.
  • the heat treatment it is necessary to control the porosity of the second ′ region from the viewpoint of more uniformly heat shrinking the precursor sintered body and suppressing cracking of the precursor sintered body. That is, the second ′ region has a porosity of 40% or more and 60% or less over 100% or more of the height of the precursor sintered body.
  • the porosity of the second 'region is less than 40% or greater than 60%, the thermal shrinkage is not uniform during pressure sintering or heat treatment, and the precursor sintered body is easily cracked.
  • the porosity of the second 'region is preferably 42% or more, more preferably 44% or more, preferably 58% or less, more preferably 56% or less.
  • the ratio of the porosity in the height direction of the precursor sintered body is less than 100%, the thermal shrinkage is not uniform, and the precursor sintered body is easily cracked.
  • FIG. 2 is a schematic diagram schematically showing a cutting position 10 from the upper surface 8 of the precursor sintered body and a cutting position 11 from the bottom surface 9 of the precursor sintered body.
  • the said figure is a schematic diagram for making an understanding of a precursor sintered compact easy, and this invention is not limited to this.
  • the cutting position 10 from the top surface 8 and the cutting position 11 from the bottom surface 9 may be, for example, a position 5 mm from the top surface 8 and a position 5 mm from the bottom surface 9 of the precursor sintered body, respectively.
  • the height of the precursor sintered body is a length between the cutting position 10 and the cutting position 11.
  • the height of the precursor sintered body is the length between the cutting position 10 and the bottom surface 9.
  • the height of the precursor sintered body is the length between the top surface 8 and the cutting position 11.
  • the porosity of the first 'region is preferably 15% or more and 30% or less, and the porosity is preferably 95% or more of the height of the precursor sintered body, Most preferably over 100%.
  • the porosity of the 3 ′ region is preferably 15% or more and 30% or less, and the porosity is preferably that of the precursor sintered body. Over 95% of the height, most preferably over 100%.
  • the porosity of the precursor sintered body may be measured in the same manner as the porosity of the cylindrical sintered body.
  • the outer diameter Do ′ [mm], the inner diameter Di ′ [mm], and the height L ′ [mm] of the precursor sintered body satisfy the following expression (2). 250 ⁇ (Do ′ + Di ′) ⁇ ⁇ ⁇ L ′ / 200 ⁇ 1000 (2)
  • the above equation (2) substantially defines the size of the precursor sintered body. That is, when the sum of the outer diameter and the inner diameter is large, the height is reduced, and when the sum of the outer diameter and the inner diameter is small, the height is increased and the precursor firing is performed so as to satisfy the above formula (2).
  • the thermal shrinkage between the outer diameter direction and the height direction of the precursor sintered body can be balanced, and cracking of the precursor sintered body can be suppressed.
  • the lower limit of the formula (2) is preferably 260, and the upper limit of the formula (1) is preferably 990.
  • the relative density of the precursor sintered body is preferably 92% or less. Moreover, it is preferable that a relative density is 88% or more from a viewpoint of suppressing the crack of a precursor sintered compact.
  • a cylindrical sintered body is obtained by further heat-treating the precursor sintered body obtained by pressure sintering.
  • the precursor sintered body obtained by pressure sintering has high resistance. This is presumably because the raw material comes into contact with the graphite mold to cause a reduction reaction, and the resistance increases due to oxygen deficiency in the precursor sintered body. Therefore, it is preferable to perform the heat treatment in the atmosphere, preferably in an atmosphere containing oxygen. By supplementing the oxygen deficient by the reduction reaction, the resistance of the finally obtained cylindrical sintered body can be reduced. it can.
  • the atmosphere containing oxygen includes, for example, an atmosphere containing 20% by volume or more of oxygen, typically air, and preferably contains 50% by volume or more, more preferably 90% by volume or more, and even more preferably 100% by volume.
  • the atmosphere typically air, and preferably contains 50% by volume or more, more preferably 90% by volume or more, and even more preferably 100% by volume.
  • the heat treatment be performed in an oxygen-containing atmosphere so that desired characteristics can be obtained.
  • Specific heat treatment conditions include the type of raw material used, the size of the precursor sintered body, or the precursor to be heat treated at one time. It may be appropriately controlled in consideration of the number of sintered bodies and the like.
  • the heat treatment is preferably performed at a temperature of 800 ° C. to 1150 ° C. for 2 to 100 hours.
  • a cylindrical sintered body having a desired low resistance can be obtained by setting the heat treatment temperature to 800 ° C. or higher. Moreover, the temperature at the time of sintering shall be 1150 degrees C or less, the weight reduction by sintering can be suppressed and the relative density of a cylindrical sintered compact can be improved. From the viewpoint of obtaining more preferable resistance and relative density, a more preferable lower limit of the heat treatment temperature is 850 ° C., and a more preferable upper limit is 1100 ° C. or less.
  • the relative density of the sintered body can be improved by setting the heat treatment time to 2 hours or longer. Further, by setting the heat treatment time to 100 hours or less, it is possible to suppress the weight loss due to sintering and to improve the relative density of the cylindrical sintered body. From the viewpoint of further improving the relative density, a more preferable lower limit of the heat treatment time is 5 hours, and a more preferable upper limit is 50 hours.
  • the heat treatment has two steps as follows. That is, by heating at a temperature of preferably 800 to 1000 ° C., more preferably 900 ° C. for 1 to 50 hours, the relative density of the precursor sintered body is kept relatively low, and oxygen is distributed to the precursor sintered body.
  • a step of reducing the resistance, and after the step, the average crystal grain size of the sintered body is increased by heating at a temperature of preferably 1050 to 1150 ° C., more preferably 1100 ° C. for 1 to 50 hours. It is preferable to combine with the step of increasing the relative density of the cylindrical sintered body whose resistance is reduced by the above.
  • Cylindrical Sputtering Target> The cylindrical sintered body containing LiCoO 2 according to the embodiment of the present invention is processed into a predetermined size by surface grinding or the like, and then joined to a backing tube made of a pure metal or an alloy to form a cylindrical sputtering target. be able to.
  • the bonding material low melting point solder, resin paste containing metal powder or conductive resin may be used, but low melting point solder is preferably used from the viewpoint of conductivity and spreadability.
  • a low melting point solder one containing 80% or more of indium as a main component is particularly preferable because of its excellent conductivity and spreadability.
  • LiCoO 2 powder a fine particle material having a purity of 99.9% or more and an average particle size of 10 ⁇ m or less was used.
  • the above raw materials were directly set in a graphite mold and subjected to pressure sintering by hot pressing under the conditions shown in Tables 1 and 4 to obtain precursor sintered bodies having the sizes shown in Tables 2 and 4.
  • cutting was performed at a position of 5 mm from the top surface to the bottom surface of the precursor sintered body and at a position of 5 mm from the bottom surface to the top surface.
  • the obtained precursor sintered body was subjected to heat treatment under the conditions shown in Tables 1 and 4, and cylindrical sintered bodies of Examples 1 to 12 and Comparative Examples 1 to 8 were obtained.
  • the outer diameter Do ′, the inner diameter Di ′, the height L ′ of the precursor sintered body and the values of the formula (2), and the outer diameter Do, the inner diameter Di, the height L and the values of the formula (1) of the cylindrical sintered body. are shown in Tables 2-4.
  • the area of the pores was calculated using image analysis software “ImageJ” manufactured by Wayne Rasband. The results are shown in Table 3. Moreover, the result of having similarly measured the porosity about 1st area
  • the porosity in the second region is 15% or more and 34% or less over 80% or more of the height of the cylindrical sintered body.
  • the relative density was as high as 92% or more, and the resistance was as low as 38 k ⁇ or less, and good characteristics were obtained.
  • all of the precursor sintered bodies obtained by pressure sintering had a porosity in the 2 ′ region, which was the height of the precursor sintered body.
  • the thermal shrinkage becomes uniform, and between the outer diameter direction and the height direction of the precursor sintered body.
  • the thermal shrinkage was balanced, it did not crack after pressure sintering, and it did not crack after the subsequent heat treatment.
  • the porosity in the second 'region of the precursor sintered body obtained by pressure sintering is as high as 70% over 100% of the height of the precursor sintered body.
  • the heat shrinkage became non-uniform and cracked after pressure sintering.
  • the top surface porosity T' and the bottom surface porosity B ' are as low as 19%. And cracked after heat treatment.
  • the portion having a porosity of 40% or more and 60% was 90% of the height of the cylindrical sintered body.
  • the porosity of the cylindrical sintered body cracked by the heat treatment is shown in Table 3 as a reference value.
  • the porosity in the 2 ′ region of the precursor sintered body obtained by pressure sintering is as low as 35% over 100% of the height of the precursor sintered body. Shrinkage became uneven and cracked after heat treatment.
  • the porosity of the cylindrical sintered body cracked by the heat treatment is shown in Table 3 as a reference value.

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Abstract

L'invention concerne un corps fritté qui comporte du LiCoO2 et présente une forme tubulaire comprenant une partie creuse définie par la surface périphérique interne du corps fritté. Une région centrale se situant dans une plage de 15 à 70 % de la distance entre la surface périphérique externe et la surface périphérique interne présente une porosité de 15 à 34 % dans une région d'au moins 80 % de la hauteur du corps fritté tubulaire, et le corps fritté satisfait la formule (1) : 200 ≤ (Do + Di) × π × L/200 ≤ 950---- (1). Do représente le diamètre extérieur [mm] du corps fritté, Di représente le diamètre intérieur [mm] du corps fritté et L représente la hauteur [mm] du corps fritté.
PCT/JP2017/022660 2016-07-27 2017-06-20 CORPS FRITTÉ COMPORTANT DU LiCoO2 ET CIBLE DE PULVÉRISATION TUBULAIRE WO2018020908A1 (fr)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2008001554A (ja) * 2006-06-22 2008-01-10 Idemitsu Kosan Co Ltd 焼結体、膜及び有機エレクトロルミネッセンス素子
WO2011086649A1 (fr) * 2010-01-15 2011-07-21 株式会社アルバック Procédé de fabrication pour un corps fritté de licoo2 et cible de pulvérisation fabriquée à partir de celui-ci
WO2014142197A1 (fr) * 2013-03-13 2014-09-18 株式会社コベルコ科研 Corps fritté comprenant du dioxyde de cobalt et de lithium (licoo2), cible de pulvérisation et procédé de production d'un corps fritté comprenant du dioxyde de cobalt et de lithium (licoo2)

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JP2008001554A (ja) * 2006-06-22 2008-01-10 Idemitsu Kosan Co Ltd 焼結体、膜及び有機エレクトロルミネッセンス素子
WO2011086649A1 (fr) * 2010-01-15 2011-07-21 株式会社アルバック Procédé de fabrication pour un corps fritté de licoo2 et cible de pulvérisation fabriquée à partir de celui-ci
WO2014142197A1 (fr) * 2013-03-13 2014-09-18 株式会社コベルコ科研 Corps fritté comprenant du dioxyde de cobalt et de lithium (licoo2), cible de pulvérisation et procédé de production d'un corps fritté comprenant du dioxyde de cobalt et de lithium (licoo2)

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Title
ZHANG, HONGTAO ET AL.: "Fabrication and Electrical Properties of Bulk Textured LiCo02", JOURNAL OF THE AMERICAN CERAMIC SOCIETY, vol. 93, no. 7, July 2010 (2010-07-01), pages 1856 - 1859, XP055160117, ISSN: 0002-7820 *

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