WO2015037330A1 - 活物質複合粉体及びリチウム電池並びにその製造方法 - Google Patents
活物質複合粉体及びリチウム電池並びにその製造方法 Download PDFInfo
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- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
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Definitions
- the present invention relates to an active material composite powder having an active material and lithium niobate adhered to at least a part of the surface thereof, a lithium battery using the same, and a method for producing them.
- a metal ion secondary battery having a solid electrolyte layer using a flame retardant solid electrolyte (for example, a lithium ion secondary battery, etc., hereinafter sometimes referred to as “all solid battery”) is used for ensuring safety. It has advantages such as easy to simplify the system.
- Patent Document 1 discloses a process of hydrolyzing an alkoxide solution containing lithium and niobium on the surface of LiCoO 2 powder particles, and then providing a LiNbO 3 coating layer on the surface of LiCoO 2 powder.
- a forming technique is disclosed.
- Patent Document 2 discloses lithium having a carbon content of 0.03% by mass or less, comprising lithium-transition metal oxide particles partially or entirely coated with a coating layer containing lithium niobate. Transition metal oxide powders are disclosed.
- Non-Patent Document 1 discloses a technique related to low-temperature synthesis of lithium niobate by a peroxo route.
- a LiNbO 3 coating layer is formed on the surface of the positive electrode active material. Therefore, a lithium ion conductive oxide layer can be interposed at the interface between the sulfide-based solid electrolyte and the positive electrode active material, and as a result, it is expected to improve the output characteristics of the all-solid battery.
- the present invention provides an active material composite powder capable of reducing the reaction resistance of the battery, a lithium battery using the same, a method for producing the active material composite powder, and a method for producing the lithium battery. Let it be an issue.
- the present inventors have used an active material composite powder having an active material having a BET specific surface area within a predetermined range and lithium niobate adhered to the surface of the active material. It has been found that the reaction resistance of a lithium battery can be reduced.
- the inventors have sprayed a solution containing a niobium peroxo complex and lithium on the surface of the active material, followed by drying in parallel with the active material composite powder. It has been found that it is possible to obtain an active material composite powder that can reduce the reaction resistance of a lithium battery.
- the present invention has been completed based on this finding.
- the present invention takes the following means. That is, The first aspect of the present invention comprises an active material and lithium niobate attached to the surface of the active material, and the BET specific surface area S [m 2 / g] is greater than 0.93, And it is an active material composite powder which is less than 1.44.
- the BET specific surface area of the active material composite powder greater than 0.93 m 2 / g, and by less than 1.44 2 / g, reducing the reaction resistance of the lithium battery using the active material composite powder It becomes possible.
- the value of the BET specific surface area in the present invention is a value obtained by rounding off the value of the third decimal place.
- the BET specific surface area S is preferably 0.97 [m 2 / g] or more.
- BET specific surface area S is preferably not 1.34 [m 2 / g] or less.
- the mass ratio M1 / M0 is preferably 99.60 ⁇ 100 ⁇ M1 / M0.
- the value of the mass ratio 100 ⁇ M1 / M0 in the present invention is a value obtained by rounding off the third decimal value.
- a second aspect of the present invention includes a positive electrode, a negative electrode, and an electrolyte that contacts the positive electrode and the negative electrode.
- the active material composite powder according to the first aspect of the present invention is provided on at least one of the positive electrode and the negative electrode. It is a lithium battery included.
- the active material composite powder according to the first aspect of the present invention can reduce the reaction resistance of a lithium battery. Therefore, by including this active material composite powder in the positive electrode or negative electrode of a lithium battery, or the positive electrode and negative electrode of a lithium battery, a lithium battery with reduced reaction resistance can be obtained.
- the amount of gas generated during heat treatment can be reduced. As a result, it is difficult to form voids that inhibit lithium ion conduction in lithium niobate. Furthermore, since the active material is hardly eroded by the solution by spray drying, the lithium ion conductivity is easily increased.
- the heat treatment temperature higher than 123 ° C., it becomes possible to reduce the residual amount of impurities such as hydration water that inhibits the conduction of lithium ions, so that the lithium ion conductivity can be easily increased. Furthermore, by setting the heat treatment temperature below 350 ° C., it becomes possible to prevent crystallization of lithium niobate.
- the active material composite powder capable of reducing the reaction resistance of the lithium battery can be manufactured by adopting such a form.
- a fourth aspect of the present invention is a method for producing a lithium battery comprising a positive electrode, a negative electrode, and an electrolyte in contact with the positive electrode and the negative electrode, wherein the solution contains a peroxo complex of niobium and lithium in the active material And, in parallel with this, the active material composite powder is obtained by heat-treating the solution at a temperature higher than 123 ° C. and lower than 350 ° C. after the spray drying step.
- a method for manufacturing a lithium battery comprising: a heat treatment step to be produced; and an electrode production step to produce a positive electrode or a negative electrode containing the produced active material composite powder.
- the amount of gas generated during heat treatment can be reduced. As a result, it is difficult to form voids that inhibit lithium ion conduction in lithium niobate. Furthermore, since the active material is hardly eroded by the solution by spray drying, the lithium ion conductivity is easily increased.
- the heat treatment temperature higher than 123 ° C., it becomes possible to reduce the residual amount of impurities such as hydration water that inhibits the conduction of lithium ions, so that the lithium ion conductivity can be easily increased. Furthermore, by setting the heat treatment temperature below 350 ° C., it becomes possible to prevent crystallization of lithium niobate.
- the non-crystallized lithium niobate has a higher lithium ion conductivity than the crystallized lithium niobate, the lithium ion conductivity is easily increased by preventing the crystallization of lithium niobate. Therefore, an active material composite powder capable of reducing the reaction resistance of the lithium battery can be produced by adopting such a form. And it becomes possible to produce the positive electrode or negative electrode which can reduce reaction resistance by producing the positive electrode or negative electrode containing the produced active material composite powder. Therefore, a lithium battery capable of reducing the reaction resistance can be manufactured by adopting such a form.
- an active material composite powder capable of reducing the reaction resistance of the battery, a lithium battery using the same, a method for producing the active material composite powder, and a method for producing the lithium battery. Can do.
- FIG. 1 is a diagram illustrating the active material composite powder of the present invention.
- one active material composite powder 10 is extracted, and this active material composite powder 10 is shown in a simplified manner.
- FIG. 1 illustrates a form in which lithium niobate 2 is attached (coated) to the surface of one active material 1, but the active material composite powder of the present invention is not limited to this form.
- the active material composite powder of the present invention may have a form in which lithium niobate is attached (coated) to the surface of the active material in the form of secondary particles in which a plurality of active materials are aggregated.
- the active material composite powder 10 includes an active material 1 and lithium niobate 2 attached to the surface of the active material 1.
- the BET specific surface area S of the active material composite powder 10 is 0.93 m 2 /g ⁇ S ⁇ 1.44 m 2 / g.
- the active material composite powder 10 is manufactured through a process in which a lithium niobate precursor is attached to the surface of the active material 1 and then heat-treated.
- this heat treatment temperature is a predetermined temperature or lower
- an active material composite powder in which impurities such as hydration water remain after the heat treatment is easily produced, and such an active material composite powder has a value of BET specific surface area. Is small. Residual impurities such as hydrated water hinder lithium ion conduction, and thus the reaction resistance of the all solid state battery using the active material composite particles in which the impurities remain is likely to increase. Therefore, in order to reduce the reaction resistance, in the present invention, the value of the BET specific surface area is made larger than a predetermined value. From this viewpoint, the BET specific surface area S of the active material composite powder 10 is set to be larger than 0.93 m 2 / g.
- the heat treatment temperature at the time of manufacturing the active material composite powder 10 is equal to or higher than a predetermined temperature, many voids are easily formed in the lithium niobate adhering to the surface of the active material. Since lithium niobate having many voids has low lithium ion conductivity, the all-solid-state battery using such active material composite particles having lithium niobate is likely to increase the reaction resistance. Therefore, in order to reduce the reaction resistance, in the present invention, the value of the BET specific surface area is made smaller than a predetermined value. From such a viewpoint, the BET specific surface area S of the active material composite powder 10 is set to less than 1.44 m 2 / g.
- the BET specific surface area S is preferably set to 0.97 m 2 / g or more from the viewpoint of obtaining an active material composite powder in a form in which reaction resistance is easily reduced.
- the BET specific surface area S By setting the BET specific surface area S to 0.97 m 2 / g or more, it becomes easy to reduce the residual amount of impurities such as hydrated water, so that the reaction resistance can be easily reduced.
- the BET specific surface area S is 1.34 m 2 / g or less from the viewpoint of obtaining an active material composite powder in a form in which reaction resistance can be easily reduced.
- the BET specific surface area S it becomes easy to form lithium niobate with a reduced amount of voids on the surface of the active material, so that the reaction resistance is easily reduced.
- the lithium niobate attached to an active material is not crystallized from a viewpoint of making into active material composite powder of the form which is easy to reduce reaction resistance.
- Lithium niobate BET specific surface area S is provided in the active material composite powder is not more than 1.34 m 2 / g is considered not crystallized, a BET specific surface area S below 1.34 m 2 / g By doing, it becomes easy to reduce reaction resistance.
- the reaction is performed in the air atmosphere at 350 ° C. for 10 minutes. It is preferable that the mass ratio M1 / M0 is 99.60 ⁇ 100 ⁇ M1 / M0, where M1 is the mass after the heat treatment that is held over and M0 is the mass before the heat treatment. From the viewpoint of making the active material composite powder in a form in which the reaction resistance can be more easily reduced, the mass ratio M1 / M0 is more preferably 99.89 ⁇ 100 ⁇ M1 / M0.
- the active material 1 is a material which can be used as an electrode active material material of a lithium ion secondary battery, it will not specifically limit.
- Such materials include LiCoO 2 , LiNi x Co 1-x O 2 (0 ⁇ x ⁇ 1), LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiMnO 2 , foreign element substituted Li—Mn Spinel (LiMn 1.5 Ni 0.5 O 4 , LiMn 1.5 Al 0.5 O 4 , LiMn 1.5 Mg 0.5 O 4 , LiMn 1.5 Co 0.5 O 4 , LiMn 1.5 Fe 0.5 O 4 , LiMn 1.5 Zn 0.5 O 4 ), lithium titanate (eg, Li 4 Ti 5 O 12 ), lithium metal phosphate (LiFePO 4 , LiMnPO 4 , LiCoPO 4 , LiNiPO 4 ), transition metal oxide (V 2 O 5, MoO 3 ), TiS 2, carbon materials such as graphite or hard carbon, LiCoN, SiO 2, Li 2 SiO 2, Li 2
- the all solid state battery using the active material composite powder of the present invention two substances having different potentials (charge / discharge potentials) for occluding and releasing lithium ions are selected from the above-mentioned substances, A substance exhibiting a potential can be used as a positive electrode active material, and a substance exhibiting a base potential can be used as a negative electrode active material. By doing in this way, it becomes possible to comprise the all-solid-state battery of arbitrary voltages.
- the form of the lithium niobate 2 is not particularly limited. However, from the viewpoint of reducing the reaction resistance, it is preferable that the remaining amount of impurities such as hydration water is small, preferably amorphous, and the number of voids is small.
- Such a form of lithium niobate can be formed by, for example, a method described later in the column of a method for producing an active material composite powder.
- FIG. 2 is a diagram for explaining a lithium battery 20 (lithium ion secondary battery 20) of the present invention.
- the lithium battery 20 is shown in a simplified manner, and description of the exterior body and the like is omitted.
- the active material Similar to the active material composite powder 10 shown in FIG. 1, the active material has lithium niobate attached to the surface of the active material, and the BET specific surface area S is 0.93 m 2 / g ⁇ S. Substances that are ⁇ 1.44 m 2 / g are denoted by reference numeral 10 in FIG. 2 and description thereof is omitted as appropriate.
- the lithium battery 20 is connected to the positive electrode 21 and the negative electrode 22, the solid electrolyte layer 23 disposed therebetween, the positive electrode current collector 24 connected to the positive electrode 21, and the negative electrode 22.
- the positive electrode 21 includes the active material composite powder 10 of the present invention, a sulfide solid electrolyte 23a, a conductive auxiliary agent 21a, and a binder 21b. And positive electrode active material 1), and lithium niobate 2 attached to the surface of the positive electrode active material 1.
- the negative electrode 22 includes a negative electrode active material 22a, a sulfide solid electrolyte 23a, and a binder 22b.
- the solid electrolyte layer 23 has a sulfide solid electrolyte 23a.
- the positive electrode active material 1 is LiNi 1/3 Co 1/3 Mn 1/3 O 2 and the negative electrode active material 22a is graphite.
- the lithium battery 20 includes the positive electrode 21 containing the active material composite powder 10 of the present invention.
- the active material composite powder 10 of the present invention can reduce the reaction resistance. Therefore, the lithium battery 20 capable of reducing the reaction resistance can be provided by providing the positive electrode 21 containing the active material composite powder 10.
- the positive electrode 21 is charged with the active material composite powder 10, the sulfide solid electrolyte 23a, the conductive additive 21a, and the binder 21b in a solvent, this is used with an ultrasonic homogenizer or the like.
- the slurry-like positive electrode composition prepared by dispersing the powder can be applied to the surface of the positive electrode current collector 24 and then dried.
- the negative electrode 22 is a slurry-like negative electrode prepared by putting a negative electrode active material 22a, a sulfide solid electrolyte 23a, and a binder 22b into a solvent and then dispersing them using an ultrasonic homogenizer or the like.
- the composition can be manufactured through a process in which the composition is applied to the surface of the negative electrode current collector 25 and then dried.
- the solid electrolyte layer 23 can be produced through processes such as pressing the sulfide solid electrolyte 23a, for example.
- the positive electrode 21, the negative electrode 22, and the solid electrolyte layer 23 are produced, as shown in FIG. 2, from one to the other, the negative electrode current collector 25, the negative electrode 22, the solid electrolyte layer 23,
- the positive electrode 21 and the positive electrode current collector 24 are laminated in an inert atmosphere (for example, an argon atmosphere, a nitrogen atmosphere, a helium atmosphere, etc.) to form a laminate.
- the lithium battery 20 can be manufactured through a process such as pressing the laminate.
- the positive electrode active material and the negative electrode active material constitute the lithium battery 20 having a target voltage from the above materials described as specific examples of the active material 1 relating to “1. Active material composite powder”.
- two substances having different potentials (charge / discharge potentials) for occluding and releasing lithium ions are selected, a substance showing a noble potential as a positive electrode active material, and a substance showing a base potential as a negative electrode active material, respectively.
- a substance showing a noble potential as a positive electrode active material a substance showing a base potential as a negative electrode active material, respectively.
- the shape of the positive electrode active material can be, for example, particulate or thin film.
- the average particle diameter (D 50 ) of the positive electrode active material is, for example, preferably from 1 nm to 100 ⁇ m, and more preferably from 10 nm to 30 ⁇ m.
- the content of the positive electrode active material in the positive electrode is not particularly limited, but is preferably 40% or more and 99% or less in mass%, for example.
- the lithium battery of the present invention can contain a known solid electrolyte that can be used for a lithium battery in the positive electrode and the negative electrode as necessary.
- the solid electrolyte that can be contained in the positive electrode and the negative electrode include Li 2 S—SiS 2 , LiI—Li 2 S—SiS 2 , LiI—Li 2 SP—S 2 S 5 , LiI—Li 2 O—.
- Examples include Li 2 S—P 2 S 5 , LiI—Li 2 S—P 2 O 5 , LiI—Li 3 PO 4 —P 2 S 5 , Li 2 S—P 2 S 5 , Li 3 PS 4. it can.
- the manufacturing method of the solid electrolyte which can be used for the lithium battery of this invention is not specifically limited, The solid electrolyte manufactured with the well-known manufacturing method can be used suitably. Further, the solid electrolyte may be amorphous or crystalline.
- a known binder that can be contained in the positive electrode of the lithium battery can be used for the positive electrode.
- a binder include acrylonitrile butadiene rubber (ABR), butadiene rubber (BR), polyvinylidene fluoride (PVdF), styrene butadiene rubber (SBR), and the like.
- the positive electrode can contain a conductive additive that improves conductivity.
- conductive aids that can be contained in the positive electrode include carbon materials such as vapor-grown carbon fiber, acetylene black (AB), ketjen black (KB), carbon nanotube (CNT), and carbon nanofiber (CNF).
- a metal material that can withstand the environment when the lithium battery is used can be exemplified.
- a positive electrode is prepared using a slurry-like positive electrode composition prepared by dispersing the positive electrode active material, solid electrolyte, conductive additive, binder, and the like in a liquid
- heptane is used as a usable liquid.
- Etc., and a nonpolar solvent can be preferably used.
- the thickness of the positive electrode is, for example, preferably from 0.1 ⁇ m to 1 mm, and more preferably from 1 ⁇ m to 100 ⁇ m.
- the positive electrode can be manufactured through a pressing process. In the present invention, the pressure when pressing the positive electrode can be about 100 MPa.
- the shape of the negative electrode active material contained in the negative electrode can be, for example, in the form of particles or a thin film.
- the average particle diameter (D 50 ) of the negative electrode active material is, for example, preferably from 1 nm to 100 ⁇ m, and more preferably from 10 nm to 30 ⁇ m.
- the content of the negative electrode active material in the negative electrode is not particularly limited, but is preferably 40% or more and 99% or less in mass%, for example.
- a binder that binds the negative electrode active material and the solid electrolyte can be used for the negative electrode, if necessary.
- a binder the said binder etc. which can be contained in a positive electrode can be illustrated.
- the negative electrode may contain a conductive additive that improves conductivity. Examples of the conductive aid that can be contained in the negative electrode include the conductive aid that can be contained in the positive electrode.
- a negative electrode when a negative electrode is produced using a slurry-like negative electrode composition prepared by dispersing a negative electrode active material, a solid electrolyte, a conductive additive, and a binder in a liquid, heptane or the like can be used as a usable liquid. And a nonpolar solvent can be preferably used.
- the thickness of the negative electrode is, for example, preferably from 0.1 ⁇ m to 1 mm, and more preferably from 1 ⁇ m to 100 ⁇ m.
- a negative electrode can be produced through the process of pressing.
- the pressure when pressing the negative electrode is preferably 200 MPa or more, and more preferably about 400 MPa.
- the solid electrolyte to be contained in the solid electrolyte layer a known solid electrolyte that can be used in an all-solid battery can be appropriately used.
- a known solid electrolyte include the solid electrolyte that can be contained in the positive electrode and the negative electrode.
- the solid electrolyte layer can contain a binder that binds the solid electrolytes from the viewpoint of developing plasticity. As such a binder, the said binder etc. which can be contained in a positive electrode can be illustrated.
- the solid electrolyte layer is included in the solid electrolyte layer from the viewpoint of preventing excessive aggregation of the solid electrolyte and enabling the formation of a solid electrolyte layer having a uniformly dispersed solid electrolyte.
- the binder is preferably 5% by mass or less.
- a solid electrolyte layer is produced through a process of applying a slurry-like solid electrolyte composition prepared by dispersing a solid electrolyte or the like in a liquid to a substrate, heptane or the like is used as a liquid for dispersing the solid electrolyte or the like.
- a nonpolar solvent can be preferably used.
- the content of the solid electrolyte material in the solid electrolyte layer is mass%, for example, preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more.
- the thickness of the solid electrolyte layer varies greatly depending on the configuration of the battery. For example, the thickness is preferably 0.1 ⁇ m or more and 1 mm or less, and more preferably 1 ⁇ m or more and 100 ⁇ m or less.
- a known metal that can be used as a current collector of a lithium battery can be used for the negative electrode current collector and the positive electrode current collector.
- a metal a metal containing one or more elements selected from the group consisting of Cu, Ni, Al, V, Au, Pt, Mg, Fe, Ti, Co, Cr, Zn, Ge, and In. Materials can be exemplified.
- the lithium battery of the present invention can be used in a state of being housed in a known exterior body that can be used for a lithium battery.
- casing, etc. can be illustrated.
- FIG. 3 is a diagram for explaining a method for producing an active material composite powder of the present invention.
- the manufacturing method of the active material composite powder of the present invention shown in FIG. 3 includes an active material preparation step (S1), a spray drying step (S2), and a heat treatment step (S3).
- the active material preparation step (hereinafter sometimes referred to as “S1”) is a step of preparing an active material in which lithium niobate is attached to the surface in a step described later.
- the form of S1 is not particularly limited as long as an active material can be prepared.
- S1 may be in the form of preparing an active material by preparing the active material, or in the form of preparing the active material by purchasing the active material.
- a solution containing niobium peroxo complex and lithium is sprayed onto the active material prepared in S1, and in parallel, the active material is sprayed. It is a step of drying the solution sprayed onto the substance.
- FIG. 4 shows the structural formula of a niobium peroxo complex.
- the solution sprayed onto the active material in S2 is obtained by, for example, preparing a transparent solution by using hydrogen peroxide water, niobic acid, and aqueous ammonia, and then adding a lithium salt to the prepared transparent solution.
- An aqueous solution (hereinafter, the aqueous solution may be referred to as a “complex solution”).
- the niobium peroxo complex can be synthesized even if the water content of niobic acid used in S2 is changed, the water content of niobic acid is not particularly limited. Further, the mixing ratio of niobic acid and aqueous ammonia is not particularly limited as long as a niobium peroxo complex can be synthesized.
- the lithium salt which can be used in S2 it may be exemplified LiOH, LiNO 3, Li 2 SO 4 and the like.
- the complex solution containing a niobium compound and a lithium compound is attached to the surface of the active material by spraying in S2.
- the volatile components such as a solvent and hydration water which are contained in the complex solution made to adhere to the surface of an active material, are removed by drying in S2.
- the form after the complex solution is dried may be referred to as “a precursor of lithium niobate”.
- the complex solution is sprayed onto the active material, and at the same time, the complex solution sprayed toward the active material and adhered to the surface of the active material is dried.
- Such S2 can be performed by using, for example, a rolling fluid coating apparatus or a spray dryer.
- the rolling fluid coating apparatus include a multiplex manufactured by Paulek, a flow coater manufactured by Freund Sangyo Co., Ltd., and the like.
- the rolling fluidized coating apparatus when attention is paid to one active material, the complex solution is dried immediately after the complex solution is sprayed on the active material, and then the lithium niobate adhering to the surface of the active material.
- S2 can be said to be a step of spraying the complex solution onto the active material and drying the complex solution adhering to the surface of the active material in parallel with this.
- hydrogen peroxide contained in the complex solution has a strong oxidizing action. Therefore, when the complex solution is brought into contact with the active material for a long time, the active material may be eroded by hydrogen peroxide, and the eroded active material is deteriorated. Therefore, in the present invention, the active material is present on the surface of the active material immediately after the complex solution is adhered to the surface of the active material by spraying the complex solution onto the active material in order to make the active material difficult to deteriorate. The complex solution is dried. By adopting such a form, it becomes possible to produce an active material composite powder capable of reducing the reaction resistance of the battery.
- the lithium niobate precursor is adhered to the surface of the active material by S2 in the form of S2 Even if the heat treatment temperature in the heat treatment step performed after the step is reduced, lithium niobate can be formed on the surface of the active material. The effect obtained by reducing the heat treatment temperature will be described later.
- the heat treatment step (hereinafter sometimes referred to as “S3”) is an active material in which a lithium niobate precursor is attached to the surface after S2 at a temperature higher than 123 ° C. and lower than 350 ° C. Is a step of heat treatment.
- S3 an active material composite powder having an active material and lithium niobate adhered to the surface of the active material can be obtained.
- the heat treatment of S3 can be performed in an air atmosphere.
- the heat treatment temperature is set higher than 123 ° C.
- impurities volatile components
- the active material composite powder manufactured by the manufacturing method of the active material composite powder of this invention is used for the all-solid-state battery using a sulfide solid electrolyte, for example.
- the sulfide solid electrolyte deteriorates by reacting with water, and as a result, the reaction resistance of the all-solid battery tends to increase. Therefore, the reaction resistance of the battery can be reduced by reducing the residual amount of the solvent of the complex solution.
- the heat treatment temperature is set to less than 350 ° C. Since S3 is performed after S2, the lithium niobate precursor is sprayed with the complex solution onto the active material, and in parallel, the S2 in the form of drying the complex solution on the surface of the active material, It is attached to the surface. With this form of S2, by attaching a lithium niobate precursor to the surface of the active material, it becomes possible to form lithium niobate even when the heat treatment temperature is lower than that of the prior art. Here, when the heat treatment temperature is increased, a large number of voids are easily formed in the lithium niobate, and as a result, the BET specific surface area of the active material composite powder tends to increase.
- this void inhibits lithium ion conduction, it contributes to an increase in the reaction resistance of the battery.
- it is effective to reduce the number of voids in the lithium niobate.
- it is effective to lower the heat treatment temperature.
- the heat treatment temperature is 350 ° C. or higher, crystallized lithium niobate is formed on the surface of the active material.
- Crystallized lithium niobate has a lower lithium ion conductivity than amorphous lithium niobate, which contributes to an increase in battery reaction resistance.
- it is effective not to crystallize lithium niobate.
- it is effective to set the heat treatment temperature below a predetermined temperature. By setting the heat treatment temperature to less than 350 ° C., it becomes possible to prevent crystallization of lithium niobate, so that the reaction resistance of the battery can be reduced.
- the reaction resistance of the battery can be reduced by forming lithium niobate on the surface of the active material by S3 heat-treated at a temperature higher than 123 ° C. and lower than 350 ° C. after S2.
- Possible active material composite powders can be produced.
- the alkoxide solution used in the prior art contains a large amount of carbon, an amount of gas is generated from the precursor of lithium niobate during heat treatment, resulting in the formation of lithium niobate having a large number of voids. It was easy.
- the heat treatment is performed. It is possible to reduce the amount of gas generated from the precursor of lithium niobate. As a result, since the number of voids in lithium niobate can be reduced, reaction resistance can be reduced. In addition, since the complex solution used in the method for producing the active material composite powder of the present invention is less expensive than the alkoxide solution, in addition to the above effects, the production cost can be reduced.
- the heat treatment temperature of S3 may be higher than 123 ° C and lower than 350 ° C.
- the upper limit temperature of the heat treatment is preferably 300 ° C. or lower. More preferably, it is 250 degrees C or less.
- the battery reaction resistance can be easily reduced.
- FIG. 5 is a diagram for explaining a method for manufacturing a lithium battery of the present invention.
- the same steps as those shown in FIG. 3 for explaining the method for producing the active material composite powder of the present invention are denoted by the same reference numerals as those used in FIG. Omitted.
- the method for manufacturing a lithium battery of the present invention shown in FIG. 5 includes an active material preparation step (S1), a spray drying step (S2), a heat treatment step (S3), and an electrode preparation step (S4). ing. Since S1 to S3 have already been described in “3. Production method of active material composite powder of the present invention”, description thereof is omitted here.
- the electrode manufacturing step (hereinafter sometimes referred to as “S4”) is a step of manufacturing a positive electrode or a negative electrode including the active material composite powder prepared in S1 to S3.
- S4 is the process of producing the positive electrode or negative electrode containing the active material composite powder of this invention, the form will not be specifically limited.
- the positive electrode 21 is manufactured in S4, the active material composite powder 10, the sulfide solid electrolyte 23a, the conductive auxiliary agent 21a, and the binder 21b are put into a solvent, and then ultrasonic waves are added.
- a slurry-like positive electrode composition prepared by dispersing using a homogenizer or the like is applied to the surface of the positive electrode current collector 24, and then dried, followed by a step of preparing the positive electrode 21. it can.
- an electrode (positive electrode or negative electrode) containing the active material composite powder of the present invention is produced by S4, another electrode (negative electrode or positive electrode) that should sandwich the electrolyte is produced together with the electrode. After producing a pair of electrodes (positive electrode and negative electrode) in this way, the lithium battery of the present invention can be produced through a process of disposing an electrolyte between the positive electrode and the negative electrode.
- the positive electrode composition obtained by dispersing the prepared positive electrode slurry with an ultrasonic homogenizer (UH-50, manufactured by SMT Co., Ltd., the same below) was applied to the upper surface of the aluminum foil, and subsequently, 100 ° C. A positive electrode was formed on the upper surface of the aluminum foil by drying in 30 minutes. Next, a positive electrode was obtained by punching an aluminum foil having a positive electrode formed on the upper surface into a size of 1 cm 2 .
- a negative electrode slurry was prepared by charging an amount of 1.2% by mass of a binder (butylene rubber, manufactured by JSR Corporation) into a container containing heptane, a negative electrode active material, or the like.
- the negative electrode composition obtained by dispersing the prepared negative electrode slurry with an ultrasonic homogenizer is applied to the upper surface of the copper foil, and subsequently dried at 100 ° C. for 30 minutes, whereby the negative electrode is formed on the upper surface of the copper foil. Formed.
- a copper foil having a negative electrode formed on the upper surface was punched out to a size of 1 cm 2 to obtain a negative electrode.
- sulfide-based solid electrolyte Li 3 PS 4
- the positive electrode and the negative electrode are placed in a cylindrical ceramic and pressed at 421.4 MPa so that the separator layer is disposed between the positive electrode and the negative electrode, and then the positive electrode side and the negative electrode side
- the all-solid-state battery of Example 1 was produced by putting a stainless-steel bar in this and restraining this at 98 MPa.
- Example 2 LiNi 1/3 Mn 1/3 Co 1/3 O 2 was adhered to the surface under the same conditions as in Example 1 except that the temperature of the heat treatment for obtaining the active material composite powder was changed to 200 ° C. Further, an active material composite powder (active material composite powder of Example 2) having lithium niobate was prepared. Further, an all solid state battery (all solid state battery of Example 2) was prepared under the same conditions as Example 1 except that the active material composite powder of Example 2 was used instead of the active material composite powder of Example 1. Produced.
- Example 3 LiNi 1/3 Mn 1/3 Co 1/3 O 2 was adhered to the surface under the same conditions as in Example 1 except that the temperature of the heat treatment for obtaining the active material composite powder was changed to 250 ° C. Further, an active material composite powder (active material composite powder of Example 3) having lithium niobate was prepared. Further, an all solid state battery (all solid state battery of Example 3) was prepared under the same conditions as Example 1 except that the active material composite powder of Example 3 was used instead of the active material composite powder of Example 1. Produced.
- Example 4 LiNi 1/3 Mn 1/3 Co 1/3 O 2 was adhered to the surface under the same conditions as in Example 1 except that the temperature of the heat treatment for obtaining the active material composite powder was changed to 300 ° C.
- an active material composite powder active material composite powder of Example 4 having lithium niobate was prepared.
- an all solid state battery all solid state battery of Example 4 was prepared under the same conditions as Example 1 except that the active material composite powder of Example 4 was used instead of the active material composite powder of Example 1. Produced.
- an active material composite powder active material composite powder of Comparative Example 1 having lithium niobate was prepared.
- an all solid state battery all solid state battery of Comparative Example 1 was prepared under the same conditions as in Example 1 except that the active material composite powder of Comparative Example 1 was used instead of the active material composite powder of Example 1. Produced.
- an active material composite powder active material composite powder of Comparative Example 2 having lithium niobate was prepared.
- an all solid state battery all solid state battery of Comparative Example 2 was prepared under the same conditions as Example 1 except that the active material composite powder of Comparative Example 2 was used instead of the active material composite powder of Example 1. Produced.
- the alkoxide solution was produced using ethoxylithium, pentaethoxyniobium, and dehydrated ethanol.
- Ethoxylithium was dissolved by putting it in a container containing dehydrated ethanol, and this was uniformly dispersed in dehydrated ethanol.
- pentaethoxyniobium was put into the container containing ethoxylithium and dehydrated ethanol so that lithium and niobium had an element ratio (molar ratio) of 1: 1.
- the alkoxide solution was obtained by stirring until pentaethoxyniobium was mixed uniformly.
- the input amount of ethoxylithium was adjusted so that the solid content ratio of the alkoxide solution was 6.9% by mass.
- ethoxylithium was used as the lithium source, but other lithium sources can be used as long as an alkoxide solution for forming lithium niobate can be prepared.
- examples of such a lithium source include lithium acetate, lithium alkoxide, and lithium hydroxide.
- pentaethoxyniobium was used as the niobium source, but other niobium sources can be used as long as an alkoxide solution for forming lithium niobate can be prepared.
- niobium sources include pentamethoxy niobium, penta-i-propoxy niobium, penta-n-propoxy niobium, penta-i-butoxy niobium, penta-n-butoxy niobium, penta-sec-butoxy niobium and the like. be able to.
- ethanol was used, but instead of this, an alkoxide solution for forming lithium niobate can be prepared by using methanol, propanol, butanol or the like.
- the surface of the positive electrode active material was coated with a layer containing a niobium compound and a lithium compound using a rolling fluid coating apparatus.
- the active material is contained in the alkoxide solution. It is also possible to cover the surface of the positive electrode active material with a layer containing a niobium compound and a lithium compound depending on the form in which the solvent is dried after the substance is immersed or the form using a spray dryer.
- Active material composite powder active material composite powder of Comparative Example 4 having LiNi 1/3 Mn 1/3 Co 1/3 O 2 and lithium niobate attached to the surface Produced.
- an all solid state battery all solid state battery of Comparative Example 4 was prepared under the same conditions as Example 1 except that the active material composite powder of Comparative Example 4 was used instead of the active material composite powder of Example 1. Produced.
- FIG. 7 is a diagram showing only the results of the sample having a reaction resistance of 8 ⁇ ⁇ cm 2 or less extracted from FIG. 6 and 7, the vertical axis represents the reaction resistance [ ⁇ ⁇ cm 2 ], and the horizontal axis represents the BET specific surface area [m 2 / g]. Moreover, the vertical axis
- Example 2 Instead of the active material composite powders of Example 1, except that lithium niobate using the positive electrode active material LiNi 1/3 Mn 1/3 Co 1/3 O 2 which is not attached to a surface, Example The reaction resistance (value obtained by rounding off the third decimal place) of the all-solid battery produced by the same method as that of No. 1 all-solid battery was 843.59 ⁇ ⁇ cm 2 .
- Example 1 in which the heat treatment temperature was set to 150 ° C. and Comparative Example 1 in which the heat treatment temperature was set to 100 ° C. were performed in Examples 2 to which the heat treatment temperature was set to 200 ° C. or more and 300 ° C. or less.
- the reaction resistance was greater than in Example 4.
- each of the active material composite powders of Examples 1 to 4 and Comparative Example 1 was subjected to heat treatment (additional heat treatment) at 350 ° C. for 10 minutes in the air.
- FIG. 9 shows the relationship between the reaction resistances of the all-solid-state batteries of Examples 1 to 4 and Comparative Example 1 manufactured using the active material composite powder before additional heat treatment. Further, Table 3 shows values of mass ratio 100 ⁇ M1 / M0 (values obtained by rounding off the third decimal place).
- Example 1 and Comparative Example 1 in which the heat treatment temperature was lower than that of Examples 2 to 4 were compared with the active material composite powders of Examples 2 to 4 in mass ratio.
- the value of 100 ⁇ M1 / M0 was small.
- the mass ratio of Example 1 and Comparative Example 1 of 100 ⁇ M1 / M0 was small because the active material composite powders of Example 1 and Comparative Example 1 were the active material composite powders of Examples 2 to 4. It can be considered that more impurities such as the solvent of the complex solution and hydration water remain than the body, and the impurities are volatilized by the additional heat treatment.
- the BET specific surface area of the active material composite powders of Example 1 and Comparative Example 1 in which lithium niobate was adhered to the surface of the active material is smaller than the BET specific surface area when lithium niobate was not adhered to the surface of the active material.
- the reason is considered as follows.
- the active material to which lithium niobate used is attached is in the form of secondary particles in which primary particles are assembled, and the lithium niobate is attached to the surface of the secondary particles.
- the active material composite powders of Example 1 and Comparative Example 1 were smaller than the BET specific surface area when lithium niobate was not attached to the surface of the active material.
- the reason why the BET specific surface area of the active material composite powders of Examples 2 to 4 is larger than the BET specific surface area when lithium niobate is not adhered to the surface of the active material is considered as follows. It is done. That is, in Examples 2 to 4 where the heat treatment temperature is higher than that of Example 1 and Comparative Example 1, impurities such as the solvent of the complex solution and the hydration water are likely to volatilize during the heat treatment, and the lithium niobate layer during the volatilization As a result of the formation of irregularities in itself, it is considered that the active material composite powders of Examples 2 to 4 were larger than the BET specific surface area when lithium niobate was not attached to the surface of the active material.
- the active material composite powders of Examples 2 to 4 had a smaller BET specific surface area than the active material composite powder of Comparative Example 3.
- the active material composite powder of Comparative Example 4 is the active material of Comparative Example 3 because the heat treatment was performed after the precursor was promoted to hydrolyze and the gas was hardly generated during the heat treatment. The value of the BET specific surface area was smaller than that of the substance composite powder.
- the BET specific surface area of the positive electrode active material LiNi 1/3 Mn 1/3 Co 1/3 O 2 used this time was 1.1 m 2 / g. Therefore, based on the BET specific surface area S0 of the active material before adhering lithium niobate, the condition of the BET specific surface area that the active material composite powder of the present invention should satisfy and the condition of the BET specific surface area that should preferably be satisfied are: It can also be expressed as follows. That is, the BET specific surface area S of the active material composite powder of the present invention is S0 ⁇ 0.17 ⁇ S ⁇ S0 + 0.34. Furthermore, the BET specific surface area S of the active material composite powder of the present invention is preferably S0-0.13 ⁇ S.
- the BET specific surface area S of the active material composite powder of the present invention is preferably S ⁇ S0 + 0.24. Even if the active material to which the lithium niobate is attached is changed, the method for attaching the lithium niobate to the surface is the same as the above method. Therefore, even if the active material to be used is changed, it is expressed using S0. It is considered that the reaction resistance of the battery can be reduced by satisfying the above BET specific surface area condition.
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Abstract
Description
本発明の第1の態様は、活物質と、該活物質の表面に付着させたニオブ酸リチウムとを有し、且つ、BET比表面積S[m2/g]が、0.93より大きく、且つ、1.44未満である、活物質複合粉体である。
図1は、本発明の活物質複合粉体を説明する図である。図1では、1粒の活物質複合粉体10を抽出し、且つ、この活物質複合粉体10を簡略化して示している。便宜上、図1には、1つの活物質1の表面にニオブ酸リチウム2を付着(被覆)させている形態を図示したが、本発明の活物質複合粉体は、当該形態に限定されない。本発明の活物質複合粉体は、複数の活物質が集合した二次粒子の形態である活物質の表面にニオブ酸リチウムを付着(被覆)させた形態であっても良い。
また、本発明において、反応抵抗を低減しやすい形態の活物質複合粉体にする観点から、活物質に付着させるニオブ酸リチウムは、結晶化していないことが好ましい。BET比表面積Sが1.34m2/g以下である活物質複合粉体に備えられているニオブ酸リチウムは結晶化していないと考えられるので、BET比表面積Sを1.34m2/g以下にすることにより、反応抵抗を低減しやすくなる。
図2は、本発明のリチウム電池20(リチウムイオン二次電池20)を説明する図である。図2では、リチウム電池20を簡略化して示しており、外装体等の記載を省略している。図1に示した活物質複合粉体10と同様に、活物質及び当該活物質の表面に付着させたニオブ酸リチウムを有し、且つ、そのBET比表面積Sが0.93m2/g<S<1.44m2/gである物質には、図2で符号10を付して示し、その説明を適宜省略する。
図3は、本発明の活物質複合粉体の製造方法を説明する図である。図3に示した本発明の活物質複合粉体の製造方法は、活物質準備工程(S1)と、噴霧乾燥工程(S2)と、熱処理工程(S3)と、を有している。
S2における噴霧により、ニオブ化合物及びリチウム化合物を含有する錯体溶液を活物質の表面に付着させる。そして、S2における乾燥により、活物質の表面に付着させた錯体溶液に含まれている、溶媒や水和水等の揮発成分を除去する。以下において、錯体溶液を乾燥した後の形態を、「ニオブ酸リチウムの前駆体」ということがある。
加えて、熱処理温度を350℃以上にすると、結晶化したニオブ酸リチウムが活物質の表面に形成される。結晶化したニオブ酸リチウムは非晶質のニオブ酸リチウムよりもリチウムイオン伝導度が低いため、電池の反応抵抗増加の一因になる。電池の反応抵抗を低減するためには、ニオブ酸リチウムを結晶化させないことが有効であり、そのためには、熱処理温度を所定温度未満にすることが有効である。熱処理温度を350℃未満にすることにより、ニオブ酸リチウムの結晶化を防止することが可能になるので、電池の反応抵抗を低減することが可能になる。
図5は、本発明のリチウム電池の製造方法を説明する図である。図5において、本発明の活物質複合粉体の製造方法について説明する図3に示した各工程と同様の工程には、図3で使用した符号と同一の符号を付し、その説明を適宜省略する。
<実施例1>
(1)活物質の準備
ニオブ酸リチウムを表面に付着させる正極活物質LiNi1/3Mn1/3Co1/3O2(日亜化学工業株式会社製)を準備した。
濃度30質量%の過酸化水素水870.4gを入れた容器へ、イオン交換水987.4g、及び、ニオブ酸(Nb2O5・3H2O(Nb2O5含水率72%))44.2gを添加した。次に、上記容器へ、濃度28質量%のアンモニア水87.9gを添加した。そして、アンモニア水を添加した後に十分に攪拌することにより、透明溶液を得た。さらに、得られた透明溶液に、水酸化リチウム・1水和物(LiOH・H2O)10.1gを加えることにより、ニオブのペルオキソ錯体及びリチウムを含有する錯体溶液を得た。得られた錯体溶液における、Li及びNbのモル濃度は、何れも0.12mol/kgであった。
上述の手順により得られた錯体溶液2000g、及び、1000gの正極活物質LiNi1/3Mn1/3Co1/3O2と、転動流動コーティング装置(MP-01、パウレック社製)とを用いて、正極活物質へ錯体溶液を噴霧し、且つ、これと並行して錯体溶液を乾燥することにより、ニオブ酸リチウムの前駆体を含む層を正極活物質の表面に被覆した。なお、転動流動コーティング装置の運転条件は、吸気ガス:窒素、吸気温度:120℃、吸気風量:0.4m3/h、ロータ回転数:毎分400回転、噴霧速度:4.5g/minとした。
噴霧乾燥により得られた、正極活物質と、該正極活物質の表面に形成されたニオブ酸リチウムの前駆体を含む層とを有する粉体について、大気中にて150℃、5時間の条件で熱処理を行うことにより、LiNi1/3Mn1/3Co1/3O2と、その表面に付着させたニオブ酸リチウムとを有する活物質複合粉体(実施例1の活物質複合粉体)を得た。
得られた実施例1の活物質複合粉体と硫化物系固体電解質(Li3PS4)とを、体積比で活物質複合粉体:硫化物系固体電解質=6:4となるように秤量し、これを、ヘプタンを入れた容器へと投入した。さらに、3質量%となる量の導電助剤(気相成長炭素繊維、昭和電工株式会社製)及び、3質量%となる量のバインダー(ブチレンラバー、JSR株式会社製)を、ヘプタン等を入れた容器へと投入することにより、正極スラリーを作製した。次いで、作製した正極スラリーを超音波ホモジナイザー(UH-50、株式会社エスエムテー製。以下において同じ。)で分散させることにより得た正極組成物を、アルミニウム箔の上面に塗工し、引き続き、100℃30分で乾燥させることにより、アルミニウム箔の上面に正極を形成した。次に、上面に正極が形成されているアルミニウム箔を1cm2の大きさに打ち抜くことにより、正極電極を得た。
一方、負極活物質(層状炭素)と硫化物系固体電解質(Li3PS4)とを、体積比で負極活物質:硫化物系固体電解質=6:4となるように秤量し、これを、ヘプタンを入れた容器へと投入した。さらに、1.2質量%となる量のバインダー(ブチレンラバー、JSR株式会社製)をヘプタンや負極活物質等を入れた容器へと投入することにより、負極スラリーを作製した。次いで、作製した負極スラリーを超音波ホモジナイザーで分散させることにより得た負極組成物を、銅箔の上面に塗工し、引き続き、100℃30分で乾燥させることにより、銅箔の上面に負極を形成した。次に、上面に負極が形成されている銅箔を1cm2の大きさに打ち抜くことにより、負極電極を得た。
次に、内径断面積1cm2の筒状セラミックスに、硫化物系固体電解質(Li3PS4)64.8mgを入れ、表面を平滑にしてから98MPaでプレスすることにより、セパレータ層を形成した。その後、このセパレータ層が正極電極と負極電極との間に配置されるように、正極電極及び負極電極を筒状セラミックスに入れ、421.4MPaでプレスした後、正極電極側、及び、負極電極側にステンレス棒を入れ、これを98MPaで拘束することにより、実施例1の全固体電池を作製した。
活物質複合粉体を得るための熱処理の温度を200℃に変更したほかは、実施例1と同じ条件で、LiNi1/3Mn1/3Co1/3O2と、その表面に付着させたニオブ酸リチウムとを有する活物質複合粉体(実施例2の活物質複合粉体)を作製した。さらに、実施例1の活物質複合粉体に代えて実施例2の活物質複合粉体を使用したほかは、実施例1と同じ条件で、全固体電池(実施例2の全固体電池)を作製した。
活物質複合粉体を得るための熱処理の温度を250℃に変更したほかは、実施例1と同じ条件で、LiNi1/3Mn1/3Co1/3O2と、その表面に付着させたニオブ酸リチウムとを有する活物質複合粉体(実施例3の活物質複合粉体)を作製した。さらに、実施例1の活物質複合粉体に代えて実施例3の活物質複合粉体を使用したほかは、実施例1と同じ条件で、全固体電池(実施例3の全固体電池)を作製した。
活物質複合粉体を得るための熱処理の温度を300℃に変更したほかは、実施例1と同じ条件で、LiNi1/3Mn1/3Co1/3O2と、その表面に付着させたニオブ酸リチウムとを有する活物質複合粉体(実施例4の活物質複合粉体)を作製した。さらに、実施例1の活物質複合粉体に代えて実施例4の活物質複合粉体を使用したほかは、実施例1と同じ条件で、全固体電池(実施例4の全固体電池)を作製した。
活物質複合粉体を得るための熱処理の温度を100℃に変更したほかは、実施例1と同じ条件で、LiNi1/3Mn1/3Co1/3O2と、その表面に付着させたニオブ酸リチウムとを有する活物質複合粉体(比較例1の活物質複合粉体)を作製した。さらに、実施例1の活物質複合粉体に代えて比較例1の活物質複合粉体を使用したほかは、実施例1と同じ条件で、全固体電池(比較例1の全固体電池)を作製した。
活物質複合粉体を得るための熱処理の温度を350℃に変更したほかは、実施例1と同じ条件で、LiNi1/3Mn1/3Co1/3O2と、その表面に付着させたニオブ酸リチウムとを有する活物質複合粉体(比較例2の活物質複合粉体)を作製した。さらに、実施例1の活物質複合粉体に代えて比較例2の活物質複合粉体を使用したほかは、実施例1と同じ条件で、全固体電池(比較例2の全固体電池)を作製した。
(1)活物質の準備
ニオブ酸リチウムを表面に付着させる正極活物質LiNi1/3Mn1/3Co1/3O2(日亜化学工業株式会社製)を準備した。
アルコキシド溶液は、エトキシリチウム、ペンタエトキシニオブ、及び、脱水エタノールを用いて作製した。エトキシリチウムを、脱水エタノールを入れた容器へと投入することにより溶解させ、これを脱水エタノール中で均一に分散させた。その後、エトキシリチウム及び脱水エタノールを入れた上記容器へ、リチウム及びニオブが元素比(モル比)で1:1になるように、ペンタエトキシニオブを入れた。そして、ペンタエトキシニオブが均一に混合されるまで攪拌することにより、アルコキシド溶液を得た。なお、エトキシリチウムの投入量は、アルコキシド溶液の固形分比率が6.9質量%になるように調整した。
上述の手順により得られたアルコキシド溶液680g、及び、1000gの正極活物質LiNi1/3Mn1/3Co1/3O2と、転動流動コーティング装置(MP-01、パウレック社製)とを用いて、正極活物質へアルコキシド溶液を噴霧し、且つ、これと並行してアルコキシド溶液を乾燥することにより、ニオブ酸リチウムの前駆体を含む層を正極活物質の表面に被覆した。ここで、転動流動コーティング装置の運転条件は、吸気ガス:窒素、吸気温度:80℃、吸気風量:0.3m3/h、ロータ回転数:毎分300回転、噴霧速度:1.5g/minとした。なお、実施例1及び比較例3の、転動流動コーティング装置の運転条件の違いは、使用する溶液の違いに起因している。
アルコキシド溶液を用いた噴霧乾燥により得られた、正極活物質と、該正極活物質の表面に形成されたニオブ酸リチウムの前駆体を含む層とを有する粉体について、大気中にて350℃、5時間の条件で熱処理を行うことにより、LiNi1/3Mn1/3Co1/3O2と、その表面に付着させたニオブ酸リチウムとを有する活物質複合粉体(比較例3の活物質複合粉体)を得た。
実施例1の活物質複合粉体に代えて比較例3の活物質複合粉体を使用したほかは、実施例1と同じ条件で、全固体電池(比較例3の全固体電池)を作製した。
噴霧乾燥後に、大気中に24時間に亘って曝露することにより、前駆体の加水分解を促進してから、大気中にて350℃、5時間の条件で熱処理を行ったほかは、比較例3と同じ条件で、LiNi1/3Mn1/3Co1/3O2と、その表面に付着させたニオブ酸リチウムとを有する活物質複合粉体(比較例4の活物質複合粉体)を作製した。さらに、実施例1の活物質複合粉体に代えて比較例4の活物質複合粉体を使用したほかは、実施例1と同じ条件で、全固体電池(比較例4の全固体電池)を作製した。
実施例1と同じ方法で調製した錯体溶液20g、及び、10gの正極活物質LiNi1/3Mn1/3Co1/3O2を準備し、これらを混合することにより、混合物を得た。
そして、得られた混合物を100℃に加熱することにより、粉体を取り出せる状態になるまで水分を蒸発させた後、大気中にて300℃、5時間の条件で熱処理を行うことにより、LiNi1/3Mn1/3Co1/3O2と、その表面に付着させたニオブ酸リチウムとを有する活物質複合粉体(比較例5の活物質複合粉体)を得た。さらに、実施例1の活物質複合粉体に代えて比較例5の活物質複合粉体を使用したほかは、実施例1と同じ条件で、全固体電池(比較例5の全固体電池)を作製した。
上述の方法で作製した実施例1乃至実施例4の活物質複合粉体、及び、比較例1乃至比較例5の活物質複合粉体のそれぞれに対し、比表面積測定装置(トライスター3000、株式会社島津製作所製)を用いて、BET比表面積を測定した。小数第3位を四捨五入することによって得られるBET比表面積の値を、表1に示す。なお、表面にニオブ酸リチウムを付着させていない正極活物質LiNi1/3Mn1/3Co1/3O2のBET比表面積は、1.1m2/gであった。
上述の方法で作製した実施例1乃至実施例4の全固体電池、及び、比較例1乃至比較例5の全固体電池のそれぞれを、電圧4.5Vまで充電し、次いで2.5Vまで放電した後に、3.6Vにおいて交流インピーダンス測定を行った。そして、ナイキストプロット(Nyquistプロット)により得られた円弧から、各全固体電池の反応抵抗[Ω・cm2]を特定した。小数第3位を四捨五入することによって得られる反応抵抗の値を、表2に示す。また、反応抵抗とBET比表面積との関係を図6及び図7に、反応抵抗と熱処理温度との関係を図8に、それぞれ示す。図7は、図6から、反応抵抗が8Ω・cm2以下であった試料の結果のみを抽出して示す図である。図6及び図7の縦軸は反応抵抗[Ω・cm2]であり、横軸はBET比表面積[m2/g]である。また、図8の縦軸は反応抵抗[Ω・cm2]であり、横軸は熱処理温度[℃]である。なお、実施例1の活物質複合粉体に代えて、表面にニオブ酸リチウムが付着していない正極活物質LiNi1/3Mn1/3Co1/3O2を用いたほかは、実施例1の全固体電池と同様の方法で作製した全固体電池の反応抵抗(小数第3位を四捨五入して得られる値)は、843.59Ω・cm2であった。
また、表1、表2、図6、及び、図7に示したように、BET比表面積Sを0.97m2/g≦S<1.44m2/gにすることにより、電池の反応抵抗を低減しやすくなり、BET比表面積Sを0.97m2/g≦S≦1.34m2/gにすることにより、電池の反応抵抗をより一層低減しやすくなることが分かった。
また、熱処理温度がこの範囲に含まれていても、錯体溶液と正極活物質との混合物を100℃に加熱することにより水分を蒸発させた後、これを大気中にて300℃、5時間の条件で熱処理した比較例5は、電池の反応抵抗が大きかった。これは、錯体溶液に含まれている過酸化水素によって正極活物質が浸食されたことにより、正極活物質が劣化したためであると考えられる。
また、表2及び図8に示したように、熱処理温度を300℃以下にすることにより、電池の反応抵抗を低減しやすくなり、熱処理温度を250℃以下にすることにより、電池の反応抵抗をより一層低減しやすくなることが分かった。さらに、熱処理温度を150℃以上にすることにより、電池の反応抵抗を低減しやすくなることが分かった。
図6乃至図8に示したように、熱処理温度を150℃にした実施例1及び熱処理温度を100℃にした比較例1は、熱処理温度を200℃以上300℃以下にした実施例2乃至実施例4よりも反応抵抗が大きかった。この原因を特定するため、実施例1乃至4及び比較例1の活物質複合粉体のそれぞれについて、大気中にて350℃、10分間の熱処理(追加の熱処理)を行った。追加の熱処理をする前の活物質複合粉体の質量をM0、追加の熱処理をした後の活物質複合粉体の質量をM1とするとき、100×M1/M0で表される質量比と、追加の熱処理をする前の活物質複合粉体を用いて作製した実施例1乃至4及び比較例1の全固体電池の反応抵抗との関係を、図9に示す。また、質量比100×M1/M0の値(小数第3位を四捨五入して得られる値)を表3に示す。
2…ニオブ酸リチウム
10…活物質複合粉体
20…リチウム電池
21…正極
21a…導電助剤
21b、22b…バインダー
22…負極
22a…負極活物質
23…固体電解質層(電解質)
23a…硫化物固体電解質
Claims (7)
- 活物質と、該活物質の表面に付着させたニオブ酸リチウムとを有し、且つ、BET比表面積S[m2/g]が、0.93より大きく、且つ、1.44未満である、活物質複合粉体。
- 前記BET比表面積S[m2/g]が、0.97以上である、請求項1に記載の活物質複合粉体。
- 前記BET比表面積S[m2/g]が、1.34以下である、請求項1に記載の活物質複合粉体。
- 大気雰囲気中且つ350℃で、10分間に亘って保持する熱処理を行った後の活物質複合粉体の質量をM1、該熱処理を行う前の活物質複合粉体の質量をM0とするとき、質量比M1/M0が、99.60<100×M1/M0である、請求項1に記載の活物質複合粉体。
- 正極と、負極と、前記正極及び前記負極に接触する電解質と、を備え、
前記正極及び前記負極の少なくとも一方に請求項1に記載の活物質複合粉体が含まれる、リチウム電池。 - 活物質へ、ニオブのペルオキソ錯体及びリチウムを含有する溶液を噴霧し、且つ、これと並行して前記溶液を乾燥する、噴霧乾燥工程と、
前記噴霧乾燥工程の後に熱処理する、熱処理工程と、を有し、
前記熱処理の温度が、123℃よりも高く、且つ、350℃未満である、活物質複合粉体の製造方法。 - 正極と、負極と、前記正極及び前記負極に接触する電解質と、を備えるリチウム電池を製造する方法であって、
活物質へ、ニオブのペルオキソ錯体及びリチウムを含有する溶液を噴霧し、且つ、これと並行して前記溶液を乾燥する、噴霧乾燥工程と、
前記噴霧乾燥工程後に123℃よりも高く、且つ、350℃未満で熱処理することにより、活物質複合粉体を作製する、熱処理工程と、
作製された前記活物質複合粉体を含む前記正極又は前記負極を作製する、電極作製工程と、を有する、リチウム電池の製造方法。
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