WO2015053357A1 - リチウム過剰型層状リチウム金属複合酸化物の製造方法 - Google Patents
リチウム過剰型層状リチウム金属複合酸化物の製造方法 Download PDFInfo
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- WO2015053357A1 WO2015053357A1 PCT/JP2014/077046 JP2014077046W WO2015053357A1 WO 2015053357 A1 WO2015053357 A1 WO 2015053357A1 JP 2014077046 W JP2014077046 W JP 2014077046W WO 2015053357 A1 WO2015053357 A1 WO 2015053357A1
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- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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- 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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- H01M4/525—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 a method for producing a lithium-rich layered lithium metal composite oxide (also referred to as “OLO”) that can be used as a positive electrode active material of a lithium ion battery.
- a lithium-rich layered lithium metal composite oxide also referred to as “OLO”
- Lithium-ion batteries are characterized by high energy density and long life, so they are used as power sources for home appliances such as video cameras and portable electronic devices such as notebook computers and mobile phones. Yes. Recently, the lithium ion battery has been applied to a large battery mounted on an electric vehicle (EV), a hybrid electric vehicle (HEV), or the like.
- EV electric vehicle
- HEV hybrid electric vehicle
- a lithium ion battery is a secondary battery with a structure in which lithium is extracted as ions from the positive electrode during charging, moves to the negative electrode, and is stored, and reversely, lithium ions return from the negative electrode to the positive electrode during discharging. It is known that it is caused by the potential of.
- LiCoO 2 has a layer structure in which a lithium atomic layer and a cobalt atomic layer are alternately stacked via an oxygen atomic layer, has a large charge / discharge capacity, and is excellent in diffusibility of lithium ion storage / desorption.
- lithium metal composite oxides having a layer structure such as LiCoO 2 .
- a lithium metal composite oxide having a layer structure such as LiCoO 2 or LiNiO 2 is represented by a general formula LiMeO 2 (Me: transition metal).
- the crystal structure of the lithium metal composite oxide having these layer structures belongs to the space group R-3m (“-” is usually attached to the upper part of “3” and indicates a reversal. The same applies hereinafter).
- Li ions, Me ions, and oxide ions occupy 3a sites, 3b sites, and 6c sites, respectively. It is known that a layer made of Li ions (Li layer) and a layer made of Me ions (Me layer) have a layered structure in which they are alternately stacked via O layers made of oxide ions.
- LiCoO 2 is the mainstream as a lithium metal composite oxide having such a layer structure, but since Co is expensive, Li has recently been added excessively to reduce the Co content.
- a lithium-rich layered lithium metal composite oxide also referred to as “OLO” or the like has attracted attention.
- LiMO 2 -based solid solution (M ⁇ Co, Ni, etc.)
- LiMO 2 -based solid solution known as a lithium-excess layered lithium metal composite oxide has a LiMO 2 structure and a Li 2 MnO 3 structure. It is a solid solution. Li 2 MnO 3 has a high capacity but is electrochemically inactive. On the other hand, LiMO 2 is electrochemically active, but its theoretical capacity is small. Therefore, the “xLi 2 MnO 3- (1-x) LiMO 2 system is used with the aim of utilizing the electrochemically highly active properties of LiMO 2 while solidifying both of them to extract the high capacity of Li 2 MnO 3.
- Patent Document 1 With respect to this type of lithium-excess layered lithium metal composite oxide, in Patent Document 1, it is composed of oxide crystal particles containing three kinds of transition metals, and the crystal structure of the crystal particles is a layer structure.
- Li [Li x (A P B Q C R ) 1-x ] O 2 (wherein A, B, and C are different from each other, each of which is a cubic close-packed arrangement of oxygen atoms constituting Element, -0.1 ⁇ x ⁇ 0.3, 0.2 ⁇ P ⁇ 0.4, 0.2 ⁇ Q ⁇ 0.4, 0.2 ⁇ R ⁇ 0.4) Is disclosed.
- a manufacturing method thereof during coprecipitation, nitrogen or argon as an inert gas is bubbled into the aqueous solution to remove dissolved oxygen, or a reducing agent is added to the aqueous solution in advance.
- nitrogen or argon as an inert gas is bubbled into the aqueous solution to remove dissolved oxygen, or a reducing agent is added to the aqueous solution in advance.
- the temperature is raised to 1000 ° C. at once, and the mixture is baked at that temperature for 10 hours.
- a method is disclosed in which annealing is performed for 5 hours, followed by cooling.
- Patent Document 2 Li z Ni 1-w M w O 2 (where, M is Co, Al, Mg, Mn, Ti, Fe, Cu, Zn, at least one selected from the group consisting of Ga And the lithium metal composite oxide powder represented by 0 ⁇ w ⁇ 0.25 and 1.0 ⁇ z ⁇ 1.1.) It is composed of primary particles and secondary particles formed by aggregating a plurality of the primary particles, the shape of the secondary particles is spherical or elliptical, and 95% or more of the secondary particles have a particle diameter of 20 ⁇ m or less.
- the average particle diameter of the secondary particles is 7 to 13 ⁇ m
- the tap density of the powder is 2.2 g / cm 3 or more
- the average particle diameter is 40 nm or less in the pore distribution measurement by the nitrogen adsorption method.
- the average volume of pores having is 0.001 ⁇ 0.008cm 3 / g
- the The positive electrode active material for a non-aqueous electrolyte secondary batteries is disclosed, wherein the mean crushing strength of the next particle is 15 ⁇ 100 MPa.
- Ni and metal M (where M is at least one metal element selected from the group consisting of Co, Al, Mg, Mn, Ti, Fe, Cu, Zn, and Ga).
- Step 1 for producing a metal composite hydroxide having a tap density of 1.7 g / cm 3 or more.
- the metal composite hydroxide and lithium hydroxide obtained in step 1 are weighed and mixed to obtain a mixture, and the mixture obtained in step 2 is heated from room temperature at a rate of heating of 0.5 to The temperature is raised to 450 to 550 ° C. at 15 ° C./min, held at that temperature for 1 to 10 hours, and the first stage firing is performed, and then further to 650 to 800 ° C. at a temperature raising rate of 1 to 5 ° C./min.
- step 3 After firing the eyes, and step 3 to obtain a positive electrode active material for a non-aqueous electrolyte secondary battery furnace cooling, method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery having it is disclosed.
- Patent Document 3 the formula Li 1 + x Ni ⁇ Mn ⁇ Co ⁇ O 2 (wherein x is in the range of about 0.05 to about 0.25, and ⁇ is about 0.1 to about 0.4.
- a lithium metal composite oxide is disclosed wherein ⁇ is in the range of about 0.4 to about 0.65, and ⁇ is in the range of about 0.05 to about 0.3.
- the pH of the solution is adjusted by, for example, dissolving a desired non-molar metal salt in an aqueous solvent such as purified water and then adding Na 2 CO 3 and / or ammonium hydroxide.
- the metal carbonate having a desired amount of metal element is precipitated, the precipitated metal carbonate is separated from the solution, washed and dried to form a powder, and after drying, the recovered metal carbonate powder
- a manufacturing method obtained by mixing Li raw materials, heat-treating at about 400 ° C. to 800 ° C., and firing at a temperature of about 700 ° C. to 1200 ° C. is disclosed.
- the present invention relates to a lithium-excess layered lithium metal composite oxide, which can increase the primary particle size and increase the volume energy density as an electrode. It is intended to propose a manufacturing method.
- the general formula Li 1 + x M 1-x O 2 (x 0.10 or more and 0.33 or less, M always contains Mn, from Ni, Co, Al, Mg, Ti, Fe and Nb)
- a lithium-excess layered lithium metal composite oxide represented by the general formula Li 1 + x M 1-x O 2 (x ⁇ ). 0.15 to 0.15, M necessarily contains Mn, and contains at least one element selected from the group consisting of Ni, Co, Al, Mg, Ti, Fe, and Nb.
- a method for producing a lithium-excess layered lithium metal composite oxide comprising the steps of mixing a composite oxide and a lithium compound and firing to obtain a lithium-excess layered lithium metal composite oxide is proposed.
- a second step of obtaining a layered lithium metal composite oxide ; We propose a method of manufacturing the over-type layered lithium metal composite oxide.
- OLO layered lithium metal composite oxide
- the primary particle size is reduced.
- a lithium compound was added to this lithium metal composite oxide and fired to produce a lithium-rich layered lithium metal composite oxide having an x range of 0.10 or more.
- the primary particles can be enlarged while maintaining good characteristics of the lithium-excess layered lithium metal composite oxide (OLO), such as the ability to increase charge / discharge capacity per mass, The volume energy density as an electrode can be increased.
- OLO lithium-excess layered lithium metal composite oxide
- the production method proposed by the present invention it is particularly excellent as a positive electrode active material for a battery mounted on a vehicle, particularly a battery mounted on an electric vehicle (EV) or a hybrid electric vehicle (HEV).
- a positive electrode active material for lithium ion batteries can be produced.
- FIG. 3 is an XRD pattern of a lithium manganese nickel-containing composite oxide powder (sample) obtained in Example 1.
- FIG. 3 is an XRD pattern of a lithium manganese nickel-containing composite oxide powder (sample) obtained in Comparative Example 1.
- 2 is an SEM image of a lithium manganese nickel-containing composite oxide powder (sample) obtained in Example 1.
- 2 is an SEM image of a lithium manganese nickel-containing composite oxide powder (sample) obtained in Comparative Example 1.
- 2 is a graph showing a charge / discharge curve of a battery using the lithium manganese nickel-containing composite oxide powder (sample) obtained in Example 1 and Comparative Example 1.
- FIG. 3 is a graph showing a charge rate characteristic index of a battery using the lithium manganese nickel-containing composite oxide powder (sample) obtained in Example 1 and Comparative Example 1.
- FIG. 3 is a graph showing a charge rate characteristic index of a battery using the lithium manganese nickel-containing composite oxide powder (sa
- the method for producing a lithium-rich layered lithium metal composite oxide proposed by the present invention mixes a predetermined lithium metal composite oxide (referred to as “lithium metal composite oxide A”) and a lithium compound. And producing a lithium-excess layered lithium metal composite oxide (referred to as “the present lithium-excess layered lithium metal composite oxide”).
- the lithium metal composite oxide A can be produced in a series of steps for producing the present lithium-excess layered lithium metal composite oxide, and the present lithium-excess layered lithium metal composite oxide is produced. It can also be produced by a series of processes different from the series of processes.
- the lithium metal composite oxide A produced by others can also be used. Among these, this embodiment demonstrates the method of producing the said lithium metal complex oxide A in a series of processes which manufacture this lithium excess layered lithium metal complex oxide.
- the method for producing a lithium-excess layered lithium metal composite oxide according to an example of this embodiment has a general formula of Li 1 + x M 1-x O 2 ( ⁇ 0.15 or more and 0.002). 15 or less, M always contains Mn, and includes at least one element selected from the group consisting of Ni, Co, Al, Mg, Ti, Fe and Nb.) “Li element” and “M element”
- a raw material composition containing the raw materials of “a) to obtain a lithium metal composite oxide A ⁇ first step>, a lithium metal composite oxide A obtained in the first step, and a lithium compound, ⁇ Second step> to obtain the present lithium-excess layered lithium metal composite oxide by firing.
- the first step, the second step, or both steps may be performed only once, or may be performed twice or more.
- the lithium metal composite oxide A and the lithium compound are mixed and baked to form the present lithium excess type.
- the lithium metal composite oxide A and the lithium compound are mixed and baked to form the present lithium excess type.
- the primary particle size of the lithium-rich layered lithium metal composite oxide finally obtained is promoted by crystal growth of the lithium metal composite oxide.
- the powder characteristics can be adjusted, for example, the tap density can be increased.
- the chemical composition and crystal structure of the lithium-rich layered lithium metal composite oxide can be adjusted.
- the present lithium-rich layered lithium metal composite oxide can be used as a positive electrode active material for a lithium ion battery. The charge / discharge efficiency when used can be improved.
- the “lithium metal composite oxide having a layer structure” is a lithium metal composite oxide particle having a layer structure in which lithium atom layers and transition metal atom layers are alternately stacked via oxygen atom layers. is there.
- a powder made of a lithium metal composite oxide includes, for example, SO 4 as an impurity if it is 1.0 wt% or less and other elements are 0.5 wt% or less, respectively. You may go out. This is because such an amount is considered to hardly affect the characteristics of the present lithium-excess layered lithium metal composite oxide.
- “X” in the above general formula is 0.10 or more and 0.33 or less, more preferably 0.11 or more and 0.30 or less, and particularly preferably 0.12 or more and 0.30 or less.
- “x” is 0.10 or more, for example, when the present lithium-excess layered lithium metal composite oxide is used as a positive electrode active material of a lithium ion battery, a preferable charge / discharge capacity can be obtained. If it is 33 or less, preferable electrochemical activity can be obtained.
- M in the above general formula must contain Mn and contain at least one element selected from the group consisting of Ni, Co, Al, Mg, Ti, Fe and Nb.
- Mn—Ni, Mn—Co, Mn—Al, Mn—Mg, Mn—Ti, Mn—Fe, Mn—Nb, Mn—Ni—Co, Mn—Ni—Al, Mn—Ni—Mg, Mn— Ni-Ti, Mn-Ni-Fe, Mn-Ni-Nb, Mn-Ni-Co-Al, Mn-Ni-Co-Mg, Mn-Ni-Co-Ti, Mn-Ni-Co-Fe, Mn- “M” made of a combination of Ni—Co—Nb and the like can be exemplified.
- any one or more of Al, Mg, Ti, Fe and Nb can be further combined with the above combination.
- the Mn content in the M element is preferably 20 to 90% by mass, more preferably 40% by mass or more and 90% by mass or less, and particularly preferably 50% by mass or more and 80% by mass or less.
- the Ni content in the M element is preferably 0 to 80% by mass, more preferably 20% by mass or more and 70% by mass or less, and particularly preferably 20% by mass or more and 50% by mass or less.
- the Co content in the M element is preferably 0 to 80% by mass, more preferably 20% by mass or more and 70% by mass or less, and particularly preferably 20% by mass or more and 50% by mass or less.
- the atomic ratio of the oxygen amount is described as “2” for convenience, but may have some non-stoichiometry.
- a raw material containing “Li element” and “M element” in the lithium metal composite oxide A represented by the general formula Li 1 + x M 1-x O 2 for example, lithium raw material, manganese raw material, nickel raw material , Raw materials such as cobalt raw materials are weighed and mixed, pulverized as necessary, granulated as necessary, fired, heat treated as necessary, pulverized as necessary, and further as necessary Thus, the lithium metal composite oxide A may be obtained.
- lithium raw material examples include lithium hydroxide (LiOH), lithium carbonate (Li 2 CO 3 ), lithium nitrate (LiNO 3 ), LiOH ⁇ H 2 O, lithium oxide (Li 2 O), other fatty acid lithium and lithium halide. Etc. Of these, lithium hydroxide salts, carbonates and nitrates are preferred.
- the manganese raw material is not particularly limited. For example, manganese carbonate, manganese nitrate, manganese chloride, manganese dioxide and the like can be used, and among these, manganese carbonate and manganese dioxide are preferable. Among these, electrolytic manganese dioxide obtained by an electrolytic method is particularly preferable.
- the nickel raw material is not particularly limited.
- nickel carbonate, nickel nitrate, nickel chloride, nickel oxyhydroxide, nickel hydroxide, nickel oxide, and the like can be used. Among these, nickel carbonate, nickel hydroxide, and nickel oxide are preferable.
- the cobalt raw material is not particularly limited.
- basic cobalt carbonate, cobalt nitrate, cobalt chloride, cobalt oxyhydroxide, cobalt hydroxide, cobalt oxide, etc. can be used, among which basic cobalt carbonate, cobalt hydroxide, cobalt oxide, cobalt oxyhydroxide are preferable.
- M element raw materials ie, Al, Mg, Ti, Fe and Nb raw materials, oxides, hydroxides, carbonates and the like of these elements can be used.
- boron compound any compound containing boron (B element) may be used.
- boric acid or lithium borate is preferably used.
- lithium borate include lithium metaborate (LiBO 2 ), lithium tetraborate (Li 2 B 4 O 7 ), lithium pentaborate (LiB 5 O 8 ), and lithium perborate (Li 2 B 2 O 5 ).
- Various forms can be used.
- Mixture As a method for mixing the raw materials, it is preferable to employ a wet mixing method in which a liquid medium such as water or a dispersant is added to form a slurry to be mixed.
- a liquid medium such as water or a dispersant
- dry pulverization may be performed.
- the granulation method may be wet or dry as long as the various raw materials mixed in the previous step are dispersed in the granulated particles without being separated.
- As the granulation method extrusion granulation method, rolling granulation method, fluidized granulation method, mixed granulation method, spray drying granulation method, pressure molding granulation method, or flake granulation method using a roll or the like But you can.
- wet granulation it is necessary to sufficiently dry before firing.
- a drying method it may be dried by a known drying method such as a spray heat drying method, a hot air drying method, a vacuum drying method, a freeze drying method, etc. Among them, the spray heat drying method is preferable.
- the spray heat drying method is preferably carried out using a heat spray dryer (spray dryer) (referred to herein as “spray drying method”).
- a heat spray dryer referred to herein as “spray drying method”.
- the coprecipitation method include a method for producing a composite hydroxide in which different elements coexist by dissolving a raw material in a solution and then adjusting the pH and other conditions to cause precipitation.
- Firing in the first step may be performed in a firing furnace in an air atmosphere, an oxygen gas atmosphere, an atmosphere in which an oxygen partial pressure is adjusted, a carbon dioxide gas atmosphere, or other atmosphere.
- firing is preferably performed in an atmosphere having an oxygen concentration of 20% or more.
- the firing temperature is higher than 800 ° C. and lower than 1500 ° C. (: means the temperature when a thermocouple is brought into contact with the fired product in the firing furnace), preferably 810 ° C. or higher or 1300 ° C. or lower, more preferably Is preferably 820 ° C. or higher or 1100 ° C. or lower.
- the firing time is preferably fired so as to hold for 0.5 to 300 hours.
- the type of firing furnace is not particularly limited. For example, it can be fired using a rotary kiln, a stationary furnace, or other firing furnace.
- the heat treatment after firing is preferably performed when the crystal structure needs to be adjusted.
- the heat treatment may be performed under conditions of an oxidizing atmosphere such as an atmosphere, an oxygen gas atmosphere, an oxygen partial pressure, and the like.
- the heat treatment may be performed after cooling to room temperature after firing. Heating may be performed, or heat treatment may be performed following the firing at a rate of temperature decrease to room temperature of 1.5 ° C./min or less.
- x is preferably ⁇ 0.15 or more and 0.15 or less, more preferably ⁇ 0.05 or more and 0.10 or less, and particularly preferably 0.00 or more and 0.05 or less.
- x when x is in the range of ⁇ 0.15 or more and 0.15 or less, the primary particle diameter of the lithium metal composite oxide can be sufficiently increased, and the lithium metal composite oxide A in this range can be used.
- a lithium-excess layered lithium metal composite oxide capable of realizing preferable battery characteristics can be produced.
- the primary particle diameter of the lithium metal composite oxide A is preferably 0.7 ⁇ m or more, more preferably 0.8 ⁇ m or more and 5.0 ⁇ m or less, and particularly preferably 0.9 ⁇ m or more or 3.0 ⁇ m or less. If the primary particle diameter of the lithium metal composite oxide A is 0.7 ⁇ m or more, the primary particle diameter of the finally obtained lithium-rich layered lithium metal composite oxide can be 1.0 ⁇ m or more.
- the transition metal composition ratio for example, the transition metal element ratio contained in M, the composition ratio such as Li: M ratio
- the raw material particle size It can be adjusted depending on the firing conditions. In particular, the primary particle size can be increased by increasing the firing temperature.
- the tap density of the lithium-metal composite oxide A is preferably at 1.3 g / cm 3 or more and preferably 1.3 g / cm 3 or more, or 3.0 g / cm 3 or less, even 1.4 g / cm 3 or more therein or It is particularly preferably 2.9 g / cm 3 or less. If the tap density of the lithium metal composite oxide A is 1.3 g / cm 3 or more, the tap density of the finally obtained lithium-rich layered lithium metal composite oxide should be 1.9 g / cm 3 or more. Can do.
- the transition metal composition ratio for example, the transition metal element ratio contained in M, the composition ratio such as the Li: M ratio
- the raw material particle size, and the firing It can be adjusted according to conditions.
- the tap density can be increased by increasing the firing temperature.
- ⁇ Second step> the lithium metal composite oxide A obtained in the first step and the lithium compound are mixed, baked, heat treated as necessary, crushed as necessary, and further as necessary.
- the present lithium-excess layered lithium metal composite oxide may be obtained.
- lithium compound As a lithium compound, if it is a compound containing lithium, it will not specifically limit. Of these, lithium hydroxide or lithium carbonate is preferably used.
- mixing method of the lithium metal composite oxide A and the lithium compound it is preferable to employ a method that does not reduce the primary particle diameter of the lithium metal composite oxide A.
- Specific examples include a mixing method such as a ball mill, an SC mill, and a mixer. However, it is not limited to these mixing methods.
- Firing in the second step may be performed in a firing furnace in an air atmosphere, an oxygen gas atmosphere, an atmosphere in which the oxygen partial pressure is adjusted, a carbon dioxide gas atmosphere, or other atmosphere.
- firing is preferably performed in an atmosphere having an oxygen concentration of 20% or more.
- the firing temperature (maximum reached temperature) in the second step is preferably higher than the firing temperature (maximum reached temperature) in the first step.
- the temperature is higher by 10 ° C. to 200 ° C. than the firing temperature in the first step, and among them, it is preferable that the temperature is higher than 20 ° C. or 180 ° C., among which only 30 ° C. or higher and 170 ° C. or lower.
- High temperature is preferable, and among them, it is more preferable that the temperature is 40 ° C. or more or 150 ° C. or less, and it is more preferable that the temperature is 100 ° C. or less.
- the firing time is preferably fired so as to hold for 0.5 to 300 hours. At this time, it is preferable to select firing conditions in which the transition metal is solid-solved at the atomic level and exhibits a single phase.
- the kind of baking furnace is not specifically limited. For example, it can be fired using a rotary kiln, a stationary furnace, or other firing furnace.
- the heat treatment after firing is preferably performed when the crystal structure needs to be adjusted.
- the heat treatment may be performed under conditions of an oxidizing atmosphere such as an atmosphere, an oxygen gas atmosphere, and an oxygen partial pressure adjusted.
- an oxidizing atmosphere such as an atmosphere, an oxygen gas atmosphere, and an oxygen partial pressure adjusted.
- such heat treatment may be performed after cooling to room temperature and then heating, and following the firing, the rate of temperature decrease to room temperature should be 1.5 ° C./min or less.
- a heat treatment may be performed.
- the primary particle diameter of the present lithium-rich layered lithium metal composite oxide can be made 1.0 ⁇ m or more by the present production method.
- the thickness can be 1.1 ⁇ m or more or 5.0 ⁇ m or less, and among them, it can be 1.2 ⁇ m or more or 4.9 ⁇ m or less.
- the primary particle size is determined by using a scanning electron microscope (SEM), selecting a plurality of particles, for example, 10 at random from the obtained SEM image, measuring the short diameter of the primary particles, and reducing the measured length to a reduced scale. The average value was defined as the primary particle size.
- SEM scanning electron microscope
- the composition ratio of transition metals for example, the ratio of transition metal elements contained in M, Li: M ratio) Etc.
- the raw material particle size, firing conditions, and the like for example, the primary particle size of the present lithium-excess layered lithium metal composite oxide can be increased by increasing the firing temperature.
- the tap density (also referred to as “TD”) of the present lithium-excess layered lithium metal composite oxide can be set to 1.9 g / cm 3 or more by this production method, and in particular, 2.0 g / cm 3. Above or 4.4 g / cm 3 or less, among them, it can be 2.1 g / cm 3 or more or 4.3 g / cm 3 or less.
- the tap density of the present lithium-rich layered lithium metal composite oxide is 1.9 g / cm 3 or more, the volume energy density as an electrode can be effectively increased.
- the tap density can be obtained, for example, by measuring the powder packing density when a sample is put in a glass graduated cylinder and tapped a predetermined number of times with a predetermined stroke using a shaking specific gravity measuring instrument.
- the tap density can be increased due to the powder characteristics of the lithium metal composite oxide A obtained in the first step.
- it is not limited to such a method.
- the average particle diameter (D50) determined by the laser diffraction scattering particle size distribution measurement method of the present lithium-excess layered lithium metal composite oxide is 1 ⁇ m to 60 ⁇ m, especially 2 ⁇ m or more or 59 ⁇ m or less, and particularly 3 ⁇ m among them. It can be made above or 58 ⁇ m or less. If the D50 of the present lithium-excess layered lithium metal composite oxide is 1 ⁇ m to 60 ⁇ m, it is advantageous from the viewpoint of electrode production.
- D50 of the present lithium-excess layered lithium metal composite oxide In order to adjust D50 of the present lithium-excess layered lithium metal composite oxide within the above range, in this production method, D50 of starting material, adjustment of firing temperature or firing time, or D50 by pulverization after firing It is preferable to make adjustments. However, it is not limited to these adjustment methods.
- the laser diffraction / scattering particle size distribution measurement method is a measurement method in which agglomerated powder particles are regarded as one particle (aggregated particle) to calculate the particle size, and the average particle size (D50) is 50% volume cumulative particle.
- the diameter that is, the diameter of 50% cumulative from the finer one of the cumulative percentage notation of the measured particle size converted into volume in the chart of the volume standard particle size distribution.
- the specific surface area (SSA) of the present lithium-excess layered lithium metal composite oxide is 0.1 to 3.0 m 2 / g, particularly 0.2 m 2 / g or more or 2.9 m 2 / g or less, depending on the production method. Among these, in particular, it can be 0.3 m 2 / g or more or 2.8 m 2 / gm or less. If the specific surface area (SSA) of the present lithium-excess layered lithium metal composite oxide is 0.1 to 3.0 m 2 / g, it is preferable from the viewpoint of rate characteristics.
- the fact that it is less than 4.0% with respect to the intensity of the main peak in the range of 16 to 20 °, that is, the peak due to the layered structure, is a single phase structure having almost no Li 2 MnO 3 structure or a structure close thereto. It is guessed.
- lithium metal composite oxidation An example is a method in which the product A is prepared, and then the lithium metal composite oxide A and the lithium compound are mixed and fired.
- the crystallite size of the present lithium-excess layered lithium metal composite oxide that is, the crystallite size determined by the measurement method by the Rietveld method (described in detail in the Examples section) is 50 nm or more by this production method.
- the thickness may be 50 nm or more or 300 nm or less, and among them, the thickness may be 51 nm or more or 290 nm or less.
- crystallite means the largest group that can be regarded as a single crystal, and can be obtained by performing XRD measurement and performing Rietveld analysis.
- the smallest unit particle composed of a plurality of crystallites and surrounded by a grain boundary when observed by SEM (for example, 3000 times) is referred to as “primary particle”.
- primary particles include single crystals and polycrystals. From this viewpoint, if the crystallite size of the present lithium-excess layered lithium metal composite oxide is 50 nm or more, the primary particles can be made larger, and the volume energy density as an electrode can be further increased.
- the composition ratio of transition metal for example, the composition ratio of transition metal element contained in M, composition ratio of Li: M ratio, etc.
- raw material particle size for example, the composition ratio of Li: M ratio, etc.
- firing conditions It may be adjusted by, for example.
- the crystallite size can be increased by increasing the firing temperature.
- the present lithium-rich layered lithium metal composite oxide can be effectively used as a positive electrode active material of a lithium battery after being crushed and classified as necessary and then mixed with other positive electrode materials as necessary.
- the positive electrode mixture can be produced by mixing the present lithium-excess layered lithium metal composite oxide, a conductive material made of carbon black or the like, and a binder made of Teflon (registered trademark) binder or the like.
- a positive electrode mixture is used as a positive electrode
- a negative electrode is made of a material capable of inserting and extracting lithium such as lithium or carbon
- a nonaqueous electrolyte is lithium such as lithium hexafluorophosphate (LiPF 6 ).
- a lithium secondary battery can be constructed using a salt dissolved in a mixed solvent such as ethylene carbonate-dimethyl carbonate.
- the present invention is not limited to the battery having such a configuration.
- a lithium battery including the present lithium-rich layered lithium metal composite oxide as a positive electrode active material is used as a power source for driving a motor particularly mounted on an electric vehicle (EV) or a hybrid electric vehicle (HEV). It is particularly excellent for use as a positive electrode active material for lithium batteries.
- the “hybrid vehicle” is a vehicle that uses two power sources, that is, an electric motor and an internal combustion engine, and includes a plug-in hybrid vehicle.
- the term “lithium battery” is intended to encompass all batteries containing lithium or lithium ions in the battery, such as lithium primary batteries, lithium secondary batteries, lithium ion secondary batteries, and lithium polymer batteries.
- SN Dispersant 5468 manufactured by San Nopco Co., Ltd.
- a pulverized slurry was obtained with an average particle size (D50) of 0.5 ⁇ m or less.
- the obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “i-8” manufactured by Okawara Chemical Co., Ltd.).
- a rotating disk was used for spraying, and granulation drying was performed by adjusting the temperature so that the rotation speed was 24,000 rpm, the slurry supply amount was 12 kg / hr, and the outlet temperature of the drying tower was 100 ° C.
- the average particle diameter (D50) of the granulated powder was 15 ⁇ m.
- the obtained granulated powder was heated to 950 ° C. at a temperature rising rate of 1.3 ° C./min using a static electric furnace and maintained at 950 ° for 20 hours. Thereafter, the temperature was decreased to 700 ° C. at a temperature decrease rate of 1.3 ° C./min, maintained at 700 ° for 10 hours, and then cooled to room temperature at a temperature decrease rate of 1.3 ° C./min.
- the obtained powder was crushed and again heated to 950 ° C. at a heating rate of 1.3 ° C./min in the atmosphere using a static electric furnace and maintained at 950 ° for 20 hours. The temperature was lowered to 700 ° C.
- lithium manganese nickel-containing composite oxide powder (sample).
- the obtained lithium manganese nickel-containing composite oxide powder (sample), it was confirmed to be Li 1.17 Ni 0.56 Mn 0.27 O 2 .
- Example 1 Lithium carbonate, electrolytic manganese dioxide, and nickel hydroxide were weighed so that the composition would be Li 1.06 Ni 0.47 Mn 0.47 O 2 , water was added, mixed and stirred to prepare a slurry with a solid content concentration of 10 wt%.
- a slurry 500 g of raw material powder
- 6 wt% of a polycarboxylic acid ammonium salt SN Dispersant 5468 manufactured by San Nopco Co., Ltd.
- the average particle size (D50) was 0.5 ⁇ m or less to obtain a pulverized slurry.
- the obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “i-8” manufactured by Okawara Chemical Co., Ltd.). At this time, a rotating disk was used for spraying, and granulation drying was performed by adjusting the temperature so that the rotation speed was 24,000 rpm, the slurry supply amount was 12 kg / hr, and the outlet temperature of the drying tower was 100 ° C.
- the average particle diameter (D50) of the granulated powder was 15 ⁇ m.
- the obtained granulated powder was heated to 700 ° C. at a heating rate of 1.5 ° C./min in the atmosphere using a static electric furnace and maintained at 700 ° for 20 hours. Then, it cooled to normal temperature with the temperature fall rate of 1.5 degreeC / min. Next, using a static electric furnace again, the temperature was raised to 1000 at a heating rate of 1.5 ° C./min in the atmosphere, maintained at 1000 ° for 30 hours, and then lowered to a cooling rate of 1.5 ° C./min. And cooled to room temperature. The fired powder thus obtained was crushed and classified with a sieve having a mesh size of 53 ⁇ m, and the sieved lithium metal composite oxide powder was recovered.
- the recovered sieving lithium metal composite oxide powder As a result of chemical analysis of the recovered sieving lithium metal composite oxide powder, it was confirmed to be Li 1.06 Ni 0.47 Mn 0.47 O 2 .
- the primary particle size of the sieved lithium metal composite oxide powder was 0.9 ⁇ m, and the tap density was 1.6 g / cm 3 .
- lithium carbonate was added to the recovered under-sieving lithium metal composite oxide powder so that the target composition was Li 1.13 Mn 0.45 Ni 0.42 O 2, and mixing was performed for 1 hour using a ball mill.
- the obtained mixed powder was heated to 1050 ° C. at a temperature rising rate of 1.3 ° C./min in the atmosphere using a stationary electric furnace and maintained at 1050 ° C. for 20 hours. Cooled to room temperature at ° C./min.
- the fired powder thus obtained was crushed and classified with a sieve having an opening of 53 ⁇ m, and the sieved powder was recovered to obtain a lithium manganese nickel-containing composite oxide powder (sample).
- the obtained lithium manganese nickel-containing composite oxide powder had a primary particle size of 1.2 ⁇ m and a tap density of 2.2 g / cm 3 .
- Example 2 Lithium metal composite oxide powder was prepared in the same manner as in Example 1, and similarly an under-sieving lithium metal composite oxide powder was obtained. As a result of chemical analysis of the obtained sieving lithium metal composite oxide powder, it was confirmed to be Li 1.06 Ni 0.47 Mn 0.47 O 2 .
- the primary particle diameter of the obtained lithium metal composite oxide powder (sample) was 0.9 ⁇ m, and the tap density was 1.6 g / cm 3 .
- Example 2 a lithium manganese nickel-containing composite oxide powder was used in the same manner as in Example 1 except that lithium carbonate was added to the sieving lithium metal composite oxide powder so that the target composition was Li 1.14 Mn 0.43 Ni 0.43 O 2. (Sample) was obtained. As a result of chemical analysis of the obtained lithium manganese nickel-containing composite oxide powder (sample), it was confirmed to be Li 1.14 Mn 0.43 Ni 0.43 O 2 . Moreover, the primary particle diameter of the obtained lithium manganese nickel-containing composite oxide powder (sample) was 1.6 ⁇ m, and the tap density was 2.5 g / cm 3 .
- Example 3 Sieve as in Example 1 except that lithium carbonate, electrolytic manganese dioxide, nickel hydroxide, and cobalt oxyhydroxide were weighed and mixed so that the composition was Li 1.06 Mn 0.47 Ni 0.33 Co 0.14 O 2.
- the lower lithium metal composite oxide powder was recovered. As a result of chemical analysis of the recovered sieving lithium metal composite oxide powder, it was confirmed to be Li 1.06 Mn 0.47 Ni 0.33 Co 0.14 O 2 .
- the primary particle size of the sieved lithium metal composite oxide powder was 0.8 ⁇ m, and the tap density was 1.4 g / cm 3 .
- lithium manganese nickel-containing composite oxidation was performed in the same manner as in Example 1 except that lithium carbonate was added to the sieving lithium metal composite oxide powder so that the target composition was Li 1.14 Mn 0.43 Ni 0.30 Co 0.13 O 2.
- a product powder (sample) was obtained.
- the primary particle diameter of the obtained lithium manganese nickel-containing composite oxide powder (sample) was 1.5 ⁇ m, and the tap density was 2.2 g / cm 3 .
- Example 4 Lithium carbonate, electrolytic manganese dioxide, cobalt oxyhydroxide, aluminum hydroxide, and nickel hydroxide were weighed and mixed so that the composition was Li 1.06 Mn 0.37 Ni 0.33 Co 0.14 Al 0.10 O 2
- the sieving lithium metal composite oxide powder was recovered in the same manner as in Example 1. As a result of chemical analysis of the recovered sieving lithium metal composite oxide powder, it was confirmed to be Li 1.06 Mn 0.37 Ni 0.33 Co 0.14 Al 0.10 O 2 .
- the primary particle diameter of the sieving lithium metal composite oxide powder was 1.1 ⁇ m, and the tap density was 2.0 g / cm 3 .
- a composite oxide powder (sample) was obtained.
- the primary particle diameter of the obtained lithium manganese nickel-containing composite oxide powder (sample) was 1.5 ⁇ m, and the tap density was 2.1 g / cm 3 .
- the primary particle size was observed with an SEM (scanning electron microscope HITACHI S-3500N) at an acceleration voltage of 20 kV and a magnification of 5000 times, and 10 particles were randomly selected from the printed photograph. The diameter was measured. The measured length was converted from the scale, and the average value was defined as the primary particle diameter.
- SEM scanning electron microscope HITACHI S-3500N
- TD Tap Density
- SSA specific surface area
- BET method The specific surface area (SSA) of the samples (powder) obtained in the examples and comparative examples was measured as follows. First, 0.5 g of a sample (powder) is weighed in a glass cell for a flow method gas adsorption specific surface area measuring device MONOSORB LOOP (“MS-18” manufactured by Yuasa Ionics Co., Ltd.), and the pretreatment device for the MONOSORB LOOP is used. After replacing the inside of the glass cell with nitrogen gas at a gas amount of 30 mL / min for 5 minutes, heat treatment was performed at 250 ° C. for 10 minutes in the nitrogen gas atmosphere. Then, the sample (powder) was measured by the BET single point method using the MONOSORB LOOP. The adsorbed gas at the time of measurement was a mixed gas of 30% nitrogen: 70% helium.
- the crystal structure is assigned to the trigonal of the space group R3-m, its 3a site is occupied by Li, 3b site by Mn, Co, Ni, and excess Li content x, and the 6c site is O , Oxygen seat occupancy (Occ.) And isotropic temperature factor (Beq.) Are variables, and refined to Rwp ⁇ 5.0 and GOF ⁇ 1.3. Went.
- Rwp and GOF are values obtained by the following formulas (see: “Practice of powder X-ray analysis”, edited by Japan Analytical Chemistry X-ray Analysis Research Roundtable, published by Asakura Shoten. February 2002) 10 days, Table 6.2 of p107).
- Rwp [ ⁇ i wi ⁇ yi-fi (x) 2 ⁇ / ⁇ i wiy i 2 ] 1/2
- Re [(NP) / ⁇ i withi 2 ] 1/2
- GOF Rwp / Re
- wi is a statistical weight
- yi an observed intensity
- fi (x) is a theoretical diffraction intensity
- N is the number of all data points
- P is the number of parameters to be refined.
- NMP N -Methylpyrrolidone
- the positive electrode sheet volume was determined by multiplying the area of the positive electrode sheet obtained above and the thickness of the positive electrode sheet measured using a micrometer (MITUTOYO MDC-30). Next, the weight of the positive electrode itself was determined by subtracting the weight of the Al foil from the weight of the positive electrode sheet. The electrode density was determined by dividing the weight of the positive electrode itself by the positive electrode sheet volume. Table 2 shows relative values (indexes) where the electrode density of Comparative Example 1 is 100.
- the positive electrode sheet obtained above was cut into a size of ⁇ 13 mm to form a positive electrode and dried at 200 ° C. for 6 hours.
- a separator in which lithium metal is cut into a size of ⁇ 15 mm to form a negative electrode, and between the positive electrode and the negative electrode is impregnated with an electrolytic solution in which LiPF 6 is dissolved to 1 mol / L in a carbonate-based mixed solution A 2032 type coin battery (electrochemical evaluation cell) was prepared by placing a porous polyethylene film).
- volume energy density index (initial discharge capacity) x (electrode density) Table 2 shows relative values (indexes) where the electrode density of Comparative Example 1 is 100.
- the primary particle size is grown large in the range of ⁇ 0.15 to 0.15, and then
- the primary particle size of the lithium-excess layered lithium metal composite oxide (OLO) can be sufficiently increased, and the tap density can be increased.
- the volume energy density as an electrode could be increased.
- the electrode density is improved, the charge acceptability is equal to or higher than that, so that it has been found that the battery has good rate characteristics, particularly good charge rate characteristics.
- FIG. 6 it can be seen that the above Examples 1 to 4 are superior in charge acceptance and rate characteristics compared to the comparative example from the difference in the length of the CV charging region. It was.
- Example 4 the general formula Li 1 + x M 1-X O 2 Oite, Co as M, but is made of a composition containing Al alone, in terms of ionic radii and the chemical stability, Co, Al, and Ni, Mg, Ti, Fe, and Nb have common properties. Therefore, even when M contains at least one element selected from the group consisting of Mg, Ti, Fe and Nb, it is considered that the same effect as the sample obtained in Example 4 can be obtained.
Abstract
Description
よって、本発明が提案する製造方法によれば、特に車載用の電池、特に電気自動車(EV:Electric Vehicle)やハイブリッド電気自動車(HEV:Hybrid Electric Vehicle)に搭載する電池の正極活物質として特に優れているリチウムイオン電池用正極材料を作製することができる。
この際、前記リチウム金属複合酸化物Aは、本リチウム過剰型層状リチウム金属複合酸化物を製造する一連の工程で作製することもできるし、また、本リチウム過剰型層状リチウム金属複合酸化物を製造する一連の工程とは別の一連の工程で作製することもできる。さらにまた、他者が作製したリチウム金属複合酸化物Aを使用することもできる。これらの中で、本実施形態では、本リチウム過剰型層状リチウム金属複合酸化物を製造する一連の工程のなかで、前記リチウム金属複合酸化物Aを作製する方法について説明する。
本実施形態の一例に係るリチウム過剰型層状リチウム金属複合酸化物の製造方法(「本製造方法」と称する)は、一般式Li1+xM1-xO2(-0.15以上0.15以下、Mは、Mnを必ず含み、Ni、Co、Al、Mg、Ti、Fe及びNbからなる群から選ばれる少なくとも1種以上の元素を含む。)における前記「Li元素」及び「M元素」の原料を含む原料組成物を焼成して、リチウム金属複合酸化物Aを得る<第1工程>と、第1工程で得られたリチウム金属複合酸化物Aと、リチウム化合物とを混合し、焼成して本リチウム過剰型層状リチウム金属複合酸化物を得る<第2工程>と、を備えた製造方法である。
本実施形態で製造する本リチウム過剰型層状リチウム金属複合酸化物は、一般式Li1+xM1-xO2(x=0.10以上0.33以下、Mは、Mnを必ず含み、Ni、Co、Al、Mg、Ti、Fe及びNbからなる群から選ばれる少なくとも1種以上の元素を含む。)で表わされる、層構造を有するリチウム金属複合酸化物からなる粉体である。
また、前記のように「リチウム金属複合酸化物からなる粉体」と言っても、例えば不純物としてSO4を1.0重量%以下、その他の元素をそれぞれ0.5重量%以下であれば含んでいてもよい。この程度の量であれば、本リチウム過剰型層状リチウム金属複合酸化物の特性にほとんど影響しないと考えられるからである。
「x」が0.10以上であれば、例えば本リチウム過剰型層状リチウム金属複合酸化物をリチウムイオン電池の正極活物質材料として用いた場合に、好ましい充放電容量を得ることができ、0.33以下であれば、好ましい電気化学的活性を得ることができる。
また、M元素中のNi含有量は0~80質量%、中でも20質量%以上或いは70質量%以下、その中でも20質量%以上或いは50質量%以下を占めることが好ましい。
また、M元素中のCo含有量は0~80質量%、中でも20質量%以上或いは70質量%以下、その中でも20質量%以上或いは50質量%以下を占めることが好ましい。
第1工程では、一般式Li1+xM1-xO2で示される前記リチウム金属複合酸化物Aにおける「Li元素」及び「M元素」を含む原料、例えばリチウム原料、マンガン原料、ニッケル原料、コバルト原料などの原料を秤量して混合し、必要に応じて粉砕し、必要に応じて造粒し、焼成し、必要に応じて熱処理し、必要に応じて解砕し、さらに必要に応じて分級して、リチウム金属複合酸化物Aを得るようにすればよい。
リチウム原料としては、例えば水酸化リチウム(LiOH)、炭酸リチウム(Li2CO3)、硝酸リチウム(LiNO3)、LiOH・H2O、酸化リチウム(Li2O)、その他脂肪酸リチウムやリチウムハロゲン化物等を挙げることができる。中でもリチウムの水酸化物塩、炭酸塩、硝酸塩が好ましい。
マンガン原料は、特に限定するものではない。例えば炭酸マンガン、硝酸マンガン、塩化マンガン、二酸化マンガンなどを用いることができ、中でも炭酸マンガン、二酸化マンガンが好ましい。その中でも、電解法によって得られる電解二酸化マンガンが特に好ましい。
コバルト原料は、特に限定するものではない。例えば塩基性炭酸コバルト、硝酸コバルト、塩化コバルト、オキシ水酸化コバルト、水酸化コバルト、酸化コバルトなどを用いることができ、中でも、塩基性炭酸コバルト、水酸化コバルト、酸化コバルト、オキシ水酸化コバルトが好ましい。
その他のM元素の原料、すなわち、Al、Mg、Ti、Fe及びNbの原料としては、これら元素の酸化物、水酸化物、炭酸化物などを用いることができる。
ホウ素化合物としては、ホウ素(B元素)を含有する化合物であればよく、例えばホウ酸或いはホウ酸リチウムを使用するのが好ましい。ホウ酸リチウムとしては、例えばメタ硼酸リチウム(LiBO2)、四硼酸リチウム(Li2B4O7)、五硼酸リチウム(LiB5O8)及び過硼酸リチウム(Li2B2O5)等の各種形態のものを用いることが可能である。
原料の混合方法としては、水や分散剤などの液媒体を加えてスラリー化させて混合する湿式混合方法を採用するのが好ましい。なお、後述するスプレードライ法を採用する場合には、得られたスラリーを湿式粉砕機で粉砕するのが好ましい。但し、乾式粉砕してもよい。
造粒方法は、前工程で混合された各種原料が分離せずに造粒粒子内で分散していれば湿式でも乾式でもよい。
造粒方法としては、押し出し造粒法、転動造粒法、流動造粒法、混合造粒法、噴霧乾燥造粒法、加圧成型造粒法、或いはロール等を用いたフレーク造粒法でもよい。但し、湿式造粒した場合には、焼成前に充分に乾燥させることが必要である。
乾燥方法としては、噴霧熱乾燥法、熱風乾燥法、真空乾燥法、フリーズドライ法などの公知の乾燥方法によって乾燥させればよく、中でも噴霧熱乾燥法が好ましい。噴霧熱乾燥法は、熱噴霧乾燥機(スプレードライヤー)を用いて行なうのが好ましい(本明細書では「スプレードライ法」と称する)。
ただし、共沈法により得られた造粒粉を用いることも可能である。共沈法としては、原料を溶液に溶解した後、pHなどの条件を調整して沈殿させることにより、異なる元素が共存する複合水酸化物の製法を例示できる。
第1工程における焼成は、焼成炉にて、大気雰囲気下、酸素ガス雰囲気下、酸素分圧を調整した雰囲気下、或いは二酸化炭素ガス雰囲気下、或いはその他の雰囲気下において焼成すればよい。中でも、酸素濃度20%以上の雰囲気で焼成するのが好ましい。
焼成時間は、0.5時間~300時間保持するように焼成するのが好ましい。
焼成後の熱処理は、結晶構造の調整が必要な場合に行うのが好ましい。
熱処理は、大気雰囲気下、酸素ガス雰囲気下、酸素分圧を調整して雰囲気下などの酸化雰囲気の条件で熱処理を行ってもよい
また、このような熱処理は、焼成後に室温まで冷却させた後、加熱するようにしてもよいし、また、焼成に引き続き、常温までの降温速度を1.5℃/min以下にするようにして、熱処理を行ってもよい。
焼成後若しくは熱処理後の解砕は、必要に応じて行えばよい。
この際の解砕方法としては、一次粒子径を低減しない手段を選択するのが好ましい。具体的には、オリエントミル解砕や乳鉢を使用した解砕などを挙げることができる。
また、低速および中速回転粉砕機などを用いて解砕してもよい。例えば、1000rpmほどの回転数を有する回転粉砕機が挙げられる。低速および中速回転粉砕機によって解砕すれば、粒子どうしが凝集していたり、焼結が弱かったりする部分を解砕することができ、しかも粒子に歪みが入るのを抑えることができる。
但し、上記解砕方法に限定する訳ではない。
焼成後の分級は、凝集粉の粒度分布調整とともに異物除去という技術的意義があるため、好ましい大きさの目開きの篩を選択して分級するのが好ましい。
第1工程で作製するリチウム金属複合酸化物Aは、一般式Li1+xM1-xO2(x=-0.15以上0.15以下、Mは、Mnを必ず含み、Ni、Co、Al、Mg、Ti、Fe及びNbからなる群から選ばれる少なくとも1種以上の元素を含む。)で表わされるリチウム金属複合酸化物であればよく、層構造を有するリチウム金属複合酸化物であるのが好ましい。
上記一般式において、xが-0.15以上0.15以下の範囲であれば、リチウム金属複合酸化物の一次粒子径を十分に大きくすることができると共に、この範囲のリチウム金属複合酸化物Aにリチウム化合物を加えて焼成することで、好ましい電池特性を実現できるリチウム過剰型層状リチウム金属複合酸化物を製造することができる。
リチウム金属複合酸化物Aの一次粒子径は0.7μm以上であるのが好ましく、中でも0.8μm以上或いは5.0μm以下、その中でも0.9μm以上或いは3.0μm以下であるのが特に好ましい。
リチウム金属複合酸化物Aの一次粒子径が0.7μm以上であれば、最終的に得られる本リチウム過剰型層状リチウム金属複合酸化物の一次粒子径を1.0μm以上とすることができる。
リチウム金属複合酸化物Aの一次粒子径を上記範囲に調整するには、遷移金属の組成比率(例えば、M中に含まれる遷移金属元素比、Li:M比等の組成比率)や原料粒度や焼成条件などによって調整することができる。特に焼成温度を高めることにより一次粒子径を大きくすることができる。
リチウム金属複合酸化物Aのタップ密度が1.3g/cm3以上であれば、最終的に得られる本リチウム過剰型層状リチウム金属複合酸化物のタップ密度を1.9g/cm3以上とすることができる。
リチウム金属複合酸化物Aのタップ密度を上記範囲に調整するには、遷移金属の組成比率(例えば、M中に含まれる遷移金属元素比、Li:M比等の組成比率)や原料粒度や焼成条件などによって調整することができる。特に焼成温度を高めることによりタップ密度を大きくすることができる。
第2工程では、前記第1工程で得られたリチウム金属複合酸化物Aと、リチウム化合物とを混合し、焼成し、必要に応じて熱処理し、必要に応じて解砕し、さらに必要に応じて分級して、本リチウム過剰型層状リチウム金属複合酸化物を得るようにすればよい。
リチウム化合物としては、リチウムを含む化合物であれば特に限定するものではない。中でも水酸化リチウム又は炭酸リチウムを用いるのが好ましい。
リチウム金属複合酸化物Aと、リチウム化合物との混合方法は、リチウム金属複合酸化物Aの一次粒子径を低減しないような方法を採用するのが好ましい。
具体的には、例えばボールミル、SCミル、ミキサーなどの混合方法を挙げることができる。但し、これらの混合方法に限定されるものではない。
第2工程における焼成は、焼成炉にて、大気雰囲気下、酸素ガス雰囲気下、酸素分圧を調整した雰囲気下、或いは二酸化炭素ガス雰囲気下、或いはその他の雰囲気下において焼成すればよい。中でも、酸素濃度20%以上の雰囲気で焼成するのが好ましい。
具体的には、900~1200℃の温度(:焼成炉内の焼成物に熱電対を接触させた場合の温度を意味する。)、好ましくは950℃以上或いは1200℃以下、より好ましくは1000℃以上或いは1100℃以下の温度であるのが好ましい。
焼成時間は、0.5時間~300時間保持するように焼成するのが好ましい。
この際、遷移金属が原子レベルで固溶し単一相を示す焼成条件を選択するのが好ましい。
焼成炉の種類は特に限定するものではない。例えばロータリーキルン、静置炉、その他の焼成炉を用いて焼成することができる。
焼成後の熱処理は、結晶構造の調整が必要な場合に行うのが好ましい。
熱処理は、大気雰囲気下、酸素ガス雰囲気下、酸素分圧を調整して雰囲気下などの酸化雰囲気の条件で熱処理を行ってもよい。
また、このような熱処理は、焼成後に室温まで冷却させた後、加熱するようにしてもよいし、また、焼成に引き続き、常温までの降温速度を1.5℃/min以下にするようにして、熱処理を行ってもよい。
焼成後若しくは熱処理後の解砕は、必要に応じて行えばよい。
この際の解砕方法としては、一次粒子径を低減しない手段を選択するのが好ましい。具体的には、オリエントミル解砕や乳鉢を使用した解砕などを挙げることができる。
また、低速および中速回転粉砕機などを用いて解砕してもよい。例えば、1000rpmほどの回転数を有する回転粉砕機が挙げられる。低速および中速回転粉砕機によって解砕すれば、粒子どうしが凝集していたり、焼結が弱かったりする部分を解砕することができ、しかも粒子に歪みが入るのを抑えることができる。
但し、上記解砕方法に限定する訳ではない。
焼成後の分級は、凝集粉の粒度分布調整とともに異物除去という技術的意義があるため、好ましい大きさの目開きの篩を選択して分級するのが好ましい。
本リチウム過剰型層状リチウム金属複合酸化物の一次粒子径は、本製造方法により、1.0μm以上とすることができる。中でも1.1μm以上あるいは5.0μm以下、その中でも1.2μm以上或いは4.9μm以下とすることができる。
本リチウム過剰型層状リチウム金属複合酸化物の一次粒子径を1.0μm以上にすることにより、電極としての体積エネルギー密度を十分に高めることができる。
本リチウム過剰型層状リチウム金属複合酸化物のタップ密度(「T.D.」とも称する)は、本製造方法により、1.9g/cm3以上とすることができ、中でも2.0g/cm3以上或いは4.4g/cm3以下、その中でも2.1g/cm3以上或いは4.3g/cm3以下とすることができる。
本リチウム過剰型層状リチウム金属複合酸化物のタップ密度が1.9g/cm3以上であれば、電極としての体積エネルギー密度を有効に高めることができる。
タップ密度は、例えば、振とう比重測定器を用いて、試料をガラス製メスシリンダーに入れて、所定のストロークで所定回数タップした場合の粉体充填密度を測定して求めることができる。
本リチウム過剰型層状リチウム金属複合酸化物のレーザー回折散乱式粒度分布測定法により求められる平均粒径(D50)は、本製造方法により、1μm~60μm、中でも2μm以上或いは59μm以下、その中でも特に3μm以上或いは58μm以下とすることができる。
本リチウム過剰型層状リチウム金属複合酸化物のD50が1μm~60μmであれば、電極作製上の観点から好都合である。
ちなみに、レーザー回折散乱式粒度分布測定法は、凝集した粉粒を一個の粒子(凝集粒子)として捉えて粒径を算出する測定方法であり、平均粒径(D50)は、50%体積累積粒径、すなわち体積基準粒度分布のチャートにおいて体積換算した粒径測定値の累積百分率表記の細かい方から累積50%の径を意味する。
本リチウム過剰型層状リチウム金属複合酸化物の比表面積(SSA)は、本製造方法により、0.1~3.0m2/g、中でも0.2m2/g以上或いは2.9m2/g以下、その中でも特に0.3m2/g以上或いは2.8m2/gm以下とすることができる。
本リチウム過剰型層状リチウム金属複合酸化物の比表面積(SSA)が0.1~3.0m2/gであれば、レート特性の観点から好ましい。
本リチウム過剰型層状リチウム金属複合酸化物の比表面積(SSA)を上記範囲に調整するには、本製造方法において、焼成条件(温度、時間、雰囲気など)や焼成後の解砕強度(解砕機回転数など)を調整すればよい。但し、この方法に限定されるものではない。
本リチウム過剰型層状リチウム金属複合酸化物は、本製造方法により、結晶構造XRD(X線回折)の回折パターンにおいて、2θ=20~22°の範囲におけるメインピークの強度が、2θ=16~20°の範囲におけるメインピークの強度に対して4.0%未満、好ましくは3.0%未満、中でも好ましくは2.0%未満とすることができる。
本リチウム過剰型層状リチウム金属複合酸化物の結晶子サイズ、すなわちリートベルト法による測定方法(詳しくは、実施例の欄に記載)により求められる結晶子サイズは、本製造方法により、50nm以上とすることができ、中でも50nm以上或いは300nm以下、その中でも51nm以上あるいは290nm以下とすることができる。
複数の結晶子によって構成され、SEM(例えば3000倍)で観察した際、粒界によって囲まれた最も小さな単位の粒子を、本発明では「一次粒子」という。したがって一次粒子には単結晶及び多結晶が含まれる。
かかる観点から、本リチウム過剰型層状リチウム金属複合酸化物の結晶子サイズは50nm以上であれば、一次粒子をより大きくすることができ、電極としての体積エネルギー密度をより一層高めることができる。
本リチウム過剰型層状リチウム金属複合酸化物は、必要に応じて解砕・分級した後、必要に応じて他の正極材料を混合して、リチウム電池の正極活物質として有効に利用することができる。
例えば、本リチウム過剰型層状リチウム金属複合酸化物と、カーボンブラック等からなる導電材と、テフロン(登録商標)バインダー等からなる結着剤とを混合して正極合剤を製造することができる。そしてそのような正極合剤を正極に用い、負極には例えばリチウムまたはカーボン等のリチウムを吸蔵・脱蔵できる材料を用い、非水系電解質には六フッ化リン酸リチウム(LiPF6)等のリチウム塩をエチレンカーボネート-ジメチルカーボネート等の混合溶媒に溶解したものを用いてリチウム二次電池を構成することができる。但し、このような構成の電池に限定する意味ではない。
なお、「ハイブリッド自動車」とは、電気モータと内燃エンジンという2つの動力源を併用した自動車であり、プラグインハイブリッド自動車も包含する。
また、「リチウム電池」とは、リチウム一次電池、リチウム二次電池、リチウムイオン二次電池、リチウムポリマー電池など、電池内にリチウム又はリチウムイオンを含有する電池を全て包含する意である。
本明細書において「X~Y」(X,Yは任意の数字)と表現する場合、特にことわらない限り「X以上Y以下」の意と共に、「好ましくはXより大きい」或いは「好ましくはYより小さい」の意も包含する。
また、「X以上」(Xは任意の数字)或いは「Y以下」(Yは任意の数字)と表現した場合、「Xより大きいことが好ましい」或いは「Y未満であることが好ましい」旨の意図も包含する。
組成がLi1.15Ni0.58Mn0.27O2となる様に、炭酸リチウムと、電解二酸化マンガンと、水酸化ニッケルとを秤量し、水を加えて混合攪拌して固形分濃度10wt%のスラリーを調製した。
得られたスラリー(原料粉500g)に、分散剤としてポリカルボン酸アンモニウム塩(サンノプコ(株)製 SNディスパーサント5468)を前記スラリー固形分の6wt%添加し、湿式粉砕機で1200rpm、20分間粉砕して平均粒径(D50)を0.5μm以下として粉砕スラリーを得た。
得られた粉砕スラリーを、熱噴霧乾燥機(スプレードライヤー、大川原化工機(株)製「i-8」)を用いて造粒乾燥させた。この際、噴霧には回転ディスクを用い、回転数24000rpm、スラリー供給量12kg/hr、乾燥塔の出口温度100℃となるように温度を調節して造粒乾燥を行なった。造粒粉の平均粒径(D50)は15μmであった。
得られたリチウムマンガンニッケル含有複合酸化物粉末(サンプル)の化学分析を行った結果、Li1.17Ni0.56Mn0.27O2であることが確認された。
組成がLi1.06Ni0.47Mn0.47O2となる様に、炭酸リチウムと、電解二酸化マンガンと、水酸化ニッケルを秤量し、水を加えて混合攪拌して固形分濃度10wt%のスラリーを調製した。
得られたスラリー(原料粉500g)に、分散剤としてポリカルボン酸アンモニウム塩(サンノプコ(株)製 SNディスパーサント5468)を前記スラリー固形分の6wt%添加し、湿式粉砕機で1200rpm、20分間粉砕して平均粒径(D50)を0.5μm以下として、粉砕スラリーを得た。
得られた粉砕スラリーを、熱噴霧乾燥機(スプレードライヤー、大川原化工機(株)製「i-8」)を用いて造粒乾燥させた。この際、噴霧には回転ディスクを用い、回転数24000rpm、スラリー供給量12kg/hr、乾燥塔の出口温度100℃となるように温度を調節して造粒乾燥を行なった。造粒粉の平均粒径(D50)は15μmであった。
回収した篩下リチウム金属複合酸化物粉の化学分析を行った結果、Li1.06Ni0.47Mn0.47O2であることが確認された。
また、篩下リチウム金属複合酸化物粉の一次粒子径は0.9μmであり、タップ密度は1.6g/cm3であった。
得られたリチウムマンガンニッケル含有複合酸化物粉末(サンプル)の化学分析を行った結果、Li1.13Ni0.45Mn0.42O2であることが確認された。
また、得られたリチウムマンガンニッケル含有複合酸化物粉末(サンプル)の一次粒子径は1.2μmであり、タップ密度は2.2g/cm3であった。
実施例1と同様にリチウム金属複合酸化物粉を作製し、同様に篩下リチウム金属複合酸化物粉を得た。得られた篩下リチウム金属複合酸化物粉の化学分析を行った結果、Li1.06Ni0.47Mn0.47O2であることが確認された。得られたリチウム金属複合酸化物粉末(サンプル)の一次粒子径は0.9μmであり、タップ密度は1.6g/cm3であった。
得られたリチウムマンガンニッケル含有複合酸化物粉末(サンプル)の化学分析を行った結果、Li1.14Mn0.43Ni0.43O2であることが確認された。
また、得られたリチウムマンガンニッケル含有複合酸化物粉末(サンプル)の一次粒子径は1.6μmであり、タップ密度は2.5g/cm3であった。
組成がLi1.06Mn0.47Ni0.33Co0.14O2となる様に、炭酸リチウムと、電解二酸化マンガンと、水酸化ニッケルと、オキシ水酸化コバルトを秤量して混合した以外、実施例1同様にして篩下リチウム金属複合酸化物粉を回収した。
回収した篩下リチウム金属複合酸化物粉の化学分析を行った結果、Li1.06Mn0.47Ni0.33Co0.14O2であることが確認された。
また、篩下リチウム金属複合酸化物粉の一次粒子径は0.8μmであり、タップ密度は1.4g/cm3であった。
得られたリチウムマンガンニッケル含有複合酸化物粉末(サンプル)の化学分析を行った結果、Li1.14Mn0.43Ni0.30Co0.13O2であることが確認された。
また、得られたリチウムマンガンニッケル含有複合酸化物粉末(サンプル)の一次粒子径は1.5μmであり、タップ密度は2.2g/cm3であった。
組成がLi1.06Mn0.37Ni0.33Co0.14Al0.10O2となる様に、炭酸リチウムと、電解二酸化マンガンと、オキシ水酸化コバルトと、水酸化アルミニウムと、水酸化ニッケルとを秤量して混合した以外、実施例1同様にして篩下リチウム金属複合酸化物粉を回収した。
回収した篩下リチウム金属複合酸化物粉の化学分析を行った結果、Li1.06Mn0.37Ni0.33Co0.14Al0.10O2であることが確認された。
また、篩下リチウム金属複合酸化物粉の一次粒子径は1.1μmであり、タップ密度は2.0g/cm3であった。
得られたリチウムマンガンニッケル含有複合酸化物粉末(サンプル)の化学分析を行った結果、Li1.14Mn0.34Ni0.30Co0.13Al0.09O2であることが確認された。
また、得られたリチウムマンガンニッケル含有複合酸化物粉末(サンプル)の一次粒子径は1.5μmであり、タップ密度は2.1g/cm3であった。
一次粒子径は、SEM(走査電子顕微鏡HITACHI S‐3500N)を使用し、加速電圧20kV、倍率5000倍にて観察し、印刷した写真からランダムに粒子を10個選び、定規でその一次粒子の短径を測定した。その測定した長さを縮尺より換算し、平均値を一次粒子径とした。
実施例及び比較例で得られたサンプル(粉体)50gを150mlのガラス製メスシリンダーに入れ、振とう比重測定器((株)蔵持科学器械製作所製KRS‐409)を用いてストローク60mmで540回タップした時の粉体充填密度(T.D.)を求めた。
実施例及び比較例で得られたサンプル(粉体)の粒度分布を次のようにして測定した。
レーザー回折粒度分布測定機用試料循環器(日機装株式会社製「Microtorac ASVR」)を用い、サンプル(粉体)を水溶液に投入し、40mL/secの流速中、40wattsの超音波を360秒間照射した後、日機装株式会社製レーザー回折粒度分布測定機「HRA(X100)」を用いて粒度分布を測定し、得られた体積基準粒度分布のチャートからD50を求めた。
なお、測定の際の水溶液には60μmのフィルターを通した水を用い、溶媒屈折率を1.33、粒子透過性条件を反射、測定レンジを0.122~704.0μm、測定時間を30秒とし、2回測定した平均値を測定値として用いた。
実施例及び比較例で得られたサンプル(粉体)の比表面積(SSA)を次のようにして測定した。
先ず、サンプル(粉体)0.5gを流動方式ガス吸着法比表面積測定装置MONOSORB LOOP(ユアサアイオニクス株式会社製「MS‐18」)用ガラスセルに秤量し、前記MONOSORB LOOP用前処理装置にて、30mL/minのガス量にて5分間窒素ガスでガラスセル内を置換した後、前記窒素ガス雰囲気中で250℃10分間、熱処理を行った。その後、前記MONOSORB LOOPを用い、サンプル(粉体)をBET一点法にて測定した。
なお、測定時の吸着ガスは、窒素30%:ヘリウム70%の混合ガスを用いた。
Cu‐Kα線を用いたX線回折装置(ブルカー・エイエックスエス(株)製D8ADVANCE)を使用して、実施例及び比較例で得られたサンプル(粉体)の粉末X線回折測定を行った。この際、FundamentalParameterを採用して解析を行った。回折角2θ=15~120°の範囲より得られたX線回折パターンを用いて、解析用ソフトウエアTopas Version3を用いて行った。
Rwp=[Σiwi{yi-fi(x)2}/Σiwiyi2]1/2
Re=[(N-P)/Σiwiyi2]1/2
GOF=Rwp/Re
但し、wiは統計的重み、yiは観測強度、fi(x)は理論回折強度、Nは全データ点数、Pは精密化するパラメータの数を示している。
(2)6cサイトの等方性温度因子のみを変数として精密化。
(3)3aサイトの等方性温度因子のみを変数として精密化。
Sample disp(mm):Refine
Detector:PSD
Detector Type:VANTEC-1
High Voltage:5616V
Discr.Lower Level:0.45V
Discr.Window Width:0.15V
Grid Lower Level:0.075V
Grid Window Width:0.524V
Flood Field Correction:Disabled
Primary radius:250mm
Secondary radius:250mm
Receiving slit width:0.1436626mm
Divergence angle:0.3°
Filament Length:12mm
Sample Length:25mm
Receiving Slit Length:12mm
Primary Sollers:2.623°
Secondary Sollers:2.623°
Lorentzian,1/Cos:0.01630098Th
Det.1 gain:80.000000
Det.1 discr.1 LL:0.690000
Det.1 discr.1 WW:1.078000
Scan Mode:Continuous Scan
Scan Type:Looked Coupled
Spinner Speed:15rpm
Divergence Slit:0.300°
Start:15.000000
Time per step:1s
Increment:0.01460
♯steps:7152
Generator voltage:35kV
Generator current:40mA
上記のようにして得られたX線回折パターンを用いて、解析用ソフトウエアEVA Version11.0.0.3を用いて、Kα2およびバックグラウンド除去を行った。除去を行ったX線回折パターンを用いて、2θ=20~22°の範囲におけるメインピークのピーク強度と、2θ=16~20°の範囲におけるメインピークのピーク強度を計測し、下記計算式より、表2に示した「XRD強度比」を算出した。
XRDのピーク強度比={(2θ=20~22°の範囲におけるメインピーク強度)/(16~20°の範囲におけるメインピーク強度)}×100
実施例・比較例で得られたリチウムマンガンニッケル含有複合酸化物粉末(サンプル)89wt%と、導電助材としてのアセチレンブラック5wt%と、結着材としてのPVDF6wt%とを混合し、NMP(N-メチルピロリドン)を加えてペースト状に調整した。このペーストを厚さ15μmのAl箔集電体に塗布し、70℃、120℃で乾燥させた。その後、20MPaの圧力でプレスを3度施して正極シートを作製した。
上記で得られた正極シートの面積と、マイクロメータ(MITUTOYO MDC-30)を用いて測定した正極シートの厚みをかけて正極シート体積を求めた。次に、正極シートの重量からAl箔の重量を差し引いて正極自体の重量を求めた。正極自体の重量を正極シート体積で除算して電極密度を求めた。
なお、表2には比較例1の電極密度を100とした相対値(指標)を示した。
上記で得られた正極シートをφ13mmの大きさに切り出して正極とし、200℃、6時間乾燥させた。一方、リチウム金属をφ15mmの大きさに切り出して負極とし、正極と負極の間に、カーボネート系の混合溶液に、LiPF6を1mol/Lになるように溶解させた電解液を含浸させたセパレータ(多孔性ポリエチレンフィルム)を置き、2032型コイン電池(電気化学評価用セル)を作製した。
上記のようにして準備した、2032型コイン電池を用いて次に記述する方法で1サイクルの充放電容量と充放電効率を求めた。すなわち、正極中の正極活物質の含有量から、25℃にて0.2C電流値で、4.9Vまで一定電流値で充電し(CC充電)、4.9Vに達した後、一定電圧値で充電した(CV充電)ときの容量から活物質の総充電容量(mAh/g)を求めた。休止時間を10minとし、次に0.2C電流値で2.0Vまで一定電流値で放電した時の容量から活物質の初期放電容量(mAh/g)を求めた。
初期放電容量(mAh/g)に、上記のようにして測定された電極密度(g/cm3)を乗ずることにより体積エネルギー密度指標(mAh/cm3)を算出した。
体積エネルギー密度指標=(初期放電容量)×(電極密度)
なお、表2には比較例1の電極密度を100とした相対値(指標)を示した。
上記のようにして測定された充電容量より、充電レート特性指標、すなわち充電受入性の指標を算出し、表2に示した。
このようにして算出された充電レート特性指標が小さければ、充電時のレート特性、すなわち充電受入れ性が良好であると評価することができる。この指標により、正極活物質のレート特性が良好であることが推測される。
充電レート特性指標=(CV充電時の容量)/(総充電容量)×100
上記実施例のように、先ずは、Li1+xM1-xO2におけるxの範囲が-0.15~0.15の範囲において、一次粒子径を大きく成長させておき、次に、リチウム化合物を加えて焼成してリチウム過剰型層状リチウム金属複合酸化物を作製したところ、リチウム過剰型層状リチウム金属複合酸化物(OLO)の一次粒子径を十分に大きくすることができ、タップ密度を高めることができ、電極としての体積エネルギー密度を高めることができた。しかも、電極密度が向上したにもかかわらず、充電の受入れ性は同等以上であるため、良好なレート特性、特に良好な充電レート特性を有することが分かった。
また、図6に見られるように、上記実施例1~4は、比較例に比べて、CV充電領域の長さの差からも、充電受け入れ性に優れ、レート特性が良好であることが分かった。
Claims (7)
- 一般式Li1+xM1-xO2(x=0.10以上0.33以下、Mは、Mnを必ず含み、Ni、Co、Al、Mg、Ti、Fe及びNbからなる群から選ばれる少なくとも1種以上の元素を含む。)で表わされるリチウム過剰型層状リチウム金属複合酸化物の製造方法であって、
一般式Li1+xM1-xO2(x=-0.15以上0.15以下、Mは、Mnを必ず含み、Ni、Co、Al、Mg、Ti、Fe及びNbからなる群から選ばれる少なくとも1種以上の元素を含む。)で表わされるリチウム金属複合酸化物と、リチウム化合物とを混合し、焼成してリチウム過剰型層状リチウム金属複合酸化物を得る工程を備えたリチウム過剰型層状リチウム金属複合酸化物の製造方法。 - 一般式Li1+xM1-xO2(x=-0.15以上0.15以下、Mは、Mnを必ず含み、Ni、Co、Al、Mg、Ti、Fe及びNbからなる群から選ばれる少なくとも1種以上の元素を含む。)における「Li元素」及び「M元素」の原料を含む原料組成物を焼成して、一般式Li1+xM1-xO2(x=-0.15以上0.15以下、Mは、Mnを必ず含み、Ni、Co、Al、Mg、Ti、Fe及びNbからなる群から選ばれる少なくとも1種以上の元素を含む。)で表わされるリチウム金属複合酸化物を得る第1工程と、
第1工程で得られたリチウム金属複合酸化物と、リチウム化合物とを混合し、焼成してリチウム過剰型層状リチウム金属複合酸化物を得る第2工程と、を備えた請求項1に記載のリチウム過剰型層状リチウム金属複合酸化物の製造方法。 - 上記リチウム金属複合酸化物の一次粒子径が0.7μm以上であることを特徴とする請求項1又は2に記載のリチウム過剰型層状リチウム金属複合酸化物の製造方法。
- 上記第1工程では、焼成を1回又は2回以上行うことを特徴とする請求項2又は3に記載のリチウム過剰型層状リチウム金属複合酸化物の製造方法。
- 上記第2工程の焼成温度は、上記第1工程の焼成温度よりも高温であることを特徴とする請求項2~4の何れかに記載のリチウム過剰型層状リチウム金属複合酸化物の製造方法。
- 上記第1工程又は上記第2工程又はこれら両方の工程は、1回又は2回以上実施することを特徴とする請求項2~5の何れかに記載のリチウム過剰型層状リチウム金属複合酸化物の製造方法。
- 上記リチウム化合物として、水酸化リチウム又は炭酸リチウムを用いることを特徴とする請求項1~6の何れかに記載のリチウム過剰型層状リチウム金属複合酸化物の製造方法。
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JPWO2015053357A1 (ja) | 2017-03-09 |
GB2536149A (en) | 2016-09-07 |
US9525173B2 (en) | 2016-12-20 |
GB2536149B (en) | 2017-01-25 |
CN105612124B (zh) | 2018-03-23 |
KR20160032246A (ko) | 2016-03-23 |
KR101613862B1 (ko) | 2016-04-20 |
CN105612124A (zh) | 2016-05-25 |
JP5809772B2 (ja) | 2015-11-11 |
US20160254539A1 (en) | 2016-09-01 |
GB201608173D0 (en) | 2016-06-22 |
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