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  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
  • 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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  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
  • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Definitions

• the present invention relates to a lithium composite oxide sintered plate used for a positive electrode of a lithium ion secondary battery and an all-solid-state secondary battery.
• a positive electrode active material layer for a lithium ion secondary battery it is obtained by kneading and molding a powder of a lithium composite oxide (typically, a lithium transition metal oxide) and an additive such as a binder or a conductive agent.
• a powder of a lithium composite oxide typically, a lithium transition metal oxide
• an additive such as a binder or a conductive agent.
• Powder-dispersed positive electrodes are widely known. Since the powder-dispersed positive electrode contains a relatively large amount (for example, about 10% by weight) of a binder that does not contribute to the capacity, the packing density of the lithium composite oxide as the positive electrode active material is low. Therefore, there is a lot of room for improvement in the powder dispersion type positive electrode in terms of capacity and charge / discharge efficiency.
• a liquid electrolyte (electrolyte solution) using a flammable organic solvent as a diluting solvent has been conventionally used as a medium for transferring ions.
• problems such as leakage of the electrolytic solution, ignition, and explosion may occur.
• solid-state batteries are being developed in which solid electrolytes are used instead of liquid electrolytes and all other elements are made of solids. ing. Since the electrolyte of such an all-solid-state battery is solid, there is no concern about ignition, liquid leakage does not occur, and problems such as deterioration of battery performance due to corrosion are unlikely to occur.
• Patent Document 1 (WO2019 / 093222A1) contains an oriented positive electrode plate which is a lithium composite oxide sintered plate having a void ratio of 10 to 50%, Ti, and 0.4 V (against Li / Li +). )
• an all-solid lithium battery including a negative electrode plate capable of inserting and removing lithium ions and a solid electrolyte having a melting point lower than the melting point or decomposition temperature of the oriented positive electrode board or the negative electrode plate is disclosed.
• Various materials such as Li 2 SO 4 ) are disclosed.
• Such a solid electrolyte can be permeated into the voids of the electrode plate as a melt, and strong interfacial contact can be realized. As a result, it is said that the battery resistance and the rate performance at the time of charging / discharging can be remarkably improved, and the yield of battery manufacturing can be significantly improved.
• Patent Document 2 Li p (Ni x , Coy, Mn z ) O 2 (in the formula, 0.9 ⁇ p ⁇ 1.3, 0 ⁇ x ⁇ 0.8, 0 )
• An oriented positive electrode plate having a layered rock salt structure having a basic composition represented by ⁇ y ⁇ 1, 0 ⁇ z ⁇ 0.7, x + y + z 1), a Li-La-Zr-O ceramic material and / or lithium phosphate.
• An all-solid lithium battery including a solid electrolyte layer made of an oxynitride (LiPON) ceramic material and a negative electrode layer is disclosed.
• LiPON oxynitride
• the present inventors have obtained the finding that among the above-mentioned low melting point solid electrolytes, the LiOH / Li 2 SO 4 system solid electrolytes such as 3 LiOH / Li 2 SO 4 exhibit high lithium ion conductivity.
• the amount of active material was increased. It was found that the discharge capacity was lower than the expected theoretical capacity.
• the present inventors have recently reduced the discharge capacity of a lithium composite oxide sintered plate used for the positive electrode of a lithium ion secondary battery by controlling the microstructure (particularly pores) of the lithium composite oxide sintered plate. We obtained the finding that it can be significantly improved.
• an object of the present invention is to provide a lithium composite oxide sintered plate capable of significantly improving the discharge capacity when incorporated as a positive electrode in a lithium ion secondary battery.
• the present invention is a lithium composite oxide sintered plate used for a positive electrode of a lithium ion secondary battery, and the lithium composite oxide sintered plate is a layered plate containing Li, Ni, Co and Mn. Consists of a lithium composite oxide with a rock salt structure, Porosity is 20-40%, The average pore diameter is 3.5 ⁇ m or more, Provided is a lithium composite oxide sintered plate having an interface length of 0.45 ⁇ m or less per unit cross section of 1 ⁇ m 2 .
• All-solid-state secondary batteries are provided, including.
• the "porosity” is the volume ratio of pores in the sintered plate. This porosity can be measured by image analysis of a cross-sectional SEM image of the sintered plate. For example, after the sintered plate is embedded with resin and the cross section is polished by ion milling, the polished cross section is observed with an SEM (scanning electron microscope) to obtain a cross section SEM image (for example, a magnification of 500 to 1000 times), and the obtained SEM is obtained. By analyzing the image, the ratio (%) of the area filled with the resin to the total area of the part of the electrode active material and the part filled with the resin (the part that was originally a pore) is calculated and fired. The pore ratio (%) of the knot may be calculated.
• the porosity may be measured without embedding the sintered plate with resin.
• the porosity of a sintered plate (positive electrode plate taken out from an all-solid secondary battery) in which the pores are filled with the solid electrolyte can be measured with the solid electrolyte still filled.
• the "average pore diameter” is the average value of the diameters of the pores contained in the sintered plate of the electrode. Such “diameter” is typically the length of a line segment (Martin diameter) that divides the projected area of the pore into two equal parts. In the present invention, the “mean value” is preferably calculated on the basis of the number of pieces.
• This average pore diameter can be measured by image analysis of a cross-sectional SEM image of the sintered plate. For example, the SEM image obtained by the above-mentioned porosity measurement is analyzed, and the portion of the sintered plate that is filled with the electrode active material and the portion filled with the resin (the portion that was originally the pores) is separated and then filled with the resin.
• the maximum Martin diameter of each region may be obtained in the region of the portion, and the average value thereof may be used as the average pore diameter of the sintered plate. If the measurement can be performed with a desired accuracy, the average pore diameter may be measured without embedding the sintered plate with resin. For example, the average pore diameter of a sintered plate (positive electrode plate taken out from an all-solid-state secondary battery) in which the pores are filled with the solid electrolyte can be measured with the solid electrolyte still filled.
• the "interface length per 1 ⁇ m 2 unit cross-sectional area" is the total length of the interface of all pores / active materials contained in the unit cross-sectional area per 1 ⁇ m 2 unit cross-sectional area of the sintered plate. be.
• This interface length can be measured by image analysis of a cross-sectional SEM image of the sintered plate. For example, the SEM image obtained by the above-mentioned porosity measurement is analyzed to separate the electrode active material portion and the resin-filled portion (the originally pore-filled portion) of the sintered plate, and then filled with the resin.
• the peripheral length of the entire region that is, the total length of the interface between the portion of the positive electrode active material and the portion filled with the resin
• the entire region analyzed that is, the portion of the positive electrode active material and the resin.
• the perimeter may be divided by the area of the entire analyzed region to obtain the interface length per unit cross-sectional area of 1 ⁇ m 2 . If the measurement can be performed with a desired accuracy, the interface length may be measured without embedding the sintered plate with resin. For example, the interface length of a sintered plate (positive electrode plate taken out from an all-solid-state secondary battery) in which the pores are filled with a solid electrolyte can be measured with the solid electrolyte still filled.
• the lithium composite oxide sintered plate according to the present invention is used for the positive electrode of a lithium ion secondary battery.
• This lithium composite oxide sintered plate is composed of a lithium composite oxide having a layered rock salt structure containing Li, Ni, Co and Mn.
• the lithium composite oxide sintered plate has a porosity of 20 to 40%, an average pore diameter of 3.5 ⁇ m or more, and an interface length of 0.45 ⁇ m or less per unit cross-sectional area of 1 ⁇ m 2 .
• the discharge capacity is significantly improved by controlling the microstructure (particularly pores) of the lithium composite oxide sintered plate. be able to.
• an all-solid lithium battery using a low melting point solid electrolyte such as a LiOH / Li 2 SO 4 system solid electrolyte is known (see, for example, Patent Document 1), and the solid electrolyte acts as a melt in the voids of the electrode plate. Interfacial contact can be realized by infiltrating into. As a result, it is possible to improve the battery resistance and the rate performance at the time of charging / discharging, and also improve the yield of battery manufacturing.
• the discharge capacity becomes lower than the theoretical capacity assumed from the amount of active material.
• the present invention by controlling the microstructure (particularly pores) of the lithium composite oxide sintered plate, it is considered that the above problems are solved or alleviated, and as a result, the discharge capacity is significantly improved. ..
• the unique microstructure having a large average pore diameter and a small interface length per unit cross-section greatly contributes to the improvement of the discharge capacity. It is considered that this is because the microstructure peculiar to the above suppresses the element diffusion between the solid electrolyte and the sintered plate, and alleviates the decrease in Li ion conductivity due to the deterioration of the solid electrolyte.
• the lithium composite oxide sintered plate is composed of a lithium composite oxide having a layered rock salt structure containing Li, Ni, Co and Mn.
• the lithium composite oxide sintered plate has a structure in which a plurality of primary particles composed of a lithium composite oxide having a layered rock salt structure containing Li, Ni, Co and Mn are bonded.
• This lithium composite oxide is also referred to as cobalt-nickel-lithium manganate, and is abbreviated as NCM.
• the layered rock salt structure is a crystal structure in which a lithium layer and a transition metal layer other than lithium are alternately laminated with an oxygen layer sandwiched between them (typically ⁇ -NaFeO type 2 structure: cubic crystal rock salt type structure [111].
• the molar ratio of Li / (Ni + Co + Mn) in the lithium composite oxide is preferably 0.95 to 1.10, more preferably 0.97 to 1.08, and even more preferably 0.98 to 1.05. Is.
• the porosity of the lithium composite oxide sintered plate is 20 to 40%, preferably 20 to 38%, more preferably 20 to 36%, and even more preferably 20 to 33%. Within such a range, when the battery is manufactured, the pores can be sufficiently filled with the solid electrolyte, and the proportion of the positive electrode active material in the positive electrode increases, so that the high energy density of the battery can be achieved. It can be realized.
• the average pore diameter of the lithium composite oxide sintered plate is 3.5 ⁇ m or more, preferably 3.5 to 15.0 ⁇ m, more preferably 3.5 to 10.0 ⁇ m, and even more preferably 3.5 to 8. It is 0.0 ⁇ m.
• the number of solid electrolyte portions solid electrolyte portions located at a distance from the interface
• the element diffusion between the solid electrolyte and the sintered plate is suppressed, the decrease in Li ion conductivity due to the deterioration of the solid electrolyte is alleviated, and the discharge capacity is improved more effectively.
• the interface length per unit cross-sectional area 1 ⁇ m 2 in the lithium composite oxide sintered plate is 0.45 ⁇ m or less, preferably 0.10 to 0.40 ⁇ m, more preferably 0.10 to 0.35 ⁇ m, and further preferably 0. .10 to 0.30 ⁇ m.
• the interface length per unit cross-sectional area 1 ⁇ m 2 in the lithium composite oxide sintered plate is 0.45 ⁇ m or less, preferably 0.10 to 0.40 ⁇ m, more preferably 0.10 to 0.35 ⁇ m, and further preferably 0. .10 to 0.30 ⁇ m.
• the thickness of the lithium composite oxide sintered plate is preferably 30 to 300 ⁇ m, more preferably 50 to 300 ⁇ m, and even more preferably 80 to 300 ⁇ m from the viewpoint of improving the energy density of the battery.
• the lithium composite oxide sintered plate of the present invention may be produced by any method, but preferably (a) preparation of NCM raw material powder, (b). It is manufactured through the production of an NCM green sheet and (c) firing of the NCM green sheet.
• NCM raw material powder is prepared.
• the preferred NCM raw material powder is Li (Ni 0.5 Co 0.2 Mn 0.3 ) O 2 powder or Li (Ni 0.3 Co 0.6 Mn 0.1 ) O 2 powder.
• the Li (Ni 0.5 Co 0.2 Mn 0.3 ) O 2 powder was weighed so that the molar ratio of Li / (Ni + Co + Mn) was 1.00 to 1.30 (Ni 0.5 Co 0 ). .2 Mn 0.3 ) (OH) 2 powder and Li 2 CO 3 powder are mixed and then fired at 700 to 1200 ° C. (preferably 750 to 1000 ° C.) for 1 to 24 hours (preferably 2 to 15 hours). Can be produced by.
• Li (Ni 0.3 Co 0.6 Mn 0.1 ) O 2 powder was weighed so that the molar ratio of Li / (Ni + Co + Mn) was 1.00 to 1.30 (Ni 0.3 ).
• Co 0.6 Mn 0.1 ) (OH) 2 powder and Li 2 CO 3 powder are mixed and then baked at 700 to 1200 ° C (preferably 750 to 1000 ° C) for 1 to 24 hours (preferably 2 to 15 hours). By doing so, it can be preferably produced.
• a large NCM raw material powder having a volume-based D50 particle size of 3 to 20 ⁇ m (preferably 5 to 15 ⁇ m) is used. It is preferable to prepare a small NCM raw material powder having a volume-based D50 particle size of 0.05 to 1 ⁇ m (preferably 0.1 to 0.6 ⁇ m) and use a mixed powder obtained by mixing these.
• the ratio of the large NCM raw material powder to the mixed powders of these two types, large and small, is preferably 50 to 99% by weight, more preferably 70 to 95% by weight.
• the smaller NCM raw material powder may be produced by pulverizing the larger NCM raw material powder by a known method such as a ball mill. At that time, it is preferable to add lithium borate (Li 3 BO 3 , etc.) or lithium sulfate (Li 2 SO 4 ) to the smaller NCM raw material powder for the purpose of promoting sintering. By adding the sintering aid in this way, it becomes easy to realize a desired microstructure (interface length, pore diameter, etc.), and the firing temperature can be lowered as compared with the case where no addition is added.
• the amount of Li 3 BO 3 or the like added to the smaller NCM raw material powder is preferably 0.3 to 69% by weight, more preferably 1.5 to 51, based on the total amount of the mixed powder after the addition of Li 3 BO 3 . % By weight.
• NCM Green Sheet NCM raw material powder (preferably the above-mentioned NCM mixed powder), solvent, binder, plasticizer, and dispersant are mixed to form a paste. After adjusting the viscosity of the obtained paste, an NCM green sheet is produced by molding into a sheet.
• NCM sintered plate Preparation of NCM Sintered Plate
• the NCM green sheet thus produced is cut into a desired size and shape, placed in a firing sheath, and fired.
• the firing rate is 50 to 600 ° C./h (preferably 100 to 300 ° C./h), and the temperature is raised to 800 to 1000 ° C. (preferably 850 to 970 ° C.) for 1 to 24 hours (preferably 2 to 2 to 970 ° C.). It is desirable to do this by holding for 12 hours).
• NCM sintered plate a lithium composite oxide sintered plate
• All-solid-state secondary battery The lithium composite oxide sintered plate according to the present invention is used for the positive electrode of a lithium-ion secondary battery (typically an all-solid-state battery). Therefore, according to a preferred embodiment of the present invention, there is provided an all-solid secondary battery including a positive electrode layer including the lithium composite oxide sintered plate of the present invention, a negative electrode layer, and a LiOH / Li 2SO4 system solid electrolyte. Will be done.
• the negative electrode layer contains a negative electrode active material.
• the LiOH / Li 2 SO 4 system solid electrolyte is interposed between the positive electrode layer and the negative electrode layer as a separator layer, and is also filled in the pores of the lithium composite oxide sintered plate.
• the all-solid-state secondary battery including the lithium composite oxide sintered plate whose microstructure (particularly pores) is controlled as the positive electrode layer is an all-solid-state secondary battery using a conventional LiOH / Li 2 SO 4 system solid electrolyte. It can exhibit a higher discharge capacity than the next battery.
• the negative electrode layer (typically the negative electrode plate) contains the negative electrode active material.
• a negative electrode active material generally used for a lithium ion secondary battery can be used.
• Examples of such general negative electrode active materials include carbon-based materials, metals or metalloids such as Li, In, Al, Sn, Sb, Bi, Si, or alloys containing any of these. ..
• an oxide-based negative electrode active material may be used.
• a particularly preferable negative electrode active material contains a material capable of inserting and removing lithium ions at 0.4 V (vs. Li / Li + ) or higher, and preferably contains Ti.
• the negative electrode active material satisfying such conditions is preferably an oxide containing at least Ti.
• Preferred examples of such a negative electrode active material include lithium titanate Li 4 Ti 5 O 12 (hereinafter, may be referred to as LTO), niobium titanium composite oxide Nb 2 TIO 7 , and titanium oxide TIO 2 .
• LTO and Nb 2 TiO 7 are preferable, and LTO is more preferable.
• LTO is typically known to have a spinel-type structure, other structures may be adopted during charging / discharging. For example, LTO reacts in a two-phase coexistence of Li 4 Ti 5 O 12 (spinel structure) and Li 7 Ti 5 O 12 (rock salt structure) during charging and discharging. Therefore, LTO is not limited to the spinel structure.
• the negative electrode may be in the form of a mixture of a negative electrode active material, an electron conduction aid, a lithium ion conductive material, a binder and the like, which is generally called a mixture electrode, but it may be a sintered plate obtained by sintering a negative electrode raw material powder. It is preferably in the form of. That is, the negative electrode or the negative electrode active material is preferably in the form of a sintered plate. Since the sintered plate does not need to contain an electron conduction aid or a binder, the energy density of the negative electrode can be increased.
• the sintered plate may be a dense body or a porous body, and a solid electrolyte may be contained in the pores of the porous body.
• the porosity of the negative electrode active material or its sintered plate is preferably 20 to 45%, more preferably 20 to 40%, and even more preferably 25 to 35%. If the porosity is within such a range, the pores in the negative electrode active material can be sufficiently filled with the solid electrolyte, and the proportion of the negative electrode active material in the negative electrode increases, so that the energy density of the battery is high. Can be realized.
• the thickness of the negative electrode active material or its sintered plate is preferably 40 to 410 ⁇ m, more preferably 65 to 410 ⁇ m, still more preferably 100 to 410 ⁇ m, and particularly preferably 107 to 270 ⁇ m from the viewpoint of improving the energy density of the battery. be.
• the solid electrolyte is a LiOH / Li 2 SO 4 system solid electrolyte.
• the LiOH / Li 2 SO 4 system solid electrolyte contains a solid electrolyte identified as 3 LiOH / Li 2 SO 4 by X-ray diffraction.
• This preferred solid electrolyte contains 3LiOH ⁇ Li 2 SO 4 as the main phase. Whether or not 3LiOH / Li 2 SO 4 is contained in the solid electrolyte can be confirmed by identifying the X-ray diffraction pattern using 032-0598 of the ICDD database.
• 3LiOH / Li 2 SO 4 refers to a crystal structure that can be regarded as the same as 3LiOH / Li 2 SO 4 , and the crystal composition does not necessarily have to be the same as 3LiOH / Li 2 SO 4 .
• the solid electrolyte contains a dopant such as boron (for example, 3LiOH / Li 2 SO 4 in which boron is dissolved and the X-ray diffraction peak is shifted to the high angle side), the crystal structure is 3LiOH / Li 2 SO. As long as it can be regarded as the same as 4 , it is referred to herein as 3LiOH ⁇ Li 2 SO 4 .
• the solid electrolyte used in the present invention also allows the inclusion of unavoidable impurities.
• the LiOH / Li 2 SO 4 system solid electrolyte may contain a different phase in addition to the main phase of 3LiOH / Li 2 SO 4 .
• the heterogeneous phase may contain a plurality of elements selected from Li, O, H, S and B, or may consist only of a plurality of elements selected from Li, O, H, S and B. May be.
• Examples of the heterogeneous phase include LiOH, Li 2 SO 4 and / or Li 3 BO 3 derived from the raw material. Regarding these heterogeneous phases, it is considered that unreacted raw materials remained when forming 3LiOH / Li2SO4 , but since they do not contribute to lithium ion conduction , the amount is smaller except for Li3BO3 . desirable.
• the heterogeneous phase containing boron such as Li 3 BO 3
• the heterogeneous phase containing boron may be contained in a desired amount because it can contribute to the improvement of the lithium ion conductivity maintenance after holding at a high temperature for a long time.
• the solid electrolyte may be composed of a single phase of 3LiOH / Li 2 SO 4 in which boron is dissolved.
• the LiOH / Li 2 SO 4 system solid electrolyte (particularly 3 LiOH / Li 2 SO 4 ) preferably further contains boron.
• boron By further containing boron in the solid electrolyte identified as 3LiOH / Li 2SO 4 , it is possible to significantly suppress the decrease in lithium ion conductivity even after holding at a high temperature for a long time. Boron is presumed to be incorporated into one of the sites of the crystal structure of 3LiOH / Li2SO4 and improve the stability of the crystal structure with respect to temperature.
• the molar ratio (B / S) of boron B to sulfur S contained in the solid electrolyte is preferably more than 0.002 and less than 1.0, more preferably 0.003 or more and 0.9 or less, still more preferably. It is 0.005 or more and 0.8 or less.
• B / S is within the above range, it is possible to improve the maintenance rate of lithium ion conductivity. Further, when the B / S is within the above range, the content of the unreacted heterogeneous phase containing boron is low, so that the absolute value of the lithium ion conductivity can be increased.
• the LiOH / Li 2 SO 4 system solid electrolyte may be a green compact of a powder obtained by crushing a melt-solidified body, but a melt-solidified body (that is, one solidified after being heated and melted) is preferable.
• the LiOH / Li 2 SO 4 system solid electrolyte is also filled in the pores of the negative electrode layer.
• the thickness of the solid electrolyte layer (excluding the portion that has entered the pores in the positive electrode layer and the negative electrode layer) is preferably 1 to 500 ⁇ m, more preferably 3 to 50 ⁇ m, from the viewpoint of charge / discharge rate characteristics and the insulating property of the solid electrolyte. More preferably, it is 5 to 40 ⁇ m.
• a positive electrode that is, the lithium composite oxide sintered plate of the present invention
• a negative electrode is prepared.
• This can be done by sandwiching a solid electrolyte between the positive electrode and the negative electrode and applying pressure, heating, or the like to integrate the positive electrode, the solid electrolyte, and the negative electrode.
• the positive electrode, the solid electrolyte, and the negative electrode may be bonded by other methods.
• a method of placing a solid electrolyte molded body or powder on one of the electrodes a method of screen-printing a paste of the solid electrolyte powder on the electrode.
• Examples thereof include a method of colliding and solidifying a solid electrolyte powder by an aerosol disposition method or the like using an electrode as a substrate, and a method of depositing a solid electrolyte powder on an electrode by an electrophoresis method to form a film.
• NCM raw material powders 1 to 10 for producing a positive electrode plate were produced. Table 1 summarizes the characteristics of these raw material powders.
• NCM raw material powder 1 Preparation of NCM raw material powder 1
• Commercially available (Ni 0.5 Co 0.2 Mn 0.3 ) (OH) 2 powder (average particle size 9 to 10 ⁇ m) and Li weighed so that the molar ratio of Li / (Ni + Co + Mn) is 1.15.
• 2 CO 3 powder (average particle size 3 ⁇ m) was mixed and then held at 750 ° C. for 10 hours to obtain NCM raw material powder 1.
• the volume-based D50 particle size of this powder was 8 ⁇ m.
• NCM raw material powder 2 [Preparation of NCM raw material powder 2] Add 2.45% by weight of Li 3 BO 3 (relative to the total amount of NCM raw material powder 1 and Li 3 BO 3 ) to the NCM raw material powder 1 and wet pulverize the ball mill to make the volume-based D50 particle size about 0.4 ⁇ m. After adjusting to the above, the mixture was dried to obtain NCM raw material powder 2.
• NCM raw material powder 3 Preparation of NCM raw material powder 3
• NCM raw material powder 4 The volume-based D50 particle size of the NCM raw material powder 1 was adjusted to about 5.5 ⁇ m by wet pulverization with a ball mill, and then dried to obtain the NCM raw material powder 4.
• NCM raw material powder 5 Preparation of NCM raw material powder 5
• 2 CO 3 powder average particle size 3 ⁇ m was mixed and then held at 850 ° C. for 10 hours to obtain NCM raw material powder 5.
• the volume-based D50 particle size of this powder was 6.5 ⁇ m.
• NCM raw material powder 6 Preparation of NCM raw material powder 6
• NCM raw material powder 7 [Preparation of NCM raw material powder 7] Add 16.8% by weight of Li 3 BO 3 to the NCM raw material powder 5 (relative to the total amount of the NCM raw material powder 5 and Li 3 BO 3 ), and wet pulverize the ball mill to make the volume-based D50 particle size about 0.4 ⁇ m. After adjusting to the above, the mixture was dried to obtain NCM raw material powder 7.
• NCM raw material powder 8 The volume-based D50 particle size of the NCM raw material powder 5 was adjusted to about 0.4 ⁇ m by wet pulverization with a ball mill, and then dried to obtain the NCM raw material powder 8.
• NCM raw material powder 9 The volume-based D50 particle size of the NCM raw material powder 5 was adjusted to about 4.3 ⁇ m by wet pulverization with a ball mill, and then dried to obtain the NCM raw material powder 9.
• NCM raw material powder 10 Preparation of NCM raw material powder 10
• Commercially available (Ni 0.3 Co 0.6 Mn 0.1 ) (OH) 2 powder (average particle size 7 to 8 ⁇ m) and Li weighed so that the molar ratio of Li / (Ni + Co + Mn) is 1.15.
• 2 CO 3 powder (average particle size 3 ⁇ m) is mixed and held at 950 ° C. for 10 hours, and the obtained powder is adjusted to a volume standard D50 particle size of about 1.9 ⁇ m by wet grinding with a ball mill and then dried. NCM raw material powder 10 was obtained.
• Example 1 (1) Preparation of positive electrode plate (1a) Preparation of NCM green sheet First, as shown in Table 1, NCM raw material powders 1 and 2 are uniformly mixed at a mixing ratio (weight ratio) of 80:20 to form an NCM mixed powder. I prepared A. This mixed powder A was mixed with a solvent for tape molding, a binder, a plasticizer, and a dispersant. After adjusting the viscosity of the obtained paste, an NCM green sheet was produced by molding it into a sheet on a PET (polyethylene terephthalate) film. The thickness of the NCM green sheet was adjusted so that the thickness after firing was 100 ⁇ m.
• NCM Sintered Plate The NCM green sheet peeled off from the PET film was punched out into a circle with a diameter of 11 mm and placed in a firing sheath. Baking was performed by raising the temperature to 940 ° C. at a heating rate of 200 ° C./h and holding it for 10 hours. The thickness of the obtained sintered plate was about 100 ⁇ m as observed by SEM. An Au film (thickness 100 nm) was formed as a current collector layer on one side of this NCM sintered plate by sputtering. In this way, a positive electrode plate was obtained.
• the thickness and porosity (% by volume) of each of the LTO sintered plates containing no electrolyte were measured as follows. First, the positive electrode plate (or the negative electrode plate) was embedded with resin, and then the cross section was polished by ion milling, and then the polished cross section was observed by SEM to obtain a cross section SEM image. The thickness was calculated from this SEM image.
• the SEM images for porosity measurement were images with a magnification of 1000 times and a magnification of 500 times.
• the obtained image is binarized using image analysis software (Image-Pro Premier manufactured by Media Cybernetics), and the positive electrode active material (or negative electrode active material) in the positive electrode plate (or negative electrode plate) is subjected to binarization treatment.
• Porosity of the positive electrode plate (or negative electrode plate) by calculating the ratio (%) of the area filled with resin to the total area of the part filled with resin and the part filled with resin (the part that was originally pores). It was set to (%).
• the threshold value for binarization was set using Otsu's binarization as a discriminant analysis method.
• the porosity of the positive electrode plate is as shown in Table 2, and the porosity of the negative electrode plate was 38%.
• the average pore diameter was measured as follows. Using image analysis software (Image-Pro Premier manufactured by Media Cybernetics), binarization processing is performed, and the positive electrode plate (or negative electrode plate) is filled with a portion of the positive electrode active material (or negative electrode active material) and a resin. The part (the part that was originally a pore) was cut out. Then, in the region of the portion filled with the resin, the maximum Martin diameter of each region was obtained, and the average value thereof was taken as the average pore diameter ( ⁇ m) of the positive electrode plate (or the negative electrode plate).
• the average pore diameter of the positive electrode plate is as shown in Table 2, and the average pore diameter of the negative electrode plate was 2.1 ⁇ m.
• the inductively coupled plasma is the molar ratio Li / (Ni + Co + Mn) of the Li content to the total content of Ni, Co and Mn in the positive electrode plate produced in (1) above. It was calculated from the measurement result of the metal element analysis by the emission spectroscopic analysis method (ICP-AES method). The results are shown in Table 2.
• Example 2 In the preparation of the positive electrode plate of (1) above, instead of 1) mixed powder A, NCM mixed powder B containing NCM raw material powders 1 and 3 shown in Table 1 in a blending ratio (weight ratio) of 90:10 is used. A positive electrode plate and a battery were produced in the same manner as in Example 1 except that the firing temperature was 950 ° C. and various evaluations were performed.
• Example 3 In the preparation of the positive electrode plate of (1) above, instead of 1) mixed powder A, NCM mixed powder C containing NCM raw material powders 5 and 6 shown in Table 1 in a blending ratio (weight ratio) of 90:10 is used. A positive electrode plate and a battery were produced in the same manner as in Example 1 except that the firing temperature was 920 ° C. and various evaluations were performed.
• Example 4 In the production of the positive electrode plate of (1) above, the positive electrode plate and the battery were produced in the same manner as in Example 3 except that the firing temperature was set to 950 ° C., and various evaluations were performed.
• Example 5 In the preparation of the positive electrode plate of (1) above, instead of 1) the mixed powder A, the NCM mixed powder D containing the NCM raw material powders 5 and 6 shown in Table 1 in a blending ratio (weight ratio) of 95: 5 is used. A positive electrode plate and a battery were produced in the same manner as in Example 1 except that the firing temperature was 920 ° C. and various evaluations were performed.
• Example 6 In the production of the positive electrode plate of (1) above, the positive electrode plate and the battery were produced in the same manner as in Example 5 except that the firing temperature was set to 950 ° C., and various evaluations were performed.
• Example 7 In the production of the positive electrode plate of (1) above, instead of 1) the mixed powder A, the NCM mixed powder E containing the NCM raw material powders 5 and 7 shown in Table 1 in a blending ratio (weight ratio) of 95: 5 is used. A positive electrode plate and a battery were produced in the same manner as in Example 1 except that the firing temperature was 920 ° C. and various evaluations were performed.
• Example 8 In the production of the positive electrode plate of (1) above, the positive electrode plate and the battery were produced in the same manner as in Example 7 except that the firing temperature was set to 950 ° C., and various evaluations were performed.
• Example 9 In the production of the positive electrode plate of (1) above, instead of 1) the mixed powder A, the NCM mixed powder F containing the NCM raw material powders 5 and 8 shown in Table 1 in a blending ratio (weight ratio) of 90:10 is used. A positive electrode plate and a battery were produced in the same manner as in Example 1 except that the firing temperature was 950 ° C. and various evaluations were performed.
• Example 10 In the preparation of the positive electrode plate of (1) above, instead of 1) the mixed powder A, the NCM mixed powder G containing the NCM raw material powders 5 and 8 shown in Table 1 in a blending ratio (weight ratio) of 95: 5 is used. A positive electrode plate and a battery were produced in the same manner as in Example 1 except that the firing temperature was 950 ° C. and various evaluations were performed.
• Example 11 In the production of the positive electrode plate of (1) above, the positive electrode plate and the battery were produced in the same manner as in Example 10 except that the firing temperature was set to 970 ° C., and various evaluations were performed.
• Example 12 (comparison) Examples of the above-mentioned (1) preparation of the positive electrode plate, except that 1) only the NCM raw material powder 4 shown in Table 1 was used instead of the mixed powder A, and 2) the firing temperature was set to 920 ° C. A positive electrode plate and a battery were produced in the same manner as in No. 1, and various evaluations were performed.
• Example 13 (comparison) Examples of the above-mentioned (1) preparation of the positive electrode plate, except that 1) only the NCM raw material powder 9 shown in Table 1 was used instead of the mixed powder A, and 2) the firing temperature was set to 920 ° C. A positive electrode plate and a battery were produced in the same manner as in No. 1, and various evaluations were performed.
• Example 14 (comparison) Examples of the above-mentioned (1) preparation of the positive electrode plate, except that 1) only the NCM raw material powder 10 shown in Table 1 was used instead of the mixed powder A, and 2) the firing temperature was set to 890 ° C. A positive electrode plate and a battery were produced in the same manner as in No. 1, and various evaluations were performed.
• Example 15 (comparison) In the production of the positive electrode plate of (1) above, the positive electrode plate and the battery were produced in the same manner as in Example 14 except that the firing temperature was set to 920 ° C., and various evaluations were performed.
• Table 2 shows the specifications of the positive electrode plates produced in each example and the evaluation results of the cells.
• the charge / discharge characteristics were compared under the same rate conditions, the discharge capacity measured in Example 13 (comparison) was set to 100, and relative values were calculated and shown in Table 2.
• the batteries of Examples 1 to 11 using the lithium composite oxide sintered plate satisfying the requirements of the present invention have a significantly higher discharge capacity than the batteries of Examples 12 to 15 (comparative example) not satisfying the requirements of the present invention. showed that. This is because the place where the positive electrode layer and the solid electrolyte cause a side reaction is reduced by reducing the interface length, and the solid electrolyte part (away from the interface) which is less susceptible to deterioration due to the side reaction due to the large average pore diameter. It is considered that this is due to the increase in the solid electrolyte part) at a distance. It is considered that this alleviates the decrease in Li ion conductivity due to the deterioration of the solid electrolyte, leading to a significant improvement in the rate characteristics or the discharge capacity.

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