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    • 专利摘要:
    The present invention relates to a grenade type ion-conducting oxide configured to inhibit the formation of lithium carbonate on the surface of its crystal particles, and a method for producing a sintered oxide electrolyte body using the ion-conducting oxide. grenade type. the conductive oxide of grenade ions represented by a general formula (lix-3y-z, ey, hz) lamßo¿ (where e is at least one element type selected from the group consisting of al, ga, fe and si; l is at least one element type selected from an alkaline earth metal and a lanthanide element: m is at least one element type selected from a transition element that has six coordinates with oxygen and typical elements in the groups. 12 to 15 of the periodic table: 3 = x? 3y - z = 7; = 0 = y <0.22; 0 = z = 2.8; 2.5 = ¿= 3.5; 1.5 = ¿= 2,5; and 11 = ¿= 13), where a half width of a diffraction peak having a higher intensity and which is observed at a diffraction angle (2¿) in the range of 29 ° to 32 ° as a result X-ray diffraction measurement using cuka radiation is 0.164 ° or less.
    公开号:BR102018068993A2
    申请号:R102018068993-2
    申请日:2018-09-18
    公开日:2019-04-16
    发明作者:Shingo Ohta
    申请人:Toyota Jidosha Kabushiki Kaisha；
    IPC主号:
    专利说明:

    “GRENADE TYPE ION CONDUCTIVE OXIDE AND METHOD FOR
    PRODUCE SINTERIZED BODY OF OXIDE ELECTROLYTE ”
    FIELD OF TECHNIQUE [001] The description refers to an ion-conducting oxide of the garnet type and a method for producing a sintered body of oxide electrolyte.
    BACKGROUND OF THE INVENTION [002] Recently, as a material for a solid electrolyte, attention is drawn to an ion-conducting oxide of the garnet type comprising at least Li, La, Zr and O (hereinafter it can be called LLZ).
    [003] When a solid electrolyte ceramic material of the garnet type or similar to the garnet is left in the air, its ionic conductivity is less than the ionic conductivity shortly after the material is synthesized or sintered, and the material cannot exert its excellent performance inherent in the maximum degree. To solve the problem, for example, Patent Literature 1 describes a method to recover the decreased ionic conductivity by heating a garnet-like or garnet-like solid electrolyte ceramic material comprising at least Li, La, Zr and O in a range of temperatures of 650 ° C or more in an inert gas atmosphere.
    [004] As a material with high proton conductivity and heat resistance, Patent Literature 2 describes an ion-conducting oxide of the garnet type, in which part of the Li atoms has been replaced by H atoms.
    Patent Literature 1: Japanese Patent Application subject to public inspection (JP-A) No. 2013-219017
    Patent Literature 2: JP-A No. 2012-096940
    Patent Literature 1: Solid State Ionics 292 (2016) 122 to 129 [005] As described in Patent Literature 1, garnet ion-conducting oxide is known to have a problem of decreased conductivity
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    2/33 ionic in the air or in dry air. One of the causes of the problem is that the ion-conducting oxide of the garnet type reacts with CO2 to form lithium carbonate (L12CO3) on the surface of the oxide crystal particles.
    [006] This problem can be avoided by manipulating the ion-conducting oxide of the grenade type only in a dry chamber. However, this presents problems such as low workability, low productivity and high cost of production.
    SUMMARY OF THE INVENTION [007] In view of the above circumstance, an ion-conducting oxide of the garnet type configured to inhibit the formation of lithium carbonate on the surface of its crystal particles, and a method for producing a sintered body of oxide electrolyte using Garnet-ion-conducting oxide will be described below.
    [008] In a first modality, an ion-conducting oxide of the garnet type is provided, represented by a general formula (Lix-3y-z, Ey, Hz) LaMpOy (where E is at least one type of element selected from the group consisting of Al, Ga, Fe and Si; L is at least one type of element selected from an alkaline earth metal and a lanthanide element: M is at least one type of element selected from a transition element that has six coordination with oxygen and typical elements in groups 12 to 15 of the periodic table: 3 <x - 3y - z <7; <0 <y <0.22; 0 <z <2.8; 2.5 <α <3 , 5; 1.5 <β <2.5; and 11 <γ <13), [009] where a half width of a diffraction peak that has a higher intensity and is observed at a diffraction angle (2θ ) in a range of 29 ° to 32 ° as a result of measuring X-ray diffraction using CuKa radiation, is 0.164 ° or less.
    [010] The element L can be La, and the element M can be at least one type of element selected from the group consisting of Zr, Nb and Ta.
    [011] The half width can be from 0.092 ° to 0.164 °.
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    3/33 [012] In another embodiment, a method is provided to produce a body sintered by oxide electrolyte, the method comprising:
    [013] prepare crystal particles of an ion-conducting oxide of the garnet type represented by a general formula (Lix-3y-z, Ey, Hz) LaMpOy (where E is at least one type of element selected from the group consisting of of Al, Ga, Fe and Si; L is at least one type of element selected from an alkaline earth metal and a lanthanide element: M is at least one type of element selected from a transition element that can have six coordinations with oxygen and typical elements in groups 12 to 15 of the periodic table; 3 <x - 3y - z <7; <0 <y <0.22; 0 <z <2.8; 2.5 <α <3, 5; 1.5 <β <2.5; and 11 <γ <13), where a half width of a diffraction peak that has a higher intensity and is observed at a diffraction angle (2θ) in a range 29 ° to 32 ° as a result of measuring X-ray diffraction using CuKa radiation, is 0.164 ° or less, prepare a flow containing lithium, and [014] sinter a mixture of the flow and the p crystal articles of ion-conducting oxide of the garnet type by heating to a temperature equal to or greater than a melting point of the flow.
    [015] The element L can be La, and the element M can be at least one type of element selected from the group consisting of Zr, Nb and Ta.
    [016] According to the described modalities, the ion-conducting oxide of the garnet type configured to inhibit the formation of lithium carbonate on the surface of its crystal particles, and a method to produce the sintered body of oxide electrolyte using the oxide conductor of grenade type ions can be provided.
    DESCRIPTION OF THE DRAWINGS
    In the attached drawings,
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    4/33 [017] Figure 1 is a schematic view showing the scheme of a solid phase flow method used in one modality.
    [018] Figure 2 shows an overview of an XRD pattern of LLZ crystal particles from Example 3 and Example 6.
    [019] Figure 3 shows an enlarged image of a peak at 30.8 ° shown in Figure 2.
    [020] A Figure 4 show results in spectrometry pastas of Example 1.[021] A Figure 5 show results in spectrometry in pastas of Example 6.[022] A Figure 6 show results in spectrometry in pastas of Example 9.[023] A Figure 7 show results in spectrometry in pastas of
    Comparative Example 1.
    [024] Figure 8 is a view in which half the width of the LLZ crystal particles produced in each example and the amount of H in the composition of the LLZ crystal particles are represented.
    [025] Figure 9 is a view showing the results of the AC impedance measurement in Reference Example 1.
    [026] Figure 10 is a view showing the results of the AC impedance measurement in Reference Example 2.
    [027] Figure 11 is a view showing the results of the AC impedance measurement in Reference Example 3.
    [028] Figure 12 is a view showing the results of the AC impedance measurement in Reference Example 4.
    DETAILED DESCRIPTION
    1. Garnet ion-conducting oxide
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    5/33 [029] The ion-conducting oxide of the garnet type of the described modalities is an ion-conducting oxide of the garnet type represented by a general formula (Lix3y-z, Ey, Hz) LaMpOy (where E is at least one type of element selected from the group consisting of Al, Ga, Fe and Si; L is at least one type of element selected from an alkaline earth metal and a lanthanide element: M is at least one type of element selected from an transition element that has six coordinations with oxygen and typical elements in groups 12 to 15 of the periodic table: 3 <x - 3y - z <7; <0 <y <0.22; 0 <z <2.8; 2 , 5 <α <3.5; 1.5 <β <2.5; and 11 <γ <13), [030] where a half width of a diffraction peak that has a higher intensity and is observed in a diffraction angle (2θ) in the range of 29 ° to 32 ° as a result of measuring X-ray diffraction using CuKa radiation, is 0.164 ° or less.
    [031] Garnet-ion-conducting oxide (LLZ) is, for example, represented by the chemical formula Li7La3Zr2O12, and more than half of its cations are lithium ions. Therefore, the concentration of lithium ions in the LLZ is very high.
    [032] In addition, since the conductivity of LLZ lithium ions is very high, lithium ions can move very easily. In addition, as lithium is one of the most basic metals, LLZ has very high reducing properties (reactivity).
    [033] Due to the above reason, LLZ causes chemical reactions represented by the following formulas (1) and (2):
    Formula (1)
    Li7La3Zr2O12 + aH2O + aCO2 + 1 / 2aO2 (Li7-a, Ha) La3Zr2O12 + aLiOH +
    1 / 2aCO2 + 1 / 2aO2
    Formula (2)
    Li7La3Zr2O12 + aH2O + aCO2 + 1 / 2aO2 (Li7-a, Ha) La3Zr2O12 + 1 / 2aLi2CO3 +
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    6/33
    1 / 2aH2O [034] For the chemical reaction represented by formula (2), it is thought that the reaction can be controlled to some extent by controlling the state of Li involved in the reaction on the surface of the LLZ crystal particles.
    [035] The reason is considered as follows: the lithium involved in the reaction with H2O or CO2 in the air, remains on the surface of the LLZ crystal particles, so that the lithium is still under the influence of the LLZ crystal, while it is on to H2O or CO2.
    [036] Furthermore, it is thought that when the affinity (attraction) of lithium in the LLZ is greater than the binding force between H2O or CO2 and lithium in formula (2), lithium can be inhibited from being extracted from LLZ and the formation of lithium carbonate (L12CO3) can be inhibited.
    [037] As a result of considerable research, it has been found that the formation of lithium carbonate on the surface of LLZ crystal particles can be inhibited by increasing the crystallinity of LLZ.
    [038] It is widely known that materials with low crystallinity show deliquescence. For example, crystalline materials such as lithium ion conducting sulfide glass and lithium ion conducting oxide glass (eg, U3PO4) generally exhibit deliquescence in the air. This is because the lithium present in an unstable position on the glass reacts preferentially with H2O.
    [039] Therefore, it is thought that deliquescence can be inhibited by increasing the crystallinity of crystalline materials.
    [040] Just like inhibiting deliquescence, lithium ions can be stably present in the particles of the LLZ crystal increasing the crystallinity of the LLZ. As a result, it is assumed that the reaction between lithium ions and CO2 on the surface of the LLZ crystal particles can be inhibited, and the formation of lithium carbonate on the surface of the LLZ crystal particles can be
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    7/33 be inhibited.
    [041] Therefore, since the garnet ion-conducting oxide of the described modalities has high crystallinity, it can inhibit the formation of lithium carbonate on the surface of the crystal particles.
    [042] The crystallinity of the garnet ion-conducting oxide can be assessed by the half width of a peak observed by X-ray diffraction.
    [043] For the garnet ion-conducting oxide of the described modalities, the upper limit of the half width of a diffraction peak that has the highest intensity and which is observed at a diffraction angle (2θ) in a range of 29 ° to 32 ° as a result of measuring X-ray diffraction using CuKa radiation, it can be 0.164 ° or less. From the point of view of further inhibition of the formation of lithium carbonate on the surface of the particles of the LLZ crystal, it may be 0.154 ° or less. The lower limit of the half width is not particularly limited and can be greater than 0 °. Considering the detection limit of an X-ray diffractometer, it can be 0.084 ° or more, or it can be 0.092 ° or more.
    [044] When the composition of Li in the general formula (Lix-3y-z, Ey, Hz) LaMpOy is x - 3y - z> 7, it is assumed that the crystalline structure of the LLZ is changed from a cubic crystalline structure to a tetragonal crystalline structure, thus impairing the symmetry of the crystal and decreasing the conductivity of lithium ions.
    [045] However, when the composition of Li in the general formula is x - 3y - z <3, it is assumed that the potential of the 96h site (a specific site in which the Li in the crystalline structure of the LLZ will be incorporated) increases and makes it difficult the incorporation of Li into the crystal, thus decreasing Li's occupation and decreasing the conductivity of lithium ions.
    [046] The element E is an element that has four coordinations as with Li and has an ionic radius close to that of Li (Li: 0.59 Á).
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    8/33 [047] In the described modalities, the LLZ can comprise, as the element E, at least one type of element selected from the group consisting of Al, Ga, Fe and Si, at least one type of element selected from from the group consisting of Al and Ga, or an element Al.
    [048] The elements Al, Ga, Fe and Si as the element E, are the main elements that are contained in oxides of the garnet type that are well known as gems.
    [049] Since Al, Ga, Fe and Si are elements contained in gems, such as garnet, they can be replaced by Li at Li's site.
    [050] The replacement of the Li site by the elements Al, Ga, Fe, Si, etc., has a stabilizing effect on the crystalline structure.
    [051] On the other hand, it is assumed that the substitution by the elements Al, Ga, Fe, Si, etc., makes the property of the crystal closer to the garnet gem (the Mohs hardness of the gem is 7.5).
    [052] As a result, it is assumed that, once large amounts of Al, Ga, Fe, Si, etc. are incorporated, instead of plastic deformation, the particles cause cracking.
    [053] Therefore, it is assumed that, although the addition of small amounts of Al, Ga, Fe, Si, etc., is allowed in order to stabilize the crystalline structure, there is an upper limit to cause plastic deformation.
    [054] In the described modalities, since element E in the general formula is contained in a range of 0 <y <0.22, the stability of the crystalline structure of the LLZ can be increased, and the synthesis of the LLZ can be easy.
    [055] From the point of view of increasing the conductivity of lithium ions, element E in the general formula can be contained in a range of 0 <y <0.12 or in a range of 0 <y <0.04 .
    [056] In the described modalities, the element L contained in the LLZ is not
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    9/33 particularly limited, provided that it is at least one type of element selected from the group consisting of an alkaline earth metal and a lanthanide element. This is because a small change in the crystal structure and high ionic conductivity can be obtained. As used here, alkaline earth metal is a concept that covers Ca, Sr, Ba and Ra. The element L can be La, since the ionic conductivity can be increased even more.
    [057] In the described modalities, as long as the L element of the general formula is contained in a range of 2.5 <α <3.5, a change in the crystalline structure of the LLZ is small, and the conductivity of the lithium ions in the LLZ can be increased. Α can be 3.
    [058] In the described modalities, the element M contained in the LLZ is not particularly limited, as long as it is at least one type of element selected from the group consisting of a transition element that can have six coordinations with oxygen and typical elements in groups 12 to 15 of the periodic table. This is because a change in the crystalline structure of the LLZ is small, and the ionic conductivity of the LLZ is high.
    [059] In the described modalities, as long as the element M of the general formula is contained in a range of 1.5 <β <2.5, a change in the crystalline structure of the LLZ is small, and the conductivity of the lithium ions of the LLZ can be increased. Β can be 2.
    [060] Like element M, examples include, but are not limited to, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn , Cd, Al, Ga, Ge, Sn, Sb and Bi.
    [061] Of these elements, element M can be at least one type of element selected from the group consisting of Zr, Nb and Ta, or it can be a combination of Zr with Nb or Ta, from the point of view of obtaining a relatively large ionic radius, inhibiting a shrinkage in the lattice constant
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    10/33 crystalline, and inhibiting a decrease in the conductivity of the lithium ions of the LLZ, and from the point of view that similar effects can be obtained, since the elements have similar physical and / or chemical properties.
    [062] The relationship between Zr and Nb or Ta in the composition of LLZ influences the physical value of the conductivity of lithium ions and the crystalline structure. As the ratio of Zr increases, the amount of Li increases.
    [063] In general, when the total amount of Li and H in the LLZ composition is greater than 6.75, the crystal structure changes from a cubic crystal structure to a tetragonal crystal structure. In general, LLZ is said to have greater ionic conductivity when the crystalline structure is a cubic crystalline structure.
    [064] Therefore, when the amount of Zr in the composition is less, the total amount of Li and H in the composition of the LLZ is small and makes it easy for the LLZ to have a cubic crystalline structure.
    [065] However, when the amount of Zr in the composition is decreased, there is a shrinkage in the trellis volume. As a result, the ion conduction path for the lithium ions that can move in the crystal is decreased in size and therefore in the conductivity of the LLZ's lithium ions.
    [066] Due to the above reason, when the element M is the combination of Zr with Nb or Ta, the amount of Zr in the composition can be in the range of 1.4 to 1.75.
    [067] On the other hand, when the element M is the combination of Zr with Nb or Ta, the amount of Nb or Ta in the composition can be in the range of 0.25 to 0.6.
    [068] In the described modalities, as long as the O oxygen contained in the LLZ composition is in a range of 11 <γ <13, a change in the crystalline structure of the LLZ may be small. The γ can be 12.
    [069] Like the ion-conducting oxide of the grenade type before part of the lithium ions is replaced by hydrogen ions (hereinafter called oxide
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    11/33 conductor of garnet ions before partial replacement of hydrogen ions), examples include, but are not limited to, Li7La3Zr2O12,
    Li6.4La3Zr1.4Nb0.6O12, Li6.5La3Zr1.7Nb0.3O12, Li6.8La3Zr1.7Nb0.3O12, (Li6.2Al0.2) La3Zr1.7Nb0.3O12, (Li5.8Al0.2) La3 (Zr1.4Nb0. 6) O12, (Li6.1Al0.13) La3 (Zr1.4Nb0.6) O12, (Li6.3Al0.02) La3 (Zr1.4Nb0.6) O12, and (Li6.2Ga0.2) La3Zr1.7Nb0. 3O12.
    [070] In the LLZ of the described modalities, the amount of hydrogen ions (protons) incorporated by the substitution is not particularly limited, as long as oz in the general formula (Lix-3y-z, Ey, Hz) LaMpOy is in a range of 0 <z <2.8. This is because a change in the crystal structure is small.
    [071] The garnet ion-conducting oxide of the described modalities has high crystallinity, even if it is not subjected to proton substitution (even if z is 0). Therefore, the ion-carrying oxide of the garnet type can inhibit the formation of lithium carbonate on the surface of the crystal particles.
    [072] The method for replacing part of the lithium ions in the LLZ of the modalities described by hydrogen ions is not particularly limited. Like the method, examples include, but are not limited to, using an LLZ powder as a raw material and stirring and / or immersing the powder in pure water for several minutes to 5 days at room temperature.
    [073] The amount of hydrogen ions incorporated by the substitution can be estimated by inductively coupled plasma (ICP) analysis of the LLZ powder before and after the substitution.
    [074] That is, the amount of hydrogen ions in the LLZ cannot be quantified by inductively coupled plasma (ICP) analysis; however, the amounts of lithium ions in the LLZ before and after the replacement of the hydrogen ions can be quantified.
    [075] Therefore, the amount of change in lithium ions before and after replacement can be calculated from the amounts of lithium ions in the
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    12/33
    LLZ before and after replacement. From the amount of change in lithium ions, it is possible to estimate the amount of lithium ions replaced by hydrogen ions.
    [076] In general, at normal temperature, the garnet-ion-conducting oxide of the described modalities is present as crystals. The crystals can be in a particulate form.
    [077] The average diameter of the crystal particles of the ion-carrying oxide of the garnet type is not particularly limited. It can be in the range of 0.1 pm to 100 pm.
    [078] In the embodiments described, unless otherwise stated, “average particle diameter” means an average particle diameter of 10% by volume (hereinafter “D10”) obtained from a particle size distribution measured with a laser diffraction / dispersion particle size distribution analyzer.
    [079] The garnet-ion-conducting oxide of the described modalities can be used as an electrode material for various types of batteries, an electrolyte material, etc. It can be used as an electrode material for fully solid-state batteries, an electrolyte material, etc.
    2. The method for producing the sintered oxide electrolyte body [080] The method for producing a sintered oxide electrolyte body according to the described modalities, comprises:
    [081] prepare crystal particles of an ion-conducting oxide of the garnet type represented by a general formula (Lix-3y-z, Ey, Hz) LaMpOy (where E is at least one type of element selected from the group consisting of of Al, Ga, Fe and Si; L is at least one type of element selected from an alkaline earth metal and a lanthanide element: M is at least one type of element selected from a transition element that has six coordinations with O
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    13/33 oxygen and typical elements in groups 12 to 15 of the periodic table: 3 <x - 3y - z <
    7; <0 <y <0.22; 0 <z <2.8; 2.5 <α <3.5; 1.5 <β <2.5; and 11 <γ <13), where a half width of a diffraction peak which has a higher intensity and which is observed at a diffraction angle (2θ) in the range of 29 ° to 32 ° as a result of the diffraction measurement of X-rays using CuKa radiation, is 0.164 ° or less, prepare a flow containing lithium, and [082] sinter a mixture of the flow and the crystal particles of the ion-conducting oxide grenade type by heating to a temperature equal to or greater than one melting point of the flow.
    [083] As described in Non-Patent Literature 1, it is considered necessary to heat to 600 ° C or more to decompose the lithium carbonate formed on the surface of the LLZ crystal particles. If the sintered oxide electrolyte body is produced while lithium carbonate remains on the surface of the LLZ crystal particles, a decrease in the conductivity of lithium ions can be caused by lithium carbonate. Therefore, it is common to heat the LLZ crystal particles to a temperature of 600 ° C or more, or the LLZ crystal particles can be heated to a temperature of 650 ° C or more.
    [084] However, the garnet-ion-conducting oxide of the described modalities can inhibit the formation of lithium carbonate on the surface of the crystal particles. Therefore, using the garnet ion-conducting oxide of the described modalities, the decomposition treatment with lithium carbonate at 600 ° C or more becomes unnecessary.
    [085] In the method to produce the sintered oxide electrolyte body according to the described modalities, the crystal particles of LLZ subjected to partial replacement by protons, are mixed with the flow containing lithium. By heating the mixture thus obtained, the protons in the LLZ crystal particles subjected to partial replacement by the protons, can be replaced with the
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    14/33 lithium ions in the stream. By using the chemical reaction caused in this resubstitution, the crystal particles of LLZ can be bonded at a lower temperature than before (for example, 350 ° C).
    [086] The crystal particles of LLZ subjected to partial replacement by protons, can be obtained by preliminary synthesis of a hydrogen-free LLZ at high temperature (eg 800 ° C to 950 ° C) and replacing part of the lithium ions in the crystal particles of hydrogen-free LLZ thus obtained by protons.
    [087] Therefore, according to the described modalities, a sintered body of oxide electrolyte with high conductivity of lithium ions can be obtained by sintering at a lower temperature than before.
    [088] As a result, the active electrode material and the oxide electrolyte can be integrated sintered, selecting a heating temperature at which the alternation, which is caused by the chemical reaction between the oxide electrolyte and the active electrode material, can be avoided in the production of the battery comprising the ion-conducting oxide of the grenade type as the oxide electrolyte.
    [089] In addition, battery production costs can be reduced by lowering the sintering temperature.
    [090] The method for producing the sintered oxide electrolyte body according to the described modalities comprises at least: (1) preparing the crystal particles of the ion-conducting oxide-like garnet, (2) preparing the flow and (3 ) sinter a mixture of them.
    (1) Prepare ion-conducting oxide crystal particles of the garnet type [091] This step aims to prepare crystal particles of an ion-carrying oxide of the garnet type represented by a general formula (Lix-3y-z, Ey, Hz) LaMpOy, where a half width of a diffraction peak that has a higher intensity and that is observed at a diffraction angle (2θ) in the range of 29 ° to 32 ° as
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    15/33 result of measuring X-ray diffraction using CuKa radiation, is 0.164 ° or less.
    [092] The crystal particles of the ion-conducting oxide garnet type will not be described here, as they can be the same as described above in “1. Garnet ion-conducting oxide ”, except that they are those subjected to proton replacement (in the general formula mentioned above, 0 <z <2.8).
    (2) Prepare a flow containing lithium
    This step aims to prepare a flow containing lithium.
    [093] The flow containing lithium is not particularly limited. It can be a flow that has a melting point around a temperature at which the hydrogen ions are desorbed from the crystal particles of the garnet-ion-conducting oxide subjected to the partial replacement of hydrogen ions (hereinafter called oxide conductor of garnet ions after partial replacement of hydrogen ions). Like the flow, examples include, but are not limited to, LiOH (melting point: 462 ° C), LiNO3 (melting point: 260 ° C) and U2SO4 (melting point: 859 ° C). From the point of view of reducing the sintering temperature, the flux can be a flux with a low melting point, and it can be LiOH or LiNO3.
    (3) Sintering [094] This step aims to sinter a mixture of the flux and the crystal particles of the ion-conducting oxide of the garnet type by heating to a temperature equal to or greater than the melting point of the flux.
    [095] The sintering temperature can be equal to or greater than the melting point of the flow. The sintering temperature can be 350 ° C or more, or it can be 400 ° C or more, from the point of view of promoting the resubstitution, with the lithium ions in the lithium-containing flux, of the protons in the crystal particles of ion-conducting oxide of the garnet type after replacement
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    16/33 partial hydrogen ions. As long as the crystalline stability of the LLZ can be maintained, the sintering temperature can be 1000 ° C or less, or it can be 850 ° C or less. When a material other than ion-carrying oxide of the garnet type and the flux is used at the time of sintering, the sintering temperature may be such that the material does not react with the ion-carrying oxide of the garnet type. In this case, the sintering temperature can be 650 ° C or less, or it can be 550 ° C or less.
    [096] According to the described modalities, even in the case of sintering at a lower temperature than before (for example, 350 ° C), the sintered oxide electrolyte body having a desired lithium ion conductivity can be obtained.
    [097] When sintering, a pressure is applied at the time of heating. The pressure is not particularly limited. From the point of view of increasing the conductivity of lithium ions in the sintered oxide electrolyte body, heating can be carried out under a pressure condition higher than atmospheric pressure. At the time of heating, the upper pressure limit is not particularly limited. For example, it can be 6 ton / cm 2 (~ 588 MPa) or less.
    [098] The mixing ratio of the crystal particles of the garnet-ion-conducting oxide and the flow is not particularly limited. It can be from 50:50 (% by volume) to 95: 5 (% by volume), since the desired oxide electrolyte sintered body can be efficiently obtained.
    [099] In sintering, the sintering atmosphere is not particularly limited.
    [0100] In this step, sintering can be carried out by hot pressing.
    [0101] As used herein, hot pressing is a method for
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    17/33 perform heating in a controlled atmosphere oven, applying pressure in a uniaxial direction.
    [0102] By hot pressing, the oxide electrolyte particles cause plastic deformation and, therefore, densification. As a result, the density of the sintered body of the oxide electrolyte is considered to increase along with an increase in the binding of the particles, thereby increasing the conductivity of the lithium ions.
    [0103] The hot press temperature can be equal to or greater than the melting point of the flow. The hot pressing temperature can be 350 ° C or more, or it can be 400 ° C or more, from the point of view of promoting resubstitution, with the lithium ions in the lithium-containing flux, of the protons in the particles crystal of ion-conducting oxide of the garnet type after partial replacement of hydrogen ions. As long as the crystalline stability of the LLZ can be maintained, the hot press temperature can be 1000 ° C or less, or it can be 850 ° C or less. When a material other than ion-carrying oxide of the garnet type and the flux is used at the time of sintering, the hot pressing temperature may be such that the material does not react with the ion-carrying oxide of the garnet type. In this case, the sintering temperature can be 650 ° C or less, or it can be 550 ° C or less.
    [0104] The hot pressing pressure can be between 1 and 6 ton / cm 2 (~ 98 to 588 MPa).
    [0105] The hot pressing time can be between 1 and 600 minutes.
    [0106] In the described embodiments, the crystal particles of the ion-conducting oxide of the garnet type are bonded by a solid phase flow reaction method, using a chemical reaction between the flow material and the crystal particles of the conductive oxide crystal. grenade-like ions (the solid phase) as a driving force,
    Petition 870180131819, of 09/18/2018, p. 49/76
    18/33 thus obtaining the sintered body of oxide electrolyte.
    [0107] Figure 1 is a schematic view showing the description of the solid phase flow reaction method used in the described modalities.
    [0108] In Figure 1, the figure on the left shows the state of the mixture “before heating”. The mixture is a mixture of the solid state flow and the crystal particles of the ion-conducting oxide of the garnet type are subjected to the replacement of part of the lithium ions (Li + ) with hydrogen ions (H + ). In Figure 1, the particles are called LLZ particles.
    [0109] In Figure 1, the figure in the center shows the state of the mixture “in the initial heating stage”. As shown in the central figure of Figure 1, when the mixture is heated to the melting point of the flow, the bond between the lithium ions (Li + ) and anions (X - ) in the flow becomes weak. At this time, the hydrogen ions (H + ) in the crystal particles of the oxide conductor of the garnet type are replaced by the lithium ions (Li + ) in the flow.
    [0110] Finally, in Figure 1, the figure on the right shows the state of the mixture “in the last stage of heating”. As shown in the right figure of Figure 1, the lithium ions (Li + ) in the flux are incorporated into the crystal of the crystal particles of the ion-conducting oxide grenade type. The hydrogen ions (H + ) released from the interior of the crystal of the crystal particles of the ion-conducting oxide of the garnet type are attached to the anions (X - ) in the flow to form a reaction product and move out of the system; therefore, they do not remain among the crystal particles of the garnet-like ion-conducting oxide.
    Examples (Example 1) [Synthesis of LLZ crystal particles] [0111] Stoichiometric amounts of LiOH (H2O) (manufactured by SigmaAldrich), La (OH) 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd.), ZrO2
    Petition 870180131819, of 09/18/2018, p. 50/76
    19/33 (manufactured by Kojundo Chemical Laboratory Co., Ltd.) and Nb2Ü5 (manufactured by
    Kojundo Chemical Laboratory Co., Ltd.) were used as starting raw materials. They were mixed to obtain a mixture.
    [0112] The mixture and a stream (NaCl) were heated from room temperature to 950 ° C for 8 hours and then maintained at 950 ° C for 20 hours, thus obtaining crystal particles of LLZ having the composition of Li6. 4La3Zr1.4Nb0.6O12. The melt in the flow was controlled to be 2 mol%.
    [0113] The average particle diameter at 10% of the volume (D10) of the crystal particles obtained was 2.8 pm.
    [Partial replacement of hydrogen ions] [0114] Then, at room temperature, 2 g of the crystal particles of LLZ thus obtained before partial replacement of hydrogen ions, were immersed in pure water (200 ml) for several minutes for replacement partial ionization of lithium ions by hydrogen ions, thus obtaining the crystal particles of LLZ after partial replacement of hydrogen ions. The amount of Li (in the composition of the LLZ) replaced by H, was 0.61. The results are shown in Table 1.
    [0115] The crystal particles of LLZ were subjected to the analysis of ICP before and after the partial replacement of hydrogen ions. From the amount of change in the lithium element in the LLZ composition before and after the partial replacement of hydrogen ions, the amount of hydrogen ions incorporated by the substitution was estimated. Then, the particle composition of the LLZ crystal after partial hydrogen ion replacement was estimated.
    (Example 2) [Synthesis of LLZ crystal particles] [0116] The crystal particles of LLZ having the composition of Li6.4La3Zr1.4Nb0.6O12 were obtained in the same manner as in Example 1.
    [Partial replacement of hydrogen ions]
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    20/33 [0117] Then, at room temperature, 2 g of the crystal particles of LLZ thus obtained before the partial replacement of hydrogen ions were immersed in pure water (200 ml).
    [0118] After several hours, 150 ml of pure water was removed, and new pure water (150 ml) was added.
    [0119] By replacing Li in the crystal particles with H, the pH of pure water was increased. Until the increase in the pH of the pure water was not seen, in which the particles of the crystal were immersed, the replacement of the pure water was repeated to partially replace the lithium ions with hydrogen ions, thus obtaining the particles of the LLZ crystal after partial replacement by hydrogen ions. The amount of Li (in the composition of the LLZ) replaced by H, was 2.32. The results are shown in Table 1.
    (Example 3) [LLZ crystal particle synthesis] [0120] Stoichiometric amounts of LiOH (H2O) (manufactured by Sigma-Aldrich), La (OH) 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd.), ZrO2 (manufactured by Kojundo Chemical Laboratory Co., Ltd.) and Nb2O5 (manufactured by Kojundo Chemical Laboratory Co., Ltd.) were used as starting raw materials. They were mixed to obtain a mixture.
    [0121] The mixture and a stream (NaCl) were heated from room temperature to 950 ° C for 8 hours and then maintained at 950 ° C for 20 hours, thus obtaining LLZ crystal particles with the Li6 composition. 4La3Zr1.4Nb0.6O12. The melt in the flow was controlled to be 2 mol%.
    [0122] The average particle diameter at 10% of the volume (D10) of the crystal particles obtained was 2.8 pm.
    [Partial replacement of hydrogen ions] [0123] Then, at room temperature, 2 g of the LLZ crystal particles
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    21/33 thus obtained before the partial replacement of hydrogen ions were immersed in pure water (200 ml) for 8 hours to partially replace the lithium ions with hydrogen ions, thus obtaining the crystal particles of LLZ after the partial replacement of hydrogen ions. The amount of Li (in the composition of the LLZ) replaced by H was 0.78. The results are shown in Table 1.
    (Example 4) [Synthesis of LLZ crystal particles] [0124] The crystal particles of LLZ with the composition of Li6.4La3Zr1.4Nb0.6O12 were obtained in the same manner as in Example 3.
    [Partial replacement of hydrogen ions] [0125] Then, at room temperature, 2 g of the LLZ crystal particles thus obtained before the partial replacement of hydrogen ions were immersed in pure water (200 ml) for 24 hours for partial replacement of lithium ions by hydrogen ions, thus obtaining the particles of the LLZ crystal after partial replacement of hydrogen ions. The amount of Li (in the LLZ composition) replaced by H was 1.48. The results are shown in Table 1.
    (Example 5) [Synthesis of LLZ crystal particles] [0126] The LLZ crystal particles with the composition of Li6.4La3Zr1.4Nb0.6O12 were obtained in the same manner as in Example 3.
    [Partial replacement of hydrogen ions] [0127] Then, at room temperature, 2 g of the crystal particles of LLZ thus obtained before partial replacement of hydrogen ions were immersed in pure water (200 ml) for 40 hours for partial replacement of lithium ions by hydrogen ions, thus obtaining the particles of the LLZ crystal after partial replacement of hydrogen ions. The amount of Li (in the composition of the LLZ) replaced by H was 1.76. The results are shown in Table 1.
    Petition 870180131819, of 09/18/2018, p. 53/76
    22/33 (Example 6) [Synthesis of LLZ crystal particles] [0128] The LLZ crystal particles with the composition of Li6.4La3Zr1.4Nb0.6O12 were obtained in the same way as in Example 3.
    [Partial replacement of hydrogen ions] [0129] Then, at room temperature, 2 g of the LLZ crystal particles thus obtained before the partial replacement of hydrogen ions were immersed in pure water (200 ml) for 56 hours for replacement partial ionization of lithium ions by hydrogen ions, thus obtaining the particles of the LLZ crystal after partial replacement of hydrogen ions. The amount of Li (in the LLZ composition) replaced by H was 2.31. The results are shown in Table 1.
    (Example 7) [Synthesis of LLZ crystal particles] [0130] Stoichiometric amounts of LiOH (H2O) (manufactured by SigmaAldrich), La (OH) 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd.), ZrO2 (manufactured by Kojundo Chemical Laboratory Co., Ltd.) and Nb2O5 (manufactured by Kojundo Chemical Laboratory Co., Ltd.) were used as starting raw materials. They were mixed to obtain a mixture.
    [0131] The mixture and a flow (Li3BO3) were heated from room temperature to 900 ° C for 90 minutes and then maintained at 900 ° C for 20 hours, thus obtaining LLZ crystal particles with the Li6 composition. 4La3Zr1.4Nb0.6O12. The melt in the flow was controlled to be 50 mol%.
    [0132] The average particle diameter at 10% by volume (D10) of the crystal particles obtained was 3.2 pm.
    [Partial replacement of hydrogen ions] [0133] Then, at room temperature, 2 g of the LLZ crystal particles thus obtained before the partial replacement of hydrogen ions were immersed in
    Petition 870180131819, of 09/18/2018, p. 54/76
    23/33 pure water (200 ml) for 24 hours for partial replacement of lithium ions with hydrogen ions, thus obtaining the particles of the LLZ crystal after partial replacement of hydrogen ions. The amount of Li (in the composition of the LLZ) replaced by H was 1.84. The results are shown in Table 1.
    (Example 8) [Synthesis of LLZ crystal particles] [0134] The LLZ crystal particles synthesized in Example 7 were prepared, the crystal particles having the composition of Li6.4La3Zr1.4Nb0.6O12.
    [Partial replacement of hydrogen ions] [0135] Then, at room temperature, 2 g of the LLZ crystal particles prepared before the partial replacement of hydrogen ions were immersed in pure water (200 ml) for 48 hours to partially replace the lithium ions with hydrogen ions, thus obtaining the particles of the LLZ crystal after the partial replacement of hydrogen ions. The amount of Li (in the composition of the LLZ) replaced by H, was 1.99. The results are shown in Table 1.
    (Comparative Example 1) [Synthesis of LLZ crystal particles] [0136] The LLZ crystal particles synthesized in Example 7 were prepared, the crystal particles having the composition of Li6.4La3Zr1.4Nb0.6O12.
    [Partial replacement of hydrogen ions] [0137] Then, at room temperature, 2 g of the LLZ crystal particles prepared before partial replacement of hydrogen ions were immersed in pure water (200 ml) for 72 hours for partial replacement of lithium ions by hydrogen ions, thus obtaining the particles of the LLZ crystal after partial replacement of hydrogen ions. The amount of Li (in the composition of the LLZ) replaced by H was 2.13. The results are shown in Table 1.
    (Comparative Example 2)
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    24/33 [0138] Stoichiometric amounts of LiOH (H2O) (manufactured by SigmaAldrich), La (OH) 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd.), ZrO2 (manufactured by Kojundo Chemical Laboratory Co., Ltd.) and Nb2O5 (manufactured by
    Kojundo Chemical Laboratory Co., Ltd.) were used as starting raw materials. They were mixed to obtain a mixture.
    [0139] The mixture and a stream (NaCl and KCl) were heated from room temperature to 800 ° C for 8 hours and then kept at 800 ° C for 20 hours, thus obtaining crystal particles of LLZ with the composition of Li6.4La3Zr1.4Nb0.6O12. The melt in the flow was controlled to be 2 m%. The NaCl and KCl used as a flow were controlled to be in a 1: 1 molar ratio.
    [0140] The average particle diameter of 10% by volume (D10) of the crystal particles obtained was 3.2 pm.
    [Partial replacement of hydrogen ions] [0141] Then, at room temperature, 2 g of the crystal particles of LLZ thus obtained before partial replacement of hydrogen ions were immersed in pure water (200 ml) for one hour for partial replacement of lithium ions by hydrogen ions, thus obtaining the crystal particles of LLZ after the partial replacement of hydrogen ions. The amount of Li (in the composition of the LLZ) replaced by H was 0.67. The results are shown in Table 1.
    (Comparative Example 3) [LLZ crystal particle synthesis] [0142] Stoichiometric amounts of LiOH (H2O) (manufactured by SigmaAldrich), La (OH) 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd.), ZrO2 ( manufactured by Kojundo Chemical Laboratory Co., Ltd.) and Nb2O5 (manufactured by Kojundo Chemical Laboratory Co., Ltd.) were used as starting raw materials. They were mixed to obtain a mixture.
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    25/33 [0143] The mixture and a flow (NaCl and KCl) were heated from room temperature to 850 ° C for 8 hours and then kept at 850 ° C for 20 hours, thus obtaining LLZ crystal particles with the composition of Li6.4La3Zr1.4Nb0.6O12. The melt in the flow was controlled to be 2 mol%. The NaCl and KCl used as flow were controlled to be in a 1: 1 molar ratio.
    [0144] The average particle diameter at 10% by volume (D10) of the crystal particles obtained was 3.2 pm.
    [Partial replacement of hydrogen ions] [0145] Then, at room temperature, 2 g of the crystal particles of LLZ thus obtained before partial replacement of hydrogen ions were immersed in pure water (200 ml) for one hour for partial replacement of lithium ions by hydrogen ions, thus obtaining the crystal particles of LLZ after the partial replacement of hydrogen ions. The amount of Li (in the LLZ composition) replaced by H was 0.66. The results are shown in Table 1.
    (Example 9) [Synthesis of LLZ crystal particles] [0146] Stoichiometric amounts of LiOH (H2O) (manufactured by SigmaAldrich), La (OH) 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd.), ZrO2 (manufactured by Kojundo Chemical Laboratory Co., Ltd.) and Nb2O5 (manufactured by Kojundo Chemical Laboratory Co., Ltd.) were used as starting raw materials. They were mixed to obtain a mixture.
    [0147] The mixture and a stream (NaCl and KCl) were heated from room temperature to 900 ° C for 8 hours and then maintained at 900 ° C for 20 hours, thus obtaining crystal particles of LLZ with the composition of Li6. 4La3Zr1.4Nb0.6O12. The melt in the flow was controlled to be 2 mol%. The NaCl and KCl used as a flow were controlled to be in a relationship
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    26/33 molar 1: 1.
    [0148] The average particle diameter at 10% by volume (D10) of the obtained crystal particles was 3.2 pm.
    [Partial replacement of hydrogen ions] [0149] Then, at room temperature, 2 g of the crystal particles of LLZ thus obtained before partial replacement of hydrogen ions were immersed in pure water (200 ml) for one hour for partial replacement of lithium ions by hydrogen ions, thus obtaining the crystal particles of LLZ after the partial replacement of hydrogen ions. The amount of Li (in the composition of the LLZ) replaced by H was 0.69. The results are shown in Table 1.
    Table 1
    ( 0 ) 2θ was going(0) Me width H age ÇO2 (mol) LLZ (mol) ÇO2 / LLZExe30,0.00.6 6.1 3.5 1.7 mplo 1911921506E-08 2385E-05 454E-03Exe30,0.12.3 7.3 2.8 2.6 mplo 2842542011E-08 008E-05 068E-03Exe30,0.00.7 3.6 3.1 1.1 mplo 3893948861 E-08 5383E-05 688E-03Exe30,0.11.4 4.8 2.7 1.7 mplo 485058295E-09 4357E-05 603E-04Exe30,0.11.7 2.6 3.6 7.3 mplo 5849186562E-08 1643E-05 449E-04Exe30,0.12.3 3.7 2.1 1.6 mplo 6844641216E-08 9073E-05 988E-03Exe30,0.11.8 6.1 2.4 2.4 mplo 7852554506E-08 6596E-05 942E-03Exe30,0.11.9 9.5 2.4 3.8 mplo 884649099E-08 4147E-05 952E-03Exemplo 30,0.12.1 1.3 2.4 5.5 Comparative1 883693509E-07 4229E-05 311E-03Exemplo 30,0.20.6 4.9 1.1 4.2 Comparative2 852377631E-07 5738E-05 882E-02Exemplo 30,0.10.6 1.1 3.4 3.1 Comparative3 893966016E-07 7854E-05 667E-03
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    27/33
    Exe 30, 0.1 0.6 1.0 2.8 3.7 mplo 9 893 58 9 767E-07 9609E-05 178E-03
    [0150] In Table 1, “Quantity of H” is the amount of hydrogen contained in the LLZ composition, and is a value calculated by analyzing ICP in the crystal particles of LLZ before and after the partial replacement of hydrogen ions and estimation the amount of hydrogen incorporated by replacing the amount of change in the lithium element.
    [0151] Also in Table 1, “CO2 (mol)” is the molar amount of CO2 adsorbed on the LLZ crystal particles. The following was obtained: the mass of the LLZ crystal particles in which H2O and CO2 are adsorbed at normal temperature is calculated; differential thermogravimetric / thermal analysis (TG-DTA) is performed on the crystal particles of LLZ; from the resulting data at 900 ° C, the mass of the LLZ crystal particles from which H2O and CO2 have been desorbed is calculated; and from the resulting data at 600 ° C to 800 ° C, the amount of CO2 adsorbed on the LLZ crystal particles is calculated and converted to a molar value.
    [0152] In Table 1, “LLZ (mol)” is a value obtained as follows: the thermogravimetric / differential thermal analysis (TG-DTA) is performed on the crystal particles of LLZ in which H2O and CO2 are adsorbed at normal temperature , and from the resulting data at 900 ° C, the mass of the LLZ crystal particles from which H2O and CO2 were desorbed, is calculated and converted to a molar value.
    [0153] In Table 1, “CO2 / LLZ” is a value of the molar quantity of CO2 adsorbed per mole of the LLZ and is obtained by dividing the “CO2 (mol)” obtained above by the “LLZ (mol)” obtained above.
    [0154] As shown in Table 1, it is clear that there is no correlation between the half width of the LLZ crystal particles and the molar amount of CO2 adsorbed per mole of the LLZ. As shown in Table 1, it is also clear that
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    28/33 there is no correlation between the amount of H in the composition of the LLZ crystal particles and the molar amount of CO2 adsorbed per mole of the LLZ.
    [XRD measurement] [0155] The XRD measurement was performed on the LLZ crystal particles after partial hydrogen ion replacement obtained in Examples 1 to 9 and Comparative Examples 1 to 3 to measure the half width of a diffraction peak which has the highest intensity and which is observed at a diffraction angle (2θ) in a range of 29 ° to 32 °. The results are shown in Table 1.
    The XRD measurement conditions are as follows.
    [0156] Device: RINT-TTRIII wide-angle X-ray diffractometer (manufactured by Rigaku Corporation)
    X-ray source: CuKa radiation
    Tube tension tube current: 50 kV-300 mA
    Step width: 0.01 degrees
    Measurement rate: one second / step
    Aperture: 0.5 degree-0.15 mm-0.5 degree
    Monochromator: curved diffraction crystal monochromator [0157] As shown in Table 1, the half width of the crystal particles of LLZ thus obtained after partial hydrogen ion replacement, is 0.092 ° in Example 1.0.154 ° in Example 2, 0.094 ° in Example 3, 0.105 ° in Example 4, 0.118 ° in Example 5, 0.146 ° in Example 7, 0.156 ° in Example 8, 0.158 ° in Example 9, 0.168 ° in Example 9, 0.169 ° in Comparative Example 1, 0.237 ° in Comparative Example 2 and 0.196 ° in Comparative Example 3.
    [0158] As an example, Figure 2 shows an overview of an XRD pattern of the LLZ crystal particles from Example 3 and Example 6.
    [0159] Figure 3 shows an enlarged image of a peak at 30.8 ° shown in Figure 2.
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    29/33
    In addition, Figure 3 shows the half width of the peak at 30.8 °.
    [Mass spectrometry] [0160] Mass spectrometry was performed on the crystal particles of LLZ after the partial replacement of hydrogen ions obtained in Examples 1 to 9 and Comparative Examples 1 to 3.
    [0161] Mass spectrometry was performed using ThermoMass simultaneous thermogravimetric differential photoionization mass spectrometer (product name, manufactured by Rigaku Corporation).
    [0162] As an example, the results of mass spectrometry from Examples 1, 6 and 9 and Comparative Example 1 are shown in Figures 4 to 7. In Figures 4 to 7, "Mass" on the vertical axis is an amount of substance (mol).
    [0163] For Example 1, only a peak around 400 ° C, which indicates CO2 decomposition, was observed. From this result, it is clear that CO2 evaporates at a temperature of 400 ° C or less.
    [0164] For Comparative Example 1, peaks around 400 ° C and around 700 ° C, which indicate the decomposition of CO2, were observed. From this result, the decomposition of CO2 was also confirmed at a temperature of approximately 700 ° C, and addition at 400 ° C. This desorption of CO2 at 700 ° C is considered due to the decomposition of lithium carbonate. This indicates that, for the LLZ crystal particles from Comparative Example 1, Li reacts with CO2 on the particle surface to form Li2CO3, and heating to approximately 700 ° C is required to decompose Li2CO3.
    [0165] For Examples 6 and 9, a slight peak at around 700 ° C, which indicates CO2 decomposition, was observed. However, it is clear that the peak is less than in Comparative Example 1.
    [0166] From the results above, the following is clear. For Example 1, lithium carbonate was not formed on the surface of the LLZ crystal particles,
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    30/33 since no peak was observed at around 700 ° C, which indicates the decomposition of CO2. For Examples 6 and 9, given that a peak around 700 °
    C, which indicates the decomposition of CO2, is less than in Comparative Example 1, the formation of lithium carbonate on the surface of the crystal particles of LLZ is inhibited.
    [Half width] [0167] Figure 8 is a view in which half the width of the crystal particles of LLZ produced in each of Examples 1 to 9 and Comparative Examples 1 to 3 and the amount of H in the composition of the particles of crystal LLZ are represented.
    [0168] As shown in Figure 8 and Table 1, it is clear that there is no correlation between the half width of the LLZ crystal particles and the amount of H in the composition of the LLZ crystal particles.
    [0169] By mass spectrometry, the crystal particles of LLZ after the partial replacement of hydrogen ions of Examples 1 to 9 and Comparative Examples 1 to 3, were checked for the presence or absence of CO2 desorption due to carbonate decomposition. lithium at a temperature of 700 ° C or more. As a result, for the LLZ crystal particles of Examples 1 to 9 having a half width of 0.164 ° or less, no peak was observed at around 700 ° C, which indicates CO2 decomposition.
    [0170] Therefore, it is assumed that, as long as the half width is 0.164 ° or less, the formation of lithium carbonate on the surface of the crystal particles of LLZ can be inhibited despite the amount of H in the composition of the particles of LLZ crystal.
    [0171] As described above, as shown in Table 1, there is no correlation between the half width of the LLZ crystal particles and the molar amount of CO2 adsorbed per mole of the LLZ.
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    31/33 [0172] Therefore, it is assumed that, since the half width is 0.164 ° or less, the formation of lithium carbonate on the surface of the crystal particles of
    LLZ can be inhibited despite the molar amount of CO2 adsorbed per mole of LLZ.
    [0173] These results are assumed to be due to the following reason: as long as the half-width is 0.164 ° or less, the LLZ crystal particles have high crystallinity, allow lithium ions to be stable within the particles, and can inhibit a reaction between lithium ions and CO2 on the surface of the particles.
    (Reference Example 1) [0174] A powder of LLZ crystal particles with half width of 0.164 ° or less was prepared. The amount of the prepared powder was 0.4 g.
    [0175] Then, the powder was pressed under conditions of 4 ton / cm 2 (~ 392 MPa) and at room temperature, thus obtaining a pressed powder.
    (Reference Example 2) [0176] A powder of LLZ crystal particles with half width of 0.164 ° or less was prepared. The amount of the prepared powder was 0.4 g.
    [0177] The powder was then mixed dry with, as a stream, a powder mixture of LiNO3 and LiOH using a mortar. The resulting mixture was hot pressed under conditions of 400 ° C and 1 ton / cm 2 (~ 98 MPa) for 480 minutes, thus obtaining a pressed powder.
    (Reference Example 3) [0178] A powder of LLZ crystal particles with a half width of more than 0.164 ° and having lithium carbonate formed therein was prepared. The amount of the prepared powder was 0.4 g.
    [0179] Then, the powder was mixed dry with, as a flow, a powder mixture of LiNO3 and LiOH by using the mortar. The resulting mixture was hot pressed under conditions of 400 ° C and 1 ton / cm 2 (~ 98 MPa) for 480
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    32/33 minutes, thus obtaining a pressed powder.
    (Reference Example 4) [0180] A powder of LLZ crystal particles with a half width of more than 0.164 ° and having lithium carbonate formed therein was prepared. The amount of powder prepared was 0.4 g.
    [0181] Then, the powder was pressed under ambient temperature and 4 ton / cm 2 (~ 392 MPa), thus obtaining a pressed powder.
    [AC impedance measurement] [0182] The AC impedance measurement was performed on the pressed powders produced in Reference Examples 1 to 4. The AC impedance measurement was performed using Potentiostat 1470 (product name, manufactured by Solartron) and of the Impedance Analyzer FRA1255B (product name, manufactured by Solartron) and under conditions of a voltage fluctuation of 25 mV, a measurement frequency (F) of 0.1 Hz to 1 MHz, a measurement temperature of 25 ° C , and normal pressure.
    [0183] The results of the AC impedance measurement are shown in Figure 9 (Reference Example 1), Figure 10 (Reference Example 2), Figure 11 (Reference Example 3) and Figure 12 (Reference Example 4). For the pressed powders of Reference Examples 1 to 4, Figures 9 to 12 are graphs with the surface resistance R '(Ω cm 2 ) of an imaginary component on the vertical axis and the surface resistance R (Ω cm 2 ) of a real component on the horizontal axis.
    [0184] Each arrow shown in Figures 9 to 11 indicates mass impedance. As shown in Figures 7 to 9, the mass impedance is 6.5 χ 10 3 in Reference Example 1, 6.5 χ 10 2 in Reference Example 2, and 3.6 χ 10 5 in Reference Example 3.
    [0185] As shown in Figure 12, mass impedance cannot be measured in Reference Example 4. Therefore, it is assumed that Reference Example 4 has very high resistance and high insulation properties.
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    33/33 [0186] From the results of the AC impedance measurement, it is clear that, as shown in Figures 9 to 11, the mass impedance of Reference Example 3 is 100 to 1000 times higher than Reference Examples 1 and 2 Therefore, it is clear that the crystal particles of LLZ in which lithium carbonate is not formed have lower mass impedance and higher conductivity of lithium ions.
    [0187] It is also clear that Reference Example 2 has less mass impedance than Reference Example 1. Therefore, it is clear that mass impedance can be reduced by means of hot pressing.
    [0188] From the results of Reference Examples 3 and 4, it is clear that when lithium carbonate is formed on the surface of the LLZ crystal particles, the lithium ion conductivity of the particles is low even after the particles are subjected to hot pressing.
    权利要求:
    Claims (5)
    [1]
    1. Garnet-ion-conducting oxide represented by a general formula (Lix-3y-z, Ey, Hz) LaMpOy (where E is at least one type of element selected from the group consisting of Al, Ga, Fe and Si; L is at least one type of element selected from an alkaline earth metal and a lanthanide element: M is at least one type of element selected from a transition element that has six coordinations with oxygen and typical elements in the groups 12 to 15 of the periodic table: 3 <x - 3y - z <7; <0 <y <0.22; 0 <z <2.8; 2.5 <α <3.5; 1.5 <β < 2,5; and 11 <γ <13), CHARACTERIZED by the fact that:
    where a half width of a diffraction peak that has a higher intensity and is observed at a diffraction angle (2θ) in the range of 29 ° to 32 ° as a result of measuring X-ray diffraction using CuKa radiation, is 0.164 ° or less.
    [2]
    2. Garnet-ion-conducting oxide, according to claim 1, CHARACTERIZED by the fact that the element L is La, and the element M is at least one type of element selected from the group consisting of Zr, Nb and Ta.
    [3]
    3. Garnet-ion-conducting oxide, according to claim 1 or 2, CHARACTERIZED by the fact that the half width is from 0.092 ° to 0.164 °.
    [4]
    4. Method to produce a sintered body of oxide electrolyte, CHARACTERIZED by the fact that it comprises:
    prepare crystal particles of an ion-conducting oxide of the garnet type represented by a general formula (Lix-3y-z, Ey, Hz) LaMpOy (where E is at least one type of element selected from the group consisting of Al, Ga, Fe and Si; L is at least one type of element selected from an alkaline earth metal and a lanthanide element: M is at least one type of element selected from a transition element that has six coordinations with oxygen and typical elements in groups 12 to 15 of the periodic table: 3 <x - 3y - z <7; <0 <y <0.22; 0 <
    Petition 870180131819, of 09/18/2018, p. 66/76
    2/2 z <2.8; 2.5 <α <3.5; 1.5 <β <2.5; and 11 <γ <13), where a half width of a diffraction peak that has a higher intensity and is observed at a diffraction angle (2θ) in the range of 29 ° to 32 ° as a result of the diffraction measurement of X-rays using CuKa radiation, is 0.164 ° or less, prepare a flow containing lithium, and sinter a mixture of the flow and the crystal particles of the ion-conducting oxide grenade type, by heating to a temperature equal to or greater than a flow fusion.
    [5]
    5. Method for producing the sintered oxide electrolyte body, according to claim 4, CHARACTERIZED by the fact that the element L is La, and the element M is at least one type of element selected from the group consisting of Zr, Nb and Ta.
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    公开号 | 公开日
    JP6962094B2|2021-11-05|
    KR20190033425A|2019-03-29|
    RU2687730C1|2019-05-16|
    EP3459920B1|2021-09-29|
    US11264640B2|2022-03-01|
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    JP2019055898A|2019-04-11|
    CN109534813A|2019-03-29|
    EP3459920A1|2019-03-27|
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    法律状态:
    2019-04-16| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    JP2017181508A|JP6962094B2|2017-09-21|2017-09-21|Method for producing garnet-type ionic conductive oxide and oxide electrolyte sintered body|
    JP2017-181508|2017-09-21|
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