CN105977529B - Lithium ion conducting oxide ceramic material having garnet-type or garnet-like crystal structure - Google Patents

Lithium ion conducting oxide ceramic material having garnet-type or garnet-like crystal structure Download PDF

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CN105977529B
CN105977529B CN201610137537.1A CN201610137537A CN105977529B CN 105977529 B CN105977529 B CN 105977529B CN 201610137537 A CN201610137537 A CN 201610137537A CN 105977529 B CN105977529 B CN 105977529B
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garnet
lithium ion
active material
powder
electrode active
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CN105977529A (en
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塚田岳夫
田中祯一
角田宏郁
益子泰辅
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TDK Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides a lithium ion-conductive oxide ceramic material having a garnet-type or garnet-like crystal structure, which has a high ion conductivity due to an intra-granular resistance component, and the lithium ion-conductive oxide ceramic material having a garnet-type or garnet-like crystal structure of the present invention contains L i, L a, Zr, and O, and further contains one or more elements selected from rare earth elements.

Description

Lithium ion conducting oxide ceramic material having garnet-type or garnet-like crystal structure
Technical Field
The present invention relates to a lithium ion-conducting oxide ceramic material having a garnet-type or garnet-like crystal structure.
Background
The all-solid-state lithium ion secondary battery has higher thermal stability than a lithium secondary battery using a nonaqueous electrolyte solution because it uses a ceramic material in which an electrolyte is sintered. However, all-solid-state lithium ion secondary batteries with high capacity have not yet been put into practical use even from the world-wide perspective. One of the reasons for this is that there is a problem with the solid electrolyte itself. The main characteristics required for the solid electrolyte include 3 characteristics of high ionic conductivity (conductivity), excellent chemical stability, and a large potential window. Among these properties, garnet-type oxide ceramic materials have the advantages of excellent chemical stability and a large potential window, and thus are promising candidates for solid electrolytes (see, for example, non-patent documents 1 and 2).
Documents of the prior art
Non-patent document
Non-patent document 1: J.Am.Ceram.Soc., 2003, volume 3, 437-440 page
Non-patent document 2: integer, int, ed, 2007, volume 46, 7778-
Patent document
Patent document 1: japanese patent No. 5083336
Disclosure of Invention
Problems to be solved by the invention
This garnet-type oxide ceramic material is expected to further improve the ion-conducting property. Generally, the ion conductivity of an ion-conductive ceramic can be considered to be divided into a conductivity contributed by an intragranular resistance component and a conductivity contributed by a grain boundary resistance component, and in a solid electrolyte ceramic used in a sufficiently thick shape, since a large number of grain boundary portions exist in the ceramic, in order to evaluate the ion conductivity of the entire electrolyte, it is necessary to consider the ion conductivity contributed by resistance components from both intragranular and grain boundary. However, in a device using a solid electrolyte layer having a smaller thickness and a larger number of crystal grains, the contribution of the grain boundary resistance component is reduced by relatively reducing the number of crystal grains, and only the conductivity of the ion conductor itself due to the intra-grain resistance becomes important.
Patent document 1 and the like calculate and evaluate ion conductivity from a resistance combining an intragranular resistance and a grain boundary resistance, but do not describe evaluation of ion conductivity only in the grains.
An object of the present invention is to provide a lithium ion-conductive oxide ceramic material having a garnet-type or garnet-like crystal structure, which has a smaller amount of resistance components in the crystal grains and an increased ion conductivity in the crystal grains, compared to conventional lithium ion-conductive oxide ceramic materials having a garnet-type or garnet-like crystal structure, and which has a further increased total ion conductivity in ceramic materials having a smaller number of crystal grain boundaries.
Here, the garnet-type crystal structure refers to a crystal having a space group of Ia to 3d, and the garnet-like crystal structure is defined as having I41Crystal group of/acd space group.
Means for solving the problems
As a result of repeated dedicated studies to achieve the above object, the present inventors have found that the ion conductivity contributed by the intra-granular resistance component is improved by including a rare earth element in a lithium ion-conductive oxide ceramic material having a garnet-type or garnet-like crystal structure, and finally completed the present invention.
That is, the lithium ion-conductive oxide ceramic material having a garnet-type or garnet-like crystal structure according to the present invention contains L i, L a, Zr, and O, and further contains at least one element selected from rare earth elements.
The lithium ion conductive oxide ceramic material having a garnet-type or garnet-like crystal structure according to the present invention is characterized by being represented by the following formula (1):
Li7+xLa3Zr2－xAxO12…(1)
(in the formula (1), A is at least one element selected from rare earth elements, and x is a number satisfying 0 < x.ltoreq.0.5).
Substitution of the rare earth element at the Zr site is considered to have an effect of increasing the lattice constant and enlarging the space for movement of L i ions, and as a result, L i ions are likely to move.
In a preferred embodiment of the present invention, a in formula (1) is preferably at least one element selected from Gd, Tb, Dy, Ho, Er, Tm, Yb, and L u.
Substitution of Gd, Tb, Dy, Ho, Er, Tm, Yb, and L u at the Zr site is considered to have an effect of forming a space suitable for movement of L i ions, and as a result, the formation of the space is considered to have an effect of exhibiting high ion conductivity.
In a preferred embodiment of the present invention, a in formula (1) is at least one element selected from Gd, Ho and Yb. Further, it is preferable that x satisfies 0 < x.ltoreq.0.30.
This is considered to have an effect of providing a space suitable for the cooperative movement of the L i ions, and as a result, a higher ion conductivity can be obtained.
In a preferred embodiment of the present invention, it is preferable that the lithium ion conductive oxide ceramic material having a garnet-type or garnet-like crystal structure contains 0.3 wt% or more and 2.0 wt% or less of Al with respect to the total weight of the material.
It is considered that the inclusion of Al makes L i easier7+xLa3Zr2－xAxO12The effect of cubic crystallization is to further improve the ion conductivity as a result.
Effects of the invention
According to the present invention, the lithium ion-conductive oxide ceramic material having a garnet-type or garnet-like crystal structure can be provided which has a higher overall ion conductivity in a ceramic material having a smaller number of grain boundaries than in a conventional lithium ion-conductive oxide ceramic material having a garnet-type or garnet-like crystal structure by increasing the ion conductivity contributed by the intra-granular resistance component.
The garnet-type lithium ion-conductive oxide of the present invention can be preferably used for a device in which the thickness of the solid electrolyte layer is reduced, and is expected to be applied to a stacked secondary battery having a plurality of thin layers.
Drawings
FIG. 1 is a diagram showing a Nyquist plot (Nyquist plot) obtained in an experiment;
fig. 2 is a cross-sectional view showing a conceptual structure of a lithium-ion secondary battery.
Description of the symbols
1 positive electrode
2 negative electrode
3 solid electrolyte
4 positive electrode current collector
5 Positive electrode active Material
6 negative electrode current collector
7 negative electrode active material
8 lithium ion secondary battery
Detailed Description
The lithium ion-conductive oxide ceramic material having a garnet-type or garnet-like crystal structure according to the present embodiment further contains one or more elements selected from rare earth elements, in comparison with a lithium ion-conductive oxide ceramic material having a garnet-type or garnet-like crystal structure composed of L i, L a, Zr, and O.
For example, L i in the compositional formula (1)7+xLa3Zr2－xAxO12… … (1) and A in the formula (1) is one or more elements selected from rare earth elements. x is a number satisfying 0 < x.ltoreq.0.5, more preferably 0 < x.ltoreq.0.3.
When a rare earth element is contained in the lithium ion conductive oxide ceramic material having a garnet-type or garnet-like crystal structure composed of L i, L a, Zr and O, it is not always necessary to replace Zr, and other metal ion sites may be substituted, and Zr is preferably substituted.
In addition, in order to identify the lithium ion-conductive oxide ceramic material having a garnet-type or garnet-like crystal structure of the present embodiment, it is possible to perform by powder X-ray diffractionxLa3Zr2O12So-called LL Z, and therefore, it is not necessarily a substance of stoichiometric composition, that is, defects such as oxygen defects may occur, and the lithium ion conductive oxide ceramic having a garnet-type or garnet-like crystal structure may be usedThe rare earth element added to the material can be quantified by high-frequency inductively coupled plasma emission spectroscopy (ICP).
The lithium ion-conductive oxide ceramic material having a garnet-type or garnet-like crystal structure of the present embodiment is considered to be represented by chemical formula L i7+xLa3Zr2－xAxO12In this case, it is known that Zr sites of a lithium ion conductive oxide having a garnet-type or garnet-like crystal structure are 6-coordinated and rare earth elements are also 6-coordinated, and in this case, the ion radius of the rare earth elements is larger than the ion radius of Zr, and the Zr sites are replaced with the rare earth elements having a larger ion radius, so that the lattice constant becomes larger, and it is considered that the space in which L i ions move is enlarged and L i ions are easily moved, and the substitution of Zr sites is caused by replacing Zr sites (4-valent sites) with 3-valent ions, and thus L i ions are required to compensate for charges7+xLa3Zr2－xAxO12… … (1) at the L i site, and thus, the amount of mobile L i ions increases it is believed that the lithium ion conducting oxide ceramic material of the present embodiment can be controlled to have the chemical formula L i due to the mechanism shown above7+xLa3Zr2－xAxO12The lattice constant of the oxide and the amount of L i ions are expressed, and therefore, the ion conductivity in the crystal grains can be improved.
It is also preferable to replace the Zr site with a rare earth element selected from Gd, Tb, Dy, Ho, Er, Tm, Yb, L u for the reason that L i ions are easily moved by enlarging the space in which L i ions move by replacing with a rare earth element having a larger ion radius than the Zr site, however, there is a space in which L i ions are easily moved with an optimal size in the space in which L i ions move, that is, it is difficult to achieve synergistic movement of L i ions even if the moving space is excessively expanded by replacing with a rare earth element having a larger ion radius, and therefore, it is considered that substitution with a rare earth element selected from Gd, Tb, Dy, Ho, Er, Tm, Yb, L u provides an optimal size in which L i ions are easily moved, and has an effect of obtaining higher ion conductivity.
In addition, x in the above composition formula (1) is preferably 0 < x.ltoreq.0.30. This can provide higher ion conductivity.
It is preferable to replace the Zr site with a rare earth element among Gd, Ho, Yb, whereby a space optimal for the synergistic movement of L i ions can be realized and higher ion conductivity can be obtained.
The reason why the lithium ion conductive oxide ceramic material having a garnet-type or garnet-like crystal structure of the present embodiment contains 0.3 wt% or more and 2.0 wt% or less of Al with respect to the total weight thereof to obtain a high ion conductivity is considered to be because the structure is likely to form L i having a cubic crystal structure7+xLa3Zr2－ xAxO12. In the case where the content of Al is less than 0.3 wt%, the effect of facilitating cubic crystallization becomes weak. In addition, in the case where the content of Al exceeds 2.0 wt%, firing may be hindered. Therefore, the sintered density is reduced, and as a result, the ionic conductivity may be reduced.
(method for producing ceramic Material)
The lithium ion conductive oxide ceramic material of the present embodiment can be obtained by firing a mixed raw material in which an L i compound, a L a compound, a Zr compound, and a compound of any one or more rare earth elements selected from rare earth elements are mixed.
Examples of the L i compound include L iOH or a hydrate thereof, L i2CO3、LiNO3、CH3COO L i, etc. examples of the L a compound include L a2O3、La(OH)3、La2(CO3)3、La(NO3)3、(CH3COO)3L a, etc. As the Zr compound, Zr is exemplified2O2、ZrO(NO3)2、ZrO(CH3COO)2、Zr(OH)2CO3、ZrO2And the like.
Further, as the rare earth compound, A is mentioned2O3、A2(CO3)3、A(NO3)3、(CH3COO)3A and the like (A is a rare earth element).
Further, the Al compound may be Al2O3、Al(OH)3、Al(NO3)3And the like.
An example of the method for producing the garnet-type lithium ion-conductive oxide ceramic of the present invention will be described. In the method for producing the oxide, the step (a) of mixing raw materials is performed, the step (b) of calcining is performed, and the step (c) of molding and main sintering is finally performed. These steps will be described in order below.
(a) Raw material mixing step
In the raw material mixing step, L i which is represented by formula (1) was weighed7+xLa3Zr2－xAxO12The initial raw materials of the respective elements (a) may be mixed in a stoichiometric ratio of the formula (1), and carbonates, sulfates, nitrates, oxalates, chlorides, hydroxides, oxides, etc. of the respective elements are preferably used as the initial raw materials, among them, carbonates that generate carbon dioxide by thermal decomposition and hydroxides that generate steam by thermal decomposition are relatively easy to be handled as gas, for example, L i carbonate, L a and a hydroxides, and Zr oxides are preferably usedFor example, 1 hour to 32 hours.
(b) Calcination Process
In the calcination step, the mixed powder obtained in the mixing step is calcined, and the calcination temperature in this case is preferably set to a temperature at which a change in the state of the starting material (for example, generation of a gas or a phase change) occurs or higher and lower than the temperature at the time of main sintering, and for example, L i is used2CO3In the case of one of the starting materials, the temperature at which the carbonate is decomposed is preferably not lower than the temperature at which the carbonate is decomposed and lower than the temperature at the time of main sintering. Accordingly, the density reduction due to the gas generation during thermal decomposition can be suppressed in the main sintering thereafter. Specifically, the calcination temperature is preferably 800 to 1000 ℃.
(c) Molding and final sintering step
In the main sintering, the material obtained in the molding and firing step (referred to as pre-main-sintering powder) is sintered at a temperature equal to or higher than the firing temperature. The molding method for obtaining the molded body may be performed by a method of adding a binder to the powder before main sintering to mold, Cold Isostatic Pressing (CIP), Hot Isostatic Pressing (HIP), hot pressing, or the like to form an arbitrary shape. Alternatively, the powder before sintering may be mixed with an organic binder, a dispersant, a plasticizer, and the like, molded into a sheet, and molded into a multilayer structure. The firing atmosphere may be performed in a reducing atmosphere, in addition to the atmospheric atmosphere, if necessary.
According to the above-described method, since the mixed powder of the starting materials is calcined at a relatively low temperature after the mixed powder is calcined, and then the main sintering is performed, the variation in composition can be suppressed with high accuracy. The method for producing the lithium ion conductive oxide ceramic material having a garnet-type or garnet-like crystal structure of the present invention is not limited to this, and other methods may be used.
(all-solid-state lithium secondary battery)
As shown in fig. 2, the all-solid lithium secondary battery of the present embodiment is composed of a positive electrode 1, a negative electrode 2, and a solid electrolyte 3, and the solid electrolyte 3 has L i, L a, Zr, and OFor example, the present invention is a lithium ion-conducting oxide ceramic material having a garnet-type or garnet-like crystal structure, characterized by having a composition formula of L i7+xLa3Zr2－xAxO12… … (1) (in the formula (1), A is at least one element selected from rare earth elements, and x is a number satisfying 0 < x.ltoreq.0.5). With such a structure, the secondary battery is more practical than the conventional secondary battery.
The positive electrode 1 and the negative electrode 2 of the all-solid-state lithium ion secondary battery according to the present embodiment are each composed of a positive electrode active material 5, a positive electrode current collector 4, a negative electrode active material 7, and a negative electrode current collector 6.
The positive electrode active material 5 and the negative electrode active material 7, which are conventionally known for use in lithium secondary batteries, may be contained and manufactured by a conventional method.
(Positive electrode active Material)
The positive electrode active material is not particularly limited, and any conventionally known positive electrode active material for all-solid batteries can be used. Specific examples of such a positive electrode active material include: manganese dioxide (MnO)2) Iron oxide, copper oxide, nickel oxide, lithium manganese composite oxide (e.g., L i)xMn2O4Or L ixMnO2) Lithium nickel composite oxide (e.g., L i)xNiO2) Lithium cobalt composite oxide (e.g., L i)xCoO2) Lithium nickel cobalt complex oxides (e.g., L iNi)1－yCoyO2) Lithium manganese cobalt composite oxides (e.g., L iMn)yCo1－yO2) Spinel type lithium manganese nickel composite oxides (e.g., L i)xMn2－yNiyO4) Lithium phosphate compounds having an olivine structure (e.g., L i)xFePO4，LixFe1－yMnyPO4，LixCoPO4，LiVOPO4) Lithium phosphate compounds of NASICON structure (e.g., L i)xV2(PO4)3，Li2VOP2O7，Li2VP2O7，Li4(VO)(PO4)2And L i9V3(P2O7)3(PO4)2) Iron (Fe) sulfate2(SO4)3) Vanadium oxide (e.g., V)2O5) These compounds may be used singly or in combination of two or more kinds, and in these formulae, x and y are preferably in the ranges of 1 < x < 5 and 0 < y < 1, among which L iCoO is preferable2、LiNiO2、LixV2(PO4)3、LiFePO4。
(negative electrode active Material)
Examples of the negative electrode active material include carbon, metallic lithium (L i), metal compounds, metal oxides, L i metal compounds, L i metal oxides (including lithium-transition metal composite oxides), boron-added carbon, graphite, and compounds having an NASICON structure3Bi、Li3Sd、Li4Si、Li4.4Sn、Li0.17C(LiC6) And the like. Examples of the metal oxide include SnO and SnO2、GeO、GeO2、In2O、In2O3、Ag2O、AgO、Ag2O3、Sb2O3、Sb2O4、Sb2O5、SiO、ZnO、CoO、NiO、TiO2L i metal compounds include L i3FeN2、Li2.6Co0.4N、Li2.6Cu0.4N. L i as metal oxide (lithium-transition metal complex oxygen)Compound (ii), exemplified by L i4Ti5O12The lithium-titanium composite oxide shown below, and the like. Examples of the boron-containing carbon include boron-containing carbon and boron-containing graphite.
(Current collector)
As a material constituting the current collector of the all-solid lithium ion secondary battery of the present embodiment, a material having a large electric conductivity is preferably used, and for example, silver, palladium, gold, platinum, aluminum, copper, nickel, or the like is preferably used. Copper is particularly preferred because it is less reactive with lithium titanium aluminum phosphate and has the effect of reducing the internal resistance of the lithium ion secondary battery. The material constituting the current collector may be the same as or different from the positive electrode and the negative electrode.
In the lithium ion secondary battery of the present embodiment, the positive electrode collector layer and the negative electrode collector layer preferably contain a positive electrode active material and a negative electrode active material, respectively.
The positive electrode collector layer and the negative electrode collector layer preferably contain a positive electrode active material and a negative electrode active material, respectively, because the adhesion between the positive electrode collector layer and the positive electrode active material layer and between the negative electrode collector layer and the negative electrode active material layer is improved.
(method for manufacturing lithium ion Secondary Battery)
The lithium ion secondary battery of the present embodiment is manufactured by slurrying each material of the positive electrode collector layer, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode collector layer, coating and drying the slurry to prepare green sheets, laminating the green sheets, and simultaneously firing the prepared laminate.
The method of slurrying is not particularly limited, and for example, powders of the above-described respective materials may be mixed into a medium to obtain a slurry. Here, the medium is a generic term of a medium in a liquid phase. The medium contains solvent and adhesive. By this method, a slurry for a positive electrode collector layer, a slurry for a positive electrode active material layer, a slurry for a solid electrolyte layer, a slurry for a negative electrode active material layer, and a slurry for a negative electrode collector layer were prepared.
The prepared slurry is applied to a substrate such as PET in a desired order, dried as necessary, and then peeled off to prepare a green sheet. The method of applying the paste is not particularly limited, and known methods such as screen printing, coating, transfer printing, and doctor blade can be used.
The produced green sheets are stacked in a desired order and number of layers, and arranged and cut as necessary to produce a laminated block. In the case of producing a parallel-type or series-parallel-type battery, it is preferable that the end faces of the positive electrode layers and the negative electrode layers are arranged and overlapped so as not to coincide with each other.
When a laminated block is produced, an active material unit described below may be prepared to produce a laminated block.
In this method, first, a solid electrolyte slurry is formed into a sheet shape on a PET film by a doctor blade method to obtain a solid electrolyte sheet, and then a positive electrode active material layer slurry is printed on the solid electrolyte sheet by screen printing and dried. Next, a positive electrode current collector layer slurry was printed on this layer by screen printing and dried. Further, the positive electrode active material slurry was printed again on this layer by screen printing, dried, and then the PET film was peeled off to obtain a positive electrode active material layer unit. In this way, a positive electrode active material layer unit was obtained in which the positive electrode active material layer slurry, the positive electrode current collector layer slurry, and the positive electrode active material slurry were sequentially formed on the solid electrolyte sheet. In the same manner, a negative electrode active material layer unit was also prepared, and a negative electrode active material layer unit in which a negative electrode active material layer slurry, a negative electrode current collector layer slurry, and a negative electrode active material slurry were formed in this order on a solid electrolyte sheet was obtained.
One positive electrode active material layer element and one negative electrode active material layer element are stacked with a solid electrolyte sheet interposed therebetween. In this case, the cells are stacked in a staggered manner such that the positive electrode collector layer slurry of the first positive electrode active material layer cell extends only from one end face, and the negative electrode collector layer slurry of the second negative electrode active material layer cell extends only from the other face. A laminated block is produced by further laminating a solid electrolyte sheet of a predetermined thickness on both sides of the laminated cell.
The produced laminate blocks were strongly bonded together. The strong adhesion is carried out while heating, and the heating temperature is set to, for example, 40 to 95 ℃.
The strongly bonded laminate block is heated to 600 to 1200 ℃ in a nitrogen atmosphere, for example, and fired. The firing time is, for example, 0.1 to 3 hours. By this firing, a laminate is completed. Examples
The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.
[ examples 1 to 10]
In order to demonstrate the effects of the present embodiment, as examples of the lithium ion-conductive oxide ceramic material having a garnet-type or garnet-like crystal structure, L i was replaced with each of the ceramic materials7.10La3.00(Zr1.90A0.10)O12(compositions of Y, Nd, Gd, Ho, Yb) (examples 1 to 5), 1.0 wt% of Al was further added to each composition2O3Composition of (example 6-example 10) L i was used as a starting material2CO3、La(OH)3、ZrO2、Y2O3、Nd2O3、Gd2O3、Ho2O3、Yb2O3And Al2O3. First, the starting materials were weighed to a stoichiometric ratio, and mixed and pulverized in ethanol for 16 hours by a ball mill (120 rpm/zirconia balls). The mixed powder of the starting materials was separated from the pellets and ethanol, and then calcined in an alumina crucible at 900 ℃ for 5 hours in an atmospheric atmosphere. Then, the calcined powder was treated in ethanol for 16 hours using a ball mill (120 rpm/zirconia balls) for mixing. Separating the pulverized powder from the balls and ethanol, and drying to obtain pre-sintering powder. Then, an organic binder is added to the pre-main-sintering powder to prepare pellets. The pellets were molded into a disk shape at 7kN using a mold having a diameter of 10 mm. The molded body was subjected to main sintering on a platinum plate at a sintering temperature of 1100 to 1150 ℃ for two hours in the atmosphere to obtain a disk-shaped sintered sample.
[ examples 11 to 26]
In addition, L i in which Zr was replaced with A respectively is proposed7.35La3.00(Zr1.65A0.35)O12Compositions (examples 11 to 18) of (A ═ Gd, Tb, Dy, Ho, Er, Tm, Yb, L u) and further addition of 1.0 wt% Al to each composition2O3Composition of (example 19-example 26) starting Material L i was used2CO3、La(OH)3、ZrO2、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Er2O3、Tm2O3、Yb2O3、Lu2O3And Al2O3. First, the starting materials were weighed to a stoichiometric ratio, and mixed and pulverized in ethanol with a ball mill (120 rpm/zirconia balls) for 16 hours. The mixed powder of the starting materials was separated from the pellets and ethanol, and then calcined in an alumina crucible at 900 ℃ for 5 hours in an atmospheric atmosphere. Then, for mixing, the calcined powder was treated in ethanol for 16 hours using a ball mill (120 rpm/zirconia balls). Separating the pulverized powder from the balls and ethanol, and drying to obtain pre-sintering powder. Next, an organic binder is added to the pre-main-sintering powder to prepare pellets. The pellets were molded into a disk shape at 7kN using a mold having a diameter of 10 mm. The molded article was subjected to main sintering in the atmosphere at a sintering temperature of 1075 to 1125 ℃ for two hours on a platinum plate to obtain a disk-shaped sintered sample.
[ examples 27 to 29]
In addition, L i7.05La3.00(Zr1.95Gd0.05)O12、Li7.25La3.00(Zr1.75Gd0.25)O12、Li7.50La3.00(Zr1.50Gd0.50)O121.0 wt% of Al was added to each of the respective portions2O3Initial feedstock usage L i2CO3、La(OH)3、ZrO2、Gd2O3And Al2O3. First, the ratio is set to be the stoichiometric ratioThe starting materials were weighed, mixed and pulverized in ethanol by a ball mill (120 rpm/zirconia balls) for 16 hours. The mixed powder of the starting materials was separated from the pellets and ethanol, and then calcined in an alumina crucible at 900 ℃ for 5 hours in an atmospheric atmosphere. Then, for mixing, the calcined powder was treated in ethanol with a ball mill (120 rpm/zirconia balls) for 16 hours. Separating the pulverized powder from the balls and ethanol, and drying to obtain pre-sintering powder. Next, an organic binder is added to the pre-main-sintering powder to prepare pellets. The pellets were molded into a disk shape at 7kN using a mold having a diameter of 10 mm. The molded body was subjected to main sintering on a platinum plate at a sintering temperature of 1100 to 1125 ℃ in the air for two hours to obtain a disk-shaped sintered sample.
[ examples 30 to 32]
In addition, pair L i7.05La3.00(Zr1.95Ho0.05)O12、Li7.25La3.00(Zr1.75Ho0.25)O12、Li7.50La3.00(Zr1.50Ho0.50)O121.0 wt% of Al was added to each of the respective portions2O3Initial feedstock usage L i2CO3、La(OH)3、ZrO2、Ho2O3And Al2O3. First, the starting materials were weighed so as to be in a stoichiometric ratio, and mixed and pulverized in ethanol by a ball mill (120 rpm/zirconia balls) for 16 hours. The mixed powder of the starting materials was separated from the pellets and ethanol, and then calcined in an alumina crucible at 900 ℃ for 5 hours in an atmospheric atmosphere. Then, for mixing, the calcined powder was treated in ethanol with a ball mill (120 rpm/zirconia balls) for 16 hours. Separating the pulverized powder from the balls and ethanol, and drying to obtain pre-sintering powder. Next, an organic binder is added to the pre-main-sintering powder to prepare pellets. The pellets were molded into a disk shape at 7kN using a mold having a diameter of 10 mm. The molded body was subjected to main sintering in the atmosphere at a sintering temperature of 1050 to 1125 ℃ for two hours on a platinum plate to obtain a disk-shaped sintered sample.
[ examples 33 to 35]
In addition, pair L i7.05La3.00(Zr1.95Yb0.05)O12、Li7.25La3.00(Zr1.75Yb0.25)O12、Li7.50La3.00(Zr1.50Yb0.50)O121.0 wt% of Al was added to each of the respective portions2O3Initial feedstock usage L i2CO3、La(OH)3、ZrO2、Yb2O3And Al2O3. First, the starting materials were weighed to a stoichiometric ratio, and mixed and pulverized in ethanol using a ball mill (120 rpm/zirconia balls) for 16 hours. The mixed powder of the starting materials was separated from the pellets and ethanol, and then calcined in an alumina crucible at 900 ℃ for 5 hours in an atmospheric atmosphere. Then, for mixing, the calcined powder was treated in ethanol with a ball mill (120 rpm/zirconia balls) for 16 hours. The pulverized powder was separated from the pellets and ethanol and dried to obtain a powder before sintering. Next, an organic binder is added to the pre-main-sintering powder to prepare pellets. The pellets were molded into a disk shape at 7kN using a mold having a diameter of 10 mm. The molded body was subjected to main sintering in the air at a sintering temperature of 1050 to 1100 ℃ for two hours on a platinum plate to obtain a disk-shaped sintered sample.
Example 36 to example 41
In addition, pair L i7.35La3.00(Zr1.65Yb0.35)O12Addition of Al2O3To Al2O3The contents (ywt%) were 0.2 wt%, 0.3 wt%, 0.7 wt%, 1.5 wt%, 2.0 wt%, and 2.1 wt%, respectively, L i was used as the starting material2CO3、La(OH)3、Yb2O3And Al2O3. First, the starting materials were weighed to a stoichiometric ratio, and mixed and pulverized in ethanol with a ball mill (120 rpm/zirconia balls) for 16 hours. The mixed powder of the starting materials was separated from the pellets and ethanol, and then calcined in an alumina crucible at 900 ℃ for 5 hours in an atmospheric atmosphere. Then, isThe calcined powder was treated in ethanol with a ball mill (120 rpm/zirconia balls) for 16 hours with mixing. The pulverized powder was separated from the pellets and ethanol and dried to obtain a powder before sintering. Next, an organic binder is added to the pre-main-sintering powder to prepare pellets. The pellets were molded into a disk shape at 7kN using a mold having a diameter of 10 mm. The molded body was subjected to main sintering on a platinum plate at a sintering temperature of 1100 to 1150 ℃ for 2 hours in the atmosphere to obtain a disk-shaped sintered sample.
Comparative example 1
Using L i7.00La3.00Zr2.00O12Composition of initial raw Material L i2CO3、La(OH)3、ZrO2. First, the starting materials were weighed to be stoichiometric, and mixed and pulverized in ethanol with a ball mill (120 rpm/zirconia balls) for 16 hours. The mixed powder of the starting materials was separated from the pellets and ethanol, and then calcined in an alumina crucible at 900 ℃ for 5 hours in an atmospheric atmosphere. Then, for mixing, the calcined powder was treated in ethanol for 16 hours using a ball mill (120 rpm/zirconia balls). Separating the pulverized powder from the balls and ethanol, and drying to obtain pre-sintering powder. Next, an organic binder is added to the pre-main-sintering powder to prepare pellets. The pellets were molded into a disk shape at 7kN using a mold having a diameter of 10 mm. The molded body was subjected to main sintering on a platinum plate at a sintering temperature of 1150 ℃ in the atmosphere for two hours to obtain a disk-shaped sintered sample.
Comparative example 2
In addition, L i is proposed7.00La3.00Zr2.00O12To which 1.0 wt% of Al is added2O3L i as the starting material2CO3、La(OH)3、ZrO2And Al2O3. First, the starting materials were weighed to a stoichiometric ratio, and mixed and pulverized in ethanol using a ball mill (120 rpm/zirconia balls) for 16 hours. The mixed powder of the starting materials was separated from the pellets and ethanol, and then calcined in an alumina crucible at 900 ℃ for 5 hours in an atmospheric air atmosphere. Then, for mixing, the calcined powder was treated in ethanol for 16 hours using a ball mill (120 rpm/zirconia balls). Separating the pulverized powder from the balls and ethanol, and drying to obtain pre-sintering powder. Next, an organic binder is added to the pre-main-sintering powder to prepare pellets. The pellets were molded into a disk shape at 7kN using a mold having a diameter of 10 mm. The molded body was subjected to main sintering on a platinum plate at a sintering temperature of 1100 ℃ in the atmosphere for two hours to obtain a disk-shaped sintered sample.
Comparative example 3
In addition, the direction L i is used7.53La3.00(Zr1.67Gd0.53)O12Added with 1.0 wt% of Al2O3L i as the starting material2CO3、La(OH)3、ZrO2、Gd2O3And Al2O3. First, the starting materials were weighed so as to be in a stoichiometric ratio, and mixed and pulverized in ethanol by a ball mill (120 rpm/zirconia balls) for 16 hours. The mixed powder of the starting materials was separated from the pellets and ethanol, and then calcined in an alumina crucible at 900 ℃ for 5 hours in an atmospheric atmosphere. Then, for mixing, the calcined powder was treated in ethanol for 16 hours using a ball mill (120 rpm/zirconia balls). Separating the pulverized powder from the balls and ethanol, and drying to obtain pre-sintering powder. Next, an organic binder is added to the pre-main-sintering powder to prepare pellets. The pellets were molded into a disk shape at 7kN using a mold having a diameter of 10 mm. The molded body was subjected to main sintering in the air at a sintering temperature of 1050 ℃ for two hours on a platinum plate to obtain a disk-shaped sintered sample.
Comparative example 4
In addition, the direction L i is used7.52La3.00(Zr1.68Ho0.52)O12To which 1.0 wt% of Al is added2O3L i as the starting material2CO3、La(OH)3、ZrO2、Ho2O3And Al2O3. First, the starting materials were weighed to be stoichiometric in ethanolThe mixture was mixed and pulverized for 16 hours by a ball mill (120 rpm/zirconia balls). The mixed powder of the starting materials was separated from the pellets and ethanol, and then calcined in an alumina crucible at 900 ℃ for 5 hours in an atmospheric atmosphere. Then, for mixing, the calcined powder was treated in ethanol for 16 hours using a ball mill (120 rpm/zirconia balls). Separating the pulverized powder from the balls and ethanol, and drying to obtain pre-sintering powder. Next, an organic binder is added to the pre-main-sintering powder to prepare pellets. The pellets were molded into a disk shape at 7kN using a mold having a diameter of 10 mm. The molded body was subjected to main sintering on a platinum plate at a sintering temperature of 1050 ℃ in the atmosphere for two hours to obtain a disk-shaped sintered sample.
Comparative example 5
In addition, the direction L i is used7.52La3.00(Zr1.68Yb0.52)O12To which 1.0 wt% of Al is added2O3L i as the starting material2CO3、La(OH)3、ZrO2、Yb2O3And Al2O3. First, the starting materials were weighed so as to be in a stoichiometric ratio, and mixed and pulverized in ethanol by a ball mill (120 rpm/zirconia balls) for 16 hours. The mixed powder of the starting materials was separated from the pellets and ethanol, and then calcined in an alumina crucible at 900 ℃ for 5 hours in an atmospheric atmosphere. Then, for mixing, the calcined powder was treated in ethanol for 16 hours using a ball mill (120 rpm/zirconia balls). Separating the pulverized powder from the balls and ethanol, and drying to obtain pre-sintering powder. Next, an organic binder is added to the pre-main-sintering powder to prepare pellets. The pellets were molded into a disk shape at 7kN using a mold having a diameter of 10 mm. The molded body was subjected to main sintering on a platinum plate at a sintering temperature of 1050 ℃ in the atmosphere for two hours to obtain a disk-shaped sintered sample.
[ calculation of relative Density ]
The sintered density of the lithium ion conductive oxide ceramic forming the disk-shaped sintered body was calculated by measuring the volume of the disk-shaped sintered body by a micrometer and dividing the dry weight of the disk-shaped sintered body by the volume. Then, the relative density (unit:%) was calculated as a percentage by dividing the sintered density by the theoretical density. The relative densities of the examples and comparative examples are shown in tables 1 to 8 described below.
[ measurement of conductivity and estimation of ion conductivity ]
In the thermostatic bath, an AC impedance analyzer (1260, manufactured by Solartron corporation) was used, the measurement temperature was 25 ℃, the measurement frequency was 0.05Hz to 30MHz, the amplitude voltage: 50mV, impedance and phase angle were measured. A Nyquist plot is plotted based on these measured values, a resistance value is obtained from the arc, and the conductivity is calculated from the resistance value. The blocking electrode as measured by an AC impedance analyzer was an Au electrode. The Au electrode was formed in a round shape of 3mm in diameter by a sputtering method.
From the above measurement, a nyquist diagram as shown in fig. 1 was obtained. The resistance value obtained from the nyquist diagram can be distinguished into resistances including the resistance inside the crystal and the grain boundary resistance according to the kind of the circular arc thereof. In this patent, the ion conductivity calculated based on the resistance inside the crystal is shown in tables 1 to 6.
[ TABLE 1]
A Firing temperature (. degree. C.) Relative density (%) Ion conductivity in Crystal grain (S/cm)
Example 1 Y 1150 86.5 1.13E-03
Example 2 Nd 1150 91.8 1.31E-03
Example 3 Gd 1150 89.5 1.42E-03
Example 4 Ho 1150 94.4 1.42E-03
Example 5 Yb 1125 93.4 1.43E-03
Comparative example-1 Is free of 1150 77.5 7.90E-04
In the samples obtained in examples 1 to 5Since L i ion movement space is enlarged and L i ion concentration is increased by substituting rare earth elements having larger ion radii at Zr sites, it was confirmed that 1.00 × 10-3High ion conductivity of S/cm or more, it was confirmed that 7.90 × 10 was exhibited in the sample obtained in comparative example 1, which was the unsubstituted rare earth element-4Lower ion conductivity of S/cm.
[ TABLE 2] A (containing Al)
A Firing temperature (. degree. C.) Relative density (%) Ion conductivity in Crystal grain (S/cm)
Example 6 Y 1125 88.3 1.18E-03
Example 7 Nd 1125 93.7 1.36E-03
Example 8 Gd 1125 91.3 1.48E-03
Example-9 Ho 1125 96.3 1.48E-03
Example 10 Yb 1100 95.3 1.49E-03
Comparative example-2 Is free of 1100 79.1 8.23E-04
In examples 6 to 10, it was confirmed that cubic crystals were easily formed and higher ion conductivity was obtained by further containing Al in place of the rare earth element, that is, 1.18 × 10-3On the other hand, in comparative example 2 containing Al but containing an unsubstituted rare earth element, it was confirmed that 8.23 × 10 is exhibited-4Lower ion conductivity of S/cm.
[ TABLE 3]
A Firing temperature (. degree. C.) Relative density (%) Ion conductivity in Crystal grain (S/cm)
Example 11 Gd 1125 89.9 3.93E-03
Example-12 Tb 1125 90.5 3.42E-03
Example 13 Dy 1125 89.2 3.31E-03
Example 14 Ho 1125 94.8 4.02E-03
Example 15 Er 1100 92.1 3.01E-03
Example 16 Tm 1100 91.1 2.87E-03
Example 17 Yb 1100 93.9 4.03E-03
Example 18 Lu 1100 89.8 2.81E-03
In particular, it was confirmed that since the L i ion movement space was further optimized in examples 11 to 18 in which Gd, Tb, Dy, Ho, Er, Tm, Yb, and L u, which are rare earth elements, were limited and the substitution amount thereof was further increased, 2.81 × 10-3High ion conductivity of S/cm or more.
[ TABLE 4] A (containing Al)
A Firing temperature (. degree. C.) Relative density (%) Ion conductivity in Crystal grain (S/cm)
Example 19 Gd 1100 91.8 4.10E-03
Example 20 Tb 1100 92.4 3.57E-03
Example 21 Dy 1100 91.0 3.45E-03
Example-22 Ho 1075 96.8 4.18E-03
Example 23 Er 1075 93.9 3.13E-03
Example 24 Tm 1075 92.9 2.99E-03
Example-25 Yb 1075 95.8 4.20E-03
Example 26 Lu 1075 91.6 2.93E-03
In examples 19 to 26, by further containing Al, cubic crystals were easily formed, and it was confirmed that high ion conductivity was obtained, namely, it was 2.93 × 10-3High ion conductivity of S/cm or more.
[ TABLE 5] containing Gd, Al
x Firing temperature (. degree. C.) Relative density (%) Ion conductivity in Crystal grain (S/cm)
Comparative example-2 0 1100 79.1 8.23E-04
Example 27 0.05 1125 82.1 9.52E-04
Example 8 0.10 1125 91.3 1.48E-03
Example 28 0.25 1125 89.6 3.44E-03
Example 19 0.35 1100 91.8 4.10E-03
Example 29 0.50 1100 87.4 1.44W-03
ComparisonExample 3 0.53 1050 87.2 3.48E-04
[ TABLE 6] A (containing Ho, Al)
x Firing temperature (. degree. C.) Relative density (%) Ion conductivity in Crystal grain (S/cm)
Comparative example-2 0 1100 79.1 8.23E-04
Example 30 0.05 1125 88.4 9.92E-04
Example-9 0.10 1125 96.3 1.48E-03
Example-31 0.25 1075 96.5 3.58E-03
Example-22 0.35 1075 96.8 4.18E-03
Example 32 0.50 1050 94.1 1.50E-03
Comparative example-4 0.52 1050 93.9 3.63E-04
[ TABLE 7 ] A (containing Yb, Al)
x Firing temperature (. degree. C.) Relative density (%) Ion conductivity in Crystal grain (S/cm)
Comparative example-2 0 1100 79.1 8.23E-04
Example 33 0.05 1100 87.5 9.95E-04
Example 10 0.10 1100 95.3 1.49E-03
Example 34 0.25 1075 95.5 3.59E-03
Example-25 0.35 1075 95.8 4.20E-03
Example 35 0.50 1050 93.1 1.50E-03
Comparative example-5 0.52 1050 92.9 3.64E-04
Among the Zr site-substituted elements, Gd, Ho and Yb were exemplified as typical examples, and the effect on the ion conductivity in the grains was confirmed by changing the substitution amounts, as shown in examples 8, 9 and 10 and examples 27 to 35, it was confirmed that the substitution amount x was from 0.05 to 0.50, and 9.50 × 10 was exhibited-4Particularly, the samples obtained in examples 8, 9, 10, 28, 29, 31, 32, 34 and 35 (the substitution amount x is 0.10 to 0.50) showed 1.45 × 10-3On the other hand, comparative example 2(x ═ 0) showed a high ion conductivity of 8.23 × 10-4Further, it was confirmed that the ionic conductivity was reduced in comparative examples 3, 4 and 5 in which the substitution amount x was set to 0.52 and 0.53, and that the ionic conductivity was 3.48 × 10-4S/cm、3.63×10-4S/cm、3.64×10-4Low ion conductivity of S/cm.
[ TABLE 8 ] A (containing Yb, Al)
Al2O3：y(wt％) Firing temperature (. degree. C.) Relative density (%) Ion conductivity in Crystal grain (S/cm)
Example 36 0.2 1100 88.8 9.97E-04
Example 37 0.3 1100 96.0 3.33E-03
Example 38 0.7 1100 96.1 5.10E-03
Example-25 1.0 1100 95.8 4.20E-03
Example 39 1.5 1125 93.5 3.35E-03
Example 40 2.0 1125 90.3 9.91E-04
Example 41 2.1 1150 75.6 9.65E-04
The effect of containing Al for improving sinterability and stabilizing cubic crystals was confirmed in examples 37 to 40, in which the Al content was from 0.3 to 2.0 wt%, and 9.90 × 10 was exhibited-4High ion conductivity of S/cm or more, particularly, the samples obtained in examples 32 to 34 (0.3 to 1.5% by weight in terms of the amount of substitution) showed 3.33 × 10-3On the other hand, it was confirmed that 9.97 × 10 was exhibited in example 36 containing as little Al as 0.2 wt% or example 41 containing as much Al as 2.1 wt%, respectively－4S/cm、9.65×10－4S/cm, lower ionic conductivity than the examples containing 0.3 wt% to 2.0 wt% Al.
[ confirmation of the formed phase ]
For each sample, phase identification was performed from the XRD measurement results, and it was confirmed that the sample was substantially single-phase, and it was judged that the rare earth element used for substitution was substituted at the Zr site, and the XRD measurement was performed under the conditions of CuK α, 2 θ: 10 to 90 °, and 0.01 ° step/1sec using X' Pert PRO manufactured by PANalytical.
[ compositional analysis ]
The chemical composition of each sample was analyzed by ICP emission spectrometry (measuring apparatus: product name: ICP-7500, manufactured by Shimadzu corporation), and it was confirmed that there was no change in the evaluation sample composition and the feed composition.
[ example 42]
Examples of the all solid-state lithium secondary battery are shown below, but the present invention is not limited to these examples. In addition, "part" means part by mass unless otherwise specified.
(preparation of Positive electrode active Material and negative electrode active Material)
L i produced by the following method was used as the positive electrode active material and the negative electrode active material3V2(PO4)3L i as the preparation method2CO3、V2O5、NH4H2PO4The obtained powder was calcined at 850 ℃ for two hours in a nitrogen-hydrogen mixed gas, wet-pulverized with a ball mill, and then dehydrated and dried to obtain a powder, and the structure of the prepared powder was confirmed to be L i using an X-ray diffraction apparatus3V2(PO4)3。
(preparation of Positive electrode active Material slurry and negative electrode active Material slurry)
The amount of the positive electrode active material slurry and the negative electrode active material slurry was 100 parts L i3V2(PO4)3To the powder of (2) was added 15 parts of ethyl cellulose as a binder and 65 parts of dihydroterpineol as a solvent, and the mixture was mixed and dispersed to prepare an active material slurry.
(preparation of solid electrolyte)
L i produced by the following method was used as a solid electrolyte7.35La3.00(Zr1.65Yb0.35)O121.0 wt% of Al is added2O3The preparation method comprises L i2CO3、La(OH)3、ZrO2、Yb2O3And Al2O3As a starting material, the mixture was mixed and pulverized for 16 hours by a ball mill (120 rpm/zirconia balls). Separating the mixed powder of the initial raw materials from the balls and ethanol, calcining in an alumina crucible at 900 deg.C in the atmosphereFiring for 5 hours, then, for mixing, the calcined powder was treated in ethanol for 16 hours with a ball mill (120 rpm/zirconia balls), the pulverized powder was separated from the balls and ethanol and dried to obtain a powder of a main solid electrolyte, and it was confirmed using an X-ray diffraction apparatus that the structure of the produced powder was L i7.35La3.00(Zr1.65Yb0.35)O12。
Then, 100 parts of ethanol and 200 parts of toluene as solvents were added to the powder by a ball mill and wet-mixed. Then, 16 parts of a polyvinyl butyral binder and 4.8 parts of butyl benzyl phthalate were further charged and mixed to prepare a solid electrolyte slurry.
(preparation of solid electrolyte sheet)
The solid electrolyte slurry was subjected to sheet molding by a doctor blade method using a PET film as a base material to obtain a solid electrolyte sheet having a thickness of 15 μm.
(preparation of Current collector slurry)
Ni and L i to be used as current collectors3V2(PO4)3The mixture was mixed at a volume ratio of 80/20, and ethyl cellulose as a binder and dihydroterpineol as a solvent were added thereto and mixed and dispersed to prepare a current collector slurry. The average particle size of Ni was 0.9. mu.m.
(preparation of terminal electrode paste)
The silver powder, the epoxy resin, and the solvent were mixed and dispersed to prepare a thermosetting terminal electrode paste.
Using these slurries, a lithium ion secondary battery was produced as follows.
(preparation of Positive electrode active Material layer Unit)
The positive electrode active material layer slurry was printed on the above solid electrolyte sheet by screen printing at a thickness of 5 μm, and dried at 80 ℃ for 10 minutes. Next, the positive electrode collector layer slurry was printed thereon by screen printing at a thickness of 5 μm, and dried at 80 ℃ for 10 minutes. Further, the positive electrode active material paste was printed again thereon by screen printing at a thickness of 5 μm and dried at 80 ℃ for 10 minutes, and then, the PET film was peeled. In this way, a sheet of a positive electrode active material layer unit in which the positive electrode active material layer slurry, the positive electrode current collector layer slurry, and the positive electrode active material layer slurry were printed and dried in this order on a solid electrolyte sheet was obtained.
(preparation of negative electrode active material layer Unit)
The negative electrode active material slurry was printed on the above solid electrolyte sheet by screen printing at a thickness of 5 μm, and dried at 80 ℃ for 10 minutes. Next, the negative electrode collector layer paste was printed thereon by screen printing at a thickness of 5 μm, and dried at 80 ℃ for 10 minutes. Further, the anode active material slurry was printed again thereon by screen printing at a thickness of 5 μm and dried at 80 ℃ for 10 minutes, and then, the PET film was peeled. In this way, a sheet in which the negative electrode active material layer unit of the negative electrode active material slurry, the negative electrode current collector layer slurry, and the negative electrode active material slurry was printed and dried in this order on the solid electrolyte sheet was obtained.
(preparation of a Stack)
One positive electrode active material layer element and one negative electrode active material layer element are stacked with a solid electrolyte sheet interposed therebetween. In this case, the cells are stacked in a staggered manner such that the positive electrode collector layer slurry of the first positive electrode active material layer cell extends only to one end face, and the negative electrode collector layer slurry of the second negative electrode active material layer cell extends only to the other face. A solid electrolyte sheet was laminated on both sides of the laminated cell to a thickness of 500 μm, and then, the laminated cell was molded by thermal adhesion and cut to produce a laminated block. Then, the laminated block was simultaneously fired to obtain a laminate. The simultaneous firing is carried out by heating the mixture to a firing temperature of 1075 ℃ at a heating rate of 200 ℃/hr in nitrogen, holding the temperature for two hours, and naturally cooling the mixture after firing.
(terminal electrode Forming Process)
The end face of the laminated block was coated with a terminal electrode paste, and heat-cured at 150 ℃ for 30 minutes to form a pair of terminal electrodes, thereby obtaining a lithium ion secondary battery.
(evaluation of Battery)
A lead was attached to the terminal electrode of the obtained lithium ion secondary battery, and a charge and discharge test was performed. Under the measurement conditions, the current during charge and discharge was 2.0 μ a, and the cut-off voltage during charge and discharge was 4.0V and 0V, respectively. As a result, it was found that the present battery was charged and discharged well, and that the discharge capacity was 0.4 μ a even when the solid electrolyte of comparative example 1 was used as the battery characteristics, but the battery characteristics were very good only when the discharge capacity was 2.4 μ a.
Industrial applicability
The invention can be used for all-solid-state lithium ion secondary batteries, in particular to devices with thin conductive layer thickness.

Claims (4)

1. A lithium ion conductive oxide ceramic material characterized in that,
having a garnet-type or garnet-like crystal structure,
and is represented by the following compositional formula (1),
Li7+xLa3Zr2－xAxO12(1)
in the formula (1), A is more than one element selected from Nd, Gd, Ho and Yb, and x is a number which satisfies 0.10-0.5.
2. The lithium ion conducting oxide ceramic material of claim 1,
a in the composition formula (1) is more than one element selected from Gd, Ho and Yb, and x is more than or equal to 0.10 and less than or equal to 0.30.
3. The lithium ion conducting oxide ceramic material according to claim 1 or 2,
further, the lithium ion conductive oxide ceramic material contains 0.3 wt% or more and 2.0 wt% or less of Al with respect to the total weight of the material.
4. An all-solid-state lithium ion secondary battery characterized in that,
a lithium ion conductive oxide ceramic material according to any one of claims 1 to 3 is used.
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