CN105977529A - Li-ion conductive oxide ceramic material with garnet type crystal structure or crystal structure similar to garnet type - Google Patents

Li-ion conductive oxide ceramic material with garnet type crystal structure or crystal structure similar to garnet type Download PDF

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Publication number
CN105977529A
CN105977529A CN201610137537.1A CN201610137537A CN105977529A CN 105977529 A CN105977529 A CN 105977529A CN 201610137537 A CN201610137537 A CN 201610137537A CN 105977529 A CN105977529 A CN 105977529A
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lithium
ion
crystal structure
powder
ceramic material
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CN105977529B (en
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塚田岳夫
田中祯
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 invention provides a Li-ion conductive oxide ceramic material with a garnet type crystal structure or a crystal structure similar to a garnet type, and internal resistance component in a crystalline grain has high contribution on ionic conductance. The Li-ion conductive oxide ceramic material with a garnet type crystal structure or a crystal structure similar to a garnet type contains Li, La, Zr, and O, and also contains more than one element selected from rare earth elements.

Description

There is the crystal structure of carbuncle type or similar carbuncle type Lithium-ion-conducting oxide ceramic material
Technical field
The lithium ion that the present invention relates to have the crystal structure of carbuncle type or similar carbuncle type passes The property led oxide ceramic material.
Background technology
Compared with the lithium secondary battery using nonaqueous electrolytic solution, all solid state type lithium rechargeable battery Using the ceramic material that electrolyte is sintered, therefore, heat stability is higher.But, high Even if all solid state type lithium rechargeable battery of capacity is not the most practical from the point of view of worldwide Change.One of its reason, the problem that there is solid electrolyte itself.Wanted as solid electrolyte The main characteristic asked, can enumerate that ionic conductance (conductivity) is high, chemical stability excellent, 3 characteristics that electrochemical window is big.Carbuncle type oxide ceramic material is owing to having in these characteristics The advantage that chemical stability is excellent, electrochemical window is big, therefore, desired for solid electrolyte One of candidate (referring for example to non-patent literature 1,2).
Prior art literature
Non-patent literature
Non-patent literature 1:J.Am.Ceram.Soc., 2003, volume 86 3,437-440 Page
Non-patent literature 2:Angew.Chem.Int.Ed., 2007, volume 46,7778-7781
Patent documentation
Patent documentation 1: No. 5083336 publications of Japanese Patent No.
Summary of the invention
Invent problem to be solved
This carbuncle type oxide ceramic material is expected to improve ionic conduction characteristic further.One For as, the ionic conductance of ionic conductivity pottery can consider to divide into crystal grain internal resistance Divide conductivity and the conductivity of grain boundary resistance components contribution of contribution, make with the thickest shape Solid electrolyte pottery in, pottery exists a large amount of crystal boundary portion, therefore, in order to evaluate The ionic conductance that electrolyte is overall, needs to consider in crystal grain and the resistance of crystal boundary both sides The ionic conductance that composition is contributed.But, the thickness in thinning solid-state electrolyte layer goes forward side by side one Step increases in the device that crystal grain uses, and reduces crystal boundary number by relative property, thus crystal boundary is electric The contribution of resistance composition diminishes, the only conductivity of the ion-conducting material caused by crystal grain internal resistance itself Become important.
In patent documentation 1 grade, the resistance according to being combined with crystal grain internal resistance and grain boundary resistance is calculated Go out ionic conductance and be evaluated, but the evaluation of the ionic conductance in being silent on only crystal grain.
It is an object of the invention to, it is provided that a kind of crystalline substance with carbuncle type or similar carbuncle type The lithium-ion-conducting oxide ceramic material of body structure, it is by having stone relative to existing The lithium-ion-conducting oxide ceramic material of the crystal structure of garnet type or similar carbuncle type, Reduce the resistance components in crystal grain and improve the ionic conductance in crystal grain, thus improving further Total ionic conductance in the less ceramic material of crystal boundary number.
Here, garnet crystal structure refer to have Ia-3d space group crystal, will be similar Garnet crystal structure is defined as having I41/ acd space group crystal group.
For solving the means of technical problem
In order to reach above-mentioned purpose, the present inventor etc. is repeated and specializes in, and result is sent out Existing, by the lithium-ion-conducting at the crystal structure with carbuncle type or similar carbuncle type Containing rare earth element in oxide ceramic material, thus improve crystal grain internal resistance components contribution from Sub-conductivity, and it is finally completed the present invention.
That is, the lithium of the crystal structure with carbuncle type or similar carbuncle type that the present invention relates to Ion-conductive oxide ceramic material, containing Li, La, Zr and O, and possibly together with selected from dilute More than one element in earth elements.
The lithium of the crystal structure with carbuncle type or similar carbuncle type involved in the present invention from Sub-conductive oxide ceramic material is characterised by, represents with following formula (1):
Li7+xLa3Zr2-xAxO12…(1)
(in formula (1), A is more than one the element in rare earth element, and x is satisfied The number of 0 ＜ x≤0.5).
Think that the rare earth element replacement in Zr site has increase lattice paprmeter and expand Li ion The effect of mobile space, its result, the effect that available Li ion is be easily moved.
In the optimal way of the present invention, the A in the most above-mentioned formula (1) be selected from Gd, Tb, More than one element in Dy, Ho, Er, Tm, Yb, Lu.
Think that Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu replacement in Zr site has Forming the effect in the space of the movement being suitable to Li ion, its result, the formation in this space can get Show the effect of higher ionic conductance.
In currently preferred mode, the A in above-mentioned formula (1) is selected from Gd, Ho, Yb In more than one element.Additionally, it is preferred that x meets 0 ＜ x≤0.30.
Think the effect in the space thus with the collaborative movement that can realize being suitable to Li ion, its knot Really, there is the effect of available higher ionic conductance.
In currently preferred mode, preferably with respect to above-mentioned, there is carbuncle type or similar Punica granatum L. The gross weight of the lithium-ion-conducting oxide ceramic material of the crystal structure of stone-type, containing 0.3wt More than % and the Al of below 2.0wt%.
Think by containing this Al, have and be prone to make Li7+xLa3Zr2-xAxO12The work of cube crystallization With, its result, the available effect improving ionic conductance further.
Invention effect
The lithium ion of the crystal structure with carbuncle type or similar carbuncle type according to the present invention Conductive oxide ceramic material, by having carbuncle type or similar Punica granatum L. relative to existing The lithium-ion-conducting oxide ceramic material of the crystal structure of stone-type, improves crystal grain internal resistance and becomes Divide the ionic conductance of contribution, such that it is able to provide in the ceramic material that crystal boundary number is fewer, The crystal structure with carbuncle type or similar carbuncle type that overall ionic conductance is higher Lithium-ion-conducting oxide ceramic material.
The carbuncle type lithium-ion-conducting oxide of the present invention is preferably for thinning solid state electrolysis The device that the thickness of matter layer uses, particularly can expect the lamination-type two with thin layer multilamellar The application of primary cell.
Accompanying drawing explanation
Fig. 1 is the figure representing the Nyquist chart (Nyquist plot) obtained in experiment；
Fig. 2 is the sectional view of the conceptual configuration representing lithium rechargeable battery.
Symbol description
1 positive pole
2 negative poles
3 solid electrolytes
4 positive electrode collectors
5 positive active materials
6 negative electrode collectors
7 negative electrode active materials
8 lithium rechargeable batteries
Detailed description of the invention
The lithium ion of the crystal structure with carbuncle type or similar carbuncle type of present embodiment Conductive oxide ceramic material has carbuncle type relative to be made up of Li, La, Zr and O Or the lithium-ion-conducting oxide ceramic material of the crystal structure of similar carbuncle type, further Containing more than one the element in rare earth element.
With such as composition formula (1) i.e. Li7+xLa3Zr2-xAxO12... (1) expression and formula (1) In A be more than one the element in rare earth element.X is the number meeting 0 ＜ x≤0.5, More preferably meet the number of 0 ＜ x≤0.3.
If be made up of with O Li, La, Zr has carbuncle type or the crystalline substance of similar carbuncle type Containing rare earth element in the lithium-ion-conducting oxide ceramic material of body structure, also it is not necessarily required to Replace Zr, it is also possible to other metal ion site is replaced, preferably replaces Zr.
Additionally, there is carbuncle type or the crystalline substance of similar carbuncle type in order to identify present embodiment The lithium-ion-conducting oxide ceramic material of body structure, can be carried out by powder X-ray diffraction. As long as further it is evident that owing to identifying LixLa3Zr2O12So-called LLZ, therefore, not It must be the material of stoichiometric composition.I.e. can also produce the defect of oxygen defect etc..Have to this The lithium-ion-conducting oxide ceramic material of the crystal structure of carbuncle type or similar carbuncle type The rare earth element of middle interpolation can pass through high-frequency inductive coupling plasma body emission spectrographic analysis (ICP) Carry out quantitatively this material powder.
Think the lithium of the crystal structure with carbuncle type or similar carbuncle type of present embodiment Ion-conductive oxide ceramic material is with chemical formula Li7+xLa3Zr2-xAxO12Represent, and profit With selected from as any one in the rare earth element of the trivalent element possessing the ionic radius bigger than Zr Above unit usually replaces the material obtained by a part of Zr.In this case, it is known that have The Zr site of the lithium-ion-conducting oxide of the crystal structure of carbuncle type or similar carbuncle type Using 6 coordinations, rare earth element is also adopted by 6 coordinations.Now, the ratio of ionic radii of rare earth element The ionic radius of Zr is big, replaces Zr site by the rare earth element that this ionic radius is bigger, thus Lattice paprmeter becomes big.Thinking the space enlargement that result Li ion moves, Li ion is be easily moved. It addition, the reason replacing Zr site is, by utilizing trivalent ionic replacement Zr site (4 valencys Site), in order to carry out charge compensation, need to make Li7+xLa3Zr2-xAxO12... in (1) Li site excess.Therefore, movable Li ionic weight increases.Think the lithium ion of present embodiment Conductive oxide ceramic material can control due to above-mentioned shown mechanism with chemical formula Li7+ xLa3Zr2-xAxO12The lattice paprmeter of the above-mentioned oxide represented and Li ionic weight, therefore can carry Ionic conductance in this crystallographic grain high.
Additionally, it is preferred that it is first with the rare earth in Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu Usually replace Zr site.For its reason, inventor etc. thinks as follows.By with ionic radius The rare earth element bigger than Zr site replaces, thus expands the space that Li ion moves, it is easy to mobile Li ion.But, in the space that Li ion moves, there is Li ion and be easily moved The space of good size.That is, replace even by the rare earth element utilizing ionic radius bigger and Excessively expand mobile space, it is also difficult to carry out the collaborative movement of Li ion.It is therefore contemplated that pass through Replace with the rare earth element in Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Can form the space with the optimal size that Li ion is be easily moved, and have can obtain higher The effect of ionic conductance.
It addition, the x in above-mentioned composition formula (1) is preferably 0 ＜ x≤0.30.Thus, available Higher ionic conductance.
Preferably replace Zr site with the rare earth element in Gd, Ho, Yb.Thus, can realize Be suitable to the space of the collaborative movement of Li ion, and available higher ionic conductance.
It addition, the crystal structure with carbuncle type or similar carbuncle type of present embodiment Lithium-ion-conducting oxide ceramic material relative to its gross weight contain more than 0.3wt% and The Al of below 2.0wt%, thus available higher ionic conductance, the most preferably.Think this It is owing to this structure is easily formed the Li that crystal structure is cubic system7+xLa3Zr2-xAxO12.? The content of Al is less than in the case of 0.3wt%, it is easy to the effect of cube crystallization dies down.It addition, In the case of the content of Al is more than 2.0wt%, may hinder and burn till.Therefore, sintered density reduces, Its result ionic conductance may reduce.
(manufacture method of ceramic material)
The lithium-ion-conducting oxide ceramic material of present embodiment can be mixed with by burning till More than Li compound, La compound, Zr compound, any one in rare earth element dilute The mixing raw material of earth elements compound and obtain.It addition, now, by above-mentioned mixing raw material The sintering aid that middle interpolation is made up of Al compound burns till, such that it is able to acceleration of sintering and Lithium-ion-conducting ceramic material to densification.
As above-mentioned Li compound, such as, can enumerate: LiOH or its hydrate, Li2CO3、 LiNO3、CH3COOLi etc..As above-mentioned La compound, La can be enumerated2O3、La(OH)3、 La2(CO3)3、La(NO3)3、(CH3COO)3La etc..As above-mentioned Zr compound, Ke Yilie Lift Zr2O2、ZrO(NO3)2、ZrO(CH3COO)2、Zr(OH)2CO3、ZrO2Deng.
It addition, as above-mentioned rare earth compound, A can be enumerated2O3、A2(CO3)3、A(NO3)3、 (CH3COO)3A etc. (A is rare earth element).
It addition, as above-mentioned Al compound, Al can be enumerated2O3、Al(OH)3、Al(NO3)3 Deng.
An example to the manufacture method of the carbuncle type lithium-ion-conducting oxide ceramics of the present invention Illustrate.In the manufacture method of this oxide, carry out (a) raw material mixed processes, then enter Row (b) calcination process, finally carries out (c) molding, formal sintering circuit.Hereinafter, successively These operations are illustrated.
(a) raw material mixed processes
In raw material mixed processes, weigh respectively containing formula (1) i.e. Li7+xLa3Zr2-xAxO12Each The initial feed of element is to becoming the stoichiometric proportion of formula (1), and mixes.As initially Raw material, it is possible to use the carbonate of each element or sulfate, nitrate, oxalates, chloride, Hydroxide, oxide etc..Wherein, carry out thermally decomposing and produce carbon dioxide carbonate and Carry out thermally decomposing and produce the hydroxide of steam be easier to carry out due to gas treatment thus Preferably.For example, it is preferable to use the carbonate of Li, the hydroxide of La and A, the oxidation of Zr Thing.In mixed method, it is also possible to do not put in solvent and carry out co-grinding by dry type, also Can put in solvent and carry out co-grinding by wet type, but come in terms of raising is blended See, be preferably placed in solvent the co-grinding carrying out wet type.This mixed method can use such as Planetary ball mill, grater, ball mill etc..As solvent, preferably not readily dissolve the solvent of Li, The organic solvent of the most such as ethanol etc..Depending on incorporation time is according to combined amount, can be set to Such as 1 hour～32 hours.
(b) calcination process
In calcination process, mixed-powder obtained in calcined mixed operation.Calcining temperature now Degree is preferably set to cause the state of initial feed to change (such as producing gas or phase change etc.) Temperature is less than temperature during formal sintering.Such as, Li is being used2CO3As the most former In the case of one of material, it is preferably the temperature of this carbonate decomposition less than when formally sintering Temperature.Accordingly, in formal sintering later, the gas in thermal decomposition can be suppressed to produce Caused density reduces.Specifically, calcining heat is preferably set to 800 DEG C～1000 DEG C.
(c) molding, formal sintering circuit
In formal sintering, material (the referred to as formally powder before sintering obtained in molding calcination process End) to rear, it is sintered with temperature more than calcining heat.As for obtaining molded body Forming method, can carry out formed in mould by adding binding agent in powder before formal sintering Method, cold isostatic compaction (CIP) or hip moulding (HIP), hot pressing etc. are shaped to appoint Meaning shape is carried out.Alternatively, it is also possible to by powder before sintering and the binding agent of organic system, dispersion Agent, plasticizer etc. mix, and are shaped to flake, and are shaped to multi-layer laminate structure.Just sintering For atmosphere, in addition to atmospheric atmosphere, it is also possible to carry out in reduction atmosphere as required.
According to the preparation method described in detail above, after the mixed-powder of calcining initial feed, owing to being Calcine with relatively low temperature, the most formally sinter, therefore, it can press down accurately The deviation of system composition.Additionally, the present invention's has carbuncle type or the crystal of similar carbuncle type The preparation method of the lithium-ion-conducting oxide ceramic material of structure is not limited to this, it would however also be possible to employ Other preparation method.
(all solid state type lithium secondary battery)
As in figure 2 it is shown, all solid state type lithium secondary battery of present embodiment is by positive pole 1, negative pole 2 Constituting with solid electrolyte 3, solid electrolyte 3 is relative to being made up of Li, La, Zr and O There is the lithium-ion-conducting oxide ceramics of the crystal structure of carbuncle type or similar carbuncle type Material contains more than one the element in rare earth element further.Such as, for having tool There is the lithium-ion-conducting oxide ceramics material of the crystal structure of carbuncle type or similar carbuncle type Material, it is characterised in that: with composition formula Li7+xLa3Zr2-xAxO12... (1) (in formula (1), A is more than one the element in rare earth element, and x is the number meeting 0 ＜ x≤0.5) table Show.By being set to this structure, compared with the past, become the secondary cell of practicality.
The positive pole 1 of all solid state type lithium rechargeable battery of present embodiment and negative pole 2 respectively by Positive active material 5, positive electrode collector 4 and negative electrode active material 7 and negative electrode collector 6 Constitute.
Can live containing currently known positive active material 5 and the negative pole for lithium secondary battery Property material 7, and manufactured by common method.
(positive active material)
As positive active material, it is not particularly limited, it is possible to use currently known for entirely The positive active material of solid state battery.As the object lesson of such positive active material, permissible Enumerate: manganese dioxide (MnO2), ferrum oxide, copper oxide, nickel oxide, lithium manganese combined oxidation Thing (such as, LixMn2O4Or LixMnO2), lithium nickel composite oxide (such as, LixNiO2)、 Lithium cobalt composite oxide (such as, LixCoO2), lithium/nickel/cobalt composite oxide (such as, LiNi1 -yCoyO2), lithium manganese cobalt composite oxide (such as, LiMnyCo1-yO2), spinel type lithium & manganese Ni compound oxide (such as, LixMn2-yNiyO4), there is the lithium phosphate chemical combination of olivine structural Thing (such as, LixFePO4, LixFe1-yMnyPO4, LixCoPO4, LiVOPO4)、NASICON Lithium phosphate compound (such as, the Li of structurexV2(PO4)3, Li2VOP2O7, Li2VP2O7, Li4(VO)(PO4)2And Li9V3(P2O7)3(PO4)2), iron sulfate (Fe2(SO4)3), barium oxide (such as, V2O5) etc..These can be used alone one, it is also possible to and with two or more. It addition, in these chemical formulas, x, y are preferably the scope of 1 ＜ x ＜ 5,0 ＜ y ＜ 1.Wherein, It is preferably LiCoO2、LiNiO2、LixV2(PO4)3、LiFePO4。
(negative electrode active material)
It is not particularly limited as negative electrode active material, it is possible to use existing known for complete solid The negative electrode active material of state battery.Such as can enumerate carbon, lithium metal (Li), metallic compound, Metal-oxide, Li metallic compound, Li metal-oxide (comprise lithium-transition metal composite oxygen Compound), add boron carbon, graphite, there is the compound etc. of NASICON structure.These can be single Solely it is used, or two or more may be used.Such as using above-mentioned lithium metal (Li) In the case of, the capacity of all-solid-state battery can be expanded.As above-mentioned carbon, such as, can enumerate stone The existing known material with carbon elements such as ink carbon, hard carbon, soft carbon.As above-mentioned metallic compound, permissible Enumerate LiAl, LiZn, Li3Bi、Li3Sd、Li4Si、Li4.4Sn、Li0.17C(LiC6) etc.. As above-mentioned metal-oxide, SnO, SnO can be enumerated2、GeO、GeO2、In2O、In2O3、 Ag2O、AgO、Ag2O3、Sb2O3、Sb2O4、Sb2O5、SiO、ZnO、CoO、NiO、 TiO2, FeO etc..As Li metallic compound, Li can be enumerated3FeN2、Li2.6Co0.4N、 Li2.6Cu0.4N etc..As Li metal-oxide (lithium-compound transition metal oxide), Ke Yilie Lift by Li4Ti5O12The lithium-titanium composite oxide etc. represented.Add boron carbon as above-mentioned, can enumerate Add boron carbon, add boron graphite etc..
(collector body)
The material of the collector body constituting all solid state type lithium rechargeable battery of present embodiment is preferred Use the bigger material of conductivity, be such as preferably used silver, palladium, gold, platinum, aluminum, copper, Nickel etc..Particularly preferably copper, because itself and titanium phosphate aluminum lithium are difficult to reaction, and has reduction lithium ion The effect of the internal resistance of secondary cell.The material constituting collector body can also positive pole and negative pole phase With, it is also possible to different.
It addition, the positive electrode collector layer of the lithium rechargeable battery of present embodiment and negative pole current collection Body layer contains positive active material and negative electrode active material the most respectively.
Positive electrode collector layer and negative electrode collector layer are by containing positive active material and negative pole respectively Active substance, thus improve positive electrode collector layer and positive electrode active material layer and negative electrode collector Layer and the adaptation of negative electrode active material layer, therefore preferably.
(manufacture method of lithium rechargeable battery)
The lithium rechargeable battery of present embodiment is manufactured by the following, i.e. by positive electrode collector Layer, positive electrode active material layer, solid-state electrolyte layer, negative electrode active material layer and negative electrode collector Each material of layer carries out slurried, and is coated being dried and making green sheet, by this green sheet Lamination, burns till the laminated body of making simultaneously.
Slurried method is not particularly limited, such as, can mix above-mentioned each material in medium Powder and obtain slurry.Here, medium is the general name of the medium in liquid phase.Medium contains Solvent, binding agent.With it, make the slurry of positive electrode collector layer, positive-active The slurry of material layer, the slurry of solid-state electrolyte layer, the slurry of negative electrode active material layer And the slurry of negative electrode collector layer.
By the slurry sequential application desirably that will make on the base materials such as PET, according to need After being dried, peeling base, make green sheet.The coating process of slurry limits the most especially Fixed, can use silk screen printing, be coated with, transfer, the known method such as scraper.
The green sheet order desirably, the lamination number that make is overlapping, arrange as required Row, cut-out etc., make lamination block.In the case of making the battery of parallel connection type or Serial-Parallel Type, In the way of the end face of anode layer and the end face of negative electrode layer are inconsistent, preferably carry out arrangement overlapping.
When making lamination block, it is also possible to prepare the active substance unit of following description, make folded Layer block.
In the method, first, PET film is passed through doctor blade method by solid electrolyte slurry shape Slabbing, after obtaining solid electrolyte sheet, on this solid electrolyte sheet, passes through silk screen Printing printing positive electrode active material layer slurry is also dried.Then, this layer passes through silk screen Printing printing positive electrode collector layer slurry is dried.Silk screen printing is passed through further on this layer Again print anode active material slurry, and be dried, then by peeling off PET film, Obtain positive electrode active material layer unit.So, obtain sequentially forming on solid electrolyte sheet Positive electrode active material layer slurry, positive electrode collector layer slurry, the positive pole of anode active material slurry Active substance layer unit.By same order, also make negative electrode active material layer unit, To sequentially forming negative electrode active material layer slurry, negative electrode collector layer on solid electrolyte sheet Slurry, the negative electrode active material layer unit of negative electrode active material slurry.
By solid to clip to a piece of positive electrode active material layer unit and a piece of negative electrode active material layer unit The mode of state electrolyte sheet is overlapping.Now, with first positive electrode active material layer unit just Electrode current collector layer slurry only stretches out at an end face, and second negative electrode active material layer unit The mode that negative electrode collector layer slurry only stretches out at another side, stagger overlap by each unit.Make On the two sides of the unit of this overlap, the solid electrolyte sheet of the most overlapping specific thickness is folded Layer block.
The lamination block strong binding in the lump that will make.Strong binding is carried out while heating, adds Hot temperature is set to such as 40～95 DEG C.
The lamination block of strong binding is heated under such as blanket of nitrogen 600 DEG C～1200 DEG C go forward side by side Row burns till.Firing time is set to such as 0.1～3 hour.Being burnt till by this, laminated body completes. Embodiment
Further illustrate present disclosure with reference to embodiment and comparative example, but the present invention does not limits Due to below example.
[embodiment 1～embodiment 10]
In order to confirm the effect of present embodiment, as having carbuncle type or similar carbuncle type The example of lithium-ion-conducting oxide ceramic material of crystal structure, propose to instead of respectively Li7.10La3.00(Zr1.90A0.10)O12The composition of (A=Y, Nd, Gd, Ho, Yb) (is implemented Example 1-embodiment 5), further each composition be with the addition of 1.0wt%Al2O3Composition (implement Example 6-embodiment 10).Initial feed employs Li2CO3、La(OH)3、ZrO2、Y2O3、 Nd2O3、Gd2O3、Ho2O3、Yb2O3And Al2O3.First, to become stoichiometric proportion Mode weighs initial feed, utilizes ball mill (120rpm/ zirconia ball) to carry out 16 in ethanol Hour co-grinding.After the mixed-powder of initial feed is separated from ball and ethanol, at oxygen Change in aluminum cup and carry out calcining 5 hours under air atmosphere with 900 DEG C.Then, in order to carry out Mixing, utilizes ball mill (120rpm/ zirconia ball) to locate in ethanol by this calcined powder Manage 16 hours.Comminuted powder separated from ball and ethanol and carries out dried, formally being burnt Powder before knot.Then, powder before these formal sintering is added organic system binding agent, making Grain.The mould that this granule uses φ 10mm is shaped to discoid with 7kN.By molded body at platinum The most formally sinter two hours with the sintering temperature of 1100 DEG C～1150 DEG C on plate, obtain Discoid sintered sample.
[embodiment 11～embodiment 26]
It addition, propose to replace respectively the Li of Zr with A7.35La3.00(Zr1.65A0.35)O12, (A=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) composition (embodiment 11-18) and the most right Each composition with the addition of 1.0wt%Al2O3Composition (embodiment 19-embodiment 26).The most former Material employs Li2CO3、La(OH)3、ZrO2、Gd2O3、Tb2O3、Dy2O3、Ho2O3、 Er2O3、Tm2O3、Yb2O3、Lu2O3And Al2O3.First, initial feed is weighed to becoming Stoichiometric proportion, carries out co-grinding with ball mill (120rpm/ zirconia ball) in ethanol 16 hours.After the mixed-powder of initial feed is separated from ball and ethanol, at oxidation aluminum earthenware Crucible carries out calcining 5 hours with 900 DEG C in air atmosphere.Then, in order to mix, will calcining Powder utilizes ball mill (120rpm/ zirconia ball) to carry out processing 16 hours in ethanol.Will Comminuted powder separates from ball and ethanol and carries out dried, is formally sintered front powder.Connect , powder before these formal sintering is added organic system binding agent, make granule.By this granule The mould using φ 10mm is shaped to discoid with 7kN.Molded body in platinum sheet with 1075 DEG C ～the sintering temperature of 1125 DEG C the most formally sinters two hours, obtain discoid sintering Sample.
[embodiment 27～embodiment 29]
It addition, to Li7.05La3.00(Zr1.95Gd0.05)O12、Li7.25La3.00(Zr1.75Gd0.25)O12、 Li7.50La3.00(Zr1.50Gd0.50)O12Add the Al of 1.0wt% respectively2O3.Initial feed uses Li2CO3、La(OH)3、ZrO2、Gd2O3And Al2O3.First, to become stoichiometric proportion Mode weighs initial feed, utilizes ball mill (120rpm/ zirconia ball) to mix in ethanol Close and pulverize 16 hours.After the mixed-powder of initial feed is separated from ball and ethanol, at oxygen Change in aluminum cup and carry out calcining 5 hours with 900 DEG C, in air atmosphere.Then, in order to mixed Close, carry out processing 16 with ball mill (120rpm/ zirconia ball) in ethanol by calcined powder Hour.Comminuted powder is separated from ball and ethanol and carries out dried, before formally being sintered Powder.Then, powder before these formal sintering is added organic system binding agent, make granule. The mould that this granule uses φ 10mm is shaped to discoid with 7kN.Molded body in platinum sheet The most formally sinter under the sintering temperature of 1100 DEG C～1125 DEG C two hours, obtain disk The sintered sample of shape.
[embodiment 30～embodiment 32]
It addition, to Li7.05La3.00(Zr1.95Ho0.05)O12、Li7.25La3.00(Zr1.75Ho0.25)O12、 Li7.50La3.00(Zr1.50Ho0.50)O12Add the Al of 1.0wt% respectively2O3.Initial feed uses Li2CO3、La(OH)3、ZrO2、Ho2O3And Al2O3.First, initial feed is weighed to become Stoichiometric proportion, utilizes ball mill (120rpm/ zirconia ball) to carry out mixed powder in ethanol Broken 16 hours.After the mixed-powder of initial feed is separated from ball and ethanol, at oxidation aluminum In crucible with 900 DEG C, carry out calcining 5 hours under air atmosphere.Then, in order to mix, will forge Burn powder to carry out processing 16 hours with ball mill (120rpm/ zirconia ball) in ethanol.Will Comminuted powder separates from ball and ethanol and carries out dried, is formally sintered front powder.Connect , powder before these formal sintering is added organic system binding agent, make granule.By this granule The mould using φ 10mm is shaped to discoid with 7kN.By molded body in platinum sheet with 1050 DEG C～the sintering temperature of 1125 DEG C the most formally sinter two hours, obtained discoid Sintered sample.
[embodiment 33～embodiment 35]
It addition, to Li7.05La3.00(Zr1.95Yb0.05)O12、Li7.25La3.00(Zr1.75Yb0.25)O12、 Li7.50La3.00(Zr1.50Yb0.50)O12Add the Al of 1.0wt% respectively2O3.Initial feed uses Li2CO3、La(OH)3、ZrO2、Yb2O3And Al2O3.First, initial feed is weighed to becoming Stoichiometric proportion, utilizes ball mill (120rpm/ zirconia ball) to carry out mixed powder in ethanol Broken 16 hours.After the mixed-powder of initial feed is separated from ball and ethanol, at oxidation aluminum With 900 DEG C in crucible, carry out calcining 5 hours under air atmosphere.Then, in order to mix, will Calcined powder carries out processing 16 hours at ethanol ball mill (120rpm/ zirconia ball).Will Comminuted powder separates from ball and ethanol and carries out dried, has obtained powder before formal sintering. Then, powder before these formal sintering is added organic system binding agent, make granule.Should Grain uses the mould of φ 10mm to be shaped to discoid with 7kN.By molded body in platinum sheet with 1050 DEG C～the sintering temperature of 1100 DEG C under the most formally sinter two hours, obtained discoid Sintered sample.
[embodiment 36～embodiment 41]
It addition, to Li7.35La3.00(Zr1.65Yb0.35)O12Add Al2O3To Al2O3Content (ywt %) respectively become 0.2wt%, 0.3wt%, 0.7wt%, 1.5wt%, 2.0wt%, 2.1wt %.Initial feed uses Li2CO3、La(OH)3、Yb2O3And Al2O3.First, at the beginning of weighing Beginning raw material, to becoming stoichiometric proportion, enters with ball mill (120rpm/ zirconia ball) in ethanol Row co-grinding 16 hours.After the mixed-powder of initial feed is separated from ball and ethanol, Oxidation aluminum cup carries out calcining 5 hours with 900 DEG C, in air atmosphere.Then, for Mixing, processes with ball mill (120rpm/ zirconia ball) in ethanol by calcined powder 16 hours.Comminuted powder separated from ball and ethanol and carries out dried, having obtained formal burning Powder before knot.Then, powder before these formal sintering is added organic system binding agent, making Grain.The mould that this granule uses φ 10mm is shaped to discoid with 7kN.Molded body is in platinum sheet On the most formally sinter 2 hours with the sintering temperature of 1100 DEG C～1150 DEG C, justified The sintered sample of plate-like.
[comparative example 1]
Use Li7.00La3.00Zr2.00O12Composition.Initial feed uses Li2CO3、La(OH)3、ZrO2。 First, weighing initial feed is to become stoichiometric proportion, in ethanol with ball mill (120rpm/ Zirconia ball) carry out co-grinding 16 hours.By the mixed-powder of initial feed from ball and second After alcohol separates, carry out calcining 5 with 900 DEG C, in air atmosphere in oxidation aluminum cup Hour.Then, in order to mix, calcined powder is utilized in ethanol ball mill (120rpm/ oxygen Change zirconium ball) carry out processing 16 hours.Comminuted powder is separated from ball and ethanol and is dried After, formally sintered front powder.Then, powder before these formal sintering is added organic system Binding agent, makes granule.The mould that this granule uses φ 10mm is shaped to discoid with 7kN. Molded body the most formally sinters two hours with the sintering temperature of 1150 DEG C in platinum sheet, Obtain discoid sintered sample.
[comparative example 2]
It addition, propose to Li7.00La3.00Zr2.00O12In with the addition of the Al of 1.0wt%2O3Composition. Initial feed uses Li2CO3、La(OH)3、ZrO2And Al2O3.First, initial feed is weighed To becoming stoichiometric proportion, ball mill (120rpm/ zirconia ball) is utilized to mix in ethanol Close and pulverize 16 hours.After the mixed-powder of initial feed is separated from ball and ethanol, at oxygen Change in aluminum cup and carry out calcining 5 hours in air atmosphere with 900 DEG C.Then, in order to mix, Calcined powder utilize ball mill (120rpm/ zirconia ball) carry out processing 16 in ethanol little Time.Comminuted powder separated from ball and ethanol and carries out dried, formally being sintered front powder End.Then, powder before these formal sintering is added organic system binding agent, make granule.Will This granule uses the mould of φ 10mm to be shaped to discoid with 7kN.Molded body in platinum sheet with The sintering temperature of 1100 DEG C the most formally sinters two hours, obtains discoid sintering Sample.
[comparative example 3]
It addition, use to Li7.53La3.00(Zr1.67Gd0.53)O12With the addition of the Al of 1.0wt%2O3's Composition.Initial feed uses Li2CO3、La(OH)3、ZrO2、Gd2O3And Al2O3.First, Weighing initial feed is to become stoichiometric proportion, and (120rpm/ aoxidizes to utilize ball mill in ethanol Zirconium ball) carry out co-grinding 16 hours.By the mixed-powder of initial feed from ball and ethanol After separation, carry out calcining 5 hours in air atmosphere with 900 DEG C in oxidation aluminum cup.So After, in order to mix, calcined powder is utilized in ethanol ball mill (120rpm/ zirconia ball) Carry out processing 16 hours.Comminuted powder separated from ball and ethanol and carries out dried, obtaining Powder before formal sintering.Then, powder before these formal sintering is added organic system binding agent, Make granule.The mould that this granule uses φ 10mm is shaped to discoid with 7kN.Molded body Platinum sheet carries out formal sintering two hours in air with the sintering temperature of 1050 DEG C, obtains disk The sintered sample of shape.
[comparative example 4]
It addition, use to Li7.52La3.00(Zr1.68Ho0.52)O12In with the addition of the Al of 1.0wt%2O3 Composition.Initial feed uses Li2CO3、La(OH)3、ZrO2、Ho2O3And Al2O3.First First, weighing initial feed, to become stoichiometric proportion, utilizes ball mill (120rpm/ in ethanol Zirconia ball) carry out co-grinding 16 hours.By the mixed-powder of initial feed from ball and second After alcohol separates, in oxidation aluminum cup, in air atmosphere, carry out calcining 5 with 900 DEG C little Time.Then, in order to mix, calcined powder utilizes ball mill in ethanol, and (120rpm/ aoxidizes Zirconium ball) carry out processing 16 hours.Comminuted powder is separated from ball and ethanol and carries out dried, Formally sintered front powder.Then, powder before these formal sintering is added organic system bonding Agent, makes granule.The mould that this granule uses φ 10mm is shaped to discoid with 7kN.Become Type body the most formally sinters two hours with the sintering temperature of 1050 DEG C in platinum sheet, To discoid sintered sample.
[comparative example 5]
It addition, use to Li7.52La3.00(Zr1.68Yb0.52)O12In with the addition of the Al of 1.0wt%2O3 Composition.Initial feed uses Li2CO3、La(OH)3、ZrO2、Yb2O3And Al2O3.First First, weighing initial feed, to become stoichiometric proportion, utilizes ball mill (120rpm/ in ethanol Zirconia ball) carry out co-grinding 16 hours.By the mixed-powder of initial feed from ball and second After alcohol separates, in oxidation aluminum cup, in air atmosphere, carry out calcining 5 with 900 DEG C little Time.Then, in order to mix, calcined powder utilizes ball mill in ethanol, and (120rpm/ aoxidizes Zirconium ball) carry out processing 16 hours.Comminuted powder is separated from ball and ethanol and carries out dried, Formally sintered front powder.Then, powder before these formal sintering is added organic system bonding Agent, makes granule.The mould that this granule uses φ 10mm is shaped to discoid with 7kN.Become Type body the most formally sinters two hours with the sintering temperature of 1050 DEG C in platinum sheet, To discoid sintered sample.
[calculating of relative density]
Close for forming the sintering of the lithium-ion-conducting oxide ceramics of above-mentioned discoid sintered body Degree, after utilizing micrometer to measure the volume of this discoid sintered body, by this discoid sintered body Dry weight is divided by this volume, thus, calculates sintered density.Then, remove by this sintered density The value calculating percentage rate with solid density is relative density (unit: %).Each embodiment, compare The relative density of example represents in table 1～8 described later.
[mensuration of conductivity and the estimation of ionic conductance]
In temperature chamber, use AC electric impedance analyzer (Solartron company system 1260), will survey Fixed temperature is set to 25 DEG C, mensuration frequency is set to 0.05Hz～30MHz, amplitude voltage: 50mV, Measure impedance and phase angle.Nyquist diagram is described based on these measured values, and according to it Circular arc tries to achieve resistance value, and calculates conductivity according to this resistance value.Utilize AC electric impedance analyzer Blocking electrode during mensuration uses Au electrode.Au electrode is formed as φ 3mm circle by sputtering method Shape.
According to said determination, obtain nyquist diagram as shown in Figure 1.From this Nyquist The resistance value that figure obtains can be distinguished into according to the kind of its circular arc include crystals resistance and The resistance of grain boundary resistance.In this patent, the ion that will calculate based on the resistance of crystals Conductivity is shown in table 1～table 6.
[table 1]
A Firing temperature (DEG C) Relative density (%) Ionic conductance (S/cm) in crystal grain
Embodiment-1 Y 1150 86.5 1.13E-03
Embodiment-2 Nd 1150 91.8 1.31E-03
Embodiment-3 Gd 1150 89.5 1.42E-03
Embodiment-4 Ho 1150 94.4 1.42E-03
Embodiment-5 Yb 1125 93.4 1.43E-03
Comparative example-1 Nothing 1150 77.5 7.90E-04
In the sample obtained in embodiment 1～embodiment 5, by Zr site substitution ion radius Bigger rare earth element, thus Li ion mobile space expands, and also improves Li ion concentration, Therefore, can confirm that display 1.00 × 10-3The high ion conductivity of more than S/cm.Relative to this not Replace in the sample obtained in the comparative example 1 of rare earth element, can confirm that display 7.90 × 10-4S/cm Relatively low ionic conductance.
[table 2] (containing Al)
A Firing temperature (DEG C) Relative density (%) Ionic conductance (S/cm) in crystal grain
Embodiment-6 Y 1125 88.3 1.18E-03
Embodiment-7 Nd 1125 93.7 1.36E-03
Embodiment-8 Gd 1125 91.3 1.48E-03
Embodiment-9 Ho 1125 96.3 1.48E-03
Embodiment-10 Yb 1100 95.3 1.49E-03
Comparative example-2 Nothing 1100 79.1 8.23E-04
In embodiment 6～embodiment 10, by replacing rare earth element and containing Al further, from And be easily formed cubic crystal, and can confirm that and can obtain higher ionic conductance.That is, display 1.18×10-3The higher ionic conductance of more than S/cm.In contrast, containing Al but do not take For in the comparative example 2 of rare earth element, can confirm that display 8.23 × 10-4The relatively low ion of S/cm passes Conductance.
[table 3]
A Firing temperature (DEG C) Relative density (%) Ionic conductance (S/cm) in crystal grain
Embodiment-11 Gd 1125 89.9 3.93E-03
Embodiment-12 Tb 1125 90.5 3.42E-03
Embodiment-13 Dy 1125 89.2 3.31E-03
Embodiment-14 Ho 1125 94.8 4.02E-03
Embodiment-15 Er 1100 92.1 3.01E-03
Embodiment-16 Tm 1100 91.1 2.87E-03
Embodiment-17 Yb 1100 93.9 4.03E-03
Embodiment-18 Lu 1100 89.8 2.81E-03
The particularly Gd in being defined in rare earth element, Tb, Dy, Ho, Er, Tm, Yb, Lu and further increase embodiment 11～the embodiment 18 of its substitution amount, optimizes further Li ion mobile space, therefore, it can confirm display 2.81 × 10-3The macroion of more than S/cm Conductivity.
[table 4] (containing Al)
A Firing temperature (DEG C) Relative density (%) Ionic conductance (S/cm) in crystal grain
Embodiment-19 Gd 1100 91.8 4.10E-03
Embodiment-20 Tb 1100 92.4 3.57E-03
Embodiment-21 Dy 1100 91.0 3.45E-03
Embodiment-22 Ho 1075 96.8 4.18E-03
Embodiment-23 Er 1075 93.9 3.13E-03
Embodiment-24 Tm 1075 92.9 2.99E-03
Embodiment-25 Yb 1075 95.8 4.20E-03
Embodiment-26 Lu 1075 91.6 2.93E-03
In embodiment 19～26, by containing Al further, it is easy to form cubic crystal, can confirm that Obtain high ionic conductance.That is, display 2.93 × 10-3The high ion conductivity of more than S/cm.
[table 5] (containing Gd, Al)
x Firing temperature (DEG C) Relative density (%) Ionic conductance (S/cm) in crystal grain
Comparative example-2 0 1100 79.1 8.23E-04
Embodiment-27 0.05 1125 82.1 9.52E-04
Embodiment-8 0.10 1125 91.3 1.48E-03
Embodiment-28 0.25 1125 89.6 3.44E-03
Embodiment-19 0.35 1100 91.8 4.10E-03
Embodiment-29 0.50 1100 87.4 1.44W-03
Comparative example-3 0.53 1050 87.2 3.48E-04
[table 6] (containing Ho, Al)
x Firing temperature (DEG C) Relative density (%) Ionic conductance (S/cm) in crystal grain
Comparative example-2 0 1100 79.1 8.23E-04
Embodiment-30 0.05 1125 88.4 9.92E-04
Embodiment-9 0.10 1125 96.3 1.48E-03
Embodiment-31 0.25 1075 96.5 3.58E-03
Embodiment-22 0.35 1075 96.8 4.18E-03
Embodiment-32 0.50 1050 94.1 1.50E-03
Comparative example-4 0.52 1050 93.9 3.63E-04
[table 7] (containing Yb, Al)
x Firing temperature (DEG C) Relative density (%) Ionic conductance (S/cm) in crystal grain
Comparative example-2 0 1100 79.1 8.23E-04
Embodiment-33 0.05 1100 87.5 9.95E-04
Embodiment-10 0.10 1100 95.3 1.49E-03
Embodiment-34 0.25 1075 95.5 3.59E-03
Embodiment-25 0.35 1075 95.8 4.20E-03
Embodiment-35 0.50 1050 93.1 1.50E-03
Comparative example-5 0.52 1050 92.9 3.64E-04
In the substituted element of Zr site, with Gd, Ho, Yb as typical example, change its substitution amount true Recognize the effect to the ionic conductance in crystal grain.Such as embodiment 8,9,10 and embodiment 27～real Execute shown in example 35, confirm substitution amount x from 0.05 to 0.50, show 9.50 × 10-4S/cm Above high ion conductivity.Particularly embodiment 8,9,10,28,29,31,32,34, The sample obtained in 35 (substitution amount x is 0.10～0.50) shows 1.45 × 10-3More than S/cm's High ion conductivity.In contrast, in comparative example 2 (x=0), show 8.23 × 10-4S/cm Low ionic conductance.Further acknowledge that further at the ratio that substitution amount x is set to 0.52,0.53 In relatively example 3,4,5, ionic conductance reduces, and shows 3.48 × 10-4S/cm、3.63×10-4S/cm、 3.64×10-4The low ionic conductance of S/cm.
[table 8] (containing Yb, Al)
Al2O3:y (wt%) Firing temperature (DEG C) Relative density (%) Ionic conductance (S/cm) in crystal grain
Embodiment-36 0.2 1100 88.8 9.97E-04
Embodiment-37 0.3 1100 96.0 3.33E-03
Embodiment-38 0.7 1100 96.1 5.10E-03
Embodiment-25 1.0 1100 95.8 4.20E-03
Embodiment-39 1.5 1125 93.5 3.35E-03
Embodiment-40 2.0 1125 90.3 9.91E-04
Embodiment-41 2.1 1150 75.6 9.65E-04
Confirm containing for improving agglutinating property and making the effect of Al of cubic crystal stabilisation.Implement The content of the Al shown in example 37～embodiment 40, from 0.3wt% to 2.0wt%, shows 9.90×10-4The high ion conductivity of more than S/cm.Particularly embodiment 32～34 is (with substitution amount Be calculated as 0.3wt%～1.5wt%) in the sample that obtains show 3.33 × 10-3The height of more than S/cm from Sub-conductivity.In contrast, can confirm that the few embodiment 36 to 0.2wt% of content at Al Or a large amount of containing to the embodiment 41 of 2.1wt%, show 9.97 × 10 respectively-4S/cm、9.65×10-4S/cm, the ionic conductance lower than the embodiment containing 0.3wt%～2.0wt%Al.
[generating the confirmation of phase]
For each sample, carry out the identification of phases from XRD determining result, confirm the most single-phase, and It is judged as replacing in Zr site for substituted rare earth element.XRD determining device uses X ' the Pert PRO of PANalytical company, and at CuK α, 2 θ: 10～90 °, 0.01 ° of step/1sec. Under conditions of measure.
[composition analysis]
For each sample, by ICP luminescence analysis (determinator: Shimadzu Seisakusho Ltd.'s system, Trade name: ICP-7500), analytical chemistry forms, and results verification is to evaluating sample composition and charging In composition unchanged.
[embodiment 42]
Hereinafter, illustrate the embodiment of all solid lithium secondary battery, but the present invention is not limited to this A little embodiments.Additionally, as long as no explanation, " part " represents mass parts.
(positive active material and the making of negative electrode active material)
As positive active material and negative electrode active material, employ and make by the following method Li3V2(PO4)3.As this manufacture method, with Li2CO3、V2O5、NH4H2PO4For initial material Material, utilizes ball mill to carry out 16 hours wet mixed, after carrying out dehydrate, the powder that will obtain Body is calcined two hours in nitrogen hydrogen mixeding gas with 850 DEG C.Ball mill is utilized to carry out calcining product wet After formula is pulverized, carry out dehydrate, obtain powder.X-ray diffraction device is used to confirm this Make powder body be configured to Li3V2(PO4)3。
(anode active material slurry and the making of negative electrode active material slurry)
For anode active material slurry and negative electrode active material slurry, it is all by 100 parts Li3V2(PO4)3Powder in add the ethyl cellulose 15 parts as binding agent, as solvent Dihydroterpineol 65 parts, carries out mixing dispersion, makes active material slurry.
(making of solid electrolyte)
As solid electrolyte, employ by following method making Li7.35La3.00(Zr1.65Yb0.35)O12Add the Al of 1.0wt%2O3Composition.Its manufacture method is, With Li2CO3、La(OH)3、ZrO2、Yb2O3And Al2O3For original material, utilize ball mill (120rpm/ zirconia ball) carries out co-grinding 16 hours.By the mixed powder of initial feed After end separates from ball and ethanol, carry out in air atmosphere with 900 DEG C in oxidation aluminum cup Calcine 5 hours.Then, in order to mix, calcined powder is utilized in ethanol ball mill (120rpm/ Zirconia ball) carry out processing 16 hours.Comminuted powder is separated from ball and ethanol and does After dry, obtain the powder of formal solid electrolyte.X-ray diffraction device is used to confirm making The structure of powder body be Li7.35La3.00(Zr1.65Yb0.35)O12。
Then, ball mill is utilized to add the ethanol 100 parts as solvent, toluene in this powder 200 parts and carry out wet mixed.Then, polyvinyl butyral resin system binding agent is put into further 16 parts and BBP(Butyl Benzyl Phthalate 4.8 parts, and mix, prepare solid electrolyte slurry.
(making of solid electrolyte sheet)
For base material, this solid electrolyte slurry is carried out thin slice one-tenth with PET film by doctor blade method Type, obtains the solid electrolyte sheet of thickness 15 μm.
(making of collector body slurry)
Ni and Li that will use as collector body3V2(PO4)3Mixing, is mixed in terms of volume ratio After being 80/20, add the ethyl cellulose as binding agent and the dihydroterpineol as solvent enters Row mixing dispersion makes collector body slurry.The mean diameter of Ni is 0.9 μm.
(making of terminal electrode slurry)
By silver powder and epoxy resin, solvent mixing dispersion, make the terminal electricity of thermohardening type Pole slurry.
These slurries are used to make lithium rechargeable battery as follows.
(making of positive electrode active material layer unit)
Above-mentioned solid electrolyte sheet is lived with thickness 5 μm printing positive pole by silk screen printing Property material layer slurry, and with 80 DEG C be dried 10 minutes.Then, thereon by silk screen printing with Thickness 5 μm printing positive electrode collector layer slurry, is dried 10 minutes with 80 DEG C.Further at it On again print anode active material slurry by silk screen printing with thickness 5 μm, and at 80 DEG C It is dried 10 minutes, then, peels off PET film.So, obtain on solid electrolyte sheet Printing is dried successively has positive electrode active material layer slurry, positive electrode collector layer slurry, positive pole to live The thin slice of the positive electrode active material layer unit of property compound paste.
(making of negative electrode active material layer unit)
Above-mentioned solid electrolyte sheet is lived with thickness 5 μm printing negative pole by silk screen printing Property compound paste, and with 80 DEG C be dried 10 minutes.Then, silk screen printing is passed through thereon with thickness Spend 5 μm printing negative electrode collector layer slurry, and be dried 10 minutes at 80 DEG C.Exist further Negative electrode active material slurry is again printed by silk screen printing with thickness 5 μm on it, and with 80 DEG C It is dried 10 minutes, then, peels off PET film.So, obtain on solid electrolyte sheet Printing is dried successively negative electrode active material slurry, negative electrode collector layer slurry, negative electrode active The thin slice of the negative electrode active material layer unit of compound paste.
(making of laminated body)
By solid to clip to a piece of positive electrode active material layer unit and a piece of negative electrode active material layer unit The mode of state electrolyte sheet is overlapping.Now, with first positive electrode active material layer unit just Electrode current collector layer slurry only stretches out in end face, and second negative electrode active material layer unit is negative Electrode current collector layer slurry only stretches out in the mode of another side, and stagger overlap by each unit.Heavy at this On the two sides of folded unit, overlapping solid electrolyte sheet is to becoming thickness 500 μm, then, and will After it is by hot strong binding molding, cuts off and make lamination block.Then, burn till lamination block simultaneously, Obtain laminated body.Burn till is to be warmed up to burn till temperature with programming rate 200 DEG C/h in nitrogen simultaneously Spend 1075 DEG C, keep two hours at such a temperature, after burning till, carry out natural cooling.
(terminal electrode formation process)
The end face of lamination block is coated with terminal electrode slurry, carries out 150 DEG C, the heat of 30 minutes Solidification, forms pair of terminal electrode, thus obtains lithium rechargeable battery.
(evaluation of battery)
The terminal electrode of the lithium rechargeable battery obtained is installed lead-in wire, carries out discharge and recharge examination Test.In condition determination, electric current during charging and discharging is all set to 2.0 μ A, during charging and when discharging Blanking voltage be set to 4.0V and 0V.Result understands this battery and carries out discharge and recharge well, It addition, as battery behavior, in the case of the solid electrolyte using comparative example 1, electric discharge Capacity is also 0.4 μ A, but when being 2.4 μ A, just has the best battery behavior.
Industrial applicability
The present invention may be used for all solid state type lithium rechargeable battery, particularly conductor layer thickness Relatively thin device.

Claims (6)

1. a lithium-ion-conducting oxide ceramic material, it is characterised in that
There is carbuncle type or the crystal structure of similar carbuncle type,
Containing Li, La, Zr and O,
And contain more than one the element in rare earth element further.
2. a lithium-ion-conducting oxide ceramic material, it is characterised in that
There is carbuncle type or the crystal structure of similar carbuncle type,
And represent with following composition formula (1),
Li7+xLa3Zr2-xAxO12 (1)
In formula (1), A is more than one the element in rare earth element, and x is for meeting 0 The number of ＜ x≤0.5.
3. lithium-ion-conducting oxide ceramic material as claimed in claim 2, its feature exists In,
A in described composition formula (1) be selected from Gd, Tb, Dy, Ho, Er, Tm, Yb, More than one element in Lu.
4. lithium-ion-conducting oxide ceramic material as claimed in claim 2 or claim 3, it is special Levy and be,
A in described composition formula (1) is more than one the unit in Gd, Ho, Yb Element, x meets 0 ＜ x≤0.30.
5. according to the lithium-ion-conducting oxide ceramics according to any one of Claims 1 to 4 Material, it is characterised in that
Further relative to the gross weight of described lithium-ion-conducting oxide ceramic material, contain More than 0.3wt% and the Al of below 2.0wt%.
6. an all solid state type lithium rechargeable battery, it is characterised in that
Employ the lithium-ion-conducting oxide ceramics material according to any one of Claims 1 to 5 Material.
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