CN105977528A - Garnet-type li-ion conductive oxide and all-solid li-ion secondary battery - Google Patents
Garnet-type li-ion conductive oxide and all-solid li-ion secondary battery Download PDFInfo
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
A garnet-type Li-ion conductive oxide containing LixLa3Zr2O12 (6<=x<=8) contains Al and element T (T is one or more from Ni, Cu, Co, and Fe). The garnet-type Li-ion conductive oxide is represented by the LixLa3Zr2O12 (6<=x<=8); the content of Al is contained, in terms of Al2O3, 2.5 mol %<=Al2O3<=15 mol % with respect to a total amount of LixLa3Zr2O12 contained in the garnet-type Li-ion conductive oxide. The content of element T is 25 mol %<=T<=100 mol % with respect to the total amount of LixLa3Zr2O12 contained in the garnet-type Li-ion conductive oxide.
Description
Technical field
The present invention relates to carbuncle type lithium-ion-conducting oxide and all solid state type lithium ion secondary
Battery.
Background technology
Compared with the lithium rechargeable battery using nonaqueous electrolytic solution, all solid state type lithium ion secondary
Battery is owing to using solid electrolyte, and therefore, heat stability is high.Wherein, consolidating of system is aoxidized
Body electrolyte has feature the most stable in chemical.As the master required by solid electrolyte
The characteristic wanted, can enumerate that lithium ion conductivity is higher, chemical stability is excellent, electrochemical window is big.
Li as carbuncle type lithium-ion-conducting oxide7La3Zr2O12(following, to be abbreviated as LLZ)
There is in such characteristic the advantage that chemical stability is excellent, electrochemical window is big, therefore, be solid
One of candidate being expected to of body electrolyte (referring for example to non-patent literature 1).
Prior art literature
Patent documentation
Patent documentation 1: No. 5132639 publications of Japanese Patent No.
Non-patent literature
Non-patent literature 1:Angew.Chem.Int.Ed., 2007, volume 46,7778-7781
Summary of the invention
Invent technical problem to be solved
In order to this carbuncle type lithium-ion-conducting oxide is used as solid electrolyte, from machine
The aspect of tool intensity is set out and is also required to improve further sintered density.
Patent Document 1 discloses by as carbuncle type lithium-ion-conducting oxide
Containing Al in LLZ, thus improve the manufacture method of the ceramic sintered bodies of ionic conductance.But
It is to can not get high sintered density.
The present invention is the technical problem having in view of above-mentioned prior art and completes, and its purpose exists
In, it is provided that it is a kind of that to have high sintering in the LLZ containing Al with good ionic conductance close
The carbuncle type lithium-ion-conducting oxide of degree, and a kind of this carbuncle type lithium of use is provided
Ion-conductive oxide is as all solid state lithium ion secondary cell of solid electrolyte.
For solving the scheme of problem
In order to reach above-mentioned purpose, the present inventor etc. finds, by containing in the LLZ containing Al
Appropriate amount selected from NiO, CuO, CoO4/3、FeO3/2In more than one oxide, from
And the carbuncle type lithium-ion-conducting oxide with high sintered densities can be obtained, and the completeest
Become the present invention.
That is, carbuncle type lithium-ion-conducting oxide involved in the present invention, with LixLa3Zr2O12
(6≤x≤8) represent, it is characterised in that containing Al, also have element T (T be Ni,
More than any one of Cu, Co, Fe), aoxidize relative to above-mentioned carbuncle type lithium-ion-conducting
The total amount of thing, containing with Al2O3It is scaled 2.5mol%≤Al2O3The amount of≤15mol% above-mentioned
Al, relative to the total amount of above-mentioned carbuncle type lithium-ion-conducting oxide, containing 25mol%≤
The above-mentioned element T of the amount of T≤100mol%.
It addition, carbuncle type lithium-ion-conducting oxide involved in the present invention, with
LixLa3Zr2O12(6≤x≤8) represent, it is characterised in that wherein, containing Al2O3And M (M
For selected from NiO, CuO, CoO4/3、FeO3/2In more than one oxide), Al2O3And
The content of M is:
2.5mol%≤Al2O3≤ 15mol%,
25mol%≤M≤100mol%.
The carbuncle type lithium-ion-conducting oxide of the invention described above has than existing containing Al's
The higher sintered density of LLZ.The present inventor etc. consider that the main cause obtaining this effect is as follows.
Think by adding selected from NiO, CuO, CoO in the LLZ containing Al4/3、FeO3/2In
More than one oxide, thus sintered density improves.
It addition, as the solid electrolyte of all solid state type lithium rechargeable battery, be preferably used
State carbuncle type lithium-ion-conducting oxide.Thus, it is possible to provide discharge capacity high entirely consolidating
State lithium rechargeable battery.
Invention effect
According to the present invention it is possible to provide a kind of have good ionic conductance containing Al's
LLZ has the carbuncle type lithium-ion-conducting oxide of high sintered densities, and provides one
Plant by using this carbuncle type lithium-ion-conducting oxide as solid electrolyte thus to have
The all solid state lithium ion secondary cell of excellent battery behavior.
Accompanying drawing explanation
Fig. 1 is to represent the stone obtained in comparative example 1, comparative example 2, embodiment 1～embodiment 4
The figure of the relative density of garnet type lithium-ion-conducting oxide；
Fig. 2 is to represent the stone obtained in comparative example 1, comparative example 2, embodiment 1～embodiment 4
The figure of the ionic conductance comprising crystal boundary of garnet type lithium-ion-conducting oxide；
Fig. 3 is to represent comparative example 3, comparative example 4, embodiment 3, embodiment 5～embodiment 7
In the figure of the relative density of carbuncle type lithium-ion-conducting oxide that obtains；
Fig. 4 is to represent comparative example 3, comparative example 4, embodiment 3, embodiment 5～embodiment 7
In the ionic conductance comprising crystal boundary of carbuncle type lithium-ion-conducting oxide that obtains
Figure；
Fig. 5 is the sectional view of the conceptual structure 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 carbuncle type lithium-ion-conducting oxide of present embodiment is with LixLa3Zr2O12(6≤x
≤ 8) represent, it is characterised in that: containing Al and element T, (T is Ni, Cu, Co, Fe's
More than any one),
Relative to the total amount of above-mentioned carbuncle type lithium-ion-conducting oxide, containing with Al2O3
It is scaled 2.5mol%≤Al2O3The above-mentioned Al of the amount of≤15mol%,
Relative to the total amount of above-mentioned carbuncle type lithium-ion-conducting oxide, containing 25mol%≤
The above-mentioned element T of the amount of T≤100mol%.
The carbuncle type lithium-ion-conducting oxide of present embodiment has than existing containing Al's
The higher sintered density of LLZ.It is thought that the effect of element T.Therefore, no matter element T
Valence mumber state, can be oxide, it is also possible to be other compound.
Additionally, identifying with LixLa3Zr2O12The carbuncle type lithium ion that (6≤x≤8) represent
In conductive oxide, can be carried out by powder X-ray diffraction.It addition, provided of course that mirror
Determine LixLa3Zr2O12So-called LLZ, therefore, it can not be stoichiometric composition
Material.I.e. can also produce the defect of oxygen defect etc..
The element T added in this carbuncle type lithium-ion-conducting oxide can be by with height
Frequently inductance coupling plasma emissioning spectral analysis (ICP) carrys out quantitative carbuncle type lithium ion conduction
The powder of property oxide.
With LixLa3Zr2O12The carbuncle type lithium-ion-conducting oxidation that (6≤x≤8) represent
In thing, containing Al2O3And M (M is selected from NiO, CuO, CoO4/3、FeO3/2In one
Plant above oxide), Al2O3And the content of M is:
2.5mol%≤Al2O3≤ 15mol%,
25mol%≤M≤100mol%.
Preferably Al2O3Content be in 2.5mol%≤Al2O3The relation of≤15mol%.This be by
In so obtaining good lithium ion conductivity.If Al2O3Content less than 2.5mol
During %, then easily generate the tetragonal phase of the low LLZ of lithium-ion-conducting, if it addition, Al2O3
Content more than 15mol%, then easily generate the LaAlO that lithium-ion-conducting is relatively low3, therefore,
Lithium ion conductivity reduces.
M is selected from NiO, CuO, CoO4/3、FeO3/2In more than one oxide.
The content of M is in the relation of 25mol%≤M≤100mol%.Thus, available height
Sintered density (relative density more than 90%).If the content of M is less than 25mol%, then see not
To the improvement effect of sufficient density, on the other hand, if it exceeds 100mol%, then ion passes
Conductance reduces.
Additionally, the qualification of LLZ and Al, M quantitatively as identification method during above-mentioned element T.
It addition, M exists with the state of oxide preferably as described above, it is preferably in LLZ
Between the particle surface of grain or granule.By there is the change of microgranule as M in such crystal boundary
Compound, thus fill LLZ void among particles, improve sintered density further.Now, M
Preferably exist with amorphous.Now, if for amorphous by can not get and M phase with X-ray diffraction
The peak value closed differentiates.
According to present embodiment, by using above-mentioned carbuncle type lithium-ion-conducting oxide,
Such that it is able to form all solid state type lithium ion secondary electricity with the high solid electrolyte of sintered density
Pond.
It follows that the manufacturer of the carbuncle type lithium-ion-conducting oxide to present embodiment
Method illustrates.The system of the carbuncle type lithium-ion-conducting oxide involved by present embodiment
The method of making can be by being blended with Li compound, La compound, Zr compound, Al2O3With
(M is selected from NiO, CuO, CoO to M4/3、FeO3/2In more than one oxide)
Mixing raw material carries out burning till obtaining.
As above-mentioned Li compound, such as, can enumerate: LiOH or its hydrate, Li2CO3、
LiNO3、CH3COOLi etc..As above-mentioned La compound, can enumerate: La2O3、La(OH)3、
La2(CO3)3、La(NO3)3、(CH3COO)3La etc..As above-mentioned Zr compound, Ke Yilie
Lift: ZrO2、ZrO(NO3)2、ZrO(CH3COO)2、Zr(OH)2CO3Deng.
(manufacture method)
For present embodiment carbuncle type lithium-ion-conducting oxide manufacture method one
Individual example illustrates.The manufacture method of this oxide includes: (1) interpolation lithium compound etc. are former
Material and Al2O3Carry out the operation of co-grinding, (2) obtain calcined powder with the calcining heat of regulation
Calcination process, (3) add as element T or M that (M is selected from NiO, CuO, CoO4/3、
FeO3/2In more than one oxide) material carry out the operation of co-grinding, (4) molding
The operation of powder, (5) carry out the operation burnt till, and below, illustrate each operation successively.
(1) raw material and the Al such as lithium compound are added2O3Carry out the operation of co-grinding
Adding raw material and the Al such as lithium compound2O3Carry out in the operation mixed, weigh respectively and comprise
Chemical formula LiXLa3Zr2O12The initial feed of each element of (in formula, X is 6≤X≤8) is to become
The stoichiometric proportion of above-mentioned chemical formula also mixes.It addition, now, by making A12O3Phase
For chemical formula LiXLa3Zr2O12(in formula, X is 6≤X≤8) is calculated as 2.5mol with mol%
In the scope of more than % and below 15mol%, such that it is able to obtain the garnet that ionic conductance is high
Type lithium-ion-conducting oxide.In mixed method, can be added without in solvent under dry type
Carry out co-grinding, it is also possible to add and solvent carries out co-grinding under wet type, but from carrying
High blended aspect is set out, and is preferably added in solvent carry out the co-grinding of wet type.This mixing
Method can use such as planetary ball mill, grater, ball mill etc..As solvent, preferably
Not readily dissolve Li, the most more preferably the organic solvent such as ethanol.Incorporation time is according to combined amount
Fixed, such as 1h～32h can be set to.
(2) calcination process of calcined powder is obtained with the calcining heat of regulation
In calcination process, calcine the mixed-powder obtained in the operation of mixing raw material.Now
Calcining heat is preferably set to cause the state of initial feed to change and (such as produces gas or phase change
Deng) temperature less than temperature when burning till.Such as, Li is being used2CO3As initially
In the case of raw material, it is preferably set to the temperature of this carbonate decomposition less than temperature when burning till
Degree.So, in burning till later, the gas in thermal decomposition can be suppressed to produce cause close
Degree reduces.Specifically, calcining heat is preferably set to 800 DEG C～1000 DEG C.
(3) add that (M is selected from NiO, CuO, CoO as element T or M4/3、FeO3/2
In more than one oxide) material and carry out the operation of co-grinding
Add as element T or M that (M is selected from NiO, CuO, CoO4/3、FeO3/2In
More than one oxide) material and carry out the operation of co-grinding, to forging with regulation
Burn temperature and obtain in the powder obtained in the calcination process of calcined powder, add the expectation of ormal weight
Selected from NiO, CuO, CoO4/3、FeO3/2In more than one oxide thus mix
Close and pulverize.The method of co-grinding can use such as planetary ball mill, grater, ball mill
Deng.As solvent, being preferably difficult to dissolve the solvent of Li, more preferably such as ethanol etc. are organic
Solvent.Depending on the co-grinding time is according to combined amount, such as 1h～32h can be set to.
(4) operation of powder for molding
In the operation of powder for molding, by the operation adding the second accessory ingredient and carrying out co-grinding
The powder compacting obtained.Molded body can pass through cold isostatic compaction (CIP) or high temperature insostatic pressing (HIP) becomes
Type (HIP), mould molding, hot pressing etc. are shaped to arbitrary shape.Pass through it addition, also can enumerate
Employ the forming method etc. that the thin slice technique of scraper or roll coater etc. is carried out.
(5) operation burnt till is carried out
In carrying out the operation burnt till, the molded body obtained in the operation of powder for molding is burnt
Become.Thus, it is possible to obtain the carbuncle type lithium-ion-conducting oxide of present embodiment.
Firing atmosphere can also be implemented in air atmosphere, but more preferably implements in reducing atmosphere.
This is owing to, in air atmosphere, the density of sintered body uprises, but ionic conductance reduces.This
Be due to, in air atmosphere, Ni and LLZ reacts, and it is low to be attended by ionic conductance in a large number
The generation of out-phase.As long as firing temperature aoxidizes at the carbuncle type lithium-ion-conducting of target
More than the amorphizing temperature of thing, in the range of the most more preferably 1050 DEG C～1150 DEG C.
If this is because, less than 1050 DEG C, then can not obtain densely sintered body, if it exceeds 1150
DEG C, then confirm volatilization or the out-phase (La of Li2Zr2O7) generation, ionic conductance reduce.
It addition, be more preferably to carry out in the range of 2 hours～20 hours at firing time.
(all solid state type lithium secondary battery)
The all solid lithium secondary battery of present embodiment is as it is shown in figure 5, by positive pole 1, negative pole 2
Constituting with solid electrolyte 3, solid electrolyte 3 is characterised by, with LixLa3Zr2O12(6
≤ x≤8) in the carbuncle type lithium-ion-conducting oxide that represents, containing Al2O3And M (M
For selected from NiO, CuO, CoO4/3、FeO3/2In more than one oxide), and Al2O3
And the content of M with:
2.5mol%≤Al2O3≤ 15mol%,
25mol%≤M≤100mol%
Represent, by being set to all solid state type lithium secondary battery of this structure, become than existing more
Practical secondary cell.
The positive pole of all solid state type lithium rechargeable battery of present embodiment and negative pole are respectively by positive pole
Active substance 5, positive electrode collector 4 and negative electrode active material 7 and negative electrode active material 6 are constituted.
The currently known positive active material for lithium secondary battery and negative electrode active can be contained
Material, 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, can
To enumerate: manganese dioxide (MnO2), ferrum oxide, copper oxide, nickel oxide, lithium manganese composite oxygen
Compound (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
Li-mn-ni compound oxide (such as, LixMn2-yNiyO4), there is the lithium phosphate of olivine structural
Compound (such as, LixFePO4、LixFe1-yMnyPO4、LixCoPO4、LiVOPO4), tool
There is lithium phosphate compound (such as, the Li of NASICON structurexV2(PO4)3、Li2VOP2O7、
Li2VP2O7、Li4(VO)(PO4)2, and Li9V3(P2O7)3(PO4)2), iron sulfate (Fe2(SO4)3)、
Barium oxide (such as, V2O5) etc..They can also be used alone one, it is also possible to and use
Two or more.Additionally, in these chemical formulas, x, y are preferably the model of 1 ＜ x ＜ 5,0 ＜ y ＜ 1
Enclose.Wherein, preferably LiCoO2、LiNiO2、LixV2(PO4)3、LiFePO4。
(negative electrode active material)
As negative electrode active material, it is not particularly limited, it is possible to use currently known for entirely
The negative electrode active material of solid state battery.Such as can enumerate: carbon, lithium metal (Li), metallization
Compound, metal-oxide, Li metallic compound, Li metal-oxide (comprise lithium-transition metal
Composite oxides), add boron carbon, graphite, there is the compound etc. of NASICON structure.These
Can be used alone one, it is also possible to and with two or more.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
Such as: the currently known material with carbon elements such as graphitic carbon, hard carbon, soft carbon.As above-mentioned metal compound
Thing, can enumerate: LiAl, LiZn, Li3Bi、Li3Sd、Li4Si、Li4.4Sn、Li0.17C(LiC6)
Deng.As above-mentioned metal-oxide, can enumerate: SnO, SnO2、GeO、GeO2、In2O、
In2O3、Ag2O、AgO、Ag2O3、Sb2O3、Sb2O4、Sb2O5、SiO、ZnO、CoO、
NiO、TiO2, FeO etc..As Li metallic compound, can enumerate: Li3FeN2、Li2.6Co0.4N、
Li2.6Cu0.4N etc..As Li metal-oxide (lithium-compound transition metal oxide), Ke Yiju
Go out with 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,
The material of nickel etc..Particularly copper, it is difficult to react with titanium phosphate aluminum lithium, and is reducing lithium ion
There is on the internal resistance of secondary cell effect, therefore preferably.The material constituting collector body can be just
Pole is identical with negative pole, 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 active material and negative pole is contained respectively by positive electrode collector layer and negative electrode collector layer
Active substance, thus positive electrode collector layer and positive electrode active material layer and negative electrode collector layer are with negative
The adaptation of pole active material layer improves, therefore preferably.
(manufacture method of lithium rechargeable battery)
The lithium rechargeable battery of present embodiment manufactures by the following method, i.e. by positive pole collection
Electrics layer, positive electrode active material layer, solid electrolyte layer, negative electrode active material layer and negative pole collection
Each material paste of electrics layer, and coating is dry thus makes green chip, by thin for these green compact
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 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 chip.The coating process of slurry is the most especially
Limit, can use silk screen printing, be coated with, transfer, the known method such as scraper.
The green chip order desirably, the lamination number that make is overlapping, carry out as required
Arrangement, cut-out etc., make lamination block.Situation at the battery making parallel connection type or Serial-Parallel Type
Under, 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, solid electrolyte slurry is passed through doctor blade method shape by PET film
Flakiness shape, after obtaining solid electrolyte flake, on this solid electrolyte flake, by silk
Wire mark is stenciled brush positive electrode active material layer slurry and is dried.Then, silk screen is passed through thereon
Printing printing positive electrode collector layer slurry is also dried.The most thereon by silk screen printing the most again
Printing anode active material slurry, and be dried, then by peeling off PET film, obtain
Positive electrode active material layer unit.So, obtain sequentially forming positive pole on solid electrolyte flake
Active material layer slurry, positive electrode collector layer slurry, the positive-active of anode active material slurry
Material layer unit.Also by same order, make negative electrode active material layer unit, obtain
Sequentially form on solid electrolyte flake negative electrode active material layer slurry, negative electrode collector layer 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 body 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 flake 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 reducing atmosphere 600 DEG C～1200 DEG C also
Burn 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 4, comparative example 1～comparative example 2]
Initial feed employs Li compound (Li2CO3), La compound (La2O3), Zrization
Compound (ZrO2)、Al2O3、NiO.First, weigh initial feed to become to mol ratio
Li:La:Zr=7:3:2, and weigh Al by following table 12O3.Then, ball milling is utilized in ethanol
Machine (rotating speed 120rpm/ zirconia ball) carries out co-grinding 16 hours.By the slurry that obtains from
After ball and ethanol separate, in oxidation aluminum cup at 900 DEG C, air atmosphere is carried out
Calcine 5 hours.Li with the main constituent relative to the calcined powder obtained7La3Zr2O12Become
The mode of 50mol% weighs NiO, and these powder are utilized ball mill (120rpm/ in ethanol
Zirconia ball) carry out co-grinding 16 hours.The slurry obtained is separated from ball and ethanol
After drying, comminuted powder is obtained.Then, these comminuted powders are added organic system binding agent,
Make granule.The mould that this granule uses φ 10mm is shaped to discoid with 7kN.Molding
Body in platinum sheet with the sintering temperature (5%H under reducing atmosphere of 1100 DEG C2/ 95%N2) carry out
Burn till two hours, obtain discoid sintered body sample.
(table 1)
[embodiment 5～embodiment 7, comparative example 3～comparative example 4]
Initial feed employs Li compound (Li2CO3), La compound (La2O3), Zrization
Compound (ZrO2)、Al2O3、NiO.First, weigh initial feed to become to mol ratio
Li:La:Zr=7:3:2, and weigh Al2O3To becoming 10mol%.Then, ball milling is used in ethanol
Machine (rotating speed 120rpm/ zirconia ball) carries out co-grinding 16 hours.By the slurry that obtains with
After ball and separation of ethanol, oxidation aluminum cup in 900 DEG C, forge in air atmosphere
Burn 5 hours.Li relative to the main constituent of the calcined powder obtained7La3Zr2O12, by following table
2 weigh NiO, are carried out with ball mill (120rpm/ zirconia ball) in ethanol by these powder
Co-grinding 16 hours.The slurry obtained is separated after drying from ball and ethanol, obtains powder
Comminuted powder.Then, these comminuted powders are added organic system binding agent and make granule.Should
Grain uses the mould of φ 10mm to be shaped to discoid with 7kN.Molded body in platinum sheet with 1100
DEG C sintering temperature (5%H under reducing atmosphere2/ 95%N2) carry out burning till two hours, justified
The sintered body sample of plate-like.
(table 2)
[embodiment 8]
Initial feed employs Li compound (Li2CO3), La compound (La2O3), Zrization
Compound (ZrO2)、Al2O3、CoO4/3.First, weigh initial feed to become to mol ratio
Li:La:Zr=7:3:2, and weigh Al2O3To becoming 10mol%, (turn with ball mill in ethanol
Speed 120rpm/ zirconia ball) carry out co-grinding 16 hours.By the slurry that obtains from ball and second
After alcohol separates, in oxidation aluminum cup with 900 DEG C, carry out calcining 5 under air atmosphere
Hour.Weigh CoO4/3Li to the main constituent relative to obtained calcined powder7La3Zr2O12
Become 50mol%, these powder are entered with ball mill (120rpm/ zirconia ball) in ethanol
Row co-grinding 16 hours.The slurry obtained is separated after drying from ball and ethanol, obtains
Comminuted powder.Then, these comminuted powders added organic system binding agent and 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 (5%H under reducing atmosphere2/ 95%N2) carry out burning till two hours,
To discoid sintered body sample.
[embodiment 9]
Initial feed employs Li compound (Li2CO3), La compound (La2O3), Zrization
Compound (ZrO2)、Al2O3、CuO.First, weigh initial feed to become to mol ratio
Li:La:Zr=7:3:2, and weigh Al2O3To becoming 10mol%, ball mill is utilized (to turn in ethanol
Speed 120rpm/ zirconia ball) carry out co-grinding 16 hours.By the slurry that obtains from ball and second
After alcohol separates, in oxidation aluminum cup with 900 DEG C, carry out calcining 5 under air atmosphere
Hour.Weigh CuO to the Li of main constituent relative to obtained calcined powder7La3Zr2O12
Become 50mol%, these powder are entered with ball mill (120rpm/ zirconia ball) in ethanol
Row co-grinding 16 hours.The slurry obtained is separated after drying from ball and ethanol, obtains
Comminuted powder.Then these comminuted powders are 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 (5%H under reducing atmosphere2/ 95%N2) carry out burning till two hours,
To discoid sintered body sample.
[embodiment 10]
Initial feed employs Li compound (Li2CO3), La compound (La2O3), Zrization
Compound (ZrO2)、Al2O3、FeO3/2.First, weigh initial feed to become to mol ratio
Li:La:Zr=7:3:2, and weigh Al2O3To becoming 10mol%, (turn with ball mill in ethanol
Speed 120rpm/ zirconia ball) carry out co-grinding 16 hours.By the slurry that obtains from ball and second
After alcohol separates, in oxidation aluminum cup with 900 DEG C, carry out calcining 5 under air atmosphere
Hour.Weigh FeO3/2Li to the main constituent relative to obtained calcined powder7La3Zr2O12
Become 50mol%, these powder are entered with ball mill (120rpm/ zirconia ball) in ethanol
Row co-grinding 16 hours.The slurry obtained is separated after drying from ball and ethanol, obtains
Comminuted powder.Then, these comminuted powders are 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 (5%H under reducing atmosphere2/ 95%N2) carry out burning till two hours,
To discoid sintered body sample.
[embodiment 11]
Initial feed employs Li compound (Li2CO3), La compound (La2O3), Zrization
Compound (ZrO2), Al compound (Al2O3)、NiO、CoO4/3.First, weighing is the most former
Expect to mol ratio to become Li:La:Zr=7:3:2, and weigh Al2O3To becoming 10mol%, in second
Alcohol utilize ball mill (rotating speed 120rpm/ zirconia ball) carry out co-grinding 16 hours.Will
After the slurry obtained separates from ball and ethanol, with 900 DEG C, air in oxidation aluminum cup
Atmosphere is calcined 5 hours.Li relative to the main constituent of obtained calcined powder7La3Zr2O12,
NiO is to becoming 25mol% in weighing, and weighs CoO4/3To becoming 25mol%, by these powder
End carries out co-grinding 16 hours with ball mill (120rpm/ zirconia ball) in ethanol.
The slurry that obtains is dried with ball and separation of ethanol, obtain comminuted powder.Then, relative to
These comminuted powders add organic system binding agent, make granule.This granule is used φ 10mm's
Mould is shaped to discoid with 7kN.Molded body in platinum sheet with the sintering temperature of 1100 DEG C also
(5%H under Primordial Qi atmosphere2/ 95%N2) carry out burning till two hours, obtain discoid sintered body sample.
[embodiment 12]
Initial feed employs Li compound (Li2CO3), La compound (La2O3), Zrization
Compound (ZrO2)、Al2O3、CuO、FeO3/2.First, weigh initial feed to become to mol ratio
For Li:La:Zr=7:3:2, and weigh Al2O3To becoming 10mol%, use ball mill in ethanol
(rotating speed 120rpm/ zirconia ball) carries out co-grinding 16 hours.By the slurry that obtains from ball
With in ethanol separate after, oxidation aluminum cup in 900 DEG C, in air atmosphere under forge
Burn 5 hours.Li relative to the main constituent of obtained calcined powder7La3Zr2O12, weigh
CuO is to becoming 25mol%, and weighs FeO3/2To becoming 25mol%, by these powder in second
Alcohol carries out co-grinding 16 hours with ball mill (120rpm/ zirconia ball).To obtain
Slurry separate from ball and ethanol after drying, obtain comminuted powder.Then, relative to these
Comminuted powder adds organic system binding agent, makes granule.This granule is used the mould of φ 10mm
It is shaped to discoid with 7kN.Molded body in platinum sheet with the sintering temperature of 1100 DEG C in reducing gases
(5%H under atmosphere2/ 95%N2) carry out burning till two hours, obtain discoid sintered body sample.
[embodiment 13]
Initial feed employs Li compound (Li2CO3), La compound (La2O3), Zrization
Compound (ZrO2)、Al2O3、NiO、CoO4/3、CuO.First, initial feed is weighed to rubbing
You become Li:La:Zr=7:3:2 by ratio, and weigh Al2O3To becoming 10mol%, use in ethanol
Ball mill (rotating speed 120rpm/ zirconia ball) carries out co-grinding 16 hours.The slurry that will obtain
After material separates from ball and ethanol, in oxidation aluminum cup with 900 DEG C, enter under air atmosphere
Row calcining 5 hours.Li relative to the main constituent of obtained calcined powder7La3Zr2O12, claim
NiO is to becoming 20mol% for amount, weighs CoO4/3To becoming 10mol%, weigh CuO to becoming
For 20mol%, these powder are carried out with ball mill (120rpm/ zirconia ball) in ethanol
Co-grinding 16 hours.The slurry obtained is separated after drying from ball and ethanol, obtains powder
Comminuted powder.Then, these comminuted powders are added organic system binding agent, make granule.Should
Granule uses the mould of φ 10mm to be shaped to discoid with 7kN.Molded body in platinum sheet with 1100
DEG C sintering temperature (5%H under reducing atmosphere2/ 95%N2) carry out burning till two hours, justified
The sintered body sample of plate-like.
[embodiment 14]
Initial feed employs Li compound (Li2CO3), La compound (La2O3), Zrization
Compound (ZrO2)、Al2O3、NiO、CoO4/3、CuO、FeO3/2.First, weighing is the most former
Expect to mol ratio to become Li:La:Zr=7:3:2, and weigh Al2O3To becoming 10mol%, in second
Alcohol carries out co-grinding 16 hours with ball mill (rotating speed 120rpm/ zirconia ball).Will
To slurry separate from ball and ethanol after, oxidation aluminum cup in 900 DEG C, air gas
Atmosphere is carried out calcine 5 hours.Main constituent relative to obtained calcined powder
Li7La3Zr2O12, NiO is to becoming 20mol% in weighing, weighs CoO4/3To becoming 10mol%,
CuO is to becoming 10mol% in weighing, weighs FeO3/2To becoming 10mol%, by these powder
Co-grinding is carried out 16 hours in ethanol with ball mill (120rpm/ zirconia ball).Will
The slurry obtained separates after drying from ball and ethanol, obtains comminuted powder.Then, to these
Comminuted powder adds organic system binding agent, makes granule.This granule is used the mould of φ 10mm
It is shaped to discoid with 7kN.Molded body in platinum sheet with the sintering temperature of 1100 DEG C in reducing gases
(5%H under atmosphere2/ 95%N2) carry out burning till two hours, obtain discoid sintered body sample.
About the relative density of the sintered body sample obtained in embodiment 8～14 with comprise crystal boundary
Ionic conductance is shown in table 3.
(table 3)
In the above embodiments and comparative example, form the most various evaluation of physical property and be carried out as follows.
[estimation of sintered density]
The sintering of the carbuncle type lithium-ion-conducting oxide forming above-mentioned discoid sintered body is close
Degree is calculated by following method, i.e. utilize slide gauge, micrometer to measure this discoid sintering
After the volume of body, by the dry weight of this discoid sintered body divided by this volume.It addition, according to
Its sintered density and solid density calculate relative density.Additionally, above-mentioned theory density uses
Li7La3Zr2O12Solid density (5.1g/cm3).It addition, in the present embodiment, by relative density
Be more than 90% sample be judged as high-quality product.
[estimation of ionic conductance]
In temperature chamber, use AC electric impedance analyzer (Solartron society system 1260), will measure
Temperature is set to 25 DEG C, and mensuration frequency is set to 0.05Hz～1MHz, and amplitude voltage is set to 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, calculates ionic conductance according to this resistance value.Utilize AC impedance analysis
Blocking electrode when instrument measures uses Au electrode.Au electrode passes through sputtering method with φ 3mm round shape
Formed.It addition, in the present embodiment, be 5.0 × 10 by the ionic conductance comprising crystal boundary-5(Scm-1)
Above sample is judged as high-quality product.
[chemical composition analysis]
The sintered body sample that will obtain in embodiment 1～embodiment 14, comparative example 1～comparative example 4
Dissolving, and carry out ICP composition analysis, results verification arrives, and has generally remained sample introduction composition.
As shown in table 1, Fig. 1 and Fig. 2, with chemical formula Li7La3Zr2O12The garnet represented
In type lithium-ion-conducting oxide, Al2O3Content be in 2.5mol%≤Al2O3≤15mol
Embodiment 1～the embodiment 4 of the scope of % can obtain the sintering higher than comparative example 1 and comparative example 2
Density, therefore, can confirm that relative density becomes more than 90%.It addition, can confirm that and comprise
The ionic conductance of crystal boundary is also 5.0 × 10-5(Scm-1More than).
As shown in table 2, Fig. 3 and Fig. 4, with chemical formula Li7La3Zr2O12The garnet represented
In type lithium-ion-conducting oxide, (M is selected from NiO, CuO, CoO to M4/3、FeO3/2
In more than one oxide) content be in the scope of 25mol%≤M≤100mol%
It is close that embodiment 3 and embodiment 5～embodiment 7 obtain the sintering higher than comparative example 3 and comparative example 4
Degree, therefore, can confirm that relative density becomes more than 90%.It addition, can confirm that and comprise crystalline substance
The ionic conductance on boundary is 5.0 × 10-5(Scm-1More than).
As shown in table 3, with chemical formula Li7La3Zr2O12The carbuncle type lithium ion conduction represented
In property oxide, (M is selected from NiO, CuO, CoO to M4/3、FeO3/2In more than one
Oxide) content be in the embodiment 8 of scope of 25mol%≤M≤100mol%～real
Execute example 14 and can get high sintered density, therefore, can confirm that relative density becomes more than 90%.
It addition, can confirm that the ionic conductance comprising crystal boundary is also 5.0 × 10-5(Scm-1More than).
[embodiment 15]
Hereinafter, represent the embodiment of all solid lithium secondary battery, but the present invention is not limited to these
Embodiment.Additionally, as long as no explanation, " part " is " 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.Calcining product ball mill is carried out wet type
After pulverizing, carry out dehydrate, obtain powder.X-ray diffraction device is used to confirm this system
The structure of the powder body made is Li3V2(PO4)3。
(anode active material slurry and the making of negative electrode active material slurry)
Anode active material slurry and negative electrode active material slurry are all by 100 parts
Li3V2(PO4)3Add 15 parts of ethyl celluloses as binding agent in powder, 65 parts as solvent
Dihydroterpineol, thus carry out mixing dispersion, make active material slurry.
(making of solid electrolyte flake)
As solid electrolyte, initial feed uses Li compound (Li2CO3), La compound
(La2O3), Zr compound (ZrO2)、Al2O3, weigh initial feed respectively and become to mol ratio
For Li:La:Zr=7:3:2, weigh Al2O3To becoming 10mol%.Then, ball is used in ethanol
Grinding machine (rotating speed 120rpm/ zirconia ball) carries out co-grinding 16 hours.The slurry that will obtain
From ball and ethanol separate after, oxidation aluminum cup in 900 DEG C, enter in air atmosphere
Row calcining 5 hours, obtains calcined powder.
Then, relative to the Li of main constituent of this calcined powder7La3Zr2O12, weigh NiO to becoming
For 50mol%, add the ethanol 100 parts as solvent, toluene 200 parts and utilize ball mill to enter
Row wet mixed is pulverized.Then, polyvinyl butyral resin system binding agent 16 parts is put into further
With BBP(Butyl Benzyl Phthalate 4.8 parts, and mix, prepare solid electrolyte slurry.
(making of solid electrolyte flake)
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 flake of thickness 15 μm.
(making of collector body slurry)
Ni and Li that will use as collector body3V2(PO4)3Mixing is to becoming in terms of volume ratio
After 80/20, add the ethyl cellulose as binding agent and the dihydroterpineol as solvent is carried out
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 by the following method.
(making of positive electrode active material layer unit)
Above-mentioned solid electrolyte flake 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.It follows that pass through screen printing on this layer
Brush and print positive electrode collector layer slurry with thickness 5 μm, be dried 10 minutes with 80 DEG C.Thereon
Anode active material slurry is again printed with thickness 5 μm further by silk screen printing, and 80
It is dried at DEG C 10 minutes, then, peels off PET film.So, obtain at solid electrolyte thin
On sheet, printing has been dried positive electrode active material layer slurry, positive electrode collector layer slurry, just successively
The thin slice of the positive electrode active material layer unit of pole active material slurry.
(making of negative electrode active material layer unit)
Above-mentioned solid electrolyte flake 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.It follows that thereon by silk screen printing with
Thickness 5 μm printing negative electrode collector layer slurry, and be dried 10 minutes at 80 DEG C.Further
Negative electrode active material slurry is again printed with thickness 5 μm thereon by silk screen printing, and with 80
DEG C be dried 10 minutes, it follows that peel off PET film.So, obtain at solid electrolyte thin
On sheet, printing is dry successively negative electrode active material slurry, negative electrode collector layer slurry, negative pole
The thin slice of the negative electrode active material layer unit of active material slurry.
(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 body electrolyte sheet is overlapping.Now, with first positive electrode active material layer unit just
Electrode current collector layer slurry only stretches out in an end face, and second negative electrode active material layer unit
Negative electrode collector layer slurry only stretches out in the mode of another side, and stagger overlap by each unit.At this
On the two sides of overlapping unit in the way of becoming thickness 500 μm overlap solid electrolyte flake,
Then, by this thin slice by hot strong binding molding after, cut off, make lamination block.So
After, burn till lamination block simultaneously, obtain laminated body.Burn till in nitrogen with programming rate 200 simultaneously
DEG C/h it is warmed up to firing temperature 1100 DEG C, keeps two hours at such a temperature, carry out after burning till
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, 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.Condition determination is set to, and electric current during charging and discharging is all set to 2.0 μ A, during charging and electric discharge
Time blanking voltage be set to 4.0V and 0V.Result understands this battery and carries out charge and discharge well
Electricity, even if it addition, as battery behavior, in the situation of the solid electrolyte using comparative example 1
Discharge capacity is also 0.4 μ A, but when being 2.5 μ A, just has the best battery behavior.
Industrial applicability
As it has been described above, according to this manufacture method, the carbuncle type lithium that sintered density is high can be made
Ion-conductive oxide, and may be used for the solid in all solid state type lithium rechargeable battery
Electrolyte.
Claims (3)
1. a carbuncle type lithium-ion-conducting oxide, it is characterised in that
This carbuncle type lithium-ion-conducting oxide is with LixLa3Zr2O12Represent, wherein, 6≤x
≤ 8,
Containing Al,
There is element T further, wherein T be Ni, Cu, Co, Fe any one more than,
Relative to the total amount of described carbuncle type lithium-ion-conducting oxide, containing with Al2O3
It is scaled 2.5mol%≤Al2O3The described Al of the amount of≤15mol%,
Relative to the total amount of described carbuncle type lithium-ion-conducting oxide, containing 25mol%≤
The described element T of the amount of T≤100mol%.
2. a carbuncle type lithium-ion-conducting oxide, it is characterised in that
With LixLa3Zr2O12Represent, wherein contain Al2O3And M, wherein,
6≤x≤8,
M is selected from NiO, CuO, CoO4/3、FeO3/2In more than one oxide,
And Al2O3And the content of M is:
2.5mol%≤Al2O3≤ 15mol%,
25mol%≤M≤100mol%.
3. an all solid state type lithium rechargeable battery, wherein,
Using the carbuncle type lithium-ion-conducting oxide described in claim 1 or 2 as solid
Electrolyte.
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| JP2016018898A JP6565724B2 (en) | 2015-03-10 | 2016-02-03 | Garnet type lithium ion conductive oxide and all solid state lithium ion secondary battery |
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| CN110229003B (en) * | 2019-06-04 | 2021-12-07 | 上海应用技术大学 | Preparation method and application of LiNiLaZrO solid electrolyte |
| CN110256068A (en) * | 2019-06-04 | 2019-09-20 | 上海应用技术大学 | A kind of LiNiLaZrMO method for preparing solid electrolyte |
| CN110256068B (en) * | 2019-06-04 | 2022-02-11 | 上海应用技术大学 | A kind of preparation method of LiNiLaZrMO solid electrolyte |
| CN110229003A (en) * | 2019-06-04 | 2019-09-13 | 上海应用技术大学 | A kind of LiNiLaZrO method for preparing solid electrolyte and application |
| CN111430808A (en) * | 2020-03-23 | 2020-07-17 | 广东东邦科技有限公司 | Lithium-containing chalcogenide-germanite solid electrolyte with dopant and preparation method thereof |
| CN116635331A (en) * | 2020-12-24 | 2023-08-22 | 新日本电工株式会社 | Lithium ion conductive oxide material and all-solid-state lithium secondary battery |
Also Published As
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| JP6565724B2 (en) | 2019-08-28 |
| JP2016169142A (en) | 2016-09-23 |
| CN105977528B (en) | 2019-02-05 |
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