CN105826601A - Li4SiO4-Li3PO4-LiBO2 solid solution ceramic lithium ion conductor - Google Patents
Li4SiO4-Li3PO4-LiBO2 solid solution ceramic lithium ion conductor Download PDFInfo
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- 239000006104 solid solution Substances 0.000 title claims abstract description 84
- 229910013178 LiBO2 Inorganic materials 0.000 title claims abstract description 58
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 56
- 239000000919 ceramic Substances 0.000 title claims abstract description 48
- 239000010416 ion conductor Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 6
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 27
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 11
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003746 solid phase reaction Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 238000010671 solid-state reaction Methods 0.000 claims description 8
- 238000000280 densification Methods 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 4
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910021655 trace metal ion Inorganic materials 0.000 abstract description 7
- 239000007784 solid electrolyte Substances 0.000 abstract description 5
- 239000004020 conductor Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 2
- 230000005484 gravity Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 19
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000001453 impedance spectrum Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- -1 oxonium ion Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002223 garnet Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910012850 Li3PO4Li4SiO4 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910010640 Li6BaLa2Ta2O12 Inorganic materials 0.000 description 1
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 1
- 229910011201 Li7P3S11 Inorganic materials 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000005387 chalcogenide glass Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000010291 electrical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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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
- C04B35/16—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 silicates other than clay
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/447—Phosphates or phosphites, e.g. orthophosphate or hypophosphite
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
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Abstract
The invention provides an Li4SiO4-Li3PO4-LiBO2 solid solution ceramic lithium ion conductor and a preparation method of the conductor; the method improves the ionic conductivity by doping trace metal ions. The ternary Li4SiO4-Li3PO4-LiBO2 system solid solution ceramic lithium ion conductor or the ternary solution ceramic lithium ion conductor doped with the trace metal ions has higher ionic conductivity and excellent electrochemical stability, compact ceramic with excellent mechanical property is easy to prepare, the specific gravity is low, and the conductor is ideal solid electrolyte in a full-solid-state battery.
Description
Technical field
The invention belongs to new energy materials and technical field, particularly to a kind of ternary Li4SiO4-Li3PO4-LiBO2
Oxide ceramics Lithium Ionic Conducting Materials.
Background technology
Along with energy storage and the growth requirement of electrokinetic cell, liquid electrolyte in current battery in the urgent need to address
The problems such as heat stability, leakage and safety.Electrochemical system is used to stablize, have higher li ionic conduction
The solid dielectric of characteristic is the important channel solving these problems.Since 70 years last century, lithium ion is led
Body solid dielectric is studied widely.These solid dielectric has polycrystalline ceramic, glass and various
Composite, they are the lithium-containing compounds of different chemical composition, it may have different crystal structures.Such as,
P.Knauth is at Solid State Ionics, the typical lithium ion conductor such as perovskite reported in 180,911 (2009)
The Li of structure1-xLnxTiO3(Ln=La, Pr, Nd, Sm)；M.Itoh et al. at Solid State Ionics, 70,203
(1994) NASICON structure Li of report in1+xTi2-xMx(PO4)3(M=Al, Sc, Y, La)；H.Aono et al.
At J.Electrochem.Soc., the chalcogenide glass pottery of the LiSICON structure of report in 136,590 (1989)
Li7P3S11；And various composite ceramic material such as T.Minami et al. is at Solid State Ionics, 177,2715
(2006) Li of report in2S–SiS2–Li3PO4Deng.Its ionic conductivity of these lithium ion conductors is 10-6To 10-3
In the range of S/cm.But when above-mentioned lithium ion conductor is as all-solid-state battery electrolyte, owing to it is with conventional
Storage lithium electrode material directly contact composition battery time, its stable electrochemical property is poor, hardly results in reality
Application.R.Murugan et al., at Angew.Chem.Int.Ed., reports garnet in 46,7778 (2007)
The lithium ion conductor of structure, such as Emission in Cubic Li7La3Zr2O12With Li6BaLa2Ta2O12The lithium ion higher due to it is led
Electricity rate (～10-4S/cm) receive publicity, also there is with electrode material contacts good chemical stability, be to use
In the solid electrolyte that solid state battery is ideal.But E.Rangasamya et al. is at Solid State Ionics,
Point out in 206,28 (2012), the multi-element metal oxide lithium ion conductor of this kind of garnet structure, current system
Preparation Method is difficult to obtain the pure Emission in Cubic of garnet structure, is usually present the Tetragonal that ionic conductivity is relatively low, burns
Form pottery and also be difficult to densification.
Binary oxidation system Li3PO4-Li4SiO4Solid solution is also typical lithium ion conductor, with regard to Li3PO4With
Li4SiO4For the two lithium-containing compound, owing to not having room in its structure, defect density is low, ionic conductance
Rate is the lowest.But both compounds can be mutually dissolved, and solid solubility reaches 60mol%, its structure keeps
γ-Li3PO4Orthorhombic phase.Owing to solid solution can produce substantial amounts of defect, particularly form lithium ion calking and oxonium ion
Room, can make lithium ion conducting characteristic dramatically increase, but the highest also simply 10-7～10-6S/cm scope, from
The level of sub-Diffusion Activation Energy is about 0.51～0.52eV, can be found in A.Khorassani et al. at Mater.Res.
Bull., the report in 16,1561 (1981).Also studies have found that doping a small amount of (1～5mol%LiBO2) conduct
Agglutinant, improves the consistency of pottery, has also properly increased binary Li3PO4-Li4SiO4The ion of solid solution ceramic
Electrical conductivity, can be found in L.Zhang et al. at Solid State Ionics, the report in 231,109 (2013).
Summary of the invention
Because the drawbacks described above of prior art, the invention provides a kind of Li4SiO4-Li3PO4-LiBO2Solid solution is made pottery
Porcelain lithium ion conductor and preparation method thereof；And by doping trace metal ion, improve its ion guide further
Electrical method.
The Li of the present invention4SiO4-Li3PO4-LiBO2In solid solution ceramic lithium ion conductor, the mol ratio of three kinds of components
For Li4SiO4: Li3PO4: LiBO2=40～48:32～40:15～20.Wherein, the raw material of three kinds of components is permissible
It is Li2O、SiO2、P2O5And B2O3Deng simple oxide；Can also be Li2CO3、LiOH、Li4SiO4、
Li3PO4And LiBO2Deng composite oxides；Can also is that the combination of above-mentioned simple oxide and composite oxides.
Specifically, Li is formed4SiO4The raw material of component is selected from by Li2O、SiO2、Li2CO3、LiOH、Li4SiO4Group
The group become；Form Li3PO4The raw material of component is selected from by Li2O、P2O5、Li2CO3、LiOH、Li3PO4Composition
Group；Form LiBO2The raw material of component is selected from by Li2O、B2O3、Li2CO3、LiOH、LiBO2Composition
Group.Wherein, if raw material selection is above-mentioned simple oxide, needs to carry out some before proportioning and simply convert.
Such as, 1mol Li4SiO4Be equivalent to 2mol Li2O adds 1mol SiO2；1mol Li3PO4Be equivalent to 1.5mol
Li2O adds 0.5mol P2O5；1mol LiBO2Be equivalent to 0.5mol Li2O adds 0.5mol B2O3.If made
Use Li2CO3, LiOH is as raw material, 1mol Li2CO3Or 2mol LiOH is i.e. equivalent to 1mol Li2O, because
During subsequent reactions, 1mol Li2CO31mol Li will be decomposed into2O and 1mol CO2；And 2mol LiOH
1mol Li will be decomposed into2O and 1mol H2O。
The Li of the present invention4SiO4-Li3PO4-LiBO2The preparation method of solid solution ceramic lithium ion conductor uses repeatedly solid
Phase reaction, forms stable solid-solution powder, more dry-pressing formed, the ceramics sample that sintering preparation is fine and close.Specifically
Ground, the Li of the present invention4SiO4-Li3PO4-LiBO2The preparation method of solid solution ceramic lithium ion conductor includes following step
Rapid:
A, Li will be formed4SiO4、Li3PO4、LiBO2The raw material of three kinds of components is Li according to mol ratio4SiO4:
Li3PO4: LiBO2=40～48:32～40:15～20 mix homogeneously, and compressing, obtain tabletting；
Mixing in above-mentioned steps A can be directly to be dry mixed, it is also possible to is to add the mixing of ethanol medium ball milling, reaches
Mixed uniformly purpose；
Under an argon atmosphere, temperature is 900～1100 DEG C and carries out solid state reaction for B, tabletting previous step obtained
2～4 hours, form solid solution, and the solid solution obtained is ground again, obtain solid-solution powder；
C, solid-solution powder previous step obtained are compressing, and repeat step B 2～4 times, obtain final
Solid-solution powder；
D, final solid-solution powder is pressed in isostatic cool pressing 15～50MPa the geometry of needs,
Sintering densification 4～6 hours under 900～1100 DEG C of argon gas atmosphere, to ensure that orthorhombic phase structure crystal grain is fully grown up, from
So cooling down is to room temperature, obtains Li4SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor.
During sintering densification in above-mentioned steps D, in order to prevent the evaporation of oxidate for lithium, need molding
Sample is imbedded in solid solution mother's powder and is sintered.
Present invention also offers the above-mentioned Li of raising4SiO4-Li3PO4-LiBO2The ion of solid solution ceramic lithium ion conductor
The method of electrical conductivity, i.e. by doping trace metal ion, improves the level of defect density in solid solution ceramic,
And reduce ion Diffusion Activation Energy, thus improve ionic conductivity.The trace metal ion chemical valence state of doping
Stable, it is possible to enter orthorhombic phase lattice, and electrochemical process can keep orthorhombic phase structure, and be formed without other
Phase structure.Doped metal ion occupies lithium ion position in orthorhombic phase lattice, can form more lithium ion
Room so that lithium ion can be susceptible to migrate in lattice.The method of doping trace metal ion has two kinds,
Can be before the most described mixing start, doped metal ion source in described raw material；Or open in step C
Before beginning, doped metal ion source uniformly mixing in solid-solution powder described in stepb.The present invention selects
The Sc of metal ion such as trivalent3+、La3+、Y3+, the Zr of tetravalence4+、Ce4+, or other tetravalence gold of fixed price
Belonging to ion, these metal ions can individually adulterate, it is also possible to combined dopants.Described metal ion is typically originated
In its metal-oxide, such as Sc2O3、La2O3、Y2O3、ZrO2、CeO2Deng, doping general control is accounting for
Li4SiO4、Li3PO4、LiBO2The mole percent of three kinds of component total amounts is 0.1～3mol% scope.
The present invention Li to preparing4SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor has carried out one
List is levied.Such as, after the polishing of solid solution ceramic sample surfaces, use X-ray diffraction (XRD) to carry out thing and tie mutually
Structure is analyzed；Use scanning electron microscope (SEM) to observe grain morphology and the size of ceramics sample, and check
Pore that may be present；Use energy disperse spectroscopy (EDS) that the distribution of solid solution crystal grain Yu each element of crystal boundary is carried out table
Levy；Electrochemical alternate impedance spectrum (EIS) is used to measure its ionic conductivity.When measuring above-mentioned performance parameter, need
Will make blocking electrode at the golden film of the surface deposition of thick of polishing sample, deposition process uses vacuum deposition method.Institute
Some samples need to be saved in the glove box of ar gas environment, to avoid water vapor in air and CO2With sample can
Can reaction.
The Li that the present invention prepares4SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor has orthorhombic phase knot
Structure, impurity phase content is less than 1%, and the relative density of pottery is also more than 99%.XRD is used to carry out phase structure
Analyzing, its typical collection of illustrative plates is as in figure 2 it is shown, show that solid solution ceramic is with γ-Li3PO4Orthogonal for basic structure
Phase, has no obvious impurity phase.Use SEM to observe grain morphology and the size of solid solution ceramic, and check
Pore that may be present, its typical photo is as it is shown in figure 1, show that the grain development of pottery solid solution is intact, greatly
Little uniformly, average out to 5 μm, crystal boundary edge clear, do not see impurity phase.
Due to different composition proportion, the Li of the present invention4SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor
Lithium ion conducting rate 10-6～10-4S/cm scope fluctuates, and can serve as solid lithium battery or lithium ion battery
Solid electrolyte, it is also possible to for lithium metal-air, the solid electrolyte of metal lithium-sulfur cell.Typically grind
Study carefully result to show, by the solid solution of the calculated undoped p metal ion of the present invention of ac impedance spectroscopy (EIS)
The ionic conductivity of pottery lithium ion conductor is 6.84 × 10-6S/cm；It is doped with metal ion Y3+Solid solution ceramic
The ionic conductivity of lithium ion conductor is 1.13 × 10-4S/cm；And it is doped with metal ion Zr4+Solid solution ceramic
The ionic conductivity of lithium ion conductor is 2.82 × 10-5S/cm。
The beneficial effects of the present invention is, ternary Li of the present invention4SiO4-Li3PO4-LiBO2System solid solution ceramic
Maintain orthorhombic phase structure, it is easy to sinter ceramic of compact into.Owing to boron is atom doped in solid solution lattice, produce
Raw more lithium ion calking, or the migration that cation vacancy, beneficially lithium ion are in lattice, conductivity carries
High to 10-6～10-5S/cm scope.Additionally, also to the ternary solid solution doping trivalent metal of trace or rare earth metal
Ion, such as Sc3+、La3+、Y3+Plasma, or quadrivalent metallic ion such as Zr4+、Ce4+Deng.This metalloid from
Son is doped in solid solution, occupies the position of lithium ion, for the charge balance of lattice local, will produce certain
Lithium ion room, advantageously in lithium ion spread.The result of doping can make the conductivity of lithium ion improve
To 10-5～10-4S/cm magnitude.
Ternary Li of the present invention4SiO4-Li3PO4-LiBO2System solid solution ceramic lithium ion conductor, or be doped with
The ternary solid solution pottery lithium ion conductor of trace metal ion, the ionic conductivity higher due to it and good
Electrochemical stability, and the easily prepared ceramic of compact obtaining satisfactory mechanical property, proportion is low, is all solid state
Preferable solid electrolyte in battery.
Accompanying drawing explanation
Fig. 1 is ternary Li of the embodiment of the present invention 14SiO4-Li3PO4-LiBO2The SEM of solid solution ceramic fracture shines
Sheet；
Fig. 2 is ternary Li of the embodiment of the present invention 14SiO4-Li3PO4-LiBO2The XRD spectra of solid solution ceramic；
Fig. 3 is ternary Li of the embodiment of the present invention 14SiO4-Li3PO4-LiBO2The electrochemical ac of solid solution ceramic
Impedance spectrum (EIS)；
Fig. 4 is the Y of the embodiment of the present invention 22O3Ternary Li of doping4SiO4-Li3PO4-LiBO2Solid solution ceramic
Electrochemical alternate impedance spectrum (EIS)；
Fig. 5 is the ZrO of the embodiment of the present invention 32Ternary Li of doping4SiO4-Li3PO4-LiBO2Solid solution ceramic
Electrochemical alternate impedance spectrum (EIS).
Detailed description of the invention
Below by mode in conjunction with the embodiments, the present invention is described in detail.
Embodiment 1: ternary Li4SiO4-Li3PO4-LiBO2Solid solution ceramic
With Li4SiO4、Li3PO4And LiBO2For raw material, it is Li according to mol ratio4SiO4: Li3PO4: LiBO2=48:
32:20, adds ethanol in proper amount, and wet-mixed is uniform, is pressed into disk.Under 1000 DEG C of argon gas atmosphere, enter
Row solid state reaction 4 hours, again grinds the reactant obtained and becomes solid-solution powder.In order to the most just obtain
Hand over phase structure solid solution powder, the solid-solution powder dry-pressing obtained become disk, repeats above solid state reaction 2 times,
And again grind the solid-solution powder becoming final.By final solid-solution powder in the molding of isostatic cool pressing 30MPa
It is the disk of 0.3cm for diameter 2.0cm, thickness, and sintering densification 6 hours under 1000 DEG C of argon gas atmosphere,
Obtain ternary Li4SiO4-Li3PO4-LiBO2Solid solution ceramic.
Using XRD that the solid solution ceramic of embodiment 1 is carried out phase structure analysis, its collection of illustrative plates is as it is shown in figure 1, table
Bright solid solution ceramic is with γ-Li3PO4Orthorhombic phase for basic structure.Due to Si4+、B3+Enter orthorhombic phase lattice,
Replace P5+Position, [-PO4]3+In tetrahedron, due to Si4+、B3+Replacement, and produce oxygen ion vacancy, this
Will assist in the migration of lithium ion, be likely to produce the calking of lithium ion simultaneously, be the most also that defect density improves,
Strengthen ion conductivity.
Use electrochemical alternate impedance spectrum (EIS), measure its ionic conductivity.Sample for measuring is pottery
Disk, after surface finish, a diameter of～1.8cm, thickness is～0.16cm, needs deposited gold film at sample surfaces
Making blocking electrode, the thickness of gold film is 0.5 μm.Its electrochemical alternate impedance spectrum EIS as it is shown on figure 3, according to
Conductivity Calculation formula, σ=(1/R) (L/S), being calculated its ionic conductivity is 6.84 × 10-6S/cm。
Embodiment 2:Y2O3Ternary Li of doping4SiO4-Li3PO4-LiBO2Solid solution ceramic
With Li4SiO4、Li3PO4、LiBO2、Y2O3For raw material, it is Li according to mol ratio4SiO4: Li3PO4: LiBO2:
Y2O3=46:32:20:2, adds ethanol in proper amount, and wet-mixed is uniform, is pressed into disk.At 1000 DEG C
Under argon gas atmosphere, carrying out solid state reaction 4 hours, again being ground by the reactant obtained becomes solid-solution powder.For
Acquisition uniform orthorhombic phase structure solid solution powder, becomes disk by the solid-solution powder dry-pressing obtained, repeat with
Upper solid state reaction 2 times, and again grind the solid-solution powder becoming final.By final solid-solution powder, cold
Isostatic pressed 30MPa is shaped to diameter 2.0cm, thickness is the disk of 0.3cm, sinters under 1000 DEG C of argon gas atmosphere
Densification 6 hours, it is thus achieved that Y2O3Ternary Li of doping4SiO4-Li3PO4-LiBO2Solid solution ceramic.
Metal ion Y3+It is doped in solid solution, occupies the position of lithium ion, for the charge balance of lattice local,
Certain lithium ion room will be produced, advantageously spread in lithium ion.Use electrochemical alternate impedance spectrum (EIS),
Measure its ionic conductivity.A diameter of～the 1.8cm of ceramics sample, thickness is～0.16cm, and gold film is made to stop electricity
Pole.As shown in Figure 4, can calculate ionic conductivity is 1.13 × 10 to its electrochemical alternate impedance spectrum EIS-4
S/cm。
Embodiment 3:ZrO2Ternary Li of doping4SiO4-Li3PO4-LiBO2Solid solution ceramic
With Li4SiO4、Li3PO4、LiBO2、ZrO2For raw material, it is Li according to mol ratio4SiO4: Li3PO4:
LiBO2: ZrO2=47.5:32:20:0.5, adds ethanol in proper amount, and wet-mixed is uniform, is pressed into disk.
Under 1000 DEG C of argon gas atmosphere, carrying out solid state reaction 4 hours, again being ground by the reactant obtained becomes solid solution
Body powder.In order to obtain uniform orthorhombic phase structure solid solution powder, the solid-solution powder dry-pressing Cheng Yuan that will obtain
Sheet, repeats above solid state reaction 2 times, and again grinds the solid-solution powder becoming final.By final solid solution
Body powder, is shaped to diameter 2.0cm in isostatic cool pressing 30MPa, thickness is the disk of 0.3cm, at 1000 DEG C
Sintering densification 6 hours under argon gas atmosphere, it is thus achieved that ZrO2Ternary Li of doping4SiO4-Li3PO4-LiBO2Solid solution
Body pottery.
Metal ion Zr4+It is doped in solid solution, occupies the position of lithium ion, produce certain lithium ion room.
But Zr4+It is difficult to completely into lattice, therefore doping, controls at below molar percentage 1.0mol%.Its electricity
Chemistry ac impedance spectroscopy EIS is as it is shown in figure 5, can calculate ionic conductivity is 2.82 × 10-5S/cm。
The preferred embodiment of the present invention described in detail above.Should be appreciated that the ordinary skill of this area is without wound
The property made work just can make many modifications and variations according to the design of the present invention.Therefore, all technology in the art
Personnel can be obtained by logical analysis, reasoning or limited test the most on the basis of existing technology
The technical scheme arrived, all should be in the protection domain being defined in the patent claims.
Claims (10)
1. a Li4SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor, it is characterised in that wherein
Li4SiO4、Li3PO4、LiBO2The mol ratio of three kinds of components is Li4SiO4: Li3PO4: LiBO2=40～48:32～40:
15～20.
2. Li as claimed in claim 14SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor, wherein shape
Become Li4SiO4The raw material of component is selected from by Li2O、SiO2、Li2CO3、LiOH、Li4SiO4The group of composition；Shape
Become Li3PO4The raw material of component is selected from by Li2O、P2O5、Li2CO3、LiOH、Li3PO4The group of composition；Formed
LiBO2The raw material of component is selected from by Li2O、B2O3、Li2CO3、LiOH、LiBO2The group of composition.
3. Li as claimed in claim 14SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor, Qi Zhongsuo
State Li4SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor is also doped with metal-oxide, described metal
Oxide is selected from Sc2O3、La2O3、Y2O3、ZrO2、CeO2In one or more, described burning
It is 0.1～3mol% that the doping of thing accounts for the mole percent of described three kinds of component integral molar quantities.
4. the Li as according to any one of claim 1-34SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion is led
Body, wherein said Li4SiO4-Li3PO4-LiBO2The lithium ion conducting rate of solid solution ceramic lithium ion conductor is
10-6～10-4S/cm。
5. Li as claimed in claim 14SiO4-Li3PO4-LiBO2The preparation side of solid solution ceramic lithium ion conductor
Method, it is characterised in that described preparation method comprises the following steps:
A, Li will be formed4SiO4、Li3PO4、LiBO2The raw material of three kinds of components is Li according to mol ratio4SiO4:
Li3PO4: LiBO2=40～48:32～40:15～20 mix homogeneously, and compressing, obtain tabletting；
Under an argon atmosphere, temperature is 900～1100 DEG C and carries out solid state reaction for B, tabletting previous step obtained
2～4 hours, form solid solution, and the solid solution obtained is ground again, obtain solid-solution powder；
C, solid-solution powder previous step obtained are compressing, and repeat step B 2～4 times, obtain final
Solid-solution powder；
D, final solid-solution powder is compressing in isostatic cool pressing 15～50MPa, at 900～1100 DEG C of argon
Sintering densification 4～6 hours under atmosphere, Temperature fall is cooled to room temperature, obtains Li4SiO4-Li3PO4-LiBO2Solid solution
Body pottery lithium ion conductor.
6. preparation method as claimed in claim 5, before the most described mixing starts, described former
Also being doped with metal-oxide in material, described metal-oxide is selected from Sc2O3、La2O3、Y2O3、ZrO2、
CeO2In one or more, the doping of described metal-oxide account for described three kinds of component integral molar quantities mole
Percent is 0.1～3mol%.
7. preparation method as claimed in claim 5, wherein before step C starts, described in stepb
Also being doped with metal-oxide in solid-solution powder, described metal-oxide is selected from Sc2O3、La2O3、Y2O3、
ZrO2、CeO2In one or more, the doping of described metal-oxide accounts for described three kinds of component integral molar quantities
Mole percent be 0.1～3mol%.
8. preparation method as claimed in claim 5, the mol ratio of wherein said three kinds of components is Li4SiO4:
Li3PO4: LiBO2=48:32:20.
Preparation method the most as claimed in claims 6 or 7, wherein said metal-oxide is Y2O3, described three kinds
The mol ratio of component and metal-oxide is Li4SiO4: Li3PO4: LiBO2: Y2O3=46:32:20:2.
Preparation method the most as claimed in claims 6 or 7, wherein said metal-oxide is ZrO2, described three
The mol ratio planting component and metal-oxide is Li4SiO4: Li3PO4: LiBO2: ZrO2=47.5:32:20:
0.5。
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