CN105826601B - Li4SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor - Google Patents

Li4SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor Download PDF

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CN105826601B
CN105826601B CN201610298047.XA CN201610298047A CN105826601B CN 105826601 B CN105826601 B CN 105826601B CN 201610298047 A CN201610298047 A CN 201610298047A CN 105826601 B CN105826601 B CN 105826601B
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CN105826601A (en
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孔向阳
杨元才
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Shanghai Jiaotong University
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    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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    • H—ELECTRICITY
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    • H01M2300/00—Electrolytes
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Abstract

The present invention provides a kind of Li4SiO4‑Li3PO4‑LiBO2Solid solution ceramic lithium ion conductor and preparation method thereof；And by adulterating trace metal ion, the method that further improves its ionic conductivity.The ternary Li of the present invention4SiO4‑Li3PO4‑LiBO2System solid solution ceramic lithium ion conductor, or it is doped with the ternary solid solution ceramics lithium ion conductor of trace metal ion, with higher ionic conductivity and good electrochemical stability, it is and easily prepared to obtain the ceramic of compact of satisfactory mechanical property, proportion is low, is preferable solid electrolyte in all-solid-state battery.

Description

Li4SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor
Technical field
The invention belongs to new energy materials and technical field, more particularly to a kind of ternary Li4SiO4-Li3PO4-LiBO2Oxidation Thing ceramics Lithium Ionic Conducting Materials.
Background technology
With energy storage and the growth requirement of power battery, the heat of liquid electrolyte is steady in current battery in the urgent need to address The problems such as qualitative, leakage and security.It is situated between using electrochemical system is stable, solid with higher li ionic conduction characteristic is electric Matter is to solve the problems, such as these important channel.Since 70 years last century, the research of lithium ion conductor solid dielectric is very wide It is general.These solid dielectric has polycrystalline ceramic, glass and various composite materials, they are different chemical compositions Lithium-containing compound, it may have different crystal structures.For example, P.Knauth is in Solid State Ionics, 180,911 (2009) Li of the typical lithium ion conductor such as perovskite structure of report in1-xLnxTiO3(Ln=La, Pr, Nd, Sm)； The NASICON structures Li of M.Itoh et al. reports in Solid State Ionics, 70,203 (1994)1+xTi2-xMx (PO4)3(M=Al, Sc, Y, La)；H.Aono et al. reports in J.Electrochem.Soc., 136,590 (1989) The chalcogenide glass ceramics Li of LiSICON structures7P3S11；And various composite ceramic materials such as T.Minami et al. is in Solid State Ionics, the Li of the middle report in 177,2715 (2006)2S–SiS2–Li3PO4Deng.Its ion-conductance of these lithium ion conductors Conductance is 10-6To 10-3In the range of S/cm.But when above-mentioned lithium ion conductor is as all-solid-state battery electrolyte, due to When it directly contacts composition battery with common storage lithium electrode material, its stable electrochemical property is poor, hardly results in reality Application.R.Murugan et al. reports the lithium of garnet structure in Angew.Chem.Int.Ed., 46,7778 (2007) Ion conductor, such as Emission in Cubic Li7La3Zr2O12With Li6BaLa2Ta2O12Due to its higher lithium ion conducting rate (~10-4S/cm) And attract attention, also there is good chemical stability with electrode material contacts, be the solid ideal for solid state battery Electrolyte.But E.Rangasamya et al. is pointed out in Solid State Ionics, 206,28 (2012), this kind of pomegranate The multi-element metal oxide lithium ion conductor of stone structure, current preparation method are difficult to obtain the pure Emission in Cubic of garnet structure, Usually there are the relatively low Tetragonal of ionic conductivity, sinter ceramics into and also be difficult to be densified.
Binary oxidation system Li3PO4-Li4SiO4Solid solution is also typical lithium ion conductor, with regard to Li3PO4With Li4SiO4 For the two lithium-containing compounds, due to not having room in its structure, defect density is low, and ionic conductivity is very low.But this two Kind compound can be mutually dissolved, and solid solubility reaches 60mol%, its structure keeps γ-Li3PO4Orthorhombic phase.Since solid solution can be with The defects of a large amount of is produced, particularly forms lithium ion calking and oxygen ion vacancy, can dramatically increase lithium ion conducting characteristic, But highest is also simply 10-7~10-6S/cm scopes, the level of ion Diffusion Activation Energy is about 0.51~0.52eV, reference can be made to Reports of the A.Khorassani et al. in Mater.Res. Bull., 16,1561 (1981).Also studies have found that doping is a small amount of (1~5mol%LiBO2) agglutinant is used as, the consistency of ceramics is improved, has also properly increased binary Li3PO4-Li4SiO4Solid solution The ionic conductivity of body ceramics, reference can be made to reports of the L.Zhang et al. in Solid State Ionics, 231,109 (2013) Road.
The content of the invention
In view of the drawbacks described above of the prior art, the present invention provides a kind of Li4SiO4-Li3PO4-LiBO2Solid solution ceramic Lithium ion conductor and preparation method thereof；And by adulterating trace metal ion, the method that further improves its ionic conductivity.
The Li of the present invention4SiO4-Li3PO4-LiBO2In solid solution ceramic lithium ion conductor, the molar ratio of three kinds of components is Li4SiO4：Li3PO4：LiBO2=40~48：32~40：15~20.Wherein, the raw material of three kinds of components can be Li2O、SiO2、 P2O5And B2O3Deng simple oxide；Can also be Li2CO3、LiOH、Li4SiO4、 Li3PO4And LiBO2Deng combined oxidation Thing；It can also be 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、Li4SiO4The group of composition；Form Li3PO4The raw material of component is selected from by Li2O、P2O5、 Li2CO3、LiOH、Li3PO4The group of composition；Form LiBO2The raw material of component is selected from by Li2O、B2O3、Li2CO3、LiOH、LiBO2 The group of composition.Wherein, if raw material selection is above-mentioned simple oxide, need to carry out some simple conversions before proportioning.Example Such as, 1mol Li4SiO4Equivalent to 2mol Li2O adds 1mol SiO2；1mol Li3PO4Equivalent to 1.5mol Li2O is added 0.5mol P2O5；1mol LiBO2Equivalent to 0.5mol Li2O adds 0.5mol B2O3.If use Li2CO3, LiOH is as former Material, 1mol Li2CO3Or 2mol LiOH are that is, 1mol Li2O, because during subsequent reactions, 1mol Li2CO3It will divide Solve as 1mol Li2O and 1mol CO2；And 2mol LiOH will be decomposed into 1mol Li2O and 1mol H2O。
The Li of the present invention4SiO4-Li3PO4-LiBO2The preparation method of solid solution ceramic lithium ion conductor uses multiple solid phase Reaction, forms stable solid-solution powder, then dry-pressing formed, and sintering prepares fine and close ceramics sample.Specifically, it is of the invention Li4SiO4-Li3PO4-LiBO2The preparation method of solid solution ceramic lithium ion conductor comprises the following steps：
A, Li will be formed4SiO4、Li3PO4、LiBO2The raw material of three kinds of components is Li according to molar ratio4SiO4： Li3PO4： LiBO2=40~48：32~40：15~20 are uniformly mixed, and compressing, obtain tabletting；
Mixing in above-mentioned steps A can be directly dry-mixed or add ethanol medium ball milling mixing, reach uniform The purpose of mixing；
B, under an argon atmosphere, temperature is 900~1100 DEG C of progress solid phase reactions 2~4 for the tabletting for obtaining previous step Hour, solid solution is formed, and obtained solid solution is ground again, obtain solid-solution powder；
C, the solid-solution powder obtained previous step is compressing, and repeat step B 2~4 times, is finally dissolved Body powder；
Final solid-solution powder is pressed into the geometry of needs in 15~50MPa of isostatic cool pressing D, 900~ When sintering densification 4~6 is small under 1100 DEG C of argon gas atmospheres, to ensure that orthorhombic phase structure crystal grain is fully grown up, Temperature fall cooling To room temperature, Li is obtained4SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor.
During sintering densification in above-mentioned steps D, the evaporation of oxidate for lithium is, it is necessary to by molded samples in order to prevent It is imbedded in solid solution female powder and is sintered.
Present invention also offers improve above-mentioned Li4SiO4-Li3PO4-LiBO2The ion-conductance of solid solution ceramic lithium ion conductor The method of conductance, i.e., by adulterating trace metal ion, improve the level of defect density in solid solution ceramic, and reduce ion Diffusion Activation Energy, so as to improve ionic conductivity.The trace metal ion chemical valence state of doping is stablized, and it is brilliant can to enter orthorhombic phase Lattice, and orthorhombic phase structure can be kept in electrochemical process, without forming other phase structures.Doped metal ion is brilliant in orthorhombic phase Lithium ion position is occupied in lattice, more lithium ion rooms can be formed so that lithium ion can easily migrate in lattice. Doping trace metal ion method have two kinds, can in step it is described mixing start before, the doping metals in the raw material Ion gun；Or before step C starts, doped metal ion source and uniformly mixed in the solid-solution powder in stepb Close.The Sc of the metal ion that the present invention selects such as trivalent3+、La3+、Y3+, the Zr of tetravalence4+、Ce4+, or other tetravalences of fixed price Metal ion, these metal ions can be adulterated individually, can also combined dopants.The metal ion is typically derived from its metal Oxide, such as Sc2O3、La2O3、Y2O3、ZrO2、CeO2Deng doping general control is accounting for Li4SiO4、Li3PO4、LiBO2Three kinds The mole percent of component total amount is 0.1~3mol% scopes.
Li of the invention to being prepared4SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor has carried out a series of Characterization.For example, after the polishing of solid solution ceramic sample surfaces, phase structure analysis is carried out using X-ray diffraction (XRD)；Using sweeping The grain morphology and size of electron microscope (SEM) observation ceramics sample are retouched, and checks stomata that may be present；Using energy disperse spectroscopy (EDS) distribution to each element of solid solution crystal grain and crystal boundary characterizes；It is measured using electrochemical alternate impedance spectrum (EIS) Ionic conductivity., it is necessary to which the golden film in the surface deposition of thick of polishing sample makees blocking electrode when measuring above-mentioned performance parameter, deposit Method uses vacuum deposition method.All samples need to be stored in the glove box of ar gas environment, are steamed to avoid water in air Gas and CO2Reacted with the possibility of sample.
The Li that the present invention is prepared4SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor has orthorhombic phase structure, Impurities phase content is less than 1%, and ceramic relative density is also more than 99%.Phase structure analysis is carried out using XRD, its is typical Collection of illustrative plates is as shown in Fig. 2, show that solid solution ceramic is with γ-Li3PO4For the orthorhombic phase of basic structure, obvious impurities phase is had no. Using the grain morphology and size of SEM observation solid solution ceramics, and check stomata that may be present, its typical photo is as schemed Shown in 1, show that the grain development of ceramic solid solution is intact, uniform in size, 5 μm of average out to, crystal boundary edge clear, does not almost see Impurities phase.
Due to different composition proportions, Li of the invention4SiO4-Li3PO4-LiBO2The lithium of solid solution ceramic lithium ion conductor Ionic conductivity is 10-6~10-4S/cm scopes fluctuate, and may be used as the solid electrolytic of solid lithium battery or lithium ion battery Matter, can be used for lithium metal-air, the solid electrolyte of metal lithium-sulfur cell.Typical result of study shows, passes through friendship The ionic conductivity for solid solution ceramic lithium ion conductor of the present invention undoped with metal ion that flow impedance spectrum (EIS) is calculated For 6.84 × 10-6S/cm；It is doped with metal ion Y3+Solid solution ceramic lithium ion conductor ionic conductivity be 1.13 × 10-4S/cm；And it is doped with metal ion Zr4+Solid solution ceramic lithium ion conductor ionic conductivity be 2.82 × 10-5S/cm。
The beneficial effects of the present invention are ternary Li of the invention4SiO4-Li3PO4-LiBO2System solid solution ceramic is kept Orthorhombic phase structure, is easy to sinter ceramic of compact into.Since boron atom is doped in solid solution lattice, more lithium ions are produced Calking, or cation vacancy, are conducive to migration of the lithium ion in lattice, and conductivity brings up to 10-6~10-5S/cm scopes.This Outside, micro trivalent metal or rare earth ion, such as Sc are also adulterated to ternary solid solution3+、La3+、Y3+Plasma, Huo Zhesi Valence metal ion such as Zr4+、Ce4+Deng.This kind of metal ion mixing occupies the position of lithium ion into solid solution, for lattice office The charge balance in portion, will produce certain lithium ion room, be more conducive to lithium ion diffusion.The result of doping can make lithium from The conductivity of son brings up to 10-5~10-4S/cm magnitudes.
The ternary Li of the present invention4SiO4-Li3PO4-LiBO2System solid solution ceramic lithium ion conductor, or be doped with micro The ternary solid solution ceramics lithium ion conductor of metal ion, due to its higher ionic conductivity and well electrochemically stable Property, and it is easily prepared obtain the ceramic of compact of satisfactory mechanical property, proportion is low, is preferable solid electrolytic in all-solid-state battery Matter.
Brief description of the drawings
Fig. 1 is the ternary Li of the embodiment of the present invention 14SiO4-Li3PO4-LiBO2The SEM photograph of solid solution ceramic fracture；
Fig. 2 is the ternary Li of the embodiment of the present invention 14SiO4-Li3PO4-LiBO2The XRD spectra of solid solution ceramic；
Fig. 3 is the ternary Li of the embodiment of the present invention 14SiO4-Li3PO4-LiBO2The electrochemical AC impedance of solid solution ceramic Compose (EIS)；
Fig. 4 is the Y of the embodiment of the present invention 22O3The ternary Li of doping4SiO4-Li3PO4-LiBO2The electrification of solid solution ceramic Learn ac impedance spectroscopy (EIS)；
Fig. 5 is the ZrO of the embodiment of the present invention 32The ternary Li of doping4SiO4-Li3PO4-LiBO2The electrification of solid solution ceramic Learn ac impedance spectroscopy (EIS).
Embodiment
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 LiBO2It is Li according to molar ratio for raw material4SiO4：Li3PO4：LiBO2=48： 32： 20, ethanol in proper amount is added, wet-mixing is uniform, is pressed into disk.Under 1000 DEG C of argon gas atmospheres, when progress solid phase reaction 4 is small, Obtained reactant is ground as solid-solution powder again.In order to obtain uniform orthorhombic phase structure solid solution powder, will The solid-solution powder dry-pressing arrived repeats above solid phase reaction 2 times, and grinding becomes final solid-solution powder again into disk. By final solid-solution powder in the disk that isostatic cool pressing 30MPa is shaped to diameter 2.0cm, thickness is 0.3cm, and at 1000 DEG C When sintering densification 6 is small under argon gas atmosphere, ternary Li is obtained4SiO4-Li3PO4-LiBO2Solid solution ceramic.
Phase structure analysis is carried out to the solid solution ceramic of embodiment 1 using XRD, its collection of illustrative plates is as shown in Figure 1, show to be dissolved Body ceramics are with γ-Li3PO4For the orthorhombic phase of basic structure.Due to Si4+、B3+Into orthorhombic phase lattice, substitute P5+Position, [-PO4]3+In tetrahedron, due to Si4+、B3+Substitution, and produce oxygen ion vacancy, this will be helpful to the migration of lithium ion, together When may also produce the calking of lithium ion, be so also that defect density improves, strengthen ion conductivity.
Using electrochemical alternate impedance spectrum (EIS), its ionic conductivity is measured.Sample for measurement is ceramic disks, After the polishing of surface, a diameter of~1.8cm, thickness is~0.16cm, needs deposited gold film to make blocking electrode, golden film in sample surfaces Thickness be 0.5 μm.Its electrochemical alternate impedance spectrum EIS is as shown in figure 3, according to Conductivity Calculation formula, σ=(1/R) (L/ S), its ionic conductivity is calculated as 6.84 × 10-6S/cm。
Embodiment 2：Y2O3The ternary Li of doping4SiO4-Li3PO4-LiBO2Solid solution ceramic
With Li4SiO4、Li3PO4、LiBO2、Y2O3It is Li according to molar ratio for raw material4SiO4：Li3PO4：LiBO2： Y2O3= 46：32：20：2, ethanol in proper amount is added, wet-mixing is uniform, is pressed into disk.Under 1000 DEG C of argon gas atmospheres, it is anti-to carry out solid phase Answer 4 it is small when, obtained reactant is ground as solid-solution powder again.In order to obtain uniform orthorhombic phase structure solid solution powder Body, by obtained solid-solution powder dry-pressing into disk, repeats above solid phase reaction 2 times, and grinding becomes final solid solution again Body powder.By final solid-solution powder, in the disk that isostatic cool pressing 30MPa is shaped to diameter 2.0cm, thickness is 0.3cm, When sintering densification 6 is small under 1000 DEG C of argon gas atmospheres, Y is obtained2O3The ternary Li of doping4SiO4-Li3PO4-LiBO2Solid solution is made pottery Porcelain.
Metal ion Y3+It is doped in solid solution, occupies the position of lithium ion, for the charge balance of lattice part, will produces Raw certain lithium ion room, is more conducive to lithium ion diffusion.Using electrochemical alternate impedance spectrum (EIS), its ion is measured Electrical conductivity.A diameter of~1.8cm of ceramics sample, thickness are~0.16cm, and golden film makees blocking electrode.Its electrochemical AC impedance Spectrum EIS is as shown in figure 4, ionic conductivity can be calculated as 1.13 × 10-4 S/cm。
Embodiment 3：ZrO2The ternary Li of doping4SiO4-Li3PO4-LiBO2Solid solution ceramic
With Li4SiO4、Li3PO4、LiBO2、ZrO2It is Li according to molar ratio for raw material4SiO4：Li3PO4： LiBO2：ZrO2 =47.5：32：20：0.5, ethanol in proper amount is added, wet-mixing is uniform, is pressed into disk.Under 1000 DEG C of argon gas atmospheres, carry out When solid phase reaction 4 is small, obtained reactant is ground as solid-solution powder again.Consolidate to obtain uniform orthorhombic phase structure Solution powder, by obtained solid-solution powder dry-pressing into disk, repeats above solid phase reaction 2 times, and grind again as final Solid-solution powder.By final solid-solution powder, diameter 2.0cm, thickness are shaped to as 0.3cm's in isostatic cool pressing 30MPa Disk, when sintering densification 6 is small under 1000 DEG C of argon gas atmospheres, obtains ZrO2The ternary Li of doping4SiO4-Li3PO4-LiBO2Gu Solution ceramics.
Metal ion Zr4+It is doped in solid solution, occupies the position of lithium ion, produces certain lithium ion room.But Zr4 +It is difficult to completely into lattice, therefore doping, control below molar percentage 1.0mol%.Its electrochemical alternate impedance spectrum EIS is as shown in figure 5, ionic conductivity can be calculated as 2.82 × 10-5S/cm。
Preferred embodiment of the invention described in detail above.It should be appreciated that the ordinary skill of this area is without wound The property made work can conceive according to the present invention makes many modifications and variations.Therefore, all technician in the art Pass through logic analysis, reasoning or the available technology of limited experiment on the basis of existing technology under this invention's idea Scheme, all should be in the protection domain being defined in the patent claims.

Claims (9)

  1. A kind of 1. Li4SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor, it is characterised in that wherein Li4SiO4、 Li3PO4、LiBO2The molar ratio of three kinds of components is Li4SiO4：Li3PO4：LiBO2=40~48：32~40：15~20；Wherein institute State Li4SiO4-Li3PO4-LiBO2Metal oxide, the metal oxide choosing are also doped with solid solution ceramic lithium ion conductor From in Sc2O3、La2O3、Y2O3、ZrO2、CeO2In one or more, the doping of the metal oxide accounts for three kinds of groups The mole percent for dividing integral molar quantity is 0.1~3mol%.
  2. 2. Li as claimed in claim 14SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor, wherein forming Li4SiO4 The raw material of component is selected from by Li2O、SiO2、Li2CO3、LiOH、Li4SiO4The group of composition；Form Li3PO4The raw material of component is selected from In by Li2O、P2O5、Li2CO3、LiOH、Li3PO4The group of composition；Form LiBO2The raw material of component is selected from by Li2O、B2O3、 Li2CO3、LiOH、LiBO2The group of composition.
  3. 3. such as the Li any one of claim 1-24SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion conductor, wherein The Li4SiO4-Li3PO4-LiBO2The lithium ion conducting rate of solid solution ceramic lithium ion conductor is 10-6~10-4S/cm。
  4. 4. Li as claimed in claim 14SiO4-Li3PO4-LiBO2The preparation method of solid solution ceramic lithium ion conductor, it is special Sign is that the preparation method comprises the following steps：
    A, Li will be formed4SiO4、Li3PO4、LiBO2The raw material of three kinds of components is Li according to molar ratio4SiO4：Li3PO4：LiBO2= 40~48：32~40：15~20 are uniformly mixed, and compressing, obtain tabletting；
    B, the tabletting for obtaining previous step under an argon atmosphere, temperature for 900~1100 DEG C carry out solid phase reactions 2~4 it is small when, Solid solution is formed, it is heavy by obtained solid-solution powder dry-pressing into disk in order to obtain uniform orthorhombic phase structure solid solution powder Above solid phase reaction 2 times again, and grinding becomes final solid-solution powder again；
    C, the solid-solution powder obtained previous step is compressing, and repeat step B 2~4 times, obtains final solid solution Powder；
    D, it is final solid-solution powder is compressing in 15~50MPa of isostatic cool pressing, burnt under 900~1100 DEG C of argon gas atmospheres When knot densification 4~6 is small, Temperature fall is cooled to room temperature, and obtains Li4SiO4-Li3PO4-LiBO2Solid solution ceramic lithium ion is led Body.
  5. 5. preparation method as claimed in claim 4, wherein before the mixing starts in step, also mixes in the raw material Miscellaneous metal oxide, the metal oxide are selected from Sc2O3、La2O3、Y2O3、ZrO2、CeO2In one or more, it is described The mole percent that the doping of metal oxide accounts for three kinds of component integral molar quantities is 0.1~3mol%.
  6. 6. preparation method as claimed in claim 4, wherein before step C starts, the solid-solution powder in stepb In be also doped with metal oxide, the metal oxide is selected from Sc2O3、La2O3、Y2O3、ZrO2、CeO2In one kind or several Kind, the mole percent that the doping of the metal oxide accounts for three kinds of component integral molar quantities is 0.1~3mol%.
  7. 7. preparation method as claimed in claim 4, wherein the molar ratio of three kinds of components is Li4SiO4：Li3PO4：LiBO2 =48：32：20.
  8. 8. the preparation method as described in claim 5 or 6, wherein the metal oxide is Y2O3, three kinds of components and metal The molar ratio of oxide is Li4SiO4：Li3PO4：LiBO2：Y2O3=46：32：20：2.
  9. 9. the preparation method as described in claim 5 or 6, wherein the metal oxide is ZrO2, three kinds of components and metal The molar ratio of oxide is Li4SiO4：Li3PO4：LiBO2：ZrO2=47.5：32：20：0.5.
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