CN112670562A - Porous/non-porous composite lithium ion conductor material - Google Patents
Porous/non-porous composite lithium ion conductor material Download PDFInfo
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Abstract
The invention discloses a lithium ion conductor material with a porous and non-porous composite structure, belonging to the field of preparation of solid electrolyte materials of solid lithium ion batteries. The material is realized by doping non-porous solid lithium ion conductor material powder; the non-porous solid lithium ion conductor powder is Li1.3Al0.3Ti1.7(PO4)3(LATP) with Li0.33La0.56TiO3(LLTO); the doping amount of the LATP is 0 wt% -20 wt%, and the doping amount of the LLTO is 0 wt% -25 wt%. The lithium ion conductor powder added to the lithium ion conductor material is one of LLTO and LATP. Compared with the undoped perovskite type lithium ion conductor material, the total conductivity of the composite lithium ion conductor material prepared by the invention is obviously improved, the lithium ion transport number of the lithium ion conductor material is close to 1, and the composite lithium ion conductor material has high lithium ion conductivity.
Description
Technical Field
The invention belongs to the field of preparation of solid electrolyte materials of solid lithium ion batteries. In particular to a lithium ion conductor material with porous/non-porous composite type.
Background
Organic liquid electrolytes are most widely used in lithium batteries, for example: mobile phones, notebook computers, new energy electric cars and the like. As the application goes deep, many problems of organic liquid electrolytes begin to be exposed, and the most important is the safety problem, leakage and corrosion of the electrolytesThe electrodes are volatile, flammable and even explosive, great potential safety hazards are buried for development and application of the electrodes, and the wide application of the electrodes in large energy storage devices is severely limited. Solid electrolytes are an important direction for current research due to their advantages of high safety, good energy storage stability, high cycle life, high chemical stability, etc. However, the solid electrolyte cannot be commercially applied in a large scale at present, mainly because the ion conductivity thereof cannot meet the commercial requirement, and a large gap is still left compared to the organic liquid electrolyte. Therefore, the development of a lithium ion conductor material with high conductivity is important to solve the problem. Li of the current NASICON type1+xTi2-xAlx(PO4)3And Li of perovskite type3xLa(2/3)-x(1/3)-2xTiO3(x is more than or equal to 0 and less than or equal to 0.16) is the research hotspot of the current lithium ion conductor material. The total conductivity of the lithium ion conductor materials with the two structures is 10 at room temperature-4～10-5S/cm. It still cannot meet the requirement of commercial application, so that improving the ionic conductivity thereof becomes an important research hotspot at present.
Disclosure of Invention
The invention aims to provide a lithium ion conductor material with a porous/non-porous composite structure; the material is realized by doping non-porous solid lithium ion conductor material powder; the non-porous solid lithium ion conductor powder is Li1.3Al0.3Ti1.7(PO4)3(LATP) with Li0.33La0.56TiO3(LLTO); the doping amount of the LATP is 0 wt% -20 wt%, and the doping amount of the LLTO is 0 wt% -25 wt%. The lithium ion conductor powder added to the lithium ion conductor material is one of LLTO and LATP.
The lithium ion conductor material is prepared by doping non-porous lithium ion conductor powder into a porous perovskite type lithium ion conductor material according to a certain proportion by using a hydrothermal synthesis method or a sol-gel method, wherein the sintering temperature is 800-1350 ℃, the heat preservation time is 6 hours, and the doping proportion of the non-porous lithium ion conductor powder is 0-25 wt%.
The lithium ion conductorThe material-doped non-porous lithium ion conductor powder LLTO is prepared by a hydrothermal synthesis method; the doping amount of LLTO is 0 wt% -25 wt%; the room temperature conductivity of the porous LLTO after being doped with the non-porous LLTO lithium ion conductor powder can reach up to 1.28x10-4S/cm, and the optimal doping amount is 15 wt%.
The non-porous lithium ion conductor powder LATP doped with the lithium ion conductor material is prepared by a sol-gel method; the doping amount of the LATP is 0-20 wt%; the highest room-temperature conductivity of the non-porous LATP lithium ion conductor material can reach 5.61x10 after the non-porous LATP lithium ion conductor powder is doped-5S/cm, the best doping amount is 0.5 wt%.
The lithium ion transport number of the lithium ion conductor material is close to 1, and the lithium ion conductor material is a pure lithium ion conductor.
The preparation method has the beneficial effects that the prepared composite lithium ion conductor material has obviously improved total conductivity compared with the undoped perovskite type lithium ion conductor material, and the lithium ion conductor material has high lithium ion conductivity.
Drawings
FIG. 1 shows N in example 12Adsorption/desorption isotherm plot.
Fig. 2 is a TEM photograph of example 1.
FIG. 3 is a graph of the total conductivity at room temperature for examples 1-9.
FIG. 4 is a TEM photograph of example 6.
FIG. 5 is a graph of the total conductivity at room temperature for examples 10-15.
FIG. 6 is a TEM photograph of example 10.
Detailed Description
The invention provides a porous/non-porous composite lithium ion conductor material; the material is realized by doping non-porous LATP and LLTO lithium ion conductor material powder; the lithium ion conductor powder added in the lithium ion conductor material is one of LLTO and LATP; the doping amount of the LATP is 0 wt% -20 wt%, and the doping amount of the LLTO is 0 wt% -25 wt%. The present invention will be described in detail with reference to the accompanying drawings and examples.
A porous/non-porous composite lithium ion conductor material is prepared by the following specific steps:
non-porous lithium ion conductor powder is doped into the porous perovskite type lithium ion conductor material according to a certain proportion by utilizing a hydrothermal synthesis method or a sol-gel method, the sintering temperature is 800-1350 ℃, the heat preservation time is 6h, and the doping proportion of the non-porous lithium ion conductor powder is 0-25 wt%.
Example 1
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is added by 10% to compensate for lithium loss at high temperature), La (NO)3)3·6H2O, butyl titanate and CTAB. Dissolving CTAB in deionized water, and adding La (NO)3)3·6H2Stirring for 30min at room temperature, dissolving butyl titanate in isopropanol, slowly dripping into the above nitrate solution, stirring for 45min, and adding LiOH. H2And O, stirring for 1h, transferring to a reaction kettle, and reacting for 36h at 180 ℃. Taking out, drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/min, keeping the temperature for 4h, heating to 800 deg.C, keeping the temperature for 2h, taking out, grinding, pressing with a tablet press, heating to 800 deg.C at a speed of 5 deg.C/min, keeping the temperature for 2h, heating to 1350 deg.C, and keeping the temperature for 6 h. The resulting coin-like sample was then smeared with silver paste, silver wire was attached, impedance was measured with an electrochemical workstation and ionic conductivity and lithium ion transport number were calculated.
The total ionic conductivity of the prepared material at room temperature is 3.33x10-5S/cm, and the TEM picture shows a regular channel structure (shown in figures 1, 2 and 3). N is a radical of2The adsorption curve and the desorption curve of the adsorption/desorption isotherm diagram do not completely coincide, which also indicates that the material has a certain porous structure. The transference number of lithium ions is close to 1, which indicates that the prepared material is a pure lithium ion conductor material.
Example 2
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is more than 10% to compensate for high temperatureLoss of lithium), La (NO)3)3·6H2O, butyl titanate. Taking La (NO)3)3·6H2Dissolving O in deionized water, stirring at room temperature for 30min, dissolving butyl titanate in isopropanol, slowly dripping into the above nitrate solution, stirring for 45min, and adding LiOH. H2And O, stirring for 1h, transferring to a reaction kettle, and reacting for 36h at 180 ℃. Taking out, drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/min, keeping the temperature for 4h, heating to 800 deg.C, keeping the temperature for 2h, taking out, grinding, pressing with a tablet press, heating to 800 deg.C at a speed of 5 deg.C/min, keeping the temperature for 2h, heating to 1350 deg.C, and keeping the temperature for 6 h. The resulting coin-like sample was then smeared with silver paste, silver wire was attached, impedance was measured with an electrochemical workstation and ionic conductivity and lithium ion transport number were calculated.
The total ionic conductivity at room temperature was 6.49x10-5S/cm, the conductivity is improved compared with that of the porous LLTO lithium ion conductor. The transference number of lithium ions is close to 1, which indicates that the prepared material is a pure lithium ion conductor material.
Example 3
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is added by 10% to compensate for lithium loss at high temperature), La (NO)3)3·6H2O, butyl titanate and CTAB. Dissolving CTAB in deionized water, adding 0.5 wt% of non-porous LLTO lithium ion conductor powder, stirring at room temperature for 1 hr, adding La (NO)3)3·6H2Stirring for 30min at room temperature, dissolving butyl titanate in isopropanol, slowly dripping into the above nitrate solution, stirring for 45min, and adding LiOH. H2And O, stirring for 1h, transferring to a reaction kettle, and reacting for 36h at 180 ℃. Taking out, drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/min, keeping the temperature for 4h, heating to 800 deg.C, keeping the temperature for 2h, taking out, grinding, pressing with a tablet press, heating to 800 deg.C at a speed of 5 deg.C/min, keeping the temperature for 2h, heating to 1350 deg.C, and keeping the temperature for 6 h. Then coating silver paste on the obtained coin-shaped sample, sticking silver wires on the sample, and measuring the sample by using an electrochemical workstationMeasuring impedance and calculating ion conductivity and lithium ion transport number.
The total ionic conductivity at room temperature was 5.33x10-5S/cm, the conductivity of the material is improved compared with that of a porous LLTO lithium ion conductor, but the conductivity of the material is reduced compared with that of a non-porous LLTO lithium ion conductor. The transference number of lithium ions is close to 1, which indicates that the prepared material is a pure lithium ion conductor material.
Example 4
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is added by 10% to compensate for lithium loss at high temperature), La (NO)3)3·6H2O, butyl titanate and CTAB. Dissolving CTAB in deionized water, adding 1 wt% of non-porous LLTO lithium ion conductor powder, stirring at room temperature for 1h, adding La (NO)3)3·6H2Stirring for 30min at room temperature, dissolving butyl titanate in isopropanol, slowly dripping into the above nitrate solution, stirring for 45min, and adding LiOH. H2And O, stirring for 1h, transferring to a reaction kettle, and reacting for 36h at 180 ℃. Taking out, drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/min, keeping the temperature for 4h, heating to 800 deg.C, keeping the temperature for 2h, taking out, grinding, pressing with a tablet press, heating to 800 deg.C at a speed of 5 deg.C/min, keeping the temperature for 2h, heating to 1350 deg.C, and keeping the temperature for 6 h. The resulting coin-like sample was then smeared with silver paste, silver wire was attached, impedance was measured with an electrochemical workstation and ionic conductivity and lithium ion transport number were calculated.
The total ionic conductivity at room temperature was 4.48x10-5S/cm, the conductivity of the material is improved compared with that of a porous LLTO lithium ion conductor, but the conductivity of the material is reduced compared with that of a non-porous LLTO lithium ion conductor and the material doped with 0.5 wt% of non-porous LLTO lithium ion conductor powder, the migration number of lithium ions is close to 1, and the prepared material is a pure lithium ion conductor material.
Example 5
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is added by 10% to compensate for lithium loss at high temperature), La (NO)3)3·6H2O, butyl titanate and CTAB. Dissolving CTAB in deionized water, adding 5 wt% LLTO lithium ion conductor powder, stirring at room temperature for 1 hr, adding La (NO)3)3·6H2Stirring for 30min at room temperature, dissolving butyl titanate in isopropanol, slowly dripping into the above nitrate solution, stirring for 45min, and adding LiOH. H2And O, stirring for 1h, transferring to a reaction kettle, and reacting for 36h at 180 ℃. Taking out, drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/min, keeping the temperature for 4h, heating to 800 deg.C, keeping the temperature for 2h, taking out, grinding, pressing with a tablet press, heating to 800 deg.C at a speed of 5 deg.C/min, keeping the temperature for 2h, heating to 1350 deg.C, and keeping the temperature for 6 h. The resulting coin-like sample was then smeared with silver paste, silver wire was attached, impedance was measured with an electrochemical workstation and ionic conductivity and lithium ion transport number were calculated.
The total ionic conductivity at room temperature was 6.28x10-5S/cm, the conductivity of the material is improved compared with that of a porous LLTO lithium ion conductor and the material doped with 0.5 wt% and 1 wt% of non-porous LLTO lithium ion conductor powder, but the conductivity of the material is reduced compared with that of a non-porous LLTO lithium ion conductor. The transference number of lithium ions is close to 1, which indicates that the prepared material is a pure lithium ion conductor material.
Example 6
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is added by 10% to compensate for lithium loss at high temperature), La (NO)3)3·6H2O, butyl titanate and CTAB. Dissolving CTAB in deionized water, adding 10 wt% LLTO lithium ion conductor powder, stirring at room temperature for 1 hr, adding La (NO)3)3·6H2Stirring for 30min at room temperature, dissolving butyl titanate in isopropanol, slowly dripping into the above nitrate solution, stirring for 45min, and adding LiOH. H2And O, stirring for 1h, transferring to a reaction kettle, and reacting for 36h at 180 ℃. Taking out, drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/min, maintaining for 4 hr, heating to 800 deg.C, and maintaining for 2 hrh, taking out, fully grinding, then pressing and forming by using a tablet press, heating to 800 ℃ at the speed of 5 ℃/min in a muffle furnace, preserving heat for 2h, heating to 1350 ℃ again, and preserving heat for 6 h. The resulting coin-like sample was then smeared with silver paste, silver wire was attached, impedance was measured with an electrochemical workstation and ionic conductivity and lithium ion transport number were calculated.
The total ionic conductivity at room temperature was 7.40x10-5S/cm, the conductivity of the composite material is improved compared with that of a porous LLTO lithium ion conductor, a non-porous LLTO lithium ion conductor and composite materials doped with 0.5 wt%, 1 wt% and 5 wt% of non-porous LLTO lithium ion conductor powder (as shown in figure 4), the lithium ion migration number is close to 1, and the prepared material is a pure lithium ion conductor material.
Example 7
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is added by 10% to compensate for lithium loss at high temperature), La (NO)3)3·6H2O, butyl titanate and CTAB. Dissolving CTAB in deionized water, adding 15 wt% LLTO lithium ion conductor powder, stirring at room temperature for 1 hr, adding La (NO)3)3·6H2Stirring for 30min at room temperature, dissolving butyl titanate in isopropanol, slowly dripping into the above nitrate solution, stirring for 45min, and adding LiOH. H2And O, stirring for 1h, transferring to a reaction kettle, and reacting for 36h at 180 ℃. Taking out, drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/min, keeping the temperature for 4h, heating to 800 deg.C, keeping the temperature for 2h, taking out, grinding, pressing with a tablet press, heating to 800 deg.C at a speed of 5 deg.C/min, keeping the temperature for 2h, heating to 1350 deg.C, and keeping the temperature for 6 h. The resulting coin-like sample was then smeared with silver paste, silver wire was attached, impedance was measured with an electrochemical workstation and ionic conductivity and lithium ion transport number were calculated.
The total ionic conductivity at room temperature was 1.28x10-4S/cm, the conductivity of the composite material is improved compared with that of a porous LLTO lithium ion conductor, a non-porous LLTO lithium ion conductor and composite materials doped with 0.5 wt%, 1 wt%, 5 wt% and 10 wt% of non-porous LLTO lithium ion conductor powder. TEM photographThe presence of grains in the material in addition to the channel structure of the porous material is shown, indicating that the doped non-porous LLTO grains have formed a composite lithium ion conductor material with the porous LLTO. The transference number of lithium ions is close to 1, which indicates that the prepared material is a pure lithium ion conductor material.
Example 8
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is added by 10% to compensate for lithium loss at high temperature), La (NO)3)3·6H2O, butyl titanate and CTAB. Dissolving CTAB in deionized water, adding 20 wt% LLTO lithium ion conductor powder, stirring at room temperature for 1 hr, adding La (NO)3)3·6H2Stirring for 30min at room temperature, dissolving butyl titanate in isopropanol, slowly dripping into the above nitrate solution, stirring for 45min, and adding LiOH. H2And O, stirring for 1h, transferring to a reaction kettle, and reacting for 36h at 180 ℃. Taking out, drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/min, keeping the temperature for 4h, heating to 800 deg.C, keeping the temperature for 2h, taking out, grinding, pressing with a tablet press, heating to 800 deg.C at a speed of 5 deg.C/min, keeping the temperature for 2h, heating to 1350 deg.C, and keeping the temperature for 6 h. The resulting coin-like sample was then smeared with silver paste, silver wire was attached, impedance was measured with an electrochemical workstation and ionic conductivity and lithium ion transport number were calculated.
The total ionic conductivity at room temperature was 8.35x10-5S/cm, the conductivity of the material was improved over the porous LLTO, non-porous LLTO lithium ion conductor and the material doped with 0.5 wt%, 1 wt%, 5 wt%, 10 wt% LLTO lithium ion conductor powder, but the conductivity began to decrease compared to the material doped with 15 wt% LLTO lithium ion conductor powder. The transference number of lithium ions is close to 1, which indicates that the prepared material is a pure lithium ion conductor material.
Example 9
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is added by 10% to compensate for lithium at high temperatureLoss of) La (NO)3)3·6H2O, butyl titanate and CTAB. Dissolving CTAB in deionized water, adding 25 wt% LLTO lithium ion conductor powder, stirring at room temperature for 1 hr, adding La (NO)3)3·6H2Stirring for 30min at room temperature, dissolving butyl titanate in isopropanol, slowly dripping into the above nitrate solution, stirring for 45min, and adding LiOH. H2And O, stirring for 1h, transferring to a reaction kettle, and reacting for 36h at 180 ℃. Taking out, drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/min, keeping the temperature for 4h, heating to 800 deg.C, keeping the temperature for 2h, taking out, grinding, pressing with a tablet press, heating to 800 deg.C at a speed of 5 deg.C/min, keeping the temperature for 2h, heating to 1350 deg.C, and keeping the temperature for 6 h. The resulting coin-like sample was then smeared with silver paste, silver wire was attached, impedance was measured with an electrochemical workstation and ionic conductivity and lithium ion transport number were calculated.
The total ionic conductivity at room temperature was 8.70x10-5S/cm, the conductivity of the material is improved compared with that of the porous LLTO, the non-porous LLTO lithium ion conductor and the material doped with 0.5 wt%, 1 wt%, 5 wt%, 10 wt% and 20 wt% of the non-porous LLTO lithium ion conductor powder, but the conductivity is reduced compared with that of the material doped with 15 wt% of the LLTO lithium ion conductor powder. The transference number of lithium ions is close to 1, which indicates that the prepared material is a pure lithium ion conductor material.
Example 10
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is added by 10% to compensate for lithium loss at high temperature), La (NO)3)3·6H2O, butyl titanate and CTAB. Dissolving CTAB in deionized water, adding 0.5 wt% of LATP lithium ion conductor powder, stirring at room temperature for 1 hr, adding La (NO)3)3·6H2Stirring for 30min at room temperature, dissolving butyl titanate in isopropanol, slowly dripping into the above nitrate solution, stirring for 45min, and adding LiOH. H2And O, stirring for 1h, transferring to a reaction kettle, and reacting for 36h at 180 ℃. Taking out, oven drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/minKeeping the temperature for 4h, then heating to 800 ℃, keeping the temperature for 2h, taking out and fully grinding, then pressing and forming by a tablet press, heating to 800 ℃ in a muffle furnace at the speed of 5 ℃/min, keeping the temperature for 2h, then heating to 1350 ℃ and keeping the temperature for 6 h. The resulting coin-like sample was then smeared with silver paste, silver wire was attached, impedance was measured with an electrochemical workstation and ionic conductivity and lithium ion transport number were calculated.
The total ionic conductivity at room temperature was 5.40x10-5S/cm, the conductivity of the porous LLTO lithium ion conductor is obviously improved. The TEM photographs showed the presence of porous LLTO channels and LATP crystallites (as shown in fig. 5.6), indicating that the LATP crystallites have been successfully incorporated into the LLTO lithium ion conductor. The ion migration number is close to 1, which indicates that the prepared material is a pure lithium ion conductor material.
Example 11
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is added by 10% to compensate for lithium loss at high temperature), La (NO)3)3·6H2O, butyl titanate and CTAB. Dissolving CTAB in deionized water, adding 1 wt% of LATP lithium ion conductor powder, stirring at room temperature for 1 hr, adding La (NO)3)3·6H2Stirring for 30min at room temperature, dissolving butyl titanate in isopropanol, slowly dripping into the above nitrate solution, stirring for 45min, and adding LiOH. H2O, stirring for 1h, transferring to a reaction kettle, and keeping the temperature at 180 ℃ for 36 h. Taking out, drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/min, keeping the temperature for 4h, heating to 800 deg.C, keeping the temperature for 2h, taking out, grinding, pressing with a tablet press, heating to 800 deg.C at a speed of 5 deg.C/min, keeping the temperature for 2h, heating to 1350 deg.C, and keeping the temperature for 6 h. The resulting coin-like sample was then smeared with silver paste, silver wire was attached, impedance was measured with an electrochemical workstation and ionic conductivity and lithium ion transport number were calculated.
The total ionic conductivity at room temperature was 4.00X10-5S/cm, higher conductivity than the porous LLTO lithium ion conductor, but lower conductivity than the material doped with 0.5 wt% LATP lithium ion conductor powderAnd the transference number of the lithium ions is close to 1, which indicates that the prepared material is a pure lithium ion conductor material.
Example 12
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is added by 10% to compensate for lithium loss at high temperature), La (NO)3)3·6H2O, butyl titanate and CTAB. Dissolving CTAB in deionized water, adding 5 wt% of LATP lithium ion conductor powder, stirring at room temperature for 1 hr, adding La (NO)3)3·6H2Stirring for 30min at room temperature, dissolving butyl titanate in isopropanol, slowly dripping into the above nitrate solution, stirring for 45min, and adding LiOH. H2And O, stirring for 1h, transferring to a reaction kettle, and reacting for 36h at 180 ℃. Taking out, drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/min, keeping the temperature for 4h, heating to 800 deg.C, keeping the temperature for 2h, taking out, grinding, pressing with a tablet press, heating to 800 deg.C at a speed of 5 deg.C/min, keeping the temperature for 2h, heating to 1350 deg.C, and keeping the temperature for 6 h. The resulting coin-like sample was then smeared with silver paste, silver wire was attached, impedance was measured with an electrochemical workstation and ionic conductivity and lithium ion transport number were calculated.
The total ionic conductivity at room temperature was 3.59x10-6S/cm, the conductivity is greatly reduced compared with that of the material which is not doped and is doped with 0.5 wt% and 1 wt% of LATP lithium ion conductor powder. The transference number of lithium ions still approaches to 1, which indicates that the prepared material is a pure lithium ion conductor material.
Example 13
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is added by 10% to compensate for lithium loss at high temperature), La (NO)3)3·6H2O, butyl titanate and CTAB. Dissolving CTAB in deionized water, adding 10 wt% of LATP lithium ion conductor powder, stirring at room temperature for 1 hr, adding La (NO)3)3·6H2Stirring for 30min at normal temperature, dissolving butyl titanate in isopropanol, and slowly drippingStirring the above nitrate solution for 45min, and adding LiOH. H2And O, stirring for 1h, transferring to a reaction kettle, and reacting for 36h at 180 ℃. Taking out, drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/min, keeping the temperature for 4h, heating to 800 deg.C, keeping the temperature for 2h, taking out, grinding, pressing with a tablet press, heating to 800 deg.C at a speed of 5 deg.C/min, keeping the temperature for 2h, heating to 1350 deg.C, and keeping the temperature for 6 h. The resulting coin-like sample was then smeared with silver paste, silver wire was attached, impedance was measured with an electrochemical workstation and ionic conductivity and lithium ion transport number were calculated.
The total ionic conductivity at room temperature was 1.29x10-6S/cm, the conductivity is further reduced compared with that of the material which is not doped with the LATP lithium ion conductor powder and is doped with 0.5 wt%, 1 wt% and 5 wt%, the transference number of lithium ions is close to 1, and the prepared material is a pure lithium ion conductor material.
Example 14
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is added by 10% to compensate for lithium loss at high temperature), La (NO)3)3·6H2O, butyl titanate and CTAB. Dissolving CTAB in deionized water, adding 15 wt% of LATP lithium ion conductor powder, stirring at room temperature for 1h, adding La (NO)3)3·6H2Stirring for 30min at normal temperature, dissolving butyl titanate in isopropanol, slowly dripping into the solution of squarylium nitrate, stirring for 45min, and adding LiOH & H2And O, stirring for 1h, transferring to a reaction kettle, and reacting for 36h at 180 ℃. Taking out, drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/min, keeping the temperature for 4h, heating to 800 deg.C, keeping the temperature for 2h, taking out, grinding, pressing with a tablet press, heating to 800 deg.C at a speed of 5 deg.C/min, keeping the temperature for 2h, heating to 1350 deg.C, and keeping the temperature for 6 h. The resulting coin-like sample was then smeared with silver paste, silver wire was attached, impedance was measured with an electrochemical workstation and ionic conductivity and lithium ion transport number were calculated.
The total ionic conductivity at room temperature was 8.05x10-7S/cm, and no dopingCompared with the material doped with 0.5 wt%, 1 wt%, 5 wt% and 10 wt% of LATP lithium ion conductor powder, the conductivity is further greatly reduced, but the transference number of lithium ions still approaches to 1, which indicates that the prepared material is a pure lithium ion conductor material.
Example 15
According to the formula Li0.33La0.56TiO3Determining raw material LiOH & H by stoichiometric ratio2O (wherein LiOH. H)2O is added by 10% to compensate for lithium loss at high temperature), La (NO)3)3·6H2O, butyl titanate and CTAB. Dissolving CTAB in deionized water, adding 20 wt% of LATP lithium ion conductor powder, stirring at room temperature for 1 hr, adding La (NO)3)3·6H2Stirring for 30min at room temperature, dissolving butyl titanate in isopropanol, slowly dripping into the above nitrate solution, stirring for 45min, and adding LiOH. H2And O, stirring for 1h, transferring to a reaction kettle, and reacting for 36h at 180 ℃. Taking out, drying, placing in a box-type muffle furnace, heating to 500 deg.C at a speed of 5 deg.C/min, keeping the temperature for 4h, heating to 800 deg.C, keeping the temperature for 2h, taking out, grinding, pressing with a tablet press, heating to 800 deg.C at a speed of 5 deg.C/min, keeping the temperature for 2h, heating to 1350 deg.C, and keeping the temperature for 6 h. The resulting coin-like sample was then smeared with silver paste, silver wire was attached, impedance was measured with an electrochemical workstation and ionic conductivity and lithium ion transport number were calculated.
The total ionic conductivity at room temperature was 7.15x10-7S/cm, the conductivity is reduced compared with that of the material which is not doped and is doped with 0.5 wt%, 1 wt%, 5 wt%, 10 wt% and 15 wt% of LATP lithium ion conductor powder, but the transference number of lithium ions is still close to 1, and the prepared material is a pure lithium ion conductor material.
Claims (5)
1. A composite lithium ion conductor material having porous and non-porous; the material is characterized in that the material is realized by doping non-porous solid lithium ion conductor material powder; the non-porous solid lithium ion conductor powder is Li1.3Al0.3Ti1.7(PO4)3(LATP) with Li0.33La0.56TiO3(LLTO); the doping amount of the LATP is 0 wt% -20 wt%, and the doping amount of the LLTO is 0 wt% -25 wt%. The lithium ion conductor powder added to the lithium ion conductor material is one of LLTO and LATP.
2. The lithium ion conductor material according to claim 1, having a porous and non-porous composite type; the method is characterized in that the lithium ion conductor material is realized by doping non-porous solid lithium ion conductor material powder by a hydrothermal synthesis method or a sol-gel method, wherein the non-porous lithium ion conductor powder is doped into the porous perovskite type lithium ion conductor material according to a certain proportion, the sintering temperature is 800-1350 ℃, the heat preservation time is 6h, and the doping proportion of the non-porous lithium ion conductor powder is 0-25 wt%.
3. The lithium ion conductor material having a porous and non-porous composite according to claim 2; the preparation method is characterized in that the non-porous lithium ion conductor powder LLTO doped with the lithium ion conductor material is prepared by a hydrothermal synthesis method; the doping amount of LLTO is 0 wt% -25 wt%; the room temperature conductivity of the porous LLTO after being doped with the non-porous LLTO lithium ion conductor powder can reach up to 1.28x10-4S/cm, and the optimal doping amount is 15 wt%.
4. The lithium ion conductor material having a porous and non-porous composite according to claim 2; the preparation method is characterized in that the doped non-porous lithium ion conductor powder LATP of the lithium ion conductor material is prepared by a sol-gel method; the doping amount of the LATP is 0-20 wt%; the highest room-temperature conductivity of the non-porous LATP lithium ion conductor material can reach 5.61x10 after the non-porous LATP lithium ion conductor powder is doped-5S/cm, the best doping amount is 0.5 wt%.
5. The lithium ion conductor material according to claim 1, having a porous and non-porous composite type; the lithium ion conductor material is characterized in that the lithium ion transference number of the lithium ion conductor material is close to 1, and the lithium ion conductor material is a pure lithium ion conductor.
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