CN109755642B - Preparation method of inorganic solid electrolyte film with three-dimensional network structure - Google Patents
Preparation method of inorganic solid electrolyte film with three-dimensional network structure Download PDFInfo
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- CN109755642B CN109755642B CN201910207608.4A CN201910207608A CN109755642B CN 109755642 B CN109755642 B CN 109755642B CN 201910207608 A CN201910207608 A CN 201910207608A CN 109755642 B CN109755642 B CN 109755642B
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Abstract
The invention relates to a preparation method of an inorganic solid electrolyte film with a three-dimensional network structure, which solves the technical problems that the existing material is easy to agglomerate and the electrochemical performance is not ideal, and comprises the following steps: step I: adding the component 1 into the component 2, and uniformly stirring to obtain an inorganic salt mixed precursor solution; step II: fully soaking the component 3 in the inorganic salt mixed precursor solution obtained in the step I; step III: sintering the component 3 which fully absorbs the component 2 in a muffle furnace to obtain a three-dimensional inorganic film; the component 1 comprises lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate hexahydrate, aluminum nitrate nonahydrate and tetrabutyl titanate; the component 2 is a polyvinylpyrrolidone solution; the component 3 is a carbon fiber fabric. The invention can be used in the field of preparation of inorganic solid electrolyte films.
Description
Technical Field
The invention relates to a preparation method of a battery material, in particular to a preparation method of an inorganic solid electrolyte film with a three-dimensional network structure.
Background
In recent years, with wider application of lithium ion batteries, people have made higher demands on energy density and safety performance of lithium ion batteries. The solid electrolyte can effectively solve the problems of easy leakage, flammability and the like of liquid electrolyte, can effectively improve the energy density of the battery, and becomes a research hotspot at home and abroad in recent years.
The solid electrolyte can be classified into a polymer solid electrolyte and an inorganic solid electrolyte, the polymer solid electrolyte is generally prepared from a polymer matrix and a lithium salt, and the common methods include a solution casting method and a melt hot-pressing method. Because the composite polymer solid electrolyte does not contain any solvent, the ionic conductivity of most of the solid electrolyte is lower, the compatibility with an electrode is poorer, but the electrochemical stability is better, the safety performance is higher, the service life is longer, and certain flexibility is realized, but the further application of the composite polymer solid electrolyte is limited by the lower ionic conductivity, so the composite polymer solid electrolyte is often prepared by compounding the composite polymer solid electrolyte with inorganic nano-filler, and the inorganic nano-filler generally comprises a ceramic material, a fast ion conductor and a ceramic fillerInert oxides with lithium ions, e.g. SiO2、TiO2、Al2O3Etc. and some ferroelectric ceramic fillers; fast ion conductors are generally lithium-containing oxides which participate in the ion transport process and thus improve the overall performance of the electrolyte, e.g., LLZO, LLTO, Li3N, and the like.
In order to further increase the ionic conductivity of the solid electrolyte and improve the electrochemical performance of the battery, multi-dimensional fillers are also applied to the solid electrolyte, such as LLTO nanowires, boron nitride and graphene nanoplatelets. The addition of the inorganic filler is effective in improving the ionic conductivity of the polymer electrolyte, but agglomeration occurs when the content is too high, and regions where agglomeration and separation occur in the filler allow lithium ions to be alternately transferred at high and low rates, thereby affecting the electrochemical properties thereof. And the template is used for constructing the three-dimensional inorganic structure, so that lithium ions can be continuously and rapidly transferred, and the electrochemical performance of the electrolyte is effectively improved.
Disclosure of Invention
The invention aims to solve the technical problems that the existing material is easy to agglomerate and the electrochemical performance of the existing material is not ideal, and provides a preparation method of an inorganic solid electrolyte film with a three-dimensional network structure, which is not easy to agglomerate and has better electrochemical performance.
Therefore, the invention provides a preparation method of an inorganic solid electrolyte film with a three-dimensional network structure, which comprises the following steps: step I: adding the component 1 into the component 2, and uniformly stirring to obtain an inorganic salt mixed precursor solution; step II: fully soaking the component 3 in the inorganic salt mixed precursor solution obtained in the step I for 24-48 h; step III: sintering the component 3 which fully absorbs the component 2 in a muffle furnace to obtain a three-dimensional inorganic film; the component 1 is used for preparing common inorganic solid electrolyte, such as lithium lanthanum zirconium oxide (Li)6.4La3Zr2Al0.2O12) Lithium lanthanum titanium oxide (Li)0.33La0.557TiO3) Reagents such as inorganic salts, including but not limited to lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate hexahydrate, aluminum nitrate nonahydrate, tetrabutyl titanate; the component 2 is polyvinylpyrrolidone solution(ii) a The component 3 is a carbon fiber fabric.
Preferably, in the component 2, the mass fraction of the polyvinylpyrrolidone is 5-10 wt%, and the solvent is an N, N-dimethylacetamide solution containing 10-20 vol% of acetic acid.
Preferably, the mass ratio of the component 1 to the component 2 is (0.03-0.05): 1.
preferably, in the component 3, the carbon fiber woven fabric is various weave structure fabrics woven by pretreated commercial T300, T700, T800 and T1000-grade carbon fibers, including plain fabrics and twill fabrics, and the areal density is 70-200 g/m2And the pretreatment condition is that the pre-oxidation is carried out for 1-2 h at 300-500 ℃ in a muffle furnace.
Preferably, in the step III, the sintering temperature of the component 3 of the component 2 in a muffle furnace is 700-900 ℃, and the time is 1.5-2 h.
The invention has the beneficial effects that the novel inorganic solid electrolyte membrane with a three-dimensional network structure is designed and prepared by adopting a template sintering method and taking carbon fibers as templates from the overall structural design of the inorganic filler of the solid electrolyte and the preparation of the solid electrolyte. The inorganic solid electrolyte obtained by the invention has a three-dimensional network structure, can provide a continuous lithium ion transmission channel, and is beneficial to improving the ionic conductivity of the solid electrolyte. The inorganic solid electrolyte with the three-dimensional network structure has a certain self-supporting function, can be integrally compounded with a polymer solid electrolyte, and avoids the agglomeration phenomenon possibly caused by the traditional method for adding the filler.
Drawings
FIGS. 1a, 1b and 1c are schematic diagrams of LLZO inorganic solid electrolyte prepared according to the present invention.
FIG. 2 is an XRD pattern of an LLZO inorganic solid state electrolyte prepared according to the present invention.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as described in the claims. The reagents in the examples are all analytical grade, not specifically indicated.
Example 1
In this example, lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate hexahydrate, aluminum nitrate nonahydrate, polyvinylpyrrolidone, N-dimethylacetamide, and acetic acid were purchased from shanghai alatin reagent, inc.
The component 1 is lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate hexahydrate and aluminum nitrate nonahydrate, and the molar ratio is 6.4:3:2: 0.2;
the component 2 is a polyvinylpyrrolidone solution, and the solvent is an N, N-dimethylacetamide solution containing 12 vol% of acetic acid, wherein the concentration of polyvinylpyrrolidone is 5 wt%;
the mass ratio of the component 1 to the component 2 is 0.03: 1;
the component 3 is T300 carbon fiber woven fabric with the surface density of 140g/m2And pre-oxidized for 2 hours at 500 ℃ in a muffle furnace.
Step I: adding the component 1 into the component 2 according to the proportion, and uniformly stirring to obtain an inorganic salt mixed precursor solution;
step II: fully soaking the component III in the inorganic salt mixed precursor solution obtained in the step I for 48 hours;
step III: and sintering the component III which fully absorbs the component II in a muffle furnace at 800 ℃ for 2h to obtain the three-dimensional inorganic membrane.
FIG. 1a shows the areal density of 140g/m after pre-oxidation2The inorganic solid film prepared by using the T300 plain woven carbon fiber fabric as the template can be seen from the figure that the inorganic film obtained by sintering is compact and regular, has a certain self-supporting effect and keeps the original carbon fiber lines.
FIG. 2 is an XRD pattern of the inorganic solid electrolyte obtained by the above preparation method, and the analysis in the XRD pattern can show that the prepared LLZO is cubic phase and has high ionic conductivity.
Example 2
In this example, lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate hexahydrate, aluminum nitrate nonahydrate, polyvinylpyrrolidone, N-dimethylacetamide, and acetic acid were purchased from shanghai alatin reagent, inc.
The component 1 is lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate hexahydrate and aluminum nitrate nonahydrate, and the molar ratio is 6.4:3:2: 0.2;
the component 2 is a polyvinylpyrrolidone solution, and the solvent is an N, N-dimethylacetamide solution containing 15 vol% of acetic acid, wherein the concentration of the polyvinylpyrrolidone is 8 wt%;
the mass ratio of the component 1 to the component 2 is 0.05: 1;
the component 3 is T300 carbon fiber woven fabric with the surface density of 120g/m2And pre-oxidized for 2 hours at 400 ℃ in a muffle furnace.
Step I: adding the component 1 into the component 2 according to the proportion, and uniformly stirring to obtain an inorganic salt mixed precursor solution;
step II: fully soaking the component III in the inorganic salt mixed precursor solution obtained in the step I for 36 hours;
step III: and sintering the component III which fully absorbs the component II in a muffle furnace at 900 ℃ for 2h to obtain the three-dimensional inorganic membrane.
FIG. 1(b) shows the areal density of 120g/m after pre-oxidation2The inorganic solid film prepared by using the T300 plain woven carbon fiber fabric as a template can be seen from the figure that the inorganic film obtained by sintering has regular appearance and certain self-supporting function. The analysis in XRD pattern shows that the prepared LLZO is cubic phase and has high ionic conductivity.
Example 3
In this example, lithium nitrate, lanthanum nitrate hexahydrate, tetrabutyltitanate, polyvinylpyrrolidone, N-dimethylacetamide, and acetic acid were purchased from shanghai alatin reagent limited.
The component 1 is lithium nitrate, lanthanum nitrate hexahydrate and tetrabutyl titanate, and the molar ratio is 0.33:0.557: 1;
the component 2 is a polyvinylpyrrolidone solution, and the solvent is an N, N-dimethylacetamide solution containing 18 vol% of acetic acid, wherein the concentration of polyvinylpyrrolidone is 7 wt%;
the mass ratio of the component 1 to the component 2 is 0.04: 1;
the component 3 is T700 twill carbon fiber woven fabric with the surface density of 140g/m2Pre-oxidizing for 2 hours in a muffle furnace at 500 ℃;
step I: adding the component 1 into the component 2 according to the proportion, and uniformly stirring to obtain an inorganic salt mixed precursor solution;
step II: fully soaking the component III in the inorganic salt mixed precursor solution obtained in the step I for 48 hours;
step III: and sintering the component III which fully absorbs the component II in a muffle furnace at 800 ℃ for 2h to obtain the three-dimensional inorganic membrane.
The inorganic solid film prepared by sintering by using the carbon fiber woven fabric as the template has regular appearance and certain self-supporting function.
Example 4
In this example, lithium nitrate, lanthanum nitrate hexahydrate, tetrabutyltitanate, polyvinylpyrrolidone, N-dimethylacetamide, and acetic acid were purchased from shanghai alatin reagent limited.
The component 1 is lithium nitrate, lanthanum nitrate hexahydrate and tetrabutyl titanate, and the molar ratio is 0.33:0.557: 1;
the component 2 is a polyvinylpyrrolidone solution, and the solvent is an N, N-dimethylacetamide solution containing 15 vol% of acetic acid, wherein the concentration of polyvinylpyrrolidone is 6 wt%;
the mass ratio of the component 1 to the component 2 is 0.05: 1;
the component 3 is T800 carbon fiber woven fabric with the surface density of 200g/m2Pre-oxidizing for 2 hours in a muffle furnace at 500 ℃;
step I: adding the component 1 into the component 2 according to the proportion, and uniformly stirring to obtain an inorganic salt mixed precursor solution;
step II: fully soaking the component III in the inorganic salt mixed precursor solution obtained in the step I for 24 hours;
step III: and sintering the component III which fully absorbs the component II in a muffle furnace at 900 ℃ for 1.5h to obtain the three-dimensional inorganic membrane.
The inorganic solid film prepared by sintering by using the carbon fiber woven fabric as the template has regular appearance and certain self-supporting function.
Comparative example 1
In this example, lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate hexahydrate, aluminum nitrate nonahydrate, polyvinylpyrrolidone, N-dimethylacetamide, and acetic acid were purchased from shanghai alatin reagent, inc.
The component 1 is lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate hexahydrate and aluminum nitrate nonahydrate, and the molar ratio is 6.4:3:2: 0.2;
the component 2 is a polyvinylpyrrolidone solution, and the solvent is an N, N-dimethylacetamide solution containing 15 vol% of acetic acid, wherein the concentration of polyvinylpyrrolidone is 5 wt%;
the mass ratio of the component 1 to the component 2 is 0.03: 1;
the component 3 is T300 carbon fiber woven fabric with the surface density of 140g/m2No pre-oxidation treatment is performed.
Step I: adding the component 1 into the component 2 according to the proportion, and uniformly stirring to obtain an inorganic salt mixed precursor solution;
step II: fully soaking the component III in the inorganic salt mixed precursor solution obtained in the step I for 48 hours;
step III: and sintering the component III which fully absorbs the component II in a muffle furnace at 800 ℃ for 2h to obtain the three-dimensional inorganic membrane.
FIG. 1(c) shows that the surface density of the alloy is 140g/m without pre-oxidation treatment2The inorganic solid film prepared by using the T300 carbon fiber woven fabric as the template can be seen from the figure that the inorganic film obtained by sintering is loose, cannot form continuous fibers and has no self-supporting effect.
Comparative example 2
In this example, lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate hexahydrate, aluminum nitrate nonahydrate, polyvinylpyrrolidone, N-dimethylacetamide, and acetic acid were purchased from shanghai alatin reagent, inc.
The component 1 is lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate hexahydrate and aluminum nitrate nonahydrate, and the molar ratio is 6.4:3:2: 0.2;
the component 2 is a polyvinylpyrrolidone solution, and the solvent is an N, N-dimethylacetamide solution containing 15 vol% of acetic acid, wherein the concentration of the polyvinylpyrrolidone is 8 wt%;
the mass ratio of the component 1 to the component 2 is 0.05: 1;
the component 3 is carbon paper.
Step I: adding the component 1 into the component 2 according to the proportion, and uniformly stirring to obtain an inorganic salt mixed precursor solution;
step II: fully soaking the component III in the inorganic salt mixed precursor solution obtained in the step I for 48 hours;
step III: and sintering the component III which fully absorbs the component II in a muffle furnace at 800 ℃ for 2h to obtain the three-dimensional inorganic membrane.
The inorganic solid electrolyte prepared and sintered by using the carbon paper as the template is powdery and does not have a three-dimensional structure.
Table 1 shows that the pre-oxidation surface density at 500 ℃ is 140g/m2The latter T300 carbon fiber was the template, the sample conditions under different preparation conditions:
Claims (3)
1. a preparation method of an inorganic solid electrolyte film with a three-dimensional network structure is characterized by comprising the following steps: step I: adding the component 1 into the component 2, and uniformly stirring to obtain an inorganic salt mixed precursor solution; step II: fully soaking the component 3 in the inorganic salt mixed precursor solution obtained in the step I for 24-48 h; step III: sintering the component 3 which fully absorbs the component 2 in a muffle furnace at 700-900 ℃ for 1.5-2 h to obtain the inorganic solid electrolyte film with the self-supporting three-dimensional network structure; the component 1 comprises: lithium nitrate required for preparing lithium lanthanum zirconium aluminum oxide (Li6.4La3Zr2Al0.2O12), lanthanum nitrate hexahydrate, zirconyl nitrate hexahydrate, aluminum nitrate nonahydrate or lithium nitrate required for preparing lithium lanthanum titanium oxide (Li0.33La0.557TiO3), lanthanum nitrate hexahydrate and tetrabutyl titanate; the component 2 is a polyvinylpyrrolidone solution; the component 3 is carbon fiber woven fabric; the carbon fiber woven fabric is various weave structure fabrics woven by pretreated commercial T300, T700, T800 and T1000-grade carbon fibers, and comprises plain fabrics and twill fabrics, the surface density is 70-200 g/m2, and the pretreatment condition is that the fabric is pre-oxidized for 1-2 hours in a muffle furnace at the temperature of 300-500 ℃.
2. The method for preparing an inorganic solid electrolyte film with a three-dimensional network structure according to claim 1, wherein in the component 2, the mass fraction of the polyvinylpyrrolidone is 5 to 10wt%, and the solvent is an N, N-dimethylacetamide solution containing 10 to 20vol% of acetic acid.
3. The method for producing an inorganic solid electrolyte film having a three-dimensional network structure according to claim 1, wherein the mass ratio of the component 1 to the component 2 is (0.03 to 0.05): 1).
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| CN101622195A (en) * | 2006-09-29 | 2010-01-06 | 阿克伦大学 | Metal oxide fibers and nanofibers, method for making same, and uses thereof |
| CN103531756A (en) * | 2013-11-01 | 2014-01-22 | 北京化工大学 | Carbon nanofiber loaded lithium titanate thin film materials and manufacturing method thereof |
| CN108511793A (en) * | 2018-02-06 | 2018-09-07 | 东华大学 | Solid-state lithium lanthanum zirconium oxygen ceramic nanofibers electrolytic thin-membrane and its preparation |
| CN108808075A (en) * | 2018-06-14 | 2018-11-13 | 东华大学 | A kind of flexible inorganic solid electrolyte film and its preparation and application |
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| US20070087265A1 (en) * | 2005-10-18 | 2007-04-19 | Cheng-Yi Lai | Lithium battery |
| KR101793168B1 (en) * | 2016-02-03 | 2017-11-20 | 한국생산기술연구원 | All solid lithium secondary batterie including llzo solid electrolyte and manufacturing method for the same |
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| CN101622195A (en) * | 2006-09-29 | 2010-01-06 | 阿克伦大学 | Metal oxide fibers and nanofibers, method for making same, and uses thereof |
| CN103531756A (en) * | 2013-11-01 | 2014-01-22 | 北京化工大学 | Carbon nanofiber loaded lithium titanate thin film materials and manufacturing method thereof |
| CN108511793A (en) * | 2018-02-06 | 2018-09-07 | 东华大学 | Solid-state lithium lanthanum zirconium oxygen ceramic nanofibers electrolytic thin-membrane and its preparation |
| CN108808075A (en) * | 2018-06-14 | 2018-11-13 | 东华大学 | A kind of flexible inorganic solid electrolyte film and its preparation and application |
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