CN111559740B - Preparation method of solid electrolyte with air gap - Google Patents
Preparation method of solid electrolyte with air gap Download PDFInfo
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- CN111559740B CN111559740B CN202010473817.6A CN202010473817A CN111559740B CN 111559740 B CN111559740 B CN 111559740B CN 202010473817 A CN202010473817 A CN 202010473817A CN 111559740 B CN111559740 B CN 111559740B
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Abstract
The invention provides a preparation method of a solid electrolyte with an air gap, which avoids serious side reaction caused by direct contact between LATP and a lithium metal cathode. The invention absorbs a proper amount of LATP through the absorbent paper, so that the LATP lithium ions injected into the holes of the double-pass AAO template are properly lost, and a proper length of the rapid conduction path of the LATP lithium ions and a proper gap size are obtained. The air gap can avoid side reactions caused by contact of LATP with the negative electrode lithium metal and can ensure transition transport of lithium ions.
Description
Technical Field
The invention relates to a preparation method of a solid electrolyte in a lithium battery, in particular to a method for preparing a solid electrolyte with an air gap in a bi-pass AAO template.
Background
In recent years, LATP in solid electrolytes has been attracting attention because of its high lithium ion conductivity, resulting in high ionic conductivity due to: (1) The aluminum ions are partially doped in the LTP framework, so that the crystal boundary energy barrier can be effectively reduced through structural change and subsequent densification; (2) The doping of Al not only enhances the mobility of lithium ions, promotes the diffusion capability of the lithium ions on different interfaces, but also reduces the activation energy.
However, the direct contact between LATP and the negative electrode of lithium metal, which converts Ti in LATP, causes serious side reactions 4+ Reduction to Ti 3+ Not only does it cause the instability of the LATP structure, but also the accumulation of the side reaction products at the interface results in the reduction of the ionic conductivity of SSE grain boundaries.
Disclosure of Invention
To solve the above technical problem, the present invention provides a continuous conductive LATP solid-state electrolyte with air gaps. The air gap can avoid side reaction caused by contact of LATP and lithium metal of the cathode and ensure transition transmission of lithium ions. The subject group has obtained the proper gap distance by controlling the amount of injected LATP through a vacuum injection method, but the above method requires special injection equipment, and the amount control is precise, and the process difficulty is large.
The technical solution of the invention is as follows:
a continuous conduction LATP solid electrolyte is characterized in that LATP nano-particles grow densely from one end of a bi-pass AAO template to the other end along the inner wall of a hole of the AAO template to form a continuous lithium ion rapid conduction path, so that the ionic conductivity can be obviously improved, and the LATP nano-particles are uniform in particle size and 20-30nm in diameter; the LATP nano-particles do not completely fill the pore diameter of the AAO template, and the distance between the length of the rapid lithium ion conduction path and the other end is 10-50nm; the other end of the AAO template is in direct contact with a lithium metal negative electrode, and a 10-50nm gap can avoid side reactions caused by contact of LATP and negative electrode lithium metal and ensure transition transmission of lithium ions.
A lithium ion battery using a continuous conduction LATP solid electrolyte is characterized in that an LATP nanowire using an AAO template as a framework is arranged between a positive electrode and a lithium metal negative electrode, wherein one end of the AAO template is directly contacted with the positive electrode, the other end of the AAO template is directly contacted with the lithium metal negative electrode, one end of the LATP nanowire in the pore diameter of the AAO template is directly contacted with the positive electrode, and an air gap of 10-50nm directly exists between the other end of the LATP nanowire and the lithium metal negative electrode.
A method for preparing a solid electrolyte with an air gap comprises the following steps:
step 1, preparation of LATP (Li) 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 ) Precursor solution;
step 2, bi-pass AAO template pretreatment: heating the AAO template under normal pressure, removing water vapor and impurities in the bi-pass AAO template, and cooling;
step 3, full-soaking and then full-capillary adsorption: fully immersing the bi-pass AAO template obtained in the step 2 into the LATP precursor solution prepared in the step 1 for 1-2 hours to ensure that the holes of the bi-pass AAO template are fully adsorbed with the LATP precursor solution;
and 4, sucking a proper amount of LATP in the bi-pass AAO template by the absorbent paper, namely, horizontally placing the bi-pass AAO template with the orifices fully absorbing the LATP precursor solution on the absorbent paper for a certain time upwards.
And 5, annealing: annealing the dual pass AAO template processed in step 4 above to obtain a continuous conductive LATP solid electrolyte with an air gap at one end.
Preferably, the length of the air gap is 10-50nm.
Preferably, the holding time is 2 to 10 seconds.
The invention has the beneficial effects that:
a continuous conductive LATP solid electrolyte and a preparation method thereof and a lithium ion battery using the same are provided, which avoid serious side reactions caused by direct contact between LATP and a lithium metal cathode. According to the invention, a proper amount of LATP is absorbed by the absorbent paper, so that the LATP injected into the holes of the double-pass AAO template is properly lost, and a proper length of LATP lithium ion rapid conduction path and a proper gap size are obtained.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a flow chart of a method of preparing a solid electrolyte with air gaps according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments are further described in detail. It should be understood that the specific embodiments described herein are merely illustrative of the invention and that the invention is not limited in this regard.
[ examples ]
A method for preparing a solid electrolyte with an air gap comprises the following steps:
step 1, preparation of Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Precursor solution; mixing lithium nitrate and nonawaterRespectively dissolving aluminum nitrate and phosphoric acid in 5ml of absolute ethyl alcohol according to the stoichiometric ratio, dripping a small amount of nitric acid in order to prevent hydrolysis of the aluminum nitrate nonahydrate, stirring for 30min, dripping lithium nitrate into the aluminum nitrate nonahydrate, and marking the obtained solution as solution A. Dissolving isopropyl titanate in 5ml of absolute ethyl alcohol according to a stoichiometric ratio, slowly dripping the solution A into the isopropyl titanate to obtain a solution B, and finally dripping phosphoric acid into the solution B to obtain a solution, namely the prepared LATP precursor solution.
Step 2, preprocessing an AAO template: weighing a certain mass of AAO template, removing water vapor and impurities under a heating state at 200 ℃, and cooling.
Step 3, fully immersing the bi-pass AAO template obtained in the step 2 into the LATP precursor solution prepared in the step 1 for 1-2 hours to ensure that holes of the bi-pass AAO template are fully adsorbed with the LATP precursor solution;
and 4, sucking away an appropriate amount of LATP in the bi-pass AAO template by absorbent paper, and horizontally placing the bi-pass AAO template with the openings filled with the LATP precursor solution on the absorbent paper for a certain time in an upward mode.
Step 5, 500-600 g under nitrogen atmosphere o And C, calcining the AAO template injected with a proper amount of LATP precursor solution for 4-6 hours, and then cooling.
Step 6, 750 again in nitrogen atmosphere o C-800 o Calcining for 15h under C to improve the uniformity of the particle size of the LATP nano particles, naturally cooling and taking out to obtain the continuous conduction solid electrolyte with air gaps in the AAO template pore canal at a distance of 10-50nm from the top. The size of the air gap is related to the retention time and the adsorption force of the absorbent paper. Taking the pure wood pulp absorbent paper produced by Loxowo shuerlai paper products Co., ltd as an example, the test data are as follows:
Claims (1)
1. a method for preparing a solid electrolyte with an air gap comprises the following steps:
step 1, preparation of Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Precursor solution; respectively dissolving lithium nitrate, aluminum nitrate nonahydrate and phosphoric acid in 5ml of absolute ethyl alcohol according to a stoichiometric ratio, dropwise adding a small amount of nitric acid to prevent the aluminum nitrate nonahydrate from being hydrolyzed, stirring for 30min, and dropwise adding the lithium nitrate into the aluminum nitrate nonahydrate, wherein the obtained solution is marked as solution A; dissolving isopropyl titanate in 5ml absolute ethyl alcohol according to a stoichiometric ratio, slowly dripping the solution A into the isopropyl titanate to obtain a solution B, and finally dripping phosphoric acid into the solution B to obtain a solution which is the prepared LATP precursor solution;
step 2, preprocessing an AAO template: weighing AAO template with certain mass at 200 oC Removing water vapor and impurities under heating state, and cooling;
step 3, fully immersing the bi-pass AAO template obtained in the step 2 into the LATP precursor solution prepared in the step 1 for 1-2 hours to ensure that the holes of the bi-pass AAO template are fully adsorbed with the LATP precursor solution;
step 4, absorbing a proper amount of LATP in the bi-pass AAO template by absorbent paper, and horizontally placing the bi-pass AAO template with the LATP precursor solution absorbed thereon for a certain time with the orifice facing upwards;
step 5, 500-600 g under nitrogen atmosphere o C, calcining the AAO template injected with a proper amount of LATP precursor solution for 4-6 hours, and then cooling;
and 6, calcining for 15 hours at 750-800 ℃ in a nitrogen atmosphere again to improve the uniformity of the particle size of the LATP nano particles, naturally cooling and taking out to obtain the continuous conduction solid electrolyte with air gaps in the AAO template pore channel 10-50nm away from the top.
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| CN114094273B (en) * | 2021-10-22 | 2024-04-19 | 上海空间电源研究所 | Thermal battery isolation layer with overflow prevention function and preparation method thereof |
| CN114804055A (en) * | 2022-05-16 | 2022-07-29 | 广东凯金新能源科技股份有限公司 | Solid electrolyte with high density and small size and preparation method thereof |
| WO2024065192A1 (en) * | 2022-09-27 | 2024-04-04 | 宁德时代新能源科技股份有限公司 | Solid-state electrolyte and preparation method therefor, positive electrode sheet and preparation method therefor, battery, and electrical device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104282930A (en) * | 2013-07-10 | 2015-01-14 | 中国科学院大连化学物理研究所 | Molten carbonate fuel cell structure |
| US20170288263A1 (en) * | 2014-09-05 | 2017-10-05 | Forschungszentrum Juelich Gmbh | Solid-state electrolytes for lithium batteries and process for production thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104282930A (en) * | 2013-07-10 | 2015-01-14 | 中国科学院大连化学物理研究所 | Molten carbonate fuel cell structure |
| US20170288263A1 (en) * | 2014-09-05 | 2017-10-05 | Forschungszentrum Juelich Gmbh | Solid-state electrolytes for lithium batteries and process for production thereof |
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