CN111009691B - High-performance solid electrolyte with NASCION structure and preparation method thereof - Google Patents

High-performance solid electrolyte with NASCION structure and preparation method thereof Download PDF

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CN111009691B
CN111009691B CN201911351854.3A CN201911351854A CN111009691B CN 111009691 B CN111009691 B CN 111009691B CN 201911351854 A CN201911351854 A CN 201911351854A CN 111009691 B CN111009691 B CN 111009691B
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CN111009691A (en
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宋英杰
徐宁
伏萍萍
马倩倩
孙瑞军
李征钰
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Tianjin B&M Science and Technology Co Ltd
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    • H—ELECTRICITY
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention discloses a high-performance solid electrolyte with an NASCION structure and a preparation method thereof. First by hydrothermal treatmentThe molecular composition of Li is prepared by the method and the high-temperature solid-phase method1.05～1.1Ti(2‑x)Srx(PO4)3The strontium-doped NASCION structure solid electrolyte is coated with a lithium phosphate fast ion conductor layer on the surface by a coprecipitation method. The hydrothermal method can directionally control the growth direction of the crystal, improve the diffusion coefficient of lithium ions, and simultaneously promote the improvement of the diffusion coefficient of the lithium ions by adding divalent Sr; the lithium phosphate fast ion conductor is coated on the surface of the solid electrolyte with the NASCION structure, so that the high ion diffusion coefficient of the solid electrolyte can be maintained, and the compatibility of the solid electrolyte and lithium can be effectively improved.

Description

High-performance solid electrolyte with NASCION structure and preparation method thereof
Technical Field
The invention relates to the field of solid electrolytes of lithium ion secondary batteries, in particular to a high-performance NASCION solid electrolyte and a preparation method thereof.
Background
Under the support of national policies, the new energy automobile industry in China is rapidly developed, and the annual output and sales volume of the new energy automobile industry in China reach more than half of the global volume. As is well known, the power battery is a core part of the new energy automobile, wherein the lithium ion battery has obvious advantages in the aspects of cost and energy density, can greatly improve the economy and the use convenience of the new energy automobile, and occupies a dominating position in the field of the power battery. However, the safety of new energy automobiles occurs recently, and the current solution type electrolyte is a flammable organic matter system and has a narrow electrochemical window, so that the problem cannot be thoroughly solved by adopting a common improvement method. The solid electrolyte has wide electrochemical window and high thermal stability, can fundamentally solve the safety problem of the lithium ion battery, greatly simplify the manufacturing and packaging process, improve the energy density of the battery (the specific energy density can be improved by 20 to 50 percent under the existing positive and negative electrode systems), and has reliability and design freedom.
The solid electrolyte is the core of the lithium ion solid battery, and directly determines key performances such as rate performance, safety performance and cycle performance of the lithium ion solid battery. The existing solid electrolyte system mainly comprises an inorganic lithium ion conductor, a polymer lithium ion conductor and a composite lithium ion conductor. In view of the intrinsic characteristics of materials, the inorganic lithium ion conductor is the most fundamental approach for solving the safety of the lithium ion battery, and structurally comprises a sodium super ion conductor, a garnet structure, a perovskite structure, a lithium halide structure and the like. Among them, the sodium super-ion conductor structure has a wider electrochemical window and better environmental adaptability, and is an important research direction of lithium ion solid electrolyte.
The common structural material of the sodium super-ion conductor is LiTi2(PO4)3However, the diffusion coefficient of lithium ion is low, and is only 10(-7～-8)S/cm-1(ii) a And the interface compatibility with metal lithium is poor, and the use requirement of the lithium ion solid-state battery cannot be met.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-performance solid electrolyte with an NASCION structure and a preparation method thereof.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for preparing high-performance solid electrolyte with NASCION structure comprises preparing Li with molecular composition by hydrothermal method and high-temperature solid-phase method1.05～1.1Ti(2-x)Srx(PO4)3The strontium-doped NASCION structure solid electrolyte is coated with a lithium phosphate fast ion conductor layer on the surface by a coprecipitation method, and the method specifically comprises the following steps:
1) according to the formula Li1.05～1.1Ti(2-x)Srx(PO4)3Weighing lithium source, titanium source and strontiumA source and a phosphate, wherein x is more than or equal to 0.05 and less than or equal to 0.10; weighing tartaric acid, tartaric acid and Li1.05～1.1Ti(2-x)Mx(PO4)3The molar ratio of (1-3) to (1); weighing deionized water, wherein the mass of the deionized water is as follows: the mass of (lithium source + titanium source + strontium source + phosphate) is (10-20): 1;
2) adding the raw materials in the step 1) into a hydrothermal kettle, and preserving heat for 12-24h at 180-210 ℃ to obtain a solid-liquid mixture I;
3) centrifuging and washing the material I to obtain a material II;
4) performing heat treatment on the material II in an air atmosphere to obtain a material III, wherein the heat treatment temperature is 800-850 ℃, and the heat treatment time is 8-16 h;
5) treating the material III in a sand mill to obtain slurry IV, wherein the solid content of the slurry is 20%, and the particle size distribution of the slurry is D50≤0.1μm；
6) Adding the slurry IV into a stirring reaction kettle at a stirring speed of 500-800 rpm, and simultaneously dropwise adding 2mol/L lithium hydroxide solution and 0.5mol/L phosphoric acid solution into the reaction kettle to obtain a solid-liquid mixture V, wherein the molar ratio of the added lithium hydroxide to the phosphoric acid solution is (3-3.05): 1, and the mass ratio of the added phosphoric acid to the slurry IV is (0.4-0.8%): 1;
7) and (4) centrifugally washing the solid-liquid mixture V, and drying to obtain a final product.
The lithium source in the step 1) is lithium nitrate and lithium acetate.
The titanium source in the step 1) is titanium nitrate.
The strontium source in the step 1) is strontium nitrate and strontium acetate.
The phosphate in the step 1) is ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
The high-performance solid electrolyte with the NASCION structure is prepared by the preparation method of the high-performance solid electrolyte with the NASCION structure.
The invention has the beneficial effects that: firstly, a molecular composition Li is prepared by a hydrothermal method and a high-temperature solid-phase method1.05～1.1Ti(2-x)Srx(PO4)3Strontium-doped NASCION structureAnd coating a lithium phosphate fast ion conductor layer on the surface of the solid electrolyte by a coprecipitation method. The growth direction of the crystal can be directionally controlled by a hydrothermal method, the diffusion coefficient of lithium ions is improved, and meanwhile, the diffusion coefficient of the lithium ions is further improved by adding divalent Sr; the lithium phosphate fast ion conductor is coated on the surface of the solid electrolyte with the NASCION structure, so that the high ion diffusion coefficient of the solid electrolyte can be maintained, and the compatibility of the solid electrolyte and lithium can be effectively improved.
Drawings
FIG. 1 is a process flow diagram of the high-performance solid electrolyte with NASCION structure and the preparation method thereof.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of the present invention.
As shown in figure 1, the preparation method of the high-performance solid electrolyte with the NASCION structure of the invention obtains a molecular composition Li by a hydrothermal method and a high-temperature solid-phase method1.05～1.1Ti(2-x)Srx(PO4)3The strontium-doped NASCION structure solid electrolyte is coated with a lithium phosphate fast ion conductor layer on the surface by a coprecipitation method, and the method specifically comprises the following steps:
1) according to the formula Li1.05～1.1Ti(2-x)Srx(PO4)3Weighing a lithium source, a titanium source, a strontium source and phosphate, wherein x is more than or equal to 0.05 and less than or equal to 0.10; weighing tartaric acid, tartaric acid and Li1.05～1.1Ti(2-x)Mx(PO4)3The molar ratio of (1-3) to (1); weighing deionized water, wherein the mass of the deionized water is as follows: the mass of (lithium source + titanium source + strontium source + phosphate) is (10-20): 1;
2) adding the raw materials in the step 1) into a hydrothermal kettle, and preserving heat for 12-24h at 180-210 ℃ to obtain a solid-liquid mixture I;
3) centrifuging and washing the material I to obtain a material II;
4) performing heat treatment on the material II in an air atmosphere to obtain a material III, wherein the heat treatment temperature is 800-850 ℃, and the heat treatment time is 8-16 h;
5) treating the material III in a sand mill to obtain slurry IV, wherein the solid content of the slurry is 20%, and the particle size distribution of the slurry is D50≤0.1μm；
6) Adding the slurry IV into a stirring reaction kettle at a stirring speed of 500-800 rpm, and simultaneously dropwise adding 2mol/L lithium hydroxide solution and 0.5mol/L phosphoric acid solution into the reaction kettle to obtain a solid-liquid mixture V, wherein the molar ratio of the added lithium hydroxide to the phosphoric acid solution is (3-3.05): 1, and the mass ratio of the added phosphoric acid to the slurry IV is (0.4-0.8%): 1;
7) and (4) centrifugally washing the solid-liquid mixture V, and drying to obtain a final product.
The lithium source in the step 1) is lithium nitrate and lithium acetate.
The titanium source in the step 1) is titanium nitrate.
The strontium source in the step 1) is strontium nitrate and strontium acetate.
The phosphate in the step 1) is ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
The high-performance solid electrolyte with the NASCION structure is prepared by the preparation method of the high-performance solid electrolyte with the NASCION structure.
Example 1
A high-performance solid electrolyte with an NASCION structure and a preparation method thereof comprise the following steps:
1) according to the formula Li1.05Ti1.95Sr0.05(PO4)3Weighing lithium nitrate, titanium nitrate, strontium nitrate and ammonium dihydrogen phosphate; weighing tartaric acid, tartaric acid and Li1.05Ti1.95Sr0.05(PO4)3In a molar ratio of 1: 1; weighing deionized water, wherein the mass of the deionized water is as follows: (lithium nitrate + titanium nitrate + strontium nitrate + ammonium dihydrogen phosphate) in a mass ratio of 10: 1;
2) adding the raw materials in the step 1) into a hydrothermal kettle, and preserving heat at 180 ℃ for 24 hours to obtain a solid-liquid mixture I;
3) centrifuging and washing the material I to obtain a material II;
4) performing heat treatment on the material II in an air atmosphere to obtain a material III, wherein the heat treatment temperature is 800 ℃, and the heat treatment time is 16 h;
5) treating the material III in a sand mill to obtain slurry IV, wherein the solid content of the slurry is 20%, and the particle size distribution of the slurry is D50＝0.06μm；
6) Adding the slurry IV into a stirring reaction kettle at a stirring speed of 500 revolutions per minute, and simultaneously dropwise adding 2mol/L lithium hydroxide solution and 0.5mol/L phosphoric acid solution into the reaction kettle to obtain a solid-liquid mixture V, wherein the molar ratio of the added lithium hydroxide to the phosphoric acid solution is 3:1, and the mass ratio of the added phosphoric acid to the slurry IV is 0.4 to 1;
7) and (4) centrifugally washing the solid-liquid mixture V, and drying to obtain a final product.
Comparative example 1
1) According to the formula Li1.05Ti2(PO4)3Weighing lithium nitrate, titanium nitrate and ammonium dihydrogen phosphate; weighing tartaric acid, tartaric acid and Li1.05Ti2(PO4)3In a molar ratio of 1: 1; weighing deionized water, wherein the mass of the deionized water is as follows: (lithium nitrate + titanium nitrate + ammonium dihydrogen phosphate) in a mass ratio of 10: 1;
the rest being the same, i.e. without Sr doping.
Comparative example 2
1) According to the formula Li1.05Ti1.95Sr0.05(PO4)3Weighing lithium nitrate, titanium nitrate, strontium nitrate and ammonium dihydrogen phosphate; weighing tartaric acid, tartaric acid and Li1.05Ti1.95Sr0.05(PO4)3In a molar ratio of 1: 1; weighing deionized water, wherein the mass of the deionized water is as follows: (lithium nitrate + titanium nitrate + strontium nitrate + ammonium dihydrogen phosphate) in a mass ratio of 10: 1;
2) drying the raw materials in the step 1) to obtain a material I;
3) performing heat treatment on the material I in an air atmosphere to obtain a material II, wherein the heat treatment temperature is 800 ℃, and the heat treatment time is 16 h;
the rest were the same, i.e. not prepared by hydrothermal method.
Comparative example 3
1) According to the formula Li1.05Ti1.95Sr0.05(PO4)3Weighing lithium nitrate, titanium nitrate, strontium nitrate and ammonium dihydrogen phosphate; weighing tartaric acid, tartaric acid and Li1.05Ti1.95Sr0.05(PO4)3In a molar ratio of 1: 1; weighing deionized water, wherein the mass of the deionized water is as follows: (lithium nitrate + titanium nitrate + strontium nitrate + ammonium dihydrogen phosphate) in a mass ratio of 10: 1;
2) adding the raw materials in the step 1) into a hydrothermal kettle, and preserving heat at 180 ℃ for 24 hours to obtain a solid-liquid mixture I;
3) centrifuging and washing the material I to obtain a material II;
4) performing heat treatment on the material II in an air atmosphere to obtain a material III, wherein the heat treatment temperature is 800 ℃, and the heat treatment time is 16 h;
5) treating the material III in a sand mill to obtain slurry IV, wherein the solid content of the slurry is 20%, and the particle size distribution of the slurry is D50＝0.06μm；
6) And centrifugally washing and drying the solid-liquid mixture IV to obtain a final product.
The rest being the same, i.e. without lithium phosphate coating
Example 2
A high-performance solid electrolyte with an NASCION structure and a preparation method thereof comprise the following steps:
1) according to the formula Li1.1Ti1.9Sr0.1(PO4)3Weighing lithium acetate, titanium nitrate, strontium acetate and diammonium phosphate; weighing tartaric acid, tartaric acid and Li1.1Ti1.9Sr0.1(PO4)3In a molar ratio of 3: 1; weighing deionized water, wherein the mass of the deionized water is as follows: the mass ratio of lithium acetate, titanium nitrate, strontium acetate and diammonium hydrogen phosphate is 20: 1;
2) adding the raw materials in the step 1) into a hydrothermal kettle, and keeping the temperature at 210 ℃ for 12 hours to obtain a solid-liquid mixture I;
3) centrifuging and washing the material I to obtain a material II;
4) performing heat treatment on the material II in an air atmosphere to obtain a material III, wherein the heat treatment temperature is 850 ℃, and the heat treatment time is 8 hours;
5) treating the material III in a sand mill to obtain slurry IV, wherein the cobalt content of the slurry is 20%, and the particle size distribution of the slurry is D50＝0.06μm；
6) Adding the slurry IV into a stirring reaction kettle at a stirring speed of 800 revolutions per minute, and simultaneously dropwise adding 2mol/L lithium hydroxide solution and 0.5mol/L phosphoric acid solution into the reaction kettle to obtain a solid-liquid mixture V, wherein the molar ratio of the added lithium hydroxide to the phosphoric acid solution is 3.05:1, and the mass ratio of the added phosphoric acid to the slurry IV is 0.8: 1;
7) and (4) centrifugally washing the solid-liquid mixture V, and drying to obtain a final product.
Example 3
A high-performance solid electrolyte with an NASCION structure and a preparation method thereof comprise the following steps:
1) according to the formula Li1.08Ti1.92Sr0.08(PO4)3Weighing lithium acetate, titanium nitrate, strontium acetate and diammonium phosphate; weighing tartaric acid, tartaric acid and Li1.08Ti1.92Sr0.08(PO4)3In a molar ratio of 3: 1; weighing deionized water, wherein the mass of the deionized water is as follows: the mass of lithium acetate, titanium nitrate, strontium acetate and diammonium hydrogen phosphate is 10: 1;
2) adding the raw materials in the step 1) into a hydrothermal kettle, and keeping the temperature at 210 ℃ for 12 hours to obtain a solid-liquid mixture I;
3) centrifuging and washing the material I to obtain a material II;
4) performing heat treatment on the material II in an air atmosphere to obtain a material III, wherein the heat treatment temperature is 850 ℃, and the heat treatment time is 12 hours;
5) treating the material III in a sand mill to obtain slurry IV, wherein the cobalt content of the slurry is 20%, and the particle size distribution of the slurry is D50＝0.05μm；
6) Adding the slurry IV into a stirring reaction kettle at a stirring speed of 800 revolutions per minute, and simultaneously dropwise adding 2mol/L lithium hydroxide solution and 0.5mol/L phosphoric acid solution into the reaction kettle to obtain a solid-liquid mixture V, wherein the molar ratio of the added lithium hydroxide to the phosphoric acid solution is 3:1, and the mass ratio of the added phosphoric acid to the slurry IV is 0.8 to 1;
7) and (4) centrifugally washing the solid-liquid mixture V, and drying to obtain a final product.
Example 4
A high-performance solid electrolyte with an NASCION structure and a preparation method thereof comprise the following steps:
1) according to the formula Li1.08Ti1.92Sr0.08(PO4)3Weighing lithium acetate, titanium nitrate, strontium nitrate and diammonium phosphate; weighing tartaric acid, tartaric acid and Li1.08Ti1.92Sr0.08(PO4)3In a molar ratio of 3: 1; weighing deionized water, wherein the mass of the deionized water is as follows: the mass ratio of lithium acetate, titanium nitrate, strontium nitrate and diammonium hydrogen phosphate is 20: 1;
2) adding the raw materials in the step 1) into a hydrothermal kettle, and keeping the temperature at 180 ℃ for 12 hours to obtain a solid-liquid mixture I;
3) centrifuging and washing the material I to obtain a material II;
4) performing heat treatment on the material II in an air atmosphere to obtain a material III, wherein the heat treatment temperature is 850 ℃, and the heat treatment time is 10 hours;
5) treating the material III in a sand mill to obtain slurry IV, wherein the cobalt content of the slurry is 20%, and the particle size distribution of the slurry is D50＝0.05μm；
6) Adding the slurry IV into a stirring reaction kettle at a stirring speed of 800 revolutions per minute, and simultaneously dropwise adding 2mol/L of lithium hydroxide solution and 0.5mol/L of phosphoric acid solution into the reaction kettle to obtain a solid-liquid mixture V, wherein the molar ratio of the added lithium hydroxide to the phosphoric acid solution is 3:1, and the mass ratio of the added phosphoric acid to the slurry IV is 0.6 to 1;
7) and (4) centrifugally washing the solid-liquid mixture V, and drying to obtain a final product.
Experimental conditions:
table 1 shows a comparative table of ionic conductivity of solid electrolytes obtained by using examples 1 to 4 and comparative examples 1 to 3. The test method is an alternating current impedance method, and the frequency range is 0.1 HZ-1.0 MHz.
TABLE 1 comparison of ionic conductivities
Figure GDA0002703250680000071
Figure GDA0002703250680000081
As can be seen from the data in the table, the solid electrolyte prepared by the method has higher ionic conductivity, and basically meets the application requirements of the lithium ion battery. The lithium ion diffusion coefficients of comparative example 1 and comparative example 2 are both significantly reduced as compared to example 1, and comparative example 3 is substantially the same as example 1. The main reasons are: comparative example 1, ion doping was not performed, and the fermi level was high, resulting in difficulty in lithium ion deintercalation; the comparative example 2 adopts a preparation method of a high-temperature solid phase, the crystal growth direction is disordered, and the diffusion of lithium ions is influenced; comparative example 3 surface coating with one layer of Li3PO4The diffusion rate of lithium ions is not affected after the lithium ion fast conductor, which shows that the coating layer and the body part are well combined.
Table 2 shows a comparison of electrical performance data for button cells prepared using the solid electrolytes of example 1 and comparative example 3, with a 523 ternary material for the positive electrode, lithium metal for the negative electrode, and a discharge current of 0.05C.
TABLE 2 comparative table of capacity retention
Sample (I) Capacity retention after 50 cycles%
Example 1 95
Comparative example 3 71
As can be seen from the data in the table, the cycle performance of comparative example 3 is significantly deteriorated, mainly due to poor compatibility of the solid electrolyte material without coating with metallic lithium, surface occurrence, and increase in interfacial resistance.
In summary, the disclosure of the present invention is not limited to the above-mentioned embodiments, and persons skilled in the art can easily set forth other embodiments within the technical teaching of the present invention, but such embodiments are included in the scope of the present invention.

Claims (6)

1. A preparation method of a high-performance solid electrolyte with an NASCION structure is characterized in that a molecular composition Li is prepared by a hydrothermal method and a high-temperature solid-phase method1.05～1.1Ti(2-x)Srx(PO4)3The strontium-doped NASCION structure solid electrolyte is coated with a lithium phosphate fast ion conductor layer on the surface by a coprecipitation method, and the method specifically comprises the following steps:
1) according to the formula Li1.05～1.1Ti(2-x)Srx(PO4)3Weighing a lithium source, a titanium source, a strontium source and phosphate, wherein x is more than or equal to 0.05 and less than or equal to 0.10; weighing tartaric acid, tartaric acid and Li1.05～1.1Ti(2-x)Srx(PO4)3The molar ratio of (1-3) to (1); weighing deionized water, wherein the mass of the deionized water is as follows: the mass of the lithium source, the titanium source, the strontium source and the phosphate is (10-20): 1;
2) adding the raw materials in the step 1) into a hydrothermal kettle, and preserving heat for 12-24h at 180-210 ℃ to obtain a solid-liquid mixture I;
3) centrifugally washing the solid-liquid mixture I to obtain a material II;
4) performing heat treatment on the material II in an air atmosphere to obtain a material III, wherein the heat treatment temperature is 800-850 ℃, and the heat treatment time is 8-16 h;
5) treating the material III in a sand mill to obtain slurry IV, wherein the solid content of the slurry is 20%, and the particle size distribution of the slurry is D50≤0.1μm；
6) Adding the slurry IV into a stirring reaction kettle at a stirring speed of 500-800 rpm, and simultaneously dropwise adding 2mol/L lithium hydroxide solution and 0.5mol/L phosphoric acid solution into the reaction kettle to obtain a solid-liquid mixture V, wherein the molar ratio of the added lithium hydroxide to the phosphoric acid solution is (3-3.05): 1, and the mass ratio of the added phosphoric acid to the slurry IV is (0.4-0.8%): 1;
7) and (4) centrifugally washing the solid-liquid mixture V, and drying to obtain a final product.
2. The method for preparing the high-performance solid electrolyte with NASCION structure according to claim 1, wherein the lithium source in step 1) is lithium nitrate or lithium acetate.
3. The method for preparing the high-performance NASCION-structure solid electrolyte according to claim 1, wherein the titanium source in step 1) is titanium nitrate.
4. The method for preparing the high-performance solid electrolyte with the NASCION structure according to claim 1, wherein the strontium source in the step 1) is strontium nitrate or strontium acetate.
5. The method for preparing the high-performance solid electrolyte with the NASCION structure according to claim 1, wherein the phosphate in the step 1) is ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
6. A high-performance solid electrolyte of NASCION structure prepared by the method of any one of claims 1-5.
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