CN113845153A - Multi-element high-entropy solid solution cathode material and preparation method and application thereof - Google Patents
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Abstract
The invention provides a multielement high-entropy solid solution cathode material, a preparation method and application thereof. The high-entropy solid solution is a layered structure formed by primary particles; the chemical formula of the multielement high-entropy solid solution cathode material is LiNixCoyMn0.95‑x‑yM0.05O2Wherein M comprises at least five metal elements, x + y is less than 0.95, and the structural composition of the high-entropy solid solution cathode material at least comprises two layered material structures. The invention prepares the stable high-entropy solid solution with high metal ion dispersion uniformity and low synthesis temperature and 5 or more elements sharing the same atomic site by a sol-gel method, so that the anode material hasThe electrochemical battery has the advantages of good structural stability, thermal stability, rate capability and the like, has more excellent electrochemical performance under high voltage and high current density, has obvious cost performance advantage, and is more suitable for application of power batteries.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a multi-element high-entropy solid solution cathode material, a preparation method and application thereof.
Background
Metal oxide lithium ion battery for use in lithium ion battery manufacturing processOf the materials, LiCoO2(lithium cobalt oxide) is one of the most mature materials commercialized at present, but the material has the problems of poor safety, poor overcharge resistance, high cost, environmental pollution and the like due to the limitations of the material, and LiNiO2The requirements on environment and conditions in the synthesis process are very strict, the reversibility is poor, and the problems of poor stability and easy potential safety hazard exist.
In the process of manufacturing the lithium ion battery, manganese-based LiMnO is also used2As a lithium battery anode material, although the material is low in price and rich in resources, the material can be converted from a layered structure to a spinel structure in the charging and discharging processes, so that the specific capacity is quickly attenuated, the electrochemical performance is unstable, and the material has a layered ternary material LiCo, Ni and Mn synergistic effectxNiyMn1-x-yO2Although effectively compensating for LiCoO2、LiNiO2、LiMnO2The respective defects have the advantages of high specific capacity, good cycle performance, simple synthesis and preparation process, good safety and stability, and the like, but the energy density is small, and the specific capacity is lower than 200mAh/g, so the application of the power battery is limited to a certain extent.
At present, the most common method for preparing the oxide material is coprecipitation and solid-phase sintering, the operation is complex, the treatment procedures are multiple, gas protection is often needed, the practical application is not facilitated, and the prepared product has non-uniform chemical components and morphology, more agglomeration is caused, the electrochemical performance is unstable, and the reproducibility is poor.
CN102544475A discloses a preparation method for preparing a lithium-rich lithium manganate solid solution cathode material by oxalate coprecipitation. The coprecipitation method generally comprises preparing a hydroxide precursor of the composite transition metal ions and then calcining the precursor and a lithium salt. Although the preparation method can improve the uniform distribution of ions, the synthesis process of the coprecipitation method is complicated, the stoichiometry is not easy to control, and the requirement on equipment is high, and if the experimental conditions are not strictly controlled, divalent metal ions in the hydroxide are easy to oxidize, so that oxide impurity phases of manganese with different valence states appear in the final product, and the electrochemical performance of the material is influenced to a certain extent.
CN101582501A discloses a preparation method of a high-capacity lithium ion battery composite anode material, which has a chemical molecular formula: xLi [ Li ]1/3Mn2/3]O2.(1-x)Li[Ni1/3Mn1/3Co1/3]O2Wherein x is more than or equal to 0 and less than or equal to 1. The preparation method comprises the following steps: the method comprises the following steps of carrying out high-energy ball milling and uniform mixing on nickel, cobalt and manganese compounds and lithium source compounds in a certain solvent medium through mechanochemical activation, drying the obtained mixture at a low temperature, placing the dried mixture in a muffle furnace for high-temperature roasting, and then cooling to room temperature to obtain the lithium ion battery anode material. However, such a one-step solid-phase reaction is disadvantageous for uniform distribution of lithium ions.
Therefore, how to obtain a positive electrode material with stable structure and better electrochemical performance is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a multi-element high-entropy solid solution cathode material, a preparation method and application thereof. According to the invention, the problem of metal ion element segregation generated in the preparation process is solved by a sol-gel method, and the prepared stable high-entropy solid solution with high metal ion dispersion uniformity and low synthesis temperature and 5 or more elements sharing the same atomic site is obtained, so that the positive electrode material has good structural stability, thermal stability, rate capability and the like, has more excellent electrochemical performance under high voltage and large current density, has obvious cost performance advantage, and is more suitable for application of power batteries.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a multi-element high-entropy solid solution cathode material, wherein the high-entropy solid solution is a layered structure formed by primary particles; the chemical formula of the multielement high-entropy solid solution cathode material is LiNixCoyMn0.95-x-yM0.05O2Wherein M comprises at least one of Ti, V, Cr, Fe, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu or ErFive, x > 0, e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, etc., y > 0, e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, etc., x + y < 0.95; the structural composition of the high-entropy solid solution cathode material at least comprises two layered material body structures.
In the invention, the multi-element high-entropy solid solution cathode material is formed by stacking lamellar primary particles, and LiNixCoyMn0.95-x-yM0.05O2Is only the chemical formula of the whole positive electrode material, and the high-entropy solid solution positive electrode material contains at least two solid solution structures, such as LiNixCoyMn0.95-x-yA0.05O2、LiNixCoyMn0.95-x-yB0.05O2There may be at least two or more elements in A, or at least two or more metal elements in B, and the sum of the elements in A and B is all the elements in M.
The multi-element high-entropy solid solution anode material provided by the invention has the advantages that the metal ions are high in dispersion uniformity, 5 or more elements share the same atomic site in a multi-element oxide system, so that the anode material is more stable in structure, high in synthesis uniformity, lower in synthesis temperature, more excellent in electrochemical performance under high-voltage and high-current density, obvious in cost performance advantage and more suitable for application requirements of power batteries on power performance.
In the invention, less than five elements in M are not beneficial to the formation of a solid solution structure, and are more prone to a single layer structure material and are not beneficial to the structural stability.
Preferably, the median particle size of the multi-element high-entropy solid solution cathode material is 1-10 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm.
In a second aspect, the present invention provides a preparation method of the multi-element high-entropy solid solution cathode material according to the first aspect, the preparation method comprising the following steps:
(1) mixing a lithium source, a metal salt solution and a complexing agent, dropwise adding ammonia water or citric acid to adjust the pH value of the solution to 2-6, such as 2, 3, 4, 5 or 6, and the like, heating and drying to obtain a gel precursor;
(2) sintering the gel precursor in the step (1) to obtain the multi-element high-entropy solid solution cathode material;
wherein the metal salt solution comprises a base metal salt solution and a doped metal salt solution; the metal in the base metal salt solution comprises nickel, cobalt and manganese, and the metal in the doped metal salt solution comprises at least five of Ti, V, Cr, Fe, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu or Er.
According to the invention, ammonia water or citric acid is selected to be added according to the initial pH values of different raw material solutions so as to adapt to the adjustment of the final pH value.
According to the invention, through a sol-gel method, the problem of poor product uniformity when various metal ions are introduced is solved, and the problems of slow diffusion and composition uniformity among reactants in the traditional high-temperature solid-phase reaction method are solved, so that the obtained anode material has the advantages of high metal ion dispersion uniformity and low synthesis temperature, and compared with the existing anode material on the market, the anode material is not increased in material cost, has higher specific discharge capacity, higher cycling stability and safety performance, is improved in rate capability to a certain extent, has more excellent electrochemical performance under high-voltage and high-current density, is obvious in cost performance advantage, and is more suitable for application of power batteries.
In the sol-gel process, citric acid or ammonia water is added dropwise to facilitate the adjustment of the pH value, and in the preparation process, the ammonia water is added to adjust the pH value to 2-6 so that the environment is kept in a relatively acidic condition to form a stable sol form, while if the reaction process is an alkaline environment, the segregation condition is easy to occur.
In the invention, because a plurality of metal ions are introduced, Ksp is different when various metal ion hydroxides are precipitated, if the traditional coprecipitation is adopted and then a solid phase method is matched, all metal ions cannot be simultaneously complexed and precipitated by using ammonia water as a complexing agent in the process, the segregation of metal elements of a product is easily caused, the structure of a positive electrode material is uneven, and the electrochemical performance of the positive electrode material is influenced.
Preferably, the metal salt solution of step (1) comprises nitrate and/or acetate.
Preferably, the complexing agent is any one of or a combination of at least two of ethylene glycol, ammonium citrate or polyvinyl alcohol.
In the invention, besides ammonia water, ethylene glycol, ammonium citrate or polyvinyl alcohol is added as a complexing agent, which is more beneficial to the uniform distribution of various metal elements.
Preferably, the molar ratio of lithium in the lithium source in step (1), the metal in the metal salt solution and the complexing agent is (0.95-1.13): (0.03-0.15): 0.95-1.13), such as 0.95:0.03:0.95, 1:0.05:1, 1.13:0.1:1, 1:0.12:1.13, 1.1:0.04:1 or 1.13:0.15: 1.13.
Preferably, the concentration of the ammonia water in the step (1) is 10 to 25 mol%, such as 10 mol%, 15 mol%, 20 mol% or 25 mol%.
Preferably, the heating in step (1) is accompanied by stirring.
Preferably, the heating temperature in step (1) is 70-90 ℃, such as 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃.
Preferably, the heating time in the step (1) is 1-3 h, such as 1h, 2h or 3 h.
Preferably, the drying temperature in the step (1) is 100-140 ℃, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃ or 140 ℃.
Preferably, the sintering of step (2) is performed under an oxygen atmosphere.
Preferably, before the sintering in the step (2), the gel precursor in the step (1) is ground.
Preferably, the sintering temperature in the step (2) is 600-800 ℃, such as 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃.
Preferably, the sintering time in the step (2) is 6-24 h, such as 6h, 10h, 15h, 20h or 24 h.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing a lithium source, a metal salt solution and a complexing agent, dropwise adding ammonia water or citric acid to adjust the pH value of the solution to 2-6, heating and stirring at 70-90 ℃ for 1-3 h, and then drying at 100-140 ℃ to obtain a gel precursor;
(2) grinding the gel precursor in the step (1), and then sintering for 6-24 hours at a sintering temperature of 600-800 ℃ in an oxygen atmosphere to obtain the multi-element high-entropy solid solution cathode material;
wherein the metal salt solution comprises a base metal salt solution and a doped metal salt solution; the metal in the base metal salt solution comprises nickel, cobalt and manganese, and the metal in the doped metal salt solution comprises at least five of Ti, V, Cr, Fe, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu or Er; the molar ratio of the lithium in the lithium source, the metal in the metal salt solution and the complexing agent in the step (1) is (0.95-1.13): (0.03-0.15): 0.95-1.13).
In a third aspect, the invention further provides a lithium ion battery, which includes the multi-element high-entropy solid solution cathode material according to the first aspect.
Preferably, the lithium ion battery is a lithium ion power battery
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the problem of metal ion element segregation generated in the preparation process is solved by a sol-gel method, and the prepared stable high-entropy solid solution with high metal ion dispersion uniformity and low synthesis temperature and 5 or more elements sharing the same atomic site is obtained, so that the positive electrode material has good structural stability, thermal stability, rate capability and the like, has more excellent electrochemical performance under high voltage and large current density, has obvious cost performance advantage, and is more suitable for application of power batteries.
Drawings
Fig. 1 is an SEM image of the multi-element high-entropy cathode material provided in example 1.
Fig. 2 is a graph of the cycle performance of the battery provided in example 1.
Fig. 3 is a discharge voltage variation curve of the battery provided in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
(1) Weighing a lithium source compound according to a molar ratio of a metal element in Li to metal salt to ammonium citrate of 1:1:1, dissolving the metal salt and the ammonium citrate in deionized water, and magnetically stirring for 4 hours, wherein the lithium source is lithium acetate; the metal source is acetate, the metal in the metal salt is nickel, cobalt, manganese, tin, zinc, magnesium, tungsten, chromium and aluminum, and the metal salt is prepared by mixing Ni, Co, Mn, Sn, Zn, Mg, W, Cr and Al, wherein the ratio of Ni to Co to Sn to Zn to W to Cr to Al is 0.8:0.13:0.02: 0.01; the molar ratio of 0.01:0.01:0.01:0.005:0.005 is proportioned to obtain a mixed solution;
(2) dropwise adding citric acid into the mixed solution obtained in the step (1) to adjust the pH value to 5, heating in a water bath, stirring and heating at 80 ℃ for 3 hours, and then drying at 120 ℃ to obtain a gel precursor;
(3) grinding the gel precursor in the step (2), sieving with a 500-mesh sieve, placing in a tube furnace, sintering at the sintering temperature of 700 ℃ for 20h in the oxygen atmosphere, cooling, grinding and sieving to obtain the layered high-entropy chemically stable cathode material LiNi0.8Co0.13Mn0.02(Sn0.01Zn0.01Mg0.01W0.01Cr0.005Al0.005)O2. The material is nano-scale primary particles with tap density of 1.8g/cm3。
Preparing 2032 button cells from the positive electrode material, and verifying related properties, wherein a SEM picture of the material prepared in example 1 is shown in figure 1; FIG. 2 shows that the button cell battery of example 1 has a discharge specific capacity of 206.3mAh/g at a voltage of 3-4.5V and a capacity retention rate of 88.1% at 0.2C cycle for 150 weeks; fig. 3 shows the discharge medium voltage variation curve of the button cell of example 1 under the test conditions of 0.2C and voltage interval of 3-4.5V, and it can be seen that the cyclic voltage drop is almost 0 after the cycle reaches 80 weeks;
example 2
The preparation method of the multi-element high-entropy solid solution material comprises the following steps:
(1) weighing a lithium source compound according to a molar ratio of a metal element in Li to a metal salt to ethylene glycol of 1.02:1:1, dissolving the metal salt and ammonium citrate in deionized water, and magnetically stirring for 4 hours, wherein the lithium source is lithium acetate; the metal source is acetate, the metal in the metal salt is nickel, cobalt, manganese, chromium, aluminum, magnesium, tin and tungsten, and the metal salt is prepared by mixing Ni, Co, Mn, Cr, Al, Mg and Sn; mixing W with the molar ratio of 0.8:0.1:0.05:0.01:0.02:0.02:0.025:0.025 to obtain a mixed solution;
(2) dropwise adding ammonia water with the concentration of 15 mol% into the mixed solution obtained in the step (1) to adjust the pH value to 6, heating in a water bath, stirring and heating at the temperature of 75 ℃, reacting for 2 hours, and drying at the temperature of 140 ℃ to obtain a gel precursor;
(3) grinding the gel precursor in the step (2), sieving with a 500-mesh sieve, placing in a tube furnace, sintering at the sintering temperature of 800 ℃ for 10h in the oxygen atmosphere, cooling, grinding and sieving to obtain the layered high-entropy chemically stable cathode material LiNi0. 8Co0.1Mn0.05Cr0.01Al0.02Mg0.02Sn0.025W0.025O2。
In conclusion, the invention overcomes the problem of metal ion element segregation generated in the preparation process by a sol-gel method, prepares a stable high-entropy solid solution with high metal ion dispersion uniformity and low synthesis temperature and 5 or more elements sharing the same atomic site, enables the positive electrode material to have good structural stability, thermal stability, rate capability and the like, has more excellent electrochemical performance under high voltage and high current density, has obvious cost performance advantage, and is more suitable for application of power batteries.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The multielement high-entropy solid solution cathode material is characterized in that the high-entropy solid solution is a layered structure formed by primary particles; the chemical formula of the multielement high-entropy solid solution cathode material is LiNixCoyMn0.95-x-yM0.05O2Wherein M comprises at least five of Ti, V, Cr, Fe, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu or Er, x is more than 0, Y is more than 0, and x + Y is less than 0.95; the structural composition of the high-entropy solid solution cathode material at least comprises two layered material body structures.
2. The multi-element high-entropy solid solution cathode material as claimed in claim 1, wherein the median particle size of the multi-element high-entropy solid solution cathode material is 1-10 μm.
3. The method for preparing a multielement high entropy solid solution positive electrode material according to claim 1 or 2, characterized in that the method comprises the steps of:
(1) mixing a lithium source, a metal salt solution and a complexing agent, dropwise adding ammonia water or citric acid to adjust the pH value of the solution to 2-6, heating, and drying to obtain a gel precursor;
(2) sintering the gel precursor in the step (1) to obtain the multi-element high-entropy solid solution cathode material;
wherein the metal salt solution comprises a base metal salt solution and a doped metal salt solution; the metal in the base metal salt solution comprises nickel, cobalt and manganese, and the metal in the doped metal salt solution comprises at least five of Ti, V, Cr, Fe, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu or Er.
4. The method for preparing a multi-element high-entropy solid-solution cathode material of claim 3, wherein the metal salt solution of the step (1) comprises nitrate and/or acetate;
preferably, the complexing agent is any one of or a combination of at least two of ethylene glycol, ammonium citrate or polyvinyl alcohol.
5. The method for preparing a multi-element high-entropy solid-solution cathode material as claimed in claim 3 or 4, wherein the molar ratio of the lithium in the lithium source, the metal in the metal salt solution and the complexing agent in the step (1) is (0.95-1.13): (0.03-0.15): (0.95-1.13).
6. The preparation method of the multi-element high-entropy solid-solution cathode material according to any one of claims 3 to 5, wherein the concentration of the ammonia water in the step (1) is 10-25 mol%.
7. A method for preparing a multi-element high-entropy solid-solution cathode material according to any one of claims 3 to 6, wherein the heating in the step (1) is accompanied by stirring;
preferably, the heating temperature in the step (1) is 70-90 ℃;
preferably, the heating time in the step (1) is 1-3 h;
preferably, the drying temperature in the step (1) is 100-140 ℃.
8. A method for preparing a multi-element high-entropy solid-solution cathode material according to any one of claims 3 to 7, wherein the sintering in the step (2) is performed in an oxygen atmosphere;
preferably, before the sintering in the step (2), the gel precursor in the step (1) is ground;
preferably, the sintering temperature in the step (2) is 600-800 ℃;
preferably, the sintering time in the step (2) is 6-24 h.
9. A method for preparing a multi-element high-entropy solid-solution cathode material according to any one of claims 3 to 8, wherein the method comprises the following steps:
(1) mixing a lithium source, a metal salt solution and a complexing agent, dropwise adding citric acid or ammonia water to adjust the pH value of the solution to 2-6, heating and stirring at 70-90 ℃ for 1-3 h, and then drying at 100-140 ℃ to obtain a gel precursor;
(2) grinding the gel precursor in the step (1), and then sintering for 6-24 hours at a sintering temperature of 600-800 ℃ in an oxygen atmosphere to obtain the multi-element high-entropy solid solution cathode material;
wherein the metal salt solution comprises a base metal salt solution and a doped metal salt solution; the metal in the base metal salt solution comprises nickel, cobalt and manganese, and the metal in the doped metal salt solution comprises at least five of Ti, V, Cr, Fe, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu or Er; the molar ratio of the lithium in the lithium source, the metal in the metal salt solution and the complexing agent in the step (1) is (0.95-1.13): (0.03-0.15): 0.95-1.13).
10. A lithium ion battery, characterized in that the lithium ion battery comprises the multi-element high-entropy solid-solution cathode material of claim 1 or 2;
preferably, the lithium ion battery is a lithium ion power battery.
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Cited By (5)
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| CN114373920A (en) * | 2022-03-21 | 2022-04-19 | 中南大学 | High-entropy oxide and preparation method and application thereof |
| CN114883522A (en) * | 2022-04-20 | 2022-08-09 | 南京邮电大学 | High-entropy-like multi-element layered transition metal oxide cathode material and preparation method and application thereof |
| CN115010190A (en) * | 2022-06-22 | 2022-09-06 | 北京理工大学重庆创新中心 | High-entropy oxide cathode material and preparation method and application thereof |
| CN116237214A (en) * | 2022-12-13 | 2023-06-09 | 中国科学院合肥物质科学研究院 | Al-Y-Cr-Fe-Er-O high-entropy composite oxide hydrogen-resistant coating and preparation method thereof |
| WO2024104240A1 (en) * | 2022-11-14 | 2024-05-23 | 北京大学 | Medium- and high-entropy layered lithium-rich positive electrode oxide and preparation method therefor |
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| CN114373920A (en) * | 2022-03-21 | 2022-04-19 | 中南大学 | High-entropy oxide and preparation method and application thereof |
| CN114373920B (en) * | 2022-03-21 | 2022-06-17 | 中南大学 | High-entropy oxide and preparation method and application thereof |
| CN114883522A (en) * | 2022-04-20 | 2022-08-09 | 南京邮电大学 | High-entropy-like multi-element layered transition metal oxide cathode material and preparation method and application thereof |
| CN114883522B (en) * | 2022-04-20 | 2024-05-28 | 南京邮电大学 | High-entropy-like multi-element layered transition metal oxide positive electrode material, and preparation method and application thereof |
| CN115010190A (en) * | 2022-06-22 | 2022-09-06 | 北京理工大学重庆创新中心 | High-entropy oxide cathode material and preparation method and application thereof |
| CN115010190B (en) * | 2022-06-22 | 2023-12-22 | 北京理工大学重庆创新中心 | High-entropy oxide positive electrode material and preparation method and application thereof |
| WO2024104240A1 (en) * | 2022-11-14 | 2024-05-23 | 北京大学 | Medium- and high-entropy layered lithium-rich positive electrode oxide and preparation method therefor |
| CN116237214A (en) * | 2022-12-13 | 2023-06-09 | 中国科学院合肥物质科学研究院 | Al-Y-Cr-Fe-Er-O high-entropy composite oxide hydrogen-resistant coating and preparation method thereof |
| CN116237214B (en) * | 2022-12-13 | 2024-01-26 | 中国科学院合肥物质科学研究院 | Al-Y-Cr-Fe-Er-O high-entropy composite oxide hydrogen-resistant coating and preparation method thereof |
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