CN113540435A - Modification method of phosphorus-containing compound on surface of high-nickel ternary material and lithium ion battery - Google Patents
Modification method of phosphorus-containing compound on surface of high-nickel ternary material and lithium ion battery Download PDFInfo
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Abstract
The invention provides a modification method of a phosphorus-containing compound on the surface of a high-nickel ternary material, which comprises the following steps: mechanically mixing the high-nickel ternary material and a modifier to obtain a mixed material; and carrying out heat treatment on the mixed material in an oxygen atmosphere. The invention finishes the surface modification of the high nickel ternary material on the premise of not adopting wet mixing; the surface modification and the electrochemical performance improvement of the high nickel material are realized by selecting a proper modification material and a proper heat treatment temperature. The preparation method selected by the invention is simple and controllable, and can be prepared by using the existing equipment.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a modification method of a phosphorus-containing compound on the surface of a high-nickel ternary material and a lithium ion battery.
Background
Clean, renewable energy is a major development trend in today's society. With the increase of energy demand, high energy density lithium ion batteries are the main development direction of lithium batteries at present. Based on this, the ternary positive electrode material has been developed from the original NCM111 to high nickel (NCM811) and higher nickel (Ni content > 90%).
Compared with a low-nickel ternary material, the high-nickel material not only can increase the content of residual alkali on the surface of the material, influence the gram capacity of the material and cause side reaction in the charging process of the material, but also can cause the side reaction between the material and electrolyte and influence the stability and capacity characteristics of the material due to the high activity of the surface. Research shows that surface modification (forming a coating layer or forming a scattered point distribution material) on the surface of the positive electrode has a positive effect on improving the stability of the material.
Research shows that part of phosphate can be used as a modification material of the cathode material based on good electrochemical stability and lithium ion conductivity. CN109244439A constructs an aqueous solution containing phosphate ions through ammonium phosphate and sodium phosphate, and constructs a coating layer with a multi-stage coating effect by combining with a metal oxide formed by earlier coating, so as to improve the thermal stability and the cycle performance of the material. CN108511715A is formed by mixing lithium dihydrogen phosphate water solution with ethanol solution of ternary material, and after the steps of filtering, drying, high-temperature sintering and the like, the positive electrode material coated with lithium pyrophosphate is formed. CN110400929A is used for preparing a metal-doped anode material coated with metal phosphate (Al, Ce, Sr and Fe), and the metal phosphate is constructed on the surface of a ternary material coated with metal nano-oxide through heat treatment. CN109244428A builds coating on the surface of the ternary material through a two-step coating method, and forms a coating structure on the surface of the anode material through the metal pyrophosphate material prepared by advanced heat treatment through mechanical stirring and a heat treatment method; and then constructing an outer coating layer in a wet coating mode.
At present, phosphate coating on the surface of a material by a wet coating method is a common method. However, wet coating often requires multiple steps to remove or recover the solvent to control the preparation cost, and the overall process is complex and has a high cost; and the risk of metal element dissolution in the ternary material exists by selecting an acidic phosphorus-containing solution as a wet coating reagent. The long-time aqueous phase wet stirring process may damage the surface structure of the material and cause lithium deficiency of the high nickel material, and the electrochemical performance of the material is reduced. In addition, as one of the important control indexes of the high nickel material, the problem of residual alkali on the surface of the material is rarely mentioned.
Therefore, a modification scheme for the high nickel ternary material is needed, and the electrochemical performance of the high nickel ternary material is improved.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a modification method of a phosphorus-containing compound on the surface of a high-nickel ternary material, which can reduce the surface residual alkali content of the high-nickel ternary material and improve the capacity of the high-nickel ternary material as a positive electrode material.
In view of the above, the present application provides a method for modifying a phosphorus-containing compound on a surface of a high-nickel ternary material, comprising the following steps:
mechanically mixing the high-nickel ternary material and a modifier to obtain a mixed material;
carrying out heat treatment on the mixed material in an oxygen atmosphere;
the modifier is selected from phosphorus-containing compounds with acidic aqueous solution;
in the transition metal elements of the high-nickel ternary material, the content of nickel atoms is more than or equal to 90 percent.
Preferably, the high-nickel ternary material is represented by formula (I):
LiaNixCoyMnzMbO2 (Ⅰ)；
wherein x is more than or equal to 0.9 and less than 1, y is more than 0 and less than 0.1, z is more than 0 and less than 0.1, b is more than or equal to 0 and less than or equal to 0.01, a is more than 0.98 and less than 1.03, x + y + z is less than or equal to 1, and M is other doped metal elements.
Preferably, the modifying agent is selected from one or more of dihydrogen phosphate, metaphosphate and pyrophosphate.
Preferably, the dihydrogen phosphate is one or more selected from ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, aluminum dihydrogen phosphate and manganese dihydrogen phosphate, the metaphosphate is selected from sodium metaphosphate, and the pyrophosphate is selected from sodium acid pyrophosphate.
Preferably, the total sum of the high-nickel ternary material and the modifier is used as the basis, the modifier is added by taking the phosphorus content as an addition standard, and the phosphorus content is 6 to 10-5～1.550*10-3ppm。
Preferably, the time of the mechanical mixing is 0.5-5 h, and the rotating speed of the mechanical mixing is 200-1500 rpm.
Preferably, the concentration of oxygen in the oxygen atmosphere is greater than 90%.
Preferably, the heating rate of the heat treatment is 1-10 ℃/min.
Preferably, the temperature of the heat treatment is 400-700 ℃, and the time is 2-20 h.
The application also provides a lithium ion battery which comprises a positive electrode and a negative electrode, wherein the material of the positive electrode is the high-nickel ternary material obtained by the modification method.
The application provides a modification method of a phosphorus-containing compound on the surface of a high-nickel ternary material. The modification method provided by the application is dry modification, and the problem of concentrated stability of the high-nickel material in aqueous solution and acidic liquid phase in the wet process is solved; the phosphorus-modified high-nickel ternary material is prepared by simple mechanical mixing and a subsequent heat treatment method, the surface performance of the high-nickel ternary material is improved, the surface residual alkali content is reduced, and the capacity performance of the high-nickel ternary material as a positive electrode material is improved.
Drawings
FIG. 1 is an SEM photograph of modified high nickel ternary materials prepared in examples 1-3 of the present invention and references 1-2;
FIG. 2 is an SEM photograph of modified high-nickel ternary materials prepared in examples 4-5 of the present invention and reference 3;
FIG. 3 is a maping test chart and a linear scan photograph of profile EDX of the modified high nickel ternary material prepared in example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the problems of unstable metal elements and unstable electrochemical performance existing in wet process phosphorus-containing compound coating in the prior art, the application provides a modification method for a phosphorus-containing compound on the surface of a high-nickel ternary material, which completes surface modification of the high-nickel ternary material on the basis of not adopting wet process mixing and realizes surface modification and improvement of electrochemical performance of the high-nickel material through proper modification materials and heat treatment. Specifically, the embodiment of the invention discloses a modification method of a phosphorus-containing compound on the surface of a high-nickel ternary material, which comprises the following steps:
mechanically mixing the high-nickel ternary material and a modifier to obtain a mixed material;
carrying out heat treatment on the mixed material in an oxygen atmosphere;
the modifier is selected from phosphorus-containing compounds with acidic aqueous solution;
in the transition metal elements of the high-nickel ternary material, the content of nickel atoms is more than or equal to 90 percent.
In the modification of the phosphorus-containing compound on the surface of the high-nickel ternary material, the high-nickel ternary material and a modifier are mechanically mixed to obtain a mixed material; in the application, the high-nickel ternary material and the modifier are directly and mechanically mixed, no solvent is involved, and the method is dry modification; in the process, the lithium carbonate and the lithium hydroxide remaining on the surface of the high-nickel ternary material enable the material to have certain alkalinity, and acid-base reaction is carried out on the surface of the material through coating of a modifier phosphorus-containing compound to remove the remaining alkali on the surface, so that the reduction of the lithium carbonate and the lithium hydroxide on the surface of the high-nickel ternary material is realized. The percentage content of nickel atoms in the high-nickel ternary material is more than or equal to 90%, and in a specific embodiment, the percentage content is 92-96%. The high-nickel ternary material is specifically shown as (I):
LiaNixCoyMnzMbO2 (Ⅰ)；
wherein x is more than or equal to 0.9 and less than 1, y is more than 0 and less than 0.1, z is more than 0 and less than 0.1, b is more than or equal to 0 and less than or equal to 0.01, a is more than 0.98 and less than 1.03, x + y + z is less than or equal to 1, and M is other doped metal elements.
In the present application, the high nickel ternary material is specifically selected from the group consisting of LiNi0.96CoyMnzO2。
The modifier is specifically selected from phosphorus-containing compounds with acidic aqueous solution, more specifically, the modifier is selected from one or more of dihydrogen phosphate, metaphosphate and pyrophosphate, more specifically, the dihydrogen phosphate is selected from one or more of ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, aluminum dihydrogen phosphate and manganese dihydrogen phosphate, the metaphosphate is selected from sodium metaphosphate, and the pyrophosphate is selected from sodium acid pyrophosphate. Based on the total amount of the high-nickel ternary material and the modifier, the modifier is added by taking phosphorus content as an addition standard, and the phosphorus content is 6-10-5～1.550*10-3ppm; in a particular embodiment, the phosphorus content is 3 x 10-4～1.24*10-3ppm (wt.%). Phosphate or metaphosphate has stable P-O bond, and Li-containing phosphate formed by the phosphate and residual lithium on the surface has certain function of fast ion conductor; meanwhile, the high bond energy of P-O has a certain protection effect on the surface of the material; since phosphate is not an electrochemically active material, an excessively high content thereof results in a decrease in the proportion of electrochemically active material per unit mass, and a decrease in the capacity of the material. The mixing mode is ball milling mixing or mixing by a high-speed mixer, the mixing time is 0.5-5 h, and the rotating speed is 200-1500 rpm; more specifically, the mixing time is 1-4 h, and the rotating speed is 300-1000 rpm.
The application then subjects the above-mentioned mixed material to a heat treatment in an oxygen atmosphere to avoid, by means of a high temperature treatment, the reduction of residual lithium on the surface due to water formed by the reaction. The temperature rise speed of the heat treatment is 1-10 ℃, the temperature is 400-700 ℃, and the time is 2-20 hours; more specifically, the temperature rise speed of the heat treatment is 2-7 ℃/min, the temperature is 450-600 ℃, and the time is 5-15 h. The heat treatment is carried out in an oxygen-enriched environment, and the oxygen content in the oxygen-enriched environment is over 90 percent in the whole heat treatment process.
In the application, the surface property of the high-nickel ternary material modified by the phosphorus-containing compound is changed, the residual alkali content on the surface of the material is reduced, and the content is reduced by 0-800 ppm; the ternary nickelic material prepared by the method has phosphorus-containing compounds distributed uniformly on the surface.
The application also provides a lithium ion battery, and the anode material of the lithium ion battery is the high-nickel ternary material modified by the scheme.
The modification method provided by the application adopts dry modification, and avoids the problems of surface property change and result change in the wet process; by surface modification of the phosphorus-containing compound, the surface property of the high-nickel ternary material is improved, the surface residual alkali content is reduced, and the side reaction of the material in a battery is favorably improved; the capacity property of the material is improved by a surface modification method. The method can realize that the phosphorus-containing compound is uniformly distributed in the ternary cathode material in a dotted manner. Furthermore, the preparation process is simple, the existing equipment conditions can be adopted for preparation, the amplification is easy, and the overall cost is lower compared with that of a wet process.
For further understanding of the present invention, the following examples are provided to illustrate the modification method of the phosphorus-containing compound on the surface of the high nickel ternary material, and the scope of the present invention is not limited by the following examples.
In the embodiment of the application, a high-nickel ternary material with the Ni content of 96% is selected as a load object, and the specific chemical formula is LiNi0.96CoyMnzO2Wherein 0.25<y＜0.35，0.05＜z<0.15。
Example 1
1kg of LiNi0.96CoyMnzO2Ball milling and mixing the material and potassium dihydrogen phosphate by a planetary ball mill; the phosphorus content is 3.1%10-4 ppm, mixing the two materials in a ball mill with 300rpm for 3 h; placing the sagger filled with the mixed material in a heat treatment furnace with oxygen flux of 10L/min for sintering; the heating rate of the furnace body is 2 ℃/min, and the temperature is kept at 600 ℃ for 12 h.
Example 2
1kg of LiNi0.96CoyMnzO2Ball milling and mixing the materials and ammonium dihydrogen phosphate by a planetary ball mill; the addition content of phosphorus is 1.24 x 10 < -3 > ppm, and the two materials are mixed for 3 hours in a ball mill with 300 rpm; placing the sagger filled with the mixed material in a heat treatment furnace with oxygen flux of 12L/min for sintering; the heating rate of the furnace body is 2 ℃/min, and the temperature is kept for 10 hours at the high temperature of 600 ℃.
Reference sample 1
High-nickel ternary material LiNi with high surface residual alkali0.96CoyMnzO2。
Reference sample 2
1kg of LiNi0.96CoyMnzO2Ball milling and mixing the material and potassium dihydrogen phosphate by a planetary ball mill; the adding content of phosphorus is 3.1 x 10-4 ppm, and the two materials are mixed for 3 hours in a ball mill with 300 rpm; placing the sagger filled with the mixed material in a heat treatment furnace with oxygen flux of 10L/min for sintering; the heating rate of the furnace body is 2 ℃/min, and the constant temperature is kept for 12h at the low temperature of 260 ℃.
Example 3
3kg of LiNi0.96CoyMnzO2Mechanically mixing the materials and aluminum dihydrogen phosphate for 25min by a high-speed mixer at the rotating speed of 1000 rpm; the content of phosphorus accounts for 4.65 x 10-4 ppm; placing the sagger filled with the mixed material in a heat treatment furnace with oxygen flux of 10L/min for sintering, wherein the oxygen content in the furnace chamber is more than 92% in the sintering process; the heating rate of the furnace body is 2 ℃/min, and the temperature is kept at 480 ℃ for 12 h; naturally cooling to room temperature.
Example 4
3kg of LiNi0.96CoyMnzO2Mechanically mixing the materials and manganese dihydrogen phosphate for 25min by a high-speed mixer at the rotating speed of 1000 rpm; phosphorus contentThe proportion is 3.096 x 10-4 ppm; placing the sagger filled with the mixed material in a heat treatment furnace with oxygen flux of 10L/min for sintering, wherein the oxygen content in the furnace chamber is more than 92% in the sintering process; heating to 570 ℃ at the heating rate of 2 ℃/min and keeping the temperature for 10 hours; naturally cooling to room temperature.
High-nickel ternary material LiNi with low surface residual alkali0.96CoyMnzO2。
Reference sample 4LiNi0.96CoyMnzO2Material
Reference sample 5
3kg of LiNi0.96CoyMnzO2Mechanically mixing the material and diammonium hydrogen phosphate for 25min by a high-speed mixer at the rotating speed of 1000 rpm; the content of phosphorus accounts for 9.3 x 10^ -4 ppm; placing the sagger filled with the mixed material in a heat treatment furnace with oxygen flux of 10L/min for sintering, wherein the oxygen content in the furnace chamber is more than 92% in the sintering process; heating to 600 ℃ at the heating rate of 2 ℃/min and keeping the temperature for 10 hours; naturally cooling to room temperature.
The physicochemical property test and the electrochemical test were performed using the same test conditions for the reference sample and the example sample, and the test results are shown in table 1 below.
TABLE 1 see contents and capacity tables for examples and reference samples
| Group of | LiOH | Li2CO3 | Free-Li | 0.2C capacity mAh/g |
| Reference sample 1 | 4178 | 8536 | 3258.88 | 213 |
| Reference sample 2 | 7056 | 7036 | 3364.84 | 213.2 |
| Example 1 | 4934 | 6612 | 2843.29 | 215 |
| Example 2 | 5092 | 6082 | 2719.36 | 215.6 |
| |
2934 | 2985 | 1416.41 | 211.0 |
| Example 3 | 2889 | 2902 | 1383.90 | 213.2 |
| Example 4 | 2138 | 2838 | 1224.24 | 213.4 |
| Reference sample 4 | 5320 | 5091 | 2474.98 | 216.8 |
| Reference sample 5 | 10037 | 3523 | 2598.86 | 211.9 |
FIG. 1 is an SEM photograph of modified high nickel ternary materials prepared in examples 1-2 of the present invention and references 1-2; as shown in FIG. 1, the shape of the primary particles on the surface of the material is affected after the surface of the material is coated with the potassium dihydrogen phosphate, and the effect of the ammonium dihydrogen phosphate is not significantly affected; the surfaces of the two materials have no obvious granularity, and the phosphate has a better dispersion modification effect on the surfaces of the materials. FIG. 2 is an SEM photograph of modified high nickel ternary materials prepared according to examples 3-4 of the present invention and reference 3; as can be seen from FIG. 2, the aluminum dihydrogen phosphate affects the morphology of the primary particles on the surface to form finer primary particles on the surface; the manganese dihydrogen phosphate can show fine particles at the grain boundary, and the whole manganese dihydrogen phosphate has a better scattering distribution effect. FIG. 3 is a maping test chart and a linear scan photograph of profile EDX of the modified high nickel ternary material prepared in example 1 of the present invention; as can be seen from FIG. 3, in the potassium dihydrogen phosphate modified material, phosphate is not only distributed on the surface of the material, but also distributed inside the particles; the modified material has better dispersion effect in the whole secondary ball.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A modification method of a phosphorus-containing compound on the surface of a high-nickel ternary material comprises the following steps:
mechanically mixing the high-nickel ternary material and a modifier to obtain a mixed material;
carrying out heat treatment on the mixed material in an oxygen atmosphere;
the modifier is selected from phosphorus-containing compounds with acidic aqueous solution;
in the transition metal elements of the high-nickel ternary material, the content of nickel atoms is more than or equal to 90 percent.
2. The modification method according to claim 1, wherein the high nickel ternary material is represented by formula (i):
LiaNixCoyMnzMbO2 (Ⅰ)；
wherein x is more than or equal to 0.9 and less than 1, y is more than 0 and less than 0.1, z is more than 0 and less than 0.1, b is more than or equal to 0 and less than or equal to 0.01, a is more than 0.98 and less than 1.03, x + y + z is less than or equal to 1, and M is other doped metal elements.
3. The modification method according to claim 1, wherein the modifying agent is selected from one or more of dihydrogen phosphate, metaphosphate, and pyrophosphate.
4. The modification method according to claim 3, wherein the dihydrogen phosphate is one or more selected from the group consisting of ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, aluminum dihydrogen phosphate, and manganese dihydrogen phosphate, the metaphosphate is selected from the group consisting of sodium metaphosphate, and the pyrophosphate is selected from the group consisting of sodium acid pyrophosphate.
5. The modification method according to claim 1, wherein the modifier is added based on the sum of the high nickel ternary material and the modifier with a phosphorus content of 6 x 10 as an addition criterion-5～1.550*10-3ppm。
6. The modification method according to claim 1, wherein the time of the mechanical mixing is 0.5 to 5 hours, and the rotation speed of the mechanical mixing is 200 to 1500 rpm.
7. The modification method according to claim 1, wherein the concentration of oxygen in the oxygen atmosphere is greater than 90%.
8. The modification method according to claim 1, wherein the temperature increase rate of the heat treatment is 1 to 10 ℃/min.
9. The modification method according to claim 1, wherein the heat treatment temperature is 400 to 700 ℃ and the time is 2 to 20 hours.
10. A lithium ion battery comprises a positive electrode and a negative electrode, and is characterized in that the material of the positive electrode is a high-nickel ternary material obtained by the modification method of any one of claims 1 to 9.
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| CN107069006A (en) * | 2017-04-24 | 2017-08-18 | 北京理工大学 | A kind of method for improving the nickelic tertiary cathode material chemical property of lithium ion battery |
| CN108777296A (en) * | 2018-06-04 | 2018-11-09 | 国联汽车动力电池研究院有限责任公司 | A kind of surface is modified nickelic tertiary cathode material and its prepares and its manufactured battery |
| CN109244428A (en) * | 2018-11-05 | 2019-01-18 | 桑顿新能源科技有限公司 | A kind of coating modification method of nickelic ternary material |
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| CN112382741A (en) * | 2020-10-12 | 2021-02-19 | 深圳市贝特瑞纳米科技有限公司 | High-nickel positive electrode material, preparation method thereof and lithium ion secondary battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114784278A (en) * | 2022-04-22 | 2022-07-22 | 天津巴莫科技有限责任公司 | Surface modification method of high-nickel anode material |
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