CN111403727B - Preparation method of modified ternary cathode material - Google Patents
Preparation method of modified ternary cathode material Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention relates to the field of lithium battery materials, in particular to a preparation method of a modified ternary cathode material with high capacity and long service life. The method comprises the following steps: dissolving nickel salt, cobalt salt and manganese salt into aqueous solution of hydrogen chloride, and adding a copper source and an iron source to obtain a pre-solution; stirring the pre-solution, adding strong base, and performing coprecipitation to obtain suspension; mixing the suspension with a complexing agent solution, and performing aging treatment to obtain an aging solution; filtering out powdery precipitates in the aging liquid, cleaning, mixing with a lithium source, and performing ball milling to obtain a precursor; and calcining the precursor to obtain the modified ternary cathode material with high capacity and long service life. The preparation method is simple and efficient; the obtained anode material has higher normal pressure (3.0V) gram capacity; the obtained cathode material has good normal-pressure cycle performance.
Description
Technical Field
The invention relates to the field of lithium battery materials, in particular to a preparation method of a modified ternary cathode material.
Background
The lithium ion battery has the advantages of high operating voltage, high specific energy, large capacity, less natural loss, excellent cycle performance and the like. At present, the positive electrode of the lithium ion battery mainly comprises lithium cobaltate, lithium iron phosphate, lithium manganate, lithium nickel cobalt aluminate, lithium nickel cobalt manganate and the like. The application range of nickel cobalt lithium manganate (namely, nickel cobalt manganese ternary cathode material) is widest, and the nickel cobalt lithium manganate is adopted by most enterprises.
However, most of the current nickel-cobalt-manganese ternary precursors are prepared by a homogeneous coprecipitation method, and then are subjected to a high-temperature solid-phase reaction with a lithium salt to obtain a positive electrode material. However, most of nickel cobalt lithium manganate ternary positive electrode materials have the problems of low capacity, rapid capacity reduction after long-time recycling, and short service life. Particularly, in most rechargeable secondary lithium batteries, the rechargeable capacity of the lithium battery is severely reduced after about 600 cycles.
For example, the patent of invention of high-voltage single-crystal lithium nickel cobalt manganese oxide cathode material and the preparation method thereof disclosed by the Chinese patent office in 2017, 1 month and 25 days, the publication number of which is CN104134791B, improves the cycle performance of the lithium nickel cobalt manganese oxide battery during working by adopting a multi-element matching mode, but has the problems of complex preparation process, high cost and the like.
Disclosure of Invention
The invention provides a preparation method of a modified ternary cathode material with high capacity and long service life, which aims to solve the problems that the existing cathode material of a lithium ion battery has limited capacity and short service life, particularly the capacity is rapidly reduced in the charge-discharge use process of 1C, the service life of the battery is easily further shortened, and the like. The invention aims to: 1. providing a preparation method of a lithium ion battery anode material; 2. the preparation method is simple and efficient; 3. the gram capacity of the prepared anode material is improved; 4. the cycle performance of the anode material is improved.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of a modified ternary cathode material with high capacity and long service life,
the preparation method comprises the following preparation steps:
1) Dissolving nickel salt, cobalt salt and manganese salt into aqueous solution of hydrogen chloride, and adding a copper source and an iron source to obtain a pre-solution;
2) Stirring the pre-solution, adding strong base, and performing coprecipitation to obtain suspension;
3) Mixing the suspension with a complexing agent solution, and performing aging treatment to obtain an aging solution;
4) Filtering out powdery precipitates in the aging liquid, cleaning, mixing with a lithium source, and performing ball milling to obtain a precursor;
5) And calcining the precursor to obtain the modified ternary cathode material with high capacity and long service life.
According to the method, three salts of nickel, cobalt and manganese are firstly dissolved in a hydrogen chloride aqueous solution, then coprecipitation is carried out by using strong base under the stirring condition to obtain suspension containing powdery precipitate, at the moment, the uniformity of the particles of the powdery precipitate is poor, the problems that part of particles are enriched and grown after nucleation and have larger particle size, part of particles are poor in nucleation and growth condition after nucleation and the like exist, then the suspension is mixed with a complexing agent, the particles in the complexing agent are in the dynamic balance of dissolution and precipitation, so that the surface of the larger particles is partially dissolved, the smaller particles continue to grow, the particle size uniformity of the precipitate particles is realized, and crystal phase structure rearrangement is carried out in the dynamic balance process, so that the precipitate structure is more stable, and a stable precursor is obtained. And finally, mixing the precursor with a lithium source, ball-milling and calcining to obtain the ternary cathode material. The obtained cathode material has a more stable structure, and is not easy to be pulverized after long-time circulation, and the performance is rapidly reduced due to crushing.
In addition, in the preparation method of the invention, the manganese salt is selected to have trivalent manganese salt or tetravalent manganese salt to form tetravalent manganese ions in the pre-solution, and an iron source and a copper source are added. The combined action of a copper source and an iron source is adopted to form a defective structure with complex solid solution doping and excellent cycle performance of a counter electrode. Particularly, the coordination of monovalent copper and tetravalent manganese and the solid solution replacement of trivalent manganese by trivalent iron enable the precursor to form structural defects and defective oxides in the subsequent ball milling and calcining processes, the structural defects and defective oxides can provide volume expansion allowance of the anode material, the problem that components are separated and finally pulverized due to different expansion effects among the components of the anode material after a large number of charge-discharge cycles is solved, meanwhile, the formed structural defects and defective oxides cannot obviously adversely affect the structural stability of the anode material, but instead, cavities beneficial to the work of the electrode material can be formed, so that the capacitance can be better reserved in the cycle process, and the cycle performance is improved.
As a preference, the first and second liquid crystal compositions are,
the molar ratio of nickel, cobalt and manganese contained in the nickel salt, the cobalt salt and the manganese salt in the step 1) is 6:2:2 or 7:2:1;
the total molar concentration of nickel, cobalt and manganese ions in the pre-solution is 1.2-1.55 mol/L.
The nickel-cobalt-manganese ternary mixture ratio has better effect when used as a high-voltage electrode. The excessive total molar concentration of the nickel, cobalt and manganese metal ions can cause the precipitation of precipitate particles to be easily enriched and have too large particle size, and the excessive concentration can also cause the problems of too small particle size of partial precipitate particles and the like, so that the performance of the cathode material is reduced.
As a preference, the first and second liquid crystal compositions are,
the nickel salt in the step 1) is any one or more of nickel chloride, nickel sulfate and nickel nitrate;
the cobalt salt in the step 1) is any one or more of cobalt chloride, cobalt sulfate and cobalt nitrate;
the manganese salt in the step 1) is prepared by mixing manganese chloride and manganese trichloride in a molar ratio of 1: (0.05-0.1) mixing the mixed salt or the manganese chloride and the manganese tetrachloride according to the molar ratio of 1: (0.02-0.06) mixed salt;
the concentration of the aqueous solution of the hydrogen chloride in the step 1) is 2.0-3.0 mol/L.
The raw materials are wide in source, easy to obtain and low in price. In addition, when dissolved in water, manganese trichloride is disproportionated to generate bivalent manganese ions and tetravalent manganese ions, while when dissolved in water, manganese tetrachloride can directly form tetravalent manganese ions, and the existence of tetravalent manganese ions is the key in the preparation process. The aqueous hydrogen chloride solution having the above concentration ensures the dissolution of substances such as cuprous chloride.
As a preference, the first and second liquid crystal compositions are,
step 1) the copper source is a mixture of elemental copper and cuprous salt;
the ferrous salt is cuprous chloride;
the molar ratio of the simple substance copper to the cuprous salt is 1: (6-8);
step 1), the iron source is ferrous salt;
the ferrous salt is any one or more of ferrous chloride, ferrous sulfate and ferrous nitrate.
Cuprous salt and simple substance copper are used as copper sources, the purpose is to keep the stability of cuprous ions by using the simple substance copper, and the simple substance copper powder can be dispersed in a pre-solution as nucleation growth points by using copper powder with the particle size of 800 meshes or more, which is beneficial to improving the uniformity of the particle size of precipitates. Ferrous salt is selected as the iron source, so that the oxidation of cuprous and elementary copper can be avoided, and the stability of the pre-solution is kept.
As a preference, the first and second liquid crystal compositions are,
the molar weight of the copper element contained in the copper source, the molar weight of the iron element contained in the iron source and the total molar weight of the nickel, cobalt and manganese elements are in a proportion of (0.01-0.03): (0.02 to 0.04): 1.
if the amount of the iron source and the copper source is too large, the defects in the positive electrode material are too large, and thus the problem of pulverization of the positive electrode material due to structural collapse occurs. And when the amount is too small, a good modification effect cannot be produced.
As a matter of preference,
the strong base in the step 2) is sodium hydroxide or potassium hydroxide;
step 2) adding strong base to adjust the pH value of the solution to 10.0-10.6;
the stirring speed in the step 2) is 450-600 rpm.
The strong base is common and readily available. Under the condition of the pH value, a good coprecipitation effect can be realized, and the excessive alkalinity can cause the excessive precipitation rate of the precipitate to generate blocky precipitate. And the problem of material waste is caused by incomplete precipitation of nickel, cobalt and manganese in the pre-solution due to the over-low pH value. Under the condition of the stirring rotating speed, the shearing at a certain degree can be realized, and the precipitate with overlarge particle size generated in the precipitation process is avoided.
As a preference, the first and second liquid crystal compositions are,
step 3), the complexing agent is ammonia water with the concentration of 1.5-2.0 mol/L;
step 3) mixing the suspension and a complexing agent in a volume ratio of 1: (1.5-2.0);
in the step 3), the aging time is 4-6 h, and the aging temperature is 30-40 ℃.
The ammonia water is used as a complexing agent, so that the dynamic balance amplitude of precursor dissolution and crystallization in the aging process can be improved, the aging effect is improved, and internal rearrangement, secondary nucleation and secondary growth of precipitate particles are facilitated.
As a preference, the first and second liquid crystal compositions are,
step 4), the lithium source is any one or more of lithium carbonate, lithium hydroxide, lithium acetate and lithium oxalate;
the mass ratio of the precursor to the lithium source is 1 (0.3-0.5);
and 4) performing ball milling for 3-6 h at 500-600 ℃.
The lithium sources are common and easily available lithium sources. Ball milling is carried out under the temperature condition, and the precursor and the lithium source can be effectively mixed. The heating ball milling under the above conditions is favorable for improving the mixing effect of the precursor and the lithium source.
As a preference, the first and second liquid crystal compositions are,
and 5) calcining the mixture at 800-1050 ℃ for 8-12 h.
The precursor is high in structural stability and density after aging, and a lithium source is difficult to directly and uniformly mix with the components of the precursor, so that the lithium element is further calcined to be uniformly diffused on the precursor to form the anode material, and Liu Yu ferric iron is calcined to carry out solid solution replacement on the ferric manganese.
The invention has the beneficial effects that:
1) The preparation method is simple and efficient;
2) The obtained anode material has higher normal pressure (3.0V) gram capacity;
3) The obtained cathode material has good normal-pressure cycle performance.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Unless otherwise specified, all the raw materials used in the examples of the present invention are commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.
Example 1
A preparation method of a modified ternary cathode material with high capacity and long service life comprises the following preparation steps:
1) Nickel chloride, cobalt chloride and manganese salt (manganese chloride and manganese trichloride in a molar ratio of 1: mixed salt mixed in a ratio of 0.05) at 6:2:2, dissolving the mixture in 2.0mol/L aqueous solution of hydrogen chloride, and adding a copper source and an iron source to obtain a pre-solution with the total molar concentration of nickel, cobalt and manganese ions being 1.2 mol/L;
wherein: the molar ratio of 800-mesh elementary copper to cuprous chloride in the copper source is 1:6; the iron source is ferrous chloride; the proportion of the molar weight of the copper element contained in the copper source, the molar weight of the iron element contained in the iron source and the total molar weight of the three elements of nickel, cobalt and manganese is 0.01:0.02:1;
2) Stirring the pre-solution at 450rpm, adding sodium hydroxide to adjust the pH value of the solution to 10.3 +/-0.3, and performing coprecipitation for 15min to obtain a suspension;
3) Mixing the suspension with ammonia water with the concentration of 1.5mol/L in a volume ratio of 1:1.5, and performing aging treatment at 30 ℃ for 6 hours to obtain an aging solution;
4) Filtering out powdery precipitate in the aging solution, soaking and washing the powdery precipitate for 5 times by using deionized water, mixing the powdery precipitate with 0.3 times of lithium carbonate by weight, and performing ball milling at 500 ℃ for 6 hours to obtain a precursor;
5) And calcining the precursor at 800 ℃ for 12h to obtain the modified ternary cathode material with high capacity and long service life.
Example 2
A preparation method of a modified ternary cathode material with high capacity and long service life comprises the following preparation steps:
1) Nickel chloride, cobalt chloride and manganese salts (manganese chloride to manganese tetrachloride in a molar ratio of 1: mixed salt mixed in a ratio of 0.02) at 6:2:2, dissolving in 2.0mol/L aqueous solution of hydrogen chloride, and adding a copper source and an iron source to obtain a pre-solution with the total molar concentration of nickel, cobalt and manganese ions of 1.2 mol/L;
wherein: the molar ratio of 800-mesh elementary copper to cuprous chloride in the copper source is 1:6; the iron source is ferrous chloride; the proportion of the molar weight of the copper element contained in the copper source, the molar weight of the iron element contained in the iron source and the total molar weight of the three elements of nickel, cobalt and manganese is 0.01:0.02:1;
2) Stirring the pre-solution at 450rpm, adding sodium hydroxide to adjust the pH value of the solution to 10.3 +/-0.3, and performing coprecipitation for 15min to obtain a suspension;
3) Mixing the suspension with ammonia water with the concentration of 1.5mol/L in a volume ratio of 1:1.5, and performing aging treatment at 30 ℃ for 6 hours to obtain an aging solution;
4) Filtering out powdery precipitate in the aging solution, soaking and washing the powdery precipitate for 5 times by using deionized water, mixing the powdery precipitate with 0.3 times of lithium carbonate by weight, and performing ball milling at 500 ℃ for 6 hours to obtain a precursor;
5) And calcining the precursor at 800 ℃ for 12 hours to obtain the modified ternary cathode material with high capacity and long service life.
Example 3
A preparation method of a modified ternary cathode material with high capacity and long service life comprises the following preparation steps:
1) Nickel chloride, cobalt chloride and manganese salt (manganese chloride to manganese trichloride in a molar ratio of 1: mixed salt mixed in a ratio of 0.1) at 7:2:1, dissolving the mixture in a 3.0mol/L aqueous solution of hydrogen chloride, and adding a copper source and an iron source to obtain a pre-solution with the total molar concentration of nickel, cobalt and manganese ions of 1.55 mol/L;
wherein: the molar ratio of 800-mesh elementary copper to cuprous chloride in the copper source is 1:8; the iron source is ferrous chloride; the proportion of the molar weight of the copper element contained in the copper source, the molar weight of the iron element contained in the iron source and the total molar weight of the three elements of nickel, cobalt and manganese is 0.03:0.04:1;
2) Stirring the pre-solution at 600rpm, adding sodium hydroxide to adjust the pH value of the solution to 10.3 +/-0.3, and performing coprecipitation for 15min to obtain a suspension;
3) Mixing the suspension with ammonia water with the concentration of 2.0mol/L in a volume ratio of 1:2.0, and performing aging treatment at 40 ℃ for 4 hours to obtain an aging solution;
4) Filtering out powdery precipitate in the aging solution, soaking and washing the powdery precipitate for 5 times by using deionized water, and mixing the powdery precipitate with 0.5-time weight part of a mixture of lithium acetate and lithium oxalate (the molar ratio is 1: 1) Mixing, and ball-milling at 600 ℃ for 3h to obtain a precursor;
5) And calcining the precursor at 1050 ℃ for 8 hours to obtain the modified ternary cathode material with high capacity and long service life.
Example 4
A preparation method of a modified ternary cathode material with high capacity and long service life comprises the following preparation steps:
1) Nickel chloride, cobalt chloride and manganese salts (manganese chloride to manganese tetrachloride in a molar ratio of 1: mixed salt mixed in a ratio of 0.06) at 7:2:1, dissolving the mixture in a 3.0mol/L aqueous solution of hydrogen chloride, and adding a copper source and an iron source to obtain a pre-solution with the total molar concentration of nickel, cobalt and manganese ions of 1.55 mol/L;
wherein: the molar ratio of 800 meshes of simple substance copper to cuprous chloride in the copper source is 1:8; the iron source is ferrous chloride; the proportion of the molar weight of the copper element contained in the copper source, the molar weight of the iron element contained in the iron source and the total molar weight of the three elements of nickel, cobalt and manganese is 0.03:0.04:1;
2) Stirring the pre-solution at 600rpm, adding sodium hydroxide to adjust the pH value of the solution to 10.3 +/-0.3, and performing coprecipitation for 15min to obtain a suspension;
3) Mixing the suspension with ammonia water with the concentration of 2.0mol/L in a volume ratio of 1:2.0, and performing aging treatment at 40 ℃ for 4 hours to obtain an aging solution;
4) Filtering out powdery precipitate in the aging solution, soaking and washing the powdery precipitate for 5 times by using deionized water, and mixing the powdery precipitate with 0.5-time weight part of a mixture of lithium acetate and lithium oxalate (the molar ratio is 1: 1) Mixing, and ball-milling at 600 ℃ for 3h to obtain a precursor;
5) And calcining the precursor at 1050 ℃ for 8 hours to obtain the modified ternary cathode material with high capacity and long service life.
Example 5
A preparation method of a modified ternary cathode material with high capacity and long service life comprises the following preparation steps:
1) Nickel chloride, cobalt chloride and manganese salt (manganese chloride, manganese trichloride and manganese tetrachloride in a molar ratio of 1:0.05: mixed salt mixed in a ratio of 0.03) at 7:2:1, dissolving the mixture in a 3.0mol/L aqueous solution of hydrogen chloride, and adding a copper source and an iron source to obtain a pre-solution with the total molar concentration of nickel, cobalt and manganese ions of 1.55 mol/L;
wherein: the molar ratio of 800-mesh elementary copper to cuprous chloride in the copper source is 1:8; the iron source is ferrous chloride; the proportion of the molar weight of the copper element contained in the copper source, the molar weight of the iron element contained in the iron source and the total molar weight of the three elements of nickel, cobalt and manganese is 0.03:0.04:1;
2) Stirring the pre-solution at 600rpm, adding sodium hydroxide to adjust the pH value of the solution to 10.3 +/-0.3, and performing coprecipitation for 15min to obtain a suspension;
3) Mixing the suspension with ammonia water with the concentration of 2.0mol/L in a volume ratio of 1:2.0, and performing aging treatment at 40 ℃ for 4 hours to obtain an aging solution;
4) Filtering out powdery precipitate in the aging solution, soaking and washing the powdery precipitate for 5 times by using deionized water, and mixing the powdery precipitate with 0.5-time weight part of a mixture of lithium acetate and lithium oxalate (the molar ratio is 1: 1) Mixing, and ball-milling at 600 ℃ for 3h to obtain a precursor;
5) And calcining the precursor at 1050 ℃ for 8 hours to obtain the modified ternary cathode material with high capacity and long service life.
Comparative example 1
The specific procedure was the same as in example 5, except that: the manganese salts are all manganese chloride (MnCl) 2 ）。
Comparative example 2
The specific procedure was the same as in example 5, except that: no iron source and copper source were added.
Comparative example 3
The specific procedure was the same as in example 5, except that: the manganese salts are all manganese chloride (MnCl) 2 ) And no iron source and copper source are added.
Comparative example 4
The specific procedure was the same as in comparative example 3, except that: aging treatment is not carried out.
And (3) carrying out cycle performance test on the prepared cathode material. The test results are shown in table 1 below.
Table 1: and (5) testing the cycle performance.
| Positive electrode material Source | Capacity protection for 800 cycles The holding rate (20 +/-1 ℃, 0.1C/3.0V) | capacity protection for 800 cycles The holding rate (45 +/-1 ℃, 0.1C/3.0V) | capacity of 800 cycles Retention rate (20. + -.1) ℃，1C/3.0V) | 60 ℃/7d thick Degree of expansion | At 85 deg.C/12 h Change in particle size Percentage of | 1C/ 3.6V | Acupuncture and moxibustion |
| Example 1 | 96.42% | 93.41% | 89.42% | 2.1% | +0.7% | Pass | Pass |
| Example 2 | 96.11% | 93.07% | 87.32% | 2.4% | +0.8% | Pass | Pass |
| Example 3 | 96.71% | 93.65% | 90.11% | 2.2% | +0.7% | Pass | Pass |
| Example 4 | 96.12% | 92.99% | 86.94% | 2.3% | +0.7% | Pass | Pass |
| Example 5 | 97.65% | 95.02% | 91.42% | 2.1% | +0.7% | Pass | Pass |
| Comparative example 1 | 69.42% | 64.12% | 60.79% | 6.5% | +3.5% | Pass | Pass |
| Comparative example 2 | 65.11% | 58.98% | 52.93% | 11.4% | +4.8% | Pass | Pass |
| Comparative example 3 | 71.12% | 68.32% | 62.16% | 12.67% | +5.1% | Pass | Pass |
| Comparative example 4 | 46.12% | 39.11% | 24.32% | 18.34% | +6.7% | Pass | Pass |
As is obvious from the detection results in the table, the cathode material prepared by the embodiment of the invention shows excellent cycle performance in the temperature ranges of normal temperature (20 +/-1 ℃) and medium temperature (45 +/-1 ℃) and under the working conditions of 0.1C/3.0V and 1.0C/3.0V.
Claims (8)
1. A preparation method of a modified ternary cathode material, which is characterized in that,
the preparation method comprises the following preparation steps:
1) Dissolving nickel salt, cobalt salt and manganese salt into aqueous solution of hydrogen chloride, and adding a copper source and an iron source to obtain a pre-solution; the molar ratio of nickel, cobalt and manganese contained in the nickel salt, the cobalt salt and the manganese salt is 6:2:2 or 7:2:1; the manganese salt is prepared by mixing manganese chloride and manganese trichloride in a molar ratio of 1: (0.05-0.1) mixing the mixed salt or the manganese chloride and the manganese tetrachloride according to the molar ratio of 1: (0.02-0.06) mixed salt; the copper source is a mixture of elemental copper and cuprous salt; the cuprous salt is cuprous chloride; the molar ratio of the simple substance copper to the cuprous salt is 1: (6-8); the iron source is ferrous salt; the ferrous salt is any one or more of ferrous chloride, ferrous sulfate and ferrous nitrate;
2) Stirring the pre-solution, adding strong base, and performing coprecipitation to obtain suspension;
3) Mixing the suspension with a complexing agent solution, and performing aging treatment to obtain an aging solution;
4) Filtering out powdery precipitates in the aging liquid, cleaning, mixing with a lithium source, and performing ball milling to obtain a precursor;
5) And calcining the precursor to obtain the modified ternary cathode material.
2. The method for preparing the modified ternary cathode material according to claim 1,
the total molar concentration of nickel, cobalt and manganese ions in the pre-solution is 1.2-1.55 mol/L.
3. The method according to claim 1, wherein the positive electrode material is a modified ternary positive electrode material,
the nickel salt in the step 1) is any one or more of nickel chloride, nickel sulfate and nickel nitrate;
the cobalt salt in the step 1) is any one or more of cobalt chloride, cobalt sulfate and cobalt nitrate;
the concentration of the aqueous solution of the hydrogen chloride in the step 1) is 2.0-3.0 mol/L.
4. The method according to claim 1, wherein the positive electrode material is a modified ternary positive electrode material,
the molar weight of the copper element contained in the copper source, the molar weight of the iron element contained in the iron source and the total molar weight of the nickel, cobalt and manganese elements are in a proportion of (0.01-0.03): (0.02-0.04): 1.
5. the method according to claim 1, wherein the positive electrode material is a modified ternary positive electrode material,
the strong base in the step 2) is sodium hydroxide or potassium hydroxide;
step 2) adding strong base to adjust the pH value of the solution to 10.0-10.6;
the stirring speed of the step 2) is 450-600 rpm.
6. The method according to claim 1, wherein the positive electrode material is a modified ternary positive electrode material,
step 3), the complexing agent is ammonia water with the concentration of 1.5-2.0 mol/L;
step 3) mixing the suspension and a complexing agent in a volume ratio of 1: (1.5-2.0);
in the step 3), the aging time is 4-6 h, and the aging temperature is 30-40 ℃.
7. The method according to claim 1, wherein the positive electrode material is a modified ternary positive electrode material,
the lithium source in the step 4) is any one or more of lithium carbonate, lithium hydroxide, lithium acetate and lithium oxalate;
the mass ratio of the precursor to the lithium source is 1 (0.3-0.5);
and 4) performing ball milling for 3-6 h at 500-600 ℃.
8. The method for preparing the modified ternary cathode material according to claim 1,
and 5) calcining the mixture at 800-1050 ℃ for 8-12 h.
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