CN112250119A - Preparation method of nickel-manganese binary precursor with high electrochemical performance - Google Patents
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Abstract
The invention provides a preparation method of a nickel-manganese binary precursor with high electrochemical performance, belonging to the technical field of battery materials. In the method, in the process of synthesizing a binary precursor by a wet method, a template agent and a structure control agent are added during a coprecipitation reaction; and then filtering, washing, drying, presintering at high temperature and calcining the mixed lithium to obtain a binary precursor product. The precursor surface structure skeleton is constructed in the precursor wet synthesis stage, the problem of reduction of cycle performance caused by structural collapse of the conventional positive electrode material is solved, cobalt-free positive electrode material is realized, the manufacturing cost of the positive electrode material is greatly reduced, and the method has great commercial value.
Description
Technical Field
The invention relates to the field of lithium ion battery anode materials, in particular to a preparation method of a nickel-manganese binary precursor with high electrochemical performance.
Background
In the field of power batteries, after decades of iterative updating, a main fluid system is a lithium iron phosphate system and a ternary system. Compared with lithium iron phosphate, the ternary system has remarkable advantages in energy density, working voltage and low-temperature operation. But the disadvantages are very obvious, high price, poor cycle performance and poor safety. The main reason for its high price is that cobalt in ternary materials is expensive. In order to reduce the cost of the ternary system, the research direction is developed towards low cobalt and even no cobalt. Cobalt has the functions of stabilizing the layered structure and improving the diffusion efficiency of lithium ions in the ternary system, and the electrochemical performance of the ternary system can be influenced by simply reducing the content of cobalt.
CN111434618A discloses a preparation method of a cobalt-free layered cathode material. After the nickel lithium manganate matrix is synthesized, an inorganic inert material is coated on the surface, so that the function of stabilizing the structure is realized. However, an interface exists between the cladding layers, and due to different components between the cladding layers, different volume changes occur in the battery charging and discharging process, and the cycle performance of the battery is poor. In addition, the method is a method of adding inert materials during the later dry sintering, and has complex process and is not suitable for industrial production. CN105322154A discloses a precursor nickel manganese oxide of electrode active material with special morphology. The synthesis steps are simple, the raw materials are low in price, the conditions in the wet synthesis process are easy to control, and the surfactant is added in the wet synthesis process, so that the binary precursor of the binary precursor has a more regular shape, but the binary precursor cannot be produced in large batch.
Disclosure of Invention
In order to overcome the current situation that the control of the compact degree of the binary precursor stacking structure is difficult to realize and other indexes such as sphericity, oxidation degree, primary particle thickness and the like are not influenced in the current binary precursor synthesis process, the invention provides a preparation method of a nickel-manganese binary precursor with high electrochemical performance.
The solution of the invention is realized by the following steps:
a preparation method of a nickel-manganese binary precursor with high electrochemical performance is characterized by comprising the following steps:
(1) in the process of synthesizing the binary precursor by a wet method, a template agent and a structure control agent are added during the coprecipitation reaction;
(2) and filtering, washing, drying, presintering at high temperature, and calcining the mixed lithium to obtain a binary precursor product.
On the basis, the preparation method of the nickel-manganese binary precursor with high electrochemical performance comprises the following steps:
(1) preparing a mixed solution A containing ammonia water and a template agent;
(2) preparing a mixed solution B containing a template agent, nickel salt and manganese salt;
(3) preparing a strong base solution and a reaction kettle bottom solution C containing ammonia water and a strong alkali solution;
(4) preparing a structure control agent solution;
(5) under the conditions of stirring, heating and introducing nitrogen, simultaneously injecting the mixed solution A, the mixed solution B, the structure control agent solution and the strong base solution into the bottom solution of the reaction kettle, controlling the pH and the temperature, and reacting to obtain the slurry of the nickel-manganese binary precursor;
(6) and filtering, washing, drying, presintering at high temperature, and calcining with lithium mixture to obtain the porous carbon-coated nickel-manganese binary anode material.
Further, in the mixed solution A of the ammonia water and the template agent, the concentration of the ammonia water is 0.5-5mol/L, the template agent is one or more of citric acid, ethylene diamine tetraacetic acid, disodium ethylene diamine tetraacetic acid, crown ether, amino acid and the like, and the concentration of the template agent is 0.1-4 mol/L.
Further, in the mixed solution B of the template agent, the nickel salt and the manganese salt, the type of the template agent is the same as that in the previous step, and the concentration of the template agent is 0.01-2 mol/L; the nickel salt and the manganese salt are one or more of nitrate, sulfate, chloride or halogen salt, and the total concentration of the nickel salt and the manganese salt is 0.5-5 mol/L.
Further, the concentration of ammonia water in the reaction kettle bottom liquid C is 0.1-8mol/L, and the pH value is 10.5-13.0; the strong alkali solution is one or more of sodium hydroxide and potassium hydroxide, the concentration of the strong alkali solution is 0.001-0.2mol/L, and the concentration of the structure control agent in the structure control agent solution is 0.05-3 mol/L.
Further, the structure control agent is one or more of phthalein coupling agents (such as tetrabutyl titanate, tetrapropyl titanate, tetraethyl titanate, and the like).
Further, in the reaction process, the temperature of C, pH is controlled to be 50-80 degrees in the reaction kettle to be 10.5-12.5, the reaction time is controlled to be 0.5-10h, and the ammonia concentration is controlled to be 0.2-2 mol/L.
Further, the temperature of pure water for washing the slurry containing the binary precursor is 60-80 ℃, and the washing time is 2-8 h.
Furthermore, the drying temperature of the slurry containing the binary precursor is 100-150 ℃, and the drying time is 3-12 h.
Further, the pre-sintering temperature of the binary precursor drying material is 200-400 ℃, and the pre-sintering time is 1-5 h.
Further, the calcination temperature of the binary precursor oxide mixed lithium is 400-800 ℃, and the calcination time is 5-8 h.
According to the invention, the structure control agent is added in the reaction stage of the binary precursor, the structure control agent is decomposed at high temperature to generate gas, and a through pore channel structure is formed in the binary precursor in the expansion and release process of the gas, so that the tightness of the stacked structure of the binary precursor is influenced.
According to the invention, the structure control agent is added in the synthesis process of the nickel-manganese binary precursor, a structural framework is formed on the surface of the binary precursor, and the structural pulverization caused by lattice stress in the charge-discharge cycle process of the nickel-manganese binary precursor as the anode material in the later period is inhibited. Meanwhile, a channel is formed on the inorganic inert structure framework by adding the template agent, and a porous structure is formed in the pre-sintering process, so that the lithium ion deintercalation and the electrolyte infiltration are facilitated. In the secondary sintering process, the structure control agent is carbonized to realize carbon coating, and metal elements are reserved, so that uniform element doping is realized, and the cycle stability of the anode material is improved to some extent. The precursor surface structure skeleton is constructed in the precursor wet synthesis stage, the problem of reduction of cycle performance caused by structural collapse of the conventional positive electrode material is solved, cobalt-free positive electrode material is realized, the manufacturing cost of the positive electrode material is greatly reduced, and the method has great commercial value.
Compared with the prior art, the invention has the following technical effects:
1. the compactness of the binary precursor accumulation is controllable, the lithium ion diffusion efficiency of the corresponding anode material can be further improved, and the multiplying power is improved;
2. the addition of the structure control agent does not change the primary particle thickness of the binary precursor and the stacking order degree, and is favorable for deeply researching the influence of single factors (primary particle thickness, stacking compactness and the like) on the electrochemical performance of the cathode material;
3. the structure control agent generates gas from inside to outside during pyrolysis, can spontaneously maintain the anaerobic environment in a reaction system, and is beneficial to reducing the cost of industrialization;
4. after the structuring agent is decomposed, a layer of carbon coating is formed on the surface, and metal elements in the structuring agent are coated on the surface of the precursor, so that the later-stage electrochemical performance is promoted to be improved;
5. meanwhile, the template agent and the structure control agent are added, so that a structure framework is formed, and a channel is formed on the framework, thereby being beneficial to lithium ion deintercalation and electrolyte infiltration.
6. The raw materials adopted for preparing the material are low in price, the preparation method is simple, and the requirement on experimental equipment is low. The preparation process conditions are easy to control, and the continuous industrial production is easy to realize.
Drawings
Fig. 1 is an SEM photograph of the binary precursor prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples and figures.
The chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
Example 1:
the embodiment comprises the following steps:
(1) preparing a mixed ammonia solution according to 1mol/L ammonia water and 1mol/L citric acid;
(2) according to the molar ratio of 2mol/L of citric acid to the sulfate of nickel salt to the sulfate of manganese salt of 9: 1 and the total concentration of the metal salt is 3mol/L to prepare mixed salt solution;
(3) preparing a reaction kettle bottom solution according to the ammonia water concentration of 1mol/L and the pH value of 12.0;
(4) preparing tetrabutyl titanate solution with the concentration of 0.2mol/L as a structure control agent solution;
(5) injecting the mixed salt solution, the mixed ammonia water solution, the structure control agent solution and the sodium hydroxide solution into the bottom solution of the reaction kettle, keeping the temperature of the reaction kettle at 50 ℃, stirring at the speed of 500rpm, and keeping the nitrogen atmosphere for reacting for 8 hours to obtain reaction slurry;
(6) and (3) washing the reaction slurry obtained after the step (5) by pure water at 60 ℃ for 3h, then drying in a forced air oven at the temperature of 130 ℃ for 8h, and then pre-burning in a tubular furnace at 220 ℃ for 3h to obtain a binary precursor oxide.
(7) And (4) calcining the binary precursor oxide obtained in the step (6) in a tubular furnace at 600 ℃ for 4h to obtain the binary anode material.
As shown in FIG. 1, SEM of the binary cathode material prepared in example 1 shows a loose packing structure, and nitrogen adsorption and desorption tests show that the specific surface area is 25m2The material has the following characteristics of a/g typical mesoporous material, wherein the internal pore diameter type is IV type, the hysteresis ring type is H4 type, and the average pore diameter is 50 nm.
Example 2:
the embodiment comprises the following steps:
(1) preparing a mixed ammonia solution according to 1.5mol/L ammonia water and 1.5mol/L ethylene diamine tetraacetic acid;
(2) according to the technical scheme, the molar ratio of sulfate of 3mol/L ethylenediamine tetraacetic acid, nickel salt and manganese salt is 8: 2, preparing a mixed salt solution with the metal salt concentration of 4.5 mol/L;
(3) preparing a reaction kettle bottom solution according to the ammonia water concentration of 1.5mol/L and the pH value of 12.5;
(4) preparing tetrapropyl titanate solution with the concentration of 0.5mol/L as structure control agent solution;
(5) injecting the mixed salt solution, the mixed ammonia water solution, the structure control agent solution and the sodium hydroxide solution into the bottom solution of the reaction kettle, keeping the temperature of the reaction kettle at 60 ℃, stirring at the speed of 600rpm, and keeping the nitrogen atmosphere for reaction for 5 hours to obtain reaction slurry;
(6) washing the reaction slurry after the step (5) for 2.5h by pure water at 65 ℃, wherein the washing material Na: 32. and S, 301, drying for 6 hours at the temperature of 140 ℃ in a blast oven, and finally pre-burning for 3.5 hours at the temperature of 230 ℃ in a tubular furnace to obtain a binary precursor.
(7) And (4) calcining the binary precursor oxide obtained in the step (6) in a tube furnace at 650 ℃ for 9h to obtain the binary anode material.
The binary precursor prepared in example 2 has a specific surface area of 30m as shown in nitrogen adsorption and desorption tests2The/g, the internal pore diameter type is IV type, the hysteresis ring type is H4 type, and the average pore diameter is 38nm, and belongs to a typical mesoporous material.
Example 3:
the embodiment comprises the following steps:
(1) preparing a mixed ammonia solution according to 0.8mol/L ammonia water and 0.8mol/L disodium ethylene diamine tetraacetate;
(2) according to the molar ratio of 0.5mol/L disodium ethylene diamine tetraacetate to the sulfate of nickel salt to the sulfate of manganese salt of 7: 3, preparing a mixed salt solution with the total concentration of the metal salt being 2 mol/L;
(3) preparing a reaction kettle bottom solution according to the ammonia water concentration of 0.8mol/L and the pH value of 11.5;
(4) preparing tetrabutyl titanate solution with the concentration of 0.8mol/L as a structure control agent solution;
(5) injecting the mixed salt solution, the mixed ammonia water solution, the structure control agent solution and the sodium hydroxide solution into the bottom solution of the reaction kettle, keeping the temperature of the reaction kettle at 55 ℃, stirring at the speed of 400rpm, and keeping the nitrogen atmosphere for reacting for 8 hours to obtain reaction slurry;
(6) and (3) washing the reaction slurry obtained after the step (5) for 2h by pure water at 70 ℃, then drying the reaction slurry in a blast oven at the temperature of 120 ℃ for 10h, and finally presintering the reaction slurry in a tubular furnace at 280 ℃ for 4h to obtain a binary precursor.
(7) And (4) calcining the binary precursor oxide obtained in the step (6) in a tube furnace at 700 ℃ for 5h to obtain the binary anode material.
The binary precursor prepared in example 3 has a specific surface area shown by nitrogen adsorption and desorption tests38m2The hysteresis ring type is H4 type, and the average pore diameter is 80 nm.
Example 4:
the embodiment comprises the following steps:
(1) preparing a mixed ammonia solution according to 2mol/L ammonia water and 2mol/L disodium ethylene diamine tetraacetate;
(2) according to the molar ratio of 0.8mol/L disodium ethylene diamine tetraacetate to the sulfate of nickel salt to the sulfate of manganese salt of 7.5: 2.5, and the total concentration of the metal salt is 4mol/L to prepare a mixed salt solution;
(3) preparing a reaction kettle bottom solution according to the ammonia water concentration of 2mol/L and the pH value of 11.0;
(4) preparing tetraethyl titanate solution with the concentration of 1.1mol/L as structure control agent solution;
(5) injecting the mixed salt solution, the mixed ammonia water solution, the structure control agent solution and the sodium hydroxide solution into the bottom solution of the reaction kettle, keeping the temperature of the reaction kettle at 65 ℃, stirring at the speed of 800rpm, and keeping the nitrogen atmosphere for reacting for 8 hours to obtain reaction slurry;
(6) and (3) washing the reaction slurry obtained after the step (5) for 1.5h by pure water at 70 ℃, then drying the reaction slurry in a blast oven at the temperature of 120 ℃ for 9h, and finally pre-burning the reaction slurry in a tubular furnace at 240 ℃ for 3.5h to obtain a binary precursor.
(7) And (4) calcining the binary precursor oxide obtained in the step (6) in a tube furnace at 700 ℃ for 4h to obtain the binary anode material.
The binary precursor structure obtained in example 4 has a specific surface area of 45m as shown by nitrogen adsorption and desorption tests2The hysteresis ring type is H4 type, and the average pore diameter is 58 nm.
Example 5:
the embodiment comprises the following steps:
(1) preparing a mixed ammonia solution according to 2.5mol/L ammonia water and 2.5mol/L disodium ethylene diamine tetraacetate;
(2) according to the molar ratio of 0.5mol/L disodium ethylene diamine tetraacetate to the sulfate of nickel salt to the sulfate of manganese salt of 8.8: 1.2, and the total concentration of the metal salt is 2mol/L to prepare a mixed salt solution;
(3) preparing a reaction kettle bottom solution according to the ammonia water concentration of 2.5mol/L and the pH value of 11.8;
(4) preparing tetrabutyl titanate solution with the concentration of 1.4mol/L as a structure control agent solution;
(5) injecting the mixed salt solution, the mixed ammonia water solution, the structure control agent solution and the sodium hydroxide solution into the bottom solution of the reaction kettle, keeping the temperature of the reaction kettle at 70 ℃, stirring at the speed of 400rpm, and keeping the nitrogen atmosphere for reacting for 8 hours to obtain reaction slurry;
(6) and (3) washing the reaction slurry obtained after the step (5) by pure water at 60 ℃ for 3h, then drying in a forced air oven at the temperature of 150 ℃ for 5h, and finally pre-burning in a tubular furnace at 290 ℃ for 3h to obtain the binary precursor.
(7) And (4) calcining the binary precursor oxide obtained in the step (6) for 6h in a tube furnace at 550 ℃ in lithium mixing manner to obtain the binary anode material.
The binary precursor obtained in example 5 has a specific surface area of 36m as shown by nitrogen adsorption and desorption tests2The hysteresis ring type is H4 type, and the average pore diameter is 45 nm.
The specific discharge capacity at 0.1C, the specific discharge capacity at 1C, and the cycle retention at 100 cycles at 1C for the precursors prepared by the methods of examples 1-5 are recorded. As a result, the electrical properties of the prepared precursor were good as shown in Table 1.
TABLE 1 cyclability of precursors prepared in examples 1-5
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| 0.1C specific discharge capacity (mAhg)-1) | 201.0 | 203.3 | 201.5 | 201.6 | 202.9 |
| Specific discharge capacity of 1C (mAhg)-1) | 185.7 | 180.9 | 182.0 | 182.5 | 183.7 |
| 1C cycle retention (%) | 96.5% | 95.5% | 94.3% | 93.1% | 96.2% |
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of a nickel-manganese binary precursor with high electrochemical performance is characterized by comprising the following steps:
(1) preparing a mixed solution A containing ammonia water and a template agent;
(2) preparing a mixed solution B containing a template agent, nickel salt and manganese salt;
(3) preparing a strong base solution and a reaction kettle bottom solution C containing ammonia water and a strong alkali solution;
(4) preparing a structure control agent solution;
(5) under the condition of stirring, injecting the mixed solution A, B, a structure control agent solution and a strong base solution into the bottom solution C of the reaction kettle, controlling the pH value and the reaction temperature of the system, and reacting to obtain reaction slurry D containing the nickel-manganese binary precursor;
(6) filtering, washing and drying the slurry D to obtain a nickel-manganese binary precursor;
(7) and (4) pre-burning the precursor obtained in the step (6), and then mixing lithium and calcining to obtain the porous carbon coated nickel-manganese binary anode material.
2. The preparation method according to claim 1, wherein in the step (1), the ammonia water concentration in the mixed solution A is 0.2-6mol/L, the template agent is one or more of citric acid, ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetic acid, crown ether, amino acid and the like, and the template agent concentration is 0.1-5 mol/L.
3. The method according to claim 1 or 2, wherein in the step (2), the type of the template is the same as that in the step (1), and the concentration of the template is 0.01 to 3 mol/L; the total concentration of the nickel salt and the manganese salt in the mixed solution B is 0.1-10 mol/L.
4. The preparation method according to claim 1, wherein in the step (3), the strong alkali solution is one or more of sodium hydroxide and potassium hydroxide, and the concentration is 0.1-5 mol/L; the concentration of ammonia water in the bottom liquid C of the reaction kettle is 0.1-10mol/L, and the concentration of strong base is 0.001-0.5 mol/L.
5. The method according to claim 1, wherein in the step (4), the structure-controlling agent is one or more of tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate, and the concentration of the structure-controlling agent is 0.01 to 5 mol/L.
6. The preparation method as claimed in claim 1, wherein in the step (5), the pH of the system is controlled to 10-13, the reaction temperature is 30-90 ℃, and the stirring rate is controlled to 200-1200 rpm.
7. The method as claimed in claim 1, wherein in the step (6), the drying temperature is 100 ℃ and 150 ℃, and the drying time is 1-12 h.
8. The preparation method according to claim 1, wherein in the step (7), the pre-sintering temperature is 200-400 ℃, the atmosphere is an oxygen atmosphere, and the pre-sintering time is 1-8 h; the calcination temperature of the lithium mixture is 400-1000 ℃, the atmosphere is nitrogen atmosphere, and the calcination time is 2-10 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114195202A (en) * | 2021-12-28 | 2022-03-18 | 中伟新材料股份有限公司 | Binary precursor and preparation method thereof, lithium ion battery anode material, lithium ion battery and power utilization equipment |
| CN115477332A (en) * | 2022-09-21 | 2022-12-16 | 广东佳纳能源科技有限公司 | Nickel-manganese binary precursor and preparation method thereof, nickel-manganese positive electrode material and battery |
| CN116282208A (en) * | 2023-02-01 | 2023-06-23 | 上海电气集团股份有限公司 | NaMn (NaMn) 1-x-y Ni x Fe y O 2 Preparation method and application thereof |
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| CN115477332B (en) * | 2022-09-21 | 2024-04-30 | 广东佳纳能源科技有限公司 | Nickel-manganese binary precursor, preparation method thereof, nickel-manganese positive electrode material and battery |
| CN116282208A (en) * | 2023-02-01 | 2023-06-23 | 上海电气集团股份有限公司 | NaMn (NaMn) 1-x-y Ni x Fe y O 2 Preparation method and application thereof |
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