CN114956208A - High-nickel ternary cathode material, preparation method thereof and application thereof in battery preparation - Google Patents
High-nickel ternary cathode material, preparation method thereof and application thereof in battery preparation Download PDFInfo
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- 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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- H01M4/525—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 discloses a high-nickel ternary cathode material, a preparation method thereof and application thereof in battery preparation. The invention utilizes the characteristics that the fluorite type oxygen ion conductor is rich in stable oxygen vacancy and has good oxygen adsorption and storage, introduces the oxygen vacancy on the surface of the primary particle of the high-nickel anode material, and adsorbs/clamps O on the surface of the anode material ‑ 、O 2 2‑ The plasma oxygen ions oxidize the intermediate state, so that irreversible processes such as continuous oxidation or reaction with electrolyte and the like can be slowed down kinetically, and the surface oxygen ions are promoted to generate reversible oxidation-reduction processes without gas generation, thereby improving the safety of the battery.
Description
Technical Field
The invention relates to the field of preparation of lithium battery anode materials, in particular to a high-nickel ternary anode material, a preparation method thereof and application thereof in battery preparation.
Background
The new energy automobile industry which takes a high-performance power battery as one of the core technologies is a great demand for energy strategy and economic development in China. The development of new energy automobiles is a necessary way for China to move from automobile kingdom to automobile forcing nation. With the rise of a new technological revolution and industry change, the new energy automobile industry enters a new stage of accelerated development, so that strong and new power is injected for economic growth of various countries, greenhouse gas emission is reduced, climate change challenge is met, and global ecological environment is improved. In the new energy automobile industry development planning (2021 + 2035), it is pointed out that the energy density of the power battery monomer can be increased to 350Wh/kg by strengthening the technical challenges of the short plate of the power battery system with high strength, light weight, high safety, low cost and long service life. This also promotes the ternary cathode material to develop to a higher nickel ratio, so the research focus of the current ternary cathode material is the structural design and performance optimization of the high nickel ternary cathode material.
However, the current high-nickel ternary cathode material still faces many fundamental scientific and technical problems, which seriously restrict the progress of the commercialization development, and the main problem is that the electrochemical performance is sharply reduced due to poor stability. The method comprises the aspects of poor crystal thermal stability, poor particle chemical and mechanical stability, unstable anode-electrolyte interface and the like.
At present, the idea of improving the stability of high-nickel NCM mainly focuses on performing "passivation" treatment on the bulk phase or surface of a high-nickel material by using elements or materials with stable electrochemical properties from the viewpoint of Ni, so as to improve the safety and service life of the material. Although the method is beneficial to improving the stability of the high-nickel NCM, the uneven condition is easy to occur when the 'passivation' treatment is carried out on the bulk phase or the surface of the high-nickel material, and the performance of the high-nickel material is influenced; and the production cost increases, making large-scale-up difficult.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a high-nickel ternary cathode material and a preparation method thereof, and aims to obtain the high-nickel cathode material with high energy density and high safety performance.
The high-nickel ternary cathode material provided by the invention is prepared by the method comprising the following steps of:
(1) preparing a mixed salt solution: preparing a mixed salt solution containing nickel salt, cobalt salt and manganese salt;
(2) preparing oxygen ion conductor component solution: preparing oxygen ion conductor precursor components Ce salt and Sm salt into a mixed salt water solution;
(3) adding water as base solution into a reaction kettle, adding mixed salt solution, alkali liquor, ammonia water and mixed salt water solution to perform chemical reaction,
(4) after the reaction is finished, carrying out solid-liquid separation on the obtained system to obtain a powdery nickel-cobalt-manganese ternary precursor;
(5) and mixing and grinding the obtained nickel-cobalt-manganese ternary precursor and LiOH, and calcining in an oxygen atmosphere to obtain the high-nickel ternary cathode material.
In the step (1), the nickel salt, the cobalt salt and the manganese salt may be sulfates;
the molar ratio of nickel ions in the nickel salt, cobalt ions in the cobalt salt and manganese ions in the manganese salt can be x: y is 1-x-y, wherein 0< x <1, 0< y <1, preferably 0.8:0.1 in that order
In the step (2), the Ce salt may specifically be Ce (NO) 3 ) 3 ·6H 2 O；
The Sm salt may specifically be Sm (NO) 3 ) 3 ·6H 2 O；
The molar ratio of Ce ions of the Ce salt to Sm ions in the Sm salt may be 8: 2;
preferably, in the step (1), the total molar concentration of the three metal ions of nickel, cobalt and manganese in the mixed salt solution can be 0.5-2.5mol/L, specifically 2 mol/L.
The alkali liquor can be sodium hydroxide solution, wherein the molar concentration of sodium hydroxide can be 3-10mol/L, and can be 4 mol/L;
the molar concentration of the ammonia water can be 0.5-5mol/L, and specifically can be 1 mol/L;
hydrazine hydrate is added into the ammonia water for controlling the potential of a reaction system; the adding amount of hydrazine hydrate is one fourthousandth of the total volume of the liquid in the reaction kettle in the step 3);
the chemical reaction is carried out under the protection of inert gas, and the inert gas can be specifically high-purity nitrogen, argon and the like;
the flow rate of the inert gas may be 1.0-3.0m 3 H, may beIs 2.0m 3 /h；
The reaction is carried out under stirring, specifically, the stirring intensity of the stirring paddle of the reaction kettle is controlled to be 600-800r/min, preferably 700 r/min;
adjusting the pH value of the reaction system to 10-13, preferably 11-12, more preferably 11.5 by adding alkali liquor and ammonia water during the reaction;
the temperature of the reaction system may be 40 to 70 ℃, preferably 50 to 60 ℃, more preferably 55 ℃;
preferably, the flow ratio of the mixed salt solution, the mixed salt water solution, the alkali liquor and the ammonia water which are added into the reaction kettle in the step (3) in a concurrent manner can be (0.5-4):1, and can be 2:2:2: 1;
preferably, the mixed salt aqueous solution (oxygen ion conductor precursor component solution) added in step (3) is added in a total amount of 1 at% to 4 at%, preferably 3 at% of the mixed salt solution;
preferably, in step (5), the LiOH is in excess (based on powdered precursor) of 1 to 3 wt%, preferably 2 wt%;
preferably, in step (5), the calcination conditions are as follows: heating to 400-700 ℃ at the speed of 2-5 ℃/min, preserving heat for 4-8h, heating to 600-800 ℃ at the speed of 2-5 ℃/min, heating to 700-900 ℃ at the speed of 1-3 ℃/min, calcining for 11-13h, and finally cooling to 500-700 ℃ at the speed of 0.3-0.7 ℃/min;
preferably, the mixture is heated to 560 ℃ at 4 ℃/min and kept at the temperature for 6h, then heated to 700 ℃ at 3 ℃/min, heated to 800 ℃ at 2 ℃/min and calcined for 12h, and finally cooled to 600 ℃ at 0.5 ℃/min.
The high-nickel ternary cathode material prepared by the method also belongs to the protection scope of the invention.
The high-nickel ternary positive electrode material is an oxygen ion conductor Ce 0.8 Sm 0.2 O 1.9 Modified high-nickel ternary cathode material.
The application of the high-nickel ternary cathode material in the preparation of the cathode material of the battery also belongs to the protection range of the invention.
The invention also provides a battery which comprises the high-nickel ternary cathode material.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
1. the fluorite type oxygen ion conductor Ce is introduced into the primary particle surface of the high-nickel anode material in situ 0.8 Sm 0.2 O 1.9 The stable oxygen vacancy has good oxygen adsorption and storage characteristics, the high-activity intermediate product formed after oxygen ions lose electrons is stabilized by means of a specific chemical environment, the further oxidation of the intermediate product to generate oxygen is inhibited, the reversible redox process of the oxygen ions in a solid phase is facilitated, and the thermal stability of the battery is further improved.
2、Ce 0.8 Sm 0.2 O 1.9 Wherein Ce 4+ Has strong oxidizing property, can convert Ni into 2+ Oxidation to Ni 3+ Reduction of Li + /Ni 2+ Mixed arrangement, and the first ring efficiency and the structural stability of the material are improved.
3. The high-nickel anode ternary material prepared by the invention has the advantages of simple preparation, rich raw materials, low energy consumption, safe and reliable production process, low production cost and easy large-scale production.
The invention utilizes the characteristics that the fluorite type oxygen ion conductor is rich in stable oxygen vacancy and has good oxygen adsorption and storage, introduces the oxygen vacancy on the surface of the primary particle of the high-nickel anode material, and adsorbs/clamps O on the surface of the anode material - 、O 2 2- The plasma oxygen ions oxidize the intermediate state, so that irreversible processes such as continuous oxidation or reaction with electrolyte and the like can be slowed down kinetically, and the surface oxygen ions are promoted to generate reversible oxidation-reduction processes without gas generation, thereby improving the safety of the battery.
Drawings
FIG. 1 is an SEM image of a high nickel ternary cathode material prepared in example 1 of the present invention;
FIG. 2 is a DSC of the charging voltage of the ternary cathode materials of high nickel positive electrode prepared in comparative example 1 and example 3, the charging voltage range is 2.8-4.35 v.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention. The examples provided below serve as a guide for further modifications by a person skilled in the art and do not constitute a limitation of the invention in any way.
The experimental procedures in the following examples, unless otherwise indicated, are conventional and are carried out according to the techniques or conditions described in the literature in the field or according to the instructions of the products. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
By using NiSO 4 ·6H 2 O、CoSO 4 ·H 2 O and MnSO 4 ·H 2 Preparing a nickel-cobalt-manganese mixed salt solution with the total molar concentration of nickel, cobalt and manganese of 2 mol/L; the oxygen ion conductor precursor component Ce (NO) 3 ) 3 ·6H 2 O and Sm (NO) 3 ) 3 ·6H 2 O is calculated according to the molar ratio of 8: 2 preparing a mixed saline solution; adding pure water as a base solution into a reaction kettle, continuously adding a mixed salt solution, an alkali liquor, ammonia water and a mixed salt water solution in parallel flow through a flow pump, and carrying out chemical reaction on the mixed salt solution, the alkali liquor, the ammonia water and the mixed salt water solution, wherein the concentration of NaOH is 4mol/L, and NH is added 3 .H 2 The concentration of O is 1mol/L, and a proper amount of hydrazine hydrate is added (the addition amount of the hydrazine hydrate is one fourthousandth of the total volume of the liquid in the reaction kettle), a proper amount of deionized water is added into the reaction kettle, the reaction kettle is heated to 55 ℃ and is kept at a constant temperature, and N is introduced in the whole process 2 As a protective atmosphere. Then, an alkali solution and ammonia water were added dropwise to the reaction vessel until the pH was 11.5, and the mixture was sufficiently stirred at a rate of 700 r/min. The flow rate of the solution is controlled by a peristaltic pump, and the pH of the reaction kettle is regulated and controlled by a pH meter. When the reaction starts, the mixed salt solution and the mixed salt solution are pumped into the reaction kettle at certain flow rate (the total content of the added mixed salt solution is 1at percent of the mixed salt solution), and the pH value is controlled by adjusting the flow rate of the alkali liquor. And after the feeding is finished, aging for 12h, taking the material out of a discharge port, performing suction filtration, repeatedly washing the solid, and drying in a vacuum oven at 120 ℃ for 12 h. Finally, the dried precursor was weighed and the amount of LiOH was calculated (with a 2 wt% excess of LiOH, based on the powdered precursor)The weight ratio of the body, i.e. LiOH to the powdered precursor, was: 1.02:1). Using acetone as dispersant to react the precursor with LiOH & H 2 And O is fully ground and then transferred into a tubular furnace for calcination, oxygen with the flow rate of 150mL/min is introduced in the sintering process, the mixture is heated to 560 ℃ at the speed of 4 ℃/min and is kept warm for 6h, then the mixture is heated to 700 ℃ at the speed of 3 ℃/min, then the mixture is heated to 800 ℃ at the speed of 2 ℃/min and is calcined for 12h, finally the mixture is cooled to 600 ℃ at the speed of 0.5 ℃/min, and the high-nickel ternary cathode material is obtained and the active material 1 is obtained.
The morphology of the resulting product was characterized (see figure 1).
Example 2, example 3 and example 4 Ce (NO) was added in different amounts except for the addition of the oxygen ion conductor component 3 ) 3 ·6H 2 O and Sm (NO) 3 ) 3 ·6H 2 The total O content was 2 at%, 3 at% and 4 at% (1 at% in example 1), and the synthesis conditions were the same. Obtaining the high-nickel ternary cathode material to obtain the active materials 2, 3 and 4.
Comparative example 1 preparation of unmodified high-nickel ternary cathode Material
By using NiSO 4 ·6H 2 O、CoSO 4 ·H 2 O and MnSO 4 ·H 2 Preparing a nickel-cobalt-manganese mixed salt solution with the total molar concentration of nickel, cobalt and manganese of 2 mol/L; adding pure water as a base solution into a reaction kettle, continuously adding a mixed salt solution, an alkali liquor and ammonia water in parallel flow through a flow pump, and carrying out chemical reaction on the mixed salt solution, the alkali liquor and the ammonia water, wherein the concentration of NaOH is 4mol/L, and NH is 3 .H 2 The concentration of O is 1mol/L, and a proper amount of hydrazine hydrate is added (the addition amount of the hydrazine hydrate is one fourthousandth of the total volume of the liquid in the reaction kettle), a proper amount of deionized water is added into the reaction kettle, the reaction kettle is heated to 55 ℃ and is kept at a constant temperature, and N is introduced in the whole process 2 As a protective atmosphere. Then, an alkali solution and ammonia water were added dropwise to the reaction vessel to adjust the pH to 11.5 while sufficiently stirring at a rate of 700 r/min. The flow rate of the solution is controlled by a peristaltic pump, and the pH of the reaction kettle is regulated and controlled by a pH meter. When the reaction starts, the mixed salt solution is pumped into the reaction kettle at a certain flow rate, and the pH value is controlled by adjusting the flow rate of the alkali liquor. Aging for 12h after the feeding is finished, taking out the material from a discharge port, performing suction filtration, repeatedly washing the solid, and putting the solid in a vacuum oven for 12hDrying at 0 deg.C for 12 h. Finally, the dried precursor was weighed and the amount of LiOH calculated, (with 2 wt% excess LiOH). Using acetone as dispersant to react the precursor with LiOH & H 2 And O is fully ground and then transferred into a tubular furnace for calcination, oxygen with the flow rate of 150mL/min is introduced in the sintering process, the mixture is heated to 560 ℃ at the speed of 4 ℃/min and is kept warm for 6h, then the mixture is heated to 700 ℃ at the speed of 3 ℃/min, then the mixture is heated to 800 ℃ at the speed of 2 ℃/min and is calcined for 12h, finally the mixture is cooled to 600 ℃ at the speed of 0.5 ℃/min, and the unmodified high-nickel ternary cathode material is obtained after furnace cooling.
Characterization of electrochemical Properties
The high-nickel ternary positive electrode materials prepared in examples 1 to 4 and the unmodified high-nickel ternary positive electrode material prepared in comparative example 1 were respectively prepared into a button cell (CR2032), wherein the active material, the conductive agent and the binder are in a mass ratio of 90: 5, the conductive agent is Super P, the binder is PVDF, the electrolyte is 1M LiPF6 dissolved in a mixed solvent of EC, DEC and DMC (in a volume ratio of 1: 1), all button cell half-cells are assembled by using a lithium sheet as a counter electrode and a foam nickel sheet as a buffer gasket, and the water and oxygen contents in the manufacturing environment are respectively: water concentration <2ppm, oxygen concentration <2ppm and filled with argon. The test voltage range is 2.8-4.35V. And testing a first round charging and discharging curve at 0.2C, wherein the cycle curve is obtained by 1C charging and 1C discharging. The results are shown in tables 1 and 2:
TABLE 1
TABLE 2
| c | a | c/a | Li + /Ni 2+ | |
| Example 1 | 14.2193 | 2.8695 | 4.9575 | 0.28 |
| Example 2 | 14.1588 | 2.8687 | 4.9626 | 0.17 |
| Example 3 | 14.2599 | 2.8607 | 4.9847 | 0 |
| Example 4 | 14.2236 | 2.8691 | 4.9576 | 0.33 |
| Comparative example 1 | 14.1549 | 2.8680 | 4.9149 | 0.54 |
As can be seen from table 1, the high nickel ternary cathode materials prepared in examples 1 to 4 have an advantage in first discharge specific capacity and a good capacity retention rate after 100 cycles, compared to the unmodified high nickel ternary cathode material prepared in comparative example 1. When the modification amount of the oxygen ion conductor is 3 at%, the electrochemical performance of the high-nickel ternary cathode material is obviously improved, so that the embodiment 3 is the best embodiment, and the oxygen ion conductor Ce provided by the invention is illustrated 0.8 Sm 0.2 O 1.9 The modified high-nickel ternary cathode material has better electrochemical performance. The rapid capacity decay of the blank during cycling is due to the release of oxygen which causes swelling deformation of the structure, cation disorder, phase change, etc., thereby affecting the structural stability of the material. Meanwhile, a thick cSEI film is generated due to side reaction at the interface during the circulation period, and Li is further hindered + This phenomenon will also be caused by the increase in electrochemical polarization resistance and concentration polarization resistance. Oxygen ion conductor Ce 0.8 Sm 0.2 O 1.9 The better electrochemical performance of the modified high-nickel ternary cathode material is attributed to the fact that Ce is added 0.8 Sm 0.2 O 1.9 After treatment, the specific surface area of the material is increased, and the material provides more Li in the charge and discharge process + The migration sites make the material more active. Meanwhile, the transmission path is shortened and the channel is widened, thereby improving the rate capability of the material.
The ratio of c/a is often used to measure whether the resulting layered structure is good, the larger the ratio, the better the layered structure of the material. The values of c/a obtained from the table 2 are not very different and are all larger than 4.9, which indicates that the prepared material has good laminated structure, and the c/a of the example 3 is the largest, which indicates that the laminated result is optimal; and Li + /Ni 2+ The degree of cation shuffling is minimal. This is mainly due to Ce 4+ Having strong oxidizing property induces Ni 2+ Ions being oxidized to Ni 3+ Thereby reducing the mixed discharging degree of lithium and nickel and fully indicating the oxygen ion conductor Ce 0.8 Sm 0.2 O 1.9 The modification method can introduce an oxygen ion conductor and also smoothly realize Ce4 + And Sm 3+ The doping of (2) is beneficial to stabilizing the laminated structure.
FIG. 1 is an SEM image of the high-nickel ternary material prepared in example 1, and it can be seen from FIG. 1 that the ternary single-crystal material prepared in example 1 has a good single-crystal morphology, uniform particle distribution and a smooth surface.
FIG. 2 is a DSC of the charging voltage of the ternary cathode materials of high nickel positive electrode prepared in comparative example 1 and example 3, the charging voltage range is 2.8-4.35 v.
As can be seen from the test results in FIG. 2, the peak decomposition temperature of example 3 was 224.14 deg.C, the peak decomposition temperature of comparative example 1 was 211.27 deg.C, the increase was 12.87 deg.C, and the escaped lattice oxygen could be enriched with oxygen vacancy-rich Ce 0.8 Sm 0.2 O 1.9 The modification layer is captured, and the precipitation of high-activity oxygen from the body structure of the material can be effectively inhibited, so that the safety performance of the battery is improved.
The present invention has been described in detail above. It will be apparent to those skilled in the art that the invention can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention and without undue experimentation. While the invention has been described with reference to specific embodiments, it will be appreciated that the invention can be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains.
Claims (10)
1. A method for preparing a high-nickel ternary cathode material comprises the following steps: (1) preparing a mixed salt solution: preparing a mixed salt solution containing nickel salt, cobalt salt and manganese salt;
(2) preparing an oxygen ion conductor component solution: preparing oxygen ion conductor precursor components Ce salt and Sm salt into a mixed salt aqueous solution;
(3) adding water as a base solution into a reaction kettle, and adding a mixed salt solution, an alkali solution, ammonia water and a mixed salt water solution to perform chemical reaction;
(4) after the reaction is finished, carrying out solid-liquid separation on the obtained system to obtain a powdery nickel-cobalt-manganese ternary precursor;
(5) and mixing and grinding the obtained nickel-cobalt-manganese ternary precursor and LiOH, and calcining in an oxygen atmosphere to obtain the high-nickel ternary cathode material.
2. The method of preparing a high-nickel ternary positive electrode material of claim 1, wherein: in the step (1), the molar ratio of nickel ions in the nickel salt, cobalt ions in the cobalt salt and manganese ions in the manganese salt is x: y is 1-x-y, wherein 0< x <1, 0< y < 1;
in the mixed salt solution, the total molar concentration of three metal ions of nickel, cobalt and manganese is 0.5-2.5 mol/L;
in the step (2), the molar ratio of Ce ions in the Ce salt to Sm ions in the Sm salt is 8: 2.
3. the method of preparing a high-nickel ternary positive electrode material of claim 2, wherein: in the step (3), the alkali liquor is a sodium hydroxide solution, wherein the molar concentration of sodium hydroxide is 3-10 mol/L;
the molar concentration of the ammonia water is 0.5-5 mol/L;
the chemical reaction is carried out under the protection of inert gas;
the reaction is carried out with stirring;
adjusting the pH value of a reaction system to 10-13 by adding alkali liquor and ammonia water in the reaction process;
the temperature of the reaction system is 40-70 ℃.
4. The method of preparing a high-nickel ternary positive electrode material of claim 3, wherein: when the mixed salt solution, the mixed salt water solution, the alkali liquor and the ammonia water are added into the reaction kettle in parallel in the step (3), the flow ratio is (0.5-4): 1;
the total content of the mixed salt solution added in the step (3) is 1at percent to 4at percent of the mixed salt solution.
5. The method of preparing a high-nickel ternary positive electrode material of claim 4, wherein: the total content of the mixed salt solution added in the step (3) is 3 at% of the mixed salt solution.
6. The method of preparing a high-nickel ternary positive electrode material of claim 5, wherein: in the step (5), the LiOH is excessive by 1-3 wt%;
in the step (5), the calcination conditions are as follows: heating to 400-700 ℃ at a speed of 2-5 ℃/min, keeping the temperature for 4-8h, heating to 600-800 ℃ at a speed of 2-5 ℃/min, heating to 700-900 ℃ at a speed of 1-3 ℃/min, calcining for 11-13h, and finally cooling to 500-700 ℃ at a speed of 0.3-0.7 ℃/min.
7. The high-nickel ternary cathode material prepared by the method for preparing the high-nickel ternary cathode material according to any one of claims 1 to 6.
8. The high-nickel ternary positive electrode material according to claim 7, characterized in that: the high-nickel ternary positive electrode material is an oxygen ion conductor Ce 0.8 Sm 0.2 O 1.9 Modified high-nickel ternary cathode material.
9. Use of the high nickel ternary positive electrode material of claim 7 in the preparation of a battery positive electrode material.
10. A battery comprising the high nickel ternary positive electrode material of claim 7 or 8.
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| CN115954464A (en) * | 2023-03-13 | 2023-04-11 | 新乡天力锂能股份有限公司 | High-nickel anode material coated by gap type oxygen ion conductor and preparation method thereof |
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