CN113582253A - Quaternary positive electrode material and preparation method and application thereof - Google Patents
Quaternary positive electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a quaternary anode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing a quaternary precursor, a niobium source, a boron source and a lithium source, and calcining for one time to obtain a boron/niobium doped quaternary anode material; (2) to the step of(1) Washing the obtained boron/niobium-doped quaternary anode material with water, drying, mixing with boric acid, and carrying out secondary calcination to obtain the quaternary anode material; wherein, the chemical formula of the quaternary precursor in the step (1) is LiNixCoyMnzAl(1‑x‑y‑z)O2，(0.9≤x<1、0<y<0.07、0<z<0.03), the method provided by the invention has the advantages that the textured microstructure of the ultra-high nickel anode material is regulated through a niobium/boron co-doping mechanism to stabilize the lattice structure and limit the generation of microcracks, so that the cycle life of the ultra-high nickel anode material is prolonged.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a quaternary anode material, and a preparation method and application thereof.
Background
Lithium ion batteries have become the most widely used electrochemical power source at present, and the most representative of such batteries is lithium secondary batteries (LIBs) which generate electric energy by the change of chemical potential when lithium ions in a positive electrode and a negative electrode are intercalated and deintercalated. The positive electrode material has a direct leading effect on the performance of LIBs, and therefore, many researchers are dedicated to realizing a positive electrode material which has a large capacity, a fast charge/discharge speed and a long cycle life and can reversibly intercalate and deintercalate lithium ions. Currently, ultra-high nickel materials are considered to be the most promising candidate materials because they can increase the specific capacity of lithium ion batteries by increasing the nickel content. However, the resulting poor cycling stability of lithium ion batteries may hinder the success of this approach.
In addition, the quaternary polycrystalline material in the ultra-high nickel material has more advantages in safety and cycling stability than the ternary cathode material, and is one of the most promising materials at present.
CN111302407A discloses a high-nickel quaternary positive electrode material precursor and a preparation method thereof, a high-nickel quaternary positive electrode material and a preparation method thereof, and a lithium ion battery. The high-nickel quaternary positive electrode material precursor comprises nickel, cobalt, manganese and aluminum elements, the content of nickel and aluminum is gradually reduced and the content of cobalt and manganese is gradually increased from the core of the high-nickel quaternary positive electrode material precursor to the surface, or the content of nickel, cobalt and aluminum is kept unchanged in a predetermined area from the core of the high-nickel quaternary positive electrode material precursor to the surface, the content of nickel and aluminum is gradually reduced and the content of cobalt and manganese is gradually increased outside the predetermined area, or the content of nickel, cobalt, aluminum and manganese is kept unchanged in the predetermined area from the core of the high-nickel quaternary positive electrode material precursor to the surface, the content of nickel and aluminum is gradually reduced and the content of cobalt and manganese is gradually increased outside the predetermined area, and the predetermined area comprises the core of the high-nickel quaternary positive electrode material precursor. The preparation method of the cathode material is complex, and the cycle performance is poor.
CN109256543A discloses a modified nickel cobalt manganese lithium aluminate cathode material and a preparation method thereof, wherein a nickel salt solution, a cobalt salt solution and a manganese salt solution are added into a precursor prepared by coprecipitation of a nickel salt solution, a cobalt salt solution and an aluminum salt solution, and the obtained precursor is sintered to obtain a modified nickel cobalt manganese lithium aluminate cathode material precursor, and then the modified nickel cobalt manganese lithium aluminate cathode material is obtained by hydrothermal reaction with graphene in a reaction kettle. The method does not clearly indicate the electrochemical performance of the anode material before coating, the improvement of the material by adding aluminum cannot be reflected after the graphene is coated and modified, the hydrothermal reaction condition requirement is higher, the control is difficult, and the synthesis process is more complex.
The method has the problems of complex preparation process or poor cycle performance of the prepared high-nickel quaternary positive electrode material, so that the development of the high-nickel quaternary positive electrode material with simple preparation method and good cycle performance is necessary.
Disclosure of Invention
The invention aims to provide a quaternary anode material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a quaternary anode material, which comprises the following steps:
(1) mixing a quaternary precursor, a niobium source, a boron source and a lithium source, and calcining for one time to obtain a boron/niobium doped quaternary anode material;
(2) washing the boron/niobium-doped quaternary anode material obtained in the step (1) with water, drying, mixing with boric acid, and performing secondary calcination to obtain the quaternary anode material;
wherein the chemical formula of the quaternary precursor in the step (1) is LiNixCoyMnzAl(1-x-y-z)O2，(0.9≤x<1 (e.g., 0.9, 0.92, 0.95, 0.96, or 0.98, etc.), 0<y<0.07 (e.g., 0.01, 0.02, 0.03, 0.04, 0.05 or 0.06, etc.), 0<z<0.03 (e.g., 0.005, 0.001, 0.015, 0.02, or 0.025, etc.)).
The ultra-high nickel (Ni molar ratio ≥ 0.9) positive electrode has poor cycle stability mainly due to resurfacing, singlet oxygen evolution, Transition Metal (TM) dissolution and microcracking within the secondary particles. In addition, the above problems become more serious with the increase of the nickel content, wherein grain crack and oxygen release are considered as main reasons of the cycle life attenuation of the nickel-rich layered positive electrode, and the invention adopts a niobium/boron co-doping mechanism to adjust the textured microstructure of the positive electrode material to stabilize the lattice structure and limit the generation of micro cracks, thereby improving the cycle life of the ultra-high nickel positive electrode material. The boron coating layer is arranged on the surface of the anode material, so that the thermal stability and the cycle performance of the material can be improved while the high nickel capacity of the material is kept.
Preferably, the niobium source comprises niobium pentoxide.
Preferably, the boron source comprises diboron trioxide.
Preferably, the lithium source comprises lithium hydroxide and/or lithium carbonate.
Preferably, in the step (1), the molar ratio of lithium in the lithium source to the transition metal in the quaternary precursor is (1-1.5): 1, for example: 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, or 1.5:1, etc.
Preferably, the mass ratio of the niobium source to the quaternary precursor is (0.003-0.005): 1, for example: 0.003:1, 0.0035:1, 0.004:1, 0.0045:1 or 0.005:1, etc.
Preferably, the mass ratio of the boron source to the quaternary precursor is (0.001-0.003): 1, for example: 0.001:1, 0.0015:1, 0.002:1, 0.0025:1 or 0.003:1, etc.
Preferably, the temperature of the primary calcination in the step (1) is 650-800 ℃, for example: 650 deg.C, 700 deg.C, 750 deg.C or 800 deg.C, etc.
Preferably, the time of the primary calcination is 6-10 h, for example: 6h, 7h, 8h, 9h or 10h and the like.
Preferably, the primary calcination is performed under an oxygen atmosphere.
Preferably, the rotation speed of the water washing in the step (2) is 200-400 rpm, for example: 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, or the like.
Preferably, the time of the water washing is 5-15 min, for example: 5min, 8min, 10min, 12min or 15min and the like.
Preferably, the drying temperature is 100-200 ℃, for example: 100 ℃, 120 ℃, 150 ℃, 180 ℃, 200 ℃ or the like.
Preferably, the drying time is 5-10 h, for example: 5h, 6h, 7h, 8h, 9h or 10h and the like.
Preferably, the mass ratio of the boric acid and the dried boron/niobium doped quaternary cathode material in the step (2) is (0.001-0.003): 1, such as: 0.001:1, 0.0015:1, 0.002:1, 0.0025:1 or 0.003:1, etc.
Preferably, the temperature of the secondary calcination in the step (2) is 250-350 ℃, for example: 250 ℃, 280 ℃, 300 ℃, 320 ℃ or 350 ℃, and the like.
Preferably, the time of the secondary calcination is 6-10 h, for example: 6h, 7h, 8h, 9h or 10h and the like.
Preferably, the secondary calcination is performed under an oxygen atmosphere.
In a second aspect, the invention provides a quaternary positive electrode material, which is prepared by the method in the first aspect, and comprises an inner core and a boron coating layer coated on the surface of the inner core, wherein the inner core is a boron/niobium doped quaternary positive electrode material.
In a third aspect, the present invention provides a positive electrode plate, wherein the positive electrode plate contains the quaternary positive electrode material according to the second aspect.
In a fourth aspect, the invention provides a lithium ion battery, which comprises the positive electrode plate according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the textured microstructure of the ultra-high nickel anode material is regulated through a niobium/boron co-doping mechanism to stabilize the lattice structure and limit the generation of microcracks, so that the cycle life of the ultra-high nickel anode material is prolonged, and the thermal stability and cycle performance of the material can be improved while the high nickel capacity of the material is maintained by arranging the boron coating layer on the surface of the anode material.
(2) The method has the advantages of simple preparation process, short period and easy synthesis, and the prepared cathode material has excellent capacity, first effect, cycling stability and the like.
Drawings
Fig. 1 is a graph showing the first charge and discharge curves of the positive electrode material described in example 1.
Fig. 2 is a graph showing the first charge and discharge of the positive electrode material according to comparative example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a quaternary positive electrode material, and a preparation method of the quaternary positive electrode material comprises the following steps:
(1) taking nickel cobalt manganese aluminum hydroxide (molar ratio: Ni: Co: Mn: Al: 90:7:2:1) and LiOH according to the transition metal: mixing Li at a molar ratio of 1:1.025, and adding Nb in an amount of 0.3% of the mass of the Ni-Co-Mn-Al hydroxide2O5And 0.1% by mass of B based on the mass of the nickel-cobalt-manganese-aluminum hydroxide2O3Mixing in a mixer by dry method, calcining the dry mixed material in a common box furnace at 700 ℃ under oxygen atmosphere for 8h, cooling, crushing and sievingObtaining a boron/niobium doped quaternary anode material;
(2) mixing the obtained boron/niobium-doped quaternary anode material with distilled water according to a ratio of 1:1, stirring at 300rpm for 10min, placing in a vacuum drying oven at 150 ℃ for 10h, drying, taking out, adding boric acid which is 0.1% of the mass of the dried boron/niobium-doped quaternary anode material, performing dry mixing to ensure that boric acid powder is uniformly attached to the surface of the dried boron/niobium-doped quaternary anode material, calcining at 300 ℃ for 8h in an oxygen atmosphere, cooling and sieving to obtain the quaternary anode material.
The first charge-discharge curve diagram of the quaternary anode material is shown in fig. 1.
Example 2
The embodiment provides a quaternary positive electrode material, and a preparation method of the quaternary positive electrode material comprises the following steps:
(1) taking nickel cobalt manganese aluminum hydroxide (molar ratio: Ni: Co: Mn: Al: 95:2:2:1) and LiOH according to the transition metal: mixing Li at a molar ratio of 1:1.15, and adding Nb in an amount of 0.4% of the mass of the Ni-Co-Mn-Al hydroxide2O5And 0.2% by mass of B based on the mass of the nickel cobalt manganese aluminum hydroxide2O3Dry mixing in a mixer, calcining the dry mixed material in a common box furnace at 750 ℃ for 9h in an oxygen atmosphere, cooling, crushing and sieving to obtain a boron/niobium doped quaternary anode material;
(2) mixing the obtained boron/niobium-doped quaternary anode material with distilled water according to a ratio of 1:1, stirring at 350rpm for 12min, placing in a vacuum drying oven at 180 ℃ for 18h, drying, taking out, adding boric acid which is 0.2% of the mass of the dried boron/niobium-doped quaternary anode material, performing dry mixing to ensure that boric acid powder is uniformly attached to the surface of the dried boron/niobium-doped quaternary anode material, calcining at 320 ℃ in an oxygen atmosphere for 8h, cooling and sieving to obtain the quaternary anode material.
Example 3
This example differs from example 1 only in that Nb is present in step (1)2O5The amount of the dopant (C) was 0.2%, and the other conditions and parameters were exactly the same as those in example 1.
Example 4
This example differs from example 1 only in that Nb is present in step (1)2O5The amount of the dopant (D) was 0.6%, and the other conditions and parameters were exactly the same as those in example 1.
Example 5
This example differs from example 1 only in that step (1) described above as B2O3The doping amount of (2) was 0.05%, and the other conditions and parameters were exactly the same as those of example 1.
Example 6
This example differs from example 1 only in that step (1) described above as B2O3The amount of the dopant (2) was 0.4%, and the other conditions and parameters were exactly the same as those in example 1.
Example 7
This example is different from example 1 only in that the amount of boric acid coated in step (2) is 0.05%, and other conditions and parameters are exactly the same as those in example 1.
Example 8
This example is different from example 1 only in that the amount of boric acid coated in step (2) is 0.4%, and other conditions and parameters are exactly the same as those in example 1.
Comparative example 1
This comparative example differs from example 1 only in that no Nb is added in step (1)2O5And B2O3Other conditions and parameters were exactly the same as those in example 1.
The first charge-discharge curve of the prepared quaternary anode material is shown in fig. 2.
Comparative example 2
This comparative example differs from example 1 only in that no Nb is added in step (1)2O5Other conditions and parameters were exactly the same as those in example 1.
Comparative example 3
This comparative example differs from example 1 only in that step (1) does not include B2O3Other conditions and parameters were exactly the same as those in example 1.
Comparative example 4
This comparative example differs from example 1 only in that boric acid is not added in step (2) and the other conditions and parameters are exactly the same as those in example 1.
Comparative example 5
This comparative example differs from example 1 only in that the boric acid of step (2) is replaced by boric oxide, and the other conditions and parameters are exactly the same as those of example 1.
And (3) performance testing:
the positive electrode materials prepared in examples 1 to 8 and comparative examples 1 to 5 were uniformly mixed with a positive electrode material having a mass ratio of 95:2.5:2.5:5, a carbon black conductive agent, a binder PVDF, and NMP to prepare a battery positive electrode slurry. Coating the slurry on an aluminum foil with the thickness of 20-40 mu M, and preparing a positive electrode plate by vacuum drying and rolling, wherein a lithium metal plate is used as a negative electrode, and the electrolyte ratio is 1.15M LiPF6DMC (1:1 vol%), and assembling the button cell.
The electrical property test of the material is carried out by adopting a blue battery test system at 45 ℃, and the test voltage range is 3-4.3V; the formation capacity is tested, and the capacity retention rate is cycled for 50 weeks. The test results are shown in table 1:
TABLE 1
From the embodiments 1 to 8, the specific charge capacity of the battery made of the positive electrode material can reach more than 223.4mAh/g, the specific discharge capacity can reach more than 202.8mAh/g, the first battery efficiency can reach more than 90.1%, and the capacity retention rate can reach more than 93.4% after 50 cycles of cycling.
Compared with the embodiment 1 and the embodiment 3-4, the doping amount of the niobium in the step (1) influences the performance of the prepared cathode material, the mass ratio of the niobium source to the quaternary precursor is controlled to be (0.003-0.005): 1, the cathode material with excellent performance can be prepared, if the doping amount of the niobium is too large, the divalent nickel is increased, the lithium-nickel mixed discharging degree can be increased, and if the doping amount of the niobium is too small, the structure is unstable, and the capacity and the cycling stability are poor.
Compared with the embodiment 1 and the embodiments 5-6, the doping amount of boron in the step (1) can influence the performance of the prepared cathode material, the mass ratio of the boron source to the quaternary precursor is controlled to be (0.001-0.003): 1, the cathode material with excellent performance can be prepared, if the doping amount of boron is too much, the growth of particles is inhibited, and if the doping amount of boron is too little, the particle refinement degree is lower, and the structure regulation and control effect cannot be realized.
Comparing example 1 with examples 7-8, the coating amount of boric acid in step (2) affects the performance of the obtained cathode material, and the mass ratio of boric acid to the dried boron/niobium doped quaternary cathode material is controlled to (0.001-0.003): 1, so that the cathode material with excellent performance can be obtained.
Compared with the comparative examples 1 to 3, the method has the advantages that the textured microstructure of the ultra-high nickel positive electrode material is adjusted through a niobium/boron co-doping mechanism to stabilize the lattice structure, so that the generation of microcracks is limited, and the cycle life of the ultra-high nickel positive electrode material is prolonged.
Compared with the comparative examples 4 to 5, the invention has the advantages that the boric acid is adopted as the coating agent, and the boric acid can be melted at 300 ℃ due to the lower melting point of the boric acid and further coated on the surface of the boron/niobium-doped quaternary anode material, so that a complete coating layer can be formed, and the damage of the coating on the internal structure of the boron/niobium-doped quaternary anode material under the high-temperature condition can be avoided.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the quaternary positive electrode material is characterized by comprising the following steps of:
(1) mixing a quaternary precursor, a niobium source, a boron source and a lithium source, and calcining for one time to obtain a boron/niobium doped quaternary anode material;
(2) washing the boron/niobium-doped quaternary anode material obtained in the step (1) with water, drying, mixing with boric acid, and performing secondary calcination to obtain the quaternary anode material;
wherein, the chemical formula of the quaternary precursor in the step (1) is LiNixCoyMnzAl(1-x-y-z)O2，(0.9≤x<1、0<y<0.07、0<z<0.03)。
2. The method of claim 1, wherein the niobium source comprises niobium pentoxide;
preferably, the boron source comprises diboron trioxide;
preferably, the lithium source comprises lithium hydroxide and/or lithium carbonate.
3. The method according to claim 1 or 2, wherein the molar ratio of lithium in the lithium source and the transition metal in the quaternary precursor in step (1) is (1-1.5): 1;
preferably, the mass ratio of the niobium source to the quaternary precursor is (0.003-0.005): 1;
preferably, the mass ratio of the boron source to the quaternary precursor is (0.001-0.003): 1.
4. The method according to any one of claims 1 to 3, wherein the temperature of the primary calcination in the step (1) is 650 to 800 ℃;
preferably, the time of the primary calcination is 6-10 h;
preferably, the primary calcination is performed under an oxygen atmosphere.
5. The method according to any one of claims 1 to 4, wherein the water washing in the step (2) is performed at a rotation speed of 200 to 400 rpm;
preferably, the time of water washing is 5-15 min;
preferably, the drying temperature is 100-200 ℃;
preferably, the drying time is 5-10 h.
6. The method according to any one of claims 1 to 5, wherein the mass ratio of the boric acid and the dried boron/niobium doped quaternary positive electrode material in the step (2) is (0.001 to 0.003): 1.
7. The method according to any one of claims 1 to 6, wherein the temperature of the secondary calcination in the step (2) is 250 to 350 ℃;
preferably, the time of the secondary calcination is 6-10 h;
preferably, the secondary calcination is performed under an oxygen atmosphere.
8. The quaternary positive electrode material is prepared by the method of any one of claims 1 to 7, and comprises an inner core and a boron coating layer coated on the surface of the inner core, wherein the inner core is the boron/niobium doped quaternary positive electrode material.
9. A positive electrode sheet comprising the quaternary positive electrode material according to claim 8.
10. A lithium ion battery comprising the positive electrode sheet of claim 9.
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| CN114524468A (en) * | 2022-02-14 | 2022-05-24 | 浙江格派钴业新材料有限公司 | Preparation method of modified single-crystal ultrahigh-nickel quaternary NCMA positive electrode material |
| CN114864923A (en) * | 2022-04-29 | 2022-08-05 | 巴斯夫杉杉电池材料有限公司 | Boron-doped nickel-cobalt-manganese positive electrode material and preparation method thereof |
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