CN113582253B - Quaternary positive electrode material, and preparation method and application thereof - Google Patents

Quaternary positive electrode material, and preparation method and application thereof Download PDF

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CN113582253B
CN113582253B CN202110875429.5A CN202110875429A CN113582253B CN 113582253 B CN113582253 B CN 113582253B CN 202110875429 A CN202110875429 A CN 202110875429A CN 113582253 B CN113582253 B CN 113582253B
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positive electrode
quaternary
electrode material
boron
niobium
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CN113582253A (en
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王壮
张树涛
白艳
马加力
王亚州
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Svolt Energy Technology Co Ltd
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Abstract

The invention provides a quaternary positive electrode material, 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 the first time to obtain a boron/niobium doped quaternary anode material; (2) Washing the boron/niobium doped quaternary positive electrode material obtained in the step (1), drying, mixing with boric acid, and performing secondary calcination to obtain the quaternary positive electrode material; wherein the chemical formula of the quaternary precursor in the step (1) is LiNi x Co y Mn z Al (1‑x‑y‑z) O 2 ，(0.9≤x<1、0<y<0.07、0<z<0.03 According to the invention, the ultra-high nickel anode material is subjected to regulation of a textured microstructure by a niobium/boron co-doping mechanism to stabilize a lattice structure and limit the generation of microcracks, so that the cycle life of the ultra-high nickel anode material is prolonged.

Description

Quaternary positive electrode material, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a quaternary positive electrode material, 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 of lithium ions in a positive electrode and a negative electrode during intercalation and deintercalation. The positive electrode material has direct leading effect on the performance of LIBs, so that many researchers aim to realize positive electrode materials with large capacity, high charging/discharging speed and long cycle life, and can perform reversible intercalation and deintercalation of 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 the lithium ion battery may prevent the success of this approach.
In addition, the quaternary polycrystalline material in the ultra-high nickel material has advantages in safety and cycle stability compared with the ternary positive electrode material, and is one of the materials with the most development prospect at present.
CN111302407a discloses a precursor of a high-nickel quaternary positive electrode material, a preparation method thereof, a high-nickel quaternary positive electrode material, 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 from the core of the high-nickel quaternary positive electrode material precursor to the surface, the content of cobalt and manganese is gradually increased, or the content of nickel, cobalt and aluminum is kept unchanged from the core of the high-nickel quaternary positive electrode material precursor to the surface in a preset area, the content of nickel and aluminum is gradually reduced outside the preset area, the content of cobalt and manganese is gradually increased, or the content of nickel, cobalt, aluminum and manganese is kept unchanged from the core of the high-nickel quaternary positive electrode material precursor to the surface in the preset area, the content of nickel and aluminum is gradually reduced outside the preset area, the content of cobalt and manganese is gradually increased, and the preset area comprises the core of the high-nickel quaternary positive electrode material precursor. The preparation method of the anode material is complex, and the cycle performance is poor.
CN109256543a discloses a modified nickel cobalt manganese lithium aluminate positive electrode material and a preparation method thereof, wherein nickel salt, cobalt salt and manganese salt solution are added into a precursor prepared by coprecipitation of nickel salt, cobalt salt and aluminum salt solution, and the precursor is sintered to obtain a modified nickel cobalt manganese lithium aluminate positive electrode material precursor, and then the precursor is subjected to hydrothermal reaction with graphene in a reaction kettle to obtain the modified nickel cobalt manganese lithium aluminate positive electrode material. 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 coating and modification by graphene, the hydrothermal reaction condition requirement is high, the control is difficult, and the synthesis process is 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 positive electrode material and a preparation method and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a quaternary positive electrode material, the method comprising the steps of:
(1) Mixing a quaternary precursor, a niobium source, a boron source and a lithium source, and calcining for the first time to obtain a boron/niobium doped quaternary anode material;
(2) Washing the boron/niobium doped quaternary positive electrode material obtained in the step (1), drying, mixing with boric acid, and performing secondary calcination to obtain the quaternary positive electrode material;
wherein the chemical formula of the quaternary precursor in the step (1) is LiNi x Co y Mn z Al (1-x-y-z) O 2 ，(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, 0.025, etc.)).
The cycling stability of the ultra-high nickel (Ni mole ratio > 0.9) positive electrode is poor, mainly due to surface reconstruction, singlet oxygen release, transition Metal (TM) dissolution and microcracking within the secondary particles. In addition, the above problems become more serious with the increase of nickel content, wherein particle cracks and oxygen release are considered as main causes of the cycle life decay of the nickel-rich layered positive electrode, and the invention adopts a niobium/boron co-doping mechanism to regulate the textured microstructure of the positive electrode material to stabilize the lattice structure and limit the generation of microcracks, thereby improving the cycle life of the ultra-high nickel positive electrode material. The boron coating layer is arranged on the surface of the positive electrode 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 maintained.
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, the molar ratio of lithium in the lithium source and transition metal in the quaternary precursor of step (1) 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 step (1) is 650 to 800 ℃, for example: 650 ℃, 700 ℃, 750 ℃, 800 ℃, etc.
Preferably, the time of the primary calcination is 6 to 10 hours, for example: 6h, 7h, 8h, 9h or 10h, etc.
Preferably, the primary calcination is performed under an oxygen atmosphere.
Preferably, the rotational speed of the washing in step (2) is 200 to 400rpm, for example: 200rpm, 250rpm, 300rpm, 350rpm or 400rpm, etc.
Preferably, the time of the water washing is 5 to 15min, for example: 5min, 8min, 10min, 12min or 15min, etc.
Preferably, the drying temperature is 100 to 200 ℃, for example: 100 ℃, 120 ℃, 150 ℃, 180 ℃ or 200 ℃ and the like.
Preferably, the drying time is 5 to 10 hours, for example: 5h, 6h, 7h, 8h, 9h or 10h, etc.
Preferably, the mass ratio of the boric acid and the dried boron/niobium doped quaternary positive electrode material in the step (2) 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 secondary calcination in step (2) is 250 to 350 ℃, for example: 250 ℃, 280 ℃,300 ℃, 320 ℃ or 350 ℃ and the like.
Preferably, the secondary calcination is carried out for a period of time ranging from 6 to 10 hours, for example: 6h, 7h, 8h, 9h or 10h, etc.
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 a core and a boron coating layer coated on the surface of the core, wherein the core is a boron/niobium doped quaternary positive electrode material.
In a third aspect, the invention provides a positive electrode sheet, which is characterized in that the positive electrode sheet comprises the quaternary positive electrode material according to the second aspect.
In a fourth aspect, the present invention provides a lithium ion battery comprising the positive electrode sheet according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the structural adjustment of the textured microstructure is carried out on the ultra-high nickel anode material by 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 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 maintained.
(2) The preparation method disclosed by the invention is simple in preparation process, short in period and easy to synthesize, and the prepared positive electrode material has excellent capacity, initial effect, circulation stability and the like.
Drawings
Fig. 1 is a graph of the first charge-discharge curve of the positive electrode material described in example 1.
Fig. 2 is a graph of the first charge-discharge curve of the positive electrode material described in comparative example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a quaternary positive electrode material, and the 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 transition metal: mixing the materials according to a molar ratio of Li of 1:1.025, and adding Nb accounting for 0.3 percent of the mass of the nickel-cobalt-manganese-aluminum hydroxide 2 O 5 And 0.1% by mass of B of nickel cobalt manganese aluminum hydroxide 2 O 3 Dry mixing in a mixer, calcining the dry mixed material for 8 hours in an oxygen atmosphere of 700 ℃ in a common box-type furnace, cooling, crushing and sieving to obtain a boron/niobium doped quaternary positive electrode material;
(2) Mixing the obtained boron/niobium doped quaternary positive electrode 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 accounting for 0.1% of the mass of the dried boron/niobium doped quaternary positive electrode material, carrying out dry mixing, enabling boric acid powder to be uniformly attached to the surface of the dried boron/niobium doped quaternary positive electrode material, calcining for 8h in an oxygen atmosphere at 300 ℃, cooling, and sieving to obtain the quaternary positive electrode material.
The first charge-discharge curve diagram of the quaternary positive electrode material is shown in fig. 1.
Example 2
The embodiment provides a quaternary positive electrode material, and the 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 transition metal: mixing the materials according to the molar ratio of Li of 1:1.15, and adding Nb accounting for 0.4 percent of the mass of the nickel-cobalt-manganese-aluminum hydroxide 2 O 5 And nickel cobalt manganese0.2% by mass of B 2 O 3 Dry mixing in a mixer, calcining the dry mixed material for 9 hours in an oxygen atmosphere of 750 ℃ in a common box-type furnace, cooling, crushing and sieving to obtain a boron/niobium doped quaternary positive electrode material;
(2) Mixing the obtained boron/niobium doped quaternary positive electrode material with distilled water according to a ratio of 1:1, stirring at 350rpm for 12min, placing for 18h in a vacuum drying oven at 180 ℃, drying, taking out, adding boric acid with the mass of 0.2% of the dried boron/niobium doped quaternary positive electrode material, carrying out dry mixing, enabling boric acid powder to be uniformly attached to the surface of the dried boron/niobium doped quaternary positive electrode material, calcining for 8h in an oxygen atmosphere at 320 ℃, cooling, and sieving to obtain the quaternary positive electrode material.
Example 3
This example differs from example 1 only in that Nb is described in step (1) 2 O 5 The doping amount of (2) was 0.2%, and the other conditions and parameters were exactly the same as in example 1.
Example 4
This example differs from example 1 only in that Nb is described in step (1) 2 O 5 The doping amount of (2) 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) is described as B 2 O 3 The doping amount of (2) was 0.05%, and the other conditions and parameters were exactly the same as in example 1.
Example 6
This example differs from example 1 only in that step (1) is described as B 2 O 3 The doping amount of (2) was 0.4%, and the other conditions and parameters were exactly the same as in example 1.
Example 7
This example differs from example 1 only in that the boric acid coating amount in step (2) was 0.05%, and other conditions and parameters were identical to those in example 1.
Example 8
This example differs from example 1 only in that the coating amount of boric acid in step (2) is 0.4%, and other conditions and parameters are exactly the same as in example 1.
Comparative example 1
This comparative example differs from example 1 only in that step (1) does not add Nb 2 O 5 And B 2 O 3 Other conditions and parameters were exactly the same as in example 1.
The first charge-discharge curve of the obtained quaternary positive electrode material is shown in fig. 2.
Comparative example 2
This comparative example differs from example 1 only in that step (1) does not add Nb 2 O 5 Other conditions and parameters were exactly the same as in example 1.
Comparative example 3
This comparative example differs from example 1 only in that step (1) does not add B 2 O 3 Other conditions and parameters were exactly the same as 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 other conditions and parameters are exactly the same as in example 1.
Comparative example 5
This comparative example differs from example 1 only in that the boric acid of step (2) is replaced with boric oxide, and other conditions and parameters are exactly the same as in example 1.
Performance test:
the positive electrode materials prepared in examples 1 to 8 and comparative examples 1 to 5 were used to prepare battery positive electrode slurry by uniformly mixing the positive electrode materials, carbon black conductive agent, binder PVDF and NMP in a mass ratio of 95:2.5:2.5:5. Coating the slurry on aluminum foil with the thickness of 20-40 mu M, vacuum drying and rolling to prepare a positive pole piece, taking a lithium metal piece as a negative pole, and preparing LiPF with the electrolyte ratio of 1.15M 6 DMC (1:1vol%) and assembled.
The electrical property test of the material is carried out by adopting a blue-electricity battery test system at 45 ℃, and the test voltage range is 3-4.3V; the formation capacity was tested and cycled for 50 weeks capacity retention. The test results are shown in table 1:
TABLE 1
Figure BDA0003190356710000081
Figure BDA0003190356710000091
The positive electrode material of the invention can be used for preparing batteries with specific charge capacity of more than 223.4mAh/g, specific discharge capacity of more than 202.8mAh/g, initial battery efficiency of more than 90.1%, and capacity retention rate of more than 93.4% after 50 cycles.
As can be seen from the comparison of examples 1 and 3-4, the doping amount of niobium in the step (1) affects the performance of the prepared cathode material, and the mass ratio of the niobium source to the quaternary precursor is controlled to be (0.003-0.005): 1, so that the cathode material with excellent performance can be prepared, if the doping amount of niobium is too large, the nickel divalent is increased, the lithium nickel mixing degree can be increased, and if the doping amount of niobium is too small, the structure is unstable, and the capacity and the cycle stability are poor.
As can be seen from the comparison of the examples 1 and 5-6, the doping amount of boron in the step (1) affects 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 excessive, the growth of particles is inhibited, and if the doping amount of boron is too small, the particle refinement degree is lower, and the effect of regulating the structure cannot be achieved.
As can be seen from the comparison of examples 1 and 7-8, the coating amount of the boric acid in the step (2) affects the performance of the prepared cathode material, and the mass ratio of the boric acid to the dried boron/niobium doped quaternary cathode material is controlled to be (0.001-0.003): 1, so that the cathode material with excellent performance can be prepared, if the coating amount of the boric acid is too large, the coating layer is too thick, the intercalation and deintercalation of lithium ions are inhibited, and if the coating amount of the boric acid is too small, the coating is uneven.
As can be seen from the comparison of the example 1 and the comparative examples 1-3, the invention stabilizes the lattice structure by adjusting the textured microstructure of the ultra-high nickel cathode material by a niobium/boron co-doping mechanism, and limits the generation of microcracks, thereby improving the cycle life of the ultra-high nickel cathode material.
As can be seen from the comparison of the example 1 and the comparative examples 4-5, the invention adopts boric acid as the coating agent, and the boric acid can be melted at 300 ℃ to further coat the surface of the boron/niobium doped quaternary positive electrode material, thereby forming a complete coating layer and avoiding the damage of the coating to the internal structure of the boron/niobium doped quaternary positive electrode material under the high temperature condition.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (19)

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 the first time to obtain a boron/niobium doped quaternary anode material;
(2) Washing the boron/niobium doped quaternary positive electrode material obtained in the step (1), drying, mixing with boric acid, and performing secondary calcination to obtain the quaternary positive electrode material;
wherein the chemical formula of the quaternary precursor in the step (1) is LiNi x Co y Mn z Al (1-x-y-z) O 2 ，(0.9≤x<1、0<y<0.07、0<z<0.03 The mass ratio of the niobium source to the quaternary precursor is (0.003-0.005): 1, and the mass ratio of the boron source to the quaternary precursor is (0.001-0.003): 1.
2. The method of making according to claim 1, wherein the niobium source comprises niobium pentoxide.
3. The method of manufacturing of claim 1, wherein the boron source comprises diboron trioxide.
4. The method of claim 1, wherein the lithium source comprises lithium hydroxide and/or lithium carbonate.
5. The method of claim 1, wherein the molar ratio of lithium in the lithium source to transition metal in the quaternary precursor in step (1) is from (1 to 1.5): 1.
6. The method of claim 1, wherein the temperature of the primary calcination in step (1) is 650 to 800 ℃.
7. The method of claim 1, wherein the time of the primary calcination is 6 to 10 hours.
8. The method of claim 1, wherein the primary calcination is performed under an oxygen atmosphere.
9. The method according to claim 1, wherein the rotational speed of the washing in step (2) is 200 to 400rpm.
10. The method according to claim 1, wherein the time for washing with water is 5 to 15 minutes.
11. The method according to claim 1, wherein the drying temperature is 100 to 200 ℃.
12. The method of claim 1, wherein the drying time is 5 to 10 hours.
13. The method of claim 1, wherein the mass ratio of the boric acid and the dried boron/niobium doped quaternary positive electrode material in step (2) is (0.001-0.003): 1.
14. The method of claim 1, wherein the temperature of the secondary calcination in step (2) is 250 to 350 ℃.
15. The method of claim 1, wherein the secondary calcination is carried out for a period of time ranging from 6 to 10 hours.
16. The method of claim 1, wherein the secondary calcination is performed under an oxygen atmosphere.
17. A quaternary positive electrode material, characterized in that the quaternary positive electrode material is prepared by the method of any one of claims 1-16, the quaternary positive electrode material comprises a core and a boron coating layer coated on the surface of the core, and the core is a boron/niobium doped quaternary positive electrode material.
18. A positive electrode sheet comprising the quaternary positive electrode material of claim 17.
19. A lithium ion battery comprising the positive electrode sheet of claim 18.
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