CN115084457A - High-compaction long-life ternary cathode material and preparation method thereof - Google Patents

High-compaction long-life ternary cathode material and preparation method thereof Download PDF

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CN115084457A
CN115084457A CN202111085689.9A CN202111085689A CN115084457A CN 115084457 A CN115084457 A CN 115084457A CN 202111085689 A CN202111085689 A CN 202111085689A CN 115084457 A CN115084457 A CN 115084457A
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small
compaction
hydroxide
particle precursor
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卢瑶
王浩
吴平
孙旭
李永红
梁正
孙全胜
张洁
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Ningxia Hanghan Graphene Technology Research Institute Co ltd
Ningxia Hanyao Graphene Energy Storage Material Technology Co ltd
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Ningxia Hanyao Graphene Energy Storage Material Technology Co ltd
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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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Abstract

The invention relates to the field of lithium ion battery cathode materials, in particular to a high-compaction long-life ternary cathode material and a preparation method thereof, wherein the raw materials of the high-compaction long-life ternary cathode material comprise a) a small-particle precursor with a single crystal or single-like morphology and an average particle size D50 of 2-4 mu m, b) a large-particle precursor with a polycrystalline morphology and an average particle size D50 of 9-11 mu m, and c) a lithium source. According to the preparation method, a small-particle precursor is coated by using a specific hydroxide, the small-particle precursor is in a single crystal or single crystal-like shape, and a large-particle precursor in a polycrystalline shape is combined to prepare the ternary cathode material which has excellent compaction density, electrical property and rate capability; the preparation method of the ternary electrode material is simple and is suitable for industrial production.

Description

High-compaction long-life ternary cathode material and preparation method thereof
Technical Field
The invention relates to the field of lithium ion battery anode materials, in particular to a high-compaction long-life ternary anode material and a preparation method thereof.
Background
The lithium ion battery has the advantages of high energy, high power density, no memory effect, good safety performance and the like, and is widely applied to electric vehicles, hybrid electric vehicles and portable electronic equipment, so that the energy supply market is led. Nickel cobalt lithium manganate ternary material (chemical formula Li (Ni)) x Co y Mn 1-x-y )O 2 Abbreviation NCM) is high in theoretical energy density, and a lithium ion power battery manufactured by using the lithium ion power battery as a positive electrode material is suitable for a pure electric vehicle or a plug-in hybrid electric vehicle because the battery system has high mass energy density and volume energy density and strong cruising ability, and meanwhile, the ternary battery pack has good high power characteristic. As is well known, the cycle life of a lithium ion battery is not only related to the selection of a positive electrode material, a negative electrode material, a diaphragm, an electrolyte, a current collector and the like of a battery system, but also the compaction density of the positive electrode material has a great influence on the battery performance. Although the energy density of the ternary material battery used in the new energy automobile is high, a cooling system is required to be added in the use process, so that the available energy of the ternary material accounts for only 47%. It can be said that the processUnder certain conditions, the higher the compaction density, the more energy available for the ternary material, the higher the initial capacity of the battery, but too high an unregulated compaction density can cause particle breakage and thus severely shorten the battery life. Therefore, the material with high compaction resistance is prepared, the positive electrode compaction density is properly improved, on one hand, the discharge capacity of the battery can be effectively increased, the internal resistance is reduced, the polarization loss is reduced, on the other hand, the cycle life of the battery is considered, and the utilization rate of the lithium ion battery is improved.
In commercial ternary materials, it is generally desirable that the material have a compacted density of 3.5g/cm 3 Above, even up to 3.8g/cm 3 The above, while the conventional materials have a compacted density of 3.4 to 3.6g/cm 3 Therefore, on the premise of ensuring that the electrical property of the cathode material meets the requirement, the improvement of the compaction density must be considered to improve the product competitiveness. The compaction density of current ternary materials has yet to be improved.
Disclosure of Invention
In view of the problems in the prior art, the first aspect of the present invention provides a high-compaction long-life ternary cathode material, which comprises a) a nickel-cobalt-manganese small particle precursor with single crystal or single crystal-like morphology and an average particle size of 2-4 μm, b) a nickel-cobalt-manganese large particle precursor with polycrystalline morphology and an average particle size of D50 of 9-11 μm, and c) a lithium source.
Polycrystal: polycrystals are a collection of single crystals of numerous oriented grains.
In one embodiment, the small particle precursor of the single crystal or single crystal-like morphology has a particle size of 3 μm.
In one embodiment, the large particle precursor of polycrystalline morphology has a particle size of 10 μm.
In one embodiment, the small particle precursor is nanoscale hydroxide coated Ni x Co y Mn (1-x-y) (OH) 2 。
In one embodiment, the large particle precursor is Ni x Co y Mn (1-x-y) (OH) 2 。
In one embodiment, the mass ratio of the large particle precursor to the small particle precursor is (10-x): x, wherein 0< x ≦ 5.
Preferably, the mass ratio of the large particle precursor to the small particle precursor is 8: 2.
preferably, the small particle precursor is a nano hydroxide-coated small particle precursor.
Further preferably, the coated nano hydroxide is selected from one or more of aluminum hydroxide, cobalt hydroxide and magnesium hydroxide;
in one embodiment, the molar amount of the nano-hydroxide in the nano-hydroxide coated small particle precursor is 0.01 to 2% by mass of the coated small particle precursor.
The molar weight of the nano hydroxide in the nano hydroxide coated small particle precursor is 0.01-2% of the mass fraction of the coated small particle precursor, which means that the molar weight of the nano hydroxide is 0.01-2% of the mass of the coated small particle precursor.
In one embodiment, the lithium source is selected from one or more of lithium carbonate, lithium acetate, lithium nitrate, lithium hydroxide.
Preferably, the lithium source is lithium carbonate.
Preferably, the molar ratio of the mixed precursor of the nano hydroxide-coated small particles and the large particles to the lithium source is 1: (1.02-1.15); more preferably, the molar ratio of the precursor doped with the large and small particles to the lithium source is 1: 1.055.
the second aspect of the invention provides a preparation method of the high-compaction long-life ternary cathode material, which comprises the following steps:
(1) mixing the small-particle precursor and the large-particle precursor to obtain a precursor with uniformly mixed large and small particles;
(2) and uniformly mixing the large and small particles with the precursor and a lithium source, roasting at 950 ℃ for 7-9h in the first stage, roasting at 950 ℃ for 1-3h in the second stage, crushing, and sieving to obtain the lithium-ion secondary battery.
In one embodiment, the large particle precursor is prepared by batch coprecipitation.
In one embodiment, the small particle precursor is prepared using a solution precipitation method.
In one embodiment, the step (1) is performed by using a high-speed mixer at 500-1000 r/min.
Preferably, the step (1) is carried out by mixing at 750r/min by using a high-speed mixer.
In one embodiment, the method for preparing the high compaction long life ternary cathode material comprises the following steps:
(1) adding the small-particle precursor into deionized water, stirring at a high speed, and adjusting the pH value to obtain a precursor suspension; adding the prepared nano-scale coating complexing agent into the precursor suspension, accelerating stirring, washing, performing suction filtration, and drying to obtain a nano-scale coating hydroxide small-particle precursor;
(2) mixing the large-particle precursor and the coated small-particle precursor, and uniformly mixing the large-particle precursor and the coated small-particle precursor by using a high-speed mixer to obtain a precursor with uniformly mixed large and small particles;
(3) and uniformly mixing the large and small particles with the precursor and a lithium source, roasting at 950 ℃ for 7-9h in the first stage, roasting at 950 ℃ for 1-3h in the second stage, and crushing and sieving to obtain the high-compaction long-life ternary cathode material.
In a preferred embodiment, the method for preparing the high compact long life ternary cathode material comprises the following steps:
(1) adding the small-particle precursor into deionized water, stirring at a high speed, and adjusting the pH value to obtain a precursor suspension; adding the prepared nano-scale coating complexing agent into the precursor suspension, accelerating stirring, washing, performing suction filtration, and drying to obtain a nano-scale coating hydroxide small-particle precursor;
(2) mixing the large-particle precursor and the coated small-particle precursor, and uniformly mixing the large-particle precursor and the coated small-particle precursor by using a high-speed mixer to obtain a precursor with uniformly mixed large and small particles;
(3) and uniformly mixing the precursor with the large and small particles and a lithium source, roasting at 950 ℃ for 8h in the first stage, roasting at 950 ℃ for 2h in the second stage, and crushing and sieving to obtain the high-compaction long-life ternary cathode material.
In the prior art, the ternary precursor is directly coated by metal oxides such as zinc oxide and the like, however, the discharge specific capacity of the ternary anode material obtained at the moment is small, after repeated cycles, the capacity retention rate is seriously reduced, so that the compaction density and the electrical property can not reach the expected standard at the same time, and the applicant unexpectedly finds in experiments, when the small-particle precursor with the average particle diameter of 2-4 mu m is coated by using the aluminum hydroxide, the cobalt hydroxide and the magnesium hydroxide in the application, meanwhile, large particle precursors with the average particle size of 9-11 mu m are combined, and when the small particle precursors are in single crystal or single crystal-like shape and the large particle precursors are in polycrystalline shape, at the moment, the problem that the compaction density and the electrical property are different and simultaneously reach the expectation in the prior art is solved, so that at a certain compaction density, more than 90% of the capacity can still be maintained after 50 cycles. The applicant believes that the possible reasons are that the small particle precursor coated by the specific nano hydroxide in the application fills the gaps between the large particle precursors of the polycrystal, at the time of the specific particle size distribution state and the crystal distribution state, the single crystal or single crystal-like anisotropy and the polycrystal isotropy improve the diffusion level of lithium ions, and in combination with the coated small particle precursor, the diffusion path of the lithium ions is shortened, so that the lithium ions are favorably embedded and detached in the material under high current density, the rate capability is improved, and excellent cycle stability is obtained.
In addition, the applicant has unexpectedly found that when the coating materials are aluminum hydroxide, cobalt hydroxide and magnesium hydroxide, and the large-particle precursor and the small-particle precursor are subjected to co-mixing roasting, the small-particle precursor can obtain a single crystal or single crystal-like morphology and the large-particle precursor can obtain a polycrystalline morphology by adopting a specific roasting mode in the application.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method, a small-particle precursor is coated by using a specific hydroxide, the small-particle precursor is in a single crystal or single crystal-like shape, and a large-particle precursor in a polycrystalline shape is combined to prepare the ternary cathode material which has excellent compaction density, electrical property and rate capability; the preparation method of the ternary electrode material is simple and is suitable for industrial production.
Drawings
FIG. 1 is an SEM image of a ternary material prepared from a large particle precursor of example 2;
FIG. 2 is an SEM image of a ternary material prepared from a small particle precursor in example 2;
FIG. 3 is an SEM image of a ternary material prepared by doping a precursor with large and small particles in example 2.
Detailed Description
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
Example 1
Embodiment 1 of the present invention provides a high-compaction long-life ternary positive electrode material, and the preparation method thereof is as follows:
(1) adding the small-particle precursor into deionized water, stirring at a high speed, and adjusting the pH value to obtain a precursor suspension; adding the prepared nano-scale coating complexing agent into the precursor suspension, accelerating stirring, washing, performing suction filtration, and drying to obtain a nano-scale coating hydroxide small-particle precursor;
(2) preparing a large particle precursor with the particle size of 10 μm D50 and a small particle precursor coated with the particle size of 3 μm D50 according to the mass ratio of 9: 1, mixing, namely uniformly mixing by using a high-speed mixer to obtain a large-particle mixed precursor and a small-particle mixed precursor;
(3) mixing the large and small particle mixed precursors with lithium carbonate, performing segmented roasting by using an oxygen furnace, roasting at 880 ℃ for 8h for the first segment, and roasting at 900 ℃ for the second segment for 2h to prepare a first-time roasting material, wherein the small particle precursors are in single crystal or single crystal-like morphology, the large particle precursors are in polycrystalline morphology, and then mechanically crushing and sieving to obtain the high-compaction ternary cathode material.
The nano-scale coated hydroxide is one or more of aluminum hydroxide, cobalt hydroxide and magnesium hydroxide, wherein the total molar amount of aluminum, cobalt and magnesium is 1% of the mass fraction of the coated small particle precursor. And (3) the rotating speed of the high-speed mixer in the step (2) is 750 r/min.
The total molar amount of the precursor nickel, cobalt and manganese and the molar ratio of the lithium carbonate are 1: 1.055.
example 2
Embodiment 2 of the present invention provides a high-compaction long-life ternary positive electrode material, and the preparation method thereof is as follows:
(1) adding the small-particle precursor into deionized water, stirring at a high speed, and adjusting the pH value to obtain a precursor suspension; adding the prepared nano-scale coating complexing agent into the precursor suspension, accelerating stirring, washing, performing suction filtration, and drying to obtain a nano-scale coating hydroxide small-particle precursor;
(2) preparing a large-particle precursor with the particle size of D50 ═ 10 μm and a small-particle precursor with the particle size of D50 ═ 3 μm coated according to the mass ratio of 8: 2, mixing and blending by using a high-speed mixer to obtain a large and small particle mixed precursor;
(3) mixing the large and small particle mixed precursors with lithium carbonate, performing segmented roasting by using an oxygen furnace, roasting at 880 ℃ for 8h for the first segment, and roasting at 900 ℃ for the second segment for 2h to prepare a first-time roasting material, wherein the small particle precursors are in single crystal or single crystal-like morphology, the large particle precursors are in polycrystalline morphology, and then mechanically crushing and sieving to obtain the high-compaction ternary cathode material.
The nano-scale coated hydroxide is one or more of aluminum hydroxide, cobalt hydroxide and magnesium hydroxide, wherein the total molar amount of aluminum, cobalt and magnesium is 1% of the mass fraction of the coated small particle precursor; and (3) the rotating speed of the high-speed mixer in the step (2) is 750 r/min.
The total molar amount of the nickel, the cobalt and the manganese and the molar ratio of the lithium carbonate are 1: 1.055.
the SEM image of the large particle precursor is shown in fig. 1, the SEM image of the coated small particle precursor is shown in fig. 2, and the SEM image of the large and small particle doped precursor is shown in fig. 3.
Example 3
Embodiment 3 of the present invention provides a high-compaction long-life ternary positive electrode material, and the preparation method thereof is as follows:
(1) adding the small-particle precursor into deionized water, stirring at a high speed, and adjusting the pH value to obtain a precursor suspension; adding the prepared nano-scale coating complexing agent into the precursor suspension, accelerating stirring, washing, performing suction filtration, and drying to obtain a nano-scale coating hydroxide small-particle precursor;
(2) preparing a large-particle precursor with the particle size of D50 ═ 10 μm and a small-particle precursor with the particle size of D50 ═ 3 μm coated according to the mass ratio of 7: 3, mixing, namely uniformly mixing by using a high-speed mixer to obtain a large-particle mixed precursor and a small-particle mixed precursor;
(3) mixing the large and small particle mixed precursors with lithium carbonate, performing segmented roasting by using an oxygen furnace, roasting at 880 ℃ for 8h for the first segment, and roasting at 900 ℃ for the second segment for 2h to prepare a first-time roasting material, wherein the small particle precursors are in single crystal or single crystal-like morphology, the large particle precursors are in polycrystalline morphology, and then mechanically crushing and sieving to obtain the high-compaction ternary cathode material.
The coated hydroxide is one or more of aluminum hydroxide, cobalt hydroxide and magnesium hydroxide, wherein the total molar amount of aluminum, cobalt and magnesium is 1% of the mass fraction of the coated small-particle precursor; and (3) the rotating speed of the high-speed mixer in the step (2) is 750 r/min.
The total molar amount of the nickel, the cobalt and the manganese and the molar ratio of the lithium carbonate are 1: 1.055.
example 4
Embodiment 4 of the present invention provides a high-compaction long-life ternary positive electrode material, and the preparation method thereof is as follows:
(1) adding the small-particle precursor into deionized water, stirring at a high speed, and adjusting the pH value to obtain a precursor suspension; adding a prepared nano-scale coating complexing agent into the precursor suspension, accelerating stirring, washing, performing suction filtration, and drying to obtain a nano-scale coating hydroxide small-particle precursor;
(2) preparing a large particle precursor with the diameter of 10 mu m and a coated small particle precursor of D50 prepared by a batch coprecipitation method according to the mass ratio of 6: 4, mixing, namely uniformly mixing by using a high-speed mixer to obtain a large-particle mixed precursor and a small-particle mixed precursor;
(3) mixing the large and small particle mixed precursor with lithium carbonate, roasting at 880 ℃ for 8h in one section and roasting at 900 ℃ for 2h in the second section by using an oxygen furnace to prepare a first-time roasting material, wherein the small particle precursor is in a single crystal or single crystal-like shape, the large particle precursor is in a polycrystalline shape, and then mechanically crushing and sieving to obtain the high-compaction ternary cathode material.
The nano-scale hydroxide is aluminum hydroxide, cobalt hydroxide and magnesium hydroxide, wherein the total molar weight of the aluminum, the cobalt and the magnesium is 1% of the mass fraction of the coated small particle precursor;
and (3) the rotating speed of the high-speed mixer in the step (2) is 750 r/min.
The total molar amount of the nickel, the cobalt and the manganese and the molar ratio of the lithium carbonate are 1: 1.055.
example 5
Embodiment 5 of the present invention provides a high-compaction long-life ternary positive electrode material, and the preparation method thereof is as follows:
(1) adding the small-particle precursor into deionized water, stirring at a high speed, and adjusting the pH value to obtain a precursor suspension; adding the prepared nano-scale coating complexing agent into the precursor suspension, accelerating stirring, washing, performing suction filtration, and drying to obtain a nano-scale coating hydroxide small-particle precursor;
(2) preparing a large particle precursor with the diameter of 10 mu m and a coated small particle precursor of D50 prepared by a batch coprecipitation method according to the mass ratio of 5: 5, mixing, namely uniformly mixing by using a high-speed mixer to obtain a large-particle mixed precursor and a small-particle mixed precursor;
(3) mixing the large and small particle mixed precursors with lithium carbonate, performing segmented roasting by using an oxygen furnace, roasting at 880 ℃ for 8h for the first segment, and roasting at 900 ℃ for the second segment for 2h to prepare a first-time roasting material, wherein the small particle precursors are in single crystal or single crystal-like morphology, the large particle precursors are in polycrystalline morphology, and then mechanically crushing and sieving to obtain the high-compaction ternary cathode material.
The nano-scale hydroxide is aluminum hydroxide, cobalt hydroxide and magnesium hydroxide, wherein the total molar weight of the aluminum, the cobalt and the magnesium is 1% of the mass fraction of the coated small particle precursor; .
And (3) the rotating speed of the high-speed mixer in the step (2) is 750 r/min.
The total molar amount of the nickel, the cobalt and the manganese and the molar ratio of the lithium carbonate are 1: 1.055.
performance evaluation
The preparation method of the blank sample comprises the following steps:
mixing a precursor of large particles of D50 ═ 10 mu m prepared by an intermittent coprecipitation method with lithium carbonate, carrying out sectional roasting by using an oxygen furnace, roasting at 880 ℃ for 8h at the first section, roasting at 900 ℃ for 2h at the second section, preparing a first roasting material, and then mechanically crushing and sieving to obtain a blank sample ternary cathode material.
The molar ratio of the large-particle precursor to the lithium carbonate is 1: 1.055.
the high-compaction long-life ternary positive electrode material obtained in each example and a blank ternary positive electrode material were prepared into a button cell, and the following performance tests were performed.
The preparation method of the button cell comprises the following steps: uniformly mixing the material or blank sample obtained in the embodiment, conductive carbon black and polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to the weight ratio of 8:1:1, and coating an aluminum foil to form a pole piece; and (3) drying the prepared pole piece for 5 hours in a vacuum drying oven at 110 ℃ for later use. And rolling the pole piece on a rolling machine, and punching the rolled pole piece into a circular pole piece. The cell assembly was carried out in a glove box filled with argon, the electrolyte of the electrolyte being 1MLiPF 6 The solvent is EC: DEC: DMC is 1:1:1 (volume ratio), and the metal lithium sheet is the counter electrode. The capacity test was performed on a blue CT model 2001A tester.
TABLE 1
Figure BDA0003265619330000081
The experimental data show that the button cell prepared from the high-voltage compact long-life ternary cathode material prepared by the method has higher compaction density, and the specific discharge capacity, the rate capability and the cycle performance of the button cell are improved to a certain extent and show more excellent electrochemical performance compared with the undoped common cathode material.

Claims (10)

1. The high-compaction long-life ternary cathode material is characterized in that raw materials comprise a) a nickel-cobalt-manganese small particle precursor with single crystal or single-like morphology and an average particle size of 2-4 mu m, b) a nickel-cobalt-manganese large particle precursor with polycrystalline morphology and an average particle size D50 of 9-11 mu m, and c) a lithium source.
2. The high-compaction long-life ternary positive electrode material according to claim 1, wherein the large particle precursor and the small particle precursor are mixed in a mass ratio of (10-x): x is mixed, wherein x is more than 0 and less than or equal to 5.
3. The high-compaction long-life ternary positive electrode material according to claim 2, wherein the small-particle precursor is a nano-hydroxide-coated small-particle precursor.
4. The high-compaction long-life ternary positive electrode material according to claim 3, wherein the nano-hydroxide is selected from one or more of aluminum hydroxide, cobalt hydroxide and magnesium hydroxide.
5. The high-compaction long-life ternary cathode material according to claim 3 or 4, wherein the molar amount of the nano-hydroxide in the nano-hydroxide-coated small particle precursor is 0.01 to 2% by mass of the coated small particle precursor.
6. The high compacted long life ternary positive electrode material according to any of claims 1 to 4, wherein the lithium source is selected from one or more of lithium carbonate, lithium acetate, lithium nitrate, lithium hydroxide.
7. The high-compaction long-life ternary cathode material according to claim 6, wherein the molar ratio of the total amount of the large-size particle-doped precursor to the lithium source is 1: (1.02-1.15).
8. A method of preparing a high compaction long life ternary positive electrode material according to any one of claims 1 to 7, comprising the steps of:
(1) mixing the small-particle precursor and the large-particle precursor to obtain a precursor with uniformly mixed large and small particles;
(2) and uniformly mixing the large and small particles with the precursor and a lithium source, roasting at 950 ℃ for 5-12h in the first stage, roasting at 950 ℃ for 1-5h in the second stage, and crushing and sieving to obtain the high-compaction long-life ternary cathode material.
9. The method according to claim 8, wherein the large particle precursor is prepared by batch coprecipitation and the small particle precursor is prepared by solution precipitation.
10. The method for preparing a high-compaction long-life ternary cathode material according to claim 8, wherein the method for preparing the nanoparticle precursor coated with the nano hydroxide in the step (1) comprises adding the nanoparticle precursor into deionized water, stirring at a high speed, and adjusting the pH to obtain a precursor suspension; adding the prepared nano-scale coating complexing agent into the precursor suspension, accelerating stirring, washing, filtering, and drying to obtain the nano-scale coating hydroxide small-particle precursor.
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