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CN112768685B - Lithium ion battery anode material and preparation method thereof - Google Patents

Lithium ion battery anode material and preparation method thereof Download PDF

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CN112768685B
CN112768685B CN202110380506.XA CN202110380506A CN112768685B CN 112768685 B CN112768685 B CN 112768685B CN 202110380506 A CN202110380506 A CN 202110380506A CN 112768685 B CN112768685 B CN 112768685B
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lithium ion
ion battery
sintering
stage
positive electrode
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CN112768685A (en
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赵俊豪
李厦
周友元
熊学
李旻
黄滔
黄承焕
周耀
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Minmetals New Energy Materials Hunan Co ltd
Jinchi Energy Materials Co Ltd
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Hunan Changyuan Lico Co Ltd
Jinchi Energy Materials Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
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    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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 long-cycle and high-power lithium ion battery anode material with a molecular formula of LiNixCoyMn1‑x‑y‑zZzO2The single crystal or single crystal-like shell layer and the hollow part are formed by mutually fusing primary particles, and the volume of the hollow part of the secondary particles accounts for 0.8-50% of the whole secondary particles. Also disclosed is a method of preparation comprising: preparing a hydroxide precursor with crystallinity and morphology difference along the radial direction; mixing the precursor with a lithium compound, and sintering the mixture in two stages to obtain the lithium-ion battery; the first sintering is rapid temperature rise, the temperature of the second sintering is higher than that of the first stage, and the second sintering can enable primary particles to be melted and fused with each other to form a single crystal shell layer. The lithium ion anode material has good normal temperature and high temperature cycle performance and safety performance, can improve mechanical and electrochemical performances and compaction density, has the characteristics of quick charging, high capacity, high voltage, high cycle and low cost, and can be suitable for high-power vehicles.

Description

Lithium ion battery anode material and preparation method thereof
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a long-cycle and high-power lithium ion battery anode material and a preparation method thereof.
Background
The lithium ion battery is used as a novel green energy storage device, and plays a significant role in the field of secondary batteries due to the excellent performance of the lithium ion battery. The positive electrode material is the core affecting the performance of the lithium ion battery, and the positive electrode materials used for the lithium ion battery at present mainly comprise lithium cobaltate, lithium manganate, lithium iron phosphate, ternary materials and the like.
However, with the continuous improvement of energy density and the excitation of national policy, the power battery presents a rapid development form, and the ternary material is used by a plurality of new energy vehicles due to the advantage of high capacity, and the current popular ternary material in the market is mainly single crystal/single crystal-like and secondary particle-like in appearance. The two have advantages, the single crystal has good circulation and insufficient capacity exertion and rate capability, and the secondary particle has advantages in capacity and rate but poor circulation performance. Various EVs, BEVs, PEVs and PHEVs of passenger vehicles on the market at present require ternary materials with corresponding functions for different vehicle types. However, as the power type pHEV has a high requirement for the rate capability of the ternary material, the material is currently designed to be a hollow/porous structure, so as to promote the lithium ions to be rapidly inserted/extracted, so as to have excellent rate capability, but the structure has certain defects, such as small compaction density, poor cycle performance and the like.
Disclosure of Invention
The invention aims to solve the problems of the conventional power type cathode material, and provides a long-cycle and high-power lithium ion battery single-crystal type hollow cathode material and a preparation method thereof so as to improve the compaction and cycle performance of the material.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the lithium ion battery anode material is in a single crystal or single crystal-like shape, secondary particles of the lithium ion battery anode material are in a hollow structure and comprise a single crystal shell layer formed by mutually fusing primary particles and a hollow part in the single crystal shell layer, and the molecular formula of the lithium ion battery anode material is LiNixCoyMn1-x-y-zZzO2And the volume of the hollow part of the secondary particle accounts for 0.8-50% of the whole secondary particle. Preferably, the primary particles are fused with each other to form a single crystal shell layer through high-temperature melting; the primary particles are completely fused with each other to form a single crystal shell layer whole.
Preferably, the molecular formula of the lithium ion battery cathode material is LiNixCoyMn1-x-y-zZzO2Wherein, 0.2<x<0.95，0<y<0.4，0<z<0.05, wherein Z is one or more of Al, Zr, Ti, Co, Mg, Nb, Mo, Sr, Ta, Sn, W, B and Y.
Preferably, the secondary particles have an average diameter of 1 to 6 μm, more preferably 1 to 5 μm, and still more preferably 2 to 4 μm, and the volume of the hollow part of the secondary particles is 2 to 10% of the entire secondary particles.
Preferably, the positive electrode material is obtained by sintering a mixture of precursor particles with crystallinity and morphology difference along the radial direction and a lithium compound in two stages, the first stage sintering is rapid temperature rise, the second stage sintering temperature is higher than that of the first stage sintering, and the second stage sintering enables primary particles to be fused with each other to form a single crystal shell layer. Based on the difference between the crystallinity and the morphology of the internal and external components of the hydroxide precursor, the hollow structure is formed by the difference of the diffusion degree of the internal and external ions under the rapid temperature rise state. The precursor particles with crystallinity and appearance difference along the radial direction mean that in a cross section of the precursor particles, an inner core is formed by stacking sparse porous small pieces, and an outer part is formed by mutually staggering thick pieces. Differences in crystallinity are seen from the primary particle size and arrangement.
Preferably, the temperature rise rate of the rapid temperature rise is 6-20 ℃/h.
As a general inventive concept, there is also provided a method for preparing a positive electrode material for a lithium ion battery, comprising the steps of:
s1, preparing a hydroxide precursor of unit or multi-element metal with crystallinity and shape difference along the radial direction;
s2, mixing the obtained hydroxide precursor with a lithium compound, and sintering the obtained mixture in an oxygen-containing atmosphere in two stages to obtain the lithium ion battery; the sintering in the first stage is rapid temperature rise, the sintering temperature in the second stage is higher than that in the first stage, and the sintering in the second stage can enable primary particles to be melted and fused with each other to form a single crystal shell layer.
The two-stage sintering process of the scheme specifically comprises the following steps: firstly, aiming at the difference of the crystallization of the internal and external core-shell structures of the precursor, the diffusion coefficient of the metal anions is different under the high-temperature state formed under the rapid temperature rise, and the diffusion outward diffusion rate of the inner core is far higher than that of the outer core, so that a hollow structure is formed; secondly, primary particles are mutually fused at high temperature to completely form a single monocrystalline shell layer.
Preferably, in step S2, when mixing the hydroxide precursor with the lithium compound, adding an additive;
the additive is one or more than two of oxides or fluorides of Al, Zr, Ti, Co, Mg, Nb, Mo, Sr, Ta, Sn, W, B and Y; further preferably one or two or more oxides of Al, Zr, Ti, Co, Sr, W, B and Y.
Preferably, in step S2, the temperature rise rate of the first stage sintering is 6 to 20 ℃/min, the temperature of the first stage sintering is 650 to 850 ℃, and the heat preservation time is 2 to 6 hours;
the temperature rise rate of the second stage is 3-20 ℃/min, the sintering temperature of the second stage is 700-1000 ℃, and the temperature range of the second stage sintering is that primary particles are fused with each other at high temperature to form a single crystal shell layer, and because the proportions of elements in the precursor are different, the melting temperature is also different, the sintering temperature range of the second stage is wider, the reasons of different components are considered, and the heat preservation time is 6-14 h.
Preferably, in step S1, the precursor preparation process includes a low-crystallinity core formation stage and a growing stage in which crystallinity gradually increases, forming a low-crystallinity core and a shell in which crystallinity gradient increases;
preferably, the pH value of the low-crystallinity core stage is controlled to be more than or equal to 12, more preferably the pH value control range is 12-13, the stirring speed is 200-600 r/min, and more preferably 300-500 r/min; the time is 10-20 h, and preferably 10-15 h;
preferably, the growth stage is formed by reducing the pH with a gradient of 0.01-0.50/h, and further preferably by controlling the pH to be reduced within a range of 0.02-0.20/pH; the stirring speed is 500-1000 r/min, and more preferably 600-800 r/min; the time is 20 to 40 hours, and more preferably 30 to 40 hours.
Preferably, in step S1, the mono-or poly-metallic hydroxide is NixCoyMnZ(OH)2Wherein x + y + z = 1;
the precursor is prepared by adopting an intermittent method, the particle size of the precursor is uniform, the precursor has a core-shell structure, the inner core is formed by stacking sparse porous small pieces, and the outer part is formed by mutually staggering thick pieces; the proportion of the hollow structure of the precursor in the primary particles is realized by adjusting the proportion of the inner core.
In the preparation process of the precursor, soluble nickel salt, soluble cobalt salt and soluble manganese salt are used as raw materials, dissolved to form a mixed solution with Ni, Co and Mn metal ions of which the concentration is 1.5-2M and a reaction kettle, then an aqueous alkali containing ammonia is introduced to adjust the pH value, a coprecipitation reaction is carried out to obtain a solid-liquid mixture, and a hydroxide precursor of unit or multi-element metal is obtained through solid-liquid separation and drying;
preferably, the compound of lithium is Li2CO3LiOH, LiF and Li3PO4One or more than two of the components are mixed;and the molar ratio of the lithium compound to the transition metal in the metal hydroxide is 0.9-1.2, preferably 1.0-1.15;
the volume concentration of oxygen in the oxygen-containing atmosphere is 21.0 to 99.9%, and more preferably 60 to 99.9%.
Preferably, after step S2, the method further includes the steps of dissociating the agglomerated particles of the material obtained by high-temperature sintering by jet milling, and then sieving to control the dissociation degree of the particles and obtain a narrower particle size range;
preferably, the jet milling is carried out by a fluidized bed or a flat jet mill;
preferably, the air pressure of the jet milling is 0.3-0.8 Mpa, and the frequency of the grading wheel is 10-50 Hz.
Compared with the prior art, the invention has the following beneficial effects:
1. the single crystal structure of the lithium ion anode material has excellent stress support, and the cracking phenomenon of the existing agglomerated material in the circulating process can be effectively solved; the closed surface can effectively prevent the permeation of electrolyte and reduce the generation of side reaction, thereby obviously improving the normal-temperature and high-temperature cycle performance and the safety use performance of the material; and the hollow structure of the hollow single crystal material has a short lithium ion transmission path, and can be suitable for rapid charge and discharge under high rate, so that the hollow single crystal material can meet the requirements of power type vehicle batteries.
2. The lithium ion anode material can further reduce the degradation of the material and the side reaction with electrolyte by modifying the surface interface by the doping elements under the condition of ensuring the high power of the material, so as to improve the cycle performance of the material; by reasonably controlling the sizes of the single crystal shell layer and the hollow part of the lithium ion cathode material, the mechanical property, the electrochemical property and the compaction density of the material are further improved.
3. The anode material has the characteristics of quick charge, high capacity, high voltage, high cycle and low cost, can be applied to the condition of quick charge and high voltage, has excellent electrochemical performance, and can be suitable for high-power vehicle models.
4. According to the preparation method, a unit or multi-metal hydroxide precursor with crystallinity and appearance difference along the radial direction is prepared, then the precursor and a lithium source are mixed and sintered at two stages, and metal anions are rapidly diffused outwards through rapid heating and high-temperature melting by utilizing the difference of the crystallinity inside and outside the precursor to form a single crystal shell layer with adjustable thickness and an internal cavity part, so that the positive electrode material which is high in compaction, good in cycle performance and safety use performance, capable of being rapidly charged and discharged under high rate is obtained, and the requirement of a power type vehicle battery can be met.
5. The preparation method of the invention obtains the hydroxide precursor of unit or multi-metal with the difference of crystallinity and appearance along the radial direction through the low-crystallinity core forming stage and the growing stage with gradually increased crystallinity, and forms the precursor shell with gradually increased crystallinity by controlling the process parameters of the growing stage.
6. The preparation method of the invention is beneficial to further optimizing the structure and performance of the material by further optimizing the process parameters of the low-crystallinity core forming stage, the two-stage sintering and other steps; through jet milling and screening, the dissociation degree of particles can be controlled, a narrower particle size range is obtained, the consistency of the structure and the performance of the material is favorably improved, and the practical application is more favorably realized.
Drawings
Fig. 1 is an SEM image of the precursor prepared in example 1.
FIG. 2 is a cross-sectional view of a precursor prepared in example 1.
Fig. 3 is an SEM image of the cathode material prepared in example 1.
Fig. 4 is a sectional view of a cathode material prepared in example 1.
Fig. 5 is a graph showing cycle performance of the positive electrode materials prepared in example 1 and comparative example 4.
Detailed Description
The present invention will be further described with reference to the following specific examples and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1:
preparation of hollow single crystal NCM622 ternary anode material
Aiming at 622 ternary anode materials, the requirements of circulation and multiplying power are integrated, the thickness of a single crystal shell layer can be reduced in a proper amount in the process of designing a structure, but the thickness of an outer layer single crystal is between 0.5 and 0.75 mu m under the condition that the particle size is comprehensively controlled to be 3.5 mu m according to the pressure intensity capable of being borne.
The invention relates to a long-cycle and high-power lithium ion battery anode material, which is in a single crystal or single-crystal-like shape, secondary particles of the lithium ion battery anode material are in a hollow structure, and the secondary particles comprise a single crystal shell layer and a hollow part inside the shell layer, wherein the single crystal shell layer and the hollow part are formed by mutually fusing a plurality of primary particles.
The molecular formula of the lithium ion battery anode material is LiNi0.6Co0.2Mn0.2O2。
The secondary particles have an average diameter of 4 μm, the hollow portions have an average diameter of 1 to 1.5 μm, and the volume of the hollow portions of the secondary particles accounts for 1.5 to 5% of the total secondary particles.
A preparation method of the lithium ion battery positive electrode material of the embodiment includes:
step 1: preparation of the precursor
Preparing 1.5M metal ion solution from nickel sulfate, manganese sulfate and cobalt sulfate according to a molar ratio of 6:2:2, respectively adding 1.5M ammonia water and 1.5M NaOH solution into a reaction kettle through a peristaltic pump, introducing nitrogen as a protective gas, controlling the pH value to be 12, stirring at a rotation speed of 400 r/min for 12h, starting to control the pH value to decrease progressively at 0.04/h, adjusting the rotation speed to 700 r/min, and reacting for 36h to finally obtain 622 precursor.
Step 2: firing of positive electrode Material
Mixing ternary precursor, LiOH and ZrO2Putting the mixture into a high-speed mixing stirrer according to the molar ratio of 1:1.10:0.004, stirring the mixture for 15min at the rotating speed of 600rpm, putting the mixture into an atmosphere furnace with the oxygen concentration of 80%, heating the mixture to 800 ℃ at the heating speed of 10 ℃/min, preserving the heat for 4h, and continuing heating the mixture to 935 ℃ at the heating speed of 10 ℃/min, preserving the heat for 12h to obtain the sintering material.
And step 3: pulverization of positive electrode Material
After the sintering material is coarsely crushed, crushing the sintering material by a fluidized bed crusher, wherein the agglomerated particles can be promoted to be fully dissociated and the particle size of the particles can be strictly controlled under the conditions that the air pressure is controlled to be 0.7Mpa and the frequency of a grading wheel is 40 Hz.
Comparative example 1:
the lithium ion battery anode material has a common single crystal shape, is solid inside, and has an average particle size of 4 microns.
A method for preparing a positive electrode material for a lithium ion battery of the present comparative example, comprising:
step 1: preparation of the precursor
Preparing 1.5M metal ion solution from nickel sulfate, manganese sulfate and cobalt sulfate according to a molar ratio of 6:2:2, respectively adding 1.5M ammonia water and 1.5M NaOH solution into a reaction kettle through a peristaltic pump, introducing nitrogen as a protective gas, controlling the pH value to be 13, and stirring at a speed of 400 r/min for 36 hours to finally complete precursor preparation.
Step 2: firing of positive electrode Material
Mixing ternary precursor, LiOH and ZrO2Putting the mixture into a high-speed mixing stirrer according to the molar ratio of 1:1.10:0.004, stirring the mixture for 15min at the rotating speed of 600rpm, putting the mixture into an atmosphere furnace with the oxygen concentration of 80%, heating the mixture to 800 ℃ at the heating speed of 3 ℃/min, preserving the heat for 4h, and continuing heating the mixture to 935 ℃ at the heating speed of 3 ℃/min, preserving the heat for 12h to obtain the sintering material.
And step 3: pulverization of positive electrode Material
The sintering material is coarsely crushed and then crushed by a fluidized bed crusher, wherein the pressure is generally controlled to be 0.7Mpa, and the frequency of a grading wheel is 40Hz to promote the fully dissociation of agglomerated particles and strictly control the particle size of the particles.
Comparative example 2:
the lithium ion battery anode material is in a single crystal shape, holes which are left by fast sintering and have the particle size of about 0.1-0.3 mu m exist inside the lithium ion battery anode material, and the average particle size of secondary particles is 4 mu m.
A method for preparing a positive electrode material for a lithium ion battery of the present comparative example, comprising:
step 1: preparation of the precursor
Preparing 1.5M metal ion solution from nickel sulfate, manganese sulfate and cobalt sulfate according to a molar ratio of 6:2:2, respectively adding 1.5M ammonia water and 1.5M NaOH solution into a reaction kettle through a peristaltic pump, introducing nitrogen as a protective gas, controlling the pH to be 13, and stirring at a speed of 400 r/min for 36 hours to finish the preparation;
step 2: firing of positive electrode Material
Mixing ternary precursor, LiOH and ZrO2Putting the mixture into a high-speed mixing stirrer according to the molar ratio of 1:1.10:0.004, stirring the mixture for 15min at the rotating speed of 600rpm, putting the mixture into an atmosphere furnace with the oxygen concentration of 80%, heating the mixture to 800 ℃ at the heating speed of 10 ℃/min, preserving the heat for 4h, and continuing heating the mixture to 935 ℃ at the heating speed of 10 ℃/min, preserving the heat for 12h to obtain the sintering material.
And step 3: pulverization of positive electrode Material
The sintering material is coarsely crushed and then crushed by a fluidized bed crusher, wherein the pressure is generally controlled to be 0.7Mpa, and the frequency of a grading wheel is 40Hz to promote the fully dissociation of agglomerated particles and strictly control the particle size of the particles.
Comparative example 3:
the lithium ion battery positive electrode material is in a single crystal shape, the average diameter of secondary particles of the lithium ion battery positive electrode material is 4 micrometers, the average diameter of hollow parts of the secondary particles is 0.5-0.8 micrometers, and the volume of the hollow parts of the secondary particles accounts for less than 0.7% of the volume of the whole secondary particles.
A method for preparing a positive electrode material for a lithium ion battery of the present comparative example, comprising:
step 1: preparation of the precursor
Preparing 1.5M metal ion solution from nickel sulfate, manganese sulfate and cobalt sulfate according to a molar ratio of 6:2:2, respectively adding 1.5M ammonia water and 1.5M NaOH solution into a reaction kettle through a peristaltic pump, introducing nitrogen as a protective gas, controlling the pH value to be 13, stirring at a rotation speed of 400 r/min for 12h, starting to control the pH value to decrease progressively at 0.04/h, adjusting the rotation speed to 700 r/min, and reacting for 36h to obtain 622 precursor.
Step 2: firing of positive electrode Material
Mixing ternary precursor, LiOH and ZrO2Putting the mixture into a high-speed mixing stirrer according to the molar ratio of 1:1.10:0.004, stirring the mixture for 15min at the rotating speed of 600rpm, putting the mixture into an atmosphere furnace with the oxygen concentration of 80%, heating the mixture to 800 ℃ at the heating speed of 3 ℃/min, preserving the heat for 4h, and continuing heating the mixture to 935 ℃ at the heating speed of 3 ℃/min, preserving the heat for 12h to obtain the sintering material.
And step 3: pulverization of positive electrode Material
The sintering material is coarsely crushed and then crushed by a fluidized bed crusher, wherein the pressure is generally controlled to be 0.7Mpa, and the frequency of a grading wheel is 40Hz to promote the fully dissociation of agglomerated particles and strictly control the particle size of the particles.
Example 2:
the lithium ion battery anode material is in a single crystal or single crystal-like shape, secondary particles of the lithium ion battery anode material are in a hollow structure, the secondary particles comprise a single crystal shell layer and a hollow part inside the shell layer, the single crystal shell layer and the hollow part are formed by mutually fusing a plurality of primary particles, the average diameter of the secondary particles is 4 mu m, the average diameter of the hollow part is 0.8-1.0 mu m, and the volume of the hollow part of the secondary particles accounts for 0.8-2% of the volume of the whole secondary particles.
A preparation method of the lithium ion battery positive electrode material of the embodiment includes:
step 1: preparation of the precursor
Preparing 1.5M metal ion solution from nickel sulfate, manganese sulfate and cobalt sulfate according to a molar ratio of 6:2:2, respectively adding 1.5M ammonia water and 1.5M NaOH solution into a reaction kettle through a peristaltic pump, introducing nitrogen as a protective gas, controlling the pH value to be 13, stirring at a rotation speed of 400 r/min for 12h, starting to control the pH value to decrease progressively at 0.04/h, adjusting the rotation speed to 700 r/min, and reacting for 36h to obtain 622 precursor.
Step 2: firing of positive electrode Material
Mixing ternary precursor, LiOH and ZrO2Adding into a high-speed mixer according to the molar ratio of 1:1.10:0.004, stirring at 600rpm for 15min, adding oxygenAnd (3) in an atmosphere furnace with gas concentration of 80%, heating to 800 ℃ at a heating rate of 10 ℃/min, then preserving heat for 4h, continuously heating to 935 ℃ at 3 ℃/min, and preserving heat for 12h to obtain the sintering material.
And step 3: pulverization of positive electrode Material
The sintering material is coarsely crushed and then crushed by a fluidized bed crusher, wherein the pressure is generally controlled to be 0.7Mpa, and the frequency of a grading wheel is 40Hz to promote the fully dissociation of agglomerated particles and strictly control the particle size of the particles.
Comparative example 4:
the lithium ion battery anode material is a secondary particle hollow structure, namely, the secondary particles are in a hollow structure and comprise an outer layer formed by primary particles and a hollow part in the outer layer.
A method for preparing a positive electrode material for a lithium ion battery of the present comparative example, comprising:
step 1: preparation of the precursor
Preparing 1.5M metal ion solution from nickel sulfate, manganese sulfate and cobalt sulfate according to a molar ratio of 6:2:2, respectively adding 1.5M ammonia water and 1.5M NaOH solution into a reaction kettle through a peristaltic pump, introducing nitrogen as a protective gas, controlling the pH value to be 13, stirring at a rotation speed of 400 r/min for 12h, starting to control the pH value to decrease progressively at 0.04/h, and adjusting the rotation speed to 700 r/min for reaction for 30h to obtain 622 precursor.
Step 2: firing of positive electrode Material
Mixing ternary precursor, LiOH and ZrO2Putting the mixture into a high-speed mixing stirrer according to the molar ratio of 1:1.10:0.004, stirring for 15min at the rotating speed of 600rpm, putting the mixture into an atmosphere furnace with the oxygen concentration of 80%, heating to 800 ℃ at the heating speed of 10 ℃/min, and then preserving the heat for 12h to obtain the sintering material.
And step 3: pulverization of positive electrode Material
After the sintering material is coarsely crushed, crushing the sintering material by a fluidized bed crusher, wherein the agglomerated particles can be promoted to be fully dissociated and the particle size of the particles can be strictly controlled under the conditions that the air pressure is controlled to be 0.3Mpa and the frequency of a grading wheel is 30 Hz.
The electrochemical performance of the positive electrode materials of the above examples and comparative examples was investigated using CR2016 type button cells.
The composite positive electrode materials of the embodiment 1 and the embodiment 2 and the comparative examples 1, 2, 3 and 4 are prepared into the positive electrode plate of the lithium ion battery, and the specific method comprises the following steps: NMP is used as a solvent, and the ratio of active substances, namely superconducting carbon black (SP): polyvinylidene fluoride (PVDF) 94:3:3 (mass ratio).
LiPF with electrolyte of 1mol/L6The solvent of the solution is a mixed solvent of Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC), and the volume ratio of the ethylene carbonate to the diethyl carbonate to the ethyl methyl carbonate is 1:1: 1.
The negative electrode of the button cell uses a lithium sheet, and the positive electrode uses the pole sheet. And assembling the positive electrode, the negative electrode, the electrolyte, the diaphragm and the battery shell into the button battery in an argon-protected glove box. The charging current is 1C/2C/5C/10C, the charging cut-off voltage is 4.3V, and the discharging cut-off voltage is 3.0V. As shown in the following table 1, which is the ratio of different multiplying powers of the button cell prepared from the materials, it can be seen that the multiplying power of the secondary spherical particles prepared in the comparative example 4 is the best, the multiplying power of the single crystal prepared in the comparative example 1 is the worst, and the multiplying power of the hollow single crystal material prepared in the example 1 is basically not much different from that of the secondary spherical particles, so that the multiplying power requirement of the high-power material is basically met.
TABLE 1
Figure 927833DEST_PATH_IMAGE001
The physical and chemical properties of the hollow single crystal 622 material prepared in example 1 are detected, and the specific surface area of the cathode material is 0.8m2In terms of a grain size of 4.0 μm, which is substantially comparable to the BET of a single crystal. The precursor prepared in example 1 was sampled and subjected to SEM observation and cross-sectional SEM observation (see fig. 1 and 2), and it was seen from the figure that the precursor was a spherical particle composed of a short rod-like shape, and consisted of two parts in a cross-sectional view, in which the inner core was a sparse porous small piece stacked and the outer portions were thick pieces interlaced with each other. The material is sampled to be subjected to SEM observation and section SEM observation (as shown in figures 3 and 4), and the material is in a single crystal morphology and particles according to the results of electron microscopyThe grain size is relatively uniform. From the results of the cross-sectional SEM, it was found that the positive electrode material was hollow single-crystal particles, and the shell portion was a shell layer formed by melting primary particles, and had a particle diameter of 3.5 μm, wherein the thickness of the hollow space (i.e., the diameter of the hollow portion) was about 1.26 μm, and the thickness of the shell layer was 1.13 μm, and the volume of the hollow portion was 4.63% of the entire secondary particles.
In order to compare the cycle performance of the cathode material prepared in example 1 with that of the hollow secondary particles prepared in comparative example 4, the button cell was subjected to a 1C cycle performance test under a voltage condition of 3.0-4.5V, and as shown in fig. 5, it can be seen that the cycle of the hollow single crystal particles is significantly better than that of the secondary particles.
Compaction density test method:
(1) cutting the original electrode plate dried after coating into electrode plates with the specification of 300mm multiplied by 250mm by a paper cutter, respectively measuring the thickness of 3 different positions of the electrode plates, and selecting the electrode plate with the thickness error less than 3 mu m as an experimental sheet.
(2) Cutting 3 electrode slices with the area of 100cm and a current collector at different positions of the original electrode slice in the step (1) by using a circular sampler, weighing the cut electrode slices and the current collector, taking the average values of the weights as M0 and M1, and calculating the surface density of the electrode slices by using a formula: s = M0-M1.
(3) Setting the linear velocity of double rollers of the roller machine to be 2.0m/min, setting the rolling pressure to take 1.3Mpa as an initial value, putting the electrode plates selected in the step (1) into the roller machine for rolling after the pressure is stable, and sequentially superposing the rolling pressure upwards by 0.65Mpa increment until the two sides of the electrode plates are wavy and vertical lines appear in the middle of the electrode plates, thus obtaining the maximum compaction density.
(4) Measuring the thickness of 3 different positions of the electrode plate rolled by different pressures by using a micrometer, recording the thickness as L1, L2 and L3, taking the difference between the numerical values of any two of the three positions by 3 mu m or more as unqualified sheets, recording the thickness of the qualified electrode plate, taking the average value as Li, measuring the thickness of a current collector pressed by a stick by using the micrometer, recording the thickness as Lo, and calculating the compaction density of the electrode plate by using a calculation formula: p = S/(Li-Lo).
The maximum compaction measured for each example and comparative example is shown in table 2.
TABLE 2
Figure 769887DEST_PATH_IMAGE002
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (10)

1. The lithium ion battery anode material is characterized in that secondary particles of the lithium ion battery anode material are of a hollow structure and comprise a single crystal or single crystal-like shell layer formed by mutually fusing primary particles and a hollow part in the shell layer, and the molecular formula of the lithium ion battery anode material is LiNixCoyMn1-x-y-zZzO2And the volume of the hollow part of the secondary particle accounts for 0.8-50% of the whole secondary particle.
2. The lithium ion battery positive electrode material of claim 1, wherein the lithium ion battery positive electrode material has a formula of 0.2< x <0.95, 0< Y <0.4, and 0< Z <0.05, wherein Z is one or more of Al, Zr, Ti, Co, Mg, Nb, Mo, Sr, Ta, Sn, W, B, and Y.
3. The positive electrode material for lithium ion batteries according to claim 1 or 2, wherein the secondary particles have an average diameter of 1 to 6 μm.
4. A preparation method of a lithium ion battery anode material is characterized by comprising the following steps:
s1, preparing a hydroxide precursor of unit or multi-element metal with crystallinity and shape difference along the radial direction;
s2, mixing the obtained hydroxide precursor with a lithium compound, and sintering the obtained mixture in an oxygen-containing atmosphere in two stages to obtain the lithium ion battery; the sintering in the first stage is rapid temperature rise, the sintering temperature in the second stage is higher than that in the first stage, and the sintering in the second stage can enable primary particles to be melted and fused with each other to form a single crystal shell layer.
5. The method for preparing a positive electrode material for a lithium ion battery according to claim 4, wherein in step S2, when the hydroxide precursor is mixed with the lithium compound, the method further comprises adding an additive;
the additive is one or a combination of several elements of oxides or fluorides of Al, Zr, Ti, Co, Mg, Nb, Mo, Sr, Ta, Sn, W, B and Y.
6. The method for preparing the positive electrode material of the lithium ion battery according to claim 4 or 5, wherein in step S2, the temperature rise speed of the first-stage sintering is 6-20 ℃/min, the temperature of the first-stage sintering is 650-850 ℃, and the heat preservation time is 2-6 h;
the temperature rise rate of the second stage is 3-20 ℃/min, the sintering temperature of the second stage is 700-1000 ℃, and the heat preservation time is 6-14 h.
7. The method for preparing the positive electrode material of the lithium ion battery according to claim 4 or 5, wherein in step S1, the precursor preparation process comprises a low-crystallinity core formation stage and a growing stage in which the crystallinity gradually increases;
controlling the pH value to be more than or equal to 12 in the low-crystallinity core forming stage, and stirring at the speed of 200-600 r/min for 10-20 h;
and in the growth stage with gradually increased crystallinity, the pH is reduced by a gradient of 0.01-0.50/h, the stirring speed is 500-1000 r/min, and the time is 20-40 h.
8. The method for preparing a positive electrode material for a lithium ion battery according to claim 4 or 5, wherein the mono-or poly-metal hydroxide is Ni in step S1aCobMn1-a-b(OH)2Wherein, 0.2<a<0.95，0<b<0.4；
The precursor is prepared by adopting a discontinuous method, has uniform particle size and a core-shell structure, and has a radial profile in which an inner core is stacked by sparse porous small pieces and an outer part is formed by mutually staggering thick pieces;
in the preparation process of the precursor, soluble nickel salt, soluble cobalt salt and soluble manganese salt are used as raw materials, dissolved to form a mixed solution with Ni, Co and Mn metal ions of which the concentration is 1.5-2M and a reaction kettle, then an aqueous alkali containing ammonia is introduced to adjust the pH value, a coprecipitation reaction is carried out to obtain a solid-liquid mixture, and the solid-liquid separation and drying are carried out to obtain the hydroxide precursor of the unit or multi-element metal.
9. The method for preparing the positive electrode material for lithium ion batteries according to claim 4 or 5, wherein the compound of lithium is Li2CO3LiOH, LiF and Li3PO4One or more than two of the components are mixed;
the volume concentration of oxygen in the oxygen-containing atmosphere is 21.0-99.9%.
10. The method for preparing the positive electrode material of the lithium ion battery according to claim 4 or 5, wherein after the step S2, the method further comprises the steps of dissociating and screening the agglomerated particles of the material obtained by high-temperature sintering by jet milling;
the jet milling is carried out by adopting a fluidized bed or a flat jet mill;
the air pressure of the jet milling is 0.3-0.8 Mpa, and the frequency of the grading wheel is 10-50 Hz.
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