CN114725344A - High-nickel positive electrode material, preparation method thereof and lithium ion battery - Google Patents
High-nickel positive electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000007774 positive electrode material Substances 0.000 title claims description 12
- 239000002245 particle Substances 0.000 claims abstract description 93
- 239000013078 crystal Substances 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 239000010406 cathode material Substances 0.000 claims abstract description 25
- 239000010405 anode material Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910013716 LiNi Inorganic materials 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 22
- 238000007873 sieving Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 10
- 238000005054 agglomeration Methods 0.000 claims description 5
- 230000002776 aggregation Effects 0.000 claims description 5
- 229910014758 LiNiaCobMnc Inorganic materials 0.000 claims description 3
- 229910013172 LiNixCoy Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 2
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 229910015950 LiNi0.90Co0.05Mn0.05O2 Inorganic materials 0.000 description 4
- 230000002902 bimodal effect Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- 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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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention provides a high-nickel anode material, a preparation method thereof and a lithium ion battery, wherein the high-nickel anode material comprises high-nickel agglomerated large particles; high nickel agglomerated/single crystal type small particles; and a coating material which coats the surfaces of the high nickel agglomerated large particles and the high nickel agglomerated/single crystal small particles. The high-nickel cathode material disclosed by the invention can reduce the adverse condition of compression cracking during the preparation of a pole piece and maintain the structural stability of the agglomerated large particles; the material and power loss of the battery in the circulating process is reduced, and the circulating retention rate of the battery is improved; the contact among the particles is tighter, the interface impedance is reduced, the DCR is reduced, the energy consumption of the battery is reduced, the coating effect is improved on the basis of shortening the heating and heat preservation time through the rapid heating secondary roasting process, and the beneficial effects of reducing the production cost and improving the cycle performance of the battery are achieved. The invention has the characteristics of simple preparation process, low cost, small pollution, good electrochemical performance, convenience for industrial production and the like.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-nickel anode material, a preparation method thereof and a lithium ion battery.
Background
With the rapid development of the market of power batteries, power automobiles with high endurance and high safety become the mainstream demand of the current society. The improvement of the energy density of the battery is one of the most effective ways to increase the use range of the electric vehicle, and therefore, the improvement of the energy density becomes the focus of the current-stage research of various batteries. The positive electrode material with the mass ratio of more than 40% in the battery determines the energy density of the whole battery, the rolling density of the positive electrode plate needs to be improved correspondingly, and the compaction density of the positive electrode material needs to be improved correspondingly.
The increase of the particle size of the agglomerated large particle sample in the anode material can improve the compacted density of the agglomerated large particle sample, but the problems of increased difficulty in precursor preparation, reduced compressive strength of the anode material particles and the like can be faced, and the single crystal type small particles have the advantages of stable material structure, high capacity, good long circulation and the like, but have the problems of high interface impedance, low compacted density and the like.
Therefore, it is necessary to provide a new high nickel cathode material to solve the above technical problems.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a high-nickel anode material, a preparation method thereof and a lithium ion battery.
In order to solve the technical problems, the invention adopts the technical scheme that:
a high nickel positive electrode material, comprising:
the chemical formula of the high nickel agglomeration type large particles is LiNixCoyMnzAl(1-x-y-z)O2Wherein x is more than or equal to 0.88 and less than or equal to 1, y is more than 0 and less than or equal to 0.12, z is more than 0 and less than or equal to 0.12, and 1-x-y-z is more than or equal to 0;
high nickel agglomerated/single crystal type small particles with the chemical formula of LiNiaCobMncAl(1-a-b-c)O2Wherein a is more than or equal to 0.8 and less than or equal to 1, b is more than 0 and less than or equal to 0.2, c is more than 0 and less than or equal to 0.2, and 1-a-b-c is more than or equal to 0;
and a coating which coats the surfaces of the high nickel agglomerated large particles and the high nickel agglomerated/single crystal small particles.
Further, the coating contains one or more elements selected from W, B, Al or Ce.
Further, the mass ratio of the high nickel agglomerated large particles to the high nickel agglomerated/single crystal small particles is (1-9): 1.
further, the particle size of the high nickel agglomeration type large particles is 8-20 um, and the particle size of the high nickel agglomeration type/single crystal type small particles is 2-7 um.
In order to solve the technical problems, the invention also adopts the technical scheme that:
a preparation method of a high-nickel cathode material comprises the following steps:
1) the chemical formula LiNi is obtained by one-time roasting, crushing, washing, drying and screeningxCoyMnzAl(1-x-y-z)O2The high nickel agglomerated large particles;
2) through one-time roasting, crushing, water washing, stoving and sieving, LiNi is obtainedaCobMncAl(1-a-b-c)O2The high nickel agglomerated/single crystal type small particles;
3) uniformly mixing the high-nickel agglomerated large particles and the high-nickel agglomerated/single-crystal small particles, then uniformly mixing the mixture with the coating at a high speed, and carrying out rapid heating secondary roasting, crushing and screening to obtain the high-nickel anode material.
Further, the mass ratio of the total mass of the high nickel agglomerated large particles and the high nickel agglomerated/single crystal type small particles in the step 3) to the mass of the coating is 1: (0 to 0.01).
Further, in the step 3), the temperature of the rapid temperature rise secondary roasting is 200-320 ℃, the temperature rise rate is 5-15 ℃/min, and the roasting time is 2-4 h.
In order to solve the technical problems, the invention also adopts the technical scheme that:
a lithium ion battery comprises the high-nickel cathode material.
Compared with the prior art, the invention has the beneficial effects that: the high-nickel cathode material disclosed by the invention can reduce the adverse condition of compression cracking during the preparation of a pole piece and maintain the structural stability of the agglomerated large particles; the material and power loss of the battery in the circulating process is reduced, and the circulating retention rate of the battery is improved; the contact among the particles is tighter, and the interface resistance is reduced, so that the DCR is reduced, and the energy consumption of the battery is reduced; through the rapid heating up secondary roasting process, the coating effect is improved on the basis of shortening the heating up and heat preservation time, and the coating process has the beneficial effects of reducing the production cost and improving the cycle performance of the battery.
Drawings
Fig. 1 is an SEM image of the high nickel cathode material prepared in example 3;
fig. 2 is an SEM image of the high nickel cathode material prepared in comparative example 1;
fig. 3 is an SEM image of the high nickel cathode material prepared in comparative example 2;
fig. 4 is a graph comparing cycle performance of the high nickel cathode materials prepared in example 3 with comparative examples 1, 2 and 3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a high-nickel cathode material, which comprises the following components:
the chemical formula of the high nickel agglomeration type large particle is LiNixCoyMnzAl(1-x-y-z)O2Wherein x is more than or equal to 0.88 and less than or equal to 1, and y is more than 0 and less than or equal to 0.12，0＜z≤0.12，1-x-y-z≥0；
High nickel agglomerated/single crystal type small particles with the chemical formula LiNiaCobMncAl(1-a-b-c)O2Wherein a is more than or equal to 0.8 and less than or equal to 1, b is more than 0 and less than or equal to 0.2, c is more than 0 and less than or equal to 0.2, and 1-a-b-c is more than or equal to 0;
and the coating is coated on the surfaces of the high-nickel agglomerated large particles and the high-nickel agglomerated/single-crystal small particles.
Preferably, the coating contains elements selected from any one or more of W, B, Al or Ce.
Preferably, the mass ratio of the high nickel agglomerated large particles to the high nickel agglomerated/single crystal small particles is (1-9): 1.
preferably, the particle size of the high nickel agglomerated large particles is 8-20 um, and the particle size of the high nickel agglomerated/single crystal small particles is 2-7 um.
The invention also provides a preparation method of the high-nickel cathode material, which comprises the following steps:
1) through one-time roasting, crushing, water washing, stoving and sieving, LiNi is obtainedxCoyMnzAl(1-x-y-z)O2The high nickel agglomerated large particles;
2) through one-time roasting, crushing, water washing, stoving and sieving, LiNi is obtainedaCobMncAl(1-a-b-c)O2The high nickel agglomerated/single crystal type small particles;
3) uniformly mixing the high-nickel agglomerated large particles and the high-nickel agglomerated/single-crystal small particles, then uniformly mixing the mixture with the coating at a high speed, and carrying out rapid heating secondary roasting, crushing and screening to obtain the high-nickel anode material.
The high nickel agglomerated large particles and the high nickel agglomerated/single crystal type small particles are uniformly mixed (Bimodal method), so that the Bimodal method can reduce the fracturing condition of the agglomerated large particle sample so as to maintain the stability of the material structure; the advantages of high capacity of high nickel agglomerated large particles, low interface impedance and high compaction density and the advantage of stable cycle performance of high nickel agglomerated/single crystal type high nickel small particles can be fully fused, so that the rolling density of the battery pole piece is effectively improved; the material and power loss in the circulation process is further reduced by adjusting and optimizing the proportion of the high-nickel agglomerated large particles and the high-nickel agglomerated/single-crystal small particles, the long circulation life and the safety performance of the battery are improved, and meanwhile, the manufacturing cost of the material is reduced by combining the rapid heating secondary roasting, the processing time is shortened, the manufacturing cost is saved, and the development purposes of cost reduction and efficiency improvement are realized. The invention has the characteristics of simple preparation process, low cost, small pollution, good electrochemical performance, convenience for industrial production and the like.
Preferably, the mass ratio of the total mass of the high nickel agglomerated large particles and the high nickel agglomerated/single crystal small particles in the step 3) to the mass of the coating is 1: (0 to 0.01).
Preferably, the temperature of the rapid temperature rise secondary roasting in the step 3) is 200-320 ℃, the temperature rise rate is 5-15 ℃/min, and the roasting time is 2-4 h.
The invention also provides a lithium ion battery which comprises the high-nickel cathode material.
Example 1
A preparation method of a high-nickel cathode material comprises the following steps:
1) through one-time roasting, crushing, water washing, stoving and sieving, 18um grain size of LiNi is obtained0.90Co0.05Mn0.04Al0.01O2The high nickel agglomerated large particles;
2) through one-time roasting, crushing, water washing, stoving and sieving, LiNi of 7um size and chemical expression is obtained0.92Co0.06Mn0.02O2The high nickel agglomerated/single crystal type small particles;
3) reacting LiNi0.90Co0.05Mn0.04Al0.01O2And LiNi0.92Co0.06Mn0.02O2According to the mass ratio of 1: 1, and then uniformly mixing the mixture with a coating containing an element B at a high speed, wherein the LiNi is0.90Co0.05Mn0.04Al0.01O2And LiNi0.92Co0.06Mn0.02O2Total mass of and packageThe mass ratio of the coating is 1: 0.002, raising the temperature to 260 ℃ at a rate of 15 ℃/min, roasting for 2 hours at the temperature, cooling, crushing and screening to obtain the high-nickel anode material.
Example 2
A preparation method of a high-nickel cathode material comprises the following steps:
1) through one-time roasting, crushing, water washing, stoving and sieving, the product with 15um grain size and LiNi chemical formula is obtained0.92Co0.04Mn0.02Al0.02O2The high nickel agglomerated large particles;
2) through one-time roasting, crushing, water washing, stoving and sieving, 5um grain size of LiNi is obtained0.96Co0.02Mn0.02O2The high nickel agglomerated/single crystal type small particles;
3) reacting LiNi0.92Co0.04Mn0.02Al0.02O2And LiNi0.96Co0.02Mn0.02O2According to the mass ratio of 1.5: 1, and then uniformly mixing with an Al-containing element to obtain a coating at a high speed, wherein the LiNi is0.92Co0.04Mn0.02Al0.02O2And LiNi0.96Co0.02Mn0.02O2The mass ratio of the total mass of (1) to the coating is 1: 0.002, rising the temperature to 280 ℃ at a rate of 12 ℃/min, roasting the mixture for 4 hours at the temperature, cooling the mixture, crushing and screening the mixture to obtain the high-nickel anode material.
Example 3
A preparation method of a high-nickel cathode material comprises the following steps:
1) through one-time roasting, crushing, water washing, stoving and sieving, 13um grain size of LiNi is obtained0.93Co0.04Mn0.02Al0.01O2The high nickel agglomerated large particles;
2) through one-time roasting, crushing, water washing, stoving and sieving, 4um grain size of LiNi is obtained0.95Co0.04Mn0.01O2The high nickel agglomerated/single crystal type small particles;
3) reacting LiNi0.93Co0.04Mn0.02Al0.01O2And LiNi0.95Co0.04Mn0.01O2According to the mass ratio of 7: 3, then uniformly mixing the mixture with a coating containing Al element and B element at a high speed, wherein the LiNi is0.93Co0.04Mn0.02Al0.01O2And LiNi0.95Co0.04Mn0.01O2The mass ratio of the total mass of (1) to the coating is 1: 0.003, the temperature is increased to 240 ℃ at the rate of 10 ℃/min, and the high nickel anode material is obtained after the high nickel anode material is roasted for 3 hours, cooled, crushed and screened.
Example 4
A preparation method of a high-nickel cathode material comprises the following steps:
1) through one-time roasting, crushing, water washing, stoving and sieving, 10um grain size chemical LiNi is obtained0.90Co0.05Mn0.05O2The high nickel agglomerated large particles;
2) through one-time roasting, crushing, water washing, stoving and sieving, the product with particle size of 3um and chemical expression of LiNi is obtained0.95Co0.03Mn0.01Al0.01O2The high nickel agglomerated/single crystal type small particles;
3) reacting LiNi0.90Co0.05Mn0.05O2And LiNi0.95Co0.03Mn0.01Al0.01O2According to the mass ratio of 4: 1, and then uniformly mixing with a coating containing W element at a high speed, wherein LiNi0.90Co0.05Mn0.05O2And LiNi0.95Co0.03Mn0.01Al0.01O2The mass ratio of the total mass of (1) to the coating is 1: 0.005, raising the temperature to 300 ℃ at the rate of 5 ℃/min, roasting at the temperature for 4 hours, cooling, crushing and screening to obtain the high-nickel anode material.
Example 5
A preparation method of a high-nickel cathode material comprises the following steps:
1) through one-time roasting, crushing, water washing, stoving and sieving, 10um grain size chemical LiNi is obtained0.90Co0.05Mn0.05O2The high nickel agglomerated large particles;
2) through one-time roasting, crushing, water washing, stoving and sieving, LiNi with grain size of 3um and chemical expression is obtained0.96Co0.02Mn0.02O2The high nickel agglomerated/single crystal type small particles;
3) reacting LiNi0.90Co0.05Mn0.05O2And LiNi0.96Co0.02Mn0.02O2According to the mass ratio of 9: 1, and then uniformly mixing with a coating containing Ce at a high speed, wherein LiNi0.90Co0.05Mn0.05O2And LiNi0.96Co0.02Mn0.02O2The mass ratio of the total mass of (1) to the coating is 1: 0.01, rising the temperature to 320 ℃ at the speed of 8 ℃/min, roasting for 4 hours at the temperature, cooling, crushing and screening to obtain the high-nickel anode material.
Example 6
1) Through one-time roasting, crushing, water washing, stoving and sieving, 13um grain size of LiNi is obtained0.93Co0.04Mn0.02Al0.01O2The high nickel agglomerated large particles;
2) through one-time roasting, crushing, water washing, stoving and sieving, 4um grain size of LiNi is obtained0.95Co0.04Mn0.01O2The high nickel agglomerated/single crystal type small particles;
3) reacting LiNi0.93Co0.04Mn0.02Al0.01O2And LiNi0.95Co0.04Mn0.01O2According to the mass ratio of 7: 3, then uniformly mixing the mixture with a coating containing Al element and B element at a high speed, wherein the LiNi is0.93Co0.04Mn0.02Al0.01O2And LiNi0.95Co0.04Mn0.01O21: 0.003, the temperature is increased to 240 ℃ at the rate of 10 ℃/min, and the high nickel anode material is obtained after the high nickel anode material is roasted for 3 hours, cooled, crushed and screened.
Comparative example 1
A preparation method of a high-nickel cathode material comprises the following steps:
1) through one-time roasting, crushing, water washing, stoving and sieving, 13um grain size of LiNi is obtained0.93Co0.04Mn0.02Al0.01O2The high nickel agglomerated large particles;
2) reacting LiNi0.93Co0.04Mn0.02Al0.01O2And a coating containing Al element and B element according to the mass ratio of 1: 0.003 of high-speed mixing, heating to 240 ℃ at the speed of 10 ℃/min, preserving the heat for 3 hours at the temperature, cooling, crushing and screening to obtain the high-nickel anode material.
Comparative example 2
A preparation method of a high-nickel cathode material comprises the following steps:
1) through one-time roasting, crushing, water washing, stoving and sieving, 4um grain size of LiNi is obtained0.95Co0.04Mn0.01O2The high nickel agglomerated/single crystal type small particles;
2) reacting LiNi0.95Co0.04Mn0.01O2And a coating containing Al element and B element according to the mass ratio of 1: 0.003 of high-speed mixing, heating to 240 ℃ at the speed of 10 ℃/min, preserving the heat for 3 hours at the temperature, cooling, crushing and screening to obtain the high-nickel anode material.
Comparative example 3
A preparation method of a high-nickel cathode material comprises the following steps:
1) through one-time roasting, crushing, water washing, stoving and sieving, 13um grain size of LiNi is obtained0.93Co0.04Mn0.02Al0.01O2The high nickel agglomerated large particles;
2) through one-time roasting, crushing, water washing, stoving and sieving, 4um grain size of LiNi is obtained0.95Co0.04Mn0.01O2The high nickel agglomerated/single crystal type small particles of (1);
3) reacting LiNi0.93Co0.04Mn0.02Al0.01O2And LiNi0.95Co0.04Mn0.01O2According to the mass ratio of 7: 3, then uniformly mixing the mixture with a coating containing Al element and B element at a high speed, wherein the LiNi is0.93Co0.04Mn0.02Al0.01O2And LiNi0.95Co0.04Mn0.01O2The mass ratio of the total mass of (1) to the coating is 1: 0.003, the temperature is raised to 240 ℃ at the rate of 1 ℃/min, and the high nickel anode material is obtained after the high nickel anode material is roasted for 3 hours, cooled, crushed and screened.
Fig. 1, fig. 2, and fig. 3 are SEM images of the high nickel cathode materials obtained in example 3, comparative example 1, and comparative example 2, respectively, and it can be seen from the SEM images that in example 3, the agglomerated/single crystal type small particles in the binodal sample obtained by performing rapid temperature rise secondary calcination after the high nickel agglomerated large particles, the high nickel agglomerated/single crystal type small particles, and the coating are uniformly mixed can sufficiently fill the gaps between the agglomerated large particles, and increase the contact between the high nickel cathode material particles.
The compacted densities of the high-nickel positive electrode materials obtained in examples 1 to 6 and comparative examples 1 to 3 were tested at 257.5MPa, and assembled into a button cell, and the first discharge specific capacity, the first coulombic efficiency, the DCR, and the capacity retention rate after 100 cycles were tested, to obtain table 1.
The test conditions of the button cell for the specific discharge capacity, the first coulombic efficiency and the DCR are LR 2032, 0.2C, 3.0-4.3V and vs. Li+(ii)/Li; the 100-time circulation test conditions are LR 2032, 0.5C, 2.5-4.25V and vs. Li+and/Li. The positive pole piece of the battery is made of a high-nickel positive pole material: conductive agent: PVDF 96: 2.5: 1.5, and conventional samples: conductive agent: PVDF 90: 5: 5, the use amount of the conductive agent is obviously reduced due to the improvement of the conductivity of the positive electrode material, so that the energy density of the battery is further effectively improved, and the rolling density of the pole piece is 3.5g/cm3The energy density of the battery can be fully improved.
TABLE 1
As can be seen from the data in table 1, the high-nickel cathode materials prepared in embodiments 1 to 6 of the present invention have both the compacted density and the capacity, reduce the first DCR, significantly improve the cycle life of the battery, and have good application prospects in the field of lithium ion batteries; in the comparative example 1, because Bimodal is not used, the contact of particles in the pole piece is poor, the DCR is obviously improved, and the energy density is low; compared with the embodiment 3, the secondary roasting does not adopt the extremely fast temperature rise, so that the coating effect is poor, and the cycle performance is seriously reduced; example 3 compared with examples 1, 2, 4, and 5, the compacted density is highest, the capacity is highest, the cycle retention rate at 100 weeks is best, the first efficiency and DCR are good, and the good Bimodal ratio can significantly improve the energy density and the long cycle life of the battery; the capacity of example 3 is better than that of example 6 because the high nickel agglomerated/single crystal type small particles can more largely fill the gaps of the high nickel agglomerated type large particles, so the compaction density of example 3 is higher and the capacity is better.
Although some embodiments of the present invention have been described in detail, the present invention is not limited to the above-described embodiments, and those skilled in the art can make equivalent modifications or substitutions without departing from the spirit of the present invention, and such equivalent modifications or substitutions are included in the scope of the present invention defined by the claims.
Claims (8)
1. A high nickel positive electrode material, comprising:
the chemical formula of the high nickel agglomeration type large particles is LiNixCoyMnzAl(1-x-y-z)O2Wherein x is more than or equal to 0.88 and less than or equal to 1, y is more than 0 and less than or equal to 0.12, z is more than 0 and less than or equal to 0.12, and 1-x-y-z is more than or equal to 0;
high nickel agglomerated/single crystal type small particles with the chemical formula of LiNiaCobMncAl(1-a-b-c)O2Wherein a is more than or equal to 0.8 and less than or equal to 1, b is more than 0 and less than or equal to 0.2, c is more than 0 and less than or equal to 0.2, and 1-a-b-c is more than or equal to 0;
and a coating which coats the surfaces of the high nickel agglomerated large particles and the high nickel agglomerated/single crystal small particles.
2. The high nickel positive electrode material according to claim 1, wherein the coating contains one or more elements selected from W, B, Al and Ce.
3. The high-nickel positive electrode material according to claim 1, wherein the mass ratio of the high-nickel agglomerated large particles to the high-nickel agglomerated/single-crystal small particles is (1 to 9): 1.
4. the high-nickel positive electrode material according to claim 1, wherein the particle size of the high-nickel agglomerated large particles is 8 to 20um, and the particle size of the high-nickel agglomerated/single crystal small particles is 2 to 7 um.
5. The method for preparing a high nickel positive electrode material according to any one of claims 1 to 4, comprising the steps of:
1) through one-time roasting, crushing, water washing, stoving and sieving, LiNi is obtainedxCoyMnzAl(1-x-y-z)O2The high nickel agglomerated large particles;
2) through one-time roasting, crushing, water washing, stoving and sieving, LiNi is obtainedaCobMncAl(1-a-b-c)O2The high nickel agglomerated/single crystal type small particles;
3) uniformly mixing high-nickel agglomerated large particles and high-nickel agglomerated/single-crystal small particles, then uniformly mixing the mixture with a coating at a high speed, and carrying out rapid heating secondary roasting, crushing and screening to obtain the high-nickel anode material.
6. The method according to claim 5, wherein the mass ratio of the total mass of the high nickel agglomerated large particles and the high nickel agglomerated/single crystal type small particles to the coating in step 3) is 1: (0 to 0.01).
7. The preparation method according to claim 5, wherein the temperature of the rapid-temperature-rise secondary roasting in the step 3) is 200-320 ℃, the temperature rise rate is 5-15 ℃/min, and the roasting time is 2-4 h.
8. A lithium ion battery is characterized by comprising the high-nickel cathode material as defined in claim 1 to 4, wherein the high-nickel cathode material is prepared by the preparation method as defined in any one of claims 5 to 7.
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