CN115064678A - High-nickel low-cobalt positive electrode material, and preparation method and application thereof - Google Patents
High-nickel low-cobalt positive electrode material, and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 95
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 86
- 239000010941 cobalt Substances 0.000 title claims abstract description 86
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010406 cathode material Substances 0.000 claims abstract description 65
- 239000011247 coating layer Substances 0.000 claims abstract description 29
- 239000011159 matrix material Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 18
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 14
- 229910052746 lanthanum Inorganic materials 0.000 claims description 13
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 239000002019 doping agent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 8
- 150000003624 transition metals Chemical class 0.000 abstract description 8
- 238000004090 dissolution Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 238000012216 screening Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
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- 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
- H01M4/485—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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- H01—ELECTRIC ELEMENTS
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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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- 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 provides a high-nickel low-cobalt positive electrode material, and a preparation method and application thereof. The high-nickel low-cobalt cathode material comprises a high-nickel low-cobalt cathode material matrix and a coating layer, wherein the coating layer is coated on the surface of the high-nickel low-cobalt cathode material matrix; the chemical formula of the high-nickel low-cobalt cathode material matrix is LiNi x Co y M 1‑x‑y‑z Q Z O 2 Wherein M is Mn and/or Al, Q is one of Mg, Ti, Zr, Y, Nb, W, Ce, Sr or SbOne or more of x is more than 0.88 and less than or equal to 0.96, y is more than or equal to 0 and less than 0.04, z is more than or equal to 0 and less than 0.04, and x + y + z is less than 1; the chemical formula of the coating layer is LaTO 3 Wherein T is one or more of Ni, Mn or Al. The high-nickel low-cobalt cathode material is used as a lithium ion battery cathode material, can inhibit the dissolution of transition metal from a cathode for a long time, does not influence the dynamic performance of the lithium ion battery cathode material, and can obviously improve the discharge specific capacity, the coulombic efficiency and the cycle life of the battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-nickel low-cobalt positive electrode material, and a preparation method and application thereof.
Background
The development of power batteries leads to the accelerated consumption of raw materials, and high-nickel low-cobalt materials and medium-nickel high-voltage materials become two major development trends of the current lithium ion battery cathode materials. Among them, the high nickel and low cobalt materials are increasingly used because of their advantages of low cost and high energy density. However, the cycle life of the battery is seriously affected by the dissolution of transition metal in the high-nickel low-cobalt material and the interface reaction between the Jahn-Teller distorted surface lattice and the electrolyte.
At present, the passivation layer is mostly coated on the surface of the anode material to solve the problems. However, most passivation layers are formed in a thermodynamic equilibrium state under low temperature conditions to avoid interdiffusion, which results in the generation of surface deposits that do not bond with the host lattice. Meanwhile, low temperature does not ensure sufficient diffusion to form a passivation layer having a non-uniform thickness, and in order to ensure better coverage, a passivation layer having a sufficient thickness is generally prepared. However, the above factors greatly limit the improvement of the cycle life of the high-nickel low-cobalt cathode material in the lithium ion battery.
Disclosure of Invention
In view of the above, the present invention provides a high nickel and low cobalt cathode material, and a preparation method and an application thereof. The coating layer is arranged on the surface of the high-nickel low-cobalt positive electrode material, has atomic-level thin thickness and is connected with the layered structure main crystal lattice in crystallography, can inhibit the dissolution of transition metal from the positive electrode for a long time, does not influence the dynamics of the transition metal, and greatly improves the discharge specific capacity, the coulombic efficiency, the cycle life and the safety performance of the battery.
In a first aspect, the invention provides a high-nickel low-cobalt cathode material, which comprises a high-nickel low-cobalt cathode material substrate and a coating layer, wherein the coating layer is coated on the surface of the high-nickel low-cobalt cathode material substrate;
the chemical formula of the high-nickel low-cobalt cathode material matrix is LiNi x Co y M 1-x-y-z Q Z O 2 Wherein M is Mn and/or Al, Q is one or more of Mg, Ti, Zr, Y, Nb, W, Ce, Sr or Sb, x is more than 0.88 and less than or equal to 0.96, Y is more than or equal to 0 and less than 0.04, z is more than or equal to 0 and less than 0.04, and x + Y + z is less than 1;
the chemical formula of the coating layer is LaTO 3 Wherein T is one or more of Ni, Mn or Al.
Preferably, the mass ratio of the coating layer to the high-nickel low-cobalt cathode material matrix is (0.002-0.025): 1.
In a second aspect, the invention provides a preparation method of the high-nickel low-cobalt cathode material, which comprises the following steps:
(1) mixing a high-nickel low-cobalt positive electrode material matrix precursor, a doping agent, a lithium source and a lanthanum source to obtain an intermediate; the chemical formula of the high-nickel low-cobalt anode material matrix precursor is Ni x Co y M 1-x-y (OH) 2 Wherein M is Mn and/or Al, x is more than 0.88 and less than or equal to 0.96, and y is more than or equal to 0 and less than or equal to 0.04; the dopant is one or more of Mg, Ti, Zr, Y, Nb, W, Ce, Sr or Sb;
(2) and roasting the intermediate to obtain the high-nickel low-cobalt cathode material.
Preferably, the molar ratio of the high-nickel low-cobalt cathode material matrix precursor to the dopant to the lithium source to the lanthanum source is 1 (0-0.02) to 1-1.08 to 0.001-0.01.
Preferably, the lithium source is selected from lithium hydroxide and/or lithium carbonate.
Preferably, the lanthanum source is selected from one or more of lanthanum oxide, lanthanum chloride, lanthanum sulfate or lanthanum nitrate.
Preferably, the roasting temperature is 600-1000 ℃, and the roasting time is 4-16 h.
In a third aspect, the invention provides a lithium ion battery, which comprises the high-nickel low-cobalt cathode material or the high-nickel low-cobalt cathode material prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention coats LaTO on the surface of a high-nickel low-cobalt anode material substrate 3 The transition metal can be inhibited from dissolving from the positive electrode for a long time, the dynamic performance of the transition metal can not be influenced, the material polarization decomposition caused by too thick coating layer and uneven coating can be avoided, and the discharge specific capacity, the coulombic efficiency and the cycle life of the battery can be obviously improved;
(2) the coating layer is an atomically thin surface layer connected with a main crystal lattice of the main layered structure and is immiscible with the main material so as to ensure uniform coating and stable structure;
(3) the preparation method provided by the invention achieves the doping and cladding effects by adopting a one-time roasting process, optimizes the process flow and reduces the production cost.
Drawings
FIG. 1 is an SEM image of the high-nickel and low-cobalt cathode material obtained in example 1;
FIG. 2 is an XRD spectrum of the high nickel and low cobalt cathode material obtained in example 1;
fig. 3 is a graph comparing cycle performance of the high nickel and low cobalt cathode materials obtained in example 1, example 5, comparative example 1 and comparative example 2.
Detailed Description
All the raw materials involved in the present invention are not particularly limited in their sources, and may be purchased from the market or prepared according to a conventional preparation method well known to those skilled in the art.
The invention provides a high-nickel low-cobalt cathode material, which comprises a high-nickel low-cobalt cathode material substrate and a coating layer, wherein the coating layer is coated on the surface of the high-nickel low-cobalt cathode material substrate; the chemical formula of the high-nickel low-cobalt cathode material matrix is LiNi x Co y M 1-x-y-z Q Z O 2 Wherein M is Mn and/or Al, Q is one or more of Mg, Ti, Zr, Y, Nb, W, Ce, Sr or Sb, and x is more than 0.88 and less than or equal to 0.96, y is more than or equal to 0 and less than 0.04, z is more than or equal to 0 and less than 0.04, and x + y + z is less than 1; the chemical formula of the coating layer is LaTO 3 Wherein T is one or more of Ni, Mn or Al.
The invention coats LaTO on the surface of a high-nickel low-cobalt anode material substrate 3 The coating layer has atomic-level thin thickness and is connected with the main crystal lattice of the main material in crystallography, so that the dissolution of transition metal from the anode can be inhibited for a long time, the kinetic performance of the coating layer can not be influenced, the polarization decomposition of the material caused by too thick coating and nonuniform coating can be avoided, and the specific discharge capacity, the coulombic efficiency, the cycle life and the safety of the battery can be obviously improved.
The coating layer is formed by the reaction of a lanthanum source and one or more of Ni, Mn or Al on the surface of a high-nickel low-cobalt cathode material matrix, and the structural formula is LaTO 3 Wherein T is one or more of Ni, Mn or Al.
The doping of Q can play a supporting role between transition metal layers and improve the dynamic performance of the high-nickel low-cobalt cathode material, thereby ensuring the stability of the layered structure of the high-nickel low-cobalt cathode material and improving the lithium ion transmission performance.
In the invention, the mass ratio of the coating layer to the high-nickel low-cobalt cathode material matrix is preferably (0.002-0.025): 1.
The mass ratio of the coating layer to the high-nickel low-cobalt cathode material substrate can be 0.002:1, 0.0021:1, 0.0022:1, 0.0023:1, 0.0024:1 or 0.0025:1, and other values in the above numerical value range can be selected, and are not described in detail herein.
The invention also provides a preparation method of the high-nickel low-cobalt cathode material, which comprises the following steps:
(1) mixing a high-nickel low-cobalt positive electrode material matrix precursor, a doping agent, a lithium source and a lanthanum source to obtain an intermediate; the chemical formula of the high-nickel low-cobalt anode material matrix precursor is Ni x Co y M 1-x-y (OH) 2 Wherein M is Mn and/or Al, x is more than 0.88 and less than or equal to 0.96, and y is more than or equal to 0 and less than or equal to 0.04; the dopant is one or more of Mg, Ti, Zr, Y, Nb, W, Ce, Sr or Sb;
(2) and roasting the intermediate to obtain the high-nickel low-cobalt cathode material.
According to the preparation method provided by the invention, the mixture of the high-nickel low-cobalt cathode material matrix precursor, the lithium source and the lanthanum source is calcined at high temperature, wherein the lanthanum source reacts with any one or more of Ni, Mn or Al on the surface of the high-nickel low-cobalt cathode material matrix precursor to form the coating layer, the whole coating process is completed by a one-step method, the process flow is reduced, the production cost is reduced, and the industrial production is facilitated.
The source of the high-nickel low-cobalt cathode material matrix precursor is not particularly limited in the invention, and the precursor can be purchased from the market or prepared according to the conventional method well known to the person skilled in the art.
In the invention, the molar ratio of the high-nickel low-cobalt cathode material matrix precursor to the dopant to the lithium source to the lanthanum source is 1 (0-0.02) to 1-1.08 to 0.001-0.01.
The molar ratio of the matrix precursor of the high-nickel low-cobalt cathode material, the dopant, the lithium source and the lanthanum source can be 1:0.01:1:0.001, 1:0.01:1.02:0.005, 1:0.01:1:0.008, 1:0.015:1:0.01, 1:0.015:1.04:0.05, 1:0.015:1.06:0.05, 1:0.2:1.08:0.001, 1:0.2:1.08:0.05, 1:0.2:1.08:0.08 or 1:0.2:1.08:0.01, and the like.
Other values within the above range can be selected, and are not further described herein.
In the present invention, the lithium source is selected from lithium hydroxide and/or lithium carbonate. The lanthanum source is selected from one or more of lanthanum oxide, lanthanum chloride, lanthanum sulfate or lanthanum nitrate.
In the invention, the roasting temperature is preferably 600-1000 ℃, and the roasting time is preferably 4-16 h.
The roasting temperature can be 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃, etc.
The roasting time can be 4h, 6h, 8h, 10h, 12h, 14h or 16h and the like.
The values in the above range can be selected, and are not described in detail herein.
In the present invention, after the intermediate is calcined, it preferably further includes cooling, crushing and screening processes in this order.
The invention also provides a lithium ion battery which comprises the high-nickel low-cobalt cathode material or the high-nickel low-cobalt cathode material prepared by the preparation method.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
To further illustrate the present invention, the following examples are provided for illustration. The experimental starting materials used in the following examples of the present invention are either commercially available or prepared according to conventional methods well known to those skilled in the art.
Example 1
The embodiment provides a high-nickel low-cobalt cathode material, and the preparation method comprises the following steps:
(1) according to LiOH ZrO 2 :La 2 O 3 :Ni 0.90 Co 0.04 Mn 0.06 (OH) 2 The ingredients were mixed at a molar ratio of 1.03:0.005:0.005:1, and mixed thoroughly to obtain a mixture.
(2) Roasting the mixture at 800 ℃ for 12h, crushing and screening to obtain a high-nickel low-cobalt positive electrode material;
in the high-nickel low-cobalt cathode material, the chemical formula of a matrix is LiNi 0.895 Co 0.040 Mn 0.060 Zr 0.005 O 2 The coating layer is La 2 O 3 Products of reaction with Ni and/or Mn at the surface of the substrate.
The positive electrode material obtained in example 1 was subjected to morphology characterization by a scanning electron microscope, and the result is shown in fig. 1, which shows that the surface of the positive electrode material was smooth and uniform and had no aggregates.
When XRD test is performed on the positive electrode material obtained in example 1, the result is shown in fig. 2, which shows that the positive electrode material has a sharp diffraction peak, indicating that the crystal structure is good and the crystallinity is high.
Example 2
The embodiment provides a high-nickel low-cobalt cathode material, and a preparation method thereof is as follows:
(1) according to LiOH to TiO 2 :LaCl 3 :Ni 0.92 Co 0.04 Mn 0.04 (OH) 2 Preparing materials according to a molar ratio of 1.02:0.005:0.005:1, and fully mixing to obtain a mixture;
(2) roasting the mixture at 770 ℃ for 15h, crushing and screening to obtain a high-nickel low-cobalt cathode material;
in the high-nickel low-cobalt cathode material, the chemical formula of a matrix is LiNi 0.915 Co 0.040 Mn 0.040 Ti 0.005 O 2 The coating layer is LaCl 3 Products of reaction with Ni and/or Mn at the surface of the substrate.
Example 3
The embodiment provides a high-nickel low-cobalt cathode material, and the preparation method comprises the following steps:
(1) according to the formula LiOH CeO 2 :La(NO 3 ) 3 :Ni 0.95 Co 0.03 Al 0.02 (OH) 2 Preparing materials according to a molar ratio of 1.05:0.01:0.01:1, and fully mixing to obtain a mixture;
(2) roasting the mixture at 830 ℃ for 10 hours, crushing and screening to obtain a high-nickel low-cobalt positive electrode material;
in the high-nickel low-cobalt cathode material, the chemical formula of a matrix is LiNi 0.940 Co 0.030 Al 0.020 Ce 0.010 O 2 The coating layer is La (NO) 3 ) 3 A product of reaction with Ni and/or Al of the surface of the substrate.
Example 4
The embodiment provides a high-nickel low-cobalt cathode material, and the preparation method comprises the following steps:
(1) according to LiOH: W 2 O 3 :SrCO 3 :La 2 (SO 4 ) 3 :Ni 0.93 Co 0.02 Mn 0.03 Al 0.02 (OH) 2 Blending according to the molar ratio of 1.08:0.002:0.002:0.01:1, and fully mixing to obtain a mixture;
(2) roasting the mixture at 830 ℃ for 10 hours, crushing and screening to obtain a high-nickel low-cobalt positive electrode material;
in the high-nickel low-cobalt cathode material, the chemical formula of a matrix is LiNi 0.924 Co 0.020 Mn 0.030 Al 0.020 W 0.004 Sr 0.002 O 2 The coating layer is La 2 (SO 4 ) 3 And a product of reaction with one or more of Ni, Al and Mn at the surface of the substrate.
Example 5
(1) According to LiOH: La 2 O 3 :Ni 0.90 Co 0.04 Mn 0.06 (OH) 2 Preparing materials according to a molar ratio of 1.03:0.005:1, and fully mixing to obtain a mixture;
(2) roasting the mixture at 800 ℃ for 12h, crushing and screening to obtain a high-nickel low-cobalt positive electrode material;
in the high-nickel low-cobalt cathode material, the chemical formula of a matrix is LiNi 0.900 Co 0.040 Mn 0.060 O 2 The coating layer is La 2 O 3 Products of reaction with Ni and/or Mn.
Comparative example 1
(1) According to LiOH ZrO 2 :Ni 0.90 Co 0.04 Mn 0.06 (OH) 2 Preparing materials according to a molar ratio of 1.03:0.005:1, and fully mixing to obtain a mixture;
(2) roasting the mixture at 800 ℃ for 12h, crushing and screening to obtain the LiNi with the chemical formula 0.895 Co 0.040 Mn 0.060 Zr 0.005 O 2 The high nickel and low cobalt cathode material.
Comparative example 2
(1) According to LiOH to Ni 0.90 Co 0.04 Mn 0.06 (OH) 2 Mixing the materials according to the molar ratio of 1.03:1, and fully mixingThen obtaining a mixture;
(2) roasting the mixture at 800 ℃ for 12h, crushing and screening to obtain the LiNi with the chemical formula 0.900 Co 0.040 Mn 0.060 O 2 The high nickel and low cobalt cathode material.
Performance testing
The positive electrode materials obtained in examples 1 to 5 and comparative examples 1 to 2 were assembled into button cells. The test conditions are LR 2032, 0.3C, 2.5-4.3V, vs + (ii)/Li; the positive pole piece of the battery is made of the following positive pole materials: the conductive agent is PVDF 96:2: 2. The test results are shown in table 1 below:
TABLE 1
As can be seen from the data in the above table, the high nickel and low cobalt cathode materials obtained in examples 1 to 4 have good dynamic performance, the assembled battery has high specific discharge capacity and good cycle performance, and example 5 has reduced specific discharge capacity and efficiency for the first time due to the absence of Q doping. Comparative example 1 resulted in poor capacity retention due to no formation of a coating layer. Comparative example 2, since no doping of Q was performed and no clad layer was formed, the first discharge specific capacity and the cycle retention rate were significantly deteriorated.
Cycle performance tests were performed on the high nickel and low cobalt positive electrode materials obtained in example 1, example 5, comparative example 1, and comparative example 2, according to the following test methods:
and performing 0.3C constant current charging and discharging for 200 weeks in a constant temperature environment of 45 ℃ within a voltage range of 2.5-4.25V.
As shown in fig. 3, it can be seen that the doping of Q and the formation of the coating both contribute to improving the capacity retention rate of the high-nickel low-cobalt cathode material, wherein the formation of the coating can more effectively protect the structural stability of the high-nickel low-cobalt cathode material, and the effect of improving the capacity retention rate is better.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A high-nickel low-cobalt cathode material comprises a high-nickel low-cobalt cathode material matrix and a coating layer, wherein the coating layer is coated on the surface of the high-nickel low-cobalt cathode material matrix;
the chemical formula of the high-nickel low-cobalt cathode material matrix is LiNi x Co y M 1-x-y-z Q Z O 2 Wherein M is Mn and/or Al, Q is one or more of Mg, Ti, Zr, Y, Nb, W, Ce, Sr or Sb, x is more than 0.88 and less than or equal to 0.96, Y is more than or equal to 0 and less than 0.04, z is more than or equal to 0 and less than 0.04, and x + Y + z is less than 1;
the chemical formula of the coating layer is LaTO 3 Wherein T is one or more of Ni, Mn or Al.
2. The high-nickel and low-cobalt positive electrode material as claimed in claim 1, wherein the mass ratio of the coating layer to the high-nickel and low-cobalt positive electrode material substrate is (0.002-0.025): 1.
3. The preparation method of the high-nickel low-cobalt cathode material as claimed in claim 1 or 2, characterized by comprising the following steps:
(1) mixing a high-nickel low-cobalt positive electrode material matrix precursor, a doping agent, a lithium source and a lanthanum source to obtain an intermediate; the chemical formula of the high-nickel low-cobalt anode material matrix precursor is Ni x Co y M 1-x-y (OH) 2 Wherein M is Mn and/or Al, x is more than 0.88 and less than or equal to 0.96, and y is more than or equal to 0 and less than or equal to 0.04; the dopant is one or more of Mg, Ti, Zr, Y, Nb, W, Ce, Sr or Sb;
(2) and roasting the intermediate to obtain the high-nickel low-cobalt cathode material.
4. The preparation method of claim 3, wherein the molar ratio of the high-nickel low-cobalt positive electrode material matrix precursor to the dopant to the lithium source to the lanthanum source is 1 (0-0.02): (1-1.08): (0.001-0.01).
5. The method according to claim 3, wherein the lithium source is selected from lithium hydroxide and/or lithium carbonate.
6. The method according to claim 3, wherein the lanthanum source is selected from one or more of lanthanum oxide, lanthanum chloride, lanthanum sulfate, or lanthanum nitrate.
7. The method for preparing the high-nickel low-cobalt cathode material as claimed in claim 3, wherein the calcination temperature is 600-1000 ℃, and the calcination time is 4-16 h.
8. A lithium ion battery, which is characterized by comprising the high-nickel low-cobalt cathode material of claim 1 or 2 or the high-nickel low-cobalt cathode material prepared by the preparation method of any one of claims 3 to 7.
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