CN115140780B - Ternary positive electrode material of two-phase coherent lithium ion battery and preparation method thereof - Google Patents
Ternary positive electrode material of two-phase coherent lithium ion battery and preparation method thereof Download PDFInfo
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- CN115140780B CN115140780B CN202210793648.3A CN202210793648A CN115140780B CN 115140780 B CN115140780 B CN 115140780B CN 202210793648 A CN202210793648 A CN 202210793648A CN 115140780 B CN115140780 B CN 115140780B
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 47
- 230000001427 coherent effect Effects 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 15
- 238000000034 method Methods 0.000 claims abstract description 41
- 230000008569 process Effects 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical group 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000002572 peristaltic effect Effects 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 11
- 230000001276 controlling effect Effects 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 32
- 239000010406 cathode material Substances 0.000 description 24
- 229910015645 LiMn Inorganic materials 0.000 description 16
- 238000001354 calcination Methods 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 229910002367 SrTiO Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 4
- 238000002715 modification method Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
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- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
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- 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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Abstract
The invention discloses a ternary positive electrode material of a two-phase coherent lithium ion battery, which is prepared by introducing a new phase into a ternary positive electrode material of LiNi xCoyMn1‑x‑yO2, wherein x is more than 0 and less than 1, and y is more than 0 and less than 1; the new phase is metal oxide, and the new phase grows in a coherent manner with a lamellar phase in the LiNi xCoyMn1‑x‑yO2 ternary positive electrode material. The two phases of co-lattice growth in the invention are a new phase which is symbiotic with lamellar phases in the particle phase of the ternary positive electrode material by regulating and controlling the components and technological parameters of the ternary positive electrode material in the material synthesis process. The lamellar phase and the new phase in the ternary positive electrode particle phase grow in a coherent mode, the new phase plays a role of pinning in crystals to prevent collapse of a crystal structure caused by anisotropic volume change in the charge and discharge process, and therefore the mechanical failure problem of the ternary positive electrode material in the circulation process can be relieved.
Description
Technical Field
The invention relates to the field of preparation of lithium ion battery materials, and discloses a ternary positive electrode material of a two-phase coherent lithium ion battery and a preparation method thereof.
Background
Since the 21 st century, new energy electric vehicles have gradually entered human daily life. Lithium ion batteries have successfully taken up the electric automobile application market due to energy density and lifetime advantages. In order to increase the service life and the cruising mileage of an electric vehicle, a ternary positive electrode material with a high specific capacity is being widely used and studied. However, the use of ternary cathode materials in high energy density lithium ion batteries also faces a number of problems. The lithium ion is extracted and intercalated with anisotropic volume change in the charge and discharge process of the ternary positive electrode material, and the process can lead to intragranular cracks and even particle breakage in the positive electrode material, and finally serious degradation of electrochemical performance is caused. Surface coating and element doping processes are often used to alleviate the problem of mechanical failure of ternary positive electrode materials. CN113363478a discloses a commercial lithium-containing compound Li 4Ti5O12 coated ternary cathode material. CN109742336a discloses a W-doped ternary cathode material. The ternary positive electrode material modified by the surface coating and element doping process can inhibit the mechanical failure problem and improve the electrochemical stability, but the surface coating and doping elements can not solve the repeated anisotropic volume change in the particles in the long-cycle process. In view of this, it is indeed necessary to provide a simple method for introducing a co-grown electrochemically inert crystalline phase within the ternary positive electrode material phase for stabilizing the structure to extend the battery life.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a ternary positive electrode material of a lithium ion battery and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
A ternary positive electrode material of a two-phase coherent lithium ion battery is characterized in that a new phase of coherent growth is induced in a ternary positive electrode material phase to stabilize a material structure. The ternary positive electrode material comprises the components of LiNi xCoyMn1-x-yO2, wherein x is more than 0 and less than 1, and y is more than 0 and less than 1; the new phase of the coherent growth is metal oxide, and further, when the component of the new phase is M xOy, M is one or more of Ni, la, sr, Y, zr, ti, nb, and x and y are required to satisfy valence state balance; when the component is LiM 2O4, M is one or more of Ni, co and Mn; when the component is LiMO 3, where M is one or more of Sr, ti, sn, zr, nb, ta, W, la; when the component is a 4[LiM]O8, wherein a is one or more of Ti, sn, zr, nb, ta, W, la; m is one or more of Mn, co, ni, ti, sn, sr, zr, ta, W. The crystal structure of the new phase grown in the coherent mode is one of a spinel structure, a perovskite structure or a rock salt structure.
The two phases of co-lattice growth in the invention are a new phase which is symbiotic with lamellar phases in the particle phase of the ternary positive electrode material by regulating and controlling the components and technological parameters of the ternary positive electrode material in the material synthesis process. The lamellar phase and the new phase in the ternary positive electrode particle phase grow in a coherent mode, the new phase plays a role of pinning in crystals to prevent collapse of a crystal structure caused by anisotropic volume change in the charge and discharge process, and therefore the mechanical failure problem of the ternary positive electrode material in the circulation process can be relieved.
By "coherent" is meant that the atoms at the interface are located at the junction of the two-phase lattice at the same time, i.e. the lattices of the two phases are joined to each other, the atoms at the interface being common to both. According to the preparation method, a small amount of new phases are introduced into the main body layered ternary material, the new phases and the main body layered structure perform coherent growth, a pinning effect is achieved in the material, and the stress change of the ternary material in the lithium removal and intercalation process is greatly limited, so that the problem of fragmentation of ternary material particles is solved through the coherent growth method for the first time.
Specifically, the preparation method of the two-phase coherent growth ternary positive electrode material comprises the following steps:
First, precursor preparation, here using a ternary coprecipitation reactor. A transition metal salt solution with a certain concentration is prepared according to the proportion of Ni, co and Mn elements, a new phase metal salt solution with a certain concentration is prepared, and the two solutions are mixed according to a specific proportion. Sodium hydroxide and aqueous ammonia solutions of a certain concentration are used to adjust the pH of the reaction system. And adding deionized water at the bottom of the three-way coprecipitation reaction kettle to serve as base solution, adding salt solution into the reaction kettle body through a peristaltic pump, simultaneously adding alkali liquor and ammonia water to maintain the pH value stable, and controlling the temperature of the reaction kettle body through a constant-temperature water area. Nitrogen is used as a shielding gas in the whole reaction process, and the stirring speed is controlled. And after the salt solution is completely added into the kettle body, continuing stirring and aging after the reaction is completely finished. Repeatedly cleaning the reaction product by deionized water and ethanol, and drying under vacuum condition to obtain precursor powder; and carrying out post-treatment on the precursor powder to realize two-phase coherent growth and obtain the ternary positive electrode material of the lithium ion battery, wherein the key of the post-treatment is to control a calcination process, and the following post-treatment process can be adopted:
The first method is that the precursor powder is mixed with a proper amount of lithium salt, and the ternary anode material with a new phase of rock salt structure is obtained through a heat treatment process 1 under pure oxygen atmosphere.
The second method is that a new phase metal salt solution is not added in the preparation process of precursor powder, but only a transition metal salt solution is added into a ternary coprecipitation reaction kettle, the precursor powder is mixed with a proper amount of lithium salt, the molar ratio of lithium to transition metal is controlled to be less than 1, and the ternary positive electrode material with a spinel structure of a new phase growing in a coherent way is obtained through a heat treatment process 2 in pure oxygen atmosphere;
The third method is that the precursor powder is subjected to a heat treatment process 3 to obtain an oxide precursor material, the oxide precursor material is mixed with a proper amount of lithium salt, and a ternary anode material with a new phase of perovskite structure is obtained through a heat treatment process 4 in pure oxygen atmosphere;
Wherein the heat treatment process 1 is three-stage heat treatment, wherein the first stage is heat treatment at 400-500 ℃ for 3-6h, the second stage is heat treatment at 600-800 ℃ for 6-10h, and the third stage is heat treatment at 900-950 ℃ for 4-6h, and then cooling along with the furnace.
Wherein the heat treatment process 2 is two-stage heat treatment, the first stage is heat treatment at 400-500 ℃ for 3-6h, and the second stage is heat treatment at 700-950 ℃ for 8-20h, and then cooling along with the furnace.
Wherein, the heat treatment process 3 is as follows: the heat treatment temperature is 400-650 ℃, the heat treatment time is 3-8 hours, and then the furnace cooling is carried out.
Wherein the heat treatment process 4 is two-stage heat treatment, the first stage is heat treatment at 300-600 ℃ for 3-6h, the second stage is heat treatment at 700-950 ℃ for 8-20h, and finally the cooling rate is set to be 1-5 ℃/min.
As a preferred technical scheme, the new phase co-lattice grown in the invention is a ternary positive electrode material, wherein the mass percentage of the ternary positive electrode material is w, and 0.1% < w <5%.
The lye in the present invention may be sodium hydroxide solution.
The lithium salt is typically one of lithium carbonate, lithium hydroxide, lithium chloride, lithium sulfate.
Compared with the prior art, the invention has the following beneficial effects:
The ternary positive electrode material with stable structure is obtained by adopting a simple method, and the lamellar phase and the new phase exist in a coherent growth mode. In the charge and discharge process, lithium ions in the lamellar phase are separated and intercalated with repeated anisotropic volume changes, and new phases which grow together are pinned in the lamellar phase, so that the lamellar phase is supported to prevent structural collapse. Due to the pinning effect of the new phase, the modified ternary positive electrode material can maintain stable crystal structure under the conditions of high voltage and long cycle, and the problem of mechanical failure of particles does not occur, so that good electrochemical performance is obtained.
Drawings
FIG. 1 is an X-ray diffraction pattern of La 2O3 co-grown ternary cathode material;
FIG. 2 is a scanning electron microscope image of La 2O3 co-grown ternary cathode material;
fig. 3 a transmission electron microscope image of la 2O3 co-grown ternary cathode material. The Disorder phase is La 2O3 phase, and the Layered phase is lamellar phase;
FIG. 4. Cycle performance of NCM811 raw sample and modified sample NCM811-La 2O3 at a current density of 40 mAh/g;
FIG. 5X-ray transmission photographs of NCM811 original and modified samples NCM811-La 2O3 after 50 cycles at a current density of 40 mAh/g.
FIG. 6 is an X-ray diffraction pattern of LiMn 2O4 co-grown ternary cathode material;
FIG. 7. Cycle performance of NCM811 raw sample and modified sample NCM811-LiMn 2O4 at 40mAh/g current density;
FIG. 8 is an X-ray diffraction pattern of La 4[LiMn]O8 co-grown ternary cathode material;
FIG. 9 is a transmission electron microscope image of La 4[LiMn]O8 co-grown ternary cathode material;
FIG. 10 is a graph of the cycling performance of a co-grown ternary positive electrode material at high cutoff voltage (4.6V);
FIG. 11 is an X-ray diffraction pattern of SrTiO 3 co-grown ternary cathode material;
FIG. 12 cycle performance of NCM811 original sample and modified sample NCM811-SrTiO 3 at 40mAh/g current density;
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the attached drawings and specific embodiments.
Example 1: la 2O3 co-grown stable ternary positive electrode material is prepared through the following steps:
(1) The sulfate solution a was prepared by mixing three sulfates of Ni, co and Mn in a molar ratio of 8:1:1, and the sulfate solution b of La was prepared. The concentration of the solution a and the solution b is 2mol/L, and the solution a and the solution b are mixed according to the volume ratio of 25:1. In addition, a sodium hydroxide solution of 2mol/L and an aqueous ammonia solution of 1mol/L were prepared. Firstly, a metering pump is used to pump the mixed solution into a reaction kettle body at a flow rate of 15L/h, and simultaneously sodium hydroxide and ammonia water solution are added into the reaction kettle to control the pH value of the reaction system to be 11. During the reaction, a nitrogen atmosphere was maintained while maintaining the reactor temperature at 60℃and stirring speed at 550rpm/min. After the reaction liquid is completely consumed, stirring is continued for 2 hours, and finally, aging is carried out for 24 hours along with the kettle. And repeatedly cleaning the reaction product with deionized water to obtain a precursor product, and then transferring the precursor product into a vacuum oven at 80 ℃ for full drying. The obtained precursor is hydroxide of metal element;
(2) 10g of precursor powder and 4.77g of lithium hydroxide monohydrate are weighed, manually mixed in a mortar for 20min, and then transferred into an alumina crucible;
(3) In pure oxygen atmosphere, the gas flow rate is controlled to be 10ml/min, the heating rate is 3 ℃/min, the calcination is carried out for 4 hours at 500 ℃, then the temperature is increased to 750 ℃, the calcination is carried out for 12 hours, and finally the calcination is carried out for 4 hours at 920 ℃, and then the calcination is carried out with the furnace cooling.
(4) Grinding and dispersing the powder obtained by calcination, and then sieving the powder with a 300-mesh sieve, wherein the sieve is named NCM811-La 2O3;
In order to study the influence of the rock salt phase coherent growth modification method on the crystal structure of the ternary cathode material, the modified cathode material is subjected to X-ray diffraction (XRD) characterization, as shown in figure 1, and a small amount of La 2O3 phases can be obtained by introducing a metal element La into the precursor preparation process. Fig. 2 is a modified ternary cathode material Scanning Electron Microscope (SEM) showing micron-sized secondary sphere particle morphology. Fig. 3 is a Transmission Electron Microscope (TEM) result of the modified cathode material, and it is apparent that the coherent grown La 2O3 phase and lamellar phase are observed. Fig. 4 is a cycle performance test of the ternary cathode material before and after modification. The initial material LiNi 0.8Co0.1Mn0.1O2 (NCM 811) which is prepared by the same method but is not modified has a first discharge specific capacity of 185mAh/g, and the NCM811-La 2O3 prepared by the method has a first discharge specific capacity of 180mAh/g. After 50 cycles, the NCM811 had a residual capacity of 134mAh/g and a capacity retention of 72.4%. In contrast, 161mAh/g was obtained after 50 cycles of NCM811-La 2O3, with a capacity retention of 89.6%. The electrochemical test result shows that the electrochemical performance of the ternary positive electrode material can be remarkably improved by introducing new phase La 2O3 with coherent growth. Fig. 5 shows the X-ray transmission photographs of the original and modified materials after 50 cycles, it is evident that the original sample particles are severely broken, while the modified sample particles remain in a complete mechanical structure with only a few cracks present.
Example 2: the stable ternary positive electrode material with spinel structure coherent growth is prepared through the following steps:
(1) The three sulfates of Ni, co and Mn are prepared into a solution with the molar ratio of 8:1:1, and the concentration of the solution is 2mol/L. In addition, a sodium hydroxide solution of 2mol/L and an aqueous ammonia solution of 1mol/L were prepared. Firstly, a transition metal solution is pumped into a reaction kettle body by using a metering pump at a flow rate of 15L/h, and simultaneously sodium hydroxide and an ammonia water solution are added into the reaction kettle to control the pH value to be 11. During the reaction, a nitrogen atmosphere was maintained while maintaining the reactor temperature at 60℃and stirring speed at 550rpm/min. After the reaction liquid is completely consumed, stirring is continued for 2 hours, finally, aging is carried out for 24 hours along with the kettle, the reaction product is repeatedly washed by deionized water to obtain precursor powder, and then, the precursor powder is transferred into a vacuum oven at 80 ℃ for full drying.
(2) Weighing 10g of precursor powder, mixing with 4.45g (the lithium preparation amount is less than 1) of lithium hydroxide monohydrate, manually grinding for 15min, and transferring into an alumina crucible;
(3) In pure oxygen atmosphere, controlling the gas flow rate to be 10ml/min, heating to 3 ℃/min, calcining for 4 hours at 500 ℃, heating to 750 ℃, calcining for 12 hours, and finally cooling along with a furnace;
To investigate the effect of the spinel-phase coherent growth modification method on the crystal structure of the ternary cathode material, XRD test was performed on the modified cathode material, as shown in fig. 6, in this example, no additional new phase component was added in step (1), but a small amount of spinel-phase LiMn 2O4 was present in the sample obtained by high-temperature calcination by controlling the molar ratio of Li to transition metal to be less than 1. Fig. 7 is a cycle performance test of the ternary cathode material before and after modification. The initial material NCM811 has a first discharge specific capacity of 185mAh/g, and the NCM811-LiMn 2O4 prepared in this example has a first discharge specific capacity of 182.5mAh/g. After 50 cycles, the NCM811 had a residual capacity of 134mAh/g and a capacity retention of 72.4%. In contrast, 169.2mAh/g was obtained after 50 cycles of NCM811-LiMn 2O4 with a capacity retention of 92.7%. Electrochemical test results show that the stability of the ternary positive electrode material can be remarkably improved by introducing the coherent-grown spinel phase LiMn 2O4.
Example 3: la 4[LiMn]O8 coherent growth stable ternary positive electrode material and preparation method thereof are as follows
(1) Preparing a sulfate solution b of La according to the molar ratio of 8:1:1, wherein the concentrations of the sulfate solution a and the sulfate solution b are 2mol/L, and mixing the sulfate solution a and the sulfate solution b according to the volume ratio of 20:1. In addition, a sodium hydroxide solution of 2mol/L and an aqueous ammonia solution of 1.5mol/L were prepared. Firstly, a transition metal solution is pumped into a reaction kettle body by using a metering pump at a flow rate of 10L/h, and simultaneously sodium hydroxide and an ammonia water solution are added into the reaction kettle to control the PH value to be 11.5. During the reaction, a nitrogen atmosphere was maintained while maintaining the reactor temperature at 60℃and stirring speed at 550rpm/min. After the reaction liquid is completely consumed, stirring is continued for 2 hours, finally, aging is carried out for 24 hours along with the kettle, the reaction product is repeatedly washed by deionized water to obtain hydroxide precursor powder, and then, the hydroxide precursor powder is transferred into a vacuum oven at 80 ℃ for full drying.
(2) Calcining the hydroxide precursor powder at 500 ℃ for 5 hours to obtain oxide powder;
(3) 3g of the oxide powder and 1.65g of lithium hydroxide monohydrate were weighed, manually mixed in a mortar for 20 minutes, and then transferred to an alumina crucible.
(4) In pure oxygen atmosphere, the gas flow rate is controlled to be 10ml/min, the heating rate is 3 ℃/min, the calcination is carried out for 5 hours at 450 ℃, then the treatment is carried out for 12 hours at 920 ℃, and finally the natural cooling to the room temperature is carried out along with the furnace.
In order to study the influence of La 4[LiMn]O8 coherent growth modification method on the crystal structure of ternary cathode material, XRD test is carried out on the modified cathode material, and as shown in figure 8, a small amount of perovskite structure La 4[LiMn]O8 is obtained by introducing La element and reasonably controlling the coprecipitation and calcination processes. As shown in fig. 9A, the perovskite structure La 4[LiMn]O8 phase and the lamellar phase are combined in a lattice symbiotic manner, and the two phases are compatible with each other; fig. 9B is a corresponding fast fourier transform spectrum, in which it can be seen that diffraction spots (014, 011, 003) of a layered structure coexist with diffraction spots (011) of a perovskite structure, and fig. 9C is a partial enlarged view of an atomic phase of La 4[LiMn]O8 of a perovskite structure, in which atomic occupation is marked by using pellets of different sizes. Fig. 10 is a cycle performance test of the ternary cathode material before and after modification. The original material NCM811 which is not modified by the same method has a first discharge specific capacity of 185mAh/g, and the NCM811-La 4[LiMn]O8 prepared by the example has a first discharge specific capacity of 182mAh/g. After 50 cycles, the NCM811 had a residual capacity of 134mAh/g and a capacity retention of 72.4%. In contrast, 169mAh/g was obtained after 50 cycles of NCM811-La 4[LiMn]O8 with a capacity retention of 92.8%. Electrochemical test results show that the stability of the ternary positive electrode material can be remarkably improved by introducing the perovskite structure La 4[LiMn]O8 which grows in a coherent mode.
Example 4: perovskite phase coherent growth stable ternary positive electrode material and preparation method thereof are as follows
(3) Preparing a by mixing three sulfates of Ni, co and Mn according to a mol ratio of 8:1:1, preparing a mixed sulfate solution b of Sr and Ti, wherein the concentrations of the solution a and the solution b are 2mol/L, and mixing the solution a and the solution b according to a volume ratio of 30:1. In addition, a sodium hydroxide solution of 2mol/L and an aqueous ammonia solution of 1mol/L were prepared. Firstly, a transition metal solution is pumped into a reaction kettle body by a metering pump at a flow rate of 15L/h, and simultaneously sodium hydroxide and an ammonia solution are added into the reaction kettle to control the PH value to be 11. During the reaction, a nitrogen atmosphere was maintained while maintaining the reactor temperature at 60℃and stirring speed at 550rpm/min. After the reaction liquid is completely consumed, stirring is continued for 2 hours, finally, aging is carried out for 24 hours along with the kettle, the reaction product is repeatedly washed by deionized water to obtain hydroxide precursor powder, and then, the hydroxide precursor powder is transferred into a vacuum oven at 80 ℃ for full drying.
(4) Calcining the hydroxide precursor powder at 500 ℃ for 5 hours to obtain oxide powder;
(3) 3g of the oxide powder and 1.6g of lithium hydroxide monohydrate were weighed, manually mixed in a mortar for 20 minutes, and then transferred to an alumina crucible.
(4) In pure oxygen atmosphere, the gas flow rate is controlled to be 10ml/min, the heating rate is 3 ℃/min, the calcination is carried out for 5 hours at 350 ℃, then the treatment is carried out for 15 hours at 890 ℃, and finally the cooling is carried out to room temperature at the cooling rate of 1.5 ℃/min.
In order to study the influence of the perovskite structure coherent growth modification method on the crystal structure of the ternary cathode material, XRD test is carried out on the modified cathode material, and as shown in FIG. 11, a small amount of perovskite structure SrTiO 3 is obtained by introducing two elements of Sr and Ti and calcining at high temperature. Fig. 12 is a cycle performance test of the ternary cathode material before and after modification. The original material NCM811 which is not modified by the same method has a first discharge specific capacity of 185mAh/g, and the NCM811-SrTiO 3 prepared by the example has a first discharge specific capacity of 182mAh/g. After 50 cycles, the NCM811 had a residual capacity of 134mAh/g and a capacity retention of 72.4%. In contrast, 163mAh/g could be obtained after 50 cycles of NCM811-SrTiO 3 with a capacity retention of 89.6%. Electrochemical test results show that the stability of the ternary positive electrode material can be improved by introducing the perovskite structure SrTiO 3 which grows in a coherent mode.
The method can prepare the ternary positive electrode material with two-phase coherent growth, and can effectively stabilize the crystal structure of the ternary positive electrode material so as to obtain improved electrochemical performance.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A preparation method of a two-phase coherent lithium ion battery ternary positive electrode material is characterized in that a new phase is introduced into a LiNi xCoyMn1-x-yO2 ternary positive electrode material, wherein x is more than 0 and less than 1, and y is more than 0 and less than 1; the new phase is metal oxide, and the mass percentage w of the new phase and the ternary positive electrode material satisfies 0.1% < w <5%; and the new phase grows in a coherent manner with the lamellar phase in the ternary positive electrode material, wherein the coherent refers to that atoms on an interface are simultaneously positioned on nodes of two-phase lattices, namely the lattices of the two phases are mutually connected, and the atoms on the interface are shared by the two phases; the new phase is of perovskite structure or rock salt structure;
The preparation method comprises the following steps: preparing a transition metal salt solution according to the proportion of Ni, co and Mn elements in a main phase of the ternary positive electrode material, preparing a new phase metal salt solution according to the proportion of metal elements in a new phase, and mixing the two solutions to obtain a salt solution; adding deionized water as a base solution into the bottom of a three-way coprecipitation reaction kettle, adding a salt solution into the reaction kettle body through a peristaltic pump, simultaneously adding alkali liquor and ammonia water to maintain the pH value stable, controlling the temperature of the reaction kettle body through a constant-temperature water bath, controlling the stirring speed in the whole reaction process by using nitrogen as a protective gas, continuing stirring after the salt solution is completely added into the kettle body, aging after the reaction is completely completed, repeatedly cleaning a reaction product through deionized water and ethanol, and drying under a vacuum condition to obtain precursor powder; performing post-treatment on the precursor powder to realize two-phase coherent growth; the post-treatment process is as follows: mixing the obtained precursor powder with lithium salt, and performing a heat treatment process 1 in pure oxygen atmosphere to obtain a ternary positive electrode material of the lithium ion battery, wherein a new phase of coherent growth is a rock salt structure; the heat treatment process 1 is three-stage heat treatment, wherein the first stage is heat treatment at 400-500 ℃ for 3-6h, the second stage is heat treatment at 600-800 ℃ for 6-10h, and the third stage is heat treatment at 900-950 ℃ for 4-6h, and then cooling along with a furnace; the post-treatment process is as follows: the precursor powder is subjected to a heat treatment process 3 to obtain an oxide precursor material, the oxide precursor material is mixed with lithium salt, and a ternary positive electrode material of the lithium ion battery is obtained through a heat treatment process 4 in pure oxygen atmosphere, wherein a new phase which grows in a coherent mode is of a perovskite structure; the heat treatment process 3 is as follows: the heat treatment temperature is 400-650 ℃, the heat treatment time is 3-8h, then the heat treatment is carried out along with furnace cooling, the heat treatment process 4 is two-stage heat treatment, wherein the first stage is heat treatment at the temperature of 300-600 ℃ for 3-6h, the second stage is heat treatment at the temperature of 700-950 ℃ for 8-20h, and finally the cooling rate is set to be 1-5 ℃/min.
2. The method of claim 1, wherein the new phase is M xOy, wherein M is one or more of Ni, la, sr, Y, zr, ti, nb, and x and y satisfy the valence balance.
3. The method of claim 1, wherein the new phase is a 4[LiM]O8, wherein a is one or more of Ti, sn, zr; m is one or more of Mn, co and Ni.
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| CN113764657A (en) * | 2021-08-06 | 2021-12-07 | 华南理工大学 | In-situ gradient doped single crystal high-nickel lithium ion battery high-voltage positive electrode material and preparation method thereof |
| CN114388758A (en) * | 2022-01-06 | 2022-04-22 | 中国科学院宁波材料技术与工程研究所 | Lithium metal oxide cathode material with novel composite phase structure and preparation method and application thereof |
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