CN111435731B - Ternary material for lithium battery coated with negative temperature coefficient material - Google Patents
Ternary material for lithium battery coated with negative temperature coefficient material Download PDFInfo
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- CN111435731B CN111435731B CN201910035390.9A CN201910035390A CN111435731B CN 111435731 B CN111435731 B CN 111435731B CN 201910035390 A CN201910035390 A CN 201910035390A CN 111435731 B CN111435731 B CN 111435731B
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- temperature coefficient
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- 239000000463 material Substances 0.000 title claims abstract description 99
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000002738 chelating agent Substances 0.000 claims abstract description 23
- 239000003513 alkali Substances 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims abstract description 8
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 229910003618 NixCoyMn1-x-y(OH)2 Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940031993 lithium benzoate Drugs 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 2
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 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 claims description 2
- -1 transition metal salt Chemical class 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 33
- 238000000576 coating method Methods 0.000 abstract description 33
- 239000010405 anode material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 4
- 238000005086 pumping Methods 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 2
- 239000011162 core material Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention belongs to the field of lithium battery anode materials, and particularly relates to a ternary material for a lithium battery coated with a negative temperature coefficient material, which is characterized by comprising the following steps of: (1) preparing a mixed solution of Ni, Co and Mn salts with a certain concentration according to a certain proportion, adding a first alkali solution with a certain concentration and a first chelating agent, fully stirring, and preserving heat at a certain temperature for a certain time to obtain a first precursor; (2) dispersing the first precursor into a lithium salt aqueous solution with a certain concentration, placing the lithium salt aqueous solution into a high-pressure reaction kettle, and preserving heat at a certain temperature for a certain time to obtain a second precursor; (3) calcining the second precursor for the first time to obtain LiNixCoyMn1‑x‑yO2(ii) a (4) Is prepared to have a coating of M3O4A ternary material of a precursor; (5) is prepared to have a coating of M3O4The negative temperature coefficient material for lithium batteries. The ternary material coating provided by the invention has good uniformity, reduces self-discharge at normal temperature, and improves the storage performance, the cycle performance and the rate performance at high temperature.
Description
Technical Field
The invention belongs to the field of lithium battery positive electrode materials, and particularly relates to a ternary material for a lithium battery coated with a negative temperature coefficient material.
Background
In recent years, with the increasing capacity of lithium ion batteries, the NCM ternary material has become a hot trend of research. However, the ternary material also has the phenomenon of self-discharge caused by the electron transfer with the electrolyte, and meanwhile, the ternary material has high activity at high temperature and is easy to generate side reaction with the electrolyte, so that the problem of poor cycle stability of the material is solved. In the prior art, Al is adopted2O3Coating or soot coating, but the above phenomena are not significantly improved.
To address the above problem, M is selected herein3O4The NTC heat-sensitive material is prepared by coating a ternary material by a hydrothermal synthesis method. The surface of the ternary material can obtain a uniform coating material through hydrothermal coating, and the self-discharge problem caused by high local electron conductance due to non-uniform coating is avoided.
M3O4The NTC heat-sensitive material is composed of two or more transition metal oxides, such as MnO2、NiO、Co2O3、Al2O3And the like. Its resistivity decreases exponentially with increasing temperature. Experiments show that the NTC material has different resistivity along with different metal content and composition. The resistivity at 25 ℃ is usually 400. omega. cm or more, while the resistivity at room temperature of the ternary material is about 150. omega. cm. Thus coating M3O4The NTC heat-sensitive material increases the resistivity of the ternary material at 25 ℃, reduces the self-discharge of the material and improves the storage performance of the material at normal temperature. Furthermore, as the temperature increases, M3O4The NTC type thermosensitive resistivity is lower than 150 omega cm, so the coating M3O4The conductivity of the NTC heat-sensitive ternary material at high temperature is restored to normal temperature without coating M3O4The ternary level of the type NTC heat-sensitive property can realize the effect that the cycle performance and the power performance at high temperature reach normal temperature.
Disclosure of Invention
In order to solve the technical problems, the invention provides the ternary material for the lithium battery, which is coated with the negative temperature coefficient material, has good coating uniformity, reduces self-discharge at normal temperature, and improves the storage performance, the cycle performance and the rate performance at high temperature.
In order to achieve the purpose of the invention, the technical scheme is as follows:
a ternary material for a lithium battery coated with a negative temperature coefficient material comprises the following steps:
(1) preparing a mixed solution of Ni, Co and Mn salts with a certain concentration according to a certain proportion, adding a first alkali solution with a certain concentration and a first chelating agent, fully stirring, and preserving heat for a certain time at a certain temperature to obtain a first precursor, wherein the reaction equation is as follows:
xNi2++yCo2++(1-x-y)Mn2++2OH-→NixCoyMn1-x-y(OH)2；
(2) dispersing the first precursor into a lithium salt aqueous solution with a certain concentration, placing the lithium salt aqueous solution into a high-pressure reaction kettle, and preserving heat for a certain time at a certain temperature to obtain a second precursor, wherein the reaction equation is as follows:
NixCoyMn1-x-y(OH)2+Li++OH-→Li NixCoyMn1-x-y(OH)3；
(3) calcining the second precursor for the first time to obtain LiNixCoyMn1-x-yO2；
(4) Reacting LiNixCoyMn1-x-yO2Mixing with solvent, placing into high pressure reactor, adding transition metal salt solution, second alkali solution and second chelating agent, stirring, and maintaining at certain temperature for certain time to obtain the final product coated with M3O4The precursor is a ternary material, wherein M is one or more of Ni, Co, Mn and Al;
(5) will be coated with M3O4Drying and calcining the precursor ternary material for the second time to obtain the M-coated ternary material3O4The negative temperature coefficient material for lithium batteries of (1);
wherein x is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 1, and 1-x-y is more than 0.
Further, in the step (1), the Ni, Co and Mn salt is sulfate of Ni, Co and Mn, chlorate of Ni, Co and Mn, acetate of Ni, Co and Mn, or nitrate of Ni, Co and Mn, and the concentration of the mixed solution of Ni, Co and Mn salt is 0.01-5 mol/L; furthermore, the concentration of the mixed solution of Ni, Co and Mn salts is 0.1-2 mol/L.
Further, the first alkali solution in the step (1) and the second alkali solution in the step (4) are NaOH, KOH and Na2CO3The concentration of the first alkali solution is 0.05-3.0mol/L, the concentration of the second alkali solution is 0.05-3.0mol/L, and the concentration of the first alkali solution is different from that of the second alkali solution; further, the concentration of the first alkali solution is 0.1-2mol/L, the concentration of the second alkali solution is 0.1-2mol/L, and the concentration of the first alkali solution is different from that of the second alkali solution.
Further, the first chelating agent in the step (1) and the second chelating agent in the step (4) are both ammonia water, the concentration of the first chelating agent is 0.05-4.0mol/L, the concentration of the second chelating agent is 0.05-4.0mol/L, and the concentration of the first chelating agent is different from that of the second chelating agent. Further, the first chelating agent concentration is 0.2-2mol/L, the second chelating agent concentration is 0.2-2mol/L, and the first chelating agent concentration and the second chelating agent concentration are different.
Further, the certain temperature in the step (1) is 40-120 ℃. Further, the certain temperature in the step (1) is 60-100 ℃.
Further, the heat preservation time in the step (1) is 6-72 h. Further, the heat preservation time in the step (1) is 8-36 h.
Further, the lithium salt in the step (2) is one or more of lithium hydroxide, lithium carbonate, lithium phosphate, dilithium hydrogen phosphate, lithium dihydrogen phosphate, lithium sulfate, lithium acetate, lithium nitrate, lithium fluoride, lithium chloride, lithium bromide, lithium oxalate, lithium formate, lithium tert-butoxide, lithium benzoate and lithium citrate.
Further, the lithium salt in the step (2) is LiOH aqueous solution, and the concentration of the LiOH aqueous solution is 0.01mol/L-5 mol/L. Further, the concentration of the lithium salt in the step (2) is 0.2-2mol/L as LiOH aqueous solution.
Further, the certain temperature in the step (2) is 80-300 ℃. Further, the certain temperature in the step (2) is 100-200 ℃.
Further, the heat preservation time in the step (2) is 8-96 h. Further, the heat preservation time in the step (2) is 10-36 h.
Further, the first calcination temperature in the step (3) is 700-. Further, the first calcination temperature in the step (3) is 750-.
Further, the first calcination time in the step (3) is 5-15 h. Further, the first calcination time in the step (3) is 10-12 h.
Further, the transition metal salt in the step (4) is an oxide of Ni, Co, Mn, or a hydroxide of Ni, Co, Mn, or a carbonate of Ni, Co, Mn, or a nitrate of Ni, Co, Mn, or a sulfate of Ni, Co, Mn, or a chloride of Ni, Co, Mn, Al, or a hydroxide of Ni, Co, Mn, Al, or a carbonate of Ni, Co, Mn, Al, or a nitrate of Ni, Co, Mn, Al, or a sulfate of Ni, Co, Mn, Al, or a chloride of Ni, Co, Mn, Al, and the concentration of the transition metal salt solution is 0.05-5 mol/L. Further, the concentration of the transition metal salt solution is 0.1 to 1 mol/L.
Further, the certain temperature in the step (4) is 80-300 ℃. Further, the certain temperature in the step (4) is 100-150 ℃.
Further, the heat preservation time in the step (4) is 4-72 h. Further, the heat preservation time in the step (4) is 6-24 h.
Further, the second calcination temperature in the step (5) is 200-1000 ℃. Further, the second calcination temperature in the step (5) is 400-600 ℃.
Further, the second calcination time in the step (5) is 2-12 h. Further, the second calcination time in the step (5) is 6-10 h.
Definition of
A first precursor: has a chemical formula of NixCoyMn1-x-y(OH)2X is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 1, and 1-x-y is more than 0.
A second precursor: chemical formula is Li NixCoyMn1-x-y(OH)3X is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 1, and 1-x-y is more than 0.
The invention has the beneficial effects that:
1. coating M of the invention3O4The ternary material ensures the uniformity of the coating and reduces the self-discharge phenomenon caused by high local electronic conductance.
2. Coating M of the invention3O4Can increase the resistivity at normal temperature, reduce the self-discharge at normal temperature and improve the storage performance at normal temperature. At the same time, M increases with temperature3O4The electrical resistivity is reduced to reach the level of a ternary material, so that the cycle performance and the rate performance at high temperature can reach the level of normal temperature.
Drawings
FIG. 1 is a schematic diagram of a ternary material particle for a lithium battery coated with a negative temperature coefficient material;
FIG. 2 is a flow chart of a process for synthesizing a ternary material for a lithium battery coated with a negative temperature coefficient material;
FIG. 3 shows Al coating in reference example 12O3And example 1 Co coating1.5Mn1.2Ni0.3O4The change curve of the cycle capacity retention rate of the negative temperature coefficient positive electrode material along with the cycle number;
FIG. 4 shows Al coating in reference example 22O3And example 2 Co coating1.5Mn1.2Ni0.3O4The change curve of the cycle capacity retention rate of the negative temperature coefficient positive electrode material along with the cycle number;
FIG. 5 shows Al coating in reference example 32O3And example 3 Co coating1.48Mn1.2Ni0.3Al0.02O4The change curve of the cycle capacity retention rate of the negative temperature coefficient positive electrode material along with the cycle number;
FIG. 6 shows Al coating of reference example 42O3And example 4 Co coating0.7Mn2.3O4The change curve of the cycle capacity retention rate of the negative temperature coefficient positive electrode material along with the cycle number;
FIG. 7 shows Al coating in reference example 12O3And examples1 coating of Co1.5Mn1.2Ni0.3O4A graph comparing the discharge (mass) specific capacity;
FIG. 8 shows Al coating in reference example 22O3And example 2 Co coating1.5Mn1.2Ni0.3O4A graph comparing the discharge (mass) specific capacity;
FIG. 9 shows Al coating of reference example 32O3And example 3 Co coating1.48Mn1.2Ni0.3Al0.02O4A graph comparing the discharge (mass) specific capacity;
FIG. 10 shows Al coating of reference example 42O3And example 4 Co coating0.7Mn2.3O4A graph comparing the discharge (mass) specific capacity;
wherein: 1-core material and 2-shell material.
Detailed Description
The technical solution of the present invention is further described and illustrated by the following specific examples, but the present invention is not limited to the following examples.
As shown in figure 1, the core material (1) of the invention is a ternary material, and the shell material (2) is a negative temperature coefficient material, specifically selected as M3O4The NTC heat-sensitive material is composed of two or more transition metal oxides, such as: MnO2、NiO、Co2O3、Al2O3、Fe2O3And the like. FIG. 2 is a synthetic scheme. Table 1 shows a comparison of examples 1 to 4 with corresponding reference examples 1 to 4. Table 2 is a 25 ℃ shelf life test table.
Reference example 1
(1) At a molar ratio of Ni2+:Co2+:Mn2+Pumping a sulfate mixed solution with the concentration of 0.5mol/L into a continuously stirred tank reactor, and pumping a NaOH solution with the concentration of 1mol/L and ammonia water with the concentration of 0.5mol/L into the continuously stirred tank reactor to be fully stirred to obtain a first precursor;
(2) placing the first precursor into a high-pressure reaction kettle, adding 1mol/L LiOH aqueous solution, and preserving heat at 250 ℃ for 36 hours to obtain a second precursor;
(3) placing the second precursor inCalcining for the first time at a certain temperature for a period of time to obtain the ternary material LiNixCoyMn1-x-yO2(0＜x≤1；0＜y≤1)；
(4) The ternary material LiNi obtained in the step (3) is subjected toxCoyMn1-x-yO2Cycling and rate performance tests were performed at 25 deg.C, 55 deg.C, as shown in FIGS. 3 and 4. In addition, the resulting ternary material was subjected to a shelf life test at 25 ℃ as shown in Table 2.
Reference example 2
The molar ratio in the step (1) is Ni2+:Co2+:Mn2+5:2: 3. The rest is the same as in reference example 1.
Reference example 3
The molar ratio in the step (1) is Ni2+:Co2+:Mn2+6:2: 2. The rest is the same as in reference example 1.
Reference example 4
The molar ratio in the step (1) is Ni2+:Co2+:Mn2+1: 8. The rest is the same as in reference example 1.
Example 1
(1) At a molar ratio of Ni2+:Co2+:Mn2+Pumping the mixed solution of Ni, Co and Mn sulfates with the concentration of 0.5mol/L into a continuous stirring tank reactor, and pumping a NaOH solution with the concentration of 1mol/L and ammonia water with the concentration of 0.5mol/L into the continuous stirring tank reactor to be fully stirred to obtain a first precursor;
(2) placing the first precursor into a high-pressure reaction kettle, adding 1mol/L LiOH aqueous solution, and preserving heat at 250 ℃ for 36 hours to obtain a second precursor;
(3) calcining the second precursor at a certain temperature for a period of time to obtain the ternary material LiNixCoyMn1-x-yO2(0＜x≤1；0＜y≤1)，
(4) Mixing the ternary material LiNixCoyMn1-x-yO2Mixing with solvent, placing into high-pressure reaction kettle, simultaneously adding Co, Mn, Ni and/or Al salt solution containing a certain concentration into high-pressure reaction kettle of precursor II, adding alkali solution and chelating agent with a certain concentration, stirring thoroughly, adding the solvent and chelating agent, stirring at a certain temperatureMaintaining at a temperature for a period of time to obtain a coating M3O4(M is one or more of Ni, Co, Mn and Al) precursor.
(5) Will be coated with M3O4Calcining the precursor ternary material at a certain temperature for a period of time to obtain the M-coated ternary material3O4The ternary material for the lithium battery of the negative temperature coefficient material. The obtained ternary material was subjected to cycle and rate performance tests at 25 ℃ and 55 ℃, as shown in fig. 3 and 7. In addition, the ternary material obtained was subjected to a shelf life test at 25 ℃ as shown in Table 2.
Example 2
The molar ratio in the step (1) is Ni2+:Co2+:Mn2+5:2: 3. The rest is the same as in example 1. The obtained ternary material was subjected to cycle and rate performance tests at 25 ℃ and 55 ℃, as shown in fig. 4 and 8. In addition, the ternary material obtained was subjected to a shelf life test at 25 ℃ as shown in Table 2.
Example 3
The molar ratio in the step (1) is Ni2+:Co2+:Mn2+6:2: 2. The rest is the same as in example 1. The obtained ternary material was subjected to cycle and rate performance tests at 25 ℃ and 55 ℃, as shown in fig. 5 and 9. In addition, the ternary material obtained was subjected to a shelf life test at 25 ℃ as shown in Table 2.
Example 4
The molar ratio in the step (1) is Ni2+:Co2+:Mn2+1: 8. The rest is the same as in example 1. The obtained ternary material was subjected to cycle and rate performance tests at 25 ℃ and 55 ℃, as shown in fig. 6 and 10. In addition, the ternary material obtained was subjected to a shelf life test at 25 ℃ as shown in Table 2.
TABLE 1 comparative tables of examples 1 to 4 and corresponding reference examples 1 to 4
TABLE 2 shelf life test table at 25 deg.C
It should be understood that the above is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent structures or equivalent flow transformations made by the present specification and drawings, or applied directly or indirectly to other related technical fields, are included in the scope of the present invention.
Claims (17)
1. A ternary material for a lithium battery coated with a negative temperature coefficient material is characterized by comprising the following steps:
(1) preparing a mixed solution of Ni, Co and Mn salts with a certain concentration according to a certain proportion, adding a first alkali solution with a certain concentration and a first chelating agent, fully stirring, and preserving heat for a certain time at a certain temperature to obtain a first precursor, wherein the reaction equation is as follows:
xNi2++yCo2++(1-x-y)Mn2++2OH-→NixCoyMn1-x-y(OH)2；
(2) dispersing the first precursor into a lithium salt aqueous solution with a certain concentration, placing the lithium salt aqueous solution into a high-pressure reaction kettle, and preserving heat for a certain time at a certain temperature to obtain a second precursor, wherein the reaction equation is as follows:
NixCoyMn1-x-y(OH)2+Li++OH-→Li NixCoyMn1-x-y(OH)3；
(3) calcining the second precursor for the first time to obtain LiNixCoyMn1-x-yO2；
(4) Reacting LiNixCoyMn1-x-yO2Mixing with solvent, placing into high pressure reactor, adding transition metal salt solution, second alkali solution and second chelating agent, stirring, and maintaining at certain temperature for certain time to obtain the final product coated with M3O4Ternary material of precursor, wherein M is Ni, Co, Mn or AlMore than two kinds of the components are adopted;
(5) will be coated with M3O4Drying and calcining the precursor ternary material for the second time to obtain the M-coated ternary material3O4The negative temperature coefficient material for lithium batteries of (1);
wherein x is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 1, and 1-x-y is more than 0.
2. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: in the step (1), the Ni, Co and Mn salt is sulfate of Ni, Co and Mn, or chlorate of Ni, Co and Mn, or acetate of Ni, Co and Mn, or nitrate of Ni, Co and Mn, and the concentration of the mixed solution of Ni, Co and Mn salt is 0.01-5 mol/L.
3. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: the first alkali solution in the step (1) and the second alkali solution in the step (4) are NaOH, KOH and Na2CO3Wherein the concentration of the first alkali solution is 0.05-3.0mol/L, the concentration of the second alkali solution is 0.05-3.0mol/L, and the concentration of the first alkali solution is different from that of the second alkali solution.
4. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: in the step (1), the first chelating agent and the second chelating agent in the step (4) are both ammonia water, the concentration of the first chelating agent is 0.05-4.0mol/L, the concentration of the second chelating agent is 0.05-4.0mol/L, and the concentrations of the first chelating agent and the second chelating agent are different.
5. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: the certain temperature in the step (1) is 40-120 ℃.
6. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: the heat preservation time in the step (1) is 6-72 h.
7. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: the lithium salt in the step (2) is one or more of lithium hydroxide, lithium carbonate, lithium phosphate, dilithium hydrogen phosphate, lithium dihydrogen phosphate, lithium sulfate, lithium acetate, lithium nitrate, lithium fluoride, lithium chloride, lithium bromide, lithium oxalate, lithium formate, lithium tert-butoxide, lithium benzoate and lithium citrate.
8. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: in the step (2), the lithium salt aqueous solution is LiOH aqueous solution, and the concentration is 0.01-5 mol/L.
9. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: in the step (2), the certain temperature is 80-300 ℃.
10. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: and (3) keeping the temperature in the step (2) for a certain time of 8-96 h.
11. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: the first calcination temperature in the step (3) is 700-1000 ℃.
12. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: the first calcination time in the step (3) is 5-15 h.
13. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: the transition metal salt in the step (4) is an oxide of Ni, Co and Mn, or a hydroxide of Ni, Co and Mn, or a carbonate of Ni, Co and Mn, or a nitrate of Ni, Co and Mn, or a sulfate of Ni, Co and Mn, or a chloride of Ni, Co and Mn, or an oxide of Ni, Co, Mn and Al, or a hydroxide of Ni, Co, Mn and Al, or a carbonate of Ni, Co, Mn and Al, or a nitrate of Ni, Co, Mn and Al, or a sulfate of Ni, Co, Mn and Al, or a chloride of Ni, Co, Mn and Al, and the concentration of the transition metal salt solution is 0.05-5 mol/L.
14. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: in the step (4), the certain temperature is 80-300 ℃.
15. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: and (4) keeping the temperature for a certain time of 4-72 h.
16. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: the second calcination temperature in the step (5) is 200-1000 ℃.
17. The ternary material for a lithium battery coated with a negative temperature coefficient material as claimed in claim 1, wherein: and (5) the time of the second calcination is 2-12 h.
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