CN114824267A - Layered lithium nickel manganese oxide positive electrode material and preparation method and application thereof - Google Patents
Layered lithium nickel manganese oxide positive electrode material and preparation method and application thereof Download PDFInfo
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- CN114824267A CN114824267A CN202210324360.1A CN202210324360A CN114824267A CN 114824267 A CN114824267 A CN 114824267A CN 202210324360 A CN202210324360 A CN 202210324360A CN 114824267 A CN114824267 A CN 114824267A
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- manganese oxide
- nickel manganese
- positive electrode
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 96
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims abstract description 64
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 48
- 235000012000 cholesterol Nutrition 0.000 claims abstract description 32
- LIPIURJJRUOGSS-UHFFFAOYSA-N dodecyl hydrogen carbonate Chemical compound CCCCCCCCCCCCOC(O)=O LIPIURJJRUOGSS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000005416 organic matter Substances 0.000 claims abstract description 21
- 239000012528 membrane Substances 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 54
- 238000000576 coating method Methods 0.000 claims description 40
- 239000011248 coating agent Substances 0.000 claims description 38
- 239000010406 cathode material Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 claims description 13
- BLYYANNQIHKJMU-UHFFFAOYSA-N manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Ni++] BLYYANNQIHKJMU-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002019 doping agent Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000463 material Substances 0.000 description 24
- 239000011572 manganese Substances 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 230000008569 process Effects 0.000 description 16
- 239000002245 particle Substances 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/52—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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- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a layered lithium nickel manganese oxide positive electrode material and a preparation method and application thereof. The surface of the layered lithium nickel manganese oxide positive electrode material is coated with a hydrophobic organic matter, the hydrophobic organic matter is coated on the surface of the layered lithium nickel manganese oxide positive electrode material in a membrane form, and the hydrophobic organic matter comprises cholesterol dodecyl carbonate. According to the invention, the surface of the positive electrode is made to be hydrophobic through the special hydrophobic organic cholesterol dodecyl carbonate coated on the surface of the layered lithium nickel manganese oxide positive electrode material, so that the electrochemical performance of the positive electrode material is prevented from being reduced due to water absorption on the surface of the layered lithium nickel manganese oxide positive electrode material in a high-moisture environment, and meanwhile, a stable Mn-C-O bond is formed with the surface of the positive electrode material, so that the circulation stability and the voltage drop of the lithium nickel manganese oxide positive electrode material are effectively improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a layered lithium nickel manganese oxide positive electrode material, and a preparation method and application thereof.
Background
In recent years, the new energy source shows an explosive growth trend, and people urgently need a cathode material with low cost, high energy density, high cycle performance and high safety. LiCoO as the anode material on the market 2 And ternary materials (NCM), all of which cannot satisfy the above conditions at the same time, mainly because the price of cobalt element is continuously high, and cobalt is also a non-environment-friendly element. Ni in ternary material in charge-discharge process 2+ And Li + The mixed discharging of the lithium-rich manganese-based layered oxide causes poor circulation stability, in addition, the high nickel material has serious gas production problem and poor low-temperature performance, the development of the high nickel material is further restricted, and the lithium-rich manganese-based layered oxide (without cobalt) has specific capacity higher than 300mAh/g and energy density of 1000Wh/kg, and is considered to be one of the most promising positive electrode materials in the next generation of lithium ion batteries. In addition, the lithium-rich manganese-based positive electrode material is low in cost and environment-friendly, but the problems of poor cycle stability and serious voltage drop exist in the current lithium-rich manganese-based positive electrode material (without cobalt), and the industrial development of the lithium-rich manganese-based positive electrode material is seriously restricted.
CN113072101A discloses a cobalt-free cathode material, a preparation method and an application thereof, wherein the preparation method comprises the following steps: (1) mixing lithium source and precursor Ni x Mn y (OH) 2 Mixing with a dopant, and carrying out primary heat treatment to obtain a base material; (2) and (2) mixing the base material obtained in the step (1) with a coating agent, and carrying out secondary heat treatment to obtain the cobalt-free anode material. It adopts single cobalt-free material, and has poor cycle stability.
CN112133903A discloses a method for preparing a cobalt-free cathode material, which comprises the following steps (1) of preparing a cobalt-free cathode material precursor: (1a) mixing nickel salt and manganese salt solution, adding a nano additive, and performing ultrasonic treatment; (1b) adding the mixed solution into a reaction kettle in a nitrogen atmosphere, adding a mixed alkali solution of strong base and ammonia water, adjusting the pH to 9-12, reacting at the temperature of 40-60 ℃, and washing, filtering and drying after the reaction is finished; (2) and (3) high-temperature sintering: and (3) uniformly mixing lithium hydroxide and the powder obtained in the step (1b), calcining at the constant temperature of 700-1000 ℃ for 5-20 h, and naturally cooling to obtain the cobalt-free anode material. The single cobalt-free material is adopted, and in the circulation process, due to lattice oxygen release and structure conversion, the structure collapse is caused in the process of lithium ion intercalation and deintercalation, and in the process, part of free lithium ions are deposited on the surface, so that the circulation stability is poor, and the commercial application is difficult.
Therefore, how to improve the cycle performance of the cobalt-free cathode material (layered lithium nickel manganese oxide cathode material) and reduce the voltage drop thereof is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a layered lithium nickel manganese oxide positive electrode material, and a preparation method and application thereof. According to the invention, the surface of the positive electrode is made to be hydrophobic through the special hydrophobic organic cholesterol dodecyl carbonate coated on the surface of the layered lithium nickel manganese oxide positive electrode material, so that the electrochemical performance of the positive electrode material is prevented from being reduced due to water absorption on the surface of the layered lithium nickel manganese oxide positive electrode material in a high-moisture environment, and meanwhile, a stable Mn-C-O bond is formed with the surface of the positive electrode material, so that the circulation stability and the voltage drop of the lithium nickel manganese oxide positive electrode material are effectively improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a layered lithium nickel manganese oxide positive electrode material, wherein the surface of the layered lithium nickel manganese oxide positive electrode material is coated with a hydrophobic organic matter, the hydrophobic organic matter is coated on the surface of the layered lithium nickel manganese oxide positive electrode material in a membrane form, and the hydrophobic organic matter comprises cholesterol dodecyl carbonate.
According to the invention, the surface of the positive electrode is made to be hydrophobic through the special hydrophobic organic cholesterol dodecyl carbonate coated on the surface of the layered lithium nickel manganese oxide positive electrode material, so that the electrochemical performance of the positive electrode material is prevented from being reduced due to water absorption on the surface of the layered lithium nickel manganese oxide positive electrode material in a high-moisture environment, and meanwhile, a stable Mn-C-O bond is formed with the surface of the positive electrode material, so that the circulation stability and the voltage drop of the lithium nickel manganese oxide positive electrode material are effectively improved.
According to the invention, the cholesterol dodecyl carbonate has a strong delocalized electron region, can absorb residual lithium on the surface of the lithium nickel manganese oxide positive electrode material, so that residual alkali of the lithium nickel manganese oxide positive electrode material is reduced, thereby improving the circulation stability, and the specific electron region can improve Li + The migration rate of the lithium nickel manganese oxide is improved, and the ion conductivity of the whole lithium nickel manganese oxide positive electrode material is improved; and a special bonding mechanism is formed on the surface of the cholesterol dodecyl carbonate and the surface of the nickel lithium manganate positive electrode material, so that the phase change process of the positive electrode material in the battery circulation process can be inhibited, and a special elastic network can be formed on the uniform surface, so that the deformation of the positive electrode in the battery circulation process is weakened, and the voltage drop of the battery in the circulation process can be effectively reduced.
According to the invention, the coating is a film-shaped coating, and a layer of film is formed on the surface of the anode material, so that compared with the conventional point-shaped coating, the coating has the advantages of more uniform coating effect and capability of effectively preventing the electrolyte from damaging the anode material.
Preferably, the thickness of the coating film of the hydrophobic organic substance is 10 to 50nm, for example, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, or 50 nm.
In the present invention, if the thickness of the coating film of the hydrophobic organic substance is too thin, the purpose of alleviating the structural damage during the battery cycle cannot be achieved, and if the thickness of the coating film is too thick, the exertion of the capacity of the positive electrode material is affected.
In a second aspect, the invention provides a preparation method of the layered lithium nickel manganese oxide cathode material according to the first aspect, and the preparation method comprises the following steps:
(1) mixing a nickel-manganese precursor with a lithium source, and sintering to obtain a pre-coated layered lithium nickel manganese oxide positive electrode material;
(2) mixing and coating the pre-coated layered lithium nickel manganese oxide positive electrode material, a hydrophobic organic matter and a solvent to obtain the layered lithium nickel manganese oxide positive electrode material;
wherein the hydrophobic organic comprises cholesterol dodecyl carbonate.
According to the invention, the surface of the layered lithium nickel manganese oxide positive electrode material is coated with the special hydrophobic organic cholesterol dodecyl carbonate, so that the surface of the positive electrode presents hydrophobicity, the electrochemical performance reduction of the positive electrode material caused by the water absorption of the surface of the layered lithium nickel manganese oxide (cobalt-free positive electrode material) in a high-moisture environment can be prevented, and meanwhile, a stable Mn-C-O bond is formed with the surface of the positive electrode material, so that the cycle stability and the voltage drop of the lithium nickel manganese oxide positive electrode material are effectively improved.
Preferably, the nickel manganese precursor comprises a nickel manganese oxide precursor and a nickel manganese hydroxide precursor.
According to the invention, the growth process of crystal grains can be effectively controlled by mixing the nickel-manganese oxide precursor and the nickel-manganese hydroxide precursor, and the sintered particles have less agglomeration, so that the cycle stability of the anode material is improved.
Preferably, the mass ratio of the nickel manganese oxide precursor to the nickel manganese hydroxide precursor is (0.2-1): 1, for example, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 1: 1.
In the invention, if the mass ratio of the nickel-manganese oxide precursor to the nickel-manganese hydroxide precursor is too large, namely, the mass ratio exceeds 1:1, the particles are seriously agglomerated and unevenly grown in the later sintering process, so that the cycle stability of the battery is influenced and the gas production is increased.
Preferably, the nickel manganese oxide precursor is obtained by pre-sintering a nickel manganese hydroxide precursor.
Preferably, the temperature of the pre-firing is 500 to 700 ℃, for example, 500 ℃, 530 ℃, 550 ℃, 580 ℃, 600 ℃, 630 ℃, 650 ℃, 68 ℃, 0 or 700 ℃, and the like.
In the invention, too high temperature for pre-sintering the nickel-manganese hydroxide precursor can cause metallic precipitation and oxygen loss, so that irreversible circulating substances are generated, and the circulating performance and voltage drop of the cathode material are further influenced.
Preferably, the pre-burning time is 5-10 h, such as 5h, 6h, 7h, 8h, 9h or 10 h.
Preferably, the mixed raw material of step (1) further comprises a dopant.
Preferably, the solvent of step (2) comprises tetrahydrofuran.
Preferably, the process of mixing and coating in step (2) comprises: dissolving the hydrophobic organic matter in a solvent to obtain a hydrophobic organic matter solution, and then adding the pre-coated layered lithium nickel manganese oxide positive electrode material in the step (1) to perform mixed coating;
preferably, the method for mixing and coating in the step (2) comprises stirring.
Preferably, the temperature of the stirring is 25 to 80 ℃, such as 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃.
According to the invention, the electrochemical performance of the prepared cathode material is reduced inversely due to overhigh stirring temperature, namely, the organic matters are not beneficial to growing on the surfaces of the particles at high temperature, and even after growing on the surfaces of the particles, the surface coating is not uniform due to the accelerated high-temperature thermal motion, so that the electrochemical performance of the prepared layered lithium nickel manganese oxide cathode material is reduced.
Preferably, the stirring time is 2-6 h, such as 2h, 3h, 4h, 5h or 6 h.
In the invention, the stirring time is too short, so that the reaction time is too short, the organic matter cannot finish forming uniform coating with the cobalt-free lithium-rich cathode material, and finally the electrochemical performance is reduced.
Preferably, the concentration of the hydrophobic organic solution is 1 to 3mol/L, such as 1mol/L, 1.1mol/L, 1.3mol/L, 1.5mol/L, 1.8mol/L, 2mol/L, 2.3mol/L, 2.5mol/L, 2.8mol/L or 3 mol/L.
In the invention, the high concentration of the hydrophobic organic solution can affect the uniform dispersion of the anode material in the solution, thereby affecting the coating effect of the organic substance on the single particles.
Preferably, after the mixing and coating in the step (2), performing suction filtration and drying in sequence.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing a nickel-manganese oxide precursor and a nickel-manganese hydroxide precursor with a lithium source and a doping agent according to the mass ratio of (0.2-1) to 1, and sintering to obtain a pre-coated layered lithium nickel manganese oxide positive electrode material;
(2) dissolving the hydrophobic organic matter in a solvent to obtain a hydrophobic organic matter solution with the concentration of 1-3 mol/L, adding the precoated layered lithium nickel manganese oxide positive electrode material obtained in the step (1), stirring for 2-6 hours at 25-80 ℃, performing suction filtration, and drying to obtain the layered lithium nickel manganese oxide positive electrode material;
wherein the hydrophobic organic comprises cholesterol dodecyl carbonate; the nickel-manganese oxide precursor is obtained by pre-sintering a nickel-manganese hydroxide precursor at 500-700 ℃ for 5-10 h.
In a third aspect, the invention further provides a lithium ion battery, where the lithium ion battery includes the layered lithium nickel manganese oxide positive electrode material according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the surface of the positive electrode is made to be hydrophobic through the special hydrophobic organic cholesterol dodecyl carbonate coated on the surface of the layered lithium nickel manganese oxide positive electrode material, the electrochemical performance of the positive electrode material is prevented from being reduced due to water absorption on the surface of the layered lithium nickel manganese oxide positive electrode material in a high-moisture environment, a stable Mn-C-O bond is formed with the surface of the positive electrode material, the growth process of crystal grains is effectively controlled due to the mixed collocation of precursors, the sintered particles are less in agglomeration, and the cycle stability and the voltage drop of the lithium nickel manganese oxide positive electrode material are finally improved. According to the battery provided by the invention, the discharge specific capacity under 1C can reach more than 205.8mAh/g, the capacity retention rate after 50-week circulation can reach more than 94.4%, and the voltage attenuation after 50 weeks is below 3.85%; the precursor material is a mixed material of a hydroxide precursor and an oxide precursor, and after the presintering temperature, the concentration of hydrophobic organic matters and the stirring time in the coating process are further adjusted, the discharge specific capacity of the battery under 1C can reach more than 210.4mAh/g, the capacity retention rate after 50 cycles can reach more than 96.8 percent, and the voltage attenuation after 50 cycles is less than 2.81 percent.
Drawings
Fig. 1 is a TEM image of the layered lithium nickel manganese oxide cathode material provided in example 1.
FIG. 2 is a TEM image of the layered lithium nickel manganese oxide positive electrode material provided in comparative example 2.
Fig. 3 is a graph comparing discharge curves of the batteries provided in example 1 and comparative examples 1 to 2.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a layered lithium nickel manganese oxide positive electrode material, the surface of the layered lithium nickel manganese oxide positive electrode material is coated with hydrophobic organic cholesterol dodecyl carbonate, the cholesterol dodecyl carbonate is coated on the surface of the layered lithium nickel manganese oxide positive electrode material in a film form, and the chemical formula of the layered lithium nickel manganese oxide positive electrode material is Li 1.23 Ni 0.35 Mn 0.65 O 2 Wherein the coating thickness is 20 nm.
The preparation method of the layered lithium nickel manganese oxide cathode material comprises the following steps:
(1) mixing cobalt-free precursor (Ni) 0.35 Mn 0.65 (OH) 2 ) Pre-sintering for 6 hours at 650 ℃ in a sintering furnace to prepare a pre-sintered precursor Ni 0.35 Mn 0.65 O 2 (ii) a Taking Ni after pre-sintering 0.35 Mn 0.65 O 2 And Ni 0.35 Mn 0.65 (OH) 2 (the mass ratio of the oxide precursor to the hydroxide precursor is 1:1) and Li 2 CO 3 (Li/Me may be 1.23) and WO 3 (doping amount is 2000ppm), uniformly stirring by using a handheld stirrer, putting the mixed material into a crucible, putting the crucible into a sintering furnace, sintering at 870 ℃ for 10 hours, crushing the sintered material, and sieving by using a 400-mesh sieve to obtain the pre-coated layered lithium nickel manganese oxide cathode material;
(2) dissolving cholesterol dodecyl carbonate into a tetrahydrofuran solution in a glove box, stirring for 2 hours, preparing a matrix solution of the cholesterol dodecyl carbonate with the concentration of 1mo/L, putting a pre-coated layered lithium nickel manganese oxide positive electrode material into the prepared matrix solution of the cholesterol dodecyl carbonate, and stirring for 2 hours at the temperature of 30 ℃; and after stirring, filtering the stirred solution by using a suction filter, putting the filtered solution into a vacuum drying oven, drying the dried solution at 100 ℃ for 12 hours, and sieving the dried solution by using a 400-mesh sieve to obtain the layered lithium nickel manganese oxide cathode material.
Fig. 1 shows a TEM image of a layered lithium nickel manganese oxide positive electrode material provided in example 1, and it can be seen from fig. 1 that the coating in the present invention is a distinct film-like coating.
Example 2
The embodiment provides a layered lithium nickel manganese oxide positive electrode material, the surface of the layered lithium nickel manganese oxide positive electrode material is coated with hydrophobic organic cholesterol dodecyl carbonate, the cholesterol dodecyl carbonate is coated on the surface of the layered lithium nickel manganese oxide positive electrode material in a film form, and the chemical formula of the layered lithium nickel manganese oxide positive electrode material is Li 1.2 Ni 0.45 Mn 0.55 O 2 Wherein the coating thickness is 30 nm.
The preparation method of the layered lithium nickel manganese oxide cathode material comprises the following steps:
(1) mixing cobalt-free precursor (Ni) 0.45 Mn 0.55 (OH) 2 ) Presintering for 10h at 500 ℃ in a sintering furnace to prepare presintering precursor Ni 0.45 Mn 0.55 O 2 B, carrying out the following steps of; taking Ni after pre-sintering 0.45 Mn 0.55 O 2 And Ni 0.45 Mn 0.55 (OH) 2 (mass ratio of oxide precursor to hydroxide precursor is 0.2:1) and Li 2 CO 3 (Li/Me may be 1.2) and ZrO 2 (the doping amount is 1500ppm), after uniformly stirring by using a handheld stirrer, putting the mixed material into a crucible, putting the crucible into a sintering furnace, sintering for 8 hours at 900 ℃, crushing the sintered material, and sieving by using a 400-mesh sieve to obtain the pre-coated layered lithium nickel manganese oxide cathode material;
(2) dissolving cholesterol dodecyl carbonate into a tetrahydrofuran solution in a glove box, stirring for 2 hours, preparing a 2mo/L matrix solution of the cholesterol dodecyl carbonate, putting a pre-coated layered lithium nickel manganese oxide positive electrode material into the prepared matrix solution of the cholesterol dodecyl carbonate, and stirring for 6 hours at 50 ℃; and after stirring, filtering the stirred solution by using a suction filter, putting the filtered solution into a vacuum drying oven, drying the dried solution at 100 ℃ for 12 hours, and sieving the dried solution by using a 400-mesh sieve to obtain the layered lithium nickel manganese oxide cathode material.
Example 3
The embodiment provides a layered lithium nickel manganese oxide positive electrode material, the surface of the layered lithium nickel manganese oxide positive electrode material is coated with hydrophobic organic cholesterol dodecyl carbonate, the cholesterol dodecyl carbonate is coated on the surface of the layered lithium nickel manganese oxide positive electrode material in a film form, and the chemical formula of the layered lithium nickel manganese oxide positive electrode material is Li 1.3 Ni 0.6 Mn 0.4 O 2 Wherein the coating thickness is 40 nm.
The preparation method of the layered lithium nickel manganese oxide cathode material comprises the following steps:
(1) mixing cobalt-free precursor (Ni) 0.6 Mn 0.4 (OH) 2 ) Presintering for 10h at 500 ℃ in a sintering furnace to prepare presintering precursor Ni 0.6 Mn 0.4 O 2 B, carrying out the following steps of; taking Ni after pre-sintering 0.6 Mn 0.4 O 2 And Ni 0.6 Mn 0.4 (OH) 2 (the mass ratio of the oxide precursor to the hydroxide precursor is 0.65:1), LiOH (Li/Me may be 1.3), and ZrO 2 (the doping amount is 1500ppm), after uniformly stirring by using a handheld stirrer, putting the mixed materials into a crucible, putting the crucible into a sintering furnace, sintering at 850 ℃ for 10 hours, crushing the sintered materials, and sieving by using a 400-mesh sieve to obtain the pre-coated layered lithium nickel manganese oxide positive electrode material;
(2) dissolving cholesterol dodecyl carbonate into a tetrahydrofuran solution in a glove box, stirring for 2 hours, preparing a 3mo/L matrix solution of the cholesterol dodecyl carbonate, putting a pre-coated layered lithium nickel manganese oxide positive electrode material into the prepared matrix solution of the cholesterol dodecyl carbonate, and stirring for 4 hours at 80 ℃; and after stirring, filtering the stirred solution by using a suction filter, putting the filtered solution into a vacuum drying oven, drying the dried solution at 100 ℃ for 12 hours, and sieving the dried solution by using a 400-mesh sieve to obtain the layered lithium nickel manganese oxide cathode material.
Example 4
The difference between this example and example 1 is that the pre-firing temperature in step (1) of this example is 750 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Example 5
This example is different from example 1 in that the molar concentration of the matrix solution of cholesterol dodecyl carbonate in step (2) of this example is 5 mol/L.
The remaining preparation methods and parameters were in accordance with example 1.
Example 6
This example differs from example 1 in that the stirring temperature after the addition of the precoating material in step (2) of this example was 100 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Example 7
The difference between this example and example 1 is that the stirring time after the pre-coating material is added in step (2) of this example is 0.5 h.
The remaining preparation methods and parameters were in accordance with example 1.
Example 8
The present comparative example is different from example 1 in that Ni is directly added in step (1) of the present comparative example 0.35 Mn 0.65 (OH) 2 Precursors with Li 2 CO 3 (Li/Me may be 1.23) and WO 3 (doping amount 2000ppm) was mixed, that is, only the hydroxide precursor was used.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
The comparative example is different from example 1 in that the step (2) is not performed in the preparation method of the comparative example, that is, the surface of the positive electrode material is not coated.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 2
The comparative example differs from example 1 in that 80g of the precoating material of step (1) and 0.2702g of Al are used for the coating in step (2) of the comparative example 2 O 3 And after uniformly mixing, putting the mixture into a box-type atmosphere furnace, calcining the mixture for 5 hours at 700 ℃, and sieving the mixture after sintering to obtain the common oxide coated layered lithium nickel manganese oxide cathode material.
The remaining preparation methods and parameters were in accordance with example 1.
Fig. 2 shows a TEM image of the layered lithium nickel manganese oxide cathode material provided in the comparative example 2, and with reference to fig. 1 and fig. 2, it can be seen that the layered lithium nickel manganese oxide cathode material coated on the surface of the cholesterol dodecyl carbonate is successfully synthesized, and is a film-shaped coating, which is obviously different from the conventional dot-shaped coating, because both hydrophobic and elastic organic matters and the organic matters of the coated cathode material have certain lithium affinity, the residual lithium on the surface of the lithium-rich material can be reduced to some extent, and on the other hand, the uniform coating is generated in the M-C ═ O bonding, and can fix Mn to reduce the structural destruction and irreversible phase change process in the battery cycle process, thereby resulting in the improvement of cycle stability and the weakening of voltage attenuation.
FIG. 3 is a graph showing a comparison of discharge curves of the batteries provided in example 1 and comparative examples 1 to 2, and it can be seen from FIG. 3 that the discharge capacity of the batteries obtained from the layered lithium nickel manganese oxide positive electrode material provided by the present invention is higher.
Comparative example 3
The present comparative example is different from example 8 in that the step (2) is not performed in the preparation method of the present comparative example, that is, the surface of the positive electrode material is not coated.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 4
The comparative example differs from example 8 in that 80g of the precoating material of step (1) and 0.2702g of Al are used for the coating in step (2) of the comparative example 2 O 3 And after uniformly mixing, putting the mixture into a box-type atmosphere furnace, calcining the mixture for 5 hours at 700 ℃, and sieving the mixture after sintering to obtain the common oxide-coated layered lithium nickel manganese oxide cathode material.
The remaining preparation methods and parameters were in accordance with example 1.
The cathode materials provided in examples 1 to 8 and comparative examples 1 to 4 were subjected to slurry coating, wherein the cathode material was superconducting carbon black SP, polyvinylidene fluoride glue solution was 90:5:5, and the solid content of PVDF glue solution was 6.05%. And performing electric buckling assembly on the prepared pole piece by adopting a BR2032 shell.
The positive electrode materials provided in examples 1 to 8 and comparative examples 1 to 4 were subjected to electrochemical performance tests under the following test conditions: the results of the charge and discharge test at a charge and discharge current of 1C, which gave a capacity retention ratio after 50 weeks of the cycle and a voltage decay after 50 weeks, are shown in table 1.
TABLE 1
From the data results of examples 1 and 4, it is understood that when the pre-firing temperature is too high, metallic precipitation and oxygen loss occur, and irreversible circulating substances are generated, thereby lowering the cycle stability and increasing the voltage decay.
As is clear from the data results of examples 1 and 5, the concentration of the hydrophobic organic material solution is too high, which is disadvantageous to uniform dispersion of the positive electrode material particles in the hydrophobic organic material solution, resulting in non-uniform coating and thus reduced cycle stability.
From the data results of examples 1 and 6, it is understood that the temperature during the stirring process is too high, and the electrochemical properties of the positive electrode material prepared thereby are degraded.
From the data results of example 1 and example 7, it is known that too short stirring time results in too short reaction time, so that the organic matter is not ready to form uniform coating with the lithium nickel manganese oxide cathode material, thereby causing the electrochemical performance to be reduced.
From the data results of example 1 and example 8, it is known that the use of a mixture of the pre-sintered precursor and the hydroxide precursor can effectively control the growth process of the crystal grains, and the sintered particles have less agglomeration, thereby improving the cycle stability.
As can be seen from the data results of example 1 and comparative example 1 (example 8 and comparative example 2), without coating, it is impossible to achieve improvement of the cycle stability of the cobalt-free lithium-rich material during battery cycling and reduction of the voltage drop caused by structural transformation of the cobalt-free lithium-rich cathode material.
From the data results of example 1 and comparative example 2 (example 8 and comparative example 4), it is understood that the positive electrode material obtained by coating the hydrophobic organic substance in the present invention has higher cycle performance and reduced voltage attenuation amplitude compared to the dot-shaped coating of the conventional oxide.
In conclusion, the surface of the layered lithium nickel manganese oxide positive electrode material is coated with the special hydrophobic organic cholesterol dodecyl carbonate, so that the surface of the positive electrode presents hydrophobicity, the electrochemical performance reduction of the positive electrode material caused by the water absorption of the surface of the layered lithium nickel manganese oxide (cobalt-free positive electrode material) in a high-moisture environment can be prevented, and meanwhile, a stable Mn-C ═ O bond is formed with the surface of the positive electrode material, so that the cycle stability and the voltage drop of the lithium nickel manganese oxide positive electrode material are effectively improved. According to the battery provided by the invention, the discharge specific capacity under 1C can reach more than 205.8mAh/g, the capacity retention rate after 50-week circulation can reach more than 94.4%, and the voltage attenuation after 50 weeks is below 3.85%; the precursor material is a mixed material of a hydroxide precursor and an oxide precursor, and after the presintering temperature, the concentration of hydrophobic organic matters and the stirring time in the coating process are further adjusted, the discharge specific capacity of the battery under 1C can reach more than 210.4mAh/g, the capacity retention rate after 50 cycles can reach more than 96.8 percent, and the voltage attenuation after 50 cycles is less than 2.81 percent.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The layered lithium nickel manganese oxide positive electrode material is characterized in that the surface of the layered lithium nickel manganese oxide positive electrode material is coated with a hydrophobic organic matter, the hydrophobic organic matter is coated on the surface of the layered lithium nickel manganese oxide positive electrode material in a membrane form, and the hydrophobic organic matter comprises cholesterol dodecyl carbonate.
2. The layered lithium nickel manganese oxide positive electrode material of claim 1, wherein the thickness of the coating film of the hydrophobic organic substance is 10-50 nm.
3. The preparation method of the layered lithium nickel manganese oxide positive electrode material as claimed in claim 1 or 2, characterized by comprising the following steps:
(1) mixing a nickel-manganese precursor with a lithium source, and sintering to obtain a pre-coated layered lithium nickel manganese oxide positive electrode material;
(2) mixing and coating the pre-coated layered lithium nickel manganese oxide positive electrode material, a hydrophobic organic matter and a solvent to obtain the layered lithium nickel manganese oxide positive electrode material;
wherein the hydrophobic organic comprises cholesterol dodecyl carbonate.
4. The preparation method of the layered lithium nickel manganese oxide cathode material according to claim 3, wherein the nickel manganese precursor comprises a nickel manganese oxide precursor and a nickel manganese hydroxide precursor;
preferably, the mass ratio of the nickel manganese oxide precursor to the nickel manganese hydroxide precursor is (0.2-1): 1.
5. The preparation method of the layered lithium nickel manganese oxide cathode material according to claim 4, wherein the nickel manganese oxide precursor is obtained by pre-sintering a nickel manganese hydroxide precursor.
6. The preparation method of the layered lithium nickel manganese oxide cathode material according to claim 5, wherein the pre-sintering temperature is 500-700 ℃;
preferably, the pre-burning time is 5-10 h;
preferably, the mixed raw material of step (1) further comprises a dopant.
7. The preparation method of the layered lithium nickel manganese oxide cathode material according to any one of claims 3 to 6, wherein the mixed coating process in the step (2) comprises the following steps: dissolving the hydrophobic organic matter in a solvent to obtain a hydrophobic organic matter solution, and then adding the precoated layered lithium nickel manganese oxide positive electrode material obtained in the step (1) to carry out mixed coating;
preferably, the solvent of step (2) comprises tetrahydrofuran;
preferably, the method for mixing and coating in the step (2) comprises stirring;
preferably, the stirring temperature is 25-80 ℃;
preferably, the stirring time is 2-6 h;
preferably, the concentration of the hydrophobic organic solution is 1-3 mol/L.
8. The preparation method of the layered lithium nickel manganese oxide cathode material according to any one of claims 3 to 7, wherein after the mixed coating in the step (2), suction filtration and drying are sequentially performed.
9. The preparation method of the layered lithium nickel manganese oxide cathode material according to any one of claims 3 to 8, wherein the preparation method comprises the following steps:
(1) mixing a nickel-manganese oxide precursor and a nickel-manganese hydroxide precursor with a lithium source and a doping agent according to the mass ratio of (0.2-1) to 1, and sintering to obtain a pre-coated layered lithium nickel manganese oxide positive electrode material;
(2) dissolving the hydrophobic organic matter in a solvent to obtain a hydrophobic organic matter solution with the concentration of 1-3 mol/L, adding the precoated layered lithium nickel manganese oxide positive electrode material obtained in the step (1), stirring for 2-6 hours at 25-80 ℃, performing suction filtration, and drying to obtain the layered lithium nickel manganese oxide positive electrode material;
wherein the hydrophobic organic comprises cholesterol dodecyl carbonate; the nickel-manganese oxide precursor is obtained by pre-sintering a nickel-manganese hydroxide precursor at 500-700 ℃ for 5-10 h.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the layered lithium nickel manganese oxide positive electrode material according to claim 1 or 2.
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