CN113178568A - Double-layer coated positive electrode lithium supplement material and lithium ion battery comprising same - Google Patents
Double-layer coated positive electrode lithium supplement material and lithium ion battery comprising same Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 71
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 61
- 239000013589 supplement Substances 0.000 title claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910008722 Li2NiO2 Inorganic materials 0.000 claims abstract description 33
- 239000011162 core material Substances 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 12
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 24
- 239000011247 coating layer Substances 0.000 claims description 23
- 239000007774 positive electrode material Substances 0.000 claims description 23
- 150000004706 metal oxides Chemical class 0.000 claims description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims description 15
- 229910052755 nonmetal Inorganic materials 0.000 claims description 11
- 238000005253 cladding Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 239000011824 nuclear material Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 12
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052810 boron oxide Inorganic materials 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000009831 deintercalation Methods 0.000 abstract description 3
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 15
- 238000005245 sintering Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229910018553 Ni—O Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000003918 potentiometric titration Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910007746 Zr—O Inorganic materials 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 206010016766 flatulence Diseases 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical group [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- H01M4/52—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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
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- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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Abstract
The invention provides a double-layer coated anode lithium supplement material and a lithium ion battery comprising the same. Meanwhile, the phenomenon that a large amount of gas and junctions are easily generated in the charging and discharging processes can be avoidedThe structure is unstable, and then a series of side reactions occur. In particular, the invention adopts zirconium dioxide and boron oxide to coat Li2NiO2On the one hand, the zirconium dioxide has a porous structure, and the boron oxide is a glassy material and can effectively inhibit the corrosion of HF in the electrolyte by coating the surface of the core material so as to protect Li2NiO2A nuclear material, while allowing free deintercalation of lithium ions; on the other hand, will be with Li2NiO2The residual lithium on the surface reacts to reduce the residual alkali value of the material, effectively inhibit the gas generation problem of the battery and stabilize the surface structure of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and mainly relates to a double-layer coated positive electrode lithium supplement material, a preparation method thereof and a lithium ion battery comprising the material.
Background
In the first charging process of the current commercial lithium ion battery, about 10 wt% of active lithium in the cathode material is consumed, and an irreversible stable SEI film is formed on the surface of the cathode, so that irreversible capacity loss is caused, and further, the energy density of the lithium ion battery is reduced.
It is the most effective way to solve the above technical problems by replenishing lithium ions consumed by the SEI film formation during the first charge of a battery. The lithium supplementing technology comes from the birth, and the lithium supplementing mode which can be realized comprises an anode, a cathode, a diaphragm and electrolyte, wherein the lithium supplementing range of the electrolyte is very small, the requirements of the diaphragm on the diaphragm and the preparation level are too high for the lithium supplementing of the diaphragm, and a large amount of residues often influence the self-discharge of a battery core. The requirement of lithium supplement of the negative electrode on the humidity of the environment is extremely strict, the cost is high, and lithium dendrite is easy to occur to influence the safety performance. The lithium supplement of the positive electrode is a lithium-rich salt, so that the lithium supplement is relatively safe and easy to process, and becomes the most possible lithium supplement mode for large-scale application, and the lithium supplement mode is widely concerned and researched.
For example by selecting Li2NiO2The material has a capacity of 486mAh/g, releases lithium ions at a voltage of 3.6V or more, can greatly improve the energy density of the battery, and is used as a ternary positive electrode material and a lithium supplement material for positive active materials such as lithium cobaltate and the like, but Li2NiO2The material has high residual alkali value and poor surface structure stability, and is easy to freeze when the battery is homogenizedThe positive pole piece can not be prepared, and moreover, a large amount of gas is easily generated in the charging and discharging process, the structure is unstable, and a series of side reactions are caused.
Disclosure of Invention
In order to improve Li in the prior art2NiO2The invention provides a double-layer coated positive electrode lithium supplement material and a lithium ion battery comprising the same.
The purpose of the invention is realized by the following technical scheme:
the positive electrode lithium supplement material comprises a core material and a coating layer, wherein the core material comprises Li2NiO2The coating layer comprises metal oxide and non-metal oxide, and the metal oxide comprises ZrO2Said non-metal oxide comprises B2O3。
According to the embodiment of the invention, the coating layer comprises a first coating layer and a second coating layer, the first coating layer is coated on the surface of the core material, and the second coating layer is coated on the surface of the first coating layer; the first cladding layer comprises a metal oxide and the second cladding layer comprises a non-metal oxide.
According to an embodiment of the invention, the ZrO2With Li2NiO2The mass ratio of (0.1-0.3): 100, such as (0.1-0.2): 100, such as 0.1:100, 0.135:100, 0.15:100, 0.175:100, 0.2:100, 0.25:100, 0.3: 100.
According to an embodiment of the present invention, B2O3With Li2NiO2The mass ratio of (0.1-0.3): 100, such as (0.1-0.2): 100, such as 0.1:100, 0.135:100, 0.15:100, 0.175:100, 0.2:100, 0.25:100, 0.3: 100.
According to an embodiment of the invention, the ZrO2And B2O3The mass ratio of (3-1) to (1-3).
According to an embodiment of the present invention, the thickness of the first coating layer is 10-60 nm, such as 20-50 nm, such as 30nm, and the thickness of the second coating layer is 10-50 nm, such as 20E40nm, such as 30 nm. The thicknesses of the first cladding layer and the second cladding layer are selected to effectively inhibit corrosion by HF in the electrolyte to protect Li2NiO2And at the same time, can allow lithium ions to be freely extracted.
According to an embodiment of the invention, the median particle diameter D of the core material502 to 8 μm, such as 4 to 6 μm. The core material is selected such that the median particle diameter D50The risk of increasing the internal resistance flatulence of the battery caused by longer lithium ion migration path can be avoided.
According to the embodiment of the invention, the median particle diameter D of the positive electrode lithium supplement material502 to 8 μm, such as 4 to 6 μm.
According to an embodiment of the present invention, the residual alkali value of the positive electrode lithium supplement material is 0.1 to 2 wt%, such as 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%. In the invention, the residual alkali value of the positive electrode lithium supplement material is the mass percentage content of residual Li (including lithium carbonate and lithium hydroxide) in the positive electrode lithium supplement material.
In the invention, the particle sizes of the nuclear material and the anode lithium supplement material can be tested by a scanning electron microscope or a laser particle sizer, and the thickness of the coating layer is tested by adopting profile EDS surface scanning and/or a high-resolution transmission electron microscope; the material composition was tested using profile EDS surface scanning. Different instruments and specific test parameters are different, and the residual alkali value of the material is tested by potentiometric titration, so the instruments belong to conventional instruments in the field, and the test methods and the parameters are also common knowledge in the field, and are not described again.
In the invention, the core material is coated by the coating layer, the structural stability of the core material is obviously improved, and the reason for analyzing is that: interaction exists between the core material and the coating layer in the positive electrode lithium supplement material with the core-shell structure. The cladding of the metal oxide and the nonmetal oxide can inhibit HF in the electrolyte from corroding the nuclear material, and the Zr-O bond energy and the B-O bond energy of the cladding are stronger than those of Ni-O bond energy, so that the Ni ions are favorably inhibited from dissolving out, the surface of the positive electrode lithium supplement material has better performance of resisting the acid environment in the electrolyte, and the surface stability of the positive electrode lithium supplement material is improved. Meanwhile, the surfaces of the cladding materials are all porous structures, so that the back-and-forth deintercalation of lithium ions in the charging and discharging process is facilitated. In addition, the metal oxide is adopted to tightly coat the core material, the tight coating of the core-shell structure can improve the electrochemical performance of the positive electrode lithium supplement material, isolate the corrosion of water in the air to the core material, improve the stability of the positive electrode lithium supplement material in the air, ensure that the positive electrode lithium supplement material does not need harsh operating environment and is beneficial to large-scale production.
The invention also provides a preparation method of the anode lithium supplement material, which comprises the following steps:
(1) mixing, grinding, drying and sintering a nuclear material and a metal source at a high temperature to obtain a metal oxide coated nuclear material;
(2) and mixing, grinding, drying and sintering the metal oxide coated nuclear material and the nonmetal source at a high temperature to obtain the metal oxide coated nuclear material coated by the nonmetal oxide, namely the positive electrode lithium supplement material.
According to an embodiment of the present invention, in the step (1), the core material is Li2NiO2。
According to an embodiment of the invention, in step (1), the metal source is selected from metal oxides, the metal comprising Zr. Among them, the metal oxide is preferably a nanoscale metal oxide. Wherein the metal oxide comprises zirconia, preferably nanoscale zirconia.
According to an embodiment of the invention, in step (1), the mass ratio of the metal source to the core material is (0.1-0.3): 100, such as (0.1-0.2): 100, such as 0.1:100, 0.135:100, 0.15:100, 0.175:100, 0.2:100, 0.3: 100.
According to an embodiment of the invention, in step (1), the mixing and grinding are carried out using methods known in the art, for example using a high-speed mixer.
According to the embodiment of the invention, in the step (1), the high-temperature sintering is performed in a pure oxygen atmosphere, and the oxygen atmosphere is selected to ensure that the synthesized positive electrode lithium supplement material has good crystallinity and purity.
According to an embodiment of the invention, in the step (1), the temperature of the high-temperature sintering is 500-900 ℃, the time of the high-temperature sintering is 3-8 h, for example, the temperature of the high-temperature sintering is 500-700 ℃, and the time of the high-temperature sintering is 3-6 h.
According to an embodiment of the invention, in step (2), the non-metal source comprises boric acid.
According to an embodiment of the invention, in step (2), the mass ratio of the non-metal source and the core material (i.e. the core material in step (1)) is (0.1-0.3): 100, such as (0.1-0.2): 100, such as 0.1:100, 0.135:100, 0.15:100, 0.175:100, 0.2:100, 0.3: 100.
According to an embodiment of the present invention, in step (2), the mixing and milling is performed using methods known in the art, for example, using a high-speed mixer.
According to the embodiment of the invention, in the step (2), the high-temperature sintering is performed in a pure oxygen atmosphere, and the oxygen atmosphere is selected to ensure that the synthesized positive electrode lithium supplement material has good crystallinity and purity.
According to an embodiment of the present invention, in the step (2), the temperature of the high-temperature sintering is 300 to 600 ℃, and the time of the high-temperature sintering is 3 to 8 hours, for example, the temperature of the high-temperature sintering is 400 to 550 ℃, and the time of the high-temperature sintering is 3 to 6 hours.
According to an embodiment of the present invention, the core material is prepared by the following method:
uniformly mixing a lithium source and a nickel source, then roasting, cooling and sieving to prepare the nuclear material, wherein the nuclear material is Li2NiO2。
Wherein the lithium source is selected from Li2O、LiOH、Li2CO3At least one of (1).
Wherein the nickel source is selected from NiO, Ni (OH)2、NiCO3At least one of (1).
Wherein the molar ratio of Li element in the lithium source to Ni element in the nickel source is (2.01-2.05): 1.0, such as 2.01:1.0, 2.02:1.0, 2.03:1.0, 2.04:1.0 and 2.05: 1.0. It was found that an excessive amount of lithium source can prevent the material from losing lithium volatilization during firing to deteriorate the crystallinity of the material.
Wherein the firing is performed in a muffle furnace.
Wherein the firing is performed in an oxygen atmosphere, and the firing in the oxygen atmosphere is effective for decomposing Li2CO3And the lithium ion material participates in oxidation reaction to synthesize a material with good crystallinity, so that the residual alkali value of the positive electrode lithium supplement material can be better reduced.
Wherein the roasting conditions are as follows: roasting for 4-8 h at 400-550 ℃; roasting for 4-8 h at 600-750 ℃; roasting for 8-12 h at 800-950 ℃; preferably, roasting at 500 ℃ for 5 h; roasting at 720 ℃ for 5 h; roasting at 800 deg.c for 10 hr.
The invention also provides a positive electrode, wherein the positive electrode comprises a positive electrode current collector and a positive electrode active material layer attached to the positive electrode current collector, and the positive electrode active material layer comprises the positive electrode lithium supplement material.
According to the embodiment of the invention, the adding amount of the positive electrode lithium supplement material accounts for 1-5 wt% of the total mass of the positive electrode active material layer, such as 1 wt%, 2 wt%, 3 wt%, 4 wt% or 5 wt%.
According to an embodiment of the present invention, the positive electrode active material layer further includes a positive electrode active material, a binder, and a conductive agent.
According to an embodiment of the present invention, the positive electrode active material is added in an amount of 85 to 97 wt% based on the total mass of the positive electrode active material layer, for example, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, or 97 wt%.
According to an embodiment of the present invention, the binder is added in an amount of 1 to 5 wt%, for example, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt% of the total mass of the positive electrode active material layer.
According to an embodiment of the present invention, the conductive agent is added in an amount of 1 to 5 wt%, for example, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt% based on the total mass of the positive electrode active material layer.
The invention also provides a lithium ion battery which comprises the anode lithium supplement material.
According to an embodiment of the present invention, the lithium ion battery includes the above-described positive electrode.
Has the advantages that:
the invention provides a double-layer coated anode lithium supplement material and a lithium ion battery comprising the same. Meanwhile, the problems that a large amount of gas is easily generated in the charging and discharging process, the structure is unstable, and then a series of side reactions are caused are solved. In particular, the invention adopts zirconium dioxide and boron oxide to coat Li2NiO2On the one hand, the zirconium dioxide has a porous structure, and the boron oxide is a glassy material and can effectively inhibit the corrosion of HF in the electrolyte by coating the surface of the core material so as to protect Li2NiO2A nuclear material, while allowing free deintercalation of lithium ions; zirconium dioxide on the other hand will be the same as Li2NiO2The residual lithium on the surface reacts, the residual alkali value of the material is reduced, the gas generation problem of the battery is effectively inhibited, and the surface structure of the battery is stabilized. The lithium ion battery composed of the positive electrode lithium supplement material can effectively supplement irreversible capacity lost when an SEI film is formed during formation of the battery during the first charge-discharge cycle, and the energy density of the battery is greatly improved.
Drawings
FIG. 1 shows Li in example 12NiO2SEM picture after lithium supplement material cladding;
fig. 2 shows the high-temperature storage thickness change rates of the batteries manufactured in example 1 and comparative examples 1 and 2, example 1 in fig. 2 being example 1, and comparative examples 1, 2 and 1 in the histogram in fig. 2, corresponding to the columns, from left to right.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
(1) According to Li2CO3With NiCO3In a molar ratio of 1.05:1.0 148.38g of Li were weighed2CO3，227.02gNiCO3Carrying out high-speed mixing;
(2) and (3) carrying out primary synthesis on the mixture in a muffle furnace, and introducing oxygen into the muffle furnace. Synthesizing the synthesis components in three sections, wherein the synthesis temperature is 500 ℃/5h in the low-temperature section; the middle temperature section is 720 ℃/5 h; the high temperature section is 800 ℃/10 h;
(3) after the muffle furnace is naturally cooled, taking out the materials and sieving the materials by a 300-mesh sieve to obtain Li2NiO2；
(4) The obtained Li2NiO2Same nano-grade ZrO2Mixing with a high-speed mixer to obtain a mixture of ZrO2In an amount according to Li2NiO20.135 wt% of the amount of the ZrO 2, sintering the ZrO 2 at 600 ℃ for 5 hours in an oxygen atmosphere, naturally cooling, taking out the discharged material, and sieving the discharged material with a 300-mesh sieve to obtain the target ZrO2Coated Li2NiO2Is denoted by Li2NiO2@ZrO2。
(5) The obtained ZrO2Coated Li2NiO2Same nano-scale H3BO3Mixing with high speed mixer, wherein H3BO3In an amount according to Li2NiO20.174 wt% of the total amount of the components, sintering the components for 5 hours at 500 ℃ in an oxygen atmosphere, naturally cooling the components, taking out the discharged materials, and sieving the discharged materials by a 300-mesh sieve to obtain a target object B2O3Coated Li2NiO2@ZrO2Is denoted by Li2NiO2@ZrO2@B2O3。
(6) The positive electrode active material (ternary NCM622 material) and the Li prepared in the above way2NiO2@ZrO2The conductive agent (conductive carbon black) and the binder (PVDF) are mixed according to the mass ratio of 92 wt%: 2wt%: 4.5 wt%: adding 1.5 wt% of the mixture into a homogenizing tank to prepare a mixture for homogenizing, wherein the solid content is 52.5-53.5%, and the viscosity is 3000-6000 mPa. Subsequently, a coating roller is used for pressing the positive plate, and the compaction density of the positive plate is controlled to be 2.9g/cm3。
(7) And (3) laminating the positive plate and the negative plate after die cutting, injecting liquid, and finally preparing a soft package battery cell for electrical property test (the capacity of the remark battery is designed according to 1.54 Ah).
For Li prepared in the step (4)2NiO2@ZrO2Performance tests were performed and the test results are listed in table 1.
Table 1 Li of example 12NiO2@ZrO2Results of performance test of
Wherein Li2CO3(wt%) is Li2NiO2@ZrO2The residual alkali value of (1) is calculated according to the volume of the consumed HCl standard solution by adopting a potentiometric titration method and indicating an end point by using a pH electrode through the neutralization reaction of hydrochloric acid and residual alkali in the filtrate.
For Li prepared in the step (5)2NiO2@ZrO2@B2O3Performance tests were performed and the test results are listed in table 2.
Table 2 Li of example 12NiO2@ZrO2@B2O3Results of performance test of
Wherein Li2CO3(wt%) is Li2NiO2@ZrO2@B2O3The residual alkali value of (1) is calculated according to the volume of the consumed HCl standard solution by adopting a potentiometric titration method and indicating an end point by using a pH electrode through the neutralization reaction of hydrochloric acid and residual alkali in the filtrate.
Comparative example 1:
the other operations are the same as example 1, except that:
preparing the positive active material (ternary NCM622 material) and the Li prepared in the step (3)2NiO2The conductive agent (conductive carbon black) and the binder (PVDF) are mixed according to the mass ratio of 92 wt%: 2 wt%: 4.5 wt%: 1.5 wt% was added to the homogenizer tank to prepare a blend homogenate.
Comparative example 2:
the other operations are the same as example 1, except that:
preparing the positive active material (ternary NCM622 material) and the Li prepared in the step (4)2NiO2@ZrO2The conductive agent (conductive carbon black) and the binder (PVDF) are mixed according to the mass ratio of 92 wt%: 2 wt%: 4.5 wt%: 1.5 wt% was added to the homogenizer tank to prepare a blend homogenate.
The lithium ion batteries prepared in example 1 and comparative examples 1-2 were subjected to performance tests, the test procedures being as follows:
(1) comparison of first circle Charge and discharge Capacity (0.2C/0.2C)
The test method is as follows: the battery is tested in a cabinet at 25 ℃, the test voltage range is set to be 3.0-4.2V, the test current is 0.2C, and the test results are shown in table 3.
(2) High-temperature storage at 60 ℃ for 30 days
The test method is as follows: recording discharge capacity after charging and discharging for 1 time at the normal temperature of 25 ℃, standing for a period of time in an open circuit state after 1C charging to reach 100% SOC, measuring voltage, internal resistance and thickness according to corresponding frequency requirements in the storage process, and taking out the battery to record the residual capacity and corresponding voltage, internal resistance and thickness measurement at the normal temperature after the test is finished. The recovery capacity was then recorded with 1C charge-discharge cycles 1 time, and the test results are shown in fig. 2.
TABLE 3 first-turn battery performance test results for the lithium ion batteries of example 1 and comparative examples 1-2
FIG. 1 shows Li in example 12NiO2Li coated with nuclear material2NiO2@ZrO2@B2O3SEM picture of the lithium-supplemented material of the positive electrode; from FIG. 1, ZrO can be seen2And B2O3Is uniformly coated with Li2NiO2Surface of nuclear material, illustrating ZrO2And B2O3The dispersibility of (A) is relatively good.
The first cycle 0.2C charge and discharge capacities of the lithium ion batteries of example 1 and comparative examples 1 and 2 are listed in table 3. As can be seen from Table 3, Li of example 1 was added2NiO2@ZrO2@B2O3First-turn discharge capacity of lithium ion battery with positive electrode lithium supplement material is compared with that of uncoated B of comparative example 22O3Li of (2)2NiO2@ZrO2The positive electrode lithium-supplementing material is 10mAh higher than the Li of the comparative example 12NiO2The nuclear material is 70mAh higher. Mainly because Zr-O bond energy is higher than Ni-O bond energy, it can stabilize Li2NiO2The surface structure is stable, and the dissolution of Ni ions is inhibited; at the same time B2O3The material is a glassy material with a three-dimensional network structure, and the B-O bond energy is higher than the Ni-O bond energy, so that the surface structure of the material can be effectively stabilized, and the corrosion of HF in the electrolyte of the material in an acidic environment is further enhanced.
FIG. 2 is a graph showing the rate of change in high-temperature storage thickness of the batteries manufactured in example 1 and comparative examples 1 and 2; as can be seen from FIG. 2, double-coated Li2NiO2@ZrO2@B2O3The thickness change rate of the positive electrode lithium supplement material under the high-temperature storage condition is the lowest. Shows that Li is effectively inhibited after double coating2NiO2The occurrence of side reactions on the surface of the nuclear material, enhancing Li2NiO2The structural stability of the nuclear material avoids causing the internal resistance of the battery to be larger and the flatulence, thereby eliminating Li2NiO2The addition of the nuclear material causes the battery to expand during high-temperature storage.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The positive electrode lithium supplement material comprises a core material and a coating layer, wherein the core material comprises Li2NiO2The coating layer comprises metal oxide and non-metal oxide, and the metal oxide comprises ZrO2Said non-metal oxide comprises B2O3。
2. The positive electrode lithium supplement material according to claim 1, wherein the coating layer comprises a first coating layer and a second coating layer, the first coating layer is coated on the surface of the core material, and the second coating layer is coated on the surface of the first coating layer; the first cladding layer comprises a metal oxide and the second cladding layer comprises a non-metal oxide.
3. The positive electrode lithium supplement material according to claim 1, wherein the ZrO2With Li2NiO2The mass ratio of (0.1-0.3) to (100); and/or the presence of a gas in the gas,
b is2O3With Li2NiO2The mass ratio of (0.1-0.3): 100.
4. The positive electrode lithium supplement material according to claim 1, wherein the thickness of the first coating layer is 10 to 60 nm; and/or the thickness of the second coating layer is 10-50 nm.
5. The positive electrode lithium supplement material according to claim 1, wherein the positive electrode lithium supplement material has a median particle diameter D502-8 μm; and/or the residual alkali value of the positive electrode lithium supplement material is 0.1-2 wt%.
6. A positive electrode, comprising a positive electrode current collector and a positive electrode active material layer coated on the positive electrode current collector, wherein the positive electrode active material layer comprises the positive electrode lithium supplement material according to any one of claims 1 to 5.
7. The positive electrode according to claim 6, wherein the positive electrode lithium supplement material is added in an amount of 1 to 5 wt% based on the total mass of the positive electrode active material layer.
8. The positive electrode according to claim 6 or 7, wherein the positive electrode active material layer further comprises a positive electrode active material, a binder, and a conductive agent, wherein the amount of the positive electrode active material added is 85 to 97 wt% of the total mass of the positive electrode active material layer, the amount of the binder added is 1 to 5 wt% of the total mass of the positive electrode active material layer, and the amount of the conductive agent added is 1 to 5 wt% of the total mass of the positive electrode active material layer.
9. A lithium ion battery comprising the positive electrode lithium supplement material according to any one of claims 1 to 5.
10. The lithium ion battery of claim 9, wherein the lithium ion battery comprises the positive electrode of any one of claims 6-8.
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