CN109704413B - High-nickel anode material and method for improving storage performance of high-nickel anode material - Google Patents
High-nickel anode material and method for improving storage performance of high-nickel anode material Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000010405 anode material Substances 0.000 title description 15
- 238000001354 calcination Methods 0.000 claims abstract description 37
- 239000007774 positive electrode material Substances 0.000 claims abstract description 30
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000010406 cathode material Substances 0.000 claims abstract description 22
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910013716 LiNi Inorganic materials 0.000 claims abstract 2
- 238000012360 testing method Methods 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000011163 secondary particle Substances 0.000 claims description 7
- 238000004458 analytical method Methods 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 239000011164 primary particle Substances 0.000 claims description 3
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229910021314 NaFeO 2 Inorganic materials 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 238000002156 mixing Methods 0.000 abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003570 air Substances 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910003678 NixCoyMnz(OH)2 Inorganic materials 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 2
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910013172 LiNixCoy Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种高镍正极材料以及提高高镍正极材料储存性能的方法。所述高镍正极材料以化学式LiNixCoyMnzAl1‑x‑y‑zO2表示；其中，0.5≤x＜1，0＜y＜0.5，0＜z＜0.5，1‑x‑y‑z＞0。所述方法是将含锰无机盐、含铝无机盐、LiOH·H2O与高镍前驱体混合，加入乙醇研磨均匀，得到固体粉末混合物；对所得的固体粉末混合物先进行预煅烧，然后升温进行煅烧，得到所述高镍正极材料。该发明所述方法有效抑制了高镍正极材料与空气中水分、二氧化碳的副反应，改善了材料表面稳定性，从而提高材料的储存性能，有利于高镍正极材料的商业化应用。
The invention discloses a high-nickel positive electrode material and a method for improving the storage performance of the high-nickel positive electrode material. The high nickel cathode material is represented by the chemical formula LiNi x Co y Mn z Al 1‑x‑y‑z O 2 ; wherein, 0.5≤x＜1, 0＜y＜0.5, 0＜z＜0.5, 1‑x‑ y‑z>0. The method comprises the following steps: mixing manganese-containing inorganic salt, aluminum-containing inorganic salt, LiOH·H 2 O and high-nickel precursor, adding ethanol and grinding evenly to obtain a solid powder mixture; pre-calcining the obtained solid powder mixture, and then heating up Perform calcination to obtain the high-nickel positive electrode material. The method of the invention effectively suppresses the side reactions of the high-nickel positive electrode material with moisture and carbon dioxide in the air, improves the surface stability of the material, thereby improves the storage performance of the material, and is beneficial to the commercial application of the high-nickel positive electrode material.
Description
Technical Field
The invention belongs to the field of chemical energy storage batteries, and particularly relates to a high-nickel positive electrode material and a method for improving the storage performance of the high-nickel positive electrode material.
Background
The rechargeable lithium ion secondary battery has the advantages of high specific energy, long charging and discharging service life, no memory effect, low self-discharging rate, quick charging, no pollution, wide working temperature range, safety, reliability and the like, and is widely applied to modern communication, portable electronic products and hybrid electric vehicles. Particularly, with the continuous development of the new energy automobile industry in recent years, higher requirements are put forward on the power lithium ion secondary battery, and researches show that the positive electrode material is a key factor for limiting the performance improvement of the power lithium battery at present. At present, commercial power battery anode materials mainly comprise lithium cobaltate and lithium iron phosphate, but the specific energy is limited, and the requirement of future new energy automobiles on high endurance mileage is difficult to meet. High nickel cathode materials are gradually favored due to their higher specific capacity and low price, but their wide application is severely limited by some defects, such as: the method has the advantages of serious phase change and oxygen release phenomena in the charging and discharging process, easy side reaction between the surface and the electrolyte, poor storage performance and the like, wherein the poor storage performance is one of important factors influencing the commercial use of the electrolyte.
Disclosure of Invention
In order to overcome the problem of poor storage performance of a high-nickel cathode material, the invention provides the high-nickel cathode material and a method for improving the storage performance of the high-nickel cathode material.
A high-nickel positive electrode material can be represented by the chemical formula LiNixCoyMnzAl1-x-y-zO2Represents; wherein x is more than or equal to 0.5 and less than 1, y is more than 0 and less than 0.5, z is more than 0 and less than 0.5, and 1-x-y-z is more than 0. For example, 0.6. ltoreq. x < 0.9, 0.1. ltoreq. y 0.4, 0.1. ltoreq. z 0.4, 1-x-y-z > 0; for another example, x is more than or equal to 0.7 and less than 0.8, y is more than or equal to 0.2 and less than or equal to 0.3, z is more than or equal to 0.2 and less than or equal to 0.3, and 1-x-y-z is more than or equal to 0. According to the material, the main crystal structure of the high-nickel anode material is alpha-NaFeO2The structure belongs to an R-3m space group. Further, the high nickel positive electrode material had an XRD spectrum pattern as shown in fig. 3, in which peaks (006)/(012) and (018)/(110) were clearly split, and peaks (003) and (104) were both shifted to a low angle.
According to the material, the primary particles of the high-nickel cathode material are nanosheets, and the thickness of the nanosheets can be 130-250 nm, for example, the thickness of the nanosheets can be 150-200 nm.
According to the material, the secondary particles of the high-nickel cathode material are spherical-like, and the diameter of the secondary particles is 8-12 microns.
A method for improving the storage performance of the high-nickel cathode material comprises the following steps:
step 1, manganese-containing inorganic salt, aluminum-containing inorganic salt and LiOH & H2Mixing O with the high-nickel precursor, adding ethanol, and grinding uniformly to obtain a solid powder mixture;
and 2, pre-calcining the obtained solid powder mixture, and then heating for calcining to obtain the high-nickel anode material.
According to the method of the invention, in step 1, the high nickel precursor has the following chemical formula: nixCoyMnz(OH)2Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.5, and x + y + z is equal to 1; for example, 0.6. ltoreq. x.ltoreq.0.9, 0.1. ltoreq. y.ltoreq.0.3, 0.1. ltoreq. z.ltoreq.0.3; exemplarily, x is 0.8, y is 0.1, and z is 0.1.
Preferably, the secondary particles of the high-nickel precursor are spherical-like, and the diameter of the secondary particles is 8-12 microns.
According to the method of the invention, in the step 1, the molar ratio of the manganese element in the manganese-containing inorganic salt to the aluminum element in the aluminum-containing inorganic salt can be (0.01-2): (0.01-2); for example, the molar ratio may be (0.1 to 1.5), or (0.5 to 1.0), (0.5 to 1.0).
According to the method of the invention, in step 1, the sum of the molar amounts of the manganese element in the manganese-containing inorganic salt and the aluminum element in the aluminum-containing inorganic salt is 0.1 to 5 percent, such as 0.5 to 4 percent and 1 to 3 percent of the molar amount of the high-nickel precursor; illustratively, it may be 1.5%, 3%, 4.5%.
According to the method of the invention, step 1, the LiOH. H2The molar amount of O is 1.00 to 1.05 times, for example 1.02 to 1.05 times, and illustratively 1.05 times the molar amount of the high nickel precursor. Specifically, m (LiOH. H)2O)＝41.96g/mol×n(NixCoyMnz(OH)2) X 1.05, wherein m (LiOH. H)2O) is LiOH. H2Mass of O, n (Ni)xCoyMnz(OH)2) Is the molar weight of the high nickel precursor.
According to the method of the invention, in step 1, the manganese-containing inorganic salt may be at least one selected from manganese sulfate, manganese nitrate, manganese acetate, and corresponding hydrates thereof; for example, the manganese-containing inorganic salt is Mn (CH)3COO)2·4H2O。
The inorganic aluminum-containing salt may be at least one selected from aluminum sulfate, aluminum nitrate, aluminum acetate, and hydrates thereof, and for example, the inorganic aluminum-containing salt is Al (NO)3)3·9H2O。
According to the method of the present invention, in step 2, the temperature range of the pre-calcination is 450 to 600 ℃, such as 480 to 550 ℃, for example, 500 ℃. The pre-calcination time is 3 to 8 hours, such as 4 to 6 hours, and exemplarily, the pre-calcination time is 5 hours.
According to the method of the invention, in step 2, the temperature of the calcination is 650 to 850 ℃, for example 700 to 800 ℃, and exemplarily 750 ℃. The calcining time is 12-36 h, such as 13-30 h and 15-24 h; illustratively 15 h.
According to the method of the invention, in step 2, the precalcination and the calcination are both carried out in a tube furnace; both the pre-calcination and the calcination are carried out in an atmosphere of oxygen, for example, an oxygen atmosphere. Further, the flow rate of the oxygen gas is 100-500 mL/min, such as 200-400 mL/min. Further, the temperature rise rate of the pre-calcination and the calcination is 1-3 ℃/min, such as 1.5-2.5 ℃/min, and exemplarily, the temperature rise rate is 2 ℃/min.
According to the method of the invention, the method further comprises: and 3, exposing the high-nickel anode material to air for treatment, and then carrying out test analysis.
According to the method of the present invention, in step 3, the relative humidity of the air may be 70 to 90%, for example 75 to 85%, and exemplarily 80%. Specifically, the high nickel cathode material may be plated in a petri dish (e.g., a 35mm diameter petri dish) and directly exposed to air having a relative humidity of 80%.
The application also provides a high-nickel cathode material prepared by the method.
A power lithium battery comprises the high-nickel cathode material. For example, the power lithium battery may be a button cell battery, preferably a CR2025 button cell battery.
The invention has the beneficial effects that:
(1) the method of the invention is directly finished by one-time calcination process (including precalcination and calcination), saves resources, and is simple and easy to realize.
(2) The method provided by the invention can be used for effectively inhibiting the interface reaction of the high-nickel anode material with moisture and carbon dioxide in the air, improving the surface stability of the material, improving the storage performance of the material and facilitating the further commercial application of the high-nickel anode material.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of a high nickel precursor and the high nickel cathode material prepared in example 1.
Fig. 2 is a graph of cycle performance testing of the high nickel positive electrode material prepared in example 1 after various exposure times.
Fig. 3 is an X-ray diffraction (XRD) pattern of the high nickel cathode material prepared in comparative example and example 2.
Fig. 4 is an impedance profile of the high nickel positive electrode material prepared in comparative example and example 2 after 45 days of exposure.
Fig. 5 is a graph of ir spectroscopy measurements of the high nickel positive electrode material prepared in example 3 after 45 days exposure.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents also fall within the scope of the 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.
In the following examples:
scanning Electron Microscope (SEM): instrument model FEI Quanta, netherlands.
Fourier infrared spectrum: instrument model Nicolet 6700, usa.
X-ray diffractometer: instrument model Rigaku Ultima IV, japan.
Alternating current impedance (AC) testing: CHI660e electrochemical workstation, china.
The test method comprises the following steps:
the samples tested were cells charged to 4.35V at 0.2C, with test frequencies ranging from 0.01Hz to 10 kHz.
Assembly and testing of CR2025 button cells: a positive electrode material (the high-nickel positive electrode material provided by the examples 1-3 and the comparative example), acetylene black and PVDF (polyvinylidene fluoride) are prepared into slurry according to the mass ratio of 8:1:1 and coated on an aluminum foil, the slurry is placed in an oven to be dried for 24 hours at 80 ℃, the dried aluminum foil loaded with the slurry is cut into small round pieces with the diameter of about 1.1cm by a cutting machine to be used as a positive electrode, a metal lithium piece is used as a negative electrode, Celgard2300 is used as a diaphragm, 1mol/L of a carbonate solution is used as an electrolyte (wherein, the solvent is a mixed solution of ethylene carbonate and dimethyl carbonate with the volume ratio of 1:1, and the solute is LiPF6), and the small round pieces are assembled into a CR2025 button cell in an argon glove box.
And (3) performing constant-current charge and discharge tests on the assembled CR2025 button cell by using a CT2001A Land cell tester, wherein the current density of 1C is defined to be 190mA/g, the charge and discharge voltage interval is 2.8V-4.35V, and the test temperature is 30 ℃.
Example 1
0.0133g of Mn (CH)3COO)2·4H2O、0.0406g Al(NO3)3·9H2O、0.4771g LiOH·H2O with 1g Ni0.8Co0.1Mn0.1(OH)2Mixing, adding about 5mLAfter the ethanol is uniformly mixed, the mixture is placed in a tubular furnace to be pre-calcined for 5h at 500 ℃ under the oxygen atmosphere, then the temperature is raised to 750 ℃ to be calcined for 15h, the heating rate of the two stages is 2 ℃/min, and the high-nickel anode material obtained by calcination is respectively exposed for 0, 10 and 45 days in the air environment with the humidity of 80% to be tested and analyzed.
SEM morphology analysis was performed on the high nickel precursor (left) and the high nickel positive electrode material (right) obtained by adding manganese acetate and aluminum nitrate and then calcining at high temperature in example 1 with a scanning electron microscope, and the magnification was 8000 times. As can be seen from fig. 1, the secondary particles of the high nickel precursor and the high nickel cathode material in example 1 are both spheroidal, which indicates that the morphology of the secondary particles of the material is not changed by calcination; but the thickness of the primary particles (nanoplatelets) after intercalation of lithium is increased from 20-50 nm to 150-200 nm. Fig. 2 shows the cycle performance of the example 1 and the comparative example after exposure to 0.2C (38mA/g) for different periods of time (0 day, 15 days, 45 days), and it can be seen that the cycle performance of the modified material is slightly improved, and the cycle performance of the high nickel cathode material obtained in the example 1 is greatly improved after long-term exposure to air.
Example 2
0.0265g of Mn (CH)3COO)2·4H2O、0.0813g Al(NO3)3·9H2O、0.4771g LiOH·H2O with 1g Ni0.8Co0.1Mn0.1(OH)2Mixing, adding about 5mL of ethanol, uniformly mixing, placing the mixture in a tubular furnace, pre-calcining for 5h at 500 ℃ in an oxygen atmosphere, then heating to 750 ℃ and calcining for 15h, wherein the heating rates of the two stages are both 2 ℃/min, and respectively exposing the high-nickel anode material obtained by calcining in an air environment with the humidity of 80% for 0, 10 and 45 days, and then carrying out test analysis.
FIG. 3 is an XRD spectrum of the samples of example 2 and comparative example exposed to day 0 respectively, and it is found that the bulk crystal structure of the high nickel cathode material of comparative example is not changed after modification with manganese acetate and aluminum nitrate, and the high nickel cathode material of example 2 is also a typical alpha-NaFeO2The structure belongs to the R-3m space group, the peak splitting of (006)/(012) and (018)/(110) is obvious, and the treated positive electrode material has the (0)03) Both the peak and (104) peak are slightly shifted at a low angle relative to the comparative high nickel positive electrode material, indicating that the interlayer spacing of the positive electrode material of example 2 is increased compared to the comparative high nickel positive electrode material, which facilitates the intercalation and deintercalation of lithium ions.
It is seen from the impedance spectrum of fig. 4 that after the material of example 2 is exposed for 45 days, the charge transfer impedance is smaller than that of the comparative high-nickel cathode material before or after the cycle, which shows that the modified high-nickel cathode material (the material of example 2) can effectively resist the side reaction with moisture and carbon dioxide in the ambient air, effectively protect the surface interface of the material, and improve the storage performance of the material.
Example 3
0.0398g of Mn (CH)3COO)2·4H2O、0.1219g Al(NO3)3·9H2O、0.4771g LiOH·H2O with 1g Ni0.8Co0.1Mn0.1(OH)2Mixing, adding about 5mL of ethanol, uniformly mixing, placing the mixture in a tubular furnace, pre-calcining for 5h at 500 ℃ in an oxygen atmosphere, then heating to 750 ℃ and calcining for 15h, wherein the heating rates of the two stages are both 2 ℃/min, and respectively exposing the high-nickel anode material obtained by calcining in an air environment with the humidity of 80% for 0, 10 and 45 days, and then carrying out test analysis.
FIG. 5 is an IR spectrum of a sample after 45 days of exposure for example 3 and comparative example, respectively, and the comparative example is found to be 860-870 cm-1Li occurring in the wavelength range2CO3The signal peak of (a) is stronger than that of the sample in example 3, and is 1430-1500 cm-1Apparent Li in the wavelength range2CO3The characteristic symmetric absorption peak shows that the modified high-nickel cathode material (the material obtained in example 3) can effectively resist the side reaction with carbon dioxide in the air, can effectively protect the surface interface of the material, and can improve the storage performance of the material. Comparative example
0.4771g of LiOH. H2O with 1g Ni0.8Co0.1Mn0.1(OH)2Mixing, adding about 5mL ethanol, mixing, and placing in a tube furnaceThe method comprises the steps of pre-calcining the high-nickel anode material at 500 ℃ for 5h in an oxygen atmosphere, then heating to 750 ℃ for calcining for 15h, wherein the heating rate of the two stages is 2 ℃/min, and the high-nickel anode material obtained by calcining is respectively exposed in an air environment with the humidity of 80% for 0, 10 and 45 days and then is subjected to test analysis.
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.
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