CN116081706B - Nickel cobalt lithium aluminate ternary positive electrode material and preparation method thereof - Google Patents
Nickel cobalt lithium aluminate ternary positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN116081706B CN116081706B CN202211587892.0A CN202211587892A CN116081706B CN 116081706 B CN116081706 B CN 116081706B CN 202211587892 A CN202211587892 A CN 202211587892A CN 116081706 B CN116081706 B CN 116081706B
- Authority
- CN
- China
- Prior art keywords
- nickel cobalt
- positive electrode
- electrode material
- lithium aluminate
- ternary positive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 37
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [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 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 14
- 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 13
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- -1 aluminum ion Chemical class 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 230000002572 peristaltic effect Effects 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 229910017238 Ni0.8Co0.15Al0.05(OH)2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a nickel cobalt lithium aluminate ternary positive electrode material, which comprises the following steps: s01, respectively preparing nickel cobalt binary hydroxide and nano aluminum hydroxide particles; s02, carrying out ultrasonic mixing on nickel cobalt binary hydroxide and nano aluminum hydroxide particles in an absolute ethyl alcohol solution, and drying; s03, weighing the dried material and LiOH-H 2 O according to a molar ratio of 1:1.03, and ball-milling in a ball mill; s04, carrying out pre-calcination treatment on the ball-milled sample; and S05, calcining the pre-calcined sample in an oxygen atmosphere. The invention also provides a nickel cobalt lithium aluminate ternary positive electrode material which is prepared by the preparation method. According to the nickel cobalt lithium aluminate ternary positive electrode material and the preparation method thereof, disclosed by the invention, the loss of Al caused by poor complexing effect of ammonia water can be avoided, so that the nickel cobalt lithium aluminate ternary positive electrode material has good capacity retention rate and rate capability, and the migration barrier of Li + can be reduced because sulfate radicals remain in the process of preparing aluminum hydroxide, so that the structural stability of the material is improved.
Description
Technical Field
The invention relates to a nickel cobalt lithium aluminate ternary positive electrode material and a preparation method thereof, and belongs to the technical field of lithium ion batteries.
Background
The nickel cobalt lithium aluminate ternary positive electrode material is considered to be the positive electrode material with the most development potential due to the higher energy density and the cycle life. The coprecipitation method is a main method for preparing the nickel cobalt lithium aluminate ternary positive electrode material, and ammonia water is used as a complexing agent in preparing the nickel cobalt aluminum ternary positive electrode material because of low cost. Although ammonia has very good complexing effect on two elements of nickel and cobalt, but has very poor complexing effect on Al, and aluminum hydroxide is an amphoteric hydroxide, hydrolysis is easy to occur under acidic and alkaline conditions, and the loss of Al is caused, so that the performance of the nickel cobalt lithium aluminate ternary positive electrode material is affected.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides the nickel cobalt lithium aluminate ternary positive electrode material capable of improving and avoiding the loss of Al caused by poor complexing effect of ammonia water, so that the nickel cobalt lithium aluminate ternary positive electrode material has good capacity retention rate and rate capability, and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
The preparation method of the nickel cobalt lithium aluminate ternary positive electrode material comprises the following steps:
s01, respectively preparing nickel cobalt binary hydroxide and nano aluminum hydroxide particles;
s02, carrying out ultrasonic mixing on nickel cobalt binary hydroxide and nano aluminum hydroxide particles in an absolute ethyl alcohol solution, and drying;
S03, weighing the dried material and LiOH-H 2 O according to a molar ratio of 1:1.03, and ball-milling in a ball mill;
s04, carrying out pre-calcination treatment on the ball-milled sample;
And S05, calcining the pre-calcined sample in an oxygen atmosphere.
In S01, the preparation of the nickel cobalt binary hydroxide comprises the following steps:
s011, weighing nickel sulfate and cobalt sulfate according to a molar ratio of 80:15 to prepare 19mmol/L metal salt solution, and stirring on a magnetic stirrer at a temperature of 50 ℃;
S012, completely dissolving the solid in the metal salt solution, and dripping ammonia water and sodium hydroxide serving as a precipitant into the metal salt solution at a stable and slow flow rate through a peristaltic pump;
S013, after the mixed solution of ammonia water and sodium hydroxide is completely dripped into the metal salt solution, reacting for 4 hours, stopping stirring, and standing and precipitating for 24 hours;
and S014, carrying out suction filtration on the supernatant obtained after the precipitation of the metal salt solution to obtain a precipitate, and washing the precipitate with deionized water twice for later use.
In S01, the preparation of the nano aluminum hydroxide particles comprises the following steps:
S015, weighing aluminum sulfate and aluminum nitrate to prepare 1mmol/L aluminum ion solution, adding 100mL formamide serving as a precipitant, and finally adding 1L deionized water;
S016, stirring for 2 hours at 90 ℃, adding 250mL of absolute ethyl alcohol, and stirring for 5 minutes;
s017, stopping stirring, standing, precipitating for 24 hours, and washing samples for later use.
In S015, the molar ratio of aluminum sulfate to aluminum nitrate was 1:9 in terms of the Al source.
In S02, the ultrasonic mixing time is 40-60 min, the drying condition is that the temperature is 80 ℃, and the drying time is 12h.
In S03, the rotating speed of the ball mill is 500r/min, and the ball milling time is 2h.
In S04, the pre-calcination temperature is 500 ℃ and the time is 5 hours.
In S05, the calcination temperature is 800 ℃ and the time is 20h.
A ternary positive electrode material of nickel cobalt lithium aluminate is prepared by a preparation method of a ternary positive electrode material of a lithium ion battery.
The invention has the beneficial effects that:
1. According to the method, the nickel cobalt binary hydroxide is prepared by a coprecipitation method, then ball-milled and mixed with an Al source and an Li source, and finally high-temperature calcination is carried out to obtain the ternary positive electrode material.
2. The morphology and the particle size of an Al source can greatly influence the distribution of Al elements in the calcination process, so that the structure and the electrochemical performance of the material are greatly influenced, aluminum hydroxide with nanometer size and high dispersibility is prepared by utilizing different nucleation capacities of aluminum sulfate and aluminum nitrate, and then the aluminum hydroxide with high dispersibility is mixed with nickel cobalt binary hydroxide to prepare the nickel cobalt lithium aluminate ternary positive electrode material, the distribution of the Al elements is more uniform, and the structure of the material is more stable.
3. The nickel cobalt lithium aluminate ternary positive electrode material prepared by the method has low cation mixing and arranging and ordered lamellar structure, and has good capacity retention rate and rate capability.
4. Aluminum sulfate and aluminum nitrate were prepared at a molar ratio of 1:9, where there was a small amount of sulfate residue in the precipitation of aluminum hydroxide, and it was found that when there was a small amount of sulfate in the ternary cathode material, the migration energy barrier of Li + could be suppressed, thereby suppressing severe shrinkage of the c-axis during cycling. The phase change from H2 to H3 caused by c-axis shrinkage is inhibited, and the cycle performance is improved. Capacity reservation may resume.
Drawings
FIG. 1 is a SEM image and a TEM image of nano aluminum hydroxide prepared by the method, wherein (a) and (c) are respectively SEM and TEM images when the molar ratio of aluminum sulfate to aluminum nitrate is 1:9, and (b) and (d) are respectively SEM and TEM images of aluminum hydroxide when the molar ratio of aluminum sulfate to aluminum nitrate is 5:5;
FIG. 2 is an XRD pattern of a nickel cobalt lithium aluminate positive electrode material prepared by the method;
FIG. 3 is a graph of cyclic data of the nickel cobalt lithium aluminate positive electrode material prepared by the invention in a voltage range of 2.5-4.3V;
FIG. 4 is a graph of the data of the multiplying power of the nickel cobalt lithium aluminate anode material prepared by the invention in the voltage range of 2.5-4.3V.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, and the following examples are only for more clearly illustrating the technical aspects of the present invention, and are not to be construed as limiting the scope of the present invention.
The invention discloses a preparation method of a nickel cobalt lithium aluminate ternary positive electrode material, which comprises the following steps:
and step one, preparing nickel cobalt binary hydroxide.
(1) The nickel sulfate and cobalt sulfate were weighed according to a molar ratio of 80:15 to prepare a 19mmol/L metal salt solution, which was stirred on a magnetic stirrer at a temperature of 50 ℃.
(2) Ammonia water is used as complexing agent, sodium hydroxide is used as precipitant, and the solid in the metal salt solution is completely dissolved, and the ammonia water and sodium hydroxide are dripped into the metal salt solution at a stable and slow flow rate through a peristaltic pump
(3) After the mixed solution of ammonia water and sodium hydroxide is completely dripped into the metal salt solution, the reaction is carried out for 4 hours. Stirring was stopped and the precipitate was allowed to stand for 24h.
(4) Filtering the supernatant, and washing the precipitate with deionized water twice
And step two, preparing the aluminum hydroxide with high dispersibility and nanometer size.
(1) Al source is provided by aluminum sulfate and aluminum nitrate, in order to reduce the particle size of aluminum hydroxide, so that the content of aluminum sulfate is reduced, solutions with the concentration of Al 3+ of 1mmol/L are respectively weighed according to the molar ratio of 1:9 and the molar ratio of 5:5, formamide is used as a precipitator, and 100mL is added. Finally, 1L of deionized water was added.
(2) After stirring at 90℃for 2h, 250mL of absolute ethanol was added and the mixture was vigorously stirred for 5min.
(3) And standing and precipitating for 24 hours, and washing the sample for later use.
In fig. 1, a and c are SEM and TEM images of highly dispersed nano aluminum hydroxide prepared when the molar ratio of aluminum sulfate to aluminum nitrate is 1:9, and it can be seen from the figures that the particle size of aluminum hydroxide is very small, so that the aluminum hydroxide is a layer of flocculent in terms of large morphology, which is caused by the excessively low content of aluminum sulfate, and the flocculent aluminum hydroxide can be more uniformly mixed with a nickel cobalt binary precursor, so that the diffusion of Al element in the high-temperature calcination process is facilitated.
As shown in b and d of fig. 1, the nucleation capability of sulfate radical and nitrate radical is different, when the proportion of aluminum nitrate is higher, the prepared particle size is smaller, when the sulfate radical is higher, the particle size is larger, when the content of aluminum sulfate is increased, the particle size of the material is obviously increased, and the aluminum hydroxide and nickel cobalt binary hydroxide are not mixed, so that the distribution of Al is uneven. In addition, if residual sulfate radicals exist in the preparation process of the aluminum hydroxide, the migration barrier of Li + can be reduced, so that the structural stability of the ternary positive electrode material is improved. Therefore, in the application, the molar ratio of the aluminum sulfate to the aluminum nitrate is 1:9, so that the aluminum hydroxide can be ensured to have smaller particles, the distribution of Al elements of the ternary positive electrode material is more uniform, and the sulfate radical remained in the preparation process of the aluminum hydroxide can be enabled to improve the cycle performance of the ternary positive electrode material. In the embodiment, the nano aluminum hydroxide with high dispersibility prepared when the molar ratio of aluminum sulfate to aluminum nitrate is 1:9 is used as the raw material for the next synthesis.
And thirdly, preparing a nickel cobalt lithium aluminate precursor.
(1) And (3) carrying out ultrasonic mixing on the nickel cobalt binary hydroxide and the nano aluminum hydroxide in an absolute ethanol solution for 40-60 min, and then drying for 12h at 80 ℃. In total, 19mmol of metal cations are present in the solution, the molar ratio of the prepared nickel cobalt binary hydroxide is 80:15, thus Ni is 16mmol, co is 3mmol, and the chemical formula of the nickel cobalt lithium aluminate is LiNi 0.8Co0.15Al0.05O2, so that the designed cation concentration is 1mmol when preparing aluminum hydroxide, ni: co: al=0.8:0.15:0.05.
(2) The dried material was weighed with LiOH. H 2 O in a molar ratio of 1:1.03 and ball milled in a high performance ball mill at 500r/min for 2H. The chemical formula of the dried material is Ni 0.8Co0.15Al0.05(OH)2, namely the dried material with a certain mass is weighed, and the mass of lithium hydroxide can be obtained by calculation according to n=m/M, and then the lithium hydroxide is weighed.
(3) The sample after ball milling was pre-calcined at 500 ℃ for 5h.
(4) Calcining at 800 ℃ for 20h in an oxygen atmosphere.
Table 1 shows ICP data of the nickel cobalt lithium aluminate positive electrode material prepared by the method, and the data can show that the proportion of three elements of nickel cobalt aluminum is close to 0.8:0.15:0.05, which is similar to that of experimental design, and further proves that the nickel cobalt lithium aluminate ternary positive electrode material prepared by the method can not cause loss of Al.
Table 1: ICP data of positive electrode material
FIG. 2 is an XRD pattern of the nickel cobalt lithium aluminate positive electrode material prepared by the method, all diffraction peaks correspond to the lamellar alpha-NaFeO 2 structure of the space group R-3m, and the material prepared by the method is proved to be a ternary positive electrode material. Wherein the value of I (003)/I (104) is 1.41, which is greater than 1.2, demonstrating that the material has a smaller cation mix. And (006) (102) and (018) (110) are split obviously, the explanation material has better lamellar structure.
Fig. 3 shows that the nickel cobalt lithium aluminate positive electrode material prepared by the invention has a specific capacity of 167mAh/g for the first time, a specific capacity of 143mAh/g for the 120 times of circulation and a capacity retention rate of 85.7% in a voltage range of 2.5-4.3V and a current density of 0.2C, and the material has good circulation stability.
Fig. 4 is a graph showing the cycle performance data at different current densities, and it can be seen from the graph that at a current density of 5C, the specific discharge capacity of the material is 100mAh/g, and the material has good cycle stability and good rate performance.
The foregoing is only a preferred embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (4)
1. A preparation method of a nickel cobalt lithium aluminate ternary positive electrode material is characterized by comprising the following steps of: the method comprises the following steps:
S01, respectively preparing nickel-cobalt binary hydroxide and nano aluminum hydroxide particles, wherein the preparation of the nickel-cobalt binary hydroxide comprises the following steps:
S011, weighing nickel sulfate and cobalt sulfate according to a molar ratio of 80:15 to prepare a metal salt solution of 19 mmol/L, and stirring the solution on a magnetic stirrer at a temperature of 50 ℃;
S012, completely dissolving the solid in the metal salt solution, and dripping ammonia water and sodium hydroxide serving as a precipitant into the metal salt solution at a stable and slow flow rate through a peristaltic pump;
S013, after the mixed solution of ammonia water and sodium hydroxide is completely dripped into the metal salt solution, reacting 4h, stopping stirring, and standing to precipitate 24 h;
S014, filtering the supernatant after precipitation of the metal salt solution to obtain a precipitate, washing the precipitate with deionized water twice for later use,
The preparation of the nanometer aluminum hydroxide particles comprises the following steps:
S015, weighing aluminum sulfate and aluminum nitrate to prepare 1 mmol/L aluminum ion solution, adding 100 mL formamide serving as a precipitant into the aluminum sulfate and aluminum nitrate according to the molar ratio of Al source of 1:9, and finally adding 1L deionized water;
s016, stirring at 90 ℃ for 2h, adding 250 mL absolute ethanol, and stirring for 5 min;
S017, stopping stirring, standing, precipitating for 24 h, and washing samples for later use;
s02, carrying out ultrasonic mixing on nickel cobalt binary hydroxide and nano aluminum hydroxide particles in an absolute ethyl alcohol solution, and drying;
S03, weighing the dried material and LiOH-H 2 O according to a molar ratio of 1:1.03, and ball milling in a ball mill;
S04, carrying out pre-calcination treatment on the ball-milled sample, wherein the pre-calcination temperature is 500 ℃ and the time is 5 hours;
S05, calcining the pre-calcined sample in an oxygen atmosphere at 800 ℃ for 20 hours.
2. The method for preparing the nickel cobalt lithium aluminate ternary positive electrode material according to claim 1, which is characterized in that: in S02, the ultrasonic mixing time is 40-60 min, the drying condition is that the temperature is 80 ℃, and the drying time is 12 h.
3. The method for preparing the nickel cobalt lithium aluminate ternary positive electrode material according to claim 1, which is characterized in that: in S03, the rotating speed of the ball mill is 500 r/min, and the ball milling time is 2h.
4. A nickel cobalt lithium aluminate ternary positive electrode material is characterized in that: prepared by the preparation method of the nickel cobalt lithium aluminate ternary positive electrode material according to any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211587892.0A CN116081706B (en) | 2022-12-11 | 2022-12-11 | Nickel cobalt lithium aluminate ternary positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211587892.0A CN116081706B (en) | 2022-12-11 | 2022-12-11 | Nickel cobalt lithium aluminate ternary positive electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116081706A CN116081706A (en) | 2023-05-09 |
| CN116081706B true CN116081706B (en) | 2024-05-10 |
Family
ID=86207244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211587892.0A Active CN116081706B (en) | 2022-12-11 | 2022-12-11 | Nickel cobalt lithium aluminate ternary positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116081706B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102747439A (en) * | 2011-04-21 | 2012-10-24 | 中国科学院合肥物质科学研究院 | Disperse nanocomposite and preparation method thereof |
| CN107331849A (en) * | 2017-07-14 | 2017-11-07 | 广东工业大学 | A kind of nickel cobalt lithium aluminate@metal oxide/carbon nano-tube composite positive poles and preparation method and application |
| CN108987740A (en) * | 2017-06-01 | 2018-12-11 | 中天新兴材料有限公司 | Nickel cobalt lithium aluminate cathode material, preparation method and the battery using it |
| CN109037669A (en) * | 2018-07-06 | 2018-12-18 | 乳源东阳光磁性材料有限公司 | Modified nickel-cobalt lithium aluminate anode material and preparation method and application thereof |
| CN111777103A (en) * | 2020-05-16 | 2020-10-16 | 北京化工大学 | Method for preparing nickel cobalt lithium aluminate anode material |
| RU2758848C1 (en) * | 2020-10-07 | 2021-11-02 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Reagent for producing aluminium hydroxide by the precipitation method and method for producing aluminium hydroxide by the precipitation method using the reagent (variants) |
-
2022
- 2022-12-11 CN CN202211587892.0A patent/CN116081706B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102747439A (en) * | 2011-04-21 | 2012-10-24 | 中国科学院合肥物质科学研究院 | Disperse nanocomposite and preparation method thereof |
| CN108987740A (en) * | 2017-06-01 | 2018-12-11 | 中天新兴材料有限公司 | Nickel cobalt lithium aluminate cathode material, preparation method and the battery using it |
| CN107331849A (en) * | 2017-07-14 | 2017-11-07 | 广东工业大学 | A kind of nickel cobalt lithium aluminate@metal oxide/carbon nano-tube composite positive poles and preparation method and application |
| CN109037669A (en) * | 2018-07-06 | 2018-12-18 | 乳源东阳光磁性材料有限公司 | Modified nickel-cobalt lithium aluminate anode material and preparation method and application thereof |
| CN111777103A (en) * | 2020-05-16 | 2020-10-16 | 北京化工大学 | Method for preparing nickel cobalt lithium aluminate anode material |
| RU2758848C1 (en) * | 2020-10-07 | 2021-11-02 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Reagent for producing aluminium hydroxide by the precipitation method and method for producing aluminium hydroxide by the precipitation method using the reagent (variants) |
Non-Patent Citations (3)
| Title |
|---|
| "Facilesize-controlledsynthesisofwell-dispersedsphericalamorphous alumina nanoparticlesviahomogeneousprecipitation";Jiatai Wang et al .;《CeramicsInternational》;20160215;第42卷;第8545-8551页 * |
| "不同铝源制备LiNi0. 8 Co0. 15 Al0. 05 O2 正极材料 及电化学性能影响";陶伟 等;《化学研究及应用》;20150731;第第27卷卷(第第7期期);第1048-1052页 * |
| 氧化铝制备技术的研究进展;王甲泰;王尔姣;张福波;周庚;开毛吉;;无机盐工业;20171031;第49卷(第10期);第12-15页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116081706A (en) | 2023-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10329162B2 (en) | Methods for preparing nickel-cobalt-aluminum precursor material and cathode material with gradient distribution of aluminum element | |
| CN109455772B (en) | Modified precursor and anode material for lithium ion battery and preparation methods of precursor and anode material | |
| CN115000399B (en) | Spherical-like sodium ion battery positive electrode material, preparation method thereof and sodium ion battery | |
| WO2019113870A1 (en) | Lithium-rich manganese-based material and preparation and application thereof | |
| CN110683590A (en) | Preparation method of nickel-cobalt-aluminum hydroxide precursor based on aluminum element concentration gradient distribution | |
| WO2022188480A1 (en) | Precursor of composite positive electrode material for lithium battery and preparation method for composite positive electrode material | |
| CN108862406B (en) | Carbonate precursor and preparation method and application thereof | |
| CN113363438B (en) | Preparation method of La and Ce co-doped NCMA quaternary precursor | |
| CN113603153B (en) | Tungsten doped high nickel cobalt-free precursor and preparation method thereof | |
| CN109473667B (en) | Precursor for lithium ion battery, positive electrode material and preparation method of precursor | |
| CN113772748B (en) | Preparation method of lithium ion battery anode material | |
| CN109037669B (en) | Modified nickel-cobalt lithium aluminate anode material and preparation method and application thereof | |
| CN103187564A (en) | Preparation method for battery anode material LiNi0.5Mn1.5O4 | |
| CN116081706B (en) | Nickel cobalt lithium aluminate ternary positive electrode material and preparation method thereof | |
| CN114538534B (en) | Aluminum-doped positive electrode material precursor, and preparation method and application thereof | |
| CN114031127B (en) | Mg-Ti co-doped high-nickel cobalt-free precursor and preparation method thereof | |
| CN112002878A (en) | Preparation method of ternary gradient material with manganese-rich surface layer | |
| CN110380018B (en) | Preparation method of composite electrode material with foam-shaped coating layer | |
| CN112225261B (en) | Lithium-rich manganese-based positive electrode material carbonate precursor and preparation method and application thereof | |
| CN113800574A (en) | Nickel-manganese-iron-aluminum-lithium cathode material and preparation method thereof | |
| CN110957488A (en) | Preparation method of peanut-like nickel cobalt lithium manganate positive electrode material | |
| CN114906885B (en) | High-magnification positive electrode material of lithium ion battery and preparation method thereof | |
| CN113555612B (en) | Lithium ion battery lithium supplement additive precursor material and preparation method thereof | |
| CN115448378B (en) | Preparation method of monodisperse nano-sheet-shaped high-nickel ternary composite precursor | |
| CN115959715A (en) | Preparation method of low-cobalt high-cycle lithium cathode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |