CN114291851A - High-nickel layered cathode material with single crystal morphology and preparation method thereof - Google Patents
High-nickel layered cathode material with single crystal morphology and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000013078 crystal Substances 0.000 title claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 39
- 239000010406 cathode material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000013067 intermediate product Substances 0.000 claims abstract description 22
- 239000012298 atmosphere Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000010405 anode material Substances 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- 239000011572 manganese Chemical class 0.000 claims description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052748 manganese Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 3
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 238000000975 co-precipitation Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 6
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 6
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 5
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 5
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910017226 Ni0.8Co0.1Mn0.1CO3 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- -1 diaphragms Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical class O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
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Images
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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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Abstract
The invention discloses a preparation method of a high-nickel layered anode material with a single crystal morphology, which comprises the following steps: s1, placing the precursor in a tube furnace, and performing heat treatment for 1-3 hours at 900-1000 ℃ under an inert atmosphere to obtain an intermediate product; s2, preparing lithium salt and the intermediate product according to the molar ratio of 1.01-1.10: 1, placing the mixture into a tubular furnace, and performing heat treatment for 12-18 hours at 750-950 ℃ in an oxygen atmosphere. The advantages are that: 1) the precursor synthesis method can effectively reduce the difficulty in precursor preparation, shorten the preparation time of the precursor, and facilitate the subsequent generation of the single crystal morphology. 2) Compared with one-step calcination, the method disclosed by the invention can effectively reduce the formation temperature of the subsequent high-nickel layered cathode material, reduce energy consumption, reduce lithium loss caused by high temperature, save the cost of actual industrial production, and simultaneously facilitate formation of single crystal morphology and capacity control.
Description
Technical Field
The invention relates to a lithium ion battery production technology, in particular to a preparation method of a lithium ion battery anode material.
Background
The worldwide demand for energy has been increasing with the rapid development of society and economy for a century, and the use of traditional fossil energy has been increasing. The use of large quantities of fossil energy also presents a series of environmental problems, such as: air pollution, greenhouse effect, water pollution, etc. These reasons have prompted the urgent development of new energy sources and energy utilization schemes that are efficient and green. With the rapid development and commercialization of electric vehicles, hybrid vehicles, and portable devices, lithium ion batteries are being expected as the most potential secondary batteries at present, and there is a high demand for their performance while the demand is increasing in large scale. Safety, low cost, high energy density and long service life are the key points of the current research, and China, the United states, Japan, European countries and the like are all actively promoting the research and development of the related technology of the lithium ion battery.
The development planning of new energy automobile industry (2021-2035) clearly proposes "implementing battery technology breakthrough action. The research on key core technologies such as anode and cathode materials, electrolyte, diaphragms, membrane electrodes and the like is developed, the technical challenges of the power battery and the fuel battery system short plate with high strength, light weight, high safety, low cost and long service life are strengthened, and the research and development and industrialization of the solid-state power battery technology are accelerated. "the high nickel layered cathode material which has the most potential for development at present and is commercially available is mainly in a polycrystalline morphology, and although the battery capacity can be further improved by increasing the nickel content, the potential safety hazard is also introduced, and the high-pressure stability and the high-temperature stability of the cathode material are reduced. And due to the stress strain anisotropy of polycrystals, micro cracks are generated in the material circulation process, further deterioration may cause structural fracture, and thus the circulation stability is poor. At present, the mainstream modification mode is mainly to carry out element doping or coating treatment on a polycrystalline high-nickel layered cathode material, and although the performance of a certain aspect can be improved to a certain extent, the requirements of high capacity, high safety and long service life are difficult to be simultaneously and effectively realized. The high-nickel layered cathode material with the single crystal morphology can effectively avoid structural breakage in the circulation process, improves the circulation stability of the material, has the characteristics of high temperature and high pressure resistance, is favorable for adapting to severe working conditions, and meets the requirement of safety.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a high-nickel layered cathode material with a single crystal morphology and a preparation method thereof.
The technical scheme adopted by the invention is as follows: the preparation method of the high-nickel layered cathode material with the single crystal morphology comprises the step of pre-sintering a precursor in an inert atmosphere before lithium is prepared and calcined.
According to the invention, a certain intermediate with a single crystal morphology is pre-formed by pre-burning under a high-temperature inert atmosphere, and then lithium is added for calcination, so that the high-nickel layered cathode material with a single crystal morphology is obtained. Compared with one-step calcination, the method disclosed by the invention can effectively reduce the formation temperature of the subsequent high-nickel layered cathode material, reduce the energy consumption, reduce the lithium loss caused by high temperature, and save the cost of actual industrial production; meanwhile, the appearance of the single crystal is easier to form and the capacity is easier to control.
The precursor of the invention can be a hydroxide precursor produced by a traditional coprecipitation method, and preferably a carbonate precursor produced by a slow-release precipitation method, and can be prepared by the following steps:
A. stirring and mixing sodium bicarbonate and deionized water uniformly to obtain an alkali solution;
B. preparing a mixed salt solution from soluble inorganic salts of nickel and soluble inorganic salts of cobalt and/or manganese by using deionized water;
C. slowly dripping the aqueous alkali into the mixed salt solution, stirring for 30-60 min, and standing for 24-48 h to obtain a standing material;
D. carrying out solid-liquid separation on the standing material to obtain a solid filtering material;
E. and drying the solid filtering material to obtain the solid filtering material.
Firstly, inorganic salt (such as sulfate) of nickel, cobalt and manganese is dissolved in distilled water according to the molar ratio required by the process, sodium bicarbonate solution prepared in advance is slowly dripped into the salt solution, and the precursor is obtained by standing and precipitating after full mixing. Therefore, the preparation difficulty of the precursor can be effectively reduced, the preparation time of the precursor is shortened, and the appearance of the single crystal can be generated more easily in the follow-up process.
It will be readily understood that the soluble inorganic salts of nickel, cobalt, manganese may be employed as the sulfate hydrates thereof, respectively.
Preferably, the solid-liquid separation mode is vacuum filtration; the drying mode is as follows: and (3) drying the solid filtering material in a vacuum oven for 36-60 hours.
The high nickel layered cathode material with single crystal morphology and the preparation method thereof can be carried out according to the following steps:
s1, placing the precursor in a tube furnace, and performing heat treatment for 1-3 hours at 900-1000 ℃ under an inert atmosphere to obtain an intermediate product;
s2, preparing lithium salt and the intermediate product according to the molar ratio of 1.01-1.10: 1, placing the lithium salt and the intermediate product into a tubular furnace, and performing heat treatment for 12-18 hours at 750-950 ℃ in an oxygen atmosphere to obtain the lithium-ion battery.
As is readily understood, the inert atmosphere may be formed by high-purity argon or high-purity nitrogen; lithium hydroxide monohydrate may be used as the lithium salt.
More preferably, the molar ratio of the lithium salt to the intermediate product is 1.04-1.06: 1.
The invention also discloses a high nickel layered anode material with single crystal morphology, which is prepared by the preparation method of the high nickel layered anode material with single crystal morphology.
The invention also discloses a production method of the lithium ion battery, which is characterized in that the production raw material comprises the high-nickel layered anode material with single crystal morphology.
The invention also discloses a lithium ion battery which is prepared by the production method of the lithium ion battery.
The invention also discloses a transportation tool containing the lithium ion battery.
The invention has the beneficial effects that: 1) the precursor synthesis method can effectively reduce the difficulty in precursor preparation, shorten the preparation time of the precursor, and facilitate the subsequent generation of the single crystal morphology. 2) Compared with one-step calcination, the method disclosed by the invention can effectively reduce the formation temperature of the subsequent high-nickel layered cathode material, reduce energy consumption, reduce lithium loss caused by high temperature, save the cost of actual industrial production, and simultaneously facilitate formation of single crystal morphology and capacity control.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of an intermediate product obtained after the calcination in example one.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the positive electrode material prepared in example one.
Fig. 3 is a Scanning Electron Microscope (SEM) image of an intermediate product obtained after the calcination in example two.
Fig. 4 is a Scanning Electron Microscope (SEM) image of the cathode material prepared in example three.
Fig. 5 is a Scanning Electron Microscope (SEM) image of an intermediate product obtained after the calcination in example four.
Fig. 6 is a graph comparing the 1C cycle capacity of button cells further prepared from the cathode material prepared in comparative example one and the cathode material prepared in example one.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
In the following examples and comparative examples, the following material characterization analysis methods were used:
scanning Electron Microscope (SEM) testing: scanning electron microscope, instrument model: ZEISS Gemini 300, Germany.
Assembly and testing of CR2025 button cells: preparing a high-nickel layered cathode material (a final product prepared in an example), acetylene black and polyvinylidene fluoride (PVDF) into slurry according to a mass ratio of 8:1:1, coating the slurry on an aluminum foil, cutting the dried aluminum foil loaded with the slurry into small round pieces with the diameter of about 1cm by using a cutting machine to serve as a cathode, using a metal lithium piece as a cathode, using Celgard2500 as a diaphragm and using a 1M carbonate solution as an electrolyte (wherein a solvent is a mixed solution of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate with the volume ratio of 1:1:1, and a solute is LiPF6) And assembling the button cell CR2025 in an argon atmosphere glove box.
The first embodiment is as follows:
the precursor used in this example is a carbonate precursor Ni produced by a slow-release precipitation method0.8Co0.1Mn0.1CO3The specific method comprises the following steps:
(1) adding 0.5mol of sodium bicarbonate into 425mL of deionized water, and stirring and mixing uniformly at room temperature for 30min to obtain an alkali solution;
(2) nickel sulfate hexahydrate, manganese sulfate monohydrate and cobalt sulfate heptahydrate are prepared into a mixture with the molar concentration of 1.33 mol.L according to the molar ratio of 8:1:1-1The mixed salt solution of (4);
(3) slowly dripping the alkali solution obtained in the step (1) into the mixed salt solution obtained in the step (2), fully stirring for 30min, and then standing for 24 h;
(4) carrying out vacuum filtration on the product obtained in the step (3) to obtain a solid filter material;
(5) drying the solid filter material obtained in the step (4) in a vacuum oven for 48 hours to obtain a carbonate precursor Ni0.8Co0.1Mn0.1CO3；
(6) Placing the carbonate precursor obtained in the step (5) in a tube furnace, and performing heat treatment for 1h at 1000 ℃ under the argon atmosphere to obtain an intermediate product;
(7) and (3) preparing lithium from lithium hydroxide monohydrate and the intermediate product obtained in the step (6) according to a molar ratio of 1.05:1, and then performing heat treatment for 15 hours at 850 ℃ in an oxygen atmosphere to obtain the high-nickel layered cathode material with the single-crystal morphology.
The scanning electron microscope result of the intermediate product prepared in the step (6) is shown in fig. 1, and it can be seen from fig. 1 that the pre-sintered material has a single crystal morphology.
The scanning electron microscope result of the obtained high nickel layered cathode material with single crystal morphology is shown in fig. 2, and as can be seen from fig. 2, the final product has single crystal morphology, has agglomeration phenomenon, and needs to be further crushed.
Example two:
the precursor used in this example is a carbonate precursor Ni produced by a slow-release precipitation method0.6Mn0.4CO3The specific method comprises the following steps:
(1) adding 0.5mol of sodium bicarbonate into 450mL of deionized water, and stirring and mixing uniformly at room temperature for 30min to obtain an alkali solution;
(2) nickel sulfate hexahydrate and manganese sulfate monohydrate are prepared into a mixture with the molar concentration of 2 mol.L according to the molar ratio of 6:4-1The mixed salt solution of (4);
(3) slowly dripping the alkali solution obtained in the step (1) into the mixed salt solution obtained in the step (2), fully stirring for 30min, and then standing for 24 h;
(4) carrying out vacuum filtration on the product obtained in the step (3) to obtain a solid filter material;
(5) drying the solid filter material obtained in the step (4) in a vacuum oven for 48 hours to obtain a carbonate precursor Ni0.6Mn0.4CO3；
(6) Placing the carbonate precursor obtained in the step (5) in a tubular furnace, and performing heat treatment for 1h at 1000 ℃ under the nitrogen atmosphere to obtain an intermediate product;
(7) and (3) preparing lithium from lithium hydroxide monohydrate and the intermediate product obtained in the step (6) according to a molar ratio of 1.05:1, and then performing heat treatment for 15h at 900 ℃ in an oxygen atmosphere to obtain the high-nickel layered cathode material with the single-crystal morphology.
The scanning electron microscope result of the intermediate product prepared in the step (6) is shown in fig. 3, and it can be seen from fig. 3 that the pre-fired material has a primary single crystal morphology.
Example three:
this example is a control experiment of example one, and differs from example one in that the precursor used in this example is a hydroxide precursor Ni produced by a coprecipitation method0.8Co0.1Mn0.1(OH)2The specific method comprises the following steps:
(1) sodium hydroxide is added into deionized water to prepare 2 mol.L-1NaOH solution of (2); adding 30 percent ammonia water solution into deionized water to prepare 2 mol.L-1The aqueous ammonia solution of (1);
(2) nickel sulfate hexahydrate, manganese sulfate monohydrate and cobalt sulfate heptahydrate are prepared into a mixture with the molar concentration of 1.33 mol.L according to the molar ratio of 8:1:1-1The mixed salt solution of (4);
(3) adding 1000mL of deionized water into a reaction kettle as a coprecipitation reaction base solution, wherein stirring and water bath processes are required in the whole reaction stage, the water bath temperature is controlled to be about 55 ℃, the stirring speed is stabilized at 800r/min, argon protective gas is introduced before the reaction is started to ensure that the whole reaction is carried out in argon atmosphere, pumping 30% ammonia water solution to control the pH of the base solution to 11, pumping the mixed salt solution, NaOH solution and ammonia water solution into a reaction kettle by a peristaltic pump, controlling the feeding speed of the metal salt solution and the ammonia water solution at 1mL/min, adjusting the feeding speed of the NaOH solution to stabilize the pH value of the reaction at 11, entering an aging stage after the feeding is finished, keeping the original temperature and the original rotating speed, continuously stirring for 2 hours, after the aging is finished, filtering and washing the hot solution, and then putting the precipitate into a vacuum drying oven at 80 ℃ for drying for 24h to finally obtain Ni.0.8Co0.1Mn0.1(OH)2And (3) precursor.
(4) Mixing Ni0.8Co0.1Mn0.1(OH)2Placing the precursor in a tube furnace, and carrying out heat treatment for 1h at 1000 ℃ under the argon atmosphere to obtain an intermediate product;
(5) and (3) preparing lithium from lithium hydroxide monohydrate and the intermediate product obtained in the step (6) according to a molar ratio of 1.05:1, and then performing heat treatment for 15 hours at 850 ℃ in an oxygen atmosphere to obtain the high-nickel layered cathode material with the single-crystal morphology.
The scanning electron microscope result of the obtained high-nickel layered cathode material with single crystal morphology is shown in fig. 4, and it can be seen from fig. 4 that the final product has a certain single crystal morphology, but compared with fig. 2, the single crystal growth of fig. 4 is not good enough, and no obvious dominant crystal face or other special morphology appears, which indicates that the precursor prepared by the slow-release precipitation method of the first embodiment is more beneficial to the formation of the single crystal morphology cathode material in the subsequent calcination process compared with the precursor prepared by the coprecipitation method of the present embodiment.
Example four:
this example is a control experiment of the second example, and differs from the second example in that the precursor used in this example is a hydroxide precursor Ni produced by a coprecipitation method0.6Mn0.4(OH)2The specific method comprises the following steps:
(1) sodium hydroxide is added into deionized water to prepare 2 mol.L-1NaOH solution of (2); adding 30 percent ammonia water solution into deionized water to prepare 2 mol.L-1The aqueous ammonia solution of (1);
(2) nickel sulfate hexahydrate and manganese sulfate monohydrate are prepared into a mixture with the molar concentration of 2 mol.L according to the molar ratio of 6:4-1The mixed salt solution of (4);
(3) adding 1000mL of deionized water into a reaction kettle as a coprecipitation reaction base solution, wherein stirring and water bath processes are required in the whole reaction stage, the temperature of the water bath is controlled to be about 55 ℃, the stirring speed is stabilized at 800r/min, argon protective gas is introduced before the reaction starts to ensure that the whole reaction is carried out in the argon atmosphere, an ammonia water solution with the mass fraction of 30 percent is pumped to control the pH of the base solution to be 11, a mixed salt solution, a NaOH solution and the ammonia water solution are pumped into the reaction kettle through a peristaltic pump to control goldThe feeding speed of the salt solution and the ammonia water solution is 1mL/min, the feeding speed of the NaOH solution is adjusted to stabilize the pH value of the reaction to be 11, the reaction is aged after the feeding is finished, the original temperature and the original rotating speed are kept to be continuously stirred for 2 hours, the hot solution is filtered and washed after the aging is finished, then the precipitate is placed into a vacuum drying oven at 80 ℃ to be dried for 24 hours, and finally the Ni is obtained0.6Mn0.4(OH)2And (3) precursor.
(4) Mixing Ni0.6Mn0.4(OH)2Placing the precursor in a tube furnace, and carrying out heat treatment for 1h at 1000 ℃ under the nitrogen atmosphere to obtain an intermediate product;
(5) and (3) preparing lithium from lithium hydroxide monohydrate and the intermediate product obtained in the step (6) according to a molar ratio of 1.05:1, and then performing heat treatment for 15h at 900 ℃ in an oxygen atmosphere to obtain the high-nickel layered cathode material with the single-crystal morphology. .
As shown in fig. 5, the scanning electron microscope result of the intermediate product prepared in step (4) is shown in fig. 5, and it can be seen from fig. 5 that although the prefired material has a certain single crystal morphology, the secondary particles of the more compact spherical hydroxide are not completely fired as compared with fig. 3. The precursor prepared by the slow-release precipitation method of the second embodiment is more beneficial to the formation of the single crystal morphology cathode material in the subsequent calcination process compared with the precursor prepared by the coprecipitation method of the present embodiment.
Comparative example one:
this comparative example is a control experiment of example one, carried out under the same conditions as example one, with the only difference that: the method does not comprise the step of pre-sintering the precursor under inert atmosphere, and comprises the following specific steps:
the precursor used in the comparative example is carbonate precursor Ni produced by adopting a slow-release precipitation method0.8Co0.1Mn0.1CO3The specific method comprises the following steps:
(1) adding 0.5mol of sodium bicarbonate into 425mL of deionized water, and stirring and mixing uniformly at room temperature for 30min to obtain an alkali solution;
(2) nickel sulfate hexahydrate, manganese sulfate monohydrate and cobalt sulfate heptahydrateThe molar ratio of 8:1:1 is prepared to have a molar concentration of 1.33 mol.L-1The mixed salt solution of (4);
(3) slowly dripping the alkali solution obtained in the step (1) into the mixed salt solution obtained in the step (2), fully stirring for 30min, and then standing for 24 h;
(4) carrying out vacuum filtration on the product obtained in the step (3) to obtain a solid filter material;
(5) drying the solid filter material obtained in the step (4) in a vacuum oven for 48 hours to obtain a carbonate precursor Ni0.8Co0.1Mn0.1CO3；
(6) And (3) preparing lithium from lithium hydroxide monohydrate and the carbonate precursor obtained in the step (5) according to a molar ratio of 1.05:1, and then performing heat treatment for 15h at 850 ℃ in an oxygen atmosphere to obtain the high-nickel layered cathode material with the single-crystal morphology.
Fig. 6 is a graph comparing the 1C cycle capacity of button cells further prepared from the cathode material prepared in comparative example one and the cathode material prepared in example one. As can be seen from fig. 6, the cycle capacity for the same synthesis and test conditions was significantly reduced when the same carbonate precursor was not subjected to pre-firing. Compared with a one-step calcining method, the method disclosed by the invention can effectively reduce the formation temperature of the subsequent high-nickel layered cathode material, reduce the energy consumption, reduce the lithium loss caused by high temperature and save the cost of actual industrial production; meanwhile, the appearance of the single crystal is easier to form and the capacity is easier to control.
Claims (10)
1. The preparation method of the high nickel layered anode material with single crystal morphology is characterized by comprising the following steps: the method comprises the step of pre-sintering the precursor in an inert atmosphere before calcining the lithium.
2. The preparation method of the high nickel layered cathode material with single crystal morphology as claimed in claim 1, wherein: the precursor is a carbonate precursor.
3. The preparation method of the high nickel layered cathode material with single crystal morphology as claimed in claim 1, wherein: the precursor is a hydroxide precursor.
4. The preparation method of the high-nickel layered cathode material with single crystal morphology according to claim 2, characterized in that the preparation method of the carbonate precursor comprises the following steps:
A. stirring and mixing sodium bicarbonate and deionized water uniformly to obtain an alkali solution;
B. preparing a mixed salt solution from soluble inorganic salts of nickel and soluble inorganic salts of cobalt and/or manganese by using deionized water;
C. slowly dripping the aqueous alkali into the mixed salt solution, stirring for 30-60 min, and standing for 24-48 h to obtain a standing material;
D. carrying out solid-liquid separation on the standing material to obtain a solid filtering material;
E. and drying the solid filtering material to obtain the solid filtering material.
5. The preparation method of the high nickel layered cathode material with single crystal morphology as claimed in claim 4, wherein: the solid-liquid separation mode is decompression suction filtration; the drying mode is as follows: and (3) drying the solid filtering material in a vacuum oven for 36-60 hours.
6. The method for preparing the high-nickel layered cathode material with the single crystal morphology according to any one of claims 1 to 5, characterized by comprising the following steps:
s1, placing the precursor in a tube furnace, and performing heat treatment for 1-3 hours at 900-1000 ℃ under an inert atmosphere to obtain an intermediate product;
s2, preparing lithium salt and the intermediate product according to the molar ratio of 1.01-1.10: 1, placing the mixture into a tubular furnace, and performing heat treatment for 12-18 hours at 750-950 ℃ in an oxygen atmosphere.
7. The high-nickel layered cathode material with single crystal morphology, which is prepared by the preparation method of the high-nickel layered cathode material with single crystal morphology as claimed in any one of claims 1 to 6.
8. A production method of a lithium ion battery is characterized in that: the production raw material comprises the high-nickel layered cathode material with single crystal morphology according to claim 7.
9. A lithium ion battery produced by the method for producing a lithium ion battery according to claim 8.
10. A vehicle comprising the lithium ion battery of claim 9.
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