CN109509875B - High-rate single crystal lithium nickel cobalt manganese oxide cathode material and preparation method thereof - Google Patents
High-rate single crystal lithium nickel cobalt manganese oxide cathode material and preparation method thereof Download PDFInfo
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- CN109509875B CN109509875B CN201811417199.2A CN201811417199A CN109509875B CN 109509875 B CN109509875 B CN 109509875B CN 201811417199 A CN201811417199 A CN 201811417199A CN 109509875 B CN109509875 B CN 109509875B
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- 239000013078 crystal Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 title claims description 11
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 title claims description 11
- 239000010406 cathode material Substances 0.000 title abstract description 7
- 239000007774 positive electrode material Substances 0.000 claims abstract description 23
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims abstract description 12
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910005518 NiaCobMnc Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 26
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 17
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 12
- 239000010405 anode material Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 claims 1
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 55
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 abstract description 29
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 29
- 159000000002 lithium salts Chemical class 0.000 abstract description 29
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- 239000011572 manganese Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- -1 molybdenum ions Chemical class 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 1
- XKGIZIQMMABGJQ-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [Mn](=O)(=O)([O-])[O-].[Mn+2].[Co+2].[Ni+2].[Li+] XKGIZIQMMABGJQ-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a high-rate single crystal nickel cobalt lithium manganate positive electrode material and a preparation method thereof, wherein the high-rate single crystal nickel cobalt lithium manganate positive electrode material comprises a single crystal inner layer formed by ternary nickel cobalt manganese oxide and a wrapping outer layer formed by double metal lithium salt, and the chemical general formula of the high-rate single crystal nickel cobalt lithium manganate positive electrode material is as follows: lixNiaCobMncYdMo3dO2Wherein x is more than or equal to 1 and less than or equal to l.10 and 0<a<l、0<b<1、0<c<1、0<d is less than or equal to 0.12, and a + b + c +4d = 1. According to the invention, a layer of double-metal lithium salt is wrapped after the single-crystal nickel-cobalt-manganese ternary cathode material is prepared, and the wrapping layer can effectively inhibit side reactions between the material and an electrolyte, so that the rate capability and the cycle performance of the material are greatly improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-rate single-crystal nickel cobalt lithium manganate positive electrode material and a preparation method thereof.
Background
The ternary material is proposed as the anode material of the lithium ion battery in 1999, and Co and Mn are adopted to replace LiNiO2Ni in (1) preparationA series of LiNi1-x-yCoxMnyO2The solid solution material is characterized in that the physical property and the electrochemical property of a solid solution material system are changed along with the change of the proportion of transition metal elements, and the change rule can be summarized as follows: the nickel element is a main capacity source, the specific capacity of the material can be greatly improved by increasing the content of the nickel, and compared with the other capacity source of cobalt, the voltage interval of the material is more matched with that of the existing electrolyte system; however, too high nickel content can cause cation mixed-arrangement phenomenon to be aggravated, the cycle performance, the rate capability and the safety performance of the material are deteriorated, the coulombic efficiency is gradually reduced, the cobalt element can provide capacity, and cobalt with proper content can effectively stabilize the layered structure and inhibit cation mixed-arrangement, thereby improving the electronic conductivity of the material and the rate capability of the material; however, the voltage range of the cobalt element for exerting capacity is higher than the current conventional 4.2V cut-off voltage, and the cost is increased due to the excessively high content of cobalt. The inert and stable Mn4+ enhances the structural stability of the material, and obviously improves the cycle performance and the thermal stability, but the manganese element does not provide capacity, and the gram capacity and the energy density of the material are obviously reduced.
At present, most of ternary cathode materials are secondary spherical particles formed by aggregating fine grains, gaps exist among primary particles of the secondary spherical particles, and the surfaces of partial primary particles cannot be wrapped during surface wrapping treatment, so that the integral wrapping of the secondary particles is difficult to avoid uneven, and the electrical property of a battery, particularly the cycle performance of the battery is affected. In addition Li [ Ni, Co, Mn ]]O2The rate capability of (a) is not ideal, and the application of the material to a hybrid power supply is prevented, which is mainly related to the electronic conductivity of the material. In addition, the material has poor cycle stability under high charge and discharge voltage.
Disclosure of Invention
To cope with Li [ Ni, Co, Mn ] of the prior art]O2The invention provides a high-rate single crystal lithium nickel cobalt manganese oxide positive electrode material, which has the defects of non-ideal rate performance and poor cycle stability, and the technical scheme is as follows:
the high-rate single crystal lithium nickel cobalt manganese oxide positive electrode material comprises a single lithium nickel cobalt manganese oxideThe lithium battery comprises a crystal inner layer and a wrapping outer layer formed by double metal lithium salts, wherein the chemical general formula of the high-rate single crystal nickel cobalt lithium manganate positive electrode material is as follows: lixNiaCobMncYdMo3dO2Wherein x is more than or equal to 1 and less than or equal to l.10 and 0<a<l、0<b<1、0<c<1、0<d is less than or equal to 0.12, and a + b + c +4d is 1.
Further, the molar ratio of the ternary nickel-cobalt-manganese oxide to the bimetallic lithium salt is 1: 0.02-0.06.
Further, the thickness of the wrapping outer layer is 10-200 nm.
The invention also aims to provide a preparation method of the high-rate single-crystal nickel cobalt lithium manganate positive electrode material, which comprises the following steps:
s1, preparing a ternary precursor: proportioning nickel sulfate solution, cobalt sulfate solution and manganese sulfate solution according to a stoichiometric proportion of a chemical general formula, adding pure water for mixing, adding ascorbic acid for stirring to prepare mixed solution, adding the mixed solution, NaOH solution and ammonia water solution into a reaction kettle for mixing and stirring, obtaining precipitate after complete reaction, and performing suction filtration and drying on the precipitate to obtain a ternary precursor of nickel-cobalt-manganese hydroxide;
s2, preparing the nickel-cobalt-manganese ternary material: sintering the ternary precursor prepared in the step S1, mixing and ball-milling a lithium source and the sintered ternary precursor to obtain mixed powder, and sintering the mixed powder at high temperature to obtain the nickel-cobalt-manganese ternary material with a single crystal structure;
s3, wrapping: weighing the double-metal lithium salt according to the molar ratio of the double-metal lithium salt to the ternary nickel-cobalt-manganese oxide, putting the weighed double-metal lithium salt and the prepared nickel-cobalt-manganese ternary material into a high-speed mixer for mixing, taking out after mixing is finished, and calcining to obtain the high-rate single crystal nickel-cobalt-manganese lithium manganate cathode material.
Preferably, in step S1, the pH value is controlled to be 11.0 to 12.0 during the mixing and stirring process; the reaction temperature is 35-65 ℃, and the stirring speed is 400-500 r/min.
Preferably, in step S1, the drying is preferably performed by using a forced air dryer, and the drying time is 8-10 h.
Preferably, in step S2, the lithium source is lithium hydroxide and/or lithium carbonate; in step S3, the bi-metal lithium salt is LiYMo3O8。
Preferably, in step S2, the high-temperature sintering process includes first heating to 550-650 ℃ for 2-18h of primary sintering, and then heating to 900-970 ℃ for 8-24h of secondary sintering after the primary sintering is completed.
Preferably, in step S3, the calcination temperature is 600-800 ℃, and the calcination time is 10-16 h.
The invention has the beneficial effects that:
(1) according to the invention, a layer of double metal lithium salt is wrapped on the basis of the single crystal type nickel-cobalt-manganese ternary cathode material, and the wrapping outer layer can effectively inhibit side reaction between the material and electrolyte, so that the cycle performance and safety performance of the material are greatly improved.
(2) The wrapping outer layer material contains lithium ions, so that the side reaction caused by direct contact of the anode material and the electrolyte can be prevented, and the reaction interface between the anode material and the electrolyte has higher ionic conductivity, thereby reducing impedance and improving the rate capability of the anode material; meanwhile, molybdenum ions in the outer layer of the coating are oxidized in the charging process, so that the specific discharge capacity of the anode material is further improved, and the rate capability of the material is also improved by the coating of the molybdenum ions.
Drawings
Fig. 1 is an SEM image of a positive electrode material obtained in example 1 of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
The preparation method of the ternary anode material of the single-crystal lithium ion battery wrapped by the bimetallic lithium salt comprises the following steps:
s1 preparation of spherical ternary precursor Ni by coprecipitation method0.5Co0.2Mn0.3(OH)2: according to the following steps: 2: 3 molar ratio battery grade NiSO4、CoSO4And MnSO4Mixing, adding high-purity water to obtain 6L of 1.0mol/L solution, and adding 48g of ascorbic acid to obtain a mixed solution; placing the mixed solution, 1mol/L ammonia water solution and 2mol/L NaOH solution into a reaction kettle in a parallel flow mode of a peristaltic pump, mixing and stirring to react, controlling the pH value to be 11.5, the reaction temperature to be 50 ℃, the stirring speed to be 400r/min, performing suction filtration on the precipitate generated by the reaction for 5 times by a fan, and drying for 8 hours by a blast drier to obtain nickel-cobalt-manganese hydroxide, namely a ternary precursor;
s2, preparing a nickel-cobalt-manganese ternary material: putting 1mol of the prepared ternary precursor and 1.10mol of battery-grade lithium hydroxide into a ball milling tank for ball milling to obtain mixed powder; placing the mixed powder in an alumina crucible, sintering for 6h at 550 ℃, and continuously raising the temperature to 970 ℃ for sintering for 15h to obtain the single-crystal nickel-cobalt-manganese ternary material;
s3, wrapping the nickel-cobalt-manganese ternary material by using a double-metal lithium salt: taking a nickel-cobalt-manganese ternary material and a double-metal lithium salt according to the proportion of 1: weighing a bimetallic lithium salt according to a molar ratio of 0.02, putting the bimetallic lithium salt and the nickel-cobalt-manganese ternary material into a high-speed mixer for 1h, and then taking out and calcining; the calcining temperature is 700 ℃, and the calcining time is 4 hours, thus obtaining the high-rate monocrystal nickel cobalt lithium manganate positive electrode material.
Example 2
The preparation method of the ternary anode material of the single crystal type lithium ion battery wrapped by the bimetallic lithium salt comprises the following steps:
s1 preparation of spherical ternary precursor Ni by coprecipitation method0.5Co0.2Mn0.3(OH)2: according to the following steps: 2: 3 molar ratio battery grade NiSO4、CoSO4And MnSO4Mixing, adding high-purity water to obtain 6L of 1.0mol/L solution, and adding 48g of ascorbic acid to obtain a mixed solution; co-current flow using peristaltic pumpsPutting the mixed solution, 1mol/L ammonia water solution and 2mol/L NaOH solution into a reaction kettle, mixing and stirring to react, controlling the pH value to be 11.50, the reaction temperature to be 50 ℃, the stirring speed to be 500r/min, carrying out suction filtration on a precipitate generated by the reaction for 5 times by a fan, and then drying for 10 hours by a blast drier to obtain nickel-cobalt-manganese hydroxide, namely a ternary precursor;
s2, preparing a nickel-cobalt-manganese ternary material: putting 1mol of the prepared ternary precursor and 1.08mol of battery-grade lithium hydroxide into a ball milling tank for ball milling to obtain mixed powder; placing the mixed powder in an alumina crucible, sintering for 6h at 600 ℃, and continuously raising the temperature to 950 ℃ for sintering for 15h to obtain the single-crystal nickel-cobalt-manganese ternary material;
s3, wrapping the nickel-cobalt-manganese ternary material by using a double-metal lithium salt: weighing the nickel-cobalt-manganese ternary material and the bimetallic lithium salt according to the molar ratio of 1:0.04, putting the bimetallic lithium salt and the nickel-cobalt-manganese ternary material into a high-speed mixer for 0.5h, taking out and calcining, and calcining at 800 ℃ for 2h to obtain the high-rate single crystal nickel-cobalt-lithium manganate positive electrode material.
Example 3
The preparation method of the ternary anode material of the single crystal type lithium ion battery wrapped by the bimetallic lithium salt comprises the following steps:
s1 preparation of spherical ternary precursor Ni by coprecipitation method0.5Co0.2Mn0.3(OH)2: according to the following steps: 2: 3 molar ratio battery grade NiSO4、CoSO4And MnSO4Mixing, adding high-purity water to obtain 6L of 1.0mol/L solution, and adding 48g of ascorbic acid to obtain a mixed solution; placing the mixed solution, 1mol/L ammonia water solution and 2mol/L NaOH solution into a reaction kettle in a parallel flow mode of a peristaltic pump, mixing and stirring to react, controlling the pH value to be 11.50, the reaction temperature to be 50 ℃, the stirring speed to be 500r/min, carrying out suction filtration on the precipitate generated by the reaction for 5 times by a fan, and then drying for 10 hours by a blast drier to obtain nickel-cobalt-manganese hydroxide, namely a ternary precursor;
s2, preparing a nickel-cobalt-manganese ternary material: putting 1mol of the prepared ternary precursor and 1.10mol of battery-grade lithium hydroxide into a ball milling tank for ball milling to obtain mixed powder; placing the mixed powder in an alumina crucible, sintering for 3h at 700 ℃, and continuously raising the temperature to 900 ℃ for sintering for 8h to obtain the single-crystal nickel-cobalt-manganese ternary material;
s3, wrapping the nickel-cobalt-manganese ternary material by using a double-metal lithium salt: weighing the nickel-cobalt-manganese ternary material and the bimetallic lithium salt according to the molar ratio of 1:0.06, putting the bimetallic lithium salt and the nickel-cobalt-manganese ternary material into a high-speed mixer for 2 hours, taking out and calcining, wherein the calcining temperature is 600 ℃, and the calcining time is 10 hours, so that the high-rate single crystal nickel-cobalt-lithium manganate positive electrode material can be obtained.
Comparative example 1
A preparation method of a lithium ion battery anode material comprises the following steps:
s1 preparation of spherical ternary precursor Ni by coprecipitation method0.5Co0.2Mn0.3(OH)2: according to the following steps: 2: 3 molar ratio battery grade NiSO4、CoSO4And MnSO4Mixing, adding high-purity water to obtain 6L of 1.0mol/L solution, and adding 48g of ascorbic acid to obtain a mixed solution; placing the mixed solution, 1mol/L ammonia water solution and 2mol/L NaOH solution into a reaction kettle in a parallel flow mode of a peristaltic pump, mixing and stirring to react, controlling the pH value to be 11.4, the reaction temperature to be 50 ℃, the stirring speed to be 500r/min, performing suction filtration on the precipitate generated by the reaction for more than 5 times by a fan, and then drying for 10 hours by a blast drier to obtain nickel-cobalt-manganese hydroxide, namely a ternary precursor;
s2, preparing a nickel-cobalt-manganese ternary material: and (3) placing 1mol of the prepared ternary precursor and battery-level lithium hydroxide in a ball milling tank for ball milling to obtain mixed powder, wherein the molar ratio of the ternary precursor to the battery-level lithium hydroxide is 1: 1.10; and placing the mixed powder into an alumina crucible, sintering for 6h at 600 ℃, and continuously raising the temperature to 950 ℃ for sintering for 15h to obtain the single-crystal nickel-cobalt-manganese ternary material, namely the lithium ion battery anode material.
Comparative example 2:
a preparation method of a ternary cathode material of a lithium ion battery comprises the following steps: s1 coprecipitation method for preparing ballShape ternary precursor Ni0.5Co0.2Mn0.3(OH)2: according to the following steps: 2: 3 molar ratio battery grade NiSO4、CoSO4And MnSO4Mixing, adding high-purity water to obtain 6L of 1.0mol/L solution, and adding 48g of ascorbic acid to obtain a mixed solution; placing the mixed solution, 1mol/L ammonia water solution and 2mol/L NaOH solution into a reaction kettle in a parallel flow mode of a peristaltic pump, mixing and stirring to react, controlling the pH value to be 11.6, the reaction temperature to be 50 ℃, the stirring speed to be 500r/min, performing suction filtration on the precipitate generated by the reaction for more than 5 times by a fan, and then drying for 10 hours by a blast drier to obtain nickel-cobalt-manganese hydroxide, namely a ternary precursor;
s2, preparing a nickel-cobalt-manganese ternary material: putting 1mol of the prepared ternary precursor and 1.10mol of battery-grade lithium hydroxide into a ball milling tank for ball milling to obtain mixed powder; placing the mixed powder in an alumina crucible, sintering for 9h at 500 ℃, and continuously raising the temperature to 930 ℃ for sintering for 15h to obtain the nickel-cobalt-manganese ternary material;
s3, wrapping the nickel-cobalt-manganese ternary material by using a double-metal lithium salt: weighing the bimetal lithium salt according to the molar ratio of 1:0.08 of the nickel-cobalt-manganese ternary material and the bimetal lithium salt, putting the bimetal lithium salt and the nickel-cobalt-manganese ternary material into a high-speed mixer for 1.5h, then taking out and calcining, wherein the calcining temperature is 650(550) DEG C, and the calcining time is 4h, thus obtaining the high-rate single crystal nickel-cobalt-lithium manganate positive electrode material.
Testing the charging and discharging specific capacity of the battery: the lithium ion battery positive electrode materials obtained in examples 1 to 3 and comparative examples 1 to 2 were respectively prepared into positive electrode sheets, and then assembled into a "2032" type button cell by using a conventional technique, a charge and discharge test was performed in a voltage range of 2.75 to 4.3V at different current densities, and the charge and discharge specific capacities of different materials were recorded, and the results are shown in table 1, wherein the cycle efficiency of the battery after 50 cycles of the last 1C was equal to 50 cycles of discharge capacity/100 cycles of discharge capacity of the first week.
TABLE 1 results of the test of the fastening properties of examples 1-3 and comparative examples 1-2
As can be seen from Table 1, the molar ratio of the nickel-cobalt-manganese ternary material of the present invention to the bimetallic lithium salt is in the range of 1: when the capacity is below 0.06, the capacity of the battery made of the nickel-cobalt-manganese ternary material is obviously higher than that of the battery without the coating; when the wrapping amount is 1: at 0.04, the discharge capacity of the battery 0.1C is 161.55mAh/g, and the first discharge specific capacity of the battery prepared from the non-wrapped ternary material is only 159.72mAh/g, because the insertion and extraction of lithium ions are not influenced by the material of the double-metal lithium salt wrapping layer, and the polarization of the material in the first circulation process is not influenced by the wrapping layer; after 50 weeks cycling, the cells made with the uncoated ternary material had the worst cycling performance.
As can be seen from table 1, when the amount of the bi-metallic lithium salt is 1: when the discharge capacity is 0.04, the rate capability of the material is optimal, and the discharge capacity of 2C and 5C is obviously higher than that of the material without the coating; as can be seen from comparative example 2, when the wrapping amount is 1: at 0.08, the rate performance rather than that of the uncoated material was deteriorated, and the measured data was rather lowered, because if the coating layer was too thick, the barrier to diffusion migration was increased, and the resistance of the coated material was increased, and the rate performance was remarkably lowered.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (8)
1. The high-rate single crystal lithium nickel cobalt manganese oxide positive electrode material is characterized by comprising a single crystal inner layer formed by ternary nickel cobalt manganese oxide and LiYMo3O8The chemical general formula of the high-rate single crystal nickel cobalt lithium manganate positive electrode material is as follows: lixNiaCobMncYdMo3dO2Wherein x is more than or equal to 1 and less than or equal to l.10 and 0<a<l、0<b<1、0<c<1、0<d is less than or equal to 0.12, and a + b + c +4d1, the ternary nickel cobalt manganese oxide and LiYMo3O8The molar ratio of (A) to (B) is 1: 0.02-0.06.
2. The high-rate single-crystal nickel cobalt lithium manganate positive electrode material of claim 1, wherein the thickness of said wrapping outer layer is 10-200 nm.
3. The preparation method of the high-rate single-crystal lithium nickel cobalt manganese oxide positive electrode material according to any one of claims 1 to 2, characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a ternary precursor: proportioning nickel sulfate solution, cobalt sulfate solution and manganese sulfate solution according to a stoichiometric proportion of a chemical general formula, adding pure water for mixing, adding ascorbic acid for stirring to prepare mixed solution, adding the mixed solution, NaOH solution and ammonia water solution into a reaction kettle for mixing and stirring, obtaining precipitate after complete reaction, and performing suction filtration and drying treatment on the precipitate to obtain a ternary precursor of nickel-cobalt-manganese hydroxide;
s2, preparing ternary nickel-cobalt-manganese oxide: sintering the ternary precursor prepared in the step S1, mixing and ball-milling a lithium source and the sintered ternary precursor to obtain mixed powder, and sintering the mixed powder at high temperature to obtain the ternary nickel-cobalt-manganese oxide with a single crystal structure;
s3, wrapping: according to LiYMo3O8Weighing LiYMo in molar ratio to ternary Ni-Co-Mn oxide3O8And weighing LiYMo3O8And mixing the prepared ternary nickel-cobalt-manganese oxide in a high-speed mixer, taking out the mixture after mixing is finished, and calcining the mixture to obtain the high-rate single crystal nickel-cobalt-manganese lithium anode material.
4. The preparation method of the high-rate single crystal lithium nickel cobalt manganese oxide positive electrode material according to claim 3, characterized by comprising the following steps: in the step S1, the pH value is controlled to be 11.0-12.0 in the mixing and stirring process; the reaction temperature is 35-65 ℃, and the stirring speed is 400-500 r/min.
5. The method for preparing the high-rate single crystal lithium nickel cobalt manganese oxide positive electrode material according to claim 3, wherein in the step S1, a blast drier is adopted for drying treatment, and the drying time is 8-10 h.
6. The preparation method of the high-rate single crystal lithium nickel cobalt manganese oxide positive electrode material according to claim 3, characterized by comprising the following steps: in step S2, the lithium source is lithium hydroxide and/or lithium carbonate.
7. The preparation method of the high-rate single crystal lithium nickel cobalt manganese oxide positive electrode material according to claim 4, characterized in that: in step S2, the high-temperature sintering process includes first heating to 550-650 ℃ for 2-18h of primary sintering, and after the primary sintering is completed, heating to 900-970 ℃ for 8-24h of secondary sintering.
8. The preparation method of the high-rate single crystal lithium nickel cobalt manganese oxide positive electrode material according to claim 3, characterized by comprising the following steps: in step S3, the calcination temperature is 600-800 ℃, and the calcination time is 10-16 h.
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