CN111129484A - Peanut shell-shaped nickel cobalt lithium manganate positive electrode material and preparation method thereof - Google Patents
Peanut shell-shaped nickel cobalt lithium manganate positive electrode material and preparation method thereof Download PDFInfo
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- 241001553178 Arachis glabrata Species 0.000 title claims abstract description 28
- 235000010777 Arachis hypogaea Nutrition 0.000 title claims abstract description 28
- 235000018262 Arachis monticola Nutrition 0.000 title claims abstract description 28
- 235000020232 peanut Nutrition 0.000 title claims abstract description 28
- 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 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000007774 positive electrode material Substances 0.000 title abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract 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 abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 7
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
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- 238000005406 washing Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 238000003487 electrochemical reaction Methods 0.000 abstract description 2
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 2
- 159000000002 lithium salts Chemical class 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000000840 electrochemical analysis Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 uniformly stirring Substances 0.000 description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- 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 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method 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
- 238000005056 compaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000007790 scraping Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
Abstract
The invention provides a peanut shell-shaped nickel cobalt lithium manganate positive electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, uniformly mixing nickel nitrate hexahydrate, cobalt nitrate hexahydrate, 50% manganese nitrate solution, a certain amount of urea and a proper amount of deionized water according to a certain proportion; and then placing the mixture into a high-pressure reaction kettle, reacting for 12-24 hours at 120-140 ℃ to obtain a peanut shell-shaped nickel-cobalt-manganese hydroxide precursor, finally adding excessive lithium salt, heating to 600 ℃ at the speed of 5 ℃/min in an argon atmosphere, and calcining for 6 hours to obtain the peanut shell-shaped nickel-cobalt-manganese acid lithium material. The peanut shell-shaped nickel cobalt lithium manganate material prepared by the method has high purity and contains abundant mesopores. Electrochemical tests show that the catalyst has high gram capacity and good cycle performance, shows a multipoint synergistic effect in the electrochemical reaction process, and has good application prospects.
Description
Technical Field
The invention belongs to the field of lithium battery positive electrode material manufacturing, and particularly provides a peanut shell-shaped nickel cobalt lithium manganate positive electrode material and a preparation method thereof.
Background
The nickel cobalt lithium manganate ternary material is widely applied to the anode material of the lithium ion power battery due to high gram capacity, good cycle performance and high energy density. However, with the development of electric vehicles, the requirements for energy density, cycle performance and other performances of lithium batteries are further increased, and the improvement of the energy density, cycle performance and other performances of the positive electrode material becomes the key of the development of the lithium batteries.
Generally speaking, the electrochemical performance of a material is not only related to the characteristics of the material, but also greatly related to the geometric morphology of the material, and the peanut shell-like material is a research hotspot in the field because the peanut shell-like material has a multi-point synergistic effect and short electron and ion transmission paths can effectively improve the electrochemical activity of the material. Therefore, the patent provides a peanut shell-shaped nickel cobalt lithium manganate positive electrode material and a preparation method thereof.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a peanut shell-shaped nickel cobalt lithium manganate positive electrode material and a preparation method thereof, wherein firstly, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, a 50% manganese nitrate solution, a certain amount of urea and a proper amount of deionized water are mixed uniformly according to a certain proportion; and then, reacting in a high-pressure reaction kettle at 120-140 ℃ for 12-24 h to obtain a peanut shell-shaped nickel-cobalt-manganese hydroxide precursor, adding a lithium salt, heating to 600 ℃ at the speed of 5 ℃/min in an argon atmosphere, and calcining the precursor for 8h to obtain the peanut shell-shaped nickel-cobalt-manganese acid lithium positive electrode material.
According to the invention, the peanut shell-shaped nickel cobalt lithium manganate material is used as the positive electrode material to measure the 0.2C gram capacity and the 0.2C cycle performance of the positive electrode material, and the peanut shell-shaped nickel cobalt lithium manganate material prepared by the method has high gram capacity and excellent cycle performance as the positive electrode material.
The technical scheme for realizing the above purpose of the invention is as follows:
(1) firstly, a certain amount of nickel nitrate (Ni) (NO) hexahydrate3)2·6H2O, cobalt nitrate hexahydrate Co (NO)3)2·6H2Dissolving O and 50% manganese nitrate solution in 100mL deionized water, and performing ultrasonic treatment for 5min to prepare Ni2+∶Co2+∶Mn2+The molar ratio is x: y: z (x + y)+ z-1) with a total cation concentration of 0.5mol/L, then 10g of urea were added thereto and magnetic stirring was continued at room temperature for 0.5 h;
(2) transferring the mixed solution into a 150mL reaction kettle, reacting for 12-24 h at 120-140 ℃, cooling to room temperature, performing centrifugal separation, alternately washing for 3 times by using deionized water and absolute ethyl alcohol, and drying for 24h at 120 ℃ to obtain a peanut shell-shaped nickel-cobalt-manganese hydroxide precursor;
(3) and (4) placing the precursor prepared in the step (3) into a tube furnace, adding a certain amount of lithium fluoride, heating to 600 ℃ at the speed of 5 ℃/min under the argon atmosphere, and calcining for 8h to obtain the peanut-shell-shaped nickel cobalt lithium manganate material.
Wherein, the ranges of x, y and z in the step (1) are respectively 0.5-0.8, 0.3-0.1 and 0.2-0.1, and preferably the ratio of x to y to z is 8: 1.
Wherein the reaction temperature in the step (2) is 120-140 ℃, preferably 130 ℃.
Wherein the reaction time in the step (2) is 12-24 h, preferably 16 h.
Wherein the calcining temperature in the step (3) is 600 ℃, preferably 600 ℃.
The nickel cobalt lithium manganate material prepared by the method is peanut shell-shaped.
The peanut shell-shaped nickel cobalt lithium manganate material prepared by the method can be used as a lithium battery positive electrode material. Specifically, the electrochemical performance of the battery is tested by adopting a half cell, and the preparation method comprises the following steps: the 2032 type button-type half battery is assembled by taking a peanut shell-shaped nickel cobalt lithium manganate material as a lithium battery positive electrode material, carbon black as a conductive agent, PVDF as a binder and NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying, roll-aligning and cutting into pieces to prepare a pole piece, taking a lithium piece as a negative electrode, taking an aluminum sheet containing the peanut shell-shaped nickel cobalt lithium manganate material as a positive electrode, taking lithium hexafluorophosphate as an electrolyte and taking a PP/PE polymer as a diaphragm.
The invention has the beneficial effects that:
1. the method has the advantages of simple and convenient operation, proper and easily controlled conditions, good experimental reproducibility and easy application to large-scale production.
2. The peanut shell-shaped nickel cobalt lithium manganate material prepared by the method provided by the invention has high purity and high compaction density. The results of the electrical property tests show that it has high gram capacity and good cycle stability.
3. The method effectively realizes the co-precipitation of cobalt, nickel and manganese in the raw materials, and the prepared peanut shell-shaped nickel cobalt lithium manganate material contains rich mesopores and has a multi-point synergistic effect in the electrochemical reaction process.
Drawings
FIG. 1 is an SEM photograph of a peanut-shell-shaped lithium nickel cobalt manganese oxide material prepared in example 1.
FIG. 2 is a charge-discharge curve of the peanut-shell-shaped lithium nickel cobalt manganese oxide material prepared in example 1 under a current of 0.2C.
FIG. 3 is a cycle capacity retention rate curve of the peanut-shell-shaped nickel cobalt lithium manganate material prepared in example 1 under a current of 0.2C.
Detailed Description
The present invention will now be illustrated by the following preferred examples, which should not be construed as limiting the scope of the invention.
Example 1:
1. firstly, a certain amount of nickel nitrate (Ni) (NO) hexahydrate3)2·6H2O, cobalt nitrate hexahydrate Co (NO)3)2·6H2Dissolving O and 50% manganese nitrate solution in 100mL deionized water, and performing ultrasonic treatment for 5min to prepare Ni2+∶Co2+∶Mn2+Mixed metal salt solution with the molar ratio of 8: 1 and the total cation concentration of 0.5mol/L, then 10g of urea is added into the mixed metal salt solution, and the mixture is continuously stirred for 0.5h by magnetic force at room temperature;
2. transferring the mixed solution into a 150mL reaction kettle, reacting at 130 ℃ for 18h, cooling to room temperature, performing centrifugal separation, alternately washing for 3 times by using deionized water and absolute ethyl alcohol, and drying at 120 ℃ for 24h to obtain a peanut shell-shaped nickel-cobalt-manganese hydroxide precursor;
3. and (3) placing the precursor prepared in the step (3) into a tube furnace, adding a certain amount of lithium fluoride, heating to 600 ℃ at the speed of 5 ℃/min under the argon atmosphere, and calcining for 8h to obtain the peanut shell-shaped nickel cobalt lithium manganate material, wherein an SEM picture of the material is shown in figure 1.
Example 2:
an electrode material prepared from a peanut-shell-shaped nickel cobalt lithium manganate material and electrochemical representation thereof.
Taking 1.8g of peanut-shell-shaped nickel cobalt lithium manganate material powder prepared in example 1, 0.1g of carbon black conductive agent and 0.1g of PVDFF, adding 5mL of NMP, and uniformly stirring; uniformly scraping the slurry onto an aluminum foil by using a scraper of 200um, and drying for 8h at 60 ℃; and then, rolling, drying and cutting into pieces to obtain the pole piece for testing. Then, the obtained pole piece was used as a positive electrode (active material content was 6.3mg), a lithium piece was used as a negative electrode, lithium hexafluorophosphate (DMC: EMC ═ 1: 1) was used as an electrolyte, and PP/PE polymer was used as a separator to assemble a 2032 type button cell.
1. And (3) carrying out electrochemical performance test on the assembled 2032 type button cell by using a Xinwei test cabinet, wherein the current is 0.2C, the voltage range is 2.5V-4.2V, the gram capacity is obtained after 1 circulation, and the discharge curve is shown in figure 2. Then, the circulation was continued for 50 cycles at 0.2C, and the cycle stability was tested, and the capacity retention rate curve is shown in FIG. 3.
Example 3:
1. firstly, a certain amount of nickel nitrate (Ni) (NO) hexahydrate3)2·6H2O, cobalt nitrate hexahydrate Co (NO)3)2·6H2Dissolving O and 50% manganese nitrate solution in 100mL deionized water, and performing ultrasonic treatment for 5min to prepare Ni2+∶Co2+∶Mn2+Mixing metal salt solution with a molar ratio of 6: 2, wherein the total cation concentration is 0.5mol/L, then adding 10g of urea, and continuing to magnetically stir for 0.5h at room temperature;
2. transferring the mixed solution into a 150mL reaction kettle, reacting at 120 ℃ for 12h, cooling to room temperature, performing centrifugal separation, alternately washing for 3 times by using deionized water and absolute ethyl alcohol, and drying at 120 ℃ for 24h to obtain a peanut shell-shaped nickel-cobalt-manganese hydroxide precursor;
3. and (4) placing the precursor prepared in the step (3) into a tube furnace, adding a certain amount of lithium fluoride, heating to 600 ℃ at the speed of 5 ℃/min under the argon atmosphere, and calcining for 8h to obtain the peanut-shell-shaped nickel cobalt lithium manganate material.
Example 4:
1. firstly, a certain amount of nickel nitrate (Ni) (NO) hexahydrate3)2·6H2O, cobalt nitrate hexahydrate Co (NO)3)2·6H2Dissolving O and 50% manganese nitrate solution in 100mL deionized water, and performing ultrasonic treatment for 5min to prepare Ni2+∶Co2+∶Mn2+Mixing metal salt solution with the molar ratio of 5: 3: 2, wherein the total cation concentration is 0.5mol/L, then adding 10g of urea into the mixed metal salt solution, and continuing to magnetically stir for 0.5h at room temperature;
2. transferring the mixed solution into a 150mL reaction kettle, reacting at 140 ℃ for 24h, cooling to room temperature, performing centrifugal separation, alternately washing for 3 times by using deionized water and absolute ethyl alcohol, and drying at 120 ℃ for 24h to obtain a peanut shell-shaped nickel-cobalt-manganese hydroxide precursor;
3. and (4) placing the precursor prepared in the step (3) into a tube furnace, adding a certain amount of lithium fluoride, heating to 600 ℃ at the speed of 5 ℃/min under the argon atmosphere, and calcining for 8h to obtain the peanut-shell-shaped nickel cobalt lithium manganate material.
Claims (5)
1. The preparation method of the peanut shell-shaped nickel cobalt lithium manganate material is characterized by comprising the following steps of:
(1) firstly, a certain amount of nickel nitrate (Ni) (NO) hexahydrate3)2·6H2O, cobalt nitrate hexahydrate Co (NO)3)2·6H2Dissolving O and 50% manganese nitrate solution in 100mL deionized water, and performing ultrasonic treatment for 5min to prepare Ni2+∶Co2+∶Mn2+Mixed metal salt solution with the molar ratio of x to y to z (x + y + z is 1) and the total cation concentration is 0.5mol/L, then 10g of urea is added into the mixed metal salt solution, and the magnetic stirring is continued for 0.5h at room temperature;
(2) transferring the mixed solution into a 150mL reaction kettle, reacting for 12-24 h at 120-140 ℃, cooling to room temperature, performing centrifugal separation, alternately washing for 3 times by using deionized water and absolute ethyl alcohol, and drying for 24h at 120 ℃ to obtain a peanut shell-shaped nickel-cobalt-manganese hydroxide precursor;
(3) and (4) placing the precursor prepared in the step (3) into a tube furnace, adding a certain amount of lithium fluoride, heating to 600 ℃ at the speed of 5 ℃/min under the argon atmosphere, and calcining for 8h to obtain the peanut-shell-shaped nickel cobalt lithium manganate material.
2. The preparation method according to claim 1, wherein the mixed metal salt solution in the step (1) has a molar ratio of Ni2+, Co2+ and Mn2+ of x: y: z (x + y + z: 1) and a total concentration of 0.5 mol/L.
3. The method according to claims 1 and 2, wherein the reaction temperature in the step (2) is in the range of 120 to 140 ℃.
4. The method according to claims 1, 2 and 3, wherein the reaction time in the step (2) is in the range of 12 to 24 hours.
5. The production method according to claims 1, 2, 3 and 4, characterized in that the calcination temperature in the step (3) is in the range of 600 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101304090A (en) * | 2008-05-28 | 2008-11-12 | 哈尔滨工业大学 | Method for synthesizing lithium ion battery anode material LiNixCoyMn(1-x-y)O2 |
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