CN103715420A - Preparation method of high-compaction-density lithium nickel cobalt aluminum oxide ternary anode material - Google Patents
Preparation method of high-compaction-density lithium nickel cobalt aluminum oxide ternary anode material Download PDFInfo
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- CN103715420A CN103715420A CN201310693527.2A CN201310693527A CN103715420A CN 103715420 A CN103715420 A CN 103715420A CN 201310693527 A CN201310693527 A CN 201310693527A CN 103715420 A CN103715420 A CN 103715420A
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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
- H01M4/52—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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- 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
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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 relates to a preparation method of a lithium electrode anode material, and specifically discloses a preparation method of a high-compaction-density lithium nickel cobalt aluminum oxide ternary anode material. The preparation method comprises the following steps of a, preparing a cobalt nitrate solution, carrying out complexation by utilizing ammonium hydroxide, and numbering as a solution 1; preparing a NaOH solution, adding a NH3.H2O solution in the NaOH solution, and numbering as a solution 2; preparing a mixed solution of cobalt nitrate, nickel nitrate and aluminium nitrate, carrying out complexation by utilizing the ammonium hydroxide, and numbering as a solution 3; preparing a NaOH solution, adding a NH3.H2O solution, and numbering as a solution 4; b, mixing the solution 1 and the solution 2 to react to obtain a cobalt oxide precursor; c, enabling the cobalt oxide precursor and the solution 3 and the solution 4 to react to obtain a nickel cobalt aluminum hydroxide precursor; d, carrying out ball-milling mixing on the lithium carbonate and the nickel cobalt aluminum hydroxide precursor; e, sintering by utilizing a muffle furnace; and f, preparing the lithium nickel cobalt aluminum oxide anode ternary material. The preparation method provided by the invention has the advantages that the compaction density of the ternary material is improved, and the battery capacity and the circulating property of the material are both remarkably improved.
Description
Technical field
The present invention relates to the preparation method of lithium electrode positive electrode, specifically a kind of preparation method of high compacted density lithium nickel cobalt alumina tertiary cathode material.
Background technology
Lithium nickel cobalt alumina ternary material has been widely used in the positive electrode of lithium battery, but existing tertiary cathode material compacted density is difficult to raising, has limited the further raising of the performances such as tertiary cathode material battery capacity and cyclicity.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of higher material compacted density that has, the preparation method of the high compacted density lithium nickel cobalt alumina tertiary cathode material that the battery capacity of while material and cycle performance are good.
The preparation method of high compacted density lithium nickel cobalt alumina tertiary cathode material of the present invention comprises the following steps:
A. configuring 2.0mol/L cobalt nitrate solution, is 6.6 with ammoniacal liquor complexing to pH, numbering solution 1;
Configuration 6.0mol/L NaOH solution, and add 0.4mol/L NH3H2O solution, the two volume ratio is 10:1, numbering solution 2;
Cobalt nitrate, nickel nitrate and aluminum nitrate mixed solution that configuration cation total concentration is 2.0mol/L, wherein nickel cobalt al mole ratio is 0.8:0.15:0.05, with ammoniacal liquor complexing, to pH, is 8.6, numbering solution 3;
Configuration 3.0mol/L NaOH solution, and add 0.8mol/L NH3H2O solution, the two volume ratio is 7:1, numbering solution 4;
B. by the solution configuring 1 and solution 2 hybrid reactions, and controlling solution 2, to make mixed solution pH be 13, and reaction temperature 28-30 ℃, passes into N2 protection in course of reaction; Question response is isolated deposit seed, with deionized water, washs post-drying; At 380-390 ℃ of calcining 6-8h, obtain cobalt oxygen precursor;
C. the cobalt oxygen precursor of preparation is added in reactor, and the solution configuring 3 and solution 4 are pumped into reactor simultaneously, and controlling solution 4, to make mixed solution pH be 10.5, stirs and keep constant temperature 55-60 ℃, in course of reaction, pass into N2 protection; Question response is isolated deposit seed, with deionized water, washs post-drying, obtains nickel hydroxide cobalt aluminium precursor;
D. by lithium carbonate and the Li/M=1.06 ball milling mixing in molar ratio of nickel hydroxide cobalt aluminium precursor; Wherein M is the molal quantity sum of three kinds of elements of nickel cobalt aluminium;
E. Muffle furnace sintering: room temperature-450 ℃,, are not incubated in the time of 450 ℃ by heating rate 3-4 ℃/min; 450-740 ℃, heating rate 1-1.5 ℃/min, 740 ℃ of insulation 18-20h; 740-350 ℃, rate of temperature fall 1.5-2.5 ℃/min, after naturally cooling with furnace temperature, in whole process, atmosphere is air, throughput is 8-10L/min;
F. after fragmentation, obtain the anodal ternary material LiNi0.78Co0.17Mn0.05O2 of lithium nickel cobalt alumina.
The present invention selects by special technological parameter and raw material, the pattern that can effectively improve material granule, has improved the compacted density of ternary material, and then has improved the performance of positive electrode, after testing and test, battery capacity and the cycle performance of its material are significantly increased.
Embodiment
The method of the embodiment of the present invention comprises the following steps:
A. configuring 2.0mol/L cobalt nitrate solution, is 6.6 with ammoniacal liquor complexing to pH, numbering solution 1;
Configuration 6.0mol/L NaOH solution, and add 0.4mol/L NH3H2O solution, the two volume ratio is 10:1, numbering solution 2;
Cobalt nitrate, nickel nitrate and aluminum nitrate mixed solution that configuration cation total concentration is 2.0mol/L, wherein nickel cobalt al mole ratio is 0.8:0.15:0.05, with ammoniacal liquor complexing, to pH, is 8.6, numbering solution 3;
Configuration 3.0mol/L NaOH solution, and add 0.8mol/L NH3H2O solution, the two volume ratio is 7:1, numbering solution 4;
B. the solution configuring 1 and solution 2 are pumped in the reactor of 10L simultaneously, mixed solution flow velocity is 200mL/min, finishes reinforcedly after 0.5h, and controlling solution 2, to make mixed solution pH be 13, stirs and keep 30 ℃ of constant temperature, passes into N2 protection in course of reaction; Question response carries out isolating deposit seed after 5h, with deionized water, washs post-drying; At 390 ℃ of calcining 8h, obtain cobalt oxygen precursor, average grain diameter 2.3 μ m;
C. the cobalt oxygen precursor of preparation is added in reactor, and the solution configuring 3 and solution 4 are pumped into reactor simultaneously, mixed solution flow velocity is 40mL/min, and controlling solution 4, to make mixed solution pH be 10.5, stir and keep 55 ℃ of constant temperature, in course of reaction, passing into N2 protection; Question response carries out isolating deposit seed after 15h, with deionized water, washs post-drying, obtains nickel hydroxide cobalt aluminium precursor, average grain diameter 8.7 μ m, and chemical composition is Ni:Co:Al=0.777:0.171:0.048;
D. by lithium carbonate and the Li/M=1.06 ball milling mixing in molar ratio of nickel hydroxide cobalt aluminium precursor, Ball-milling Time is 4h; Wherein M is the molal quantity sum of three kinds of elements of nickel cobalt aluminium;
E. Muffle furnace sintering: room temperature-450 ℃,, are not incubated in the time of 450 ℃ by heating rate 3-4 ℃/min; 450-740 ℃, heating rate 1-1.5 ℃/min, 740 ℃ of insulation 19h; 740-350 ℃, rate of temperature fall 1.5-2.5 ℃/min, after naturally cooling with furnace temperature, in whole process, atmosphere is air, throughput is 10L/min;
F. rear mistake 200 eye mesh screens of omnipotent fragmentation, obtain the anodal ternary material LiNi0.78Co0.17Mn0.05O2 of lithium nickel cobalt alumina.
Positive electrode prepared by the embodiment of the present invention, after testing and test, result is as follows:
1, tap density: testing this material tap density with BT-300 tap density tester is 2.35g/cm
3;
2, compacted density: the compacted density that records this material under 30Mpa is 3.96g/cm
3;
2, SEM observes this material secondary granule-morphology almost spherical;
3, to record this material specific area be 0.71m to liquid nitrogen absorption method
2/ g;
4, battery testing under normal temperature: 3.0 ~ 4.4V, under 1C, this material first discharge specific capacity is 198.3mAh/g, efficiency is 90.2%; Capability retention >=88.6% after 1C circulation 100 times.
Claims (1)
1. a preparation method for high compacted density lithium nickel cobalt alumina tertiary cathode material, is characterized in that: the method comprises the following steps,
A. configuring 2.0mol/L cobalt nitrate solution, is 6.6 with ammoniacal liquor complexing to pH, numbering solution 1;
Configuration 6.0mol/L NaOH solution, and add 0.4mol/L NH3H2O solution, the two volume ratio is 10:1, numbering solution 2;
Cobalt nitrate, nickel nitrate and aluminum nitrate mixed solution that configuration cation total concentration is 2.0mol/L, wherein nickel cobalt al mole ratio is 0.8:0.15:0.05, with ammoniacal liquor complexing, to pH, is 8.6, numbering solution 3;
Configuration 3.0mol/L NaOH solution, and add 0.8mol/L NH3H2O solution, the two volume ratio is 7:1, numbering solution 4;
B. by the solution configuring 1 and solution 2 hybrid reactions, and controlling solution 2, to make mixed solution pH be 13, and reaction temperature 28-30 ℃, passes into N2 protection in course of reaction; Question response is isolated deposit seed, with deionized water, washs post-drying; At 380-390 ℃ of calcining 6-8h, obtain cobalt oxygen precursor;
C. the cobalt oxygen precursor of preparation is added in reactor, and the solution configuring 3 and solution 4 are pumped into reactor simultaneously, and controlling solution 4, to make mixed solution pH be 10.5, stirs and keep constant temperature 55-60 ℃, in course of reaction, pass into N2 protection; Question response is isolated deposit seed, with deionized water, washs post-drying, obtains nickel hydroxide cobalt aluminium precursor;
D. by lithium carbonate and the Li/M=1.06 ball milling mixing in molar ratio of nickel hydroxide cobalt aluminium precursor; Wherein M is the molal quantity sum of three kinds of elements of nickel cobalt aluminium;
E. Muffle furnace sintering: room temperature-450 ℃,, are not incubated in the time of 450 ℃ by heating rate 3-4 ℃/min; 450-740 ℃, heating rate 1-1.5 ℃/min, 740 ℃ of insulation 18-20h; 740-350 ℃, rate of temperature fall 1.5-2.5 ℃/min, after naturally cooling with furnace temperature, in whole process, atmosphere is air, throughput is 8-10L/min;
F. after fragmentation, obtain the anodal ternary material LiNi0.78Co0.17Mn0.05O2 of lithium nickel cobalt alumina.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106654251A (en) * | 2016-11-30 | 2017-05-10 | 浙江天能能源科技股份有限公司 | Modified lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN109179518A (en) * | 2018-07-16 | 2019-01-11 | 昆明理工大学 | A kind of preparation method of high density doping nickel hydroxide cobalt precursor |
| CN111082030A (en) * | 2019-12-31 | 2020-04-28 | 河北科技大学 | Dual-modified nickel-rich ternary material and preparation method and application thereof |
Citations (4)
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| JPH1116572A (en) * | 1997-06-24 | 1999-01-22 | Sumitomo Metal Mining Co Ltd | Positive electrode material for lithium secondary battery, and preparation of precursor composition thereof |
| US20090176147A1 (en) * | 2005-12-19 | 2009-07-09 | Panasonic Corporation | Lithium Ion Secondary Battery |
| CN102074679A (en) * | 2010-12-18 | 2011-05-25 | 中南大学 | Method for preparing spherical aluminum-doped nickel lithium carbonate for lithium ion battery positive electrode material |
| CN103296263A (en) * | 2012-12-28 | 2013-09-11 | 深圳市天骄科技开发有限公司 | Preparation method of lithium-ion battery positive electrode material spherical nickel-cobalt-lithium aluminate |
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- 2013-12-18 CN CN201310693527.2A patent/CN103715420B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1116572A (en) * | 1997-06-24 | 1999-01-22 | Sumitomo Metal Mining Co Ltd | Positive electrode material for lithium secondary battery, and preparation of precursor composition thereof |
| US20090176147A1 (en) * | 2005-12-19 | 2009-07-09 | Panasonic Corporation | Lithium Ion Secondary Battery |
| CN102074679A (en) * | 2010-12-18 | 2011-05-25 | 中南大学 | Method for preparing spherical aluminum-doped nickel lithium carbonate for lithium ion battery positive electrode material |
| CN103296263A (en) * | 2012-12-28 | 2013-09-11 | 深圳市天骄科技开发有限公司 | Preparation method of lithium-ion battery positive electrode material spherical nickel-cobalt-lithium aluminate |
Non-Patent Citations (1)
| Title |
|---|
| GUORONG HU ET AL: "Synthesis and electrochemical properties of LiNi0.8Co0.15Al0.05O2 prepared from the precursor Ni0.8Co0.15Al0.05OOH", 《JOURNAL OF POWER SOURCES》, vol. 198, no. 2012, 5 October 2011 (2011-10-05), pages 258 - 263 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106654251A (en) * | 2016-11-30 | 2017-05-10 | 浙江天能能源科技股份有限公司 | Modified lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN109179518A (en) * | 2018-07-16 | 2019-01-11 | 昆明理工大学 | A kind of preparation method of high density doping nickel hydroxide cobalt precursor |
| CN111082030A (en) * | 2019-12-31 | 2020-04-28 | 河北科技大学 | Dual-modified nickel-rich ternary material and preparation method and application thereof |
| CN111082030B (en) * | 2019-12-31 | 2023-08-08 | 河北科技大学 | Dual-modified nickel-rich ternary material and preparation method and application thereof |
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