CN103715420B - The preparation method of high-compaction-density lithium nickel cobalt aluminum oxide ternary anode material - Google Patents
The preparation method of high-compaction-density lithium nickel cobalt aluminum oxide ternary anode material Download PDFInfo
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- CN103715420B CN103715420B CN201310693527.2A CN201310693527A CN103715420B CN 103715420 B CN103715420 B CN 103715420B CN 201310693527 A CN201310693527 A CN 201310693527A CN 103715420 B CN103715420 B CN 103715420B
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- cobalt
- nickel cobalt
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- nitrate
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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
-
- 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 present invention relates to the preparation method of lithium electrode anode material, specifically a kind of preparation method of high-compaction-density lithium nickel cobalt aluminum oxide ternary anode material.The method comprises the following steps: a. configures cobalt nitrate solution, uses ammoniacal liquor complexing, numbering solution 1; Configuration NaOH solution, and add NH3H2O solution, numbering solution 2; Configuration cobalt nitrate, nickel nitrate and aluminum nitrate mixed solution, use ammoniacal liquor complexing, numbering solution 3; Configuration NaOH solution, and add NH3H2O solution, numbering solution 4; B. by solution 1 and solution 2 hybrid reaction, cobalt oxygen precursor is obtained; C. cobalt oxygen precursor and solution 3 and solution 4 are reacted, obtain nickel cobalt aluminum hydroxide precursor; D. by lithium carbonate and the mixing of nickel cobalt aluminum hydroxide precursor ball milling; E. Muffle furnace sintering; F. lithium nickel cobalt alumina positive pole ternary material is obtained.Invention increases the compacted density of ternary material, battery capacity and the cycle performance of its material are significantly increased.
Description
Technical field
The present invention relates to the preparation method of lithium electrode anode material, specifically a kind of preparation method of high-compaction-density lithium nickel cobalt aluminum oxide ternary anode 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 improve, and limits 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, provides a kind of and has higher material compacted density, simultaneously the preparation method of the battery capacity of material and the excellent high-compaction-density lithium nickel cobalt aluminum oxide ternary anode material of cycle performance.
The preparation method of high-compaction-density lithium nickel cobalt aluminum oxide ternary anode 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/LNaOH solution, and add 0.4mol/LNH
3h
2o solution, the two volume ratio is 10:1, numbering solution 2;
Configuration cation total concentration is the cobalt nitrate of 2.0mol/L, nickel nitrate and aluminum nitrate mixed solution, and wherein nickel cobalt al mole ratio is 0.8:0.15:0.05, is 8.6 with ammoniacal liquor complexing to pH, numbering solution 3;
Configuration 3.0mol/LNaOH solution, and add 0.8mol/LNH
3h
2o solution, the two volume ratio is 7:1, numbering solution 4;
B. by the solution 1 that configures and solution 2 hybrid reaction, and control solution 2 and make mixed solution pH be 13, reaction temperature 28-30 DEG C, in course of reaction, pass into N2 protection; Question response isolates deposit seed, spends deionized water post-drying; At 380-390 DEG C of calcining 6-8h, obtain cobalt oxygen precursor;
C. the cobalt oxygen precursor of preparation is added in reactor, and the solution 3 configured and solution 4 are pumped into reactor simultaneously, and control solution 4 and make mixed solution pH be 10.5, stir and keep constant temperature 55-60 DEG C, in course of reaction, pass into N2 protection; Question response isolates deposit seed, spends deionized water post-drying, obtains nickel cobalt aluminum hydroxide precursor;
D. by lithium carbonate and the Li/M=1.06 ball milling mixing in molar ratio of nickel cobalt aluminum hydroxide precursor; Wherein M is the molal quantity sum of nickel cobalt aluminium three kinds of elements;
E. Muffle furnace sintering: room temperature-450 DEG C, is not incubated when 450 DEG C by heating rate 3-4 DEG C/min; 450-740 DEG C, heating rate 1-1.5 DEG C/min, 740 DEG C of insulation 18-20h; 740-350 DEG C, rate of temperature fall 1.5-2.5 DEG C/min, after naturally cool with furnace temperature, in whole process, atmosphere is air, and throughput is 8-10L/min;
F., after fragmentation, lithium nickel cobalt alumina positive pole ternary material LiNi is obtained
0.78co
0.17al
0.05o
2.
The present invention is selected by special technological parameter and raw material, effectively can improve the pattern of material granule, improve the compacted density of ternary material, and then improve 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/LNaOH solution, and add 0.4mol/LNH
3h
2o solution, the two volume ratio is 10:1, numbering solution 2;
Configuration cation total concentration is the cobalt nitrate of 2.0mol/L, nickel nitrate and aluminum nitrate mixed solution, and wherein nickel cobalt al mole ratio is 0.8:0.15:0.05, is 8.6 with ammoniacal liquor complexing to pH, numbering solution 3;
Configuration 3.0mol/LNaOH solution, and add 0.8mol/LNH
3h
2o solution, the two volume ratio is 7:1, numbering solution 4;
B. the solution 1 configured and solution 2 are pumped in the reactor of 10L, mixed solution flow velocity is terminate reinforced after 200mL/min, 0.5h, and controls solution 2 and makes mixed solution pH be 13, stir and keep constant temperature 30 DEG C, passing into N2 and protect in course of reaction simultaneously; Question response isolates deposit seed after carrying out 5h, spends deionized water post-drying; At 390 DEG C of calcining 8h, obtain cobalt oxygen precursor, average grain diameter 2.3 μm;
C. the cobalt oxygen precursor of preparation is added in reactor, and the solution 3 configured and solution 4 are pumped into reactor simultaneously, mixed solution flow velocity is 40mL/min, and controls solution 4 and make mixed solution pH be 10.5, stir and keep constant temperature 55 DEG C, in course of reaction, passing into N2 protection; Question response isolates deposit seed after carrying out 15h, spends deionized water post-drying, obtains nickel cobalt aluminum hydroxide precursor, average grain diameter 8.7 μm, 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 cobalt aluminum hydroxide precursor, Ball-milling Time is 4h; Wherein M is the molal quantity sum of nickel cobalt aluminium three kinds of elements;
E. Muffle furnace sintering: room temperature-450 DEG C, is not incubated when 450 DEG C by heating rate 3-4 DEG C/min; 450-740 DEG C, heating rate 1-1.5 DEG C/min, 740 DEG C of insulation 19h; 740-350 DEG C, rate of temperature fall 1.5-2.5 DEG C/min, after naturally cool with furnace temperature, in whole process, atmosphere is air, and throughput is 10L/min;
F. omnipotent fragmentation rear mistake 200 eye mesh screen, obtains lithium nickel cobalt alumina positive pole ternary material LiNi
0.78co
0.17al
0.05o
2.
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 recording this material under 30Mpa is 3.96g/cm
3;
2, SEM observes this material secondary granule-morphology almost spherical;
3, liquid nitrogen absorption method records this material specific surface area is 0.71m
2/ g;
4, battery testing under normal temperature: under 3.0 ~ 4.4V, 1C, this material first discharge specific capacity is 198.3mAh/g, and efficiency is 90.2%; 1C circulates capability retention >=88.6% after 100 times.
Claims (1)
1. a preparation method for high-compaction-density lithium nickel cobalt aluminum oxide ternary anode 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/LNaOH solution, and add 0.4mol/LNH
3h
2o solution, the two volume ratio is 10:1, numbering solution 2;
Configuration cation total concentration is the cobalt nitrate of 2.0mol/L, nickel nitrate and aluminum nitrate mixed solution, and wherein nickel cobalt al mole ratio is 0.8:0.15:0.05, is 8.6 with ammoniacal liquor complexing to pH, numbering solution 3;
Configuration 3.0mol/LNaOH solution, and add 0.8mol/LNH
3h
2o solution, the two volume ratio is 7:1, numbering solution 4;
B. by the solution 1 that configures and solution 2 hybrid reaction, and control solution 2 and make mixed solution pH be 13, reaction temperature 28-30 DEG C, in course of reaction, pass into N2 protection; Question response isolates deposit seed, spends deionized water post-drying; At 380-390 DEG C of calcining 6-8h, obtain cobalt oxygen precursor;
C. the cobalt oxygen precursor of preparation is added in reactor, and the solution 3 configured and solution 4 are pumped into reactor simultaneously, and control solution 4 and make mixed solution pH be 10.5, stir and keep constant temperature 55-60 DEG C, in course of reaction, pass into N2 protection; Question response isolates deposit seed, spends deionized water post-drying, obtains nickel cobalt aluminum hydroxide precursor;
D. by lithium carbonate and the Li/M=1.06 ball milling mixing in molar ratio of nickel cobalt aluminum hydroxide precursor; Wherein M is the molal quantity sum of nickel cobalt aluminium three kinds of elements;
E. Muffle furnace sintering: room temperature-450 DEG C, is not incubated when 450 DEG C by heating rate 3-4 DEG C/min; 450-740 DEG C, heating rate 1-1.5 DEG C/min, 740 DEG C of insulation 18-20h; 740-350 DEG C, rate of temperature fall 1.5-2.5 DEG C/min, after naturally cool with furnace temperature, in whole process, atmosphere is air, and throughput is 8-10L/min;
F., after fragmentation, lithium nickel cobalt alumina positive pole ternary material LiNi is obtained
0.78co
0.17al
0.05o
2.
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| 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 |
| CN109179518B (en) * | 2018-07-16 | 2020-12-15 | 昆明理工大学 | Preparation method of high-density doped nickel cobalt hydroxide precursor |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| 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 |
| WO2007072833A1 (en) * | 2005-12-19 | 2007-06-28 | Matsushita Electric Industrial Co., Ltd. | Lithium ion secondary battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| Synthesis and electrochemical properties of LiNi0.8Co0.15Al0.05O2 prepared from the precursor Ni0.8Co0.15Al0.05OOH;Guorong Hu et al;《Journal of Power Sources》;20111005;第198卷(第2012期);全文 * |
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Effective date of registration: 20180329 Address after: 753000 the Ningxia Hui Autonomous Region Shizuishan high tech Industrial Park, medium and small business incubator No. 9 workshop Patentee after: JIANGSU KING LITHIUM CELL CO., LTD. Address before: 9 No. 212006 Zhenjiang province Jiangsu City Jingkou Industrial Park Jinyang Avenue Patentee before: Jiangsu King Lithium Cell Co.,Ltd. |
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