CN106784801A - A kind of preparation method of the modified NCA positive electrodes of power type, high power capacity - Google Patents
A kind of preparation method of the modified NCA positive electrodes of power type, high power capacity Download PDFInfo
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- CN106784801A CN106784801A CN201611258975.XA CN201611258975A CN106784801A CN 106784801 A CN106784801 A CN 106784801A CN 201611258975 A CN201611258975 A CN 201611258975A CN 106784801 A CN106784801 A CN 106784801A
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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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- 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 provides a kind of preparation method of the modified NCA positive electrodes of power type, high power capacity, comprises the following steps：(1) according to molecular formula LiNi0.80Co0.15Al0.05O2In metering ratio weigh lithium acetate, nickel acetate, Co respectively3O4And Al2O3；(2) carry out uniformly mixing to obtain mixture；(3) add mixture to and mixed solution 1 is formed in the mixed solution of lithium acetate, nickel acetate, (4) add and citric acid to mixed solution 1, match and obtain solution 2；(5) it is 9 solution 2 to be adjusted into pH with ammoniacal liquor, forms purple gel；(6) by purple gel drying precursor solid powder；Calcining, grinding, obtain tertiary cathode material, the present invention provide the modified NCA positive electrodes of a kind of power type, high power capacity preparation method have efficiently, quick, energy-conservation the characteristics of, and the tertiary cathode material NCA synthesized by the synthetic method has the advantages that capacity high, high-temperature stable, good cycle, charging rate are fast, with great economical and practical value.
Description
Technical field
The present invention relates to a kind of method for preparing anode material, and in particular to the modified NCA positive pole materials of a kind of power type, high power capacity
The preparation method of material.
Background technology
LiNi0.8Co0.15Al0.05O2Material has superior volumetric properties and power-performance, can be as preferable power
Cell positive material, process in the synthesis of NCA materials, due to Ni2+It is more difficult to be oxidized to Ni3+, during synthesis inevitably it is remaining not
Oxidized Ni2+, due to Ni2+Polarization force is small, easily forms symmetrical unordered rock salt structure high.When there is Ni in NCA2+When, part
Ni2+Replace Ni3+(3b) position so that cationic charge reduction, be keep charge balance, part Ni2+Occupy monovalence Li+(3a) position, this phenomenon is usually said Li/Ni cation disorders distribution or cation mixing, due to Radius is less than Li+(r Li+=0.76), and it is oxidized to the smaller Ni3+ (r of radius during de- lithium
Ni3+=0.56), interlayer partial structurtes are caused to collapse so that Li+It is difficult to the position that insertion is collapsed again, causes the capacity of material to damage
Lose, in addition LiNi of the prior art0.8Co0.15Al0.05O2The preparation method of material often has that production cost is high, efficiency is low
Shortcoming, needs further improvement.
The content of the invention
The technical problems to be solved by the invention are directed to above-mentioned the deficiencies in the prior art and provide a kind of efficient power
The preparation method of the modified NCA positive electrodes of type, high power capacity.
The present invention is for the used technical scheme that solves the above problems：
The present invention provides a kind of preparation method of the modified NCA positive electrodes of power type, high power capacity, comprises the following steps：
(1) according to NCA tertiary cathode material molecular formula LiNi0.80Co0.15Al0.05O2In metering ratio weigh acetic acid respectively
Lithium, nickel acetate, Co3O4And Al2O3；
(2) by Co3O4And Al2O3Uniformly mixed, added ball milling dispersion after dispersant, 200 mesh were crushed after drying
Sieve, the mixture after being sieved；；
(3) by Co prepared in step (2)3O4And Al2O3Mixture is added to the mixed solution of lithium acetate, nickel acetate
Middle formation mixed solution 1,
(4) added and citric acid to mixed solution 1, citric acid is in molar ratio 2 with lithium acetate, nickel acetate:1:1, carry out
Proportioning, obtains solution 2；
(5) it is 9 solution 2 to be adjusted into pH with ammoniacal liquor, is stirred continuously until to form purple gel at 60 DEG C；
(6) purple gel that will be obtained drying precursor solid powder at 80~180 DEG C；And the preceding body that will be obtained
Body solid powder carries out calcine by steps in high temperature process furnances, and the material after calcining is ground, and obtains final product power-type lithium ion
Battery richness lithium tertiary cathode material.
Further, described calcine by steps controls the temperature to carry out precalcining 3h for 350 DEG C first, then with 5 DEG C/
The speed of min is warming up to 800 DEG C of calcining 7h.
Further, the Al2O3Average grain diameter≤200nm.
The beneficial effects of the present invention are：
The preparation method that the present invention provides the modified NCA positive electrodes of a kind of power type, high power capacity has efficient, quick, section
Can the characteristics of, and the tertiary cathode material NCA synthesized by the synthetic method have capacity high, high-temperature stable, good cycle,
The advantages of charging rate is fast, with great economical and practical value.
Brief description of the drawings
Fig. 1 is the X diffraction patterns of tertiary cathode material NCA synthesized by embodiment 2；
Fig. 2 is the SEM figures of tertiary cathode material NCA synthesized by embodiment 2；
Fig. 3 is tertiary cathode material NCA first charge-discharge curves synthesized by embodiment 2；
Fig. 4 is tertiary cathode material NCA room temperature cycles characteristic curves synthesized by embodiment 2；
Fig. 5 is tertiary cathode material NCA high-temperature cycle curves synthesized by embodiment 2；
Specific embodiment
Embodiments of the present invention are specifically illustrated below in conjunction with the accompanying drawings, and accompanying drawing is only for reference and explanation is used, and it is right not constitute
The limitation of scope of patent protection of the present invention.
Embodiment 1
The present embodiment provides a kind of preparation method of the modified NCA positive electrodes of power type, high power capacity, comprises the following steps：
(1) according to NCA tertiary cathode material molecular formula LiNi0.80Co0.15Al0.05O2In metering ratio weigh acetic acid respectively
Lithium, nickel acetate, Co3O4And Al2O3；
(2) by Co3O4And Al2O3Uniformly mixed, added ball milling dispersion after dispersant, 200 mesh were crushed after drying
Sieve, the mixture after being sieved；；
(3) by Co prepared in step (2)3O4And Al2O3Mixture is added to the mixed solution of lithium acetate, nickel acetate
Middle formation mixed solution 1,
(4) added and citric acid to mixed solution 1, citric acid is in molar ratio 2 with lithium acetate, nickel acetate:1:1, carry out
Proportioning, obtains solution 2；
(5) it is 9 solution 2 to be adjusted into pH with ammoniacal liquor, is stirred continuously until to form purple gel at 60 DEG C；
(6) purple gel that will be obtained drying precursor solid powder at 80 DEG C；And the precursor that will be obtained is consolidated
Body powder carries out calcine by steps in high temperature process furnances, and the material after calcining is ground, and obtains final product power-type lithium ion battery
Rich lithium tertiary cathode material.
In the present embodiment, described calcine by steps controls the temperature to carry out precalcining 3h for 350 DEG C first, then with 5 DEG C/
The speed of min is warming up to 800 DEG C of calcining 7h.
In the present embodiment, the Al2O3Average grain diameter≤200nm.
Embodiment 2
The present embodiment provides a kind of preparation method of the modified NCA positive electrodes of power type, high power capacity, comprises the following steps：
(1) according to NCA tertiary cathode material molecular formula LiNi0.80Co0.15Al0.05O2In metering ratio weigh acetic acid respectively
Lithium, nickel acetate, Co3O4And Al2O3；
(2) by Co3O4And Al2O3Uniformly mixed, added ball milling dispersion after dispersant, 200 mesh were crushed after drying
Sieve, the mixture after being sieved；；
(3) by Co prepared in step (2)3O4And Al2O3Mixture is added to the mixed solution of lithium acetate, nickel acetate
Middle formation mixed solution 1,
(4) added and citric acid to mixed solution 1, citric acid is in molar ratio 2 with lithium acetate, nickel acetate:1:1, carry out
Proportioning, obtains solution 2；
(5) it is 9 solution 2 to be adjusted into pH with ammoniacal liquor, is stirred continuously until to form purple gel at 60 DEG C；
(6) purple gel that will be obtained drying precursor solid powder at 150 DEG C；And the precursor that will be obtained is consolidated
Body powder carries out calcine by steps in high temperature process furnances, and the material after calcining is ground, and obtains final product power-type lithium ion battery
Rich lithium tertiary cathode material.
In the present embodiment, described calcine by steps controls the temperature to carry out precalcining 3h for 350 DEG C first, then with 5 DEG C/
The speed of min is warming up to 800 DEG C of calcining 7h.
In the present embodiment, the Al2O3Average grain diameter≤200nm.
Embodiment 3
The present embodiment provides a kind of preparation method of the modified NCA positive electrodes of power type, high power capacity, comprises the following steps：
(1) according to NCA tertiary cathode material molecular formula LiNi0.80Co0.15Al0.05O2In metering ratio weigh acetic acid respectively
Lithium, nickel acetate, Co3O4And Al2O3；
(2) by Co3O4And Al2O3Uniformly mixed, added ball milling dispersion after dispersant, 200 mesh were crushed after drying
Sieve, the mixture after being sieved；；
(3) by Co prepared in step (2)3O4And Al2O3Mixture is added to the mixed solution of lithium acetate, nickel acetate
Middle formation mixed solution 1,
(4) added and citric acid to mixed solution 1, citric acid is in molar ratio 2 with lithium acetate, nickel acetate:1:1, carry out
Proportioning, obtains solution 2；
(5) it is 9 solution 2 to be adjusted into pH with ammoniacal liquor, is stirred continuously until to form purple gel at 60 DEG C；
(6) purple gel that will be obtained drying precursor solid powder at 180 DEG C；And the precursor that will be obtained is consolidated
Body powder carries out calcine by steps in high temperature process furnances, and the material after calcining is ground, and obtains final product power-type lithium ion battery
Rich lithium tertiary cathode material.
In the present embodiment, described calcine by steps controls the temperature to carry out precalcining 3h for 350 DEG C first, then with 5 DEG C/
The speed of min is warming up to 800 DEG C of calcining 7h.
In the present embodiment, the Al2O3Average grain diameter≤200nm.
NCA tertiary cathode materials synthesized by embodiment 2 are analyzed as follows：It can be seen that in institute from Fig. 1 and Fig. 2
The target product synthesized under conditions of selected has crystallinity higher, and as shown in Figure 3, synthesized compound has preferable
Chemical property, initial charge specific capacity reaches 190mAh/g, and first discharge specific capacity reaches 190mAh/g, has Fig. 3 by Fig. 4 institutes
Show that synthesized material has relatively stable cycle performance at ambient temperature, it is left to remain at 173mAh/g by 40 circulations
The right side, as shown in Figure 5, specific discharge capacity remains at 100mAh/g after circulation 50 times under the conditions of 50 DEG C of the high temperature.
The preparation method that the present invention provides the modified NCA positive electrodes of a kind of power type, high power capacity has efficient, quick, section
Can the characteristics of, and the tertiary cathode material NCA synthesized by the synthetic method have capacity high, high-temperature stable, good cycle,
The advantages of compacted density is high, charging rate is fast.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (3)
1. the preparation method of the modified NCA positive electrodes of a kind of power type, high power capacity, it is characterised in that comprise the following steps：
(1) according to NCA tertiary cathode material molecular formula LiNi0.80Co0.15Al0.05O2In metering ratio weigh lithium acetate, second respectively
Sour nickel, Co3O4And Al2O3；
(2) by Co3O4And Al2O3Uniformly mixed, added ball milling dispersion after dispersant, 200 mesh sieves were crushed after drying, obtained
Mixture after sieving；；
(3) by Co prepared in step (2)3O4And Al2O3Mixture is formed in being added to the mixed solution of lithium acetate, nickel acetate
Mixed solution 1,
(4) added and citric acid to mixed solution 1, citric acid is in molar ratio 2 with lithium acetate, nickel acetate:1:1, matched,
Obtain solution 2；
(5) it is 9 solution 2 to be adjusted into pH with ammoniacal liquor, is stirred continuously until to form purple gel at 60 DEG C；
(6) purple gel that will be obtained drying precursor solid powder at 80~180 DEG C；And the precursor that will be obtained is consolidated
Body powder carries out calcine by steps in high temperature process furnances, and the material after calcining is ground, and obtains final product power-type lithium ion battery
Rich lithium tertiary cathode material.
2. the preparation method of the modified NCA positive electrodes of a kind of power type as claimed in claim 2, high power capacity, it is characterised in that：
Described calcine by steps controls the temperature to carry out precalcining 3h for 350 DEG C first, is then warming up to 800 with the speed of 5 DEG C/min
DEG C calcining 7h.
3. the preparation method of the modified NCA positive electrodes of a kind of power type, high power capacity according to claim 1, it is characterised in that：
The Al2O3Average grain diameter≤200nm.
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| CN201611258975.XA CN106784801A (en) | 2016-12-30 | 2016-12-30 | A kind of preparation method of the modified NCA positive electrodes of power type, high power capacity |
| PCT/CN2017/110594 WO2018121100A1 (en) | 2016-12-30 | 2017-11-10 | Method for preparing power-type and high-capacity modified nca anode material |
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| CN201611258975.XA CN106784801A (en) | 2016-12-30 | 2016-12-30 | A kind of preparation method of the modified NCA positive electrodes of power type, high power capacity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018121100A1 (en) * | 2016-12-30 | 2018-07-05 | 徐茂龙 | Method for preparing power-type and high-capacity modified nca anode material |
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| CN112680791A (en) * | 2020-12-09 | 2021-04-20 | 北京理工大学重庆创新中心 | Single crystal type IV-VI-VIII group lithium-rich disordered rock salt structure cathode material and preparation method thereof |
| CN113471424B (en) * | 2021-07-12 | 2022-05-24 | 青海师范大学 | Ternary cathode material of lithium ion battery and preparation method thereof |
| CN114551876A (en) * | 2021-07-28 | 2022-05-27 | 万向一二三股份公司 | Spherical ternary composite cathode material of lithium ion battery and preparation method thereof |
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|---|---|---|---|---|
| CN103159264A (en) * | 2013-03-18 | 2013-06-19 | 昆明理工大学 | Method for preparing positive material NCA of lithium ion cell by virtue of pure solid phase method |
| CN103280574A (en) * | 2013-05-29 | 2013-09-04 | 上海电力学院 | Lithium-enriched ternary anode material of power lithium-ion battery and preparation method of lithium-enriched ternary anode material |
| CN104253265A (en) * | 2013-06-28 | 2014-12-31 | 江南大学 | Cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof |
| CN105810937A (en) * | 2014-12-30 | 2016-07-27 | 河南科隆新能源有限公司 | Preparation method of lithium ion battery cathode material NCA with high specific energy |
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| EP0806397B1 (en) * | 1995-11-24 | 2002-03-27 | Fuji Chemical Industry Co., Ltd. | Lithium-nickel composite oxide, process for preparing the same, and positive active material for secondary battery |
| TW363940B (en) * | 1996-08-12 | 1999-07-11 | Toda Kogyo Corp | A lithium-nickle-cobalt compound oxide, process thereof and anode active substance for storage battery |
| CN103956478A (en) * | 2014-05-07 | 2014-07-30 | 北京理工大学 | Preparation method of high-specific-capacity lithium-rich anode material |
| CN106784801A (en) * | 2016-12-30 | 2017-05-31 | 惠州龙为科技有限公司 | A kind of preparation method of the modified NCA positive electrodes of power type, high power capacity |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159264A (en) * | 2013-03-18 | 2013-06-19 | 昆明理工大学 | Method for preparing positive material NCA of lithium ion cell by virtue of pure solid phase method |
| CN103280574A (en) * | 2013-05-29 | 2013-09-04 | 上海电力学院 | Lithium-enriched ternary anode material of power lithium-ion battery and preparation method of lithium-enriched ternary anode material |
| CN104253265A (en) * | 2013-06-28 | 2014-12-31 | 江南大学 | Cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof |
| CN105810937A (en) * | 2014-12-30 | 2016-07-27 | 河南科隆新能源有限公司 | Preparation method of lithium ion battery cathode material NCA with high specific energy |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018121100A1 (en) * | 2016-12-30 | 2018-07-05 | 徐茂龙 | Method for preparing power-type and high-capacity modified nca anode material |
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