CN103199238B - Anode material for lithium-ion batteries and preparation method thereof - Google Patents
Anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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- CN103199238B CN103199238B CN201310126541.4A CN201310126541A CN103199238B CN 103199238 B CN103199238 B CN 103199238B CN 201310126541 A CN201310126541 A CN 201310126541A CN 103199238 B CN103199238 B CN 103199238B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010405 anode material Substances 0.000 title claims abstract description 13
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000010406 cathode material Substances 0.000 claims abstract description 19
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims 2
- 229910052596 spinel Inorganic materials 0.000 claims 2
- 239000011029 spinel Substances 0.000 claims 2
- 239000013078 crystal Substances 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 abstract description 4
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910019737 (Ni0.5Co0.2Mn0.3)(OH)2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910006025 NiCoMn Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
Anode material for lithium-ion batteries and preparation method thereof, relates to a kind of lithium ion battery complex ternary-manganate cathode material for lithium and preparation method thereof.Anode material for lithium-ion batteries of the present invention is by ternary material precursor Ni
xco
ymn
z(OH)
2, manganate precursor for lithium MnO
2, the baking mixed complex ternary-manganate cathode material for lithium of lithium carbonate, wherein: ternary forerunner Ni
xco
ymn
z(OH)
2particle diameter be 5-10 micron, x:y:z=1:1:1,5:2:3,6:2:2,8:1:1 or 4:2:4; Manganate precursor for lithium MnO
2particle diameter be 2-10 micron; The mol ratio of ternary precursor and electrolytic manganese dioxide is 8:2,7:3 or 6:4.The present invention, under the prerequisite of not expendable material structural stability, reduces costs, and improves material gram volume, improves material circulation performance and high rate performance, improves security performance and the cryogenic property of tertiary cathode material, Optimal improvements preparation technology.
Description
Technical field
The present invention relates to a kind of lithium ion battery complex ternary-manganate cathode material for lithium and preparation method thereof.
Background technology
Lithium ion battery ternary material LiNi
1-x-yco
xmn
yo
2due to high gram volume, the advantage such as fail safe is good, with low cost, operating voltage is mated with existing electrolyte, non-environmental-pollution, be considered to replace cobalt acid lithium and the positive electrode with development potentiality.Due to synergy, the performance of ternary material is better than arbitrary unit material.The ratio of control Ni, Co, Mn element is one of key factor optimizing tertiary cathode material performance, Ni too high levels can make battery safety decline, Co too high levels can make material cost improve, but minimizing two constituent contents can cause again the problems such as material capacity is low, structural instability.The element Ni of current synthetic material, the ratio of Co, Mn are 1:1:1,4:2:4,5:2:3,6:2:2,8:1:1, by coprecipitation, coating modification is carried out to material, but still do not find a better method of modifying to balance the synergy of element, have a strong impact on performance and the product commercialization of material.
With LiNi
0.5co
0.2mn
0.3o
2for the security performance of the power lithium-ion battery of positive electrode is troubling, its cryogenic property also cannot meet the needs of consumer.Therefore in order to improve its security performance and cryogenic property, most power lithium-ion battery manufacturer is by LiNi
0.5co
0.2mn
0.3o
2and LiMn
2o
4used in combination, to improve fail safe and cryogenic property, and improve the market competitiveness of power lithium-ion battery with this.
Summary of the invention
For prior art Problems existing, the invention provides a kind of anode material for lithium-ion batteries and preparation method thereof.
Anode material for lithium-ion batteries of the present invention is by ternary material precursor Ni
xco
ymn
z(OH)
2, manganate precursor for lithium MnO
2, the baking mixed complex ternary-manganate cathode material for lithium of lithium carbonate, wherein: ternary forerunner Ni
xco
ymn
z(OH)
2particle diameter be 5-10 micron, x:y:z=1:1:1,5:2:3,6:2:2,8:1:1 or 4:2:4; Manganate precursor for lithium MnO
2particle diameter be 2-10 micron; The mol ratio of ternary precursor and electrolytic manganese dioxide is 8:2,7:3 or 6:4; The mol ratio of lithium carbonate and both sums is 1.02-1.12:1.
The preparation method of above-mentioned complex ternary-manganate cathode material for lithium is: the presoma of screening granule ternary material and LiMn2O4, after adding lithium carbonate mixing again, calcine after 400-600 rev/min of ball milling 4-12h, rise to 450-600 DEG C with 5-10 DEG C/min heating rate from room temperature, constant temperature 4-6h, 800-950 DEG C is risen to again with same heating rate, constant temperature 10-16h, then lowers the temperature, logical oxygen after cooling 1.5-3h, naturally cool to room temperature after 4-8h, obtain complex ternary-manganate cathode material for lithium.
The presoma of the ternary material that the present invention adopts can be bought by business and obtain, and following coprecipitation also can be adopted to obtain:
Nickel source compound, cobalt source compound, manganese source compound is taken respectively in molar ratio for 1:1:1,5:2:3,6:2:2,8:1:1 or 4:2:4, and be dissolved in after in deionized water and mix, precipitation reagent NaOH or sodium carbonate and a certain amount of complexing agent ammoniacal liquor are dropwise added wherein, control slaine and ammoniacal liquor mol ratio are 1:0.75, the pH value of reaction is between 8-12,50-60 DEG C of reaction 4-16h, and be 400-800 rev/min of constantly stirring with speed, reaction terminates rear suction filtration, cyclic washing, removing impurity, obtains ternary anode material precursor after drying.
Above-mentioned cobalt source compound is cobaltous sulfate, cobalt acetate or cobalt nitrate; Nickel source compound is nickelous sulfate, nickel hydroxide, nickel acetate or nickel nitrate; Manganese source compound is manganese sulfate, manganese acetate or manganese nitrate.
Complex ternary-manganate cathode material for lithium that the present invention adopts the method for simple mixed calcining to prepare can under the prerequisite of not expendable material structural stability, reduce costs, improve material gram volume, improve material circulation performance and high rate performance, improve security performance and the cryogenic property of tertiary cathode material, improve the processing characteristics of ternary material, Optimal improvements preparation technology, its gram volume is 110-150mAh/g simultaneously.
Embodiment
The present invention is further illustrated below, but do not limit to so, everyly modifies to technical solution of the present invention or equivalently to replace, and do not depart from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment one: the presoma of screening granule ternary material and LiMn2O4, then add lithium carbonate roasting together, obtain complex ternary-manganate cathode material for lithium, concrete steps are as follows:
1) nickelous sulfate, cobaltous sulfate, manganese sulfate is taken respectively for 5:2:3 in molar ratio, and be dissolved in after in deionized water and mix, 2mol/L precipitation reagent NaOH and a certain amount of complexing agent ammoniacal liquor are dropwise added wherein, controls slaine and ammoniacal liquor mol ratio is 1:0.75, the pH value of reaction is between 10-11,60 DEG C of reaction 12h, and be 600 revs/min of constantly stirrings with speed, reaction terminates rear suction filtration, cyclic washing, removing impurity, 80 DEG C of dry 24h, synthesis of ternary positive electrode material precursor (Ni
0.5co
0.2mn
0.3) (OH)
2, its particle diameter is 6.5 microns.
Ternary precursor also can be that commercialization is bought.
2) electrolytic manganese dioxide and lithium carbonate is taken respectively, wherein, ternary precursor and electrolytic manganese dioxide mol ratio are 7:3, the mol ratio of lithium carbonate and both sums is 1.05:1, the particle diameter of manganese dioxide is 7 microns, after mixing, calcine after 400 revs/min of ball milling 6h, rise to 600 DEG C with 10 DEG C/min heating rate from room temperature, constant temperature 6h, then rise to 900 DEG C with same heating rate, constant temperature 12h, after cooling 3h, logical oxygen, naturally cools to room temperature after 8h, obtains the complex ternary-manganate cathode material for lithium of simple blend.
Embodiment two: present embodiment prepares complex ternary-manganate cathode material for lithium in accordance with the following steps:
1) nickelous sulfate, cobaltous sulfate, manganese sulfate is taken respectively for 1:1:1 in molar ratio, and be dissolved in after in deionized water and mix, 2mol/L precipitation reagent sodium carbonate sodium and a certain amount of complexing agent ammoniacal liquor are dropwise added wherein, control slaine and ammoniacal liquor mol ratio are 1:0.75, the pH value of reaction is between 8-9,60 DEG C of reaction 12h, and be 600 revs/min of constantly stirrings with speed, reaction terminates rear suction filtration, cyclic washing, removing impurity, 80 DEG C of dry 24h, synthesis of ternary positive electrode material precursor (NiCoMn) (OH)
2, its particle diameter is 8 microns.
Ternary precursor also can be that commercialization is bought.
2) electrolytic manganese dioxide and lithium carbonate is taken respectively, wherein, ternary precursor and electrolytic manganese dioxide mol ratio are 8:2, the mol ratio of lithium carbonate and both sums is 1.05:1, the particle diameter of manganese dioxide is 5 microns, after mixing, calcine after 400 revs/min of ball milling 6h, rise to 500 DEG C with 10 DEG C/min heating rate from room temperature, constant temperature 6h, then rise to 800 DEG C with same heating rate, constant temperature 16h, after cooling 2h, logical oxygen, naturally cools to room temperature after 6h, obtains the complex ternary-manganate cathode material for lithium of simple blend.
Embodiment three: present embodiment prepares complex ternary-manganate cathode material for lithium in accordance with the following steps:
Take ternary precursor Ni respectively
0.8co
0.1mn
0.1(OH)
2, electrolytic manganese dioxide and lithium carbonate, wherein, ternary precursor and electrolytic manganese dioxide mol ratio are 6:4, the mol ratio of lithium carbonate and both sums is 1.05:1, the particle diameter of ternary precursor is 6 microns, the particle diameter of manganese dioxide is 5 microns, after mixing, 400 revs/min of ball millings? calcine after 6h, rise to 500 DEG C with 10 DEG C/min heating rate from room temperature, constant temperature 6h, 800 DEG C are risen to again, constant temperature 16h, logical oxygen after cooling 2h with same heating rate, naturally cool to room temperature after 6h, obtain the complex ternary-manganate cathode material for lithium of simple blend.
Embodiment four: present embodiment prepares complex ternary-manganate cathode material for lithium in accordance with the following steps:
Take ternary precursor Ni respectively
0.4co
0.2mn
0.4(OH)
2, electrolytic manganese dioxide and lithium carbonate, wherein, ternary precursor and electrolytic manganese dioxide mol ratio are 7:3, the mol ratio of lithium carbonate and both sums is 1.05:1, the particle diameter of ternary precursor is 7 microns, the particle diameter of manganese dioxide is 5 microns, after mixing, calcine after 400 revs/min of ball milling 6h, rise to 400 DEG C with 5 DEG C/min heating rate from room temperature, constant temperature 4h, 900 DEG C are risen to again, constant temperature 10h, logical oxygen after cooling 3h with same heating rate, naturally cool to room temperature after 8h, obtain the complex ternary-manganate cathode material for lithium of simple blend.
Claims (5)
1. a preparation method for anode material for lithium-ion batteries, is characterized in that described method is as follows:
Screening granule ternary material precursor Ni
xco
ymn
z(OH)
2with lithium manganate having spinel structure presoma electrolysis MnO
2, then adding lithium carbonate mixing, the mol ratio controlling ternary precursor and electrolytic manganese dioxide is 8: 2,7: 3 or 6: 4, described ternary forerunner Ni
xco
ymn
z(OH)
2in, x: y: z=1: 1: 1,5: 2: 3,6: 2: 2,8: 1: 1 or 4: 2: 4, calcine after 400-600 rev/min of ball milling 4-12h, rise to 450-600 DEG C with 5-10 DEG C/min heating rate from room temperature, constant temperature 4-6h, 800-950 DEG C is risen to again with same heating rate, constant temperature 10-16h, then lowers the temperature, logical oxygen after cooling 1.5-3h, naturally cool to room temperature after 4-8h, obtain the ternary-manganate cathode material for lithium of different crystal forms compound.
2. the preparation method of anode material for lithium-ion batteries according to claim 1, is characterized in that the particle diameter of described ternary forerunner is 5-10 micron, and the particle diameter of lithium manganate having spinel structure presoma is 5-10 micron.
3. the preparation method of anode material for lithium-ion batteries according to claim 1, is characterized in that the mol ratio of described lithium carbonate and ternary material precursor and manganese dioxide sum is 1.05: 1.
4. the preparation method of anode material for lithium-ion batteries according to claim 3, is characterized in that described ternary forerunner Ni
xco
ymn
z(OH)
2employing coprecipitation is prepared from, and concrete steps are as follows:
Be 1: 1: 1 in molar ratio, 5: 2: 3, 6: 2: 2, 8: 1: 1 or 4: 2: 4 take nickel source compound respectively, cobalt source compound, manganese source compound, and be dissolved in after in deionized water and mix, precipitation reagent NaOH or sodium carbonate and a certain amount of complexing agent ammoniacal liquor are dropwise added wherein, control slaine and ammoniacal liquor mol ratio are 1: 0.75, the pH value of reaction is between 8-12, 50-60 DEG C of reaction 4-16h, and be 400-800 rev/min of constantly stirring with speed, reaction terminates rear suction filtration, cyclic washing, removing impurity, ternary anode material precursor is obtained after drying.
5. the preparation method of anode material for lithium-ion batteries according to claim 4, is characterized in that described cobalt source compound is cobaltous sulfate, cobalt acetate or cobalt nitrate; Nickel source compound is nickelous sulfate, nickel hydroxide, nickel acetate or nickel nitrate; Manganese source compound is manganese sulfate, manganese acetate or manganese nitrate.
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|---|---|---|---|---|
| CN103413926B (en) * | 2013-08-31 | 2015-04-15 | 张宝 | Preparation method of lithium nickel cobalt manganese oxide precursor |
| CN104993121B (en) * | 2015-05-21 | 2017-10-10 | 中信国安盟固利电源技术有限公司 | A kind of nickel manganese blending anode material for lithium-ion batteries and preparation method thereof |
| CN107394197B (en) * | 2017-07-18 | 2021-05-25 | 宁波富理电池材料科技有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN107528060A (en) * | 2017-09-05 | 2017-12-29 | 国联汽车动力电池研究院有限责任公司 | A kind of nickelic positive electrode of gradient and preparation method thereof and lithium ion battery |
| CN107946578B (en) * | 2017-11-27 | 2020-07-17 | 中南大学 | Lithium cobaltate-coated nickel cobalt lithium aluminate cathode material and preparation method thereof |
| CN110247031A (en) * | 2019-05-24 | 2019-09-17 | 乳源东阳光磁性材料有限公司 | Nickelic tertiary cathode material of a kind of cobalt acid lithium cladding and preparation method thereof |
| CN110416540A (en) * | 2019-07-26 | 2019-11-05 | 陕西科技大学 | A kind of nickelic tertiary cathode material and preparation method thereof |
| CN111129463B (en) * | 2019-12-26 | 2020-11-17 | 格林美股份有限公司 | Preparation method of MOF-coated single crystal ternary cathode material and precursor thereof |
| CN111816875A (en) * | 2020-07-01 | 2020-10-23 | 淮安新能源材料技术研究院 | Composite cathode material of aluminum-titanium double-doped lithium manganate and 523-type ternary material and preparation method thereof |
| CN112909242B (en) * | 2021-05-08 | 2021-07-16 | 蜂巢能源科技有限公司 | Cobalt-free cathode material and preparation method and application thereof |
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| CN102447097A (en) * | 2010-10-09 | 2012-05-09 | 青海佛照锂电正极材料有限公司 | Preparation method of lithium ion cathode material nickel manganese cobalt |
| CN102593442A (en) * | 2012-03-02 | 2012-07-18 | 宁波金和新材料股份有限公司 | Preparation method of high compact density lithium battery cathode material |
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