CN103682316A - Method for preparing ternary anode material of long-service-life and high-capacity lithium ion battery - Google Patents
Method for preparing ternary anode material of long-service-life and high-capacity lithium ion battery Download PDFInfo
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- CN103682316A CN103682316A CN201310711940.7A CN201310711940A CN103682316A CN 103682316 A CN103682316 A CN 103682316A CN 201310711940 A CN201310711940 A CN 201310711940A CN 103682316 A CN103682316 A CN 103682316A
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000010405 anode material Substances 0.000 title description 3
- 239000010406 cathode material Substances 0.000 claims abstract description 67
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000001354 calcination Methods 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000007774 positive electrode material Substances 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 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
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 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
- 239000012535 impurity Substances 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 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
- 229910052759 nickel Inorganic materials 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
- 238000003756 stirring Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 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
- 238000000975 co-precipitation Methods 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
- 239000007791 liquid phase Substances 0.000 claims description 2
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 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
- 239000007790 solid phase Substances 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims 1
- 229940044175 cobalt sulfate Drugs 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000002427 irreversible effect Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 2
- 238000009830 intercalation Methods 0.000 abstract 1
- 230000002687 intercalation Effects 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 238000001994 activation Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 230000004087 circulation Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000004088 simulation Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910019737 (Ni0.5Co0.2Mn0.3)(OH)2 Inorganic materials 0.000 description 2
- 229910006025 NiCoMn Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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Classifications
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
长寿命、高容量锂离子电池三元正极材料的制备方法，属于材料合成技术领域。所述方法为：称取锂源和NixCoyMnz(OH)2均匀混合，400~600℃预烧2~6h，700~1000℃煅烧6~16h；将三元正极材料、锂源及纳米TiO2混合均匀；在700~950℃煅烧3~8h，得到二次加锂煅烧三元正极材料。本发明通过二次加锂煅烧制备三元正极材料，利用二次加锂煅烧引入的额外锂源对负极进行电化学预嵌锂。同时，Ti4+掺杂能有效提高Li+扩散速率，减少不可逆容量损失。在2.3~4.6V区间内，放电平台延长，材料的首次放电容量、循环性能和倍率性能显著提高。本发明简单有效，经济实用，工业化应用效果明显。The invention discloses a method for preparing a ternary cathode material for a lithium-ion battery with long life and high capacity, and belongs to the technical field of material synthesis. The method is as follows: weighing the lithium source and Ni x Co y Mnz (OH) 2 and mixing them uniformly, pre-calcining at 400-600°C for 2-6 hours, and calcining at 700-1000°C for 6-16 hours; and nano-TiO 2 are evenly mixed; calcined at 700-950°C for 3-8 hours to obtain a secondary lithium-added calcined ternary cathode material. In the present invention, the ternary positive electrode material is prepared by secondary lithium addition and calcination, and the electrochemical pre-intercalation of lithium is performed on the negative electrode by using the additional lithium source introduced by the secondary lithium addition and calcination. At the same time, Ti 4+ doping can effectively increase the Li + diffusion rate and reduce the irreversible capacity loss. In the range of 2.3~4.6V, the discharge platform is extended, and the initial discharge capacity, cycle performance and rate performance of the material are significantly improved. The invention is simple and effective, economical and practical, and has obvious industrial application effect.
Description
Technical field
The invention belongs to field of material synthesis technology, relate to a kind of preparation method of anode material for lithium-ion batteries, relate in particular to the preparation method of long-life, high-capacity lithium ion cell tertiary cathode material.
Background technology
Lithium ion battery, as another secondary cell after lead-acid battery, nickel-cadmium cell and Ni-MH battery, has the remarkable advantages such as memory-less effect, operating voltage is high, self-discharge rate is little, is the one preferred technique that solves the problems such as the contemporary energy and biological environment.In recent years, lithium ion battery is used widely in high-energy battery field, and expands to gradually electrokinetic cell field.
In lithium ion battery forms, positive electrode is determining the main performance of battery.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, the positive electrode that is considered to replace cobalt acid lithium and has development potentiality receives much concern always.But the poor shortcoming of existing tertiary cathode material cycle performance has restricted its development as electrokinetic cell, and as the power battery anode material that has potential using value, its energy density still needs further to be improved.
Usually, battery can be because forming solid electrolyte interface (SEI) film in battery cathode (lithium metal or graphite cathode etc.) when first charge-discharge, this SEI film forming process is irreversible, consumed the part lithium source in positive electrode, seriously limit the utilance of positive electrode, reduced actual reversible specific capacity and the cycle performance of lithium ion battery.
As can be seen here, the spontaneous process of SEI film has become the technical bottleneck of limiting lithium ion performance, in the urgent need to research and development, can offset the technical matters that SEI film forms the negative effect that brings, for the preparation of high power capacity, extended-life lithium ion battery provides technical guarantee.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of long-life, high-capacity lithium ion cell tertiary cathode material, adds lithium calcining by secondary and prepares tertiary cathode material, and the extra lithium source anticathode that utilizes secondary to add lithium calcining introducing carries out the pre-embedding lithium of electrochemistry.Meanwhile, Ti
4+doping can effectively improve Li
+diffusion rate, reduces irreversible capacity loss.In 2.3 ~ 4.6V interval, discharge platform extends, and discharge capacity first, cycle performance and the high rate performance of material significantly improve.The present invention is simply effective, economical and practical, industrial applications successful.
The present invention prepares long-life, high-capacity lithium ion cell tertiary cathode material in accordance with the following steps:
One, Li:Ni in molar ratio
xco
ymn
z(OH)
2=1 ~ 1.2:1 takes lithium source and ternary material presoma Ni
xco
ymn
z(OH)
2evenly mix, with 5 ~ 10 ℃/min heating rate, from room temperature, rise to 400 ~ 600 ℃, pre-burning 2 ~ 6 h, then rise to 700 ~ 1000 ℃ with identical heating rate, calcining 6 ~ 16 h, obtain tertiary cathode material;
Two, by the tertiary cathode material obtaining, lithium source and nano-TiO
21:0.02 ~ 0.15:0 ~ 0.05 takes and mixes in molar ratio, and this step lithium used source is identical with step 1 lithium derived components used;
Three, mixture is risen to 700 ~ 950 ℃ with 5 ~ 10 ℃/min heating rate from room temperature, calcining 3 ~ 8 h, obtain secondary and add lithium calcining tertiary cathode material.
In above-mentioned preparation method, described ternary forerunner Ni
xco
ymn
z(OH)
2d50 particle diameter be 5 ~ 10 microns.
In above-mentioned preparation method, described ternary forerunner Ni
xco
ymn
z(OH)
2in, x:y:z=1:1:1,5:2:3,70:15:15,8:1:1 or 42:16:42.
In above-mentioned preparation method, described ternary precursor Ni
xco
ymn
z(OH)
2can buy acquisition by business, also can adopt following coprecipitation to obtain:
In molar ratio for 1:1:1,5:2:3,70:15:15,8:1:1 or 42:16:42 take respectively nickel source compound, cobalt source compound, manganese source compound, and be dissolved in deionized water and mix, precipitation reagent NaOH or sodium carbonate and a certain amount of complexing agent ammoniacal liquor are dropwise added wherein, controlling slaine and ammoniacal liquor mol ratio is 1:0.75, the pH value of reaction is between 8 ~ 12,50 ~ 60 ℃ of reaction 4 ~ 16 h, and take speed as 400 ~ 800 revs/min of constantly stirrings, reaction finishes rear suction filtration, cyclic washing, remove impurity, after being dried, obtain tertiary cathode material presoma.
In above-mentioned preparation method, 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.
In above-mentioned preparation method, described lithium source is one or more the mixture in lithium hydroxide, lithium acetate, lithium nitrate, lithium ethoxide, lithium formate, lithium carbonate.
In above-mentioned preparation method, described hybrid mode be liquid phase mix and solid phase mixing in a kind of.
In above-mentioned preparation method, described secondary clacining temperature is lower than calcining heat first.
In above-mentioned preparation method, described calcination atmosphere is air.
The present invention adds lithium calcining by secondary and introduces extra lithium source for tertiary cathode material, and this extra lithium source can, for negative pole carries out the pre-embedding lithium of electrochemistry in activation process, effectively supplement lithium ion battery and consume lithium source because forming SEI film.Meanwhile, Ti
4+doping can effectively improve Li
+diffusion rate, reduces irreversible capacity loss.In 2.3 ~ 4.6V interval, discharge platform extends, and discharge capacity first, cycle performance and the high rate performance of material significantly improve.Technique of the present invention is simple, industrial applications successful, and the tertiary cathode material of preparation has higher capacity and excellent cycle performance.
Accompanying drawing explanation
Fig. 1 is that secondary prepared by the present invention adds the XRD figure that lithium is calcined tertiary cathode material.
Fig. 2 is that secondary prepared by the present invention adds the SEM figure that the multiplication factor of lithium calcining tertiary cathode material is 1800.
Fig. 3 is that secondary prepared by the present invention adds the SEM figure that the multiplication factor of lithium calcining tertiary cathode material is 3500.
Fig. 4 is the charging and discharging curve that the secondary of the specific embodiment of the invention one preparation adds lithium calcining tertiary cathode material.
Fig. 5 is the cycle performance curve (1C multiplying power) that the secondary of the specific embodiment of the invention one preparation adds lithium calcining tertiary cathode material.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited to this; every technical solution of the present invention is modified or is equal to replacement, and not departing 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: present embodiment is prepared in accordance with the following steps secondary and added lithium calcining tertiary cathode material:
One, for 1:1:1, take respectively nickelous sulfate, cobaltous sulfate, manganese sulfate in molar ratio, and mix after being dissolved in deionized water, 2 mol/L precipitation reagent sodium carbonate and a certain amount of complexing agent ammoniacal liquor are dropwise added wherein, controlling slaine and ammoniacal liquor mol ratio is 1:0.75, the pH value of reaction is between 8 ~ 9,60 ℃ of reaction 12 h, and take speed as 600 revs/min of constantly stirrings, reaction finishes rear suction filtration, cyclic washing, remove impurity, 80 ℃ of dry 24 h, synthesis of ternary positive electrode presoma (NiCoMn) is (OH)
2, its D50 particle diameter is 8 microns.
Ternary precursor also can be bought acquisition by business.
Two, Li:NiCoMn (OH) in molar ratio
2=1.05:1 takes lithium hydroxide and tertiary cathode material presoma, and evenly mixes with alcohol mixed solution at deionized water, with 10 ℃/min heating rate, from room temperature, rises to 500 ℃, pre-burning 5 h, with identical heating rate, rise to 950 ℃ again, calcining 13 h, obtain tertiary cathode material;
Three, taking is the tertiary cathode material of 1:0.015:0.002, above-mentioned lithium source, nano-TiO in molar ratio
2, at deionized water, evenly mix with alcohol mixed solution;
Four, said mixture is put into industrialization kiln in air atmosphere, with 20 ℃/min heating rate, from room temperature, risen to 700 ℃ and calcine 8 h, obtain secondary and add lithium calcining tertiary cathode material.
The XRD that secondary prepared by present embodiment adds lithium calcining tertiary cathode material as shown in Figure 1; As shown in Figures 2 and 3, the powder particle that this secondary adds lithium calcining tertiary cathode material is spherical, and average grain diameter is about 10 microns, and BET specific area is 0.21 m
2/ g.The secondary obtaining is added to lithium calcining tertiary cathode material assembly simulation lithium ion battery, carry out electrochemical property test, with 0.2 C activation, carry out, efficiency can reach 86.5% first; As shown in Figure 4, under 1C, charging and discharging capacity can reach respectively 172.2 mAh/g and 171.8 mAh/g; As shown in Figure 5, carry out the rear specific discharge capacity of 50 circulations and can reach 164.1 mAh/g under 1C, capability retention is 95.5%.
Embodiment two: present embodiment is prepared in accordance with the following steps secondary and added lithium calcining tertiary cathode material:
One, for 5:2:3, take respectively nickelous sulfate, cobaltous sulfate, manganese sulfate in molar ratio, and mix after being dissolved in deionized water, 2mol/L precipitation reagent NaOH and a certain amount of complexing agent ammoniacal liquor are dropwise added wherein, controlling slaine and ammoniacal liquor mol ratio is 1:0.75, the pH value of reaction is between 10 ~ 11,60 ℃ of reaction 12h, and take speed as 600 revs/min of constantly stirrings, reaction finishes rear suction filtration, cyclic washing, remove impurity, 80 ℃ of dry 24h, synthesis of ternary positive electrode presoma (Ni
0.5co
0.2mn
0.3) (OH)
2, its D50 particle diameter is 9 microns.
Ternary precursor also can be bought acquisition by business.
Two, Li:(Ni in molar ratio
0.5co
0.2mn
0.3) (OH)
2=1.03:1 takes lithium acetate and tertiary cathode material presoma, and evenly mixes with alcohol mixed solution at deionized water, with 15 ℃/min heating rate, from room temperature, rises to 500 ℃, pre-burning 5 h, with identical heating rate, rise to 900 ℃ again, calcining 12h, obtains tertiary cathode material;
Three, taking is the tertiary cathode material of 1:0.015:0.002, above-mentioned lithium source, nano-TiO in molar ratio
2, at deionized water, evenly mix with alcohol mixed solution;
Four, said mixture is put into industrialization kiln in air atmosphere, with 15 ℃/min heating rate, from room temperature, risen to 800 ℃ and calcine 8 h, obtain secondary and add lithium calcining tertiary cathode material.
The powder particle that secondary prepared by present embodiment adds lithium calcining tertiary cathode material is spherical, and average grain diameter is about 12 microns.The secondary obtaining is added to lithium calcining tertiary cathode material assembly simulation lithium ion battery, carry out electrochemical property test, with 0.2 C activation, carry out, efficiency can reach 85.9% first; Under 1C, charging and discharging capacity can reach respectively 168.7 mAh/g and 167.4 mAh/g; Carry out 50 circulations under 1C after, specific discharge capacity can reach 160.2 mAh/g, and capability retention is 95.7%.
Embodiment three: present embodiment is prepared in accordance with the following steps secondary and added lithium calcining tertiary cathode material:
One, Li:Ni in molar ratio
0.42co
0.16mn
0.42(OH)
2=1.10:1 takes lithium carbonate and tertiary cathode material presoma, and evenly mixes with alcohol mixed solution at deionized water, with 20 ℃/min heating rate, from room temperature, rises to 500 ℃, pre-burning 5 h, with identical heating rate, rise to 1000 ℃ again, calcining 10 h, obtain tertiary cathode material;
Two, taking is the tertiary cathode material of 1:0.015:0.002, above-mentioned lithium source, nano-TiO in molar ratio
2, at deionized water, evenly mix with alcohol mixed solution;
Three, said mixture is put into industrialization kiln in air atmosphere, with 20 ℃/min heating rate, from room temperature, risen to 850 ℃ and calcine 5 h, obtain secondary and add lithium calcining tertiary cathode material.
The powder particle that secondary prepared by present embodiment adds lithium calcining tertiary cathode material is spherical, and average grain diameter is about 10 microns.The secondary obtaining is added to lithium calcining tertiary cathode material assembly simulation lithium ion battery, carry out electrochemical property test, with 0.2 C activation, carry out, efficiency can reach 87.1% first; Under 1C, charging and discharging capacity can reach respectively 174.7 mAh/g and 172.4 mAh/g; Carry out 50 circulations under 1C after, specific discharge capacity can reach 165.4 mAh/g, and capability retention is 95.9%.
Embodiment four: present embodiment is prepared in accordance with the following steps secondary and added lithium calcining tertiary cathode material:
One, Li:Ni in molar ratio
0.70co
0.15mn
0.15(OH)
2=1.05:1 takes lithium source and tertiary cathode material presoma, lithium source is the mixture that lithium acetate, lithium nitrate mass ratio are 1:1, and evenly mix with alcohol mixed solution at deionized water, with 20 ℃/min heating rate, from room temperature, rise to 500 ℃, pre-burning 5 h, with identical heating rate, rise to 1000 ℃ again, calcining 10 h, obtain tertiary cathode material;
Two, taking is the tertiary cathode material of 1:0.015:0.002, above-mentioned lithium source, nano-TiO in molar ratio
2, at deionized water, evenly mix with alcohol mixed solution;
Three, said mixture is put into industrialization kiln in air atmosphere, with 20 ℃/min heating rate, from room temperature, risen to 900 ℃ and calcine 8 h, obtain secondary and add lithium calcining tertiary cathode material.
The powder particle that secondary prepared by present embodiment adds lithium calcining tertiary cathode material is spherical, and average grain diameter is about 11 microns.The secondary obtaining is added to lithium calcining tertiary cathode material assembly simulation lithium ion battery, carry out electrochemical property test, with 0.2 C activation, carry out, efficiency can reach 85.7% first; Under 1C, charging and discharging capacity can reach respectively 166.7 mAh/g and 165.4 mAh/g; Carry out 50 circulations under 1C after, specific discharge capacity can reach 158.8 mAh/g, and capability retention is 96.0%.
Embodiment five: present embodiment is prepared in accordance with the following steps secondary and added lithium calcining tertiary cathode material:
One, by execution mode two, prepare tertiary cathode material forerunner (Ni
0.5co
0.2mn
0.3) (OH)
2, its D50 particle diameter is 9 microns.
Ternary precursor also can be bought acquisition by business.
Two, Li:(Ni in molar ratio
0.5co
0.2mn
0.3) (OH)
2=1.03:1 takes lithium source and tertiary cathode material presoma, lithium source is the mixture that lithium acetate, lithium nitrate and lithium carbonate mass ratio are 1:1:1, and evenly mix with alcohol mixed solution at deionized water, with 15 ℃/min heating rate, from room temperature, rise to 500 ℃, pre-burning 5 h, with identical heating rate, rise to 900 ℃ again, calcining 12h, obtains tertiary cathode material;
Three, taking is the tertiary cathode material of 1:0.015:0.002, above-mentioned lithium source, nano-TiO in molar ratio
2, at deionized water, evenly mix with alcohol mixed solution;
Four, said mixture is put into industrialization kiln in air atmosphere, with 15 ℃/min heating rate, from room temperature, risen to 800 ℃ and calcine 8 h, obtain secondary and add lithium calcining tertiary cathode material.
The powder particle that secondary prepared by present embodiment adds lithium calcining tertiary cathode material is spherical, and average grain diameter is about 12 microns.The secondary obtaining is added to lithium calcining tertiary cathode material assembly simulation lithium ion battery, carry out electrochemical property test, with 0.2 C activation, carry out, efficiency can reach 86.3% first; Under 1C, charging and discharging capacity can reach respectively 171.7 mAh/g and 170.4 mAh/g; Carry out 50 circulations under 1C after, specific discharge capacity can reach 163.2 mAh/g, and capability retention is 95.8%.
Claims (10)
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