CN103531763B - A kind of method preparing nickle cobalt lithium manganate - Google Patents
A kind of method preparing nickle cobalt lithium manganate Download PDFInfo
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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
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- 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
- H01M4/50—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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention relates to a kind of method preparing nickle cobalt lithium manganate, adopt sol-gel process and the method that porous alumina formwork method combines to prepare uniform particle sizes, appearance structure is consistent, stable performance is excellent nickel-cobalt lithium manganate material.Its step is by aluminium foil frosted, immersion, cleaning and under the atmosphere of nitrogen, after heat treated, carries out electrochemical polishing treatment to it; Using the aluminium foil after polishing as anode, adopt twice Fabrication porous alumina template by anodization method; The colloidal sol of configuration containing a certain proportion of nickel source, cobalt source, manganese source, lithium source, and porous alumina formwork is soaked in colloidal sol, take out, under certain condition, sintering is repeatedly; Finally, immersed by the Woelm Alumina of nickel-loaded cobalt manganic acid lithium in alkaline solution, filter, cleaning, evaporative crystallization, ball milling sieves, and obtains nickle cobalt lithium manganate product.Operation is simple for this method, and effectively can control appearance structure and the size of crystal, the preparation for high performance nickel-cobalt lithium manganate material provides new approach.
Description
Technical field
The invention belongs to field of lithium ion battery, relate to a kind of preparation method of anode material for lithium-ion batteries, particularly a kind of method preparing nickle cobalt lithium manganate.
Background technology
Lithium ion battery is new green environment protection power supply, has the advantage such as high energy density, high discharge platform, is widely used in the electronic products such as mobile phone, camera, notebook computer.Along with the development of digital product industry, the demand of people to battery increases day by day.Nickle cobalt lithium manganate is a kind of important anode material of lithium battery, and produce and use increasingly extensive, market demand is larger.
The positive electrode of lithium battery is the important component part of lithium battery, is the major effect factor of lithium battery performance, and present business-like positive electrode mainly contains cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate and LiFePO4.In recent years, because the price of nickle cobalt lithium manganate is lower, specific capacity is higher, and the scope of application is more and more wider.
The method of synthesis anode material nickel cobalt manganic acid lithium mainly comprises: solid phase method, coprecipitation, rare earth method, complexometry, sol-gel process.Solid phase method technique is simple, and cost is lower, but distribution of particles is uneven, crystal morphology irregularity; Coprecipitation process is relatively simple, but thing phase uniformity coefficient is not easy to control; There is a large amount of micropore in sol-gel process, will overflow again in dry run much gas and organic substance, and produce shrink, make pattern and size inconsistent.Utilize sol-gel process in conjunction with the technology of template, the appearance and size of the synthesis of nickle cobalt lithium manganate and nickle cobalt lithium manganate can be controlled to combine, the preparation for high performance nickel-cobalt lithium manganate material provides new approach.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of method preparing nickle cobalt lithium manganate.
The present invention is achieved through the following technical solutions:
Prepare a method for nickle cobalt lithium manganate, comprise the following steps:
(1) two-step electrochemical anodizing method is adopted to prepare Woelm Alumina.
(2) (0.3 ~ 1) is pressed in nickel source, cobalt source, manganese source and lithium source: (0.3 ~ 1): (0.3 ~ 1): the mol ratio of 1 is soluble in water, subsequently, adds ethylene glycol in the aqueous solution, after mixing, heating evaporation at 60 ~ 70 DEG C, forms colloidal sol.
(3) Woelm Alumina that step (1) obtains is soaked in step (2) colloidal sol, after taking-up, at 600 DEG C ~ 800 DEG C, sinters 5 ~ 8h, then immerse colloidal sol, then sinter, so repeat 3 ~ 5 times, obtain the Woelm Alumina of nickel-loaded cobalt manganic acid lithium.
(4) Woelm Alumina of nickel-loaded cobalt manganic acid lithium is immersed 30 ~ 60min in 3 ~ 5mol/L alkaline solution.
(5) after filtering, with water and ethanol purge, evaporative crystallization, then ball milling screening, obtains nickle cobalt lithium manganate product.
Employing two-step electrochemical anodizing method described in step (1) prepares Woelm Alumina, and its preparation method comprises the following steps:
(I) aluminium foil is polished, soak, after washed with de-ionized water, be heated to 100 ~ 200 DEG C under nitrogen atmosphere, keep 1 ~ 2h.
(II) with the aluminium foil in step (I) for anode, graphite rod is negative electrode, and calomel electrode is reference electrode, and 0.1 ~ 0.2mol/L acetic acid is electrolyte, under normal temperature, under 4 ~ 6V voltage, electrochemical polish 3 ~ 5min, take out, by washed with de-ionized water, drying, for subsequent use, obtain polished aluminium foil.
(III) with aluminium foil polished in step (II) for anode, graphite rod is negative electrode, and calomel electrode is reference electrode, and 0.1 ~ 0.3mol/L acid is electrolyte, ice-water bath, and under 20 ~ 30V voltage, electrochemical oxidation 1 ~ 2h, obtains the aluminium foil after electrochemical oxidation.
(IV) by after the aluminium foil taking-up after step (III) electrochemical oxidation, washed with de-ionized water, drying, be placed in the mixed solution of acid, at 40 ~ 50 DEG C, soak 30 ~ 60min, obtain the aluminium foil after once oxidation.
(V) with the aluminium foil after once oxidation in step (IV) for anode, graphite rod is negative electrode, and calomel electrode is reference electrode, and 0.2 ~ 0.6mol/L acid is electrolyte, ice-water bath, and under 40 ~ 60V voltage, electrochemical oxidation 3 ~ 6h, obtains the aluminium foil after secondary oxidation.
(VI) aluminium foil after secondary oxidation in step (V) is placed in the mixed liquor that 5 ~ 6mL contains slaine and phosphoric acid and soaks 30 ~ 40min at 50 ~ 60 DEG C; Then add the 0.5mol/L phosphoric acid solution of 5 ~ 6mL, at 50 ~ 60 DEG C, soak 1 ~ 2h; Take out, by washed with de-ionized water, obtain Woelm Alumina.
Aluminium foil described in step (I) adopts sand papering, and with acetone or alcohol-pickled 15 ~ 30min.
Step (III) and the acid described in step (V) are tartaric acid, phosphoric acid or sulfuric acid, and step (III) is identical with the acid described in step (V).
Described in step (IV), the mixed solution of acid is mixed by acetic acid and phosphoric acid, and in the mixed solution of acid, the concentration of acetic acid is 0.5 ~ 1mol/L, and the concentration of phosphoric acid is 0.1 ~ 0.2mol/L, and mixed solution consumption is 5 ~ 6mL.
The concentration of step (V) described acid is 2 times of step (III) described acid concentration; Described voltage is 2 times of the voltage described in step (III).
In step (VI) described mixed liquor, the concentration of slaine is 0.1mol/L, and the concentration of phosphoric acid is 0.1mol/L, and wherein slaine is molysite, zinc salt or pink salt.
Nickel source described in step (2) is nickel acetate, nickel chloride or nickelous sulfate, and cobalt source is cobalt acetate, cobalt chloride or cobaltous sulfate, and manganese source is manganese acetate, manganese chloride or manganese sulfate, and lithium source is lithium hydroxide; The consumption of described water is 100 ~ 200mL; In the described aqueous solution, the concentration in nickel source is 0.3 ~ 2mol/L, and the concentration in cobalt source is 0.3 ~ 2mol/L, and the concentration in manganese source is 0.3 ~ 2mol/L, and the concentration in lithium source is 1 ~ 2mol/L; The volume ratio of described ethylene glycol and water is 1:1.
Step (3) described soaking conditions: temperature is 30 ~ 40 DEG C, soak time is 10 ~ 20min.
Step (4) described alkaline solution is sodium hydroxide solution or potassium hydroxide solution.
The formation of anode material lithium nickle cobalt manganic acid of lithium ion battery experienced by two stages of coring and increment.Nickle cobalt lithium manganate nucleus is nucleation on the hole of aluminium oxide first, and then nickle cobalt lithium manganate crystal grows with the vertical direction of alumina formwork from nucleus.The aperture of aluminium oxide and consistency, determine particle diameter and the consistency of nucleus, thus determine by the particle diameter of the nickle cobalt lithium manganate crystal of nucleus growth and consistency.
For lithium ion cell positive, reactivity site, lithium ion and electron transfer diffusion rate determine the chemical property of lithium ion battery.Reactivity site is more, lithium ion and electron transfer diffusion rate faster, then the capacity of lithium ion battery is larger, and discharge-rate is higher.Sol-gel-template a kind ofly prepares that particle diameter is little, the method for the positive electrode of size uniform.Template used aperture is little and evenly, and the material grown from pore size of template has that particle diameter is little, the feature of size uniform.The material that particle diameter is little, surface area is large, and thus reactivity site is more.The material of size uniform, between particle, mutual transmission efficiency is high, improves lithium ion and electron transfer diffusion rate.Therefore, sol-gel-template can improve the chemical property of anode material for lithium-ion batteries.
Relative to prior art, the present invention has following advantage and effect:
(1) the present invention adopts Woelm Alumina to be template, and nickle cobalt lithium manganate nucleus homogeneous nucleation can grow in the aluminium oxide of porous, and therefore nickle cobalt lithium manganate uniform particle sizes, appearance structure is consistent.
(2) the present invention adopts alumina formwork to be dipped in colloidal sol, then sinters, and repeats method for several times, is conducive to the growth of nickle cobalt lithium manganate crystal load on alumina formwork, solves pore size too little, be unfavorable for the problem of crystal growth.
(3) nickle cobalt lithium manganate prepared of the present invention due to appearance structure consistency high, thus better performances.
Accompanying drawing explanation
Fig. 1 is the SEM figure of nickle cobalt lithium manganate prepared by embodiment 1.
Fig. 2 is the discharge capacity resolution chart of the nickle cobalt lithium manganate that embodiment 1 ~ 3 is prepared with comparative example.
Fig. 3 is the cycle life figure of the nickle cobalt lithium manganate that embodiment 1 ~ 3 is prepared with comparative example.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) be the aluminium foil of 0.5mm by thickness, with 50 object sand paperings, make aluminium foil surface smooth, be conducive to forming ordered porous template, soak 30min with acetone, after washed with de-ionized water, be heated to 100 DEG C under a nitrogen, keep 1h.
(2) take aluminium foil as anode, graphite rod is negative electrode, and calomel electrode is reference electrode, and 0.1mol/L acetic acid solution is electrolyte, and under normal temperature, under 4V voltage, electrochemical polish 3min, after taking-up, uses washed with de-ionized water drying for standby.
(3) with polished aluminium foil for anode, graphite rod is negative electrode, and calomel electrode is reference electrode, and 0.1mol/L sulfuric acid is electrolyte, ice-water bath (about 0 DEG C), under 20V voltage, electrochemical oxidation 1h.
(4) taken out by the aluminium foil after once oxidation, cleaning, after drying, be soaked in the mixed solution of acetic acid and phosphoric acid, in mixed liquor, acetic acid concentration is 0.5mol/L, the concentration of phosphoric acid is 0.1mol/L, and the volume of mixed liquor is 5mm, at 40 DEG C, soak 30min.The object be soaked in by aluminium foil in the mixed liquor of acid is that aluminium flake is through first time anodized, the multiaperture pellumina that sequence is poor can be formed, soaked by mixed acid, the alumina layer that removing first time anodic oxidation is formed, orderly periodicity pit can be left on aluminium substrate surface simultaneously, be conducive to second time anodic oxidation and be formed with the good perforated membrane of sequence.
(5) with the aluminium foil after once oxidation for anode, graphite rod is negative electrode, and calomel electrode is reference electrode, and 0.2mol/L sulfuric acid is electrolyte, ice-water bath, under 40V voltage, electrochemical oxidation 3h.
(6) be soaked in by the aluminium foil after secondary oxidation containing in ferrous sulfate and phosphoric acid mixed solution, in mixed liquor, ferrous sulfate concentration is 0.1mol/L, phosphoric acid concentration is 0.1mol/L, and mixeding liquid volume is 5mL, at 50 DEG C, soak 30min; Add 5mL0.5mol/L phosphoric acid solution again, at 50 DEG C, soak 1h; Take out, by washed with de-ionized water, obtain Woelm Alumina.
(7) prepare the aqueous solution 100mL of 1mol/L nickelous sulfate, 1mol/L cobaltous sulfate, 1mol/L manganese sulfate, 1mol/L lithium hydroxide, add 100mL ethylene glycol, after mixing, heating evaporation at 60 DEG C, forms colloidal sol.
(8) at 30 DEG C, be soaked in 10min in colloidal sol with the Woelm Alumina that step (6) obtains, after taking-up, at 600 DEG C, sinter 5h, repeat to immerse colloidal sol, sintering, then immerses colloidal sol, and reburn knot 3 times, obtains the Woelm Alumina of nickel-loaded cobalt manganic acid lithium.
(9) Woelm Alumina of nickel-loaded cobalt manganic acid lithium is immersed 45min in 4mol/L NaOH.
(10) after filtering, with water and ethanol purge, evaporative crystallization, then ball milling screening, obtains nickle cobalt lithium manganate product.
Prepared nickle cobalt lithium manganate uniform particle sizes, appearance structure is consistent, as shown in Figure 1.
Embodiment 2
(1) be the aluminium foil of 0.5mm by thickness, with 50 object sand paperings, use alcohol-pickled 30min, after washed with de-ionized water, be heated to 150 DEG C under a nitrogen, keep 1.5h.
(2) take aluminium foil as anode, graphite rod is negative electrode, and calomel electrode is reference electrode, and 0.15mol/L acetic acid is electrolyte, and under normal temperature, under 5V voltage, electrochemical polish 4min, after taking-up, uses washed with de-ionized water drying for standby.
(3) with polished aluminium foil for anode, graphite rod is negative electrode, and calomel electrode is reference electrode, and 0.2mol/L tartaric acid is electrolyte, ice-water bath, under 25V voltage, electrochemical oxidation 1.5h.
(4) by after the aluminium foil taking-up after once oxidation, cleaning, drying, being soaked in component is in the solution of 0.75mol/L acetic acid and 0.15mol/L phosphoric acid, and liquor capacity is 5.5mL, at 45 DEG C, soak 45min.
(5) with the aluminium foil after once oxidation for anode, graphite rod is negative electrode, and calomel electrode is reference electrode, and 0.4mol/L tartaric acid is electrolyte, ice-water bath, under 50V voltage, electrochemical oxidation 4h.
(6) aluminium foil after secondary oxidation being soaked in 5.5mL component is in the solution of 0.1mol/L zinc sulfate and 0.1mol/L phosphoric acid, at 55 DEG C, soak 35min; Add 5.5mL0.5mol/L phosphoric acid solution again, at 55 DEG C, soak 1.5h; Take out, by washed with de-ionized water, obtain Woelm Alumina.
(7) prepare the aqueous solution 150mL of 0.3mol/L nickel acetate, 0.3mol/L cobalt acetate, 0.3mol/L manganese acetate, 1mol/L lithium hydroxide, add 150mL ethylene glycol, after mixing, heating evaporation at 65 DEG C, forms colloidal sol.
(8) at 35 DEG C, be soaked in 15min in colloidal sol with the Woelm Alumina that step (6) obtains, after taking-up, at 700 DEG C, sinter 7h, repeat to immerse colloidal sol, sintering, then immerses colloidal sol, and reburn knot 4 times, obtains the Woelm Alumina of nickel-loaded cobalt manganic acid lithium.
(9) Woelm Alumina of nickel-loaded cobalt manganic acid lithium is immersed 45min in 4mol/L potassium hydroxide.
(10) after filtering, with water and ethanol purge, evaporative crystallization, then ball milling screening, obtains nickle cobalt lithium manganate product.
Embodiment 3
(1) be the aluminium foil of 0.5mm by thickness, with 50 object sand paperings, soak 30min with acetone, after washed with de-ionized water, be heated to 200 DEG C under a nitrogen, keep 2h.
(2) take aluminium foil as anode, graphite rod is negative electrode, and calomel electrode is reference electrode, and 0.2mol/L acetic acid is electrolyte, and under normal temperature, under 6V voltage, electrochemical polish 5min, after taking-up, uses washed with de-ionized water drying for standby.
(3) with polished aluminium foil for anode, graphite rod is negative electrode, and calomel electrode is reference electrode, and 0.3mol/L phosphoric acid is electrolyte, ice-water bath (about 0 DEG C), under 30V voltage, electrochemical oxidation 2h.
(4) by after the aluminium foil taking-up after once oxidation, cleaning, drying, being soaked in component is in the solution of 1mol/L acetic acid and 0.2mol/L phosphoric acid, and liquor capacity is 6mL, at 50 DEG C, soak 1h.
(5) with the aluminium foil after once oxidation for anode, graphite rod is negative electrode, and calomel electrode is reference electrode, and 0.6mol/L phosphoric acid is electrolyte, ice-water bath (about 0 DEG C), under 60V voltage, electrochemical oxidation 6h.
(6) aluminium foil after secondary oxidation being soaked in 6mL component is in the solution of 0.1mol/L stannic chloride and 0.1mol/L phosphoric acid, at 60 DEG C, soak 40min; Add 6mL0.5mol/L phosphoric acid solution again, at 60 DEG C, soak 2h; Take out, by washed with de-ionized water, obtain Woelm Alumina.
(7) prepare the aqueous solution 200mL of 0.6mol/L nickel chloride, 0.6mol/L cobalt chloride, 0.6mol/L manganese chloride, 2mol/L lithium hydroxide, add 200mL ethylene glycol, after mixing, heating evaporation at 70 DEG C, forms colloidal sol.
(8) at 40 DEG C, be soaked in 20min in colloidal sol with the Woelm Alumina that step (6) obtains, after taking-up, at 800 DEG C, sinter 8h, repeat to immerse colloidal sol, sintering, then immerses colloidal sol, and reburn knot 5 times, obtains the Woelm Alumina of nickel-loaded cobalt manganic acid lithium.
(9) Woelm Alumina of nickel-loaded cobalt manganic acid lithium is immersed 1h in 5mol/L sodium hydroxide solution.
(10) after filtering, with water and ethanol purge, evaporative crystallization, then ball milling screening, obtains nickle cobalt lithium manganate product.
Comparative example
(1) prepare the aqueous solution 100mL of 1mol/L nickelous sulfate, 1mol/L cobaltous sulfate, 1mol/L manganese sulfate, 1mol/L lithium hydroxide, add 100mL ethylene glycol, after mixing, heating evaporation at 60 DEG C, forms colloidal sol.
(2) at 30 DEG C, be soaked in 10min in colloidal sol with aluminium foil, after taking-up, at 600 DEG C, sinter 5h, repeat to immerse colloidal sol, sintering, then immerses colloidal sol, and reburn knot 3 times, obtains the aluminium foil of nickel-loaded cobalt manganic acid lithium.
(3) aluminium foil of nickel-loaded cobalt manganic acid lithium is immersed 30min in 3mol/L NaOH.
(4) after filtering, with water and ethanol purge, evaporative crystallization, then ball milling screening, obtains nickle cobalt lithium manganate comparative sample.
Performance Detection:
Take lithium metal as negative pole, respectively with the nickle cobalt lithium manganate of embodiment 1, embodiment 2, embodiment 3 and comparative example for positive pole, be assembled into battery, carry out discharge test first with 1C multiplying power, as shown in Figure 2.Result shows, under 1C multiplying power, the first discharge specific capacity of nickel-cobalt lithium manganate cathode material of the present invention is than the height of common sol-gel method, the specific capacity of embodiment 1 is 151.3mAh/g, the specific capacity of embodiment 2 is 149.6mAh/g, the specific capacity of embodiment 3 is 147.9mAh/g, and the specific capacity of comparative example only has 144.1mAh/g.
100 charge and discharge cycles tests are carried out, as shown in Figure 3 with 1C multiplying power.Result shows, the specific capacity of nickel-cobalt lithium manganate cathode material of the present invention is after 100 circulations, than the height of common sol-gel method, the capability retention of embodiment 1 is 90.4%, the capability retention of embodiment 2 is 89.9%, the capability retention of embodiment 3 is 87.3%, and the capability retention of comparative example only has 84.8%.
Above-described embodiment is the present invention's preferably execution mode; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. prepare a method for nickle cobalt lithium manganate, it is characterized in that comprising the following steps:
(1) two-step electrochemical anodizing method is adopted to prepare Woelm Alumina;
(2) (0.3 ~ 1) is pressed in nickel source, cobalt source, manganese source and lithium source: (0.3 ~ 1): (0.3 ~ 1): the mol ratio of 1 is soluble in water, subsequently, in the aqueous solution, ethylene glycol is added, after mixing, heating evaporation at 60 ~ 70 DEG C, forms colloidal sol;
(3) Woelm Alumina that step (1) obtains is soaked in step (2) colloidal sol, after taking-up, at 600 DEG C ~ 800 DEG C, sinters 5 ~ 8h, immerse colloidal sol again, sinter again, so repeat 3 ~ 5 times, obtain the Woelm Alumina of nickel-loaded cobalt manganic acid lithium;
(4) Woelm Alumina of nickel-loaded cobalt manganic acid lithium is immersed 30 ~ 60min in 3 ~ 5mol/L alkaline solution;
(5) after filtering, with water and ethanol purge, evaporative crystallization, then ball milling screening, obtains nickle cobalt lithium manganate product;
Employing two-step electrochemical anodizing method described in step (1) prepares Woelm Alumina, comprises the following steps:
(I) aluminium foil is polished, soak, after washed with de-ionized water, be heated to 100 ~ 200 DEG C under nitrogen atmosphere, keep 1 ~ 2h;
(II) with the aluminium foil in step (I) for anode, graphite rod is negative electrode, calomel electrode is reference electrode, 0.1 ~ 0.2mol/L acetic acid solution is electrolyte, under normal temperature, under 4 ~ 6V voltage, electrochemical polish 3 ~ 5min, take out, by washed with de-ionized water, drying, for subsequent use, obtain polished aluminium foil;
(III) with aluminium foil polished in step (II) for anode, graphite rod is negative electrode, and calomel electrode is reference electrode, 0.1 ~ 0.3mol/L acid is electrolyte, and ice-water bath, under 20 ~ 30V voltage, electrochemical oxidation 1 ~ 2h, obtains the aluminium foil after electrochemical oxidation;
(IV) by the aluminium foil taking-up after step (III) electrochemical oxidation, washed with de-ionized water, drying be placed on acid mixed solution in, at 40 ~ 50 DEG C soak 30 ~ 60min, obtain the aluminium foil after once oxidation; The mixed solution of described acid is mixed by acetic acid and phosphoric acid, and in the mixed solution of acid, the concentration of acetic acid is 0.5 ~ 1mol/L, and the concentration of phosphoric acid is 0.1 ~ 0.2mol/L;
(V) with the aluminium foil after once oxidation in step (IV) for anode, graphite rod is negative electrode, and calomel electrode is reference electrode, 0.2 ~ 0.6mol/L acid is electrolyte, and ice-water bath, under 40 ~ 60V voltage, electrochemical oxidation 3 ~ 6h, obtains the aluminium foil after secondary oxidation;
(VI) aluminium foil after secondary oxidation in step (V) is placed in the mixed liquor that 5 ~ 6mL contains slaine and phosphoric acid, at 50 ~ 60 DEG C, soaks 30 ~ 40min; Then add the 0.5mol/L phosphoric acid solution of 5 ~ 6mL, at 50 ~ 60 DEG C, soak 1 ~ 2h; Take out, by washed with de-ionized water, obtain Woelm Alumina.
2. the method preparing nickle cobalt lithium manganate according to claim 1, is characterized in that: aluminium foil described in step (I) adopts sand papering, and with acetone or alcohol-pickled 15 ~ 30min.
3. the method preparing nickle cobalt lithium manganate according to claim 1, it is characterized in that: step (III) and the acid described in step (V) are tartaric acid, phosphoric acid or sulfuric acid, step (III) is identical with the acid described in step (V).
4. the method preparing nickle cobalt lithium manganate according to claim 1, is characterized in that: described in step (IV), mixed solution consumption is 5 ~ 6mL.
5. the method preparing nickle cobalt lithium manganate according to claim 1, is characterized in that: the concentration of step (V) described acid is 2 times of step (III) described acid concentration; Described voltage is 2 times of the voltage described in step (III).
6. the method preparing nickle cobalt lithium manganate according to claim 1, is characterized in that: in step (VI) described mixed liquor, the concentration of slaine is 0.1mol/L, and the concentration of phosphoric acid is 0.1mol/L, and wherein slaine is molysite, zinc salt or pink salt.
7. the method preparing nickle cobalt lithium manganate according to claim 1, it is characterized in that: the nickel source described in step (2) is nickel acetate, nickel chloride or nickelous sulfate, cobalt source is cobalt acetate, cobalt chloride or cobaltous sulfate, and manganese source is manganese acetate, manganese chloride or manganese sulfate, and lithium source is lithium hydroxide; The consumption of described water is 100 ~ 200mL; In the described aqueous solution, the concentration in nickel source is 0.3 ~ 2mol/L, and the concentration in cobalt source is 0.3 ~ 2mol/L, and the concentration in manganese source is 0.3 ~ 2mol/L, and the concentration in lithium source is 1 ~ 2mol/L; The volume ratio of described ethylene glycol and water is 1:1.
8. the method preparing nickle cobalt lithium manganate according to claim 1, is characterized in that: step (3) described soaking conditions: temperature is 30 ~ 40 DEG C, and soak time is 10 ~ 20min.
9. the method preparing nickle cobalt lithium manganate according to claim 1, is characterized in that: step (4) described alkaline solution is sodium hydroxide solution or potassium hydroxide solution.
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| CN104362335B (en) * | 2014-11-29 | 2016-09-07 | 广州鸿森材料有限公司 | A kind of preparation method of nickel-cobalt lithium manganate cathode material |
| CN105140470B (en) * | 2015-07-10 | 2017-05-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of carbon nanotube @ ternary @ silver composite material of lithium-ion battery |
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