CN106025199A - Preparation method of nanometer lithium lanthanum titanate coated 0.5Li2MnO3 0.5LiNi0.5Mn0.5O2 material - Google Patents

Preparation method of nanometer lithium lanthanum titanate coated 0.5Li2MnO3 0.5LiNi0.5Mn0.5O2 material Download PDF

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CN106025199A
CN106025199A CN201610340380.2A CN201610340380A CN106025199A CN 106025199 A CN106025199 A CN 106025199A CN 201610340380 A CN201610340380 A CN 201610340380A CN 106025199 A CN106025199 A CN 106025199A
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lithium
preparation
nickel
source
lanthanum
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王秀田
海滨
杨玉梅
朱广燕
赵志刚
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Chery Automobile Co Ltd
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SAIC Chery Automobile Co Ltd
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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 invention provides a preparation method of a nanometer lithium lanthanum titanate coated 0.5Li2MnO3 0.5LiNi0.5Mn0.5O2 material. Compared with the prior art, the method has the advantages that the lithium lanthanum titanate is a very good lithium conductor, is applicable to fast migration of lithium ions, and achieves the effect of improving the material rate capability; meanwhile, due to the surface coating, the protection effect is achieved on the body material; the contact between the material and electrolyte can be reduced; the occurrence of side reaction can be reduced; the manganese ion dissolution separation due to corrosion of HF on the material per se is reduced; the coulombic efficiency and the circulation stability are improved. By controlling the preparation process parameters, the 0.5Li2MnO3 0.5LiNi0.5Mn0.5O2 material with good performance is obtained through preparation; then, the material is subjected to uniform nanometer lithium lanthanum titanate surface coating, so that the first-time coulombic efficiency, the rate capability and the circulation stability are improved.

Description

A kind of 0.5Li of nano barium titanate lanthanum lithium cladding2MnO3·0.5LiNi0.5Mn0.5O2Material Preparation method
Technical field
The invention belongs to technical field of lithium ion, relate to changing of anode material for lithium-ion batteries Journal of Sex Research, is specifically related to a kind of nano barium titanate lanthanum lithium cladding 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2The preparation method of material.
Background technology
Electric automobile field has the anode material for lithium-ion batteries of application prospect mainly to have iron phosphate Lithium, LiMn2O4 etc..Although the LiFePO4 cost price with olivine structural is low, the most forthright Can good, but due to its energy density low (generally less than 120Wh/Kg), processing concordance poor, The problems such as poor performance at low temperatures, limit its industrialization level and application prospect；It addition, have point The LiMn2O4 of spinel structure has three-dimensional deintercalation channel design, the one-tenth being especially suitable for lithium ion and passing in and out The advantages such as this low, good rate capability, but owing to its specific capacity is low, high temperature cyclic performance difference etc. Defect, have impact on the large-scale application of such material.
Therefore people are actively finding new lithium ion power battery cathode material, Li2MnO3 With layered oxide LMO2The rich lithium richness manganese anode material (being called for short LNMO) that (M=Ni, Co, Mn) forms It is a kind of α-NaFeO2Type solid-solution material, has specific capacity height, running voltage height, energy The high (> 250Wh/Kg of density), the safety advantage such as preferably is it is considered to be most under application prospect One of lithium ion power battery cathode material of a generation, becomes current anode material for lithium-ion batteries Study hotspot.
Although but people under study for action it was also found that LNMO have higher specific discharge capacity and Energy density, but there is also that coulombic efficiency first is low, high rate performance is poor, capacity attenuation etc. is asked Topic, so needing by the surface modification of this kind of material is reached electric automobile to lithium-ion electric The requirement of the performances such as pond high magnification, high-energy-density and long-life.
In order to overcome high rate performance difference that rich lithium richness manganese solid solution battery material occurs in the application and The problems such as capacity attenuation, current industry mainly passes through material for the solution of problem above Bulk doped is or/and what Surface coating was carried out, and the kind of Surface coating material and battery material The performance of material is closely-related.
Summary of the invention
It is an object of the invention to, it is provided that a kind of nano barium titanate lanthanum lithium cladding 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2The preparation method of material, improves its coulomb effect first Rate, high rate performance and cyclical stability.
A kind of nano barium titanate lanthanum lithium cladding that the present invention provides 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2The preparation method of material, comprises the following steps:
(1) by preparation nickel presoma and the mixed aqueous solution of manganese presoma, alkaline solution is added, Regulation pH is 10-12, after stirring, through being centrifuged, wash, being dried to obtain nickel manganese presoma Ni0.5Mn1.5(OH)4；
(2) nickel manganese presoma Ni prepared by lithium source and step (1)0.5Mn1.5(OH)4Mixing, Obtain mixed powder；
(3) by the mixed powder of step (2) gained under an oxygen-containing atmosphere, heating and thermal insulation is calcined, Naturally cool to room temperature, i.e. obtain 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material；
(4) titanium source is dissolved in the mixed solution of hydrogenperoxide steam generator and ammonia spirit, adds Stabilizer, adds lithium salts and the nitric acid in lanthanum source or sulfuric acid solution, obtains mixture；Stirring is mixed After even, drip ethylene glycol solution, stir, add and step (3) obtains 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material, obtains other product, after heating evaporating water, Calcining, is naturally cooling to room temperature, i.e. obtains nano barium titanate lanthanum lithium surface coated 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material.
Further, nickel presoma and the mol ratio Ni Mn=1 of manganese presoma in step (1) 3；Described nickel presoma be the one in nickel nitrate, nickel acetate, nickel sulfate, Nickel dichloride. or Several；Described manganese presoma is for the one in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride Or it is several；Described alkaline solution is NaOH solution or KOH solution or LiOH solution.
It is dried described in step (1) and is specially 100-120 DEG C of dry 10-15h.
Further, in step (2), before mixing with lithium source, it is also possible to by nickel manganese presoma Ni0.5Mn1.5(OH)4Under an oxygen-containing atmosphere, it is heated to the programming rate of 1-5 DEG C/min 500-600 DEG C, heat preservation sintering 5-10h, obtain pretreated nickel manganese presoma, then with lithium source Mixing.
Step (2) described lithium source and step (1) nickel manganese presoma Ni0.5Mn1.5(OH)4Mixing is pressed Mol ratio Li:Ni:Mn=4.0-4.3:1:3 mixes；
Step (2) mixed method is wet ball grinding, particularly as follows: by ethanol and lithium source and step (1) nickel manganese presoma Ni0.5Mn1.5(OH)4Mixture, in 1:(1-2) ratio of mL/g Mixing, with the rotating speed ball milling 2-16h of 300-500r/min；
Lithium source described in step (2) be lithium carbonate, Lithium hydrate, lithium acetate, lithium nitrate, One or more in lithium oxide；
The calcining of heating and thermal insulation described in step (3) is particularly as follows: with the intensification of 0.5-10 DEG C/min Speed is heated to 800-1000 DEG C, calcines 8-24h.
In step (4), titanium source is selected from butyl titanate, and described hydrogenperoxide steam generator mass concentration is 20-30%, mass concentration 15-30% of ammonia spirit；Wherein, titanium source and the matter of mixed solution Amount ratio is 10:1-6:1；The purpose adding titanium source is to form titanyl compound.
Further, stabilizer described in step (4) is selected from ammonium citrate, citric acid, second One or more in hydramine and diethanolamine, are 1:3-1:6 with the mol ratio in titanium source.
Described in step (4), the mass concentration of nitric acid or sulfuric acid solution is 20-30%；Described lithium Salt is selected from lithium carbonate, Lithium hydrate, lithium acetate, lithium nitrate or lithium oxide；Described lanthanum source is selected from One or more in lanthana, lanthanum carbonate and Lanthanum (III) nitrate；Lithium salts and lanthanum source institute in the mixture The weight/mass percentage composition accounted for is at 1%-8%；Lithium salts and lanthanum source mol ratio are 1:1.
Stirring and evenly mixing described in step (4) is specially at 40 DEG C stirring mixing 30-60min.
Step (4) adds 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2The quality of material is at precursor The weight/mass percentage composition accounted in product is 92%-99%.
Evaporating water is heated particularly as follows: first heat 1h at 60 DEG C described in step (4), with After at 90 DEG C heat 1h, evaporated unnecessary moisture, next at 120 DEG C heat 20min, evaporation solid carbon dioxide divides.
Further, calcining described in step (4) is particularly as follows: be warmed up to 300 DEG C-400 DEG C Heating 2-3h.
The principle of the present invention is chemically and physically characteristic based on lanthanium titanate lithium, due to lanthanium titanate lithium It is extraordinary lithium ion conductor, is suitable to the fast transferring of lithium ion, serve lifting material times The effect of rate performance；Simultaneously because the cladding on surface serves the protective effect to bulk material, The contact between material and electrolyte can be reduced, reduce the generation of side reaction, decrease HF Solution modeling to the manganese ion that the corrosion of material itself causes, improves coulombic efficiency and circulation Stability.
Compared with prior art, the present invention, by controlling preparation technology parameter, prepares performance Excellent 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material, is then carried out this material uniformly Nano barium titanate lanthanum lithium Surface coating, thus improve its coulombic efficiency, high rate performance and follow first Ring stability.
Accompanying drawing explanation
Fig. 1 is that the nano barium titanate lanthanum lithium of embodiment 1 preparation is surface coated 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material discharging cycle performance figure；
Fig. 2 is that the nano barium titanate lanthanum lithium of embodiment 1 preparation is surface coated 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material discharges under different charge-discharge magnifications, and does not wraps The material comparison diagram covered.
Detailed description of the invention
Embodiment 1
A kind of 0.5Li of nano barium titanate lanthanum lithium cladding2MnO3·0.5LiNi0.5Mn0.5O2The system of material Preparation Method, comprises the following steps:
(1) coprecipitation prepares nickel manganese presoma Ni0.5Mn1.5(OH)4
Ni Mn=1 3 prepares the mixed aqueous solution of nickel nitrate and manganese nitrate in molar ratio, Under stirring, in mixed aqueous solution, drip the NaOH solution of 2M, by mixed solution PH value controls 10.5, to ensure Ni2+、Mn2+Precipitation is complete, after standing 2h, sucking filtration, Wash three times, 110 DEG C of dry 12h obtain presoma Ni0.5Mn1.5(OH)4；
(2) nickel manganese presoma Ni0.5Mn1.5(OH)4Pretreatment:
Li Ni Mn=4.1 13 is by lithium carbonate, presoma in molar ratio Ni0.5Mn1.5(OH)4Mixing to obtain solid mixture, wherein Li somewhat excess is follow-up in order to make up A small amount of volatilization loss of lithium in pyroprocess；And be 1 in the ratio of ethanol Yu solid mixture: 2mL/g adds ball mill, with the rotating speed ball milling 13h of 400r/min, obtains powder mixture；Will Powder mixture takes out and is dried, and then under pure oxygen atmosphere, adds with the programming rate of 3 DEG C/min Hot to 500 DEG C, heat preservation sintering 5h, obtain pretreated nickel manganese presoma；
(3) solid phase synthesis
Under an oxygen-containing atmosphere, it is heated to 800 DEG C with the programming rate of 10 DEG C/min, calcines 8h； Finally naturally cool to room temperature, i.e. obtain 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material；
(4) surface modification
Titanium granule 0.05g (0.001mol) is dissolved in 20% hydrogenperoxide steam generator 0.2g With in the mixed solution of the ammonia spirit 0.3g of 25%, the mass ratio of the amount in mixed liquor and titanium source Between 10:1-6:1, form yellow transparent liquid, at this moment add 0.0002mol citric acid Amine, adds 20% salpeter solution 5-10ml of lithium carbonate and lanthana, lithium carbonate and lanthana The amount of material is respectively that the shared in the mixture percent mass in 0.001mol, lithium salts and lanthanum source contains Amount is at 1%-8%；At 40 DEG C, stirring mixing 30min, finally gives the metal combination that pH value is 6 Thing；In metal complex solution, drip ethylene glycol solution, mixture be uniformly dispersed, Stir, reenter step 3) in the 0.5Li that obtains2MnO3·0.5LiNi0.5Mn0.5O2Material 5g, then heats 1h at 60 DEG C, heats 1h subsequently at 90 DEG C, evaporated unnecessary Moisture, next heats 20min at 120 DEG C, and evaporation solid carbon dioxide divides, and collects the material obtained, Transfer in tube furnace, be warmed up to 350 DEG C heating 2h, after be naturally cooling to room temperature, i.e. obtain Nano barium titanate lanthanum lithium Surface coating 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material.
With prepared nano barium titanate lanthanum lithium Surface coating 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2 Material prepares experimental cell pole piece and test battery.Prepare the process of experimental cell pole piece For: by 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Positive electrode and conductive agent acetylene black, PVDF According to mass ratio 811 mix homogeneously, with NMP, this mixture is modulated into slurry, uniformly Being coated on aluminium foil, put in baking oven and dry, take out and be washed into pole piece, at 90 DEG C, vacuum is done Dry 12h, carries out tabletting, then proceedes to be vacuum dried 12h and prepares experimental cell pole piece.
The process of assemble and test is: with the pole piece of above-mentioned preparation as positive pole, with lithium sheet be To electrode, electrolyte be concentration be the LiPF of 1mol/L6Solution, its solvent is EC (second Base carbonic ester)+DMC (dimethyl carbonate), wherein EC (ethyl carbonate ester) and DMC (two Methyl carbonic) volume ratio be 11, barrier film is celgard2400 film, at full argon Being assembled into CR2025 type button cell in the glove box of gas atmosphere, discharge and recharge by voltage is 2.0-4.8V.Charge and discharge cycles is set to: the 1-5 time charging and discharging currents is 0.1C, 6-45 Secondary charging and discharging currents is 0.2C (1C=250mA/g).High rate performance test setting: charging current For 0.1C, discharge current is respectively 0.1C, 0.2C, 0.5C, 1C, each circulation 3 Secondary.
The discharge cycles test data of material prepared by the present embodiment are shown in Table 1.
As it is shown in figure 1, what nano barium titanate lanthanum lithium prepared by the present embodiment was coated with 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material discharging cycle performance is good.
As in figure 2 it is shown, what nano barium titanate lanthanum lithium prepared by the present embodiment was coated with 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material is electric discharge cycle performance under different charge-discharge magnifications Well, compare with uncoated material.
Embodiment 2
A kind of 0.5Li of nano barium titanate lanthanum lithium cladding2MnO3·0.5LiNi0.5Mn0.5O2The system of material Preparation Method, comprises the following steps:
(1) nickel manganese presoma Ni is prepared in co-precipitation0.5Mn1.5(OH)4
In mole ratio Ni Mn=1:3 preparation nickel nitrate and nickel acetate (both materials Amount ratio be 1:1), the mixed aqueous solution of manganese sulfate, under being stirred vigorously state, to mixed Dripping molar concentration in Heshui solution is the KOH solution of 2M, is controlled by the pH value of mixed solution About 10, to ensure Ni2+、Mn2+Precipitation is complete, after standing 2h, and sucking filtration, washing three Secondary, 110 DEG C of dry 12h obtain presoma Ni0.5Mn1.5(OH)4；
(2) nickel manganese presoma Ni0.5Mn1.5(OH)4Pretreatment
By step 1) gained presoma Ni0.5Mn1.5(OH)4Be dried, burn in air atmosphere Knot, is heated to 600 DEG C with the programming rate of 5 DEG C/min, and heat preservation sintering 5h obtains nickel-manganese-oxygen Compound Ni0.5Mn1.5O4；Then in amount ratio Li:Ni:Mn=4.15:1:3 of material by carbon Acid lithium and the nickel manganese presoma Ni of preparation0.5Mn1.5(OH)4Mixing, obtains solid mixture, wherein Li somewhat excess is to make up a small amount of volatilization loss of lithium during subsequent high temperature；By ethanol It is that 1:1mL/g adds ball mill, with the rotating speed ball of 500r/min with the ratio of solid mixture Mill 10h, obtains powder mixture.
(3) solid phase synthesis
Powder mixture step (2) obtained takes out and is dried, then under pure oxygen atmosphere Sintering, is heated to 950 DEG C with the programming rate of 1 DEG C/min, calcines 12h；Last fall naturally Warm to room temperature, i.e. obtain 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material.
(4) surface treatment step
By titanium granule 0.2g (0.0042mol) at the hydrogenperoxide steam generator of mass concentration 30% In the ammonia spirit of the 1.2g of 0.8g and mass concentration 25%, the matter of the amount in mixed liquor and titanium source Amount ratio, between 10:1-6:1, forms yellow transparent liquid, at this moment adds 0.0008mol second Glycol amine, adds lithium chloride and 20% salpeter solution 20-40ml of lanthanum carbonate, wherein contains chlorine Change lithium 0.004mol and lanthanum carbonate 0.002mol, stirring mixing 30min at 40 DEG C, finally Obtaining pH value is 6 metal complexs, drips ethylene glycol solution in metal complex solution, Mixture is uniformly dispersed, stirs, at this moment add and step (3) obtains 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material 77.616g, then heats 2 at 60 DEG C Hour, at 90 DEG C, heating 1h subsequently, evaporated unnecessary moisture, next at 120 DEG C Lower heating 30min, evaporation solid carbon dioxide divides, and collects the material obtained, transfers in tube furnace, rises Temperature to 350 DEG C heating 2h, after be naturally cooling to room temperature, i.e. obtain nano barium titanate lanthanum lithium surface bag Cover 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material.
With the prepared nano barium titanate surface coated 0.5Li of lanthanum lithium2MnO3·0.5LiNi0.5Mn0.5O2 The battery pole piece of material assembling and test battery.Prepare pole piece and method of testing and embodiment 1 In method identical.
The discharge cycles test data of material prepared by the present embodiment are shown in Table 1.
Embodiment 3
A kind of nano barium titanate surface coated 0.5Li of lanthanum lithium2MnO3·0.5LiNi0.5Mn0.5O2Material Preparation method, comprise the following steps:
(1) nickel manganese presoma Ni is prepared in co-precipitation0.5Mn1.5(OH)4
Nickel sulfate, manganese chloride and manganese sulfate (two is prepared in the amount ratio Ni Mn=1 3 of material The amount ratio of the material of person is 1 1) mixed aqueous solution, under stirring, to mixing molten Liquid drips the LiOH solution that molar concentration is 2M, the pH value of mixed solution is controlled 10.1, to ensure Ni2+、Mn2+Precipitation is complete, after standing 2h, and sucking filtration, washing three times, 110 DEG C Dry 12h obtains presoma Ni0.5Mn1.5(OH)4；
(2) nickel manganese presoma Ni0.5Mn1.5(OH)4Pretreatment, in the amount ratio Li Ni of material Mn=4.20 13 is by lithium acetate and presoma Ni0.5Mn1.5(OH)4Batch mixing obtains solid mixture, Wherein Li somewhat excess is to make up a small amount of volatilization loss of lithium during subsequent high temperature；And It is that 1:1.3mL/g adds ball mill, with 300r/min in the ratio of ethanol Yu solid mixture Rotating speed ball milling 16h, obtain powder mixture.Powder mixture is taken out and is dried, then at sky Under gas atmosphere, it is heated to 550 DEG C with the programming rate of 4 DEG C/min, heat preservation sintering 8h, obtain pre- Nickel manganese presoma after process；
(3) solid phase synthesis
In air atmosphere, it is heated to 850 DEG C with the programming rate of 6 DEG C/min, calcines 24h； Finally it is naturally cooling to room temperature, i.e. obtains 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material；
(4) surface modification
Titanium granule 0.3g (0.0063mol) is dissolved in the peroxide of mass concentration 30% In the ammonia spirit of the 1.8g changing hydrogen solution 1.2g and mass concentration 25%, form yellow transparent Liquid, at this moment adds the ethanolamine of 0.0012mol, adds the 20% of lithium carbonate and lanthanum carbonate Salpeter solution 30-60ml, wherein contains lithium carbonate and each 0.006mol of lanthanum carbonate, at 40 DEG C Lower stirring mixing 20min, finally gives the metal complex that pH value is 5, toward metal combination Thing solution drips ethylene glycol solution, mixture is uniformly dispersed, stirs, at this moment add The 0.5Li obtained in step (3)2MnO3·0.5LiNi0.5Mn0.5O2Material 23.598g, then Heat at 60 DEG C 1 hour, at 90 DEG C, heat 1h, evaporated unnecessary water subsequently Point, at 120 DEG C, next heating 20min, evaporation solid carbon dioxide divides, and collects the material obtained, Transfer in tube furnace, be warmed up to 350 DEG C heating 2h, after be naturally cooling to room temperature, i.e. obtain Nano barium titanate lanthanum lithium Surface coating 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material.
With the prepared nano barium titanate surface coated 0.5Li of lanthanum lithium2MnO3·0.5LiNi0.5Mn0.5O2 The battery pole piece of material assembling and test battery.Prepare pole piece and method of testing and embodiment 1 In method identical.
The discharge cycles test data of material prepared by the present embodiment are shown in Table 1.
Embodiment 4
A kind of nano barium titanate surface coated 0.5Li of lanthanum lithium2MnO3·0.5LiNi0.5Mn0.5O2Material Preparation method, comprises the following steps:
(1) nickel manganese presoma Ni is prepared in co-precipitation0.5Mn1.5(OH)4
The mixing preparing nickel acetate and manganese acetate in the amount ratio Ni Mn=1 3 of material is water-soluble Liquid, under stirring, dripping molar concentration in mixed aqueous solution is the NaOH solution of 2M, The pH value of mixed solution is controlled about 10.4, to ensure Ni2+、Mn2+Precipitation is complete, After standing 2h, sucking filtration, washing three times, 110 DEG C of dry 12h obtain presoma Ni0.5Mn1.5(OH)4； (2) nickel manganese presoma Ni0.5Mn1.5(OH)4Pretreatment
By step 1) gained presoma Ni0.5Mn1.5(OH)4Be dried, under pure oxygen atmosphere sinter, It is heated to 500 DEG C with the programming rate of 2 DEG C/min, heat preservation sintering 12h, obtain nickel-manganese-oxygen Thing Ni0.5Mn1.5O4, then in the amount ratio Li Ni Mn=4.05 13 of material by hydrogen-oxygen Change lithium and this Ni, Mn oxide batch mixing obtains solid mixture；And press the ratio of ethanol and solid mixture Example is that 1:1.5mL/g adds ball mill, with the rotating speed ball milling 6h of 500r/min, obtains powder body Mixture；
(3) solid phase synthesis
Powder mixture step (2) prepared takes out and is dried, and then burns under pure oxygen atmosphere Knot, is heated to 900 DEG C with the programming rate of 8 DEG C/min, calcines 24h；Last Temperature fall To room temperature, i.e. obtain 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material.
(4) surface modification
Titanium granule 0.4g (0.00835mol) is dissolved in the hydrogen peroxide that mass concentration 30% is In the mixed solution of the ammonia spirit of the 2.4g of solution 1.6g and mass concentration 25%, mixed liquor And the mass ratio of the amount in titanium source is between 10:1-6:1, forms yellow transparent liquid, at this moment add Enter the Fructus Citri Limoniae acid amide of 0.0016mol, add 20% salpeter solution of lithium chloride and lanthanum carbonate, 40-80ml, containing lithium chloride 0.008mol and lanthanum carbonate 0.004mol；Stir at 40 DEG C Mixing 30min, finally gives the metal complex that pH value is 6, toward metal complex solution Mixture is uniformly dispersed by middle dropping ethylene glycol solution, stirs, and at this moment adds step (3) In the 0.5Li that obtains2MnO3·0.5LiNi0.5Mn0.5O2Material 29.792g, then at 60 DEG C Heating 1h, heats 1h subsequently at 90 DEG C, and evaporated unnecessary moisture, next at 120 DEG C Lower heating 20min, evaporation solid carbon dioxide divides, and collects the material obtained, transfers in tube furnace, rises Temperature to 350 DEG C heating 2h, after be naturally cooling to room temperature, i.e. obtain nano barium titanate lanthanum lithium surface bag Cover 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material.
With the prepared nano barium titanate surface coated 0.5Li of lanthanum lithium2MnO3·0.5LiNi0.5Mn0.5O2 The battery pole piece of material assembling and test battery.Prepare pole piece and method of testing and embodiment 1 In method identical.The discharge cycles test data of material prepared by the present embodiment are shown in Table 1.
The nano barium titanate lanthanum lithium that table 1 is prepared for embodiment 1-4 is surface coated 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material compares.
Table 1

Claims (10)

1. the 0.5Li of a nano barium titanate lanthanum lithium cladding2MnO3·0.5LiNi0.5Mn0.5O2The preparation of material Method, it is characterised in that described preparation method comprises the following steps:
(1) by preparation nickel presoma and the mixed aqueous solution of manganese presoma, alkaline solution is added, Regulation pH is 10-12, after stirring, through being centrifuged, wash, being dried to obtain nickel manganese presoma Ni0.5Mn1.5(OH)4；
(2) nickel manganese presoma Ni prepared by lithium source and step (1)0.5Mn1.5(OH)4Mixing, Obtain mixed powder；
(3) by the mixed powder of step (2) gained under an oxygen-containing atmosphere, heating and thermal insulation is calcined, Naturally cool to room temperature, i.e. obtain 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material；
(4) titanium source is dissolved in the mixed solution of hydrogenperoxide steam generator and ammonia spirit, adds Stabilizer, adds lithium salts and the nitric acid in lanthanum source or sulfuric acid solution, obtains mixture；Stirring is mixed After even, drip ethylene glycol solution, stir, add and step (3) obtains 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material, obtains other product, after heating evaporating water, Calcining, is naturally cooling to room temperature, i.e. obtains nano barium titanate lanthanum lithium surface coated 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Material.
Preparation method the most according to claim 1, it is characterised in that in step (1) before nickel Drive the mol ratio Ni Mn=1 3 of body and manganese presoma；Described nickel presoma is nickel nitrate, vinegar One or more in acid nickel, nickel sulfate, Nickel dichloride.；Described manganese presoma is manganese nitrate, One or more in manganese acetate, manganese sulfate, manganese chloride.
3. according to the preparation method described in any one of claim 1-2, it is characterised in that step (2) In, before mixing with lithium source, it is also possible to by nickel manganese presoma Ni0.5Mn1.5(OH)4At oxygen-containing atmosphere Under, it is heated to 500-600 DEG C with the programming rate of 1-5 DEG C/min, heat preservation sintering 5-10h, Obtain pretreated nickel manganese presoma, then mix with lithium source.
4. according to the preparation method described in any one of claim 1-3, it is characterised in that step (2) Described lithium source and step (1) nickel manganese presoma Ni0.5Mn1.5(OH)4Mix Li:Ni in molar ratio: Mn=4.0-4.3:1:3 mixes；Described lithium source be lithium carbonate, Lithium hydrate, lithium acetate, One or more in lithium nitrate, lithium oxide.
5. according to the preparation method described in any one of claim 1-4, it is characterised in that step (3) Described in heating and thermal insulation calcine particularly as follows: be heated to the programming rate of 0.5-10 DEG C/min 800-1000 DEG C, calcine 8-24h.
6. according to the preparation method described in any one of claim 1-5, it is characterised in that step (4) Middle titanium source is selected from butyl titanate；Titanium source is 10:1-6:1 with the mass ratio of mixed solution.
7. according to the preparation method described in any one of claim 1-6, it is characterised in that step (4) Described in stabilizer one in ammonium citrate, citric acid, ethanolamine and diethanolamine or Several, it is 1:3-1:6 with the mol ratio in titanium source.
8. according to the preparation method described in any one of claim 1-7, it is characterised in that step (4) Described lithium salts is selected from lithium carbonate, Lithium hydrate, lithium acetate, lithium nitrate or lithium oxide；Described lanthanum One or more in lanthana, lanthanum carbonate and Lanthanum (III) nitrate of source；Lithium salts and lanthanum source are in mixing Weight/mass percentage composition shared in thing is at 1%-8%；Lithium salts and lanthanum source mol ratio are 1:1.
9. according to the preparation method described in any one of claim 1-8, it is characterised in that step (4) Middle addition 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2The matter that the quality of material accounts in other product Amount percentage composition is 92%-99%.
10. according to the preparation method described in any one of claim 1-9, it is characterised in that step (4) Described in heat evaporating water particularly as follows: first heat 1h at 60 DEG C, add at 90 DEG C subsequently Hot 1h, evaporated unnecessary moisture, at 120 DEG C, next heat 20min, evaporation is dry Moisture；Described calcining is particularly as follows: be warmed up to 300 DEG C-400 DEG C heating 2-3h.
CN201610340380.2A 2016-05-21 2016-05-21 Preparation method of nanometer lithium lanthanum titanate coated 0.5Li2MnO3 0.5LiNi0.5Mn0.5O2 material Pending CN106025199A (en)

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