CN109326778A - A kind of tertiary cathode material and preparation method thereof of nickel acid lanthanum cladding - Google Patents

A kind of tertiary cathode material and preparation method thereof of nickel acid lanthanum cladding Download PDF

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CN109326778A
CN109326778A CN201811057797.3A CN201811057797A CN109326778A CN 109326778 A CN109326778 A CN 109326778A CN 201811057797 A CN201811057797 A CN 201811057797A CN 109326778 A CN109326778 A CN 109326778A
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lanthanum
cathode material
nickel
tertiary cathode
lanio
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CN109326778B (en
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余志勇
金皓
杨吉
刘韩星
尧中华
曹明贺
郝华
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Wuhan University of Technology WUT
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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
    • 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
    • H01M4/50—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
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of tertiary cathode material and preparation method thereof of nickel acid lanthanum cladding, this method it is creative using nickel acid lanthanum as LiNi0.5Co0.2Mn0.3O2The covering material of tertiary cathode material, while significantly improving its cycle performance and high rate performance.The preparation process of the cell positive material is specific as follows: first with soluble lanthanum salt and nickel salt and citric acid, polyethylene glycol, hydration at LaNiO3Colloidal sol adds LiNi0.5Co0.2Mn0.3O2Tertiary cathode material simultaneously stirs, and is finally dried to powder, high temperature sintering to obtain the final product.

Description

A kind of tertiary cathode material and preparation method thereof of nickel acid lanthanum cladding
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of tertiary cathode material coated using nickel acid lanthanum And preparation method thereof.
Background technique
Positive electrode directly affects lithium ion battery as the material of lithium ion, performance quality is provided in lithium ion battery Performance.In recent years, the LiNi of layer structure0.5Co0.2Mn0.3O2Positive electrode is high, cheap, hot steady due to theoretical capacity The advantages that qualitative good, has received widespread attention, but the Layered Structural Positive Electrode Materials but have high rate performance and poor circulation, Especially under high blanking voltage the problems such as poor circulation, its extensive use is constrained.
Up to the present, there are many document reports that can improve the property of nickelic ternary layered positive electrode by coating Can, the covering material used includes Al2O3(Journal of Power Sources,2011,196:3317-3324、)、 ZnO(Electrochimica Acta,2009,54:5796-5803、)、TiO2(Journal of Power Sources, The metal oxides such as 2014,256:20-27).These covering materials improve LiNi to a certain extent0.5Co0.2Mn0.3O2 (NCM523) cyclical stability, but since these oxide conducting performances are poor, it is unfavorable for tertiary cathode material high rate performance Performance.
In addition to there are also the claddings that other substances can be used for tertiary cathode material, such as boron carbide for oxide (CN108400301A), silica-graphene (CN108390037A), vanadic salts and manganese salt (CN108390034A), Li7La3Zr2O12(CN108376770A), yttrium acid lithium (CN10823214A) etc..These covering material one side preparation process are more On the other hand complicated, higher cost is not still fully solved LiNi0.5Co0.2Mn0.3O2The above problem existing for positive electrode. Nickel acid lanthanum (LaNiO3) it is the oxide that several classes have metalline, belong to perovskite complex rare-earth oxidate containing valuable metal, at room temperature Its resistivity is low and has good electron conduction.Electricity can not only be improved as the coating of lithium nickel cobalt manganese positive electrode material The cycle performance in pond, and its high rate performance can also be significantly improved.
Summary of the invention
It is an object of the invention to be directed to existing lithium nickel cobalt manganese positive electrode material coating technology above shortcomings, by big Amount experiment has determined a kind of new covering material (LaNiO3) and corresponding method for coating, cycle performance and multiplying power has thus been made The more excellent LiNi of performance0.5Co0.2Mn0.3O2Tertiary cathode material.To achieve the above object, skill of the present invention Art scheme is as follows:
A kind of preparation method of the tertiary cathode material of nickel acid lanthanum cladding, specifically includes the following steps:
LaNiO is prepared first3Colloidal sol, then by tertiary cathode material and LaNiO3Colloidal sol is uniformly mixed, and gained mixture is dry Grind into powder after dry, is finally sintered to obtain the final product.
LaNiO3The preparation method of colloidal sol is specific as follows: in deionized water by lanthanum source and nickel source dissolution, adding lemon Acid and polyethylene glycol, gained mixed solution, which is placed at 60-90 DEG C, reacts 6-24h, obtains LaNiO3Colloidal sol.
Further, the lanthanum source is selected from lanthanum nitrate or its hydrate, lanthanum carbonate or its hydrate, lanthanum sulfate or its hydration One of object, the nickel source is in citric acid nickel or its hydrate, nickelous carbonate or its hydrate, nickel sulfate or its hydrate One kind.
Further, LaNiO is prepared3The molar ratio of lanthanum element and nickel element is 1:1, the mole dosage of citric acid when colloidal sol It is 1-1.2 times of the sum of lanthanum source and nickel source molal quantity, the dosage of citric acid and water is respectively equivalent to the 118- of polyethylene glycol quality 141 times and 10000-30000 times.
Further, the tertiary cathode material is stratiform LiNi0.5Co0.2Mn0.3O2。
Further, tertiary cathode material and LaNiO when mixing3The mass ratio of nickel acid lanthanum in colloidal sol is (1-x): x, 1%≤x≤5%.
Further, tertiary cathode material and LaNiO36-24h is stirred after colloidal sol mixing, is then placed in 120-150 DEG C of ring Dry 5-15h in border, obtained solid, which is pulverized, last is warming up to 600-900 DEG C of heat preservation 10-30h.
Another object of the present invention is to provide the tertiary cathode materials coated according to nickel acid lanthanum made from a kind of above method Material, composition include stratiform LiNi0.5Co0.2Mn0.3O2And it is coated on the LaNiO on its surface3。
Compared with prior art, the invention has the following advantages: (1) has determined that one kind is new by many experiments screening Covering material LaNiO3, and completed using it to LiNi0.5Co0.2Mn0.3O2Effective cladding of positive electrode；(2) material is coated Material preparation process and method for coating are simple, are easily achieved, reproducible；(3) LaNiO made from3Cladding LiNi0.5Co0.2Mn0.3O2Positive electrode cycle performance and high rate performance have obtained biggish improvement simultaneously, certain performances relative to Other covering materials are more prominent.
Detailed description of the invention
Fig. 1 is the LiNi0.5Co0.2Mn0.3O2 anode material of 0wt%, 1wt%, 3wt%, 5wt%LaNiO3 cladding processing Expect the XRD diagram of sample；
Fig. 2 is the SEM of the LiNi0.5Co0.2Mn0.3O2 positive electrode sample of 0wt% and 3wt%LaNiO3 cladding processing Figure；
Fig. 3 is the low range TEM of the LiNi0.5Co0.2Mn0.3O2 positive electrode sample of 3wt%LaNiO3 cladding processing Figure；
Fig. 4 is the cyclic curve of the LiNi0.5Co0.2Mn0.3O2 positive electrode sample of 0wt% and 1wt% cladding processing Figure；
Fig. 5 is that the LiNi0.5Co0.2Mn0.3O2 positive electrode sample of 0wt% and 3wt% cladding processing passes through electricity respectively The specific discharge capacity conservation rate figure that current density obtains after being each cycle charge-discharge of 0.2C, 0.5C, 1C, 2C and 5C 10 times.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific Embodiment is further described.
Embodiment 1
A kind of preparation method of nickel acid lanthanum cladding tertiary cathode material, specific as follows:
0.588g lanthanum nitrate hexahydrate and 0.5g citric acid nickel hydrate are first weighed, 162g deionized water is dissolved in In, it is subsequently added into 0.633g citric acid and 0.0054g polyethylene glycol.Gained mixed liquor is heated with 60 DEG C of constant temperature of water-bath, is stirred It obtains after mixing 24 hours containing about 0.33gLaNiO3Colloidal sol.Again by 33gLiNi0.5Co0.2Mn0.3O2Powder is added in colloidal sol, is held Mixture for 24 hours, is then placed in 120 DEG C of baking ovens dry 15h, presoma powder is obtained, after being ground into powder by continuous stirring It is placed in Muffle furnace and heats, be warming up to 600 DEG C of heat preservation 30h, obtains finally coating product --- 1wt%LaNiO3Cladding LiNi0.5Co0.2Mn0.3O2Tertiary cathode material.
Embodiment 2
A kind of preparation method of nickel acid lanthanum cladding tertiary cathode material, specific as follows:
1.763g lanthanum nitrate hexahydrate and 1.5g citric acid nickel hydrate are first weighed, 112g deionized water is dissolved in In, it is subsequently added into 1.581g citric acid and 0.0112g polyethylene glycol.Gained mixed liquor is heated with 60 DEG C of constant temperature of water-bath, is stirred It obtains after mixing 10 hours containing about 1gLaNiO3Colloidal sol.Again by 33gLiNi0.5Co0.2Mn0.3O2Powder is added in colloidal sol, is continued 8h is stirred, then mixture is placed in in 150 DEG C of baking oven dry 6h, obtain presoma powder, be ground into powder postposition It is heated in Muffle furnace, is warming up to 700 DEG C of heat preservation 10h, obtains final cladding product --- 3wt%LaNiO3Cladding LiNi0.5Co0.2Mn0.3O2Tertiary cathode material.
Embodiment 3
A kind of preparation method of nickel acid lanthanum cladding tertiary cathode material, specific as follows:
1.763g lanthanum nitrate hexahydrate and 1.5g citric acid nickel hydrate are first weighed, 483g deionized water is dissolved in In, it is subsequently added into 1.898g citric acid and 0.0161g polyethylene glycol.Gained mixed liquor is heated with 80 DEG C of constant temperature of water-bath, is stirred It obtains after mixing 6 hours containing about 1gLaNiO3Colloidal sol.Again by 32.33gLiNi0.5Co0.2Mn0.3O2Powder is added in colloidal sol, is held Mixture, is then placed in 150 DEG C of baking oven dry 8h, presoma powder is obtained, after being ground into powder by continuous stirring 8h It is placed in Muffle furnace and heats, be warming up to 800 DEG C of heat preservation 20h, obtain final cladding product --- 3wt%LaNiO3Cladding LiNi0.5Co0.2Mn0.3O2Tertiary cathode material.
Embodiment 4
A kind of preparation method of nickel acid lanthanum cladding tertiary cathode material, specific as follows:
1.763g lanthanum nitrate hexahydrate and 1.5g citric acid nickel hydrate are first weighed, 320g deionized water is dissolved in In, it is subsequently added into 1.78g citric acid and 0.0137g polyethylene glycol.Gained mixed liquor is heated with 90 DEG C of constant temperature of water-bath, stirring 1gLaNiO must be contained after 6 hours3Colloidal sol.Again by 19gLiNi0.5Co0.2Mn0.3O2Powder is added in colloidal sol, persistently stirs 6h, Then place it in 150 DEG C of baking oven dry 5h, obtain presoma powder, be ground into powder be placed in Muffle furnace plus Heat is warming up to 900 DEG C of heat preservation 10h, obtains final cladding product --- 5wt%LaNiO3The LiNi of cladding0.5Co0.2Mn0.3O2 Tertiary cathode material.
Embodiment 5
A kind of preparation method of nickel acid lanthanum cladding tertiary cathode material, specific as follows:
1.763g lanthanum nitrate hexahydrate and 1.5g citric acid nickel hydrate are first weighed, 135g deionized water is dissolved in In, it is subsequently added into 1.898g citric acid and 0.0135g polyethylene glycol.Gained mixed liquor is heated with 80 DEG C of constant temperature of water-bath, is stirred It obtains after mixing 8 hours containing about 1gLaNiO3Colloidal sol.Again by 32.33gLiNi0.5Co0.2Mn0.3O2Powder is added in colloidal sol, is held Then continuous stirring 7h places it in dry 5h in 130 DEG C of baking oven, obtains presoma powder, be ground into powder and be placed on It is heated in Muffle furnace, is warming up to 800 DEG C of heat preservation 10h, obtains final cladding product --- 3wt%LaNiO3Cladding LiNi0.5Co0.2Mn0.3O2Tertiary cathode material.
Embodiment 6
A kind of preparation method of nickel acid lanthanum cladding tertiary cathode material, specific as follows:
1.763g lanthanum nitrate hexahydrate and 1.5g citric acid nickel hydrate are first weighed, 200g deionized water is dissolved in In, it is subsequently added into 1.581g citric acid and 0.0112g polyethylene glycol.Gained mixed liquor is heated with 70 DEG C of constant temperature of water-bath, is stirred It obtains after mixing 10 hours containing about 1gLaNiO3Colloidal sol.Again by 19gLiNi0.5Co0.2Mn0.3O2Powder is added in colloidal sol, is continued 8h is stirred, dry 6h in 150 DEG C of baking oven is then placed it in, obtains presoma powder, be ground into powder and be placed on horse It is heated in boiling stove, is warming up to 700 DEG C of heat preservation 15h, obtains final cladding product --- 5wt%LaNiO3Cladding LiNi0.5Co0.2Mn0.3O2Tertiary cathode material.
Embodiment 7
A kind of preparation method of nickel acid lanthanum cladding tertiary cathode material, specific as follows:
1.763g lanthanum nitrate hexahydrate and 1.5g citric acid nickel hydrate are first weighed, 280g deionized water is dissolved in In, it is subsequently added into 1.685g citric acid and 0.014g polyethylene glycol.Gained mixed liquor is heated with 80 DEG C of constant temperature of water-bath, stirring It obtains after 12 hours containing about 1gLaNiO3Colloidal sol.Again by 32.33gLiNi0.5Co0.2Mn0.3O2Powder is added in colloidal sol, is continued 6h is stirred, dry 5h in 150 DEG C of baking oven is then placed it in, obtains presoma powder, be ground into powder and be placed on horse It is heated in boiling stove, is warming up to 700 DEG C of heat preservation 10h, obtains final cladding product --- 3wt%LaNiO3Cladding LiNi0.5Co0.2Mn0.3O2Tertiary cathode material.
One, XRD, SEM and tem analysis characterization
To 1wt%, 3wt%, 5wt%LaNiO made from uncoated processing (0wt%) and embodiment 1-73Cladding processing LiNi0.5Co0.2Mn0.3O2Tertiary cathode material has carried out XRD and SEM test, as a result as shown in Figs. 1-3 respectively.
Fig. 1-a is the LiNi of uncoated processing0.5Co0.2Mn0.3O2The XRD diagram of sample, 1-b, 1-c, 1-d be respectively for The LiNi of 1wt%, 3wt%, 5wt% nickel acid lanthanum cladding processing0.5Co0.2Mn0.3O2The XRD diagram of sample.As shown in Figure 1, by not With the LaNiO of content3Treated that tertiary cathode material is still layer structure for cladding；Work as LaNiO3Content has when reaching 5% Apparent LaNiO3Peak occurs.
Fig. 2-a, 2-b are respectively without cladding processing and through 3wt%LaNiO3Coat the LiNi of processing0.5Co0.2Mn0.3O2 Sample SEM figure, 2-c, 2-d, 2-e, 2-f, 2-g are respectively indicated to 3wt%LaNiO3Coat the tertiary cathode material of processing LiNi0.5Co0.2Mn0.3O2Carry out O, Ni, Co, Mn, La distribution diagram of element that energy spectrum analysis obtains.Fig. 2 combination Fig. 1 it is found that 3wt%LaNiO3When cladding processing, LaNiO3Successfully it is coated on LiNi0.5Co0.2Mn0.3O2Surface.Other coating contents (1% Similar conclusion has also been obtained with sample 5%).
Fig. 3 is 3wt%LaNiO3Coat the LiNi of processing0.5Co0.2Mn0.3O2Low range TEM image.Inside the figure (top) Material LiNi based on color Dark grey0.5Co0.2Mn0.3O2, grayish surface (on the lower) is LaNiO3Clad.This Further prove LaNiO3Successfully it is coated on LiNi0.5Co0.2Mn0.3O2Surface.
Two, battery performance test
The positive electrode of cladding front and back and metal lithium sheet cathode are assembled into CR2025 button cell, respectively in 2.8V- In 4.2V, 2.8V-4.5V, 2.8V-4.7V voltage range and 0.2C, 0.5C, 1C, 2C, 5C (1C=150mAh/g) all or Certain number is recycled under portion of electrical current density to be tested.
Comparative example 1
The tertiary cathode material LiNi of cladding processing is not carried out0.5Co0.2Mn0.3O2Battery 2.8V-4.2V voltage range, It is tested under 0.2C current density, first discharge specific capacity 155mAh/g, after 50 circle circulations, specific discharge capacity is 139.5mAh/g, capacity retention ratio 90%.
Comparative example 2
The tertiary cathode material LiNi of cladding processing is not carried out0.5Co0.2Mn0.3O2Battery 2.8V-4.5V voltage range, It is tested under 0.2C current density, first discharge specific capacity 183.7mAh/g, after 50 circle circulations, specific discharge capacity is 151.3mAh/g, capacity retention ratio 82.4%.
Comparative example 3
The tertiary cathode material LiNi of cladding processing is not carried out0.5Co0.2Mn0.3O2Battery 2.8V-4.7V voltage range, It is tested under 0.2C current density, first discharge specific capacity 197mAh/g, after 50 circle circulations, specific discharge capacity is 163.6mAh/g, capacity retention ratio 83%.
Comparative example 4
The tertiary cathode material LiNi of cladding processing is not carried out0.5Co0.2Mn0.3O2Battery 2.8V-4.2V voltage range, The successively charge and discharge under 0.2C, 0.5C, 1C, 2C, 5C and 0.2C current density, 0.5C/0.2C, 1C/0.2C, 2C/0.2C, 5C/ The electric discharge ratio of 0.2C is respectively 90.7%, 78.7%, 66% and 41.3%.
1wt%, 3wt%LaNiO made from 1-2 of the embodiment of the present invention3Coat the LiNi of processing0.5Co0.2Mn0.3O2Battery exists Tested under 2.8V-4.2V voltage range, 0.2C current density, first discharge specific capacity be respectively 156.6mAh/g, 158.3mAh/g, after 50 circle circulations, specific discharge capacity is respectively 154mAh/g, 156.9mAh/g, capacity retention ratio difference It is 98.3%, 99.1%, much higher than the correspondence parameter in comparative example 1.This explanation is improved really by cladding LiNi0.5Co0.2Mn0.3O2Cycle performance.
3wt%, 5wt%LaNiO made from 3-4 of the embodiment of the present invention3Cladding treated LiNi0.5Co0.2Mn0.3O2? Tested under 2.8V-4.5V voltage range, 0.2C current density, first discharge specific capacity be respectively 187.4mAh/g, 183.3mAh/g, after 50 circle circulations, specific discharge capacity is respectively 180.5mAh/g, 169.2mAh/g, capacity retention ratio point Not Wei 96.3% and 92.3%, much higher than the correspondence parameter in comparative example 2.This also illustrates to improve really by cladding LiNi0.5Co0.2Mn0.3O2Cycle performance.
3wt%LaNiO obtained3Cladding treated LiNi0.5Co0.2Mn0.3O2In 2.8V-4.7V voltage range, 0.2C It is tested under current density, first discharge specific capacity 199.7mAh/g, after 50 circle circulations, specific discharge capacity is 175.8mAh/g, capacity retention ratio 88%, much higher than the correspondence parameter in comparative example 3.This also illustrates improved by cladding LiNi0.5Co0.2Mn0.3O2Cycle performance.
5wt%LaNiO obtained3Cladding treated LiNi0.5Co0.2Mn0.3O2In 2.8V-4.5V voltage range, 0.2C It is tested under current density, first discharge specific capacity 183.3mAh/g, after 50 circle circulations, specific discharge capacity is 169.2mAh/g, capacity retention ratio 92.3%, much higher than the correspondence parameter in comparative example 2.Illustrate to improve by cladding LiNi0.5Co0.2Mn0.3O2Cycle performance.
3wt%LaNiO obtained3Coat the tertiary cathode material LiNi of processing0.5Co0.2Mn0.3O2Battery is in 2.8V-4.2V In voltage range, the successively charge and discharge under 0.2C, 0.5C, 1C, 2C, 5C and 0.2C current density, wherein 0.5C/0.2C, 1C/ The electric discharge ratio of 0.2C, 2C/0.2C, 5C/0.2C are respectively 94.4%, 85.6%, 81.37%, 62.73%, are superior to compare Relevant parameter in example 4.This illustrates 3wt%LaNiO3Cladding processing improves LiNi really0.5Co0.2Mn0.3O2Tertiary cathode material Multiplying power discharging property.

Claims (8)

1. a kind of preparation method of the tertiary cathode material of nickel acid lanthanum cladding, which comprises the following steps: prepare first LaNiO3Colloidal sol, then by tertiary cathode material and LaNiO3Colloidal sol is uniformly mixed, grind into powder after gained mixture is dry, It is finally sintered to obtain the final product.
2. preparation method as described in claim 1, which is characterized in that LaNiO3The preparation method of colloidal sol is specific as follows: by lanthanum source In deionized water with nickel source dissolution, citric acid and polyethylene glycol are added, gained mixed solution, which is placed at 60-90 DEG C, reacts 6- For 24 hours to obtain the final product.
3. preparation method as claimed in claim 2, it is characterised in that: the lanthanum source is selected from lanthanum nitrate or its hydrate, carbonic acid One of lanthanum or its hydrate, lanthanum sulfate or its hydrate, the nickel source be selected from citric acid nickel or its hydrate, nickelous carbonate or One of its hydrate, nickel sulfate or its hydrate.
4. preparation method as claimed in claim 2, it is characterised in that: prepare LaNiO3Lanthanum element and nickel element rubs when colloidal sol You are than being 1:1, and the mole dosage of citric acid is 1-1.2 times of the sum of lanthanum source and nickel source molal quantity, the dosage point of citric acid and water It is not equivalent to 118-141 times and 10000-30000 times of polyethylene glycol quality.
5. preparation method as described in claim 1, it is characterised in that: the tertiary cathode material is stratiform LiNi0.5Co0.2Mn0.3O2。
6. preparation method as described in claim 1, it is characterised in that: tertiary cathode material and LaNiO when mixing3Nickel in colloidal sol The mass ratio of sour lanthanum is (1-x): x, 1%≤x≤5%.
7. preparation method as described in claim 1, it is characterised in that: tertiary cathode material and LaNiO3It is stirred after colloidal sol mixing 6-24h, is then placed in 120-150 DEG C of environment dry 5-15h, and obtained solid, which is pulverized, last is warming up to 600-900 DEG C of guarantor Warm 10-30h.
8. the tertiary cathode material of the cladding of nickel acid lanthanum made from claim any one of 1-7, it is characterised in that: the tertiary cathode material The composition of material includes stratiform LiNi0.5Co0.2Mn0.3O2And it is coated on the LaNiO on its surface3。
CN201811057797.3A 2018-09-11 2018-09-11 Lanthanum nickelate coated ternary cathode material and preparation method thereof Active CN109326778B (en)

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