CN108878821A - A kind of nickelic tertiary cathode material and preparation method thereof of surface cladding lanthana - Google Patents
A kind of nickelic tertiary cathode material and preparation method thereof of surface cladding lanthana Download PDFInfo
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- CN108878821A CN108878821A CN201810632115.0A CN201810632115A CN108878821A CN 108878821 A CN108878821 A CN 108878821A CN 201810632115 A CN201810632115 A CN 201810632115A CN 108878821 A CN108878821 A CN 108878821A
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/50—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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- 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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Abstract
The present invention relates to a kind of nickelic tertiary cathode material and preparation method thereof of surface cladding lanthana, the molecular formula of nickelic tertiary cathode material is LiNi0.8Co0.1Mn0.1O2, the quality of lanthana is the 0.5-10wt% of nickelic tertiary cathode material quality；Solution A is configured to by the way that nickel source, manganese source, cobalt source to be dissolved in deionized water；Precipitating reagent is dissolved in deionized water and is configured to solution B；Solution A and solution B are subjected to coprecipitation reaction, are aged, are filtered, washed, drying and to obtain nickel cobalt manganese presoma；Lithium source and lanthanum source are dissolved in deionized water, are added in nickel cobalt manganese presoma, stirring is evaporated to gel, dry mixture；Mixture is once calcined, secondary clacining is carried out after grinding uniformly, cools down, is ground up, sieved to obtain product；The present invention carries out surface to nickelic ternary material and coats lanthana modification, is effectively reduced erosion of the electrolyte to electrode material, inhibits the generation of positive electrode surface adverse reaction, improves the cyclical stability of nickelic tertiary cathode material.
Description
Technical field
The present invention relates to technical field of lithium ion, especially a kind of nickelic tertiary cathode material of surface cladding lanthana
Material and preparation method thereof.
Background technique
The lithium ion battery of high-energy density just can solve the course continuation mileage problem of new-energy automobile, is positive with nickelic ternary
The lithium ion battery of pole material can increase substantially the energy density of battery, become the research and development weight of domestic and international each Li electricity company
Point.It is corresponding although the electric discharge gram volume of positive electrode can be improved as Ni content increases in ternary Ni-Co-Mn material
The deterioration of cycle performance can be brought.Therefore by stablizing electrode structure in nickelic tertiary cathode material surface cladding layer of substance,
Alleviate erosion of the electrolyte to positive electrode, improves the circulation ability of battery.
In existing literature, describe using Al2O3、AlPO4、Co3PO4Material circulation performance is improved, also useful Li3PO4It mentions
High material electrochemical performance, but there has been no coat LiNi by lanthana at present0.8Co0.1Mn0.1O2Ternary material is nickelic to improve
The report of cycle performance of lithium ion battery.
Summary of the invention
The purpose of the present invention is to provide a kind of surface cladding lanthana nickelic tertiary cathode material and preparation method thereof,
Improve the cyclical stability of nickelic tertiary cathode material.To achieve the above object, the invention adopts the following technical scheme：
A kind of nickelic tertiary cathode material of surface cladding lanthana, the molecular formula of the nickelic tertiary cathode material are
LiNi0.8Co0.1Mn0.1O2, the quality of the lanthana is the 0.5-10wt% of nickelic tertiary cathode material quality.
A kind of preparation method of the nickelic tertiary cathode material of above-mentioned surface cladding lanthana, includes the following steps：
S1, it nickel source, manganese source, cobalt source is dissolved in deionized water is configured to solution A；Precipitating reagent is dissolved in deionized water and is matched
Solution B is made；Solution A and solution B are added in reaction unit and carry out coprecipitation reaction, after reaction, aged, filtering,
It washs, be dried to obtain nickel cobalt manganese presoma；
S2, lithium source and lanthanum source are dissolved in deionized water and obtain solution C, the nickel cobalt manganese then obtained by solution C and through S1
Presoma is uniformly mixed, and is evaporated to gel, is dried to obtain mixture；
S3, the mixture obtained through S2 is once calcined, after grinding uniformly, secondary clacining is carried out, after being down to room temperature
It is ground up, sieved, obtains the nickelic tertiary cathode material of surface cladding lanthana.
Preferably, the total mol concentration of the nickel source in the solution A, manganese source and cobalt source is 0.8-2.0mol/L；Nickel source, cobalt
The molar ratio of source and manganese source is 8:1:1.
Preferably, the precipitating reagent is the mixture of one or more of sodium hydroxide, sodium carbonate, sodium oxalate.
Preferably, the ratio between molal quantity of total mole number and precipitating reagent of the nickel source, cobalt source and manganese source is 1：1-1：2.
Preferably, the nickel source is the mixture of one or more of nickel sulfate, nickel acetate, nickel nitrate；The manganese
Source is one of manganese sulfate, manganese acetate, manganese nitrate or a variety of mixtures；The cobalt source is cobaltous sulfate, cobalt acetate, cobalt nitrate
One of or a variety of mixtures；The lithium source be lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, lithium chloride, lithium fluoride,
One of lithium phosphate, lithium hydrogen phosphate, lithium dihydrogen phosphate or a variety of mixtures；The lanthanum source is lanthanum nitrate, lanthanum chloride, acetic acid
One of lanthanum or a variety of mixtures.
Preferably, solution A and solution B are added drop-wise in reaction kettle in the S1 simultaneously and carry out coprecipitation reaction, be added dropwise
It is 7-11 with the pH value of ammonia water conditioning system during solution A and solution B；The coprecipitation reaction under nitrogen atmosphere into
Row, the temperature of coprecipitation reaction are 35-55 DEG C, time 4-12h.
Preferably, the digestion time in the S1 is 6-12h.
Preferably, the S2 the specific steps are：Lithium source and Lan Yuan are successively dissolved in deionized water and obtain solution C, it will
Nickel cobalt manganese presoma in S1 is dispersed in container, and solution C is added dropwise, and 30-60min is sufficiently stirred by magnetic force, is mixed
After closing uniformly, magnetic agitation is evaporated to gel at 60-90 DEG C, places into vacuum oven, dry at 60-100 DEG C
6-24h obtains mixture.
Preferably, the technique once calcined is：By the mixture obtained through S2 under air or oxygen atmosphere, with 3-
The heating rate of 5 DEG C/min is heated to 400-550 DEG C, keeps the temperature 3-8h；The technique of the secondary clacining is：With 3-5 DEG C/min's
Heating rate is heated to 700-900 DEG C, keeps the temperature 10-16h.
The device have the advantages that as follows：
The present invention is to LiNi0.8Co0.1Mn0.1O2Nickelic ternary material carries out surface and coats lanthana modification, is effectively reduced
Erosion of the electrolyte to electrode material inhibits the generation of positive electrode surface adverse reaction, hence it is evident that improve
LiNi0.8Co0.1Mn0.1O2The cyclical stability of nickelic tertiary cathode material；Meanwhile the method for the present invention is easy to operate, in nickel cobalt manganese
Lanthana is directly coated on presoma, avoiding nickel cobalt manganese oxidate for lithium and contacting with water causes material surface alkalinity to increase, unfavorable
In storage, while double sintering is avoided to nickel cobalt manganese oxidate for lithium structural damage, reduce energy consumption, the reaction item of whole process
Part is easily-controllable, and production cost is low, is conducive to industrialized production.
Detailed description of the invention
Fig. 1 is the SEM figure for the nickelic tertiary cathode material that surface prepared by the embodiment of the present invention 1 coats 1wt% lanthana；
Fig. 2 is that surface prepared by the embodiment of the present invention 1 coats the nickelic tertiary cathode material of 1wt% lanthana and right
Cycle performance curve graph of the nickelic tertiary cathode material of surface prepared by ratio 1 without cladding lanthana under 1C multiplying power.
Specific embodiment
Hereinafter, technical solution of the present invention is described in detail by specific embodiment.
Comparative example 1
Prepare LiNi of the surface without cladding0.8Co0.1Mn0.1O2Tertiary cathode material, steps are as follows：
It S1, by nickel acetate, cobalt acetate, manganese acetate is in molar ratio 8：1：1, nickel acetate, cobalt acetate, manganese acetate are dissolved in
The solution A that concentration is 1mol/L is configured in ionized water；Sodium hydroxide is dissolved in deionized water and is configured to solution B；Using compacted
Solution A and solution B are instilled progress coprecipitation reaction 6h in reaction kettle by dynamic pump simultaneously, wherein solution A and solution B is being added dropwise
In the process, it is 10 with the pH value of ammonia water conditioning system, persistently leads to N during coprecipitation reaction2, temperature is 50 DEG C, and reaction terminates
After be aged 12h, be filtered, washed later, drying to obtain nickel cobalt manganese presoma, i.e. (Ni0.8Co0.1Mn0.1)(OH)2Presoma；
S2, it lithium hydroxide is dissolved in deionized water obtains solution C, then by (Ni0.8Co0.1Mn0.1)(OH)2Presoma is equal
It is even to be scattered in container, (Ni then is added dropwise in solution C0.8Co0.1Mn0.1)(OH)2In presoma, and magnetic force is sufficiently stirred
60min, after mixing, magnetic force heating stirring is evaporated to gel at 85 DEG C, places into vacuum oven with 100 DEG C of temperature
It spends dry 12h and obtains mixture；
S3, by the mixture in S2 under oxygen atmosphere, be heated to 450 DEG C with the heating rate of 5 DEG C/min, and warm herein
Degree is lower to keep the temperature 6h, is heated to 800 DEG C again after grinding uniformly with the heating rate of 5 DEG C/min, keeps the temperature 12h at this temperature, be down to
It is ground up, sieved after room temperature to get the LiNi to surface without cladding0.8Co0.1Mn0.1O2Positive electrode.
Embodiment 1
A kind of nickelic tertiary cathode material of surface cladding lanthana, the molecular formula of the nickelic tertiary cathode material are
LiNi0.8Co0.1Mn0.1O2, the quality of the lanthana is the 1wt% of nickelic tertiary cathode material quality.
A kind of preparation method of the nickelic tertiary cathode material of above-mentioned surface cladding lanthana is as follows：
S1, by nickel acetate, manganese acetate, cobalt acetate in molar ratio 8：1：1, it is dissolved in deionized water and is configured to concentration and is
The solution A of 1mol/L；Sodium hydroxide is dissolved in deionized water and prepares solution B；Using peristaltic pump by solution A and solution B simultaneously
It instills and carries out coprecipitation reaction 6h in reaction kettle, the ratio between nickel source, the total mole number of cobalt source and manganese source and molal quantity of precipitating reagent are
1：2；It wherein, is 10 with the pH value of ammonia water conditioning system during solution A and solution B is added dropwise, during coprecipitation reaction
Persistently lead to N2, temperature is 50 DEG C, is aged 12h after reaction, is filtered, washed later, drying to obtain nickel cobalt manganese presoma, i.e.,
(Ni0.8Co0.1Mn0.1)(OH)2Presoma.
S2, the 1wt% that nickelic tertiary cathode material quality is accounted for by the quality of lanthana in final product, and according to nickel cobalt manganese
The quality of presoma can determine that the quality of required lithium source and lanthanum source, the lithium source of the present embodiment use lithium hydroxide, and lanthanum source is adopted
Use lanthanum nitrate；It weighs lithium source and lanthanum source is successively dissolved in deionized water and obtains solution C, then by (Ni0.8Co0.1Mn0.1)(OH)2Before
It drives body to be dispersed in container, (Ni then is added dropwise in above-mentioned solution C0.8Co0.1Mn0.1)(OH)2In presoma, and magnetic
60min is sufficiently stirred in power, and after mixing, magnetic force heating stirring is evaporated to gel at 85 DEG C, places into vacuum oven
In with the dry 12h of 100 DEG C of temperature obtain mixture.
S3, by the mixture in S2 under oxygen atmosphere, be heated to 450 DEG C with 5 DEG C/min heating rate, and in this temperature
Lower heat preservation 6h is equally heated to 800 DEG C again after grinding uniformly with 5 DEG C/min heating rate, keeps the temperature 12h at this temperature, be down to
It is ground up, sieved after room temperature to get the LiNi for the lanthana for coating 1wt% to surface0.8Co0.1Mn0.1O2Positive electrode.
The SEM figure such as Fig. 1 of the nickelic tertiary cathode material for the surface cladding 1wt% lanthana being prepared through embodiment 1
Shown, the material after cladding, material surface have lanthanum oxide particles as seen from Figure 1, and particle keeps good spherical shape
Looks, lanthana do not destroy the sphere pattern of material.
By the nickelic tertiary cathode material of the resulting surface of embodiment 1 cladding 1wt% lanthana by being coated and dried, fill
It is made into fastening lithium ionic cell, carries out 1C constant current charge-discharge test；And with surface in comparative example 1 without cladding lanthana nickelic three
First positive electrode is compared, and the cycle performance of the two is as shown in Figure 2.
As shown in Figure 2, in embodiment 1 surface cladding 1wt% lanthana LiNi0.8Co0.1Mn0.1O2Anode material of lithium from
Sub- battery first discharge specific capacity under 1C multiplying power, compared to the LiNi of uncoated 1wt% lanthana0.8Co0.1Mn0.1O2Positive material
The 186.6mAhg of material-1It improves to 190.4mAhg-1, improve 3.8mAhg-1, circulation is after 50 weeks, the capacity retention ratio of embodiment 1
Also it is significantly promoted, is increased to 93.7% by 75.5% before.
Embodiment 2
A kind of nickelic tertiary cathode material of surface cladding lanthana, the molecular formula of the nickelic tertiary cathode material are
LiNi0.8Co0.1Mn0.1O2, the quality of the lanthana is the 0.5wt% of nickelic tertiary cathode material quality.
A kind of preparation method of the nickelic tertiary cathode material of above-mentioned surface cladding lanthana is as follows：
S1, by nickel sulfate, manganese sulfate, cobaltous sulfate in molar ratio 8：1：1, it is dissolved in deionized water and is configured to concentration and is
The solution A of 0.8mol/L；Sodium carbonate is dissolved in deionized water and prepares solution B；Using peristaltic pump by solution A and solution B simultaneously
It instills and carries out coprecipitation reaction 4h in reaction kettle, the ratio between nickel source, the total mole number of cobalt source and manganese source and molal quantity of precipitating reagent are
1：1；It wherein, is 7 with the pH value of ammonia water conditioning system during solution A and solution B is added dropwise, during coprecipitation reaction
Persistently lead to N2, temperature is 35 DEG C, is aged 6h after reaction, is filtered, washed later, drying to obtain nickel cobalt manganese presoma, i.e.,
(Ni0.8Co0.1Mn0.1)CO3Presoma.
S2, the 0.5wt% that nickelic tertiary cathode material quality is accounted for by the quality of lanthana in final product, and according to nickel cobalt
The quality of manganese presoma can determine that the quality of required lithium source and lanthanum source, the lithium source of the present embodiment use lithium carbonate, and lanthanum source is adopted
Use lanthanum chloride；It weighs lithium source and lanthanum source is successively dissolved in deionized water and obtains solution C, then by (Ni0.8Co0.1Mn0.1)CO3Forerunner
Body is dispersed in container, and (Ni then is added dropwise in above-mentioned solution C0.8Co0.1Mn0.1)CO3In presoma, and magnetic force fills
Point stirring 30min, after mixing, magnetic force heating stirring is evaporated to gel at 60 DEG C, place into vacuum oven with
The dry 6h of 60 DEG C of temperature obtains mixture.
S3, by the mixture in S2 under oxygen atmosphere, be heated to 400 DEG C with 3 DEG C/min heating rate, and in this temperature
Lower heat preservation 3h is equally heated to 700 DEG C again after grinding uniformly with 3 DEG C/min heating rate, keeps the temperature 10h at this temperature, be down to
It is ground up, sieved after room temperature to get the LiNi for the lanthana for coating 0.5wt% to surface0.8Co0.1Mn0.1O2Positive electrode.
The SEM figure of the nickelic tertiary cathode material for the surface cladding 0.5wt% lanthana being prepared through embodiment 2 is same
It can be with reference to shown in Fig. 1；The nickelic tertiary cathode material of the resulting surface of embodiment 2 cladding 0.5wt% lanthana is passed through into painting
Cloth, drying are assembled into fastening lithium ionic cell, carry out 1C constant current charge-discharge test；And with surface without the nickelic of cladding lanthana
Tertiary cathode material is compared, and test result and result shown in Fig. 2 are essentially identical.
Embodiment 3
A kind of nickelic tertiary cathode material of surface cladding lanthana, the molecular formula of the nickelic tertiary cathode material are
LiNi0.8Co0.1Mn0.1O2, the quality of the lanthana is the 5wt% of nickelic tertiary cathode material quality.
A kind of preparation method of the nickelic tertiary cathode material of above-mentioned surface cladding lanthana is as follows：
S1, by nickel nitrate, manganese nitrate, cobalt nitrate in molar ratio 8：1：1, it is dissolved in deionized water and is configured to concentration and is
The solution A of 1.5mol/L；Sodium oxalate is dissolved in deionized water and prepares solution B；Using peristaltic pump by solution A and solution B simultaneously
It instills and carries out coprecipitation reaction 9h in reaction kettle, the ratio between nickel source, the total mole number of cobalt source and manganese source and molal quantity of precipitating reagent are
1：1；It wherein, is 11 with the pH value of ammonia water conditioning system during solution A and solution B is added dropwise, during coprecipitation reaction
Persistently lead to N2, temperature is 40 DEG C, is aged 9h after reaction, is filtered, washed later, drying to obtain nickel cobalt manganese presoma, i.e.,
(Ni0.8Co0.1Mn0.1)C2O4Presoma.
S2, the 5wt% that nickelic tertiary cathode material quality is accounted for by the quality of lanthana in final product, and according to nickel cobalt manganese
The quality of presoma can determine that the quality of required lithium source and lanthanum source, the lithium source of the present embodiment use lithium nitrate, lithium acetate,
Lanthanum source uses lanthanum acetate；It weighs lithium source and lanthanum source is successively dissolved in deionized water and obtains solution C, then by (Ni0.8Co0.1Mn0.1)
C2O4Presoma is dispersed in container, and (Ni then is added dropwise in above-mentioned solution C0.8Co0.1Mn0.1)C2O4In presoma,
And 40min is sufficiently stirred in magnetic force, after mixing, magnetic force heating stirring is evaporated to gel at 70 DEG C, and it is dry to place into vacuum
Mixture is obtained with the dry 18h of 80 DEG C of temperature in dry case.
S3, by the mixture in S2 under oxygen atmosphere, be heated to 500 DEG C with 4 DEG C/min heating rate, and in this temperature
Lower heat preservation 4h is equally heated to 750 DEG C again after grinding uniformly with 4 DEG C/min heating rate, keeps the temperature 13h at this temperature, be down to
It is ground up, sieved after room temperature to get the LiNi for the lanthana for coating 5wt% to surface0.8Co0.1Mn0.1O2Positive electrode.
The SEM figure of the nickelic tertiary cathode material for the surface cladding 5wt% lanthana being prepared through embodiment 3 equally may be used
With reference to shown in Fig. 1；By the nickelic tertiary cathode material of the resulting surface of embodiment 3 cladding 5wt% lanthana by being coated with, doing
It is dry, it is assembled into fastening lithium ionic cell, carries out 1C constant current charge-discharge test；And the nickelic ternary with surface without cladding lanthana is just
Pole material is compared, and test result and result shown in Fig. 2 are essentially identical.
Embodiment 4
A kind of nickelic tertiary cathode material of surface cladding lanthana, the molecular formula of the nickelic tertiary cathode material are
LiNi0.8Co0.1Mn0.1O2, the quality of the lanthana is the 10wt% of nickelic tertiary cathode material quality.
A kind of preparation method of the nickelic tertiary cathode material of above-mentioned surface cladding lanthana is as follows：
S1, by nickel nitrate, manganese nitrate, cobalt nitrate in molar ratio 8：1：1, it is dissolved in deionized water and is configured to concentration and is
The solution A of 2.0mol/L；Sodium oxalate is dissolved in deionized water and prepares solution B；Using peristaltic pump by solution A and solution B simultaneously
It instills and carries out coprecipitation reaction 12h in reaction kettle, the ratio between nickel source, the total mole number of cobalt source and manganese source and molal quantity of precipitating reagent are
1：1；It wherein, is 11 with the pH value of ammonia water conditioning system during solution A and solution B is added dropwise, during coprecipitation reaction
Persistently lead to N2, temperature is 55 DEG C, is aged 12h after reaction, is filtered, washed later, drying to obtain nickel cobalt manganese presoma, i.e.,
(Ni0.8Co0.1Mn0.1)C2O4Presoma.
S2, the 10wt% that nickelic tertiary cathode material quality is accounted for by the quality of lanthana in final product, and according to nickel cobalt
The quality of manganese presoma can determine the quality of required lithium source and lanthanum source, and the lithium source of the present embodiment is using lithium chloride, fluorination
Lithium, lanthanum source use lanthanum acetate；It weighs lithium source and lanthanum source is successively dissolved in deionized water and obtains solution C, then will
(Ni0.8Co0.1Mn0.1)C2O4Presoma is dispersed in container, and (Ni then is added dropwise in above-mentioned solution C0.8Co0.1Mn0.1)
C2O4In presoma, and 50min is sufficiently stirred in magnetic force, and after mixing, magnetic force heating stirring is evaporated to gel at 90 DEG C,
It places into vacuum oven and obtains mixture for 24 hours with 90 DEG C of temperature dryings.
S3, by the mixture in S2 under air atmosphere, be heated to 550 DEG C with 5 DEG C/min heating rate, and in this temperature
Lower heat preservation 8h is equally heated to 900 DEG C again after grinding uniformly with 5 DEG C/min heating rate, keeps the temperature 16h at this temperature, be down to
It is ground up, sieved after room temperature to get the LiNi for the lanthana for coating 10wt% to surface0.8Co0.1Mn0.1O2Positive electrode.
The SEM figure of the nickelic tertiary cathode material for the surface cladding 10wt% lanthana being prepared through embodiment 4 is same
It can be with reference to shown in Fig. 1；The nickelic tertiary cathode material of the resulting surface of embodiment 4 cladding 10wt% lanthana is passed through into painting
Cloth, drying are assembled into fastening lithium ionic cell, carry out 1C constant current charge-discharge test；And with surface without the nickelic of cladding lanthana
Tertiary cathode material is compared, and test result and result shown in Fig. 2 are essentially identical.
Embodiment 5
A kind of nickelic tertiary cathode material of surface cladding lanthana, the molecular formula of the nickelic tertiary cathode material are
LiNi0.8Co0.1Mn0.1O2, the quality of the lanthana is the 1wt% of nickelic tertiary cathode material quality.
A kind of preparation method of the nickelic tertiary cathode material of above-mentioned surface cladding lanthana is as follows：
S1, by nickel acetate, manganese acetate, cobalt acetate in molar ratio 8：1：1, it is dissolved in deionized water and is configured to concentration and is
The solution A of 1mol/L；Sodium hydroxide is dissolved in deionized water and prepares solution B；Using peristaltic pump by solution A and solution B simultaneously
It instills and carries out coprecipitation reaction 6h in reaction kettle, the ratio between nickel source, the total mole number of cobalt source and manganese source and molal quantity of precipitating reagent are
1：2；It wherein, is 10 with the pH value of ammonia water conditioning system during solution A and solution B is added dropwise, during coprecipitation reaction
Persistently lead to N2, temperature is 50 DEG C, is aged 12h after reaction, is filtered, washed later, drying to obtain nickel cobalt manganese presoma, i.e.,
(Ni0.8Co0.1Mn0.1)(OH)2Presoma.
S2, the 1wt% that nickelic tertiary cathode material quality is accounted for by the quality of lanthana in final product, and according to nickel cobalt manganese
The quality of presoma can determine that the quality of required lithium source and lanthanum source, the lithium source of the present embodiment use lithium phosphate, lithium hydrogen phosphate
And lithium dihydrogen phosphate, lanthanum source use lanthanum nitrate；It weighs lithium source and lanthanum source is successively dissolved in deionized water and obtains solution C, then will
(Ni0.8Co0.1Mn0.1)(OH)2Presoma is dispersed in container, and then above-mentioned solution C is added dropwise
(Ni0.8Co0.1Mn0.1)(OH)2In presoma, and 60min is sufficiently stirred in magnetic force, and after mixing, magnetic force heating is stirred at 85 DEG C
It mixes and is evaporated to gel, place into vacuum oven and mixture is obtained with the dry 12h of 100 DEG C of temperature.
S3, by the mixture in S2 under oxygen atmosphere, be heated to 450 DEG C with 5 DEG C/min heating rate, and in this temperature
Lower heat preservation 6h is equally heated to 800 DEG C again after grinding uniformly with 5 DEG C/min heating rate, keeps the temperature 12h at this temperature, be down to
It is ground up, sieved after room temperature to get the LiNi for the lanthana for coating 1wt% to surface0.8Co0.1Mn0.1O2Positive electrode.
The SEM figure of the nickelic tertiary cathode material for the surface cladding 1wt% lanthana being prepared through embodiment 5 is equally such as
Shown in Fig. 1.By the nickelic tertiary cathode material of the resulting surface of embodiment 5 cladding 1wt% lanthana by being coated and dried, fill
It is made into fastening lithium ionic cell, carries out 1C constant current charge-discharge test；And the nickelic tertiary cathode material with surface without cladding lanthana
Material is compared, and the cycle performance of the two is also shown in FIG. 2.
Embodiment described above only describe the preferred embodiments of the invention, not to model of the invention
It encloses and is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical side of the invention
The various changes and improvements that case is made should all be fallen into the protection scope that claims of the present invention determines.
Claims (10)
1. a kind of nickelic tertiary cathode material of surface cladding lanthana, it is characterised in that：The nickelic tertiary cathode material
Molecular formula is LiNi0.8Co0.1Mn0.1O2, the quality of the lanthana is the 0.5-10wt% of nickelic tertiary cathode material quality.
2. a kind of preparation method of the nickelic tertiary cathode material of surface cladding lanthana according to claim 1, special
Sign is, includes the following steps：
S1, it nickel source, manganese source, cobalt source is dissolved in deionized water is configured to solution A；Precipitating reagent is dissolved in deionized water and is configured to
Solution B；Solution A and solution B are added in reaction unit and carry out coprecipitation reaction, after reaction, it is aged, be filtered, washed,
It is dried to obtain nickel cobalt manganese presoma；
S2, lithium source and lanthanum source are dissolved in deionized water and obtain solution C, the nickel cobalt manganese forerunner then obtained by solution C and through S1
Body is uniformly mixed, and is evaporated to gel, is dried to obtain mixture；
S3, the mixture obtained through S2 is once calcined, after grinding uniformly, carries out secondary clacining, ground after being down to room temperature
Sieving obtains the nickelic tertiary cathode material of surface cladding lanthana.
3. a kind of preparation method of the nickelic tertiary cathode material of surface cladding lanthana according to claim 2, special
Sign is that the total mol concentration of nickel source, manganese source and cobalt source in the solution A is 0.8-2.0mol/L；Nickel source, cobalt source and manganese source
Molar ratio be 8:1:1.
4. a kind of preparation method of the nickelic tertiary cathode material of surface cladding lanthana according to claim 2, special
Sign is that the precipitating reagent is the mixture of one or more of sodium hydroxide, sodium carbonate, sodium oxalate.
5. a kind of preparation method of the nickelic tertiary cathode material of surface cladding lanthana according to claim 2, special
Sign is that the ratio between molal quantity of the nickel source, the total mole number of cobalt source and manganese source and precipitating reagent is 1：1-1：2.
6. a kind of preparation method of the nickelic tertiary cathode material of surface cladding lanthana according to claim 2, special
Sign is that the nickel source is the mixture of one or more of nickel sulfate, nickel acetate, nickel nitrate；The manganese source is sulfuric acid
One of manganese, manganese acetate, manganese nitrate or a variety of mixtures；The cobalt source is one of cobaltous sulfate, cobalt acetate, cobalt nitrate
Or a variety of mixture；The lithium source be lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, lithium chloride, lithium fluoride, lithium phosphate,
One of lithium hydrogen phosphate, lithium dihydrogen phosphate or a variety of mixtures；The lanthanum source is lanthanum nitrate, in lanthanum chloride, lanthanum acetate
One or more mixtures.
7. a kind of preparation method of the nickelic tertiary cathode material of surface cladding lanthana according to claim 2, special
Sign is, is added drop-wise in reaction kettle solution A and solution B simultaneously in the S1 and carries out coprecipitation reaction, and solution A and molten is being added dropwise
It is 7-11 with the pH value of ammonia water conditioning system during liquid B；The coprecipitation reaction carries out under nitrogen atmosphere, co-precipitation
The temperature of reaction is 35-55 DEG C, time 4-12h.
8. a kind of preparation method of the nickelic tertiary cathode material of surface cladding lanthana according to claim 2, special
Sign is that the digestion time in the S1 is 6-12h.
9. a kind of preparation method of the nickelic tertiary cathode material of surface cladding lanthana according to claim 2, special
Sign is, the S2 the specific steps are：Lithium source and Lan Yuan are successively dissolved in deionized water and obtain solution C, by the nickel in S1
Cobalt manganese presoma is dispersed in container, and solution C is added dropwise, and 30-60min is sufficiently stirred by magnetic force, after mixing,
Magnetic agitation is evaporated to gel at 60-90 DEG C, places into vacuum oven, and dry 6-24h is obtained at 60-100 DEG C
Mixture.
10. a kind of preparation method of the nickelic tertiary cathode material of surface cladding lanthana according to claim 2, special
Sign is that the technique once calcined is：By the mixture obtained through S2 under air or oxygen atmosphere, with 3-5 DEG C/min
Heating rate be heated to 400-550 DEG C, keep the temperature 3-8h；The technique of the secondary clacining is：With the heating rate of 3-5 DEG C/min
It is heated to 700-900 DEG C, keeps the temperature 10-16h.
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