CN109411724A - A kind of preparation method of core-shell structure tertiary cathode material - Google Patents
A kind of preparation method of core-shell structure tertiary cathode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- 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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—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
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- H—ELECTRICITY
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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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- H—ELECTRICITY
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- 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
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Abstract
The present invention provides a kind of preparation methods of core-shell structure tertiary cathode material, the following steps are included: (1) prepares the higher soluble metal salt solution of nickel content, it is spray-dried after mixing, carries out ball milling after the powder low temperature calcination of collection, nickelic kernel presoma I is made；(2) the lower soluble metal salt solution of nickel content is prepared, kernel presoma I is dispersed therein, secondary spray drying is carried out, carries out ball milling after the powder low temperature calcination of collection, core-shell structure presoma II is made；(3) core-shell structure presoma II is calcined under oxygen atmosphere, up to target product after cooling sieving.The method largely improves the phenomenon that material internal Elemental redistribution is uneven and surface residual alkali is higher, improves material structure stability and cycle performance.In addition, the method simple process, high production efficiency, it is easy to accomplish industrialization.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries technical field, specifically a kind of core-shell structure tertiary cathode material
Preparation method.
Background technique
Lithium ion battery is high with energy density, operating voltage range is wide, has extended cycle life, has a safety feature, is memoryless
The features such as effect, obtains in fields such as portable electronic device, electric car industry, power energy storage, smart grid, unmanned plane science and technology
To extensive use.However, remaining some problems in the preparation process of anode material for lithium-ion batteries, battery restrict
The development of industry.
Nickel cobalt lithium aluminate (NCA)/nickle cobalt lithium manganate (NCM) as being commercialized more mature tertiary cathode material at present,
Its energy density is high, and price is low, and safety is good, is widely recognized as by battery industry.Currently, preparing the master of tertiary cathode material
Stream method has high temperature solid-state method, sol-gal process, hydro-thermal method, coprecipitation etc..High temperature solid-state method simple process, production cost
It is low, but the method cannot reach the mixing of atomic level, and homogeneity of product is poor.Sol-gal process and hydro-thermal method preparation process are opposite
Cumbersome, higher cost is not suitable for large-scale commercial production.Coprecipitation is prepared in materials process, due to manganese and nickel, cobalt it is molten
Degree product 2 orders of magnitude of difference, aluminium differs 18 orders of magnitude with the solubility product of nickel, cobalt, therefore nickel cobalt and manganese/aluminium are difficult simultaneously homogeneously
Precipitating causes material internal Elemental redistribution uneven, largely influences the structural stability of material.Secondly, high-nickel material surface
Residual alkali is higher, is easy to and H2O and CO2It chemically reacts, reduces the storge quality of material, exacerbate between material and electrolyte
Side reaction, and then cause battery use process in flatulence phenomenon.
In view of the above-mentioned problems, Chinese patent CN103094546A uses coprecipitation, NaAlO is utilized2In coprecipitation reaction
It can slowly hydrolyze to form in the process Al (OH)3Characteristic, using it as aluminium salt, to reach the precipitation from homogeneous solution of each element.But
NaAlO2Solution itself is unstable, easy crystallization, so as to cause the deviation of products therefrom each component content and design value.Chinese patent
CN106532035A coats low nickel material using shearing for nickelic system material and changes using ternary hydroxide presoma as raw material
Kind material surface pH and residual alkali problem, and then the cycle performance of material is improved, however hydroxide precursor original is prepared
Material itself needs certain technological operation, long preparation period, and subsequent solid phase is needed to coat with lithium and solid state shear, it is difficult to guarantee each
The homogeneity of Elemental redistribution.Therefore, it is necessary to develop a kind of new preparation method, material various aspects are improved, to be promoted
Its chemical property.
Summary of the invention
The invention proposes a kind of preparation methods of core-shell structure tertiary cathode material, using spray drying-high temperature sintering
A kind of simple process route designed in conjunction, largely improves material internal Elemental redistribution unevenness and surface residual alkali is higher
The phenomenon that, improve material structure stability and cycle performance.In addition, the method simple process, high production efficiency, it is easy to accomplish work
Industry.
It realizes the technical scheme is that a kind of preparation method of core-shell structure tertiary cathode material, including following step
It is rapid:
(1) it is molten that the soluble metallic salt of metallic nickel, cobalt, lithium and M the preparation of nickelic kernel ternary precursor: are configured to metal salt
Liquid, wherein M is any one of aluminium or manganese, is spray-dried to metal salt solution, by obtained powder under air atmosphere
Low temperature calcination and high-energy ball milling processing are carried out, kernel persursor material I is obtained；
(2) it is molten that the soluble metallic salt of metallic nickel, cobalt, lithium and M the preparation of core-shell structure ternary precursor: are configured to metal salt
Liquid, wherein M is any one of aluminium or manganese, and dispersing agent is added, is stirring evenly and then adding into the kernel presoma material that step (1) obtains
Material I forms uniform solution, uniform solution is carried out secondary spray drying treatment, obtained powder is carried out under air atmosphere
Low temperature calcination and high-energy ball milling processing, obtain finely dispersed core-shell structure persursor material II；
(3) preparation of core-shell structure tertiary cathode material: core-shell structure ternary precursor material II is transferred to calcining furnace, in oxygen
Atmosphere encloses lower carry out low temperature calcination, then carries out high-temperature calcination, is crushed and is sieved up to target product after natural cooling.
The ratio between amount of substance of metallic nickel, cobalt, lithium and M is a:b:c:(1-a-b in the step (1)), wherein 0.8≤a
≤ 1, a+b≤1,1≤c≤1.15；The ratio between amount of substance of metallic nickel, cobalt, lithium and M is x:y:z:(1-x-y in step (2)),
Wherein 0.3≤x≤0.8, x+y≤1,1≤z≤1.15.
Metal salt is the mixing of one or more of nitrate, carbonate, oxalates, acetate in the step (1)
Object.
The condition of step (1) spray drying and step (2) secondary spray drying is: metal salt solution spray rate is
300~600mL/h, inlet temperature be 180~220 DEG C, outlet temperature be 100~130 DEG C, spray air pressure be 0.2~
0.4Mpa, 0.5~1.5m3/min of dry air flow adjustment range.
The solvent of soluble metallic salt is water in the step (1), in step (2) solvent of soluble metallic salt be water,
The mixture of one or more of ethylene glycol and polyethylene glycol.
The concentration of metal salt is 1~3mol/L in the step (1) and (2).
Dispersing agent is the mixing of one or more of polyvinylpyrrolidone, starch and guar gum in the step (2)
Object, additive amount are the 1~7% of total metal salt quality.
The rate of high-energy ball milling is 100~400r/min in the step (1) and step (2).
The step (1) and step (2) heating rate are 3~8 DEG C/min, and low temperature calcination temperature is 400~600 DEG C, are protected
Warm 3~6h of time.
Heating rate is 3~8 DEG C/min in the step (3), and low temperature calcination temperature is 400~600 DEG C, soaking time 3
~6h, high-temperature calcination temperature are 700~850 DEG C, 10~18h of soaking time.
The beneficial effects of the present invention are:
(1) inner element distribution height is uniform.By using soluble metallic salt as raw material, using spray drying and solid-phase sintering skill
Tertiary cathode material made from the method that art combines, inner element distribution have high level of homogeneity, the lithium of material are effectively reduced
Nickel mixing phenomenon further promotes material internal structure stability, reduces cyclicity caused by structure collapses in charge and discharge process
The phenomenon that capable of reducing.
(2) material surface residual alkali is effectively reduced.Core-shell structure is being made just by the method that low nickel material coats high-nickel material
Pole material, surface residual alkali are greatly lowered, and effectively inhibit material to the sensibility of water in air and carbon dioxide, reduce material
Side reaction between surface and electrolyte promotes its cycle performance, reduces the flatulence phenomenon of battery.
(3) production efficiency is improved, production energy consumption is reduced.When the method greatly shortens the preparation of tertiary cathode material
Between, it is not necessarily to subsequent washing, the tedious steps such as drying, while low for equipment requirements, operating procedure simplicity.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the scanning electron microscope (SEM) photograph of ternary composite cathode material presoma prepared by the present embodiment one；
Fig. 2 is the scanning electron microscope (SEM) photograph of ternary composite cathode material prepared by the present embodiment one；
Fig. 3 is the ternary composite cathode material of the preparation of the present embodiment one in the mA of 0.1C(1C=180 g-1) filling under multiplying power for the first time
Discharge curve；
Fig. 4 be the present embodiment one prepare ternary composite cathode material under 0.2C multiplying power charge and discharge it is electro-active 4 circle after, at 0.5C times
Charge-discharge performance curve under rate.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
In the present embodiment, the preparation method of core-shell structure tertiary cathode material, the specific steps are as follows:
(1) preparation of nickelic kernel ternary precursor: claim by metal molar ratio Li:Ni:Co:Mn=1.05:0.83:0.1:0.07
Take lithium acetate, nickel acetate, cobalt acetate, manganese nitrate is dissolved in deionized water, and it is molten to be prepared into the metal salt that concentration is 1.5mol/L
Liquid is spray-dried after mixing evenly with the feed rate of 300mL/h, and inlet temperature is adjusted to 200 DEG C, and outlet temperature is
130 DEG C, spray air pressure 0.2Mpa, dry air adjustable range 1.5m3/min, obtained powder will be collected and be placed in calcining
In furnace, the lower 8 DEG C/min of air conditions is warming up to 400 DEG C of holding 5h, after natural cooling, utilizes ball mill 400r/min ball mill crushing
3h obtains submicron order persursor material；
(2) preparation of core-shell structure ternary precursor: according to metal molar ratio Li:Ni:Co:Al=1.05:0.8:0.15:0.05
Weigh lithium acetate, nickel acetate, cobalt acetate, aluminum nitrate is dissolved in deionized water: in the solution of polyethylene glycol=3:2 (volume ratio), system
The standby metal salt solution for being 1mol/L at concentration, in the ratio of total metal quality 7% weigh starch and guar gum (the two mass ratio=
1:1), it is added in above-mentioned solution after mixing evenly, is added in obtained in step 1 in the ratio that the total metal molar of nucleocapsid is 5:1
Nuclear material after high-speed stirred is uniform, is spray-dried with the feed rate of 400mL/h, and inlet temperature is adjusted to 200 DEG C, out
Mouth temperature is 125 DEG C, spray air pressure 0.4Mpa, and the powder that dry air adjustable range 1.5m3/min is collected is set
In in calcining furnace, the lower 3 DEG C/min of air atmosphere is warming up to 500 DEG C of holding 5h, takes out after natural cooling, is put into ball grinder, 200r/
Min ball mill crushing 2h obtains the finely dispersed core-shell structure persursor material of particle；
(3) preparation of core-shell structure tertiary cathode material: above-mentioned persursor material is transferred to high-temperature calcination stove, under Oxygen Condition
5 DEG C/min is warming up to 500 DEG C of holding 6h, is continuously heating to 760 DEG C of holding 15h, is crushed and is sieved up to target product after cooling.
Embodiment 2
In the present embodiment, the preparation method of core-shell structure tertiary cathode material, the specific steps are as follows:
(1) preparation of nickelic kernel ternary precursor: metal molar ratio Li:Ni:Co:Mn=1.1:0.85:0.075:0.075 is pressed
Weigh lithium acetate, nickel acetate, cobalt nitrate, manganese oxalate is dissolved in deionized water, and it is molten to be prepared into the metal salt that concentration is 2.5mol/L
Liquid is spray-dried after mixing evenly with the feed rate of 600mL/h, and inlet temperature is adjusted to 180 DEG C, and outlet temperature is
100 DEG C, spray air pressure 0.27Mpa, dry air adjustable range 1m3/min, obtained powder will be collected and be placed in calcining
In furnace, the lower 6 DEG C/min of air conditions is warming up to 480 DEG C of calcining 6h, after natural cooling, utilizes ball mill 350r/min ball mill crushing
3h obtains submicron order kernel persursor material；
(2) lithium acetate, acetic acid the preparation of core-shell structure ternary precursor: are weighed by metal molar ratio Li:Ni:Co=1:0.7:0.3
Nickel, cobalt nitrate are dissolved in deionized water: in the solution of polyethylene glycol=3:2 (volume ratio), being prepared into the metal that concentration is 1.2mol/L
Salting liquid weighs starch in the ratio of total metal quality 5%, is added in above-mentioned solution after mixing evenly, by the total metal molar of nucleocapsid
Ratio is obtained for 4:1, inner nuclear material obtained in step 1 is added, after high-speed stirred is uniform, carried out with the feed rate of 400mL/h
Spray drying, inlet temperature are adjusted to 220 DEG C, and outlet temperature is 118 DEG C, spray air pressure 0.4Mpa, dry air tune
The powder that adjusting range 1.2m3/min is collected is placed in calcining furnace, and the lower 3 DEG C/min of air atmosphere is warming up to 450 DEG C of calcining 5h,
It is taken out after cooling, is put into ball grinder, 200r/min ball mill crushing 5h obtains the finely dispersed core-shell structure presoma material of particle
Material；
(3) preparation of core-shell structure tertiary cathode material: above-mentioned persursor material is transferred to high-temperature calcination stove, under Oxygen Condition
5 DEG C/min is warming up to 500 DEG C of holding 5h, is continuously heating to 780 DEG C of holding 15h, is crushed and is sieved up to target product after cooling.
Embodiment 3
In the present embodiment, the preparation method of core-shell structure tertiary cathode material, the specific steps are as follows:
(1) preparation of nickelic kernel ternary precursor: carbonic acid is weighed by metal molar ratio Li:Ni:Co=1.15:0.85:0.15
Lithium, nickel oxalate, cobalt oxalate are dissolved in deionized water, are prepared into the metal salt solution that concentration is 3mol/L, after mixing evenly, with
The feed rate of 550mL/h is spray-dried, and inlet temperature is adjusted to 200 DEG C, and outlet temperature is 108 DEG C, spray air pressure
Power is 0.26Mpa, dry air adjustable range 1.2m3/min, will collect obtained powder and is placed in calcining furnace, under air conditions
3 DEG C/min is warming up to 450 DEG C of holding 4h, after natural cooling, using ball mill 350r/min ball mill crushing 3h, obtains submicron order
Persursor material；
(2) preparation of core-shell structure ternary precursor: claim according to metal molar ratio Li:Ni:Co:Mn=1.03:0.3:0.4:0.3
Take nickel nitrate, cobalt nitrate, manganese nitrate, lithium acetate is dissolved in deionized water: in ethylene glycol=1:2 solution (volume ratio), being prepared into
Concentration is the metal salt solution of 1.3mol/L, in the ratio of total metal quality 1.5% weigh PVP and guar gum (the two mass ratio=
1:1), it is added in above-mentioned solution after mixing evenly, is added in obtained in step 1 in the ratio that the total metal molar of nucleocapsid is 5:3
Nuclear material after high-speed stirred is uniform, is spray-dried with the feed rate of 300mL/h, and inlet temperature is adjusted to 210 DEG C, out
Mouth temperature is 115 DEG C, spray air pressure 0.2Mpa, and the powder that dry air adjustable range 0.5m3/min is collected is set
In in calcining furnace, the lower 3 DEG C/min of air atmosphere is warming up to 550 DEG C of holding 5h, takes out after cooling, is put into ball grinder, 300r/min
Ball mill crushing 2.5h obtains the finely dispersed core-shell structure persursor material of particle；
(3) preparation of core-shell structure tertiary cathode material: above-mentioned persursor material is transferred to high-temperature calcination stove, under Oxygen Condition
3 DEG C/min is warming up to 500 DEG C of holding 5h, is continuously heating to 850 DEG C of holding 10h, is crushed and is sieved up to target product after cooling.
Embodiment 4
In the present embodiment, the preparation method of core-shell structure tertiary cathode material, the specific steps are as follows:
(1) preparation of nickelic kernel ternary precursor: lithium acetate is weighed by metal molar ratio Li:Ni=1:1, nickel acetate is dissolved in
Ionized water is prepared into the metal salt solution that concentration is 1mol/L and is sprayed after mixing evenly with the feed rate of 500mL/h
Dry, inlet temperature is adjusted to 220 DEG C, and outlet temperature is 110 DEG C, spray air pressure 0.4Mpa, and dry air adjusts model
0.8m3/min is enclosed, obtained powder will be collected is placed in the lower 5 DEG C/min of air conditions in calcining furnace and be warming up to 450 DEG C of holdings 4h, oneself
So after cooling, using ball mill 350r/min ball mill crushing 3h, submicron order kernel persursor material is obtained；
(2) preparation of core-shell structure ternary precursor: claim by metal molar ratio Li:Ni:Co:Al=1.05:0.8:0.15:0.05
Take lithium carbonate, nickel nitrate, cobalt nitrate, aluminum nitrate is dissolved in deionized water: in the solution of ethylene glycol=3:2 (volume ratio), being prepared into
Concentration is the metal salt solution of 1.5mol/L, weighs PVP in the ratio of total metal quality 1%, is added in above-mentioned solution and stirs evenly
Afterwards, inner nuclear material obtained in step 1 is added in the ratio that the total metal molar of nucleocapsid is 3:1, after high-speed stirred is uniform, with
The feed rate of 400mL/h is spray-dried, and inlet temperature is adjusted to 200 DEG C, and outlet temperature is 102 DEG C, spray air pressure
Power is 0.25Mpa, and the powder that dry air adjustable range 1m3/min is collected is placed in calcining furnace, lower 8 DEG C of air atmosphere/
Min is warming up to 500 DEG C of holding 3h, takes out after natural cooling, is put into ball grinder, and 200r/min ball mill crushing 2h obtains particle point
Dissipate uniform core-shell structure persursor material；
(3) preparation of core-shell structure tertiary cathode material: above-mentioned persursor material is transferred to high-temperature calcination stove, under Oxygen Condition
3 DEG C/min is warming up to 500 DEG C of holding 5h, is continuously heating to 700 DEG C of holding 18h, is crushed and is sieved up to target product after cooling.
Embodiment 5
In the present embodiment, the preparation method of core-shell structure tertiary cathode material, the specific steps are as follows:
(1) preparation of nickelic kernel ternary precursor: claim by metal molar ratio Li:Ni:Co:Al=1.06:0.83:0.1:0.07
Taking lithium carbonate, nickel oxalate, cobalt oxalate, aluminum nitrate is dissolved in deionized water, it is prepared into the metal salt solution that concentration is 1mol/L,
After mixing evenly, it is spray-dried with the feed rate of 430mL/h, inlet temperature is adjusted to 220 DEG C, outlet temperature 110
DEG C, spray air pressure 0.25Mpa, dry air adjustable range 1.1m3/min will collect obtained powder and be placed in calcining furnace
Interior, the lower 8 DEG C/min of air atmosphere is warming up to 500 DEG C of holding 3h, after natural cooling, utilizes ball mill 100r/min ball mill crushing
5h obtains submicron order persursor material；
(2) preparation of core-shell structure ternary precursor: acetic acid is weighed according to metal molar ratio Li:Ni:Co=1.15:0.8:0.2
Lithium, nickelous carbonate, cobalt nitrate are dissolved in deionized water: ethylene glycol=1:3(volume ratio) solution in, be prepared into concentration be 1.4mol/L
Metal salt solution, weigh PVP and guar gum (the two mass ratio=1:1) in the ratio of total metal quality 5%, above-mentioned solution be added
In after mixing evenly, inner nuclear material obtained in step 1 is added in the ratio that the total metal molar of nucleocapsid is 5:1, high-speed stirred is equal
It after even, is spray-dried with the feed rate of 300mL/h, inlet temperature is adjusted to 180 DEG C, and outlet temperature is 100 DEG C, spraying
Air pressure is 0.25Mpa, and the powder that dry air adjustable range 1.2m3/min is collected is placed in calcining furnace, air atmosphere
It encloses lower 5 DEG C/min and is warming up to 600 DEG C of holding 3h, taken out after cooling, be put into ball grinder, 300r/min ball mill crushing 3h is obtained
The finely dispersed core-shell structure persursor material of grain；
(3) preparation of core-shell structure tertiary cathode material: above-mentioned persursor material is transferred to high-temperature calcination stove, under Oxygen Condition
3 DEG C/min is warming up to 500 DEG C of holding 5h, is continuously heating to 750 DEG C of holding 15h, is crushed and is sieved up to target product after cooling.
Embodiment 6
In the present embodiment, the preparation method of core-shell structure tertiary cathode material, the specific steps are as follows:
(1) preparation of nickelic kernel ternary precursor: weighing lithium acetate by metal molar ratio Li:Ni:Co=1.06:0.8:0.2,
Nickel acetate, cobalt acetate are dissolved in deionized water, are prepared into the metal salt solution that concentration is 1.2mol/L, after mixing evenly, with
The feed rate of 450mL/h is spray-dried, and inlet temperature is adjusted to 220 DEG C, and outlet temperature is 110 DEG C, spray air pressure
Power is 0.35Mpa, dry air adjustable range 1.4m3/min, will collect obtained powder and is placed in calcining furnace, under air conditions
3 DEG C/min is warming up to 550 DEG C of holding 4h, after natural cooling, using ball mill 400r/min ball mill crushing 4h, obtains submicron order
Persursor material；
(2) preparation of core-shell structure ternary precursor: claim according to metal molar ratio Li:Ni:Co:Mn=1.05:0.5:0.2:0.3
Take nickel nitrate, cobalt nitrate, manganese nitrate, lithium oxalate is dissolved in deionized water: in the solution of polyethylene glycol=1:1 (volume ratio), preparation
The metal salt solution for being 1mol/L at concentration, weighs PVP and starch (the two mass ratio=1:1) in the ratio of total metal quality 1%,
It is added in above-mentioned solution after mixing evenly, kernel material obtained in step 1 is added in the ratio that the total metal molar of nucleocapsid is 5:1
Material, after high-speed stirred is uniform, is spray-dried with the feed rate of 400mL/h, and inlet temperature is adjusted to 230 DEG C, outlet temperature
Degree is 113 DEG C, spray air pressure 0.4Mpa, dry air adjustable range 1.3m3The powder that/min is collected, which is placed in, to be forged
It burns in furnace, the lower 5 DEG C/min of air atmosphere is warming up to 600 DEG C of holding 5h, takes out after natural cooling, is put into ball grinder, 250r/min
Ball mill crushing 2h obtains the finely dispersed core-shell structure persursor material of particle；
(3) preparation of core-shell structure tertiary cathode material: above-mentioned persursor material is transferred to high-temperature calcination stove, under Oxygen Condition
5 DEG C/min is warming up to 500 DEG C of holding 5h, is continuously heating to 780 DEG C of holding 13h, is crushed and is sieved up to target product after cooling.
Table 1 is the chemical property of the ternary composite cathode material prepared in each embodiment
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of core-shell structure tertiary cathode material, it is characterised in that the following steps are included:
(1) it is molten that the soluble metallic salt of metallic nickel, cobalt, lithium and M the preparation of nickelic kernel ternary precursor: are configured to metal salt
Liquid, wherein M is any one of aluminium or manganese, is spray-dried to metal salt solution, by obtained powder under air atmosphere
Low temperature calcination and high-energy ball milling processing are carried out, kernel persursor material I is obtained；
(2) it is molten that the soluble metallic salt of metallic nickel, cobalt, lithium and M the preparation of core-shell structure ternary precursor: are configured to metal salt
Liquid, wherein M is any one of aluminium or manganese, and dispersing agent is added, is stirring evenly and then adding into the kernel presoma material that step (1) obtains
Material I forms uniform solution, uniform solution is carried out secondary spray drying treatment, obtained powder is carried out under air atmosphere
Low temperature calcination and high-energy ball milling processing, obtain finely dispersed core-shell structure persursor material II；
(3) preparation of core-shell structure tertiary cathode material: core-shell structure ternary precursor material II is transferred to calcining furnace, in oxygen
Atmosphere encloses lower carry out low temperature calcination, then carries out high-temperature calcination, is crushed and is sieved up to target product after natural cooling.
2. the preparation method of core-shell structure tertiary cathode material according to claim 1, it is characterised in that: the step
(1) the ratio between amount of substance of metallic nickel, cobalt, lithium and M is a:b:c:(1-a-b in), wherein 0.8≤a≤1, a+b≤1,1≤c≤
1.15；The ratio between amount of substance of metallic nickel, cobalt, lithium and M is x:y:z:(1-x-y in step (2)), wherein 0.3≤x≤0.8, x+
Y≤1,1≤z≤1.15.
3. the preparation method of core-shell structure tertiary cathode material according to claim 1, it is characterised in that: the step
(1) metal salt is the mixture of one or more of nitrate, carbonate, oxalates, acetate in.
4. the preparation method of core-shell structure tertiary cathode material according to claim 1, which is characterized in that the step
(1) be spray-dried and the condition of step (2) secondary spray drying is: metal salt solution spray rate is 300~600mL/h, is entered
Mouth temperature is 180~220 DEG C, and outlet temperature is 100~130 DEG C, and spray air pressure is 0.2~0.4Mpa, dry air stream
Measure 0.5~1.5m3/min of adjustable range.
5. the preparation method of core-shell structure tertiary cathode material according to claim 1, it is characterised in that: the step
(1) solvent of soluble metallic salt is water in, and the solvent of soluble metallic salt is water, ethylene glycol and polyethylene glycol in step (2)
One or more of mixture.
6. the preparation method of core-shell structure tertiary cathode material according to claim 1, it is characterised in that: the step
(1) and in (2) concentration of metal salt is 1~3mol/L.
7. the preparation method of core-shell structure tertiary cathode material according to claim 1, it is characterised in that: the step
(2) dispersing agent is the mixture of one or more of polyvinylpyrrolidone, starch and guar gum in, and additive amount is total metal
The 1~7% of salt quality.
8. the preparation method of core-shell structure tertiary cathode material according to claim 1, it is characterised in that: the step
(1) and in step (2) rate of high-energy ball milling is 100~400r/min.
9. the preparation method of core-shell structure tertiary cathode material according to claim 1, it is characterised in that: the step
(1) and step (2) heating rate is 3~8 DEG C/min, and low temperature calcination temperature is 400~600 DEG C, 3~6h of soaking time.
10. the preparation method of core-shell structure tertiary cathode material according to claim 1, it is characterised in that: the step
(3) heating rate is 3~8 DEG C/min in, and low temperature calcination temperature is 400~600 DEG C, 3~6h of soaking time, high-temperature calcination temperature
It is 700~850 DEG C, 10~18h of soaking time.
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