CN109879333A - The method that secondary molten-salt growth method prepares core-shell structure anode material of lithium battery - Google Patents
The method that secondary molten-salt growth method prepares core-shell structure anode material of lithium battery Download PDFInfo
- Publication number
- CN109879333A CN109879333A CN201910301582.XA CN201910301582A CN109879333A CN 109879333 A CN109879333 A CN 109879333A CN 201910301582 A CN201910301582 A CN 201910301582A CN 109879333 A CN109879333 A CN 109879333A
- Authority
- CN
- China
- Prior art keywords
- salt
- core
- shell structure
- lithium battery
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses nickelic ternary monocrystal, the chemical formula of the nickelic ternary monocrystal is LiNixCoyMnzO2, the invention also discloses a kind of core-shell structure anode material of lithium battery and preparation method thereof.Nickel content (nickelic ternary material) Lai Tisheng battery capacity is improved in material disclosed by the invention, core part, and shell parts (low nickel ternary material) improve manganese content to improve the structural stability of material.Core and shell have similar lattice structure, also can be relieved the two crystal lattice mismatch phenomenon.Surface coating layer can be improved the interface stability of nickelic ternary monocrystal, reduce the erosion of electrolyte, and nickelic ternary monocrystalline surface parasitic reaction is finally effectively reduced, improves the long-life cycle performance of material.
Description
Technical field
The invention belongs to lithium battery preparation technical fields, and in particular to secondary molten-salt growth method prepares core-shell structure lithium battery anode
The method of material.
Background technique
Currently, the commercialized LiCoO that succeeded2、LiFePO4、LiMn2O4Equal anode material of lithium battery, are not able to satisfy still
The demand in market.Stratiform transition metal oxide with more height ratio capacity is paid close attention to, wherein nickelic ternary material is (without stringent
Definition, LiNixCoyMnzO2, x+y+z=1, usual x >=0.5) and specific capacity is reachable up to 200mAh/g, single battery energy density
300Wh/kg is more able to satisfy the urgent need of current automobile-used lithium ion battery with high energy density compared with other positive electrode systems.But
It is that nickelic ternary material faces serious capacity and voltage droop problem, is to limit its commercialized crucial problem.Numerous researchs
It was found that nickelic ternary material surface stability is poor, (1) cause material easily with the CO in air2And H2O generation side reaction,
(2) there is serious parasitic reaction between electrolyte.Therefore, from material source Curve guide impeller, in nickelic ternary monocrystalline surface
The core-shell structure of heterogeneous clad is constructed, nickel content (nickelic ternary material) Lai Tisheng battery capacity, shell parts are improved in core part
(low nickel ternary material) improves manganese content to improve the structural stability of material.With this, nickelic ternary material surface and ring are blocked
The direct contact in border (electrolyte) effectively improves the long-life cycle performance of battery to improve the surface stability of material.Phase
Than in other inactive surfaces covering materials the material of lithium (refer to can not store up), low nickel ternary material can both change as heterogeneous clad
It is apt to nickelic ternary material surface stability, participates in charge and discharge electrochemical reaction but also as positive electrode.
Molten-salt growth method as reaction medium, has liquid phase appearance in synthesis process, nickel, cobalt, manganese reactant exist using low melting point salt
Wherein there is certain solubility, greatly accelerate the diffusion rate of ion, nickel, cobalt, manganese Metal ion is made to realize original in the liquid phase
Sub- scale mixing, reaction are converted into solid-liquid reaction by solid-solid reaction.By regulation reactant and fused salt mass ratio and react warm
Gradient is spent, realizes the controllable of the processes such as nucleus formation, crystal growth.In recent years, crystal growth from flux is synthesized in inorganic non-metallic material
Field is widely studied, and application range is also more and more extensive.Especially in homogenization micron order monocrystal preparation field tool
It has a clear superiority.
Summary of the invention
Goal of the invention: in view of the problems of the existing technology, technical problem to be solved by the invention is to provide nickelic
Ternary monocrystal.
Also there is provided a kind of core-shell structure anode material of lithium battery for technical problems to be solved by the present invention.
Also there is provided the preparation methods of nickelic ternary monocrystal for technical problems to be solved by the present invention.
The last technical problems to be solved of the present invention are to provide secondary molten-salt growth method and prepare core-shell structure anode material of lithium battery
Method.
The present invention prepares that cost of material is low, equipment is simple, fused salt is recyclable recycles, without the row of solid, liquid, gas waste
It puts.Nickel content (nickelic ternary material) Lai Tisheng battery is improved in monocrystal disclosed by the invention/heterosphere core-shell structure, core part
Capacity, shell parts (low nickel ternary material) improve manganese content to improve the structural stability of material.Core and shell have similar crystalline substance
Lattice structure also can be relieved the two crystal lattice mismatch phenomenon.Compared to other inactive surfaces covering materials, (lithium can not be stored up by referring to
Material), low nickel ternary material can both improve nickelic ternary material surface stability as heterogeneous clad, but also as positive material
Material participates in charge and discharge electrochemical reaction.
Technical solution: in order to solve the above technical problems, the present invention adopts the following technical scheme: the present invention provides nickelic three
First monocrystal, the chemical formula of the nickelic ternary monocrystal are LiNixCoyMnzO2, wherein x+y+z=1,1 x >=0.7 >.
The content of present invention further includes a kind of core-shell structure anode material of lithium battery, the core-shell structure anode material of lithium battery
Core be the nickelic ternary monocrystal, the shell is low nickel ternary material nanometer clad.
Wherein, the chemical formula of the low nickel ternary material nanometer clad is LiNixCoyMnzO2, wherein x+y+z=1,0
X≤0.4 <, 1 z >=0.3 >) clad accounts for the 1~5% of material (core-shell structure anode material of lithium battery) total mass ratio.
The content of present invention further includes the method that secondary molten-salt growth method prepares core-shell structure anode material of lithium battery, including following step
It is rapid:
1) it configures fused salt: weighing NaCl, KCl and Na respectively2SO4, it is fully ground, to be uniformly mixed so as to obtain fused salt spare；
2) configure raw material: raw material lithium salts, nickel salt needed for preparing nickelic ternary material, manganese salt grinding, mix cobalt salt
It is spare to obtain reactant 1, raw material lithium salts needed for low nickel ternary material will be prepared, nickel salt, cobalt salt, manganese salt grinding, mix it is spare
Obtain reactant 2；Wherein, in two raw materials (reactant 1 and reactant 2), lithium salts is more excessive than its stoichiometric ratio aequum
5%；
3) the nickelic ternary micron monocrystal of molten-salt growth method high―temperature nuclei: the fused salt of step 1) and the reactant 1 of step 2) are filled
Divide mixing, grinding, pyroreaction, after reaction, furnace cooling obtains mixture 1 after cooling；
4) mixture 1 is dissolved in solvent and forms suspension, reactant 2 is added, stirring and dissolving, drying, is ground concentration
Obtain mixture 2；
5) fused salt reacts the mixture 2 that step 4) obtains again, and it is nickelic that synthesis obtains low nickel ternary material nanometer layer cladding
The product of ternary micron monocrystal；
6) product of step 5) is washed, separated and collected the nickelic ternary single crystal material up to surface modification.
Wherein, NaCl, KCl and Na of step 1)2SO4Mass ratio be 30-60%:20-35%:20-40%.
Wherein, the lithium salts of step 2) is the one or two of lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate；Nickel salt is oxygen
Change the one or two of nickel, nickel acetate, nickelous carbonate, nickel chloride, nickel sulfate；Manganese salt is manganese dioxide, manganese acetate, manganese carbonate, chlorine
Change the one or two of manganese, manganese sulfate；Cobalt salt is cobaltosic oxide, cobalt acetate, cobalt carbonate, cobalt nitrate, cobalt chloride, cobaltous sulfate
It is one or two kinds of.
Wherein, the high―temperature nuclei step of step 3) is divided into two stages, 600-900 DEG C of first stage reaction temperature, synthesis
Time 2-6h, subsequent 700-900 DEG C of second stage reaction temperature, generated time 5-12h.
Wherein, the rate of temperature fall of step 3) is 20-60 DEG C/h, furnace cooling after being cooled to 500 DEG C.
Wherein, step 4) stirring rate is 200-500rpm, is concentrated after dissolution in 80 DEG C of water-baths, obtained solid air blast is dry
It is dry, grind, mix it is spare.
Wherein, step 4) solvent is one or both of deionized water, ethyl alcohol, isopropanol.
Wherein, fused salt reaction temperature is 600-800 DEG C, generated time 2-6h to step 5) again, cold with furnace after reaction
But.
Wherein, nickelic ternary material obtained in step 3) is micron monocrystal, and granular size (D50) is at 1.5-6 microns
Between.
The nickelic ternary single crystal material of surface modification obtained by step 6) is assembled into lithium ion battery as positive electrode,
Test chemical property.
Wherein, in air atmosphere high-temperature process, intracavitary atmosphere is atmospheric air, cavity gas flow rate 100- for fused salt reaction twice
400mL/min。
Wherein, fused salt and target positive electrode mass ratio are 1.1-5.0: 1.
The utility model has the advantages that the present invention synthesizes the nickelic ternary material (LiNi of micron monocrystalline figure using molten-salt growth methodxCoyMnzO2, x+
Y+z=1,1 x >=0.7 >), and then molten-salt growth method obtains a kind of material of monocrystal/heterosphere core-shell structure again, clad is
LiNixCoyMnzO2(x+y+z=1,0 x≤0.4 <, 1 z >=0.3 >), clad accounts for the 1~5% of material total mass ratio.This hair
Bright disclosed material, nickel content (nickelic ternary material) Lai Tisheng battery capacity, shell parts (low nickel ternary material are improved in core part
Material) manganese content is improved to improve the structural stability of material.Core and shell have similar lattice structure, also can be relieved the two interface
Lattice mismatch phenomenon.Surface coating layer can be improved the interface stability of nickelic ternary monocrystal, reduce the erosion of electrolyte, most
Nickelic ternary monocrystalline surface parasitic reaction is effectively reduced eventually, improves the long-life cycle performance of material.
Detailed description of the invention
The X-ray diffractogram of 5 sample of Fig. 1 embodiment；
The scanning electron microscope (SEM) photograph of 6 sample of Fig. 2 embodiment；
The transmission electron microscope picture of 7 sample of Fig. 3 embodiment；
The scanning electron microscope (SEM) photograph of 8 gained sample of Fig. 4 embodiment.
Specific embodiment
The following are the preferred embodiment of the present invention, for explaining only the invention, and is not intended to limit the present invention, and by this
Illustrate that made related improve belongs to the range that appended claims of the present invention are protected.
The nickelic ternary monocrystal LiNi of embodiment 10.7Co0.15Mn0.15O2Preparation
1) NaCl-KCl-Na is configured according to mass ratio 30%: 30%: 40%2SO4Fused salt, be fully ground in dry environment,
It mixes spare.By nickelic ternary material LiNi0.7Co0.15Mn0.15O2Required raw material weighs lithium hydroxide, carbon according to stoichiometric ratio
Sour nickel, manganese carbonate grinding, mixes and spare obtains reactant 1 cobalt carbonate.Wherein, lithium hydroxide quality is than its stoichiometric ratio institute
Requirement excessive 5%.The mass ratio of fused salt and target positive electrode (core-shell structure anode material of lithium battery) is 5: 1.
2) fused salt is sufficiently mixed with reactant 1, ground, pyroreaction: reacting 3h at 600 DEG C, continued thereafter at 900 DEG C
React 10h.After reaction, rate of temperature fall is 60 DEG C/h, and furnace cooling obtains reaction product after being cooled to 500 DEG C, the reaction
Product is mixture.
3) reaction product separation, solvent washed, dried, resulting nickelic ternary material is the nickelic ternary of micron monocrystal
Material is micron monocrystal, 6 microns of granular size (D50).
The nickelic ternary material LiNi of embodiment 20.8Co0.1Mn0.1O2Preparation
1) NaCl-KCl-Na is configured according to mass ratio 60%: 20%: 20%2SO4Fused salt, be fully ground in dry environment,
It mixes spare.By nickelic ternary material LiNi0.8Co0.1Mn0.1O2Required raw material lithium hydroxide, nickelous carbonate, cobalt carbonate, manganese carbonate
Stoichiometrically weigh, grind, mix it is spare.Lithium hydroxide quality is more excessive by 5% than its stoichiometric ratio aequum.Fused salt with
The mass ratio of target positive electrode is 1.1: 1
2) fused salt and reactant are sufficiently mixed, ground, pyroreaction.In 600 DEG C of reaction 3h, continue thereafter at 700 DEG C
React 10h.After reaction, rate of temperature fall is 20 DEG C/h, and furnace cooling obtains reaction product after being cooled to 500 DEG C, the reaction
Product is mixture.
3) reaction product separation, solvent washed, dried, resulting nickelic ternary material is the nickelic ternary of micron monocrystal
Material is micron monocrystal, 1.8 microns of granular size (D50).
The nickelic ternary material LiNi of embodiment 30.8Co0.1Mn0.1O2Preparation
1) NaCl-KCl-Na is configured according to mass ratio 40%: 20%: 40%2SO4Fused salt, be fully ground in dry environment,
It mixes spare.By nickelic ternary material LiNi0.8Co0.1Mn0.1O2Required raw material lithium hydroxide, nickelous carbonate, cobalt carbonate, manganese carbonate
Stoichiometrically weigh, grind, mix it is spare.Lithium hydroxide quality is more excessive by 5% than its stoichiometric ratio aequum.Fused salt with
The mass ratio of target positive electrode is 2.0: 1.
2) fused salt and reactant are sufficiently mixed, ground, pyroreaction.In 800 DEG C of reaction 3h, continue thereafter at 750 DEG C
React 10h.Rate of temperature fall is 50 DEG C/h after reaction, and furnace cooling obtains reaction product after being cooled to 500 DEG C, which produces
Object is mixture.
3) reaction product separation, solvent washed, dried, resulting nickelic ternary material is the nickelic ternary of micron monocrystal
Material is micron monocrystal, 3.5 microns of granular size (D50).
The nickelic ternary material LiNi of embodiment 40.8Co0.1Mn0.1O2Preparation
1) NaCl-KCl-Na is configured according to mass ratio 40%: 20%: 40%2SO4Fused salt, be fully ground in dry environment,
It mixes spare.By nickelic ternary material LiNi0.8Co0.1Mn0.1O2Required raw material lithium hydroxide, nickelous carbonate, cobalt carbonate, manganese carbonate
Stoichiometrically weigh, grind, mix it is spare.Lithium hydroxide quality is more excessive by 5% than its stoichiometric ratio aequum.Fused salt with
The mass ratio of target positive electrode is 3.0: 1.
2) fused salt and reactant are sufficiently mixed, ground, pyroreaction.In 900 DEG C of reaction 3h, continue thereafter at 750 DEG C
React 10h.Rate of temperature fall is 40 DEG C/h after reaction, and furnace cooling obtains reaction product after being cooled to 500 DEG C, which produces
Object is mixture.
3) reaction product separation, solvent washed, dried, resulting nickelic ternary material is the nickelic ternary of micron monocrystal
Material is micron monocrystal, 4 microns of granular size (D50).
The preparation of nickelic ternary single crystal material-core-shell structure anode material of lithium battery of 5 surface modification of embodiment
By mixture obtained by embodiment 1 " step 2) ", it is dissolved in deionized water, is completely dissolved fused salt, is sufficiently stirred to obtain
Suspension.By low nickel ternary material LiNi1/3Co1/3Mn1/3O2Reaction raw materials weigh lithium hydroxide, vinegar according to stoichiometric ratio
Sour nickel, cobalt acetate, manganese acetate are added in aforementioned suspension, and being sufficiently stirred is completely dissolved soluble salt.The suspension exists
It is concentrated under 600rpm stirring condition, under 80 DEG C of water-baths.Obtained solid forced air drying, grinding, mixing are spare.It is accounted for according to clad
The 1% of core-shell structured cathode material total mass ratio weighs the reaction raw material of clad.
Fused salt reacts again, in 800 DEG C of reaction 2h, generates low nickel ternary material nanometer layer and is coated on nickelic ternary micron list
Plane of crystal.Furnace cooling after reaction.Products therefrom washing removal fused salt, separation, drying, collection are spare.Fused salt can return
It receives and recycles.Fig. 1 is the X-ray diffractogram of the sample, feature spectral peak and nickelic ternary material in figure
LiNi0.7Co0.15Mn0.15O2Standard spectrogram peak position it is consistent, free from admixture peak, diffraction maximum sharply shows that material crystalline degree is high.
The preparation of nickelic ternary single crystal material-core-shell structure anode material of lithium battery of 6 surface modification of embodiment
By mixture obtained by embodiment 2 " step 2) ", reaction product is dissolved in deionized water, is completely dissolved fused salt, sufficiently
Stir to get suspension.
By low nickel ternary material LiNi1/3Co1/3Mn1/3O2Reaction raw materials lithium hydroxide, nickel acetate, cobalt acetate, manganese acetate
It stoichiometrically weighs, is added in aforementioned suspension, being sufficiently stirred is completely dissolved soluble salt.The suspension is in 600rpm
It is concentrated under stirring condition, under 80 DEG C of water-baths.Obtained solid forced air drying, grinding, mixing are spare.It is total that material is accounted for according to clad
The 5% of mass ratio weighs the reaction raw material of clad.
Fused salt reacts again, in 600 DEG C of reaction 6h, generates low nickel ternary material nanometer layer and is coated on nickelic ternary micron list
Plane of crystal.Furnace cooling after reaction.Products therefrom washing removal fused salt, separation, drying, collection are spare, and fused salt can return
It receives and recycles.Resulting materials are consistent with corresponding standard spectrogram peak position, free from admixture peak.
The preparation of nickelic ternary single crystal material-core-shell structure anode material of lithium battery of 7 surface modification of embodiment
By mixture obtained by embodiment 3 " step 2) ", it is dissolved in deionized water, is completely dissolved fused salt, is sufficiently stirred to obtain
Suspension.
By low nickel ternary material LiNi0.4Co0.2Mn0.4O2Reaction raw materials lithium hydroxide, nickel acetate, cobalt acetate, manganese acetate
It stoichiometrically weighs, is added in aforementioned suspension, being sufficiently stirred is completely dissolved soluble salt.The suspension is in 600rpm
It is concentrated under stirring condition, under 80 DEG C of water-baths.Obtained solid forced air drying, grinding, mixing are spare.It is total that material is accounted for according to clad
The 2.0% of mass ratio weighs the reaction raw material of clad.
Fused salt reacts again, in 750 DEG C of reaction 5h, generates low nickel ternary material nanometer layer and is coated on nickelic ternary micron list
Plane of crystal.Furnace cooling after reaction.Products therefrom washing removal fused salt, separation, drying, collection are spare.Fused salt can return
It receives and recycles.Resulting materials are consistent with corresponding standard spectrogram peak position, free from admixture peak.
The preparation of nickelic ternary single crystal material-core-shell structure anode material of lithium battery of 8 surface modification of embodiment
By mixture obtained by embodiment 4 " step 2) ", it is dissolved in deionized water/ethyl alcohol (volume ratio 0.7: 0.3), keeps fused salt complete
Fully dissolved is sufficiently stirred to obtain suspension.
By low nickel ternary material LiNi1/3Co1/3Mn1/3O2Reaction raw materials lithium hydroxide, nickel acetate, cobalt acetate, manganese acetate
It stoichiometrically weighs, is added in aforementioned suspension, being sufficiently stirred is completely dissolved soluble salt.The suspension is in 300rpm
It is concentrated under stirring condition, under 75 DEG C of water-baths.Obtained solid forced air drying, grinding, mixing are spare.It is total that material is accounted for according to clad
The 2.0% of mass ratio weighs the reaction raw material of clad.
Fused salt reacts again, in 700 DEG C of reaction 4h, generates low nickel ternary material nanometer layer and is coated on nickelic ternary micron list
Plane of crystal.Furnace cooling after reaction.Products therefrom washing removal fused salt, separation, drying, collection are spare.Fused salt can return
It receives and recycles.Resulting materials are consistent with corresponding standard spectrogram peak position, free from admixture peak.
Comparative example
The nickelic ternary material of micron monocrystalline figure of surface modification non-in embodiment 1 is assembled into lithium as positive electrode
Ion battery tests chemical property.
Experimental example:
By the nickelic ternary single crystal material of 5~8 gained surface modification of embodiment and the non-surface modification of comparative example
The micron nickelic ternary material of monocrystalline figure assembles lithium ion battery as positive electrode, tests chemical property.As a result referring to
Table 1.
Chemical property (lamination soft-package battery, the cathode: graphite, voltage zone of table 1 embodiment 5~8 and comparative example
Between: 3-4.3V, current density 18mA/g)
*Using x-ray photoelectron spectroscopy (XPS) measuring method, data are metal ion and graphite peak area ratio.It can send out
Existing, the non-surface modification of comparative example, after multiple charge and discharge cycles, trace metal ion is dissolved out in sample, and by electrolysis
Liquid is deposited in cathode graphite surface.And the sample Jing Guo surface modification, after circulation, corresponding cathode graphite surface detection metal from
Sub- content is only the 10% of comparative example.Obviously, nickelic ternary monocrystalline surface decorative layer can effectively improve the steady of material of main part
It is qualitative, to improve the cycle performance and capacity of battery.
Claims (10)
1. nickelic ternary monocrystal, which is characterized in that the chemical formula of the nickelic ternary monocrystal is LiNixCoyMnzO2, wherein
X+y+z=1,1 x >=0.7 >.
2. a kind of core-shell structure anode material of lithium battery, which is characterized in that the core of the core-shell structure anode material of lithium battery is
Nickelic ternary monocrystal described in claim 1, the shell are low nickel ternary material nanometer clads.
3. core-shell structure anode material of lithium battery according to claim 2, which is characterized in that the low nickel ternary material is received
The chemical formula of rice clad is LiNixCoyMnzO2, wherein x+y+z=1,0<x ￡ 0.4,1 z>=0.3 >.
4. the method that two molten-salt growth methods prepare core-shell structure anode material of lithium battery described in claim 2 or 3, feature exist
In, comprising the following steps:
Configuration fused salt: NaCl, KCl and Na are weighed respectively2SO4, it is fully ground, to be uniformly mixed so as to obtain fused salt spare；
Configure raw material: raw material lithium salts needed for preparing nickelic ternary single crystal material, cobalt salt, manganese salt grinding, mixes nickel salt
Spare to obtain reactant 1, raw material lithium salts needed for preparing low nickel ternary single crystal material, cobalt salt, manganese salt grinding, mixes nickel salt
It is even spare to obtain reactant 2；
The nickelic ternary micron monocrystal of molten-salt growth method high―temperature nuclei: the reactant 1 of the fused salt of step 1) preparation and step 2 is abundant
Mixing, grinding, pyroreaction, after reaction, furnace cooling obtains mixture 1 after cooling；
Mixture 1 is dissolved in water and forms suspension, reactant 2 is added, stirring and dissolving, drying, is ground and is mixed concentration
Object 2；
Fused salt reacts the mixture 2 that step 4) obtains again, and it is micro- that synthesis obtains the nickelic ternary of low nickel ternary material nanometer layer cladding
The product of rice monocrystal；
By the product washing of step 5), separate and collect the nickelic ternary single crystal material up to surface modification.
5. the method that secondary molten-salt growth method according to claim 4 prepares core-shell structure anode material of lithium battery, feature exist
In NaCl, KCl and Na of step 1)2SO4Mass ratio be 30-60%:20-35%:20-40%.
6. the method that secondary molten-salt growth method according to claim 4 prepares core-shell structure anode material of lithium battery, feature exist
In the lithium salts of step 2 is the one or two of lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate；Nickel salt is nickel oxide, acetic acid
The one or two of nickel, nickelous carbonate, nickel chloride, nickel sulfate；Manganese salt is manganese dioxide, manganese acetate, manganese carbonate, manganese chloride, sulfuric acid
The one or two of manganese；Cobalt salt is cobaltosic oxide, cobalt acetate, cobalt carbonate, cobalt nitrate, cobalt chloride, one kind of cobaltous sulfate or two
Kind.
7. the method that secondary molten-salt growth method according to claim 4 prepares core-shell structure anode material of lithium battery, feature exist
It is divided into two stages in, the high―temperature nuclei step of step 3), 600-900 DEG C of first stage reaction temperature, generated time 2-6h, with
700-900 DEG C of second stage reaction temperature afterwards, generated time 5-12h.
8. the method that secondary molten-salt growth method according to claim 4 prepares core-shell structure anode material of lithium battery, feature exist
In the rate of temperature fall of step 3) is 20-60 DEG C/h, furnace cooling after being cooled to 500 DEG C.
9. the method that secondary molten-salt growth method according to claim 4 prepares core-shell structure anode material of lithium battery, feature exist
In step 4) stirring rate is 200-500 rpm.
10. the method that secondary molten-salt growth method according to claim 4 prepares core-shell structure anode material of lithium battery, feature exist
In fused salt reaction temperature is 600-800 DEG C to step 5) again, generated time 2-6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910301582.XA CN109879333B (en) | 2019-04-15 | 2019-04-15 | Method for preparing lithium battery anode material with core-shell structure by secondary molten salt method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910301582.XA CN109879333B (en) | 2019-04-15 | 2019-04-15 | Method for preparing lithium battery anode material with core-shell structure by secondary molten salt method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109879333A true CN109879333A (en) | 2019-06-14 |
| CN109879333B CN109879333B (en) | 2021-07-27 |
Family
ID=66937357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910301582.XA Active CN109879333B (en) | 2019-04-15 | 2019-04-15 | Method for preparing lithium battery anode material with core-shell structure by secondary molten salt method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109879333B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112357972A (en) * | 2020-09-30 | 2021-02-12 | 宜宾光原锂电材料有限公司 | Low-nickel cobalt-free precursor, cathode material and preparation method thereof |
| CN113013395A (en) * | 2021-03-26 | 2021-06-22 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
| CN113381005A (en) * | 2021-05-27 | 2021-09-10 | 厦门大学 | Single-crystal ternary cathode material, continuous preparation method and device and application |
| CN115084506A (en) * | 2022-05-18 | 2022-09-20 | 广东邦普循环科技有限公司 | Large-particle-size single crystal ternary cathode material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324504A (en) * | 2011-10-24 | 2012-01-18 | 中南大学 | Lithium ion battery anode material with LiCoO2 coated on surface and preparation method for lithium ion battery anode material |
| CN104409716A (en) * | 2014-10-30 | 2015-03-11 | 中国科学院过程工程研究所 | Nickel lithium ion battery positive material with concentration gradient, and preparation method thereof |
| CN106848296A (en) * | 2017-03-20 | 2017-06-13 | 华南师范大学 | A kind of lithium ion battery manganese base lithium-rich anode material and preparation method thereof |
| CN108172799A (en) * | 2017-12-28 | 2018-06-15 | 清远佳致新材料研究院有限公司 | A kind of tertiary cathode material of nucleocapsid structure lithium ion battery and preparation method thereof |
-
2019
- 2019-04-15 CN CN201910301582.XA patent/CN109879333B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324504A (en) * | 2011-10-24 | 2012-01-18 | 中南大学 | Lithium ion battery anode material with LiCoO2 coated on surface and preparation method for lithium ion battery anode material |
| CN104409716A (en) * | 2014-10-30 | 2015-03-11 | 中国科学院过程工程研究所 | Nickel lithium ion battery positive material with concentration gradient, and preparation method thereof |
| CN106848296A (en) * | 2017-03-20 | 2017-06-13 | 华南师范大学 | A kind of lithium ion battery manganese base lithium-rich anode material and preparation method thereof |
| CN108172799A (en) * | 2017-12-28 | 2018-06-15 | 清远佳致新材料研究院有限公司 | A kind of tertiary cathode material of nucleocapsid structure lithium ion battery and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112357972A (en) * | 2020-09-30 | 2021-02-12 | 宜宾光原锂电材料有限公司 | Low-nickel cobalt-free precursor, cathode material and preparation method thereof |
| CN113013395A (en) * | 2021-03-26 | 2021-06-22 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
| CN113381005A (en) * | 2021-05-27 | 2021-09-10 | 厦门大学 | Single-crystal ternary cathode material, continuous preparation method and device and application |
| CN113381005B (en) * | 2021-05-27 | 2022-10-11 | 厦门大学 | Single-crystal ternary cathode material, continuous preparation method and device and application |
| CN115084506A (en) * | 2022-05-18 | 2022-09-20 | 广东邦普循环科技有限公司 | Large-particle-size single crystal ternary cathode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109879333B (en) | 2021-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106207138B (en) | A kind of method for preparing anode material of lithium-ion battery and its application | |
| CN109879333A (en) | The method that secondary molten-salt growth method prepares core-shell structure anode material of lithium battery | |
| CN104201367B (en) | High density small particle nickel cobalt manganese hydroxide and preparation method thereof | |
| CN110127777B (en) | Wet zirconium-doped nickel-cobalt-aluminum ternary precursor with gradient concentration and preparation method thereof | |
| CN109560276A (en) | A kind of monocrystalline tertiary cathode material and preparation method thereof and lithium ion battery with concentration gradient distribution primary particle oriented growth | |
| CN109778301A (en) | The preparation of one type monocrystalline lithium-rich oxide material and application | |
| JP7265096B2 (en) | MOF-coated single-crystal ternary positive electrode material and method for producing its precursor | |
| CN102683645A (en) | Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery | |
| CN106602015A (en) | Preparation method for fluorine-doped nickel-cobalt-manganese system ternary positive electrode material and prepared material | |
| CN105244501A (en) | Active substance precursor nickel manganese carbonate of lithium ion battery electrode | |
| CN115000399B (en) | Spherical-like sodium ion battery positive electrode material, preparation method thereof and sodium ion battery | |
| CN111018006A (en) | Preparation method of core-shell structure high-nickel ternary cathode material | |
| CN110620230A (en) | Positive active material, preparation method thereof, positive plate and lithium battery | |
| WO2007000075A1 (en) | Method for preparing spherical nickelous hydroxide which is dopped and multiple metal oxides, and lithium ion secondary battery | |
| CN113651374B (en) | Preparation method of ferrozirconium-doped nickel-cobalt-manganese ternary precursor | |
| CN112830524A (en) | Transition metal oxide positive electrode material of single crystal lithium and preparation method and application thereof | |
| CN113735190A (en) | Small-particle ternary precursor and preparation method thereof | |
| CN109346718B (en) | Single crystal nickel cobalt lithium manganate precursor and preparation method and application thereof | |
| CN112928253A (en) | Nickel-manganese-titanium composite material and preparation method and application thereof | |
| CN111072075A (en) | Preparation method of lithium ion battery anode material | |
| CN115231627B (en) | Preparation method of large monocrystal nickel-cobalt-manganese positive electrode material | |
| CN112811477A (en) | Method for controlling synthesis of single crystal ternary cathode material through precursor | |
| CN111769277A (en) | Gradient single crystal high-nickel cathode material and preparation method thereof | |
| CN112744872A (en) | Liquid-phase phosphorus element doping modification preparation method of high-nickel anode material | |
| CN112582587A (en) | Core-shell structure high-nickel cathode material with single crystal as core and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |