CN109305699A - A kind of preparation method of amorphous monocrystalline oxidation of precursor object - Google Patents
A kind of preparation method of amorphous monocrystalline oxidation of precursor object Download PDFInfo
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- CN109305699A CN109305699A CN201811051733.2A CN201811051733A CN109305699A CN 109305699 A CN109305699 A CN 109305699A CN 201811051733 A CN201811051733 A CN 201811051733A CN 109305699 A CN109305699 A CN 109305699A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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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
- 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
- H01M4/50—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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- 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 a kind of preparation methods of amorphous monocrystalline oxidation of precursor object of technical field of lithium ion, amorphous ternary precursor hydroxide is prepared by coprecipitation, a kind of amorphous monocrystalline pattern ternary precursor oxide is obtained by high temperature thermal decomposition again, using amorphous monocrystalline ternary forerunner oxide as novel anode material for lithium-ion batteries, the high temperature cyclic performance and high temperature high rate performance of lithium ion battery can be effectively improved, improve the charge and discharge voltage platform of existing ternary material, effectively promote the high temperature safe of existing lithium-ion battery systems, circulation and high rate charge-discharge performance；A kind of the present invention provides manufacturing costs low, good electrical property novel anode material for lithium-ion batteries, compensates for the defect of existing anode material for lithium-ion batteries, effectively improves the low problem of anode material for lithium-ion batteries capacity.
Description
Technical field
The present invention relates to technical field of lithium ion, specially a kind of preparation side of amorphous monocrystalline oxidation of precursor object
Method.
Background technique
Compared with the secondary cells such as traditional plumbic acid, lithium ion battery possesses that voltage is high, capacity is high, energy density is big, follows
Ring performance is good, many-sided advantage such as environmental-friendly.The performance of lithium ion battery is largely more dependent upon positive electrode.Cobalt acid
When positive electrode of the lithium as lithium ion battery, there are at high cost, thermal stability be poor and the series of negative such as cobalt pollution environment
Problem, it is therefore desirable to develop novel anode material for lithium-ion batteries.
Anode material for lithium-ion batteries is manufactured in existing technical field of lithium ion mainly first to make using conventional method
Then standby amorphous ternary precursor is directly added into lithium salts by calcining and is prepared into amorphous ternary material, this method has work
The simple feature of skill, equipment, but the ternary material electrical property for calcining preparation is general, and high temperature cyclic performance is poor with high rate performance.
For the ternary precursor product defects of conventional method preparation, occur in the prior art a kind of using second particle
Spherical ternary precursor hydroxide is added lithium carbonate mixing and is prepared into class monocrystalline ternary material by high-temperature calcination thermal chemical reaction
The technique of material, this method have many advantages, such as that high temperature cyclic performance is preferable with high rate performance, but material preparation energy consumption is high, cost compared with
Height, monoclinic crystal structure and crystallinity are poor.
At present in technical field of lithium ion there are also it is a kind of prepare ternary precursor after, by heat treatment be prepared into ternary
The product of the technique of material precursor oxide, this method preparation is all spherical shape made of being assembled as primary particle or spherical two
Secondary particle, the pattern easily cause second particle fragmentation in the positive electrode preparation in later period and cell fabrication processes, influence electricity
The cycle performance and stable charge/discharge in pond.
Summary of the invention
In view of the above technical problems, the present invention provides a kind of amorphous monocrystalline pattern ternary precursor oxide and preparation side
Method, this method effectively improve the low problem of anode material for lithium-ion batteries capacity, improve the high rate performance of lithium ion preparation
And cycle performance.
The present invention adopts the following technical scheme:
A kind of amorphous monocrystalline oxidation of precursor object preparation method, comprising the following steps:
S1 prepares the amorphous ternary precursor of composite construction；
S2, by the amorphous ternary precursor of S1 preparation by obtaining amorphous monocrystalline ternary after Equipment for Heating Processing high temperature thermal decomposition
Oxidation of precursor object；
S3 adds lithium carbonate or lithium hydroxide in the amorphous monocrystalline ternary precursor oxide of S2 preparation, forges by high temperature
Lithiumation is burnt to handle to obtain tertiary cathode material.
Preferably, the amorphous ternary precursor of composite construction is prepared by coprecipitation.
Preferably, S1 specifically includes the following steps:
The supplementary material solution of S101, preparing metal salting liquid and liquid alkaline solution as coprecipitation reaction, is added reaction kettle for pure water
Pure water in reaction kettle is heated in dischargeable capacity position, and the liquid alkaline solution adjustment pH range of preparation is then added, it is anti-to obtain co-precipitation
The bottom liquid answered；
S102, the prepared metal salt solution of S101 and liquid alkaline solution are added simultaneously in the reaction kettle for preparing bottom liquid carry out it is coprecipitated
It forms sediment and reacts, material in reactor is flowed out by the coprecipitation reaction of 2-20 hour by discharge port, and resulting solid-liquid mixing is without fixed
The amorphous ternary precursor of composite construction is obtained after the washed impurity of shape ternary precursor slurry, filtering, dehydration, drying, point
Minor are as follows: NixCoyMn1-x-y(OH)2。
Preferably, in S101, metal salt solution presses Conventional processing methods mixed preparing by nickel salt, cobalt salt, manganese salt
It forms, the prepared total metal ion solubility of liquid alkaline solution is 0.5-2mol/L, and the concentration of prepared liquid alkaline solution is 3-
12mol/L, nickel salt, cobalt salt, manganese salt are nitrate, in acetate, sulfate, citrate, chlorate, carbonate, oxalates
At least one, liquid alkaline solution is caustic soda, piece alkali, soda ash, weight at least one of alkali.
Preferably, in S101, the temperature environment of pure water is 40-70 DEG C in reaction kettle, adjusts the bottom in reaction kettle
Liquid pH range is 11.0-13.0, and the revolving speed of internal stirrer paddle is 300-600r/min, and metal salt solution is added into reaction kettle
Flow with liquid alkaline solution is 15-100L/h.
Preferably, in S2, the Equipment for Heating Processing uses the push plate with heating, cooling and dust collection function
Furnace, track furnace, rotary furnace, any one in steel belt furnace.
Preferably, in S2, the temperature environment of high temperature thermal decomposition processing is 500-1000 DEG C, high temperature thermal decomposition processing
Time be 8-36h.
Preferably, in S2, by the dusty material after high-temperature heat treatment by collecting, being crushed, be classified, be sieved, remove
After magnetic, amorphous monocrystalline ternary precursor oxide, molecular formula Ni are obtainedxCoyMn1-x-yO。
Amorphous monocrystalline ternary precursor oxide prepared by the present invention has the smooth mirror surface of polyhedron shape solid
Shape, continuity lattice crystal structure, product cut size are 2~6um, and specific surface area is 0.1~0.5m2/g, tap density
Greater than 2.5g/cm.
Compared with prior art, the invention has the following advantages:
1. preparing amorphous monocrystalline oxidation of precursor object as novel lithium ion cell positive material using method of the invention
Material, can effectively improve the high temperature cyclic performance and high temperature high rate performance of lithium ion battery, improve the charge and discharge of existing ternary material
Voltage platform reaches the mesh of the high temperature safe for effectively promoting existing lithium-ion battery systems, circulation and high rate charge-discharge performance
's；
2. prepared by the method amorphous monocrystalline oxidation of precursor object is as novel anode material for lithium-ion batteries, by
It is small in amorphous monocrystalline oxidation of precursor object surface area, granular boundary permeance property is good, effectively increase lithium ion diffusion effect
Energy and distributing homogeneity, more traditional anode material for lithium-ion batteries have better electrochemistry cycle performance；
3. prepared by the method amorphous monocrystalline oxidation of precursor object is as novel anode material for lithium-ion batteries, by
In the single crystal grain characteristic that amorphous monocrystalline oxidation of precursor object surface has height flat and smooth, after being assembled into lithium ion battery
The contact surface of particle surface and electrolyte reduces, and the side reaction of corresponding positive electrode and electrolyte is significantly reduced, is effectively reduced
Due to the heat release of side reaction generation, phenomenon of deflation, make battery that there is better high temperature safe performance and high temperature high rate performance；
4. having prevented existing in amorphous monocrystalline oxidation of precursor object preparation process prepared by the present invention that complexing agent is not added
Preparation method adds complexing agent to be influenced to environment bring, while being manufactured and not needed that complexing agent is added in raw material, and original is reduced
The input cost of material；
5. the present invention prepares the preferable amorphous monocrystalline oxidation of precursor object of surface electrochemistry activity by heat treatment process, make
For novel anode material for lithium-ion batteries, the low defect of existing anode material of lithium battery electro-chemical activity is effectively made up, it can
The preferable specific capacity for promoting lithium ion battery.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Fig. 2 is the amorphous ternary precursor SEM figure of composite construction of the present invention.
Fig. 3 is the amorphous monocrystalline ternary precursor oxide S EM figure of the present invention.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
As shown in Fig. 1, a kind of preparation method of amorphous monocrystalline oxidation of precursor object, comprising the following steps:
S1 prepares the amorphous ternary precursor of composite construction by coprecipitation；
The supplementary material solution of S101, preparing metal salting liquid and liquid alkaline solution as coprecipitation reaction, is added reaction kettle for pure water
Pure water in reaction kettle is heated in dischargeable capacity position, and the liquid alkaline solution adjustment pH range of preparation is then added, it is anti-to obtain co-precipitation
The bottom liquid answered；
In S101, metal salt solution is formed by nickel salt, cobalt salt, manganese salt by Conventional processing methods mixed preparing, prepared liquid
The total metal ion solubility of aqueous slkali is 0.5-2mol/L, and the concentration of prepared liquid alkaline solution is 3-12mol/L, nickel salt, cobalt salt,
Manganese salt is at least one of nitrate, acetate, sulfate, citrate, chlorate, carbonate, oxalates, liquid alkaline solution
For at least one of caustic soda, piece alkali, soda ash, weight alkali.
The prepared metal salt solution of S101 and liquid alkaline solution are added in the reaction kettle for preparing bottom liquid simultaneously and carry out by S102
Coprecipitation reaction, material in reactor are flowed out by the coprecipitation reaction of 2-20 hour by discharge port, resulting solid-liquid mixing
The washed impurity of amorphous ternary precursor slurry, filtering, dehydration, it is dry after obtain the amorphous ternary forerunner of composite construction
Body, molecular formula are as follows: NixCoyMn1-x-y(OH)2。
In S102, the temperature environment of pure water is 40-70 DEG C in reaction kettle, and the bottom liquid pH range adjusted in reaction kettle is
11.0-13.0, the revolving speed of internal stirrer paddle are 300-600r/min, and the flow of metal salt solution is 15-100L/h.
The Equipment for Heating Processing use pusher furnace with heating, cooling and dust collection function, track furnace, rotary furnace,
Any one in steel belt furnace.
S2, by the amorphous ternary precursor of S1 preparation by obtaining amorphous monocrystalline after Equipment for Heating Processing high temperature thermal decomposition
Ternary precursor oxide；
In S2, the temperature environment of high temperature thermal decomposition processing is 500-1000 DEG C, and the time of high temperature thermal decomposition processing is 8-36h,
The Equipment for Heating Processing use pusher furnace with heating, cooling and dust collection function, track furnace, rotary furnace, in steel belt furnace
Any one, high temperature thermal decomposition processing temperature environment be 500-1000 DEG C, high temperature thermal decomposition processing time be 8-36h,
By the dusty material after high-temperature heat treatment by collecting, being crushed, be classified, be sieved, except obtaining amorphous monocrystalline ternary forerunner after magnetic
Oxide body, molecular formula NixCoyMn1-x-yO。
S3 adds lithium carbonate or lithium hydroxide, through excessively high in the amorphous monocrystalline ternary precursor oxide of S2 preparation
Temperature calcining lithiumation handles to obtain tertiary cathode material.
Method of the invention prepares amorphous monocrystalline oxidation of precursor object as novel anode material for lithium-ion batteries, energy
The high temperature cyclic performance and high temperature high rate performance for enough effectively improving lithium ion battery, the charge and discharge for improving existing ternary material flatten
Platform achievees the purpose that effectively to promote the high temperature safe of existing lithium-ion battery systems, circulation and high rate charge-discharge performance.
Since amorphous monocrystalline oxidation of precursor object surface area is small, granular boundary permeance property is good, effectively increase lithium from
The diffusion efficiency and distributing homogeneity of son, more traditional anode material for lithium-ion batteries have better electrochemistry cycle performance；
Due to the single crystal grain characteristic that amorphous monocrystalline oxidation of precursor object surface has height flat and smooth, it is assembled into lithium ion
The contact surface of particle surface and electrolyte reduces after battery, and the side reaction of corresponding positive electrode and electrolyte significantly reduces, has
Heat release, the phenomenon of deflation that reduction is generated due to side reaction are imitated, battery is made to have better high temperature safe performance and high temperature forthright again
Energy；
The preferable amorphous monocrystalline oxidation of precursor object of surface electrochemistry activity is prepared by heat treatment process, as novel lithium
Ion battery positive electrode effectively makes up the low defect of existing anode material of lithium battery electro-chemical activity, can preferably be promoted
The specific capacity of lithium ion battery.
Embodiment 1:
Firstly, pure water is added into reaction kettle and is heated to 40 DEG C, the liquid alkaline solution adjustment pH that preparation is then added is 11.0, instead
Stirrer paddle inside kettle is answered to be uniformly mixed with the revolving speed of 300r/min, preparation obtains the bottom liquid of coprecipitation reaction, then with 15L/h
Flow the metal salt solution of 0.5mol/L and the liquid alkaline solution of 3mol/L is added, the coprecipitated of 2 hours occurs in a kettle
It forms sediment after reaction, is flowed out from the discharge port of reaction kettle, obtain solid-liquid and mix the washed impurity of amorphous ternary precursor slurry, mistake
The amorphous ternary precursor of composite construction is obtained after filter, dehydration, drying, by amorphous ternary precursor in 500 DEG C of temperature rings
High temperature thermal decomposition processing is carried out under border, the time of high temperature thermal decomposition processing is 8h, and the dusty material after high-temperature heat treatment is passed through
Collect, be broken, classification, sieving, except after magnetic, obtaining amorphous monocrystalline ternary precursor oxide, then by amorphous monocrystalline ternary
Lithium carbonate or lithium hydroxide are added in oxidation of precursor object, handle to obtain tertiary cathode material by high-temperature calcination lithiumation.
Embodiment 2
Firstly, pure water is added into reaction kettle and is heated to 55 DEG C, the liquid alkaline solution adjustment pH that preparation is then added is 12.0, instead
Stirrer paddle inside kettle is answered to be uniformly mixed with the revolving speed of 450r/min, preparation obtains the bottom liquid of coprecipitation reaction, then with 60L/h
Flow the metal salt solution of 1.25mol/L and the liquid alkaline solution of 9mol/L is added, being total to for 11 hours occurs in a kettle
It after precipitation reaction, is flowed out from the discharge port of reaction kettle, obtains solid-liquid and mix the washed impurity of amorphous ternary precursor slurry, mistake
The amorphous ternary precursor of composite construction is obtained after filter, dehydration, drying, by amorphous ternary precursor in 750 DEG C of temperature rings
High temperature thermal decomposition processing is carried out under border, the time of high temperature thermal decomposition processing is 22h, and the dusty material after high-temperature heat treatment is passed through
Collect, be broken, classification, sieving, except after magnetic, obtaining amorphous monocrystalline ternary precursor oxide, then by amorphous monocrystalline ternary
Lithium carbonate or lithium hydroxide are added in oxidation of precursor object, handle to obtain tertiary cathode material by high-temperature calcination lithiumation.
Embodiment 3
Firstly, pure water is added into reaction kettle and is heated to 70 DEG C, the liquid alkaline solution adjustment pH that preparation is then added is 13.0, instead
Stirrer paddle inside kettle is answered to be uniformly mixed with the revolving speed of 600r/min, preparation obtains the bottom liquid of coprecipitation reaction, then with 100L/
The metal salt solution of 2mol/L and the liquid alkaline solution of 12mol/L is added in the flow of h, and the coprecipitated of 20 hours occurs in a kettle
It forms sediment after reaction, is flowed out from the discharge port of reaction kettle, obtain solid-liquid and mix the washed impurity of amorphous ternary precursor slurry, mistake
The amorphous ternary precursor of composite construction is obtained after filter, dehydration, drying, by amorphous ternary precursor in 1000 DEG C of temperature rings
High temperature thermal decomposition processing is carried out under border, the time of high temperature thermal decomposition processing is 36h, and the dusty material after high-temperature heat treatment is passed through
Collect, be broken, classification, sieving, except after magnetic, obtaining amorphous monocrystalline ternary precursor oxide, then by amorphous monocrystalline ternary
Lithium carbonate or lithium hydroxide are added in oxidation of precursor object, handle to obtain tertiary cathode material by high-temperature calcination lithiumation.
Comparative example 1
Firstly, pure water is added into reaction kettle and is heated to 55 DEG C, the liquid alkaline solution adjustment pH that preparation is then added is 11.60,
Stirrer paddle is uniformly mixed with the revolving speed of 450r/min inside reaction kettle, and preparation obtains the bottom liquid of coprecipitation reaction, then with
The metal salt solution of 1.3mol/L and the liquid alkaline solution of 12mol/L is added in the flow of 45L/h, and 38 hours occur in a kettle
Coprecipitation reaction after, flowed out from the discharge port of reaction kettle, obtaining solid-liquid, to mix amorphous ternary precursor slurry washed miscellaneous
Conventional three-way presoma is obtained after matter, filtering, dehydration, drying, then lithium carbonate or hydroxide will be added in conventional three-way presoma
Lithium handles to obtain monocrystalline tertiary cathode material by calcining lithiumation under 1050 DEG C of hot environments.
Comparative example 2
Firstly, pure water is added into reaction kettle and is heated to 60 DEG C, the liquid alkaline solution adjustment pH that preparation is then added is 11.80,
Stirrer paddle is uniformly mixed with the revolving speed of 400r/min inside reaction kettle, and preparation obtains the bottom liquid of coprecipitation reaction, then with
The metal salt solution of 1.6mol/L and the liquid alkaline solution of 9mol/L is added in the flow of 50L/h, and 48 hours occur in a kettle
Coprecipitation reaction after, flowed out from the discharge port of reaction kettle, obtaining solid-liquid, to mix amorphous ternary precursor slurry washed miscellaneous
Conventional three-way presoma is obtained after matter, filtering, dehydration, drying, then conventional three-way presoma is carried out under 500 DEG C of temperature environments
High temperature thermal decomposition processing, the time of high temperature thermal decomposition processing are 6h, and the dusty material after high-temperature heat treatment is passed through and collects, is broken
Broken, classification, sieving after removing magnetic, obtain ternary precursor oxide, then lithium carbonate or hydrogen will be added in ternary precursor oxide
Lithia handles to obtain monocrystalline tertiary cathode material by 1000 DEG C of high-temperature calcination lithiumations.
Amorphous monocrystalline ternary precursor oxide prepared by embodiment 1-3 and comparative example 1-2 carries out granularity, specific surface
The characteristic tests such as product, compacted density, test result is as follows shown in table 1:
Table 1
Amorphous monocrystalline ternary precursor oxide monocrystal grain diameter manufactured in the present embodiment is equal it can be seen from 1 data of table
It is even, consistency is good；Specific surface area is smaller, and the contact area that can be effectively reduced with electrolyte is made after battery, reduces and electrolyte
Side reaction；Compacted density is higher, can effectively promote the volume and capacity ratio of battery.
Testing electronic microscope point is scanned to the amorphous monocrystalline ternary precursor oxide product in the present embodiment
Analysis obtains SEM figure as shown in Figures 2 and 3.Amorphous monocrystalline ternary precursor oxide product in the present embodiment is pressed into M/Li
It is uniformly mixed, uniformly mixed material is calcined 5 hours by 500 DEG C, 870 DEG C are calcined 12 hours than 1:1.07 addition lithium carbonate
It is sintered after thermal decomposition process calcining as complete monocrystalline pattern tertiary cathode material, obtained monocrystalline tertiary cathode material is made
At CR2025 type button cell, electric performance test so is carried out under 25 DEG C, 0.5C charge-discharge magnification, first charge-discharge efficiency is
92.6%, the capacity retention ratio after recycling for 100 weeks is 97.1%.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (10)
1. a kind of preparation method of amorphous monocrystalline oxidation of precursor object, comprising the following steps:
S1 prepares the amorphous ternary precursor of composite construction；
S2, by the amorphous ternary precursor of S1 preparation by obtaining amorphous monocrystalline ternary after Equipment for Heating Processing high temperature thermal decomposition
Oxidation of precursor object；
S3 adds lithium carbonate or lithium hydroxide in the amorphous monocrystalline ternary precursor oxide of S2 preparation, forges by high temperature
Lithiumation is burnt to handle to obtain tertiary cathode material.
2. a kind of preparation method of amorphous monocrystalline oxidation of precursor object according to claim 1, it is characterised in that: pass through
Coprecipitation prepares the amorphous ternary precursor of composite construction.
3. a kind of preparation method of amorphous monocrystalline oxidation of precursor object according to claim 2, it is characterised in that: S1 tool
Body the following steps are included:
The supplementary material solution of S101, preparing metal salting liquid and liquid alkaline solution as coprecipitation reaction, is added reaction kettle for pure water
Pure water in reaction kettle is heated in dischargeable capacity position, and the liquid alkaline solution adjustment pH range of preparation is then added, it is anti-to obtain co-precipitation
The bottom liquid answered；
S102, the prepared metal salt solution of S101 and liquid alkaline solution are added simultaneously in the reaction kettle for preparing bottom liquid carry out it is coprecipitated
It forms sediment and reacts, material in reactor is flowed out by the coprecipitation reaction of 2-20 hour by discharge port, and resulting solid-liquid mixing is without fixed
The amorphous ternary precursor of composite construction is obtained after the washed impurity of shape ternary precursor slurry, filtering, dehydration, drying, point
Minor are as follows: NixCoyMn1-x-y(OH)2。
4. a kind of preparation method of amorphous monocrystalline oxidation of precursor object according to claim 3, it is characterised in that:
In S101, metal salt solution is formed by nickel salt, cobalt salt, manganese salt by Conventional processing methods mixed preparing, and prepared metal salt is molten
Liquid solubility is 0.5-2mol/L, and prepared liquid alkaline solution concentration is 3-12mol/L.
5. a kind of preparation method of amorphous monocrystalline oxidation of precursor object according to claim 3, it is characterised in that:
In S101, nickel salt, cobalt salt, manganese salt are nitrate, in acetate, sulfate, citrate, chlorate, carbonate, oxalates
It is at least one.
6. a kind of preparation method of amorphous monocrystalline oxidation of precursor object according to claim 3, it is characterised in that:
In S101, liquid alkaline solution is at least one of caustic soda, piece alkali, soda ash, weight alkali.
7. according to a kind of described in any item preparation methods of amorphous monocrystalline oxidation of precursor object of claim 3-6, feature
Be: in S101, the temperature environment in reaction kettle is set as 40-70 DEG C, and adjusting the bottom liquid pH in reaction kettle is 11.0-
13.0, the revolving speed of internal stirrer paddle is 300-600r/min, and the stream of metal salt solution and liquid alkaline solution is added into reaction kettle
Amount is 15-100L/h.
8. a kind of preparation method of amorphous monocrystalline oxidation of precursor object according to claim 1, it is characterised in that: in S2
In, the Equipment for Heating Processing uses pusher furnace, track furnace, rotary furnace, steel belt furnace with heating, cooling and dust collection function
In any one.
9. a kind of preparation method of amorphous monocrystalline oxidation of precursor object according to claim 8, it is characterised in that: in S2
In, the temperature environment of high temperature thermal decomposition processing is 500-1000 DEG C, and the time of high temperature thermal decomposition processing is 8-36h.
10. a kind of preparation method of amorphous monocrystalline oxidation of precursor object according to claim 9, it is characterised in that:
In S2, by the dusty material after high-temperature heat treatment by collecting, being crushed, be classified, be sieved, except obtaining amorphous monocrystalline three after magnetic
First oxidation of precursor object, molecular formula NixCoyMn1-x-yO。
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| CN112687870A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Positive electrode material precursor and preparation method thereof, and positive electrode material and application thereof |
| CN113036095A (en) * | 2020-03-27 | 2021-06-25 | 湖南杉杉能源科技股份有限公司 | Preparation method of single-crystal-morphology lithium ion battery positive electrode material |
| CN113764655A (en) * | 2020-06-03 | 2021-12-07 | 湖南杉杉能源科技股份有限公司 | Nickel-cobalt-manganese-aluminum quaternary precursor and preparation method thereof |
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| WO2023165130A1 (en) * | 2022-03-01 | 2023-09-07 | 合肥国轩高科动力能源有限公司 | Modified monocrystal high-nickel ternary material, preparation method therefor and use thereof |
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