CN109301185A - A kind of tertiary cathode material and preparation method thereof that conductivity is high - Google Patents
A kind of tertiary cathode material and preparation method thereof that conductivity is high Download PDFInfo
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- CN109301185A CN109301185A CN201811049727.3A CN201811049727A CN109301185A CN 109301185 A CN109301185 A CN 109301185A CN 201811049727 A CN201811049727 A CN 201811049727A CN 109301185 A CN109301185 A CN 109301185A
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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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- 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
- H01M4/485—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
- 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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- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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- 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
A kind of tertiary cathode material that conductivity is high, it is characterised in that: formed including kernel and the shell for being coated on kernel outer surface；With following chemical formula: LicNiaCobMn1‑a‑bO2Wherein, 0≤a≤1,0≤b≤1,0.4≤c≤1.5；The kernel is the ternary material that lithium coats nickel, cobalt, manganese, and the shell is the film of conducting polymer.In the present invention, the conductivity of the film of shell is higher, can reduce the surface impedance of ternary material, to improve the high rate performance of battery.Meanwhile tertiary cathode material of the invention can be preferably combined with binder, can be prevented becoming larger for charge and discharge process middle impedance to a certain extent, be improved the cycle performance of material.
Description
Technical field
The present invention relates to a kind of lithium ion battery more particularly to a kind of tertiary cathode materials that the conductivity of lithium ion battery is high
Material and preparation method thereof.
Background technique
Currently, fossil fuel is still main for electric resources.However as the mankind unreasonable exploitation and utilization, fossil
Energy day is becoming tight, and environmental pollution is got worse.Therefore, new cleaning resource and renewable energy, such as sun are developed and used
Energy, wind energy, tide energy etc. become the task of top priority.But then, the normal operation of power grid needs the power generation of steady and continuous, too
The restriction by factors such as weather, place and times such as positive energy, wind energy, tide energy, significantly limits it and answers on a large scale
With with it is universal.In order to solve this problem, extensive electricity storage technology becomes an important field of research.Wherein, secondary cell
Due to energy density with higher and transformation efficiency, become the preferential selection of extensive storage, and has extended cycle life and have
The lithium ion battery for having highest energy density is considered as most promising secondary cell.From lithium-ion electric the 1990s
Since pond successfully comes out, electric car, in terms of obtained the application of considerable scale, but with lithium from
Sub- battery is constantly progressive and develops, and a series of hidden danger has also gradually been exposed in the visual field of people.
Under high pressure, in electrolyte at branch decompose generate bulk gas corrode positive electrode, thus dissolve metal from
Son.Modified metal oxide ternary material surface is used under these conditions, can be good at solving the problems, such as that this is a, and can increase
Add the cycle performance of material, but a new problem can be brought by carrying out modification with metal oxide, exactly will increase ternary material
The surface impedance of material, so that the first discharge specific capacity of material is small.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide a kind of tertiary cathode that conductivity is high
Material and preparation method thereof.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows: a kind of tertiary cathode material that conductivity is high,
Including kernel and the shell for being coated on kernel outer surface；With following chemical formula:
LicNiaCobMn1-a-bO2
Wherein, 0≤a≤1,0≤b≤1,0.4≤c≤1.5；
The kernel is the ternary material that lithium coats nickel, cobalt, manganese, and the shell is the film of conducting polymer；The conduction
Polymer is carried out polymerization reaction by acetylene, pyrroles, thiophene and derivatives and is obtained.
In the present invention, the highly stable film of one layer of chemical property is formed in core surface, this layer film is one layer of non-gold
Belong to film, do not interfere with the thematic structure of kernel, while electrolyte can be stopped to decompose the gas pair of generation under high pressure
The corrosion of kernel, protection materials structure；From the perspective of chemically reacting, the decomposition of electrolyte can be inhibited to a certain extent.
In the present invention, the conductivity of the film of shell is higher, can reduce the surface impedance of ternary material, to improve
The conductive capability of anode, to improve the high rate performance of battery.Meanwhile the cladding of conducting polymer can prevent charge and discharge process
Middle impedance becomes larger, and improves the cycle performance of material.The cycle performance of lithium battery is the circulation after being matched by anode with electrolyte
Circulation after performance, cathode are matched with electrolyte one of can newly report to the leadship after accomplishing a task in the two to determine.
It is known that the cathode of lithium battery typically now uses carbon coated aluminum foil/copper foil, it is exactly by scattered conductive nano
Graphite and carbon coating grain uniformly, fine and smoothly are coated on aluminium foil/copper foil.It can provide splendid static conductive performance, collect and live
Property substance micro-current, so as to the contact resistance being greatly lowered between positive/negative material and afflux, and both can improve
Between adhesive ability, the usage amount of binder can be reduced, so make battery overall performance generate be obviously improved.Nanometer is led
Electro-graphitic is excellent electric conductor, can reduce the internal resistance of cell, the dynamic internal resistance amplification during inhibiting charge and discharge cycles.
The anode of lithium battery is bonded since the conductive agent of active material thereon only accounts for 3% or so of positive electrode weight
The dosage of agent is more for cathode, and the cycle performance after anode is matched with electrolyte under normal circumstances is without anode and electricity
It is high to solve the matched cycle performance of liquid；Therefore improving the cycle performance after anode is matched with electrolyte is actually to improve lithium battery
Cycle performance.
The conducting polymer that shell uses in the present invention is organic material, and thermostabilization is good, keeps at 120 DEG C
1000h, conductivity are basically unchanged；And industrially generally use bonding of the Kynoar (PVDF) as lithium ion battery
Agent；The conducting polymer that shell uses in the present invention can be combined with binder it is even closer, being capable of better stable anode
The structure of pole piece.In the cyclic process of some lithium ion battery charge and discharge, inside lithium ion cell can generate heat in fact, binder
A degree of expansion and contraction are had, traditional tertiary cathode material is all metal ion, the coefficient of expansion with binder
Difference is huge, it is easy to there is the phenomenon that tertiary cathode material and binder de- knot, thus increase active material and binder it
Between resistance, also increase the internal resistance of lithium ion battery.Conducting polymer in the present invention, on tertiary cathode material surface
In the presence of certain buffer function can be played between bonding agent and kernel, so that gluing in continuous expansion and contraction process
Knot agent tertiary cathode material is completely embedded, and guarantees the electronic contact between active material and collector.
The high tertiary cathode material of above-mentioned conductivity, it is preferred that the partial size of the kernel is 2-20 μm, the shell
With a thickness of 5-50nm.
A kind of preparation method for the tertiary cathode material that conductivity is high includes the following steps the nickel for 1) configuring preset ratio
The Diversity solution of salt, cobalt salt and manganese salt,
2) the Diversity solution of step 1) is added to reacting containing bottom liquid with ammonium hydroxide and sodium hydroxide solution cocurrent
In device, carries out coprecipitation reaction and obtain sodium hydroxide object presoma；Whole process carries out under the atmosphere protection of inert gas；
3) sediment is obtained by filtration in the reaction product of step 2), and is washed with deionized to filtrate and is in neutrality；
4) it is dried in heated-air circulation oven by 10-12h, obtains ternary material precursor；
5) by the ternary precursor of step 4) and Li2CO3According to stoichiometric ratio 2:1.1 mixed grinding it is uniform after burnt
Knot, obtains kernel；The D50 for the kernel granularity that the present invention obtains is 10-12um, tap density 1.8-2.5g/cm3, specific surface area
4-7g/m2。
6) kernel of step 5) is immersed in conducting polymer monomer solution, first uses mechanical stirring 0.5-10h, then surpasses
Sound disperses 0.5-72h；Monomer solution includes monomer and dehydrated alcohol, and the molar ratio of monomer and dehydrated alcohol is 1:10-1:1.It is interior
The solid-to-liquid ratio of core and monomer solution is 40-60g/L.
7) kernel of step 6) is dry under conditions of room temperature~70 DEG C, drying time 30-360min；Dry
When, excessive monomer solution can be volatilized, to guarantee the thickness of shell cladding.
8) kernel of step 7) is immersed in oxidant, oxidant is to toluene yellow acid iron, ammonium persulfate, persulfuric acid
One of sodium, ammonium sulfate, iron chloride are a variety of；10~70wt% of oxidizing agent solution concentration；It is dried after being impregnated with oxidant in polymerization
Case carries out polymerization reaction, and the maximum temperature of reaction is 200 DEG C, reaction time 55min-65min；
9) by tertiary cathode material ethanol washing that step 8) obtains and be filtered, at a temperature of 40-120 DEG C into
Row dries to arrive product.
The preparation method of the high tertiary cathode material of above-mentioned conductivity, it is preferred that the low liquid in the step 2) is hydrogen
The mixed liquor of sodium oxide molybdena and ammonium hydroxide；The concentration of sodium hydroxide solution is 7.5-10mol/L, ammonia concn 6-8mol/ in the liquid of bottom
L。
The preparation method of the high tertiary cathode material of above-mentioned conductivity, it is preferred that in step 1), the nickel salt is nitric acid
At least one of nickel, nickel chloride, nickel acetate, nickel sulfate；The manganese salt is manganese nitrate, in manganese chloride, manganese acetate, manganese sulfate
At least one；The cobalt salt is at least one of cobalt nitrate, cobalt chloride, cobalt acetate, cobaltous sulfate.
The preparation method of the high tertiary cathode material of above-mentioned conductivity, it is preferred that the step 1) obtains polynary mixed
The total ion concentration for closing solution is 1mol/L-1.5mol/L, and the concentration of sodium hydroxide solution flowed into step 2) is 7.5-
10mol/L, the ammonia concn of inflow are 6-8mol/L.
The preparation method of the high tertiary cathode material of above-mentioned conductivity, it is preferred that in step 2) middle mixed solution into
Expect that speed is 90-150ml/min, sodium hydroxide charging rate is 30-70ml/min, ammonium hydroxide charging rate is 5-40ml/min.
The range endoparticle speed of growth is stablized, good sphericity.
The preparation method of the high tertiary cathode material of above-mentioned conductivity, it is preferred that the PH of coprecipitation reaction in step 2)
For 10-12, ammonium ion concentration is 5-9g/L, and reaction temperature is 50-60 DEG C, speed of agitator 200-400r/min.The range
Inside be conducive to evengranular growth, good dispersion avoids particle agglomeration.
The preparation method of the high tertiary cathode material of above-mentioned conductivity, it is preferred that three steps of the sintering of the step 5) point
It carries out, 1. according to 4 DEG C of min of heating rate-1It is warming up to 400-420 DEG C of isothermal holding 3h；2. then according to 2 DEG C of heating rate
min-1It is warming up to 580-600 DEG C, keeps the temperature 3h；3. according to 1 DEG C of min of heating rate-1It is warming up to 750-900 DEG C of heat preservation 15h, is obtained
To product.
The preparation method of the high tertiary cathode material of above-mentioned conductivity, it is preferred that conducting polymer in the step 6)
Monomer include acetylene, pyrroles, thiophene and derivatives.
The preparation method of the high tertiary cathode material of above-mentioned conductivity, it is preferred that in the step 8, polymerization reaction point
For two 60~65 DEG C of first stage in stage temperature, it polymerize 25~30min, 165~170 DEG C of second stage temperature, polyase 13 0~
35min。
In the present invention, the highly stable film of one layer of chemical property is formed in core surface, this layer film is one layer of non-gold
Belong to film, do not interfere with the thematic structure of kernel, while electrolyte can be stopped to decompose the gas pair of generation under high pressure
The corrosion of kernel, protection materials structure；From the perspective of chemically reacting, the decomposition of electrolyte can be inhibited to a certain extent.
In the present invention, the conductivity of the film of shell is higher, can reduce the surface impedance of ternary material, to improve
The conductive capability of anode, to improve the high rate performance of battery.Meanwhile tertiary cathode material of the invention can preferably with it is viscous
Knot agent is combined, and can be prevented becoming larger for charge and discharge process middle impedance to a certain extent, be improved the cycle performance of material.
Specific embodiment
To facilitate the understanding of the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment,
But the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Embodiment 1
A kind of preparation method for the tertiary cathode material that conductivity is high includes the following steps and 1) configures nickel salt, cobalt salt and manganese
The Diversity solution of salt, in mixed solution, stoichiometric ratio Ni:Co:Mn=5:2:3.
2) the Diversity solution of step 1) is added to reacting containing bottom liquid with ammonium hydroxide and sodium hydroxide solution cocurrent
In device, carries out coprecipitation reaction and obtain sodium hydroxide object presoma；Whole process is in N2Atmosphere protection lower carry out；
3) sediment is obtained by filtration in the reaction product of step 2), and is washed with deionized to filtrate and is in neutrality；
4) it is dried in heated-air circulation oven by 10-12h, obtains Ni0.5Co0.2Mn0.3(OH)2Presoma；
5) by the ternary precursor of step 4) and Li2CO3According to stoichiometric ratio 2:1.1 mixed grinding it is uniform after burnt
Knot, LiNi0.5Co0.2Mn0.3Material, i.e. kernel；
6) kernel of step 5) is immersed in 3,4-rthylene dioxythiophene (EDOT) monomer solution, first uses mechanical stirring
2h, then ultrasonic disperse 5h；Monomer solution includes monomer and dehydrated alcohol, and the molar ratio of monomer and dehydrated alcohol is 1:10.It is interior
The solid-to-liquid ratio of core and monomer solution is 45g/L.
7) kernel of step 6) is dried at room temperature, drying time 360min；
8) kernel of step 7) is immersed in oxidant, oxidant is to toluene yellow acid iron；Oxidizing agent solution concentration
35wt%；Polymerization reaction is carried out in polymerization baking oven after impregnation oxidant, and the maximum temperature of reaction is 200 DEG C, and the reaction time is
55min-65min；Polymerization reaction is divided into two 60~65 DEG C of first stage in stage temperature, polymerize 25~30min, second stage temperature
165~170 DEG C of degree, 0~35min of polyase 13.
9) it by tertiary cathode material ethanol washing that step 8) obtains and is filtered, is carried out at a temperature of 120 DEG C
It dries to get the LiNi coated to PEDOT0.5Co0.2Mn0.3。
The LiNi that step 5) is obtained0.5Co0.2Mn0.3The PEDOT cladding that material (being labeled as material 1) and step 9) obtain
LiNi0.5Co0.2Mn0.3Material (being labeled as material 2) makes lithium ion battery respectively as positive electrode active materials.It is adopted on anode
Use Kynoar (PVDF) as bonding agent, N-Methyl pyrrolidone (NMP) does dispersing agent, and cathode is adopted as artificial graphite,
The mass ratio that electrolyte is all made of solvent EC, DMC and EMC is 1: 1: 1, and electrolyte lithium salt is 1.0M, is fabricated to nominal appearance
Amount is the battery of 20Ah, and 1C charge and discharge cycles are carried out in 2.7~4.5V voltage range, as a result such as the following table 1.
Table 1
| Material | Discharging efficiency for the first time | Cycle-index | Capacity retention ratio (%) |
| 1 | 87.2 | 300 | 85.1 |
| 2 | 88.9 | 300 | 90.1 |
Come as can be seen from Table 1, is put using the lithium ion battery that tertiary cathode material of the invention is made for the first time
There is biggish promotion on the cycle performance of electrical efficiency and battery.
Claims (11)
1. a kind of tertiary cathode material that conductivity is high, it is characterised in that: including kernel and the shell for being coated on kernel outer surface；
With following chemical formula:
LicNiaCobMn1-a-bO2
Wherein, 0≤a≤1,0≤b≤1,0.4≤c≤1.5；
The kernel is the ternary material that lithium coats nickel, cobalt, manganese, and the shell is the film of conducting polymer；The conducting polymer
Object is carried out polymerization reaction by acetylene, pyrroles, thiophene and derivatives and is obtained.
2. the high tertiary cathode material of conductivity according to claim 1, it is characterised in that: the partial size of the kernel is 2-
20 μm, the shell with a thickness of 5-50nm.
3. a kind of preparation method for the tertiary cathode material that conductivity of any of claims 1 or 2 is high, it is characterised in that: including
Following steps 1) nickel salt of preset ratio, the Diversity solution of cobalt salt and manganese salt are configured,
2) the Diversity solution of step 1) and ammonium hydroxide and sodium hydroxide solution cocurrent are added to the reaction unit containing bottom liquid
In, it carries out coprecipitation reaction and obtains sodium hydroxide object presoma；Whole process carries out under the atmosphere protection of inert gas；
3) sediment is obtained by filtration in the reaction product of step 2), and is washed with deionized to filtrate and is in neutrality；
4) it is dried in heated-air circulation oven by 10-12h, obtains ternary material precursor；
5) by the ternary precursor of step 4) and Li2CO3According to stoichiometric ratio 2:1.1 mixed grinding it is uniform after be sintered, obtain
To kernel；
6) kernel of step 5) is immersed in conducting polymer monomer solution, first uses mechanical stirring 0.5-10h, then ultrasound point
Dissipate 0.5-72h；
7) kernel of step 6) is dry under conditions of room temperature~70 DEG C, drying time 30-360min；
8) kernel of step 7) is immersed in oxidant, oxidant is to toluene yellow acid iron, ammonium persulfate, sodium peroxydisulfate, sulphur
One of sour ammonium, iron chloride are a variety of；10~70wt% of oxidizing agent solution concentration；It polymerize in baking oven after impregnation oxidant and carries out
Polymerization reaction, the maximum temperature of reaction are 200 DEG C, reaction time 55min-65min；
9) it by tertiary cathode material ethanol washing that step 8) obtains and is filtered, is dried at a temperature of 40-120 DEG C
It does to get product is arrived.
4. the preparation method of the high tertiary cathode material of conductivity according to claim 3, it is characterised in that: the step
2) the low liquid in is the mixed liquor of sodium hydroxide and ammonium hydroxide；The concentration of sodium hydroxide solution is 7.5-10mol/L, ammonium hydroxide in the liquid of bottom
Concentration is 6-8mol/L.
5. the preparation method of the high tertiary cathode material of conductivity according to claim 3, it is characterised in that: step 1)
In, the nickel salt is at least one of nickel nitrate, nickel chloride, nickel acetate, nickel sulfate；The manganese salt is manganese nitrate, chlorination
At least one of manganese, manganese acetate, manganese sulfate；The cobalt salt be cobalt nitrate, cobalt chloride, cobalt acetate, in cobaltous sulfate at least
It is a kind of.
6. the preparation method of the high tertiary cathode material of conductivity according to claim 3, it is characterised in that: the step
1) total ion concentration of the Diversity solution obtained is 1mol/L-1.5mol/L, the sodium hydroxide solution flowed into step 2)
Concentration is 7.5-10mol/L, and the ammonia concn of inflow is 6-8mol/L.
7. the preparation method of the high tertiary cathode material of conductivity according to claim 3, it is characterised in that: in step 2)
The charging rate of middle mixed solution is 90-150ml/min, sodium hydroxide charging rate is 30-70ml/min, ammonium hydroxide charging rate
For 5-40ml/min.
8. the preparation method of the high tertiary cathode material of conductivity according to claim 3, it is characterised in that: in step 2)
The PH of coprecipitation reaction is 10-12, and ammonium ion concentration is 5-9g/L, and reaction temperature is 50-60 DEG C, speed of agitator 200-
400r/min。
9. the preparation method of the high tertiary cathode material of conductivity according to claim 3, it is characterised in that: the step
5) sintering is carried out in three steps, 1. according to 4 DEG C of min of heating rate-1It is warming up to 400-420 DEG C of isothermal holding 3h；2. then pressing
According to 2 DEG C of min of heating rate-1It is warming up to 580-600 DEG C, keeps the temperature 3h；3. according to 1 DEG C of min of heating rate-1It is warming up to 750-
900 DEG C of heat preservation 15h, obtain product.
10. the preparation method of the high tertiary cathode material of conductivity according to claim 3, it is characterised in that: the step
It is rapid 6) in conducting polymer monomer include acetylene, pyrroles, thiophene and derivatives.
11. the preparation method of the high tertiary cathode material of conductivity according to claim 3, it is characterised in that: the step
In rapid 8, polymerization reaction is divided into two 60~65 DEG C of first stage in stage temperature, polymerize 25~30min, second stage temperature 165
~170 DEG C, 0~35min of polyase 13.
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| CN110137472A (en) * | 2019-05-17 | 2019-08-16 | 贵州梅岭电源有限公司 | A kind of preparation method of composite positive pole |
| CN110828795A (en) * | 2019-10-29 | 2020-02-21 | 陈璞 | Zinc-manganese-oxygen cathode material and preparation method and application thereof |
| CN111584842A (en) * | 2020-05-19 | 2020-08-25 | 湖南省正源储能材料与器件研究所 | Preparation method of double-shell spherical lithium-rich layered oxide cathode material with crystal grain size arranged in direction |
| CN111987317A (en) * | 2020-09-24 | 2020-11-24 | 昆山宝创新能源科技有限公司 | Ternary material precursor with gradient distribution of nickel elements and preparation method and application thereof |
| CN114824193A (en) * | 2022-03-17 | 2022-07-29 | 合肥国轩高科动力能源有限公司 | alpha-Fe 2 O 3 Lithium ion ternary cathode material coated with initiation conductive polymer and preparation method thereof |
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