CN108574099A - A kind of preparation method of lithium ion battery composite cathode material - Google Patents
A kind of preparation method of lithium ion battery composite cathode material Download PDFInfo
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- CN108574099A CN108574099A CN201810595889.0A CN201810595889A CN108574099A CN 108574099 A CN108574099 A CN 108574099A CN 201810595889 A CN201810595889 A CN 201810595889A CN 108574099 A CN108574099 A CN 108574099A
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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
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Abstract
The present invention relates to a kind of preparation methods of lithium ion battery composite cathode material, belong to technical field of lithium ion.The preparation method of the lithium ion battery composite cathode material of the present invention, includes the following steps：1) anode material for lithium-ion batteries, carbon nanotube, organic carbon source are uniformly mixed with organic solvent and spinning solution is made, composite precursor is made in electrostatic spinning；The anode material for lithium-ion batteries is one or more of nickel cobalt lithium aluminate, LiFePO4；The organic carbon source is polyvinylpyrrolidone；The organic solvent is N, N dimethylformamides；2) by composite precursor made from step 1) be carbonized to get.In composite positive pole prepared by the preparation method of the lithium ion battery composite cathode material of the present invention, positive active material is coated by carbon fiber, electronic conductivity and lithium ion diffusion coefficient are all improved, and material shows good chemical property, have higher high rate performance.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium ion battery composite cathode material, belong to lithium ion battery technology neck
Domain.
Background technology
The advantages that lithium ion battery is high, energy density is high with output voltage is in necks such as portable electronic device, new energy vehicles
It is used widely in domain.Electronic product, which updates, to make rapid progress, and new energy vehicle industry development is swift and violent, all to lithium ion battery
It is required that further increasing.Currently, the research and development of lithium ion battery enterprise product focus mostly in high energy storage, high rate capability, height
The directions such as cyclical stability.Commercial lithium-ion batteries positive electrode mainly has cobalt acid lithium, LiMn2O4, LiFePO4 etc..Japan
Sony companies are manufactured that using graphitic carbon material as cathode, cobalt acid lithium is the lithium rechargeable battery of anode, realizes lithium ion
The commercialization of battery.But cobalt resource is rare, expensive, and production cost Continued, the application of cobalt acid lithium material is by very big
Limitation.LiMn2O4 raw material resources are abundant, but its material self-capacity is low, decaying is fast, material circulation poor performance, application prospect also by
To limitation.Although its cycle performance of LiFePO4 is preferable, that there is also electronic conductivities is low for it, volume energy density is small etc. asks
Topic.Ternary material combines the characteristics of multiple material, such as nickel cobalt aluminic acid lithium material, higher Ni contents make the capacity of material compared with
Height, Al elements play a supportive role in total, can improve the cyclical stability and thermal stability of material, and Co can be effective
Inhibit cationic mixing, material layer structure apparent.The collaboration generated the advantages of different materials is preferably utilized in ternary material
Effect becomes the very popular positive electrode with development prospect.But material itself there is also cycle performance, high rate performance compared with
The problems such as poor, prevents material further extensive commercial application.Material with carbon-coated surface can improve the electric conductivity of material, inhibit
Polarization, the stability for improving material surface, it is considered to be improve the effective means of chemical property.
Application publication number is that the Chinese invention patent of CN104900869A discloses a kind of carbon coating nickel cobalt aluminium tertiary cathode
The preparation method of material, including after mixing by anode material nickel cobalt aluminium ternary material and organic carbon source, catalyst, in inertia
Under atmosphere, it is heat-treated 1-10 hours in 400-500 DEG C, obtains carbon-coated nickel cobalt aluminium tertiary cathode material.But this material
In carbon be in the outer surface of positive electrode particle, it is smaller to the Conductivity of the material inside positive electrode particle so that
The performance of the high rate performance of positive electrode is limited.
Invention content
The purpose of the present invention is to provide a kind of preparation method of lithium ion battery composite cathode material, made from this method
Lithium ion battery composite cathode material has good high rate performance.
To achieve the above object, the technical scheme is that：
A kind of preparation method of lithium ion battery composite cathode material, includes the following steps：
1) anode material for lithium-ion batteries, carbon nanotube, organic carbon source are uniformly mixed with organic solvent and spinning solution are made,
Composite precursor is made in electrostatic spinning；The anode material for lithium-ion batteries be nickel cobalt lithium aluminate, one kind in LiFePO4 or
It is several；The organic carbon source is polyvinylpyrrolidone；The organic solvent is N,N-dimethylformamide；
2) by composite precursor made from step 1) be carbonized to get.
The anode material for lithium-ion batteries is made of nickel cobalt lithium aluminate, LiFePO4.The nickel cobalt lithium aluminate, ferric phosphate
The mass ratio of lithium is 7-8：1-1.5.
The anode material for lithium-ion batteries, carbon nanotube mass ratio be 8-9.5:0.5-2.
The dosage of organic carbon source is that the anode material for lithium-ion batteries that every total weight is 1g and carbon nanotube are corresponded to and used
The organic carbon source of 1.2-6.5g.Preferably, the organic carbon source of corresponding 2.6-6.5g, it is further preferred that corresponding 2.6-4.3g has
Machine carbon source.
The dosage of organic solvent is 5-25mL in step 1).
Anode material for lithium-ion batteries, carbon nanotube, organic carbon source are uniformly mixed with organic solvent, spinning solution packet is made
Include following steps：Anode material for lithium-ion batteries, carbon nanotube are mixed into obtain mixture with organic solvent, by organic carbon source with have
Solvent mixes to obtain mixed liquor, then uniformly mixes mixture with mixed liquor.
Anode material for lithium-ion batteries, carbon nanotube are mixed with organic solvent be first by anode material for lithium-ion batteries with
Carbon nanotube mix grinding obtains premix, then again mixes premix with organic solvent.The mix grinding be first by lithium ion battery just
Pole material, carbon nanotube are ground, then ball milling.The time of the grinding is 3min~10min.The time of the ball milling is
30min~2h.The rotating speed of the ball milling is 50~150r/min.Premix is mixed with organic solvent be by premix with it is organic
It is ultrasonically treated after solvent mixing.The time of the supersound process is 20-30min.When premix is mixed with organic solvent,
2-10mL organic solvents are corresponded to per 1g premixes.
The mass fraction of the mixed liquor is 10%-15%.
Organic carbon source is mixed with organic solvent mixed liquor is that organic carbon source is added in organic solvent, at 40-60 DEG C
Lower stirring 5-10h.Described 40-60 DEG C is oil bath heating.
It is to mix mixture with mixed liquor that mixture is uniformly mixed with mixed liquor, with the speed of 500~900r/min
Stir 2-10h.
The propeller fltting speed 0.005-0.05mL/min of the electrostatic spinning.The reception spacing of electrostatic spinning be 10~
15cm.The high direct voltage of electrostatic spinning is 10-15kV.
The carbonization is the heat preservation 1-3h at 300 DEG C~700 DEG C.
The carbonization carries out under mixed atmosphere, and the mixed atmosphere is the mixed atmosphere of argon gas and hydrogen.The argon gas
Volume ratio with hydrogen is 90-95:5-10.
The heating rate that 300 DEG C~700 DEG C are warming up to when carbonization is 3 DEG C~5 DEG C/min.It is cooled down after carbonization.It is described
Cooling is cooled to room temperature.It is ground after cooling.
The composite precursor first carries out pre-oxidation treatment before carbonization.The pre-oxidation treatment is to be protected at 100-250 DEG C
Warm 0.5-2h.Preferably, 150~250 DEG C of heat preservation 1h.
The heating rate that 150~250 DEG C are warming up to when pre-oxidation treatment is 0.5~2 DEG C/min.It is carried out after pre-oxidation treatment
It is cooling.The cooling is cooled to room temperature.
Composite precursor is first stood into 10~15h before pre-oxidation treatment.Standing is carried out in alumina crucible.
The lithium ion battery composite cathode material of the present invention is made by above-mentioned preparation method.The lithium ion battery packet of the present invention
Include positive plate, positive plate includes plus plate current-collecting body and the positive electrode material layer that is arranged on plus plate current-collecting body, and positive electrode material layer includes
Positive active material, the positive active material are above-mentioned lithium ion battery composite cathode material.
The beneficial effects of the invention are as follows：
In composite positive pole prepared by the preparation method of the lithium ion battery composite cathode material of the present invention, positive-active
Substance is coated by carbon fiber, and electronic conductivity and lithium ion diffusion coefficient are all improved, and material shows good electrochemistry
Performance has higher high rate performance.
In composite positive pole prepared by the present invention, active material particle is uniformly distributed at electrostatic spinning combination subsequent thermal
In the carbon nano-fiber (carbon base body) of science and engineering skill carbonization gained, carbon base body can effectively inhibit or active material particle is prevented to exist
The reunion growth question of the process in which materials crystal grain such as heat treatment.
Preparation method of the invention is simple for process, reproducibility is high, is suitble to the electrode for extending to industrialized production, preparing
Material performance in the operating temperature range of material is stablized.
Description of the drawings
Fig. 1 is the cycle performance test curve of embodiment 1 and the lithium ion battery in comparative example；
Fig. 2 is discharge curve of the lithium ion battery under different multiplying in embodiment 1 and comparative example.
Specific implementation mode
Technical scheme of the present invention is described further with reference to specific embodiment.
Embodiment 1
The preparation method of the lithium ion battery composite cathode material of the present embodiment includes the following steps：
1) it is 80 according to mass ratio：15：5 take nickel cobalt lithium aluminate, LiFePO4 and multi-walled carbon nanotube, are added in mortar and grind
Then ball milling 1h in ball grinder is added in mill mixing 10min, the rotating speed of ball milling is 150r/min.Mixture after ball milling is taken
0.5g is placed in small beaker, and 2mL n,N-Dimethylformamide (DMF) is added thereto, and being ultrasonically treated 30min keeps its dispersion equal
It is even to obtain mixture.
2) by polyvinylpyrrolidone (polyvinyl pyrrolidone, PVP) be added n,N-Dimethylformamide (N,
N-Dimethylformamide, DMF) in, 40 DEG C of oil bath heatings, and magnetic agitation 8h, it is 13% to be configured to PVP mass fractions
Polyvinylpyrrolidone DMF solution.
The DMF solution of mixture and polyvinylpyrrolidone that step 1) is obtained is according to mass ratio 1：9 ratio mixing,
With rotating speed for 900r/min high speed magnetic stirring 10h, the electrostatic spinning presoma of certain viscosity is uniformly mixed and had.
3) the electrostatic spinning presoma that step 2) obtains is subjected to electrostatic spinning under the following conditions：Positive high voltage is 12kV,
Negative high voltage is 1kV, and the distance between receiver board and syringe needle point are 10cm, and envionmental humidity 10%, temperature is room temperature,
Propeller fltting speed is 0.015mL/min.Random fiber film is obtained after electrostatic spinning.
4) the Random fiber film that step 3) obtains is placed in alumina crucible, stands 10h in air, be subsequently placed in horse
Not in stove, first 200 DEG C are warming up to the speed of 1 DEG C/min and pre-oxidize 1h.It cools to room temperature with the furnace, takes out, be placed in tube furnace
In, in mixed atmosphere, 500 DEG C of calcining 2h are warming up to the speed of 3 DEG C/min and are carbonized, mixed atmosphere is that volume ratio is
95:5 argon gas and hydrogen.With stove cooled to room temperature, takes out, with mortar grinder at powder, it is compound just to obtain lithium ion battery
Pole material.
The lithium ion battery of the present embodiment includes positive plate, negative plate, diaphragm, electrolyte.Positive plate includes anode collection
Body and the positive electrode material layer being arranged on plus plate current-collecting body, positive electrode material layer include positive active material, conductive agent, binder,
Positive active material, conductive agent, binder mass ratio be 80：10：10.Positive active material is that above-mentioned lithium ion battery is compound
Positive electrode, conductive agent are carbon black, binder PVDF.
The preparation method of the lithium ion battery of the present embodiment includes the following steps：
Above-mentioned lithium ion battery composite cathode material and carbon black, PVDF are pressed 80：10：10 mass ratio is weighed, and mixing is equal
It is even, NMP grindings are added, anode sizing agent is made, then coating is dried in vacuo 12h in 80 DEG C of forced air drying 1h at 110 DEG C.Then
Cut-parts obtain positive plate, coordinate with negative plate lithium piece, are assembled into button cell (2032 type).
Embodiment 2
The preparation method of the lithium ion battery composite cathode material of the present embodiment includes the following steps：
1) it is 80 according to mass ratio：15：5 take nickel cobalt lithium aluminate (NCA), LiFePO4 (LiFePO4) and multi-wall carbon nano-tube
It manages (Multi-walled carbon nanotubea, MWCNT), ground and mixed 10min in mortar is added, ball milling is then added
The rotating speed of ball milling 1h in tank, ball milling are 150r/min.It takes 1g to be placed in small beaker the mixture after ball milling, is added thereto
2mL n,N-Dimethylformamide (DMF), being ultrasonically treated 30min makes it be uniformly dispersed to obtain mixture.
2) by polyvinylpyrrolidone (polyvinyl pyrrolidone, PVP) be added n,N-Dimethylformamide (N,
N-Dimethylformamide, DMF) in, 40 DEG C of oil bath heatings, and magnetic agitation 8h, it is 13% to be configured to PVP mass fractions
Polyvinylpyrrolidone DMF solution.
The DMF solution of mixture and polyvinylpyrrolidone that step 1) is obtained is according to mass ratio 1：9 ratio mixing,
With rotating speed for 900r/min high speed magnetic stirring 10h, the electrostatic spinning presoma of certain viscosity is uniformly mixed and had.
3) the electrostatic spinning presoma that step 2) obtains is subjected to electrostatic spinning under the following conditions：Positive high voltage is 12kV,
Negative high voltage is 1kV, and the distance between receiver board and syringe needle point are 10cm, and envionmental humidity 10%, temperature is room temperature,
Propeller fltting speed is 0.015mL/min.Random fiber film is obtained after electrostatic spinning.
4) the Random fiber film that step 3) obtains is placed in alumina crucible, stands 10h in air, be subsequently placed in horse
Not in stove, first 200 DEG C are warming up to the speed of 1 DEG C/min and pre-oxidize 1h.It cools to room temperature with the furnace, takes out, be placed in tube furnace
In, in mixed atmosphere, 300 DEG C of calcining 2h are warming up to the speed of 3 DEG C/min and are carbonized, mixed atmosphere is that volume ratio is
95:5 argon gas and hydrogen.With stove cooled to room temperature, takes out, with mortar grinder at powder, it is compound just to obtain lithium ion battery
Pole material.
The lithium ion battery of the present embodiment includes positive plate, negative plate, diaphragm, electrolyte.Positive plate includes anode collection
Body and the positive electrode material layer being arranged on plus plate current-collecting body, positive electrode material layer include positive active material, conductive agent, binder,
Positive active material, conductive agent, binder mass ratio be 80：10：10.Positive active material is that above-mentioned lithium ion battery is compound
Positive electrode, conductive agent are carbon black, binder PVDF.
The preparation method of the lithium ion battery of the present embodiment includes the following steps：
Above-mentioned lithium ion battery composite cathode material and carbon black, PVDF are pressed 80：10：10 mass ratio is weighed, and mixing is equal
It is even, NMP grindings are added, anode sizing agent is made, then coating is dried in vacuo 12h in 80 DEG C of forced air drying 1h at 110 DEG C.Then
Cut-parts obtain positive plate, coordinate with negative plate lithium piece, are assembled into button cell (2032 type).
Embodiment 3
The preparation method of the lithium ion battery composite cathode material of the present embodiment includes the following steps：
1) it is 80 according to mass ratio：15：5 take nickel cobalt lithium aluminate, LiFePO4 and multi-walled carbon nanotube, are added in mortar and grind
Then ball milling 1h in ball grinder is added in mill mixing 10min, the rotating speed of ball milling is 150r/min.Mixture after ball milling is taken into 1g
It is placed in small beaker, 2mL n,N-Dimethylformamide (DMF) is added thereto, being ultrasonically treated 30min makes it be uniformly dispersed
To mixture.
2) by polyvinylpyrrolidone (polyvinyl pyrrolidone, PVP) be added n,N-Dimethylformamide (N,
N-Dimethylformamide, DMF) in, 40 DEG C of oil bath heatings, and magnetic agitation 8h, it is 13% to be configured to PVP mass fractions
Polyvinylpyrrolidone DMF solution.
The DMF solution of mixture and polyvinylpyrrolidone that step 1) is obtained is according to mass ratio 1：9 ratio mixing,
With rotating speed for 900r/min high speed magnetic stirring 10h, the electrostatic spinning presoma of certain viscosity is uniformly mixed and had.
3) the electrostatic spinning presoma that step 2) obtains is subjected to electrostatic spinning under the following conditions：Positive high voltage is 12kV,
Negative high voltage is 1kV, and the distance between receiver board and syringe needle point are 10cm, and envionmental humidity 10%, temperature is room temperature,
Propeller fltting speed is 0.015mL/min.Random fiber film is obtained after electrostatic spinning.
4) the Random fiber film that step 3) obtains is placed in alumina crucible, stands 10h in air, be subsequently placed in horse
Not in stove, first 200 DEG C are warming up to the speed of 1 DEG C/min and pre-oxidize 1h.It cools to room temperature with the furnace, takes out, be placed in tube furnace
In, in mixed atmosphere, 700 DEG C of calcining 2h are warming up to the speed of 3 DEG C/min and are carbonized, mixed atmosphere is that volume ratio is
95:5 argon gas and hydrogen.With stove cooled to room temperature, takes out, with mortar grinder at powder, it is compound just to obtain lithium ion battery
Pole material.
The lithium ion battery of the present embodiment includes positive plate, negative plate, diaphragm, electrolyte.Positive plate includes anode collection
Body and the positive electrode material layer being arranged on plus plate current-collecting body, positive electrode material layer include positive active material, conductive agent, binder,
Positive active material, conductive agent, binder mass ratio be 80：10：10.Positive active material is that above-mentioned lithium ion battery is compound
Positive electrode, conductive agent are carbon black, binder PVDF.
The preparation method of the lithium ion battery of the present embodiment includes the following steps：
Above-mentioned lithium ion battery composite cathode material and carbon black, PVDF are pressed 80：10：10 mass ratio is weighed, and mixing is equal
It is even, NMP grindings are added, anode sizing agent is made, then coating is dried in vacuo 12h in 80 DEG C of forced air drying 1h at 110 DEG C.Then
Cut-parts obtain positive plate, coordinate with negative plate lithium piece, are assembled into button cell (2032 type).
Embodiment 4
The preparation method of the lithium ion battery composite cathode material of the present embodiment includes the following steps：
1) it is 80 according to mass ratio：15：5 take nickel cobalt lithium aluminate, LiFePO4 and multi-walled carbon nanotube, are added in mortar and grind
Then ball milling 1h in ball grinder is added in mill mixing 10min, the rotating speed of ball milling is 150r/min.Mixture after ball milling is taken into 1g
It is placed in small beaker, 2mL n,N-Dimethylformamide (DMF) is added thereto, being ultrasonically treated 30min makes it be uniformly dispersed
To mixture.
2) by polyvinylpyrrolidone (polyvinyl pyrrolidone, PVP) be added n,N-Dimethylformamide (N,
N-Dimethylformamide, DMF) in, 40 DEG C of oil bath heatings, and magnetic agitation 8h, it is 13% to be configured to PVP mass fractions
Polyvinylpyrrolidone DMF solution.
The DMF solution of mixture and polyvinylpyrrolidone that step 1) is obtained is according to mass ratio 1：9 ratio mixing,
With rotating speed for 900r/min high speed magnetic stirring 10h, the electrostatic spinning presoma of certain viscosity is uniformly mixed and had.
3) the electrostatic spinning presoma that step 2) obtains is subjected to electrostatic spinning under the following conditions：Positive high voltage is 12kV,
Negative high voltage is 1kV, and the distance between receiver board and syringe needle point are 10cm, and envionmental humidity 10%, temperature is room temperature,
Propeller fltting speed is 0.015mL/min.Random fiber film is obtained after electrostatic spinning.
4) the Random fiber film that step 3) obtains is placed in alumina crucible, stands 10h in air, be subsequently placed in horse
Not in stove, first 150 DEG C are warming up to the speed of 1 DEG C/min and pre-oxidize 1h.It cools to room temperature with the furnace, takes out, be placed in tube furnace
In, in mixed atmosphere, 500 DEG C of calcining 2h are warming up to the speed of 3 DEG C/min and are carbonized, mixed atmosphere is that volume ratio is
95:5 argon gas and hydrogen.With stove cooled to room temperature, takes out, with mortar grinder at powder, it is compound just to obtain lithium ion battery
Pole material.
The lithium ion battery of the present embodiment includes positive plate, negative plate, diaphragm, electrolyte.Positive plate includes anode collection
Body and the positive electrode material layer being arranged on plus plate current-collecting body, positive electrode material layer include positive active material, conductive agent, binder,
Positive active material, conductive agent, binder mass ratio be 80：10：10.Positive active material is that above-mentioned lithium ion battery is compound
Positive electrode, conductive agent are carbon black, binder PVDF.
The preparation method of the lithium ion battery of the present embodiment includes the following steps：
Above-mentioned lithium ion battery composite cathode material and carbon black, PVDF are pressed 80：10：10 mass ratio is weighed, and mixing is equal
It is even, NMP grindings are added, anode sizing agent is made, then coating is dried in vacuo 12h in 80 DEG C of forced air drying 1h at 110 DEG C.Then
Cut-parts obtain positive plate, coordinate with negative plate lithium piece, are assembled into button cell (2032 type).
Embodiment 5
The preparation method of the lithium ion battery composite cathode material of the present embodiment includes the following steps：
1) it is 95 according to mass ratio：5 take nickel cobalt lithium aluminate and multi-walled carbon nanotube, and ground and mixed 10min in mortar is added,
Then ball milling 1h in ball grinder is added, the rotating speed of ball milling is 150r/min.1g is taken to be placed in small beaker the mixture after ball milling,
2mL n,N-Dimethylformamide (DMF) is added thereto, being ultrasonically treated 30min makes it be uniformly dispersed to obtain mixture.
2) by polyvinylpyrrolidone (polyvinyl pyrrolidone, PVP) be added n,N-Dimethylformamide (N,
N-Dimethylformamide, DMF) in, 40 DEG C of oil bath heatings, and magnetic agitation 8h, it is 13% to be configured to PVP mass fractions
Polyvinylpyrrolidone DMF solution.
The DMF solution of mixture and polyvinylpyrrolidone that step 1) is obtained is according to mass ratio 1：9 ratio mixing,
With rotating speed for 900r/min high speed magnetic stirring 10h, the electrostatic spinning presoma of certain viscosity is uniformly mixed and had.
3) the electrostatic spinning presoma that step 2) obtains is subjected to electrostatic spinning under the following conditions：Positive high voltage is 12kV,
Negative high voltage is 1kV, and the distance between receiver board and syringe needle point are 10cm, and envionmental humidity 10%, temperature is room temperature,
Propeller fltting speed is 0.015mL/min.Random fiber film is obtained after electrostatic spinning.
4) the Random fiber film that step 3) obtains is placed in alumina crucible, stands 10h in air, be subsequently placed in horse
Not in stove, first 200 DEG C are warming up to the speed of 1 DEG C/min and pre-oxidize 1h.It cools to room temperature with the furnace, takes out, be placed in tube furnace
In, in mixed atmosphere, 500 DEG C of calcining 2h are warming up to the speed of 3 DEG C/min and are carbonized, mixed atmosphere is that volume ratio is
95:5 argon gas and hydrogen.With stove cooled to room temperature, takes out, with mortar grinder at powder, it is compound just to obtain lithium ion battery
Pole material.
The lithium ion battery of the present embodiment includes positive plate, negative plate, diaphragm, electrolyte.Positive plate includes anode collection
Body and the positive electrode material layer being arranged on plus plate current-collecting body, positive electrode material layer include positive active material, conductive agent, binder,
Positive active material, conductive agent, binder mass ratio be 80：10：10.Positive active material is that above-mentioned lithium ion battery is compound
Positive electrode, conductive agent are carbon black, binder PVDF.
The preparation method of the lithium ion battery of the present embodiment includes the following steps：
Above-mentioned lithium ion battery composite cathode material and carbon black, PVDF are pressed 80：10：10 mass ratio is weighed, and mixing is equal
It is even, NMP grindings are added, anode sizing agent is made, then coating is dried in vacuo 12h in 80 DEG C of forced air drying 1h at 110 DEG C.Then
Cut-parts obtain positive plate, coordinate with negative plate lithium piece, are assembled into button cell (2032 type).
Comparative example
Using the nickel cobalt lithium aluminate NCA in embodiment 1 as positive active material, nickel cobalt lithium aluminate NCA and carbon black, PVDF are pressed
80：10：10 mass ratio is weighed, and is uniformly mixed, and NMP grindings are added and are made anode sizing agent, coating, in 80 DEG C of forced air drying 1h,
Then 12h is dried in vacuo at 110 DEG C.Then cut-parts obtain positive plate, coordinate with negative plate lithium piece, are assembled into button cell
(2032 type).
Test example
Lithium ion battery (half-cell) in Example 1-5 and comparative example, carry out in accordance with the following steps cycle performance and
High rate performance is tested, and test environment is all isoperibol：
Cycle performance test is the half-cell test carried out under conditions of charge-discharge magnification is 1C, charging/discharging voltage window
Mouthful：2.75V-4.25V；High rate performance test is progress under the conditions of charge-discharge magnification is 0.2C, 0.5C, 1C, 2C, 5C respectively
Half-cell is tested, charging/discharging voltage window：2.75V-4.25V.Measurement result is shown in Table 1~table 2.
The cycle performance of 1 embodiment 1-5 of table and the half-cell in comparative example
The high rate performance of 2 embodiment 1-5 of table and the half-cell in comparative example
Note：In table 2 under each different discharge-rate, prepared half-cell sample carries out the constant current charge and discharge of 10 cycles
Electrical testing, data area are that cycle starts to cycle to terminate the Natural Attenuation of battery specific capacity under corresponding current density.
Wherein, the cycle performance and high rate performance curve of embodiment 1 and the lithium ion battery in comparative example respectively such as Fig. 1 and
Shown in Fig. 2.Wherein NCA and NCA-1 respectively represents comparative example and embodiment 1.
By table 1, table 2 and Fig. 1 and Fig. 2 it is found that battery prepared by lithium ion battery composite cathode material produced by the present invention
There are preferable cycle performance and high rate performance.
Claims (8)
1. a kind of preparation method of lithium ion battery composite cathode material, it is characterised in that：Include the following steps：
1) anode material for lithium-ion batteries, carbon nanotube, organic carbon source are uniformly mixed with organic solvent and spinning solution is made, electrostatic
Composite precursor is made in spinning；The anode material for lithium-ion batteries is nickel cobalt lithium aluminate, one kind in LiFePO4 or several
Kind；The organic carbon source is polyvinylpyrrolidone；The organic solvent is N,N-dimethylformamide；
2) by composite precursor made from step 1) be carbonized to get.
2. the preparation method of lithium ion battery composite cathode material according to claim 1, it is characterised in that：The lithium from
Sub- cell positive material is made of nickel cobalt lithium aluminate and LiFePO4.
3. the preparation method of lithium ion battery composite cathode material according to claim 1, it is characterised in that：The lithium from
Sub- cell positive material, carbon nanotube mass ratio be 8-9.5:0.5-2.
4. the preparation method of lithium ion battery composite cathode material according to claim 1, it is characterised in that：It is described organic
The dosage of carbon source is that the anode material for lithium-ion batteries that every total weight is 1g and carbon nanotube are corresponded to using the organic of 1.2g-6.5g
Carbon source.
5. the preparation method of lithium ion battery composite cathode material according to claim 1, it is characterised in that：By lithium ion
Cell positive material, carbon nanotube, organic carbon source are uniformly mixed with organic solvent to be made spinning solution and includes the following steps：By lithium from
Sub- cell positive material, carbon nanotube mix to obtain mixture with organic solvent, and organic carbon source is mixed to obtain to mixing with organic solvent
Then liquid uniformly mixes mixture with mixed liquor.
6. the preparation method of lithium ion battery composite cathode material according to claim 5, it is characterised in that：By lithium ion
Cell positive material, carbon nanotube mixed with organic solvent be first anode material for lithium-ion batteries and carbon nanotube mix grinding are obtained it is pre-
Then batch mixing again mixes premix with organic solvent.
7. the preparation method of the lithium ion battery composite cathode material according to claim 1-6 any one, feature exist
In：The carbonization is the heat preservation 1-3h at 300 DEG C~700 DEG C.
8. the preparation method of the lithium ion battery composite cathode material according to claim 1-6 any one, feature exist
In：The composite precursor first carries out pre-oxidation treatment before carbonization, and the pre-oxidation treatment is to be kept the temperature at 150~250 DEG C
0.5-2h。
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| CN111584874A (en) * | 2020-05-28 | 2020-08-25 | 西安建筑科技大学 | Sodium ion battery positive electrode material based on nanofiber framework and preparation method and application thereof |
| CN114204019A (en) * | 2021-11-23 | 2022-03-18 | 五邑大学 | Battery positive electrode material and preparation method and application thereof |
| CN114497474A (en) * | 2021-12-24 | 2022-05-13 | 江苏华峰超纤材料有限公司 | Preparation method of nickel-rich NCM811 nanoparticles |
| CN114792804A (en) * | 2022-04-28 | 2022-07-26 | 北京理工大学重庆创新中心 | 3D printing positive electrode ink, and positive electrode forming method and application applying same |
| CN114899370A (en) * | 2022-04-15 | 2022-08-12 | 山东精工电子科技有限公司 | Carbon-coated lithium ion battery positive electrode material and preparation method thereof |
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Application publication date: 20180925 |