CN110137483A - A kind of nickle cobalt lithium manganate composite material and preparation method and application - Google Patents
A kind of nickle cobalt lithium manganate composite material and preparation method and application Download PDFInfo
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- CN110137483A CN110137483A CN201910527164.2A CN201910527164A CN110137483A CN 110137483 A CN110137483 A CN 110137483A CN 201910527164 A CN201910527164 A CN 201910527164A CN 110137483 A CN110137483 A CN 110137483A
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- 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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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a kind of nickle cobalt lithium manganate composite material and preparation method and application, preparation, precalcining, calcining, sieving including material previously treated and etc..Nickle cobalt lithium manganate composite material made from the method for the present invention can inhibit the precipitation of lithium and nickel cobalt manganese heavy metal, with good electric conductivity, specific capacity, cycle performance, high rate performance and thermal stability, the thermal stability of material is further increased simultaneously and meets the requirement of material height ratio capacity, meet high magnification, height ratio capacity lithium ion battery development trend, and simple process, structure-controllable, easy popularization, suitable for application of the nickel-cobalt lithium manganate material lithium ion battery.
Description
Technical field
The invention belongs to lithium ion battery material technical field more particularly to a kind of nickle cobalt lithium manganate composite material and its systems
Preparation Method and application.
Background technique
Lithium ion battery is a kind of secondary cell (rechargeable battery), it relies primarily on lithium ion and moves between a positive electrode and a negative electrode
It moves and carrys out work.In charge and discharge process, Li+Insertion and deintercalation back and forth between two electrodes: when charging, Li+From positive deintercalation,
It is embedded in cathode by electrolyte, cathode is in lithium-rich state；It is then opposite when electric discharge.Lithium ion battery is used as 21 century most
It is daily common portable to have been widely used for camera, mobile phone, laptop etc. for the clean and effective energy of development potentiality
Mobile device, and be gradually applied to electric car and get more and more people's extensive concerning.Anode material for lithium-ion batteries is lithium ion
The part of most critical in battery, exactly because many problems of positive electrode, limit some applications of lithium ion battery, and
By the development of many years, however it remains many problems, these problems seriously limit the further genralrlization of lithium ion battery
Using.In order to develop the application range of lithium ion battery towards enlargement more extensively, more easily, the anode of lithium ion battery is improved
Material property becomes particularly important.
Common anode material for lithium-ion batteries includes cobalt acid lithium, LiFePO4, LiMn2O4 and nickel cobalt manganese LiMn2O4
Deng.Wherein, cobalt acid lithium market share occupation rate is maximum, but cobalt acid lithium due to cobalt resource it is seriously in short supply, cause material price expensive,
Application cost is higher；LiFePO 4 material tap density is low, and poor processability, specific capacity is low, limits further answering for material
With；LiMn2O4 structural stability, especially high-temperature stability need to be further increased；Nickel manganese cobalt acid lithium replaces cobalt acid by nickel manganese
A large amount of cobalt, material cost advantage greatly improve in lithium, while the content for increasing nickel greatly improves the specific capacity of material, simultaneously
The material structure is stablized, and has a safety feature, and is the material of most possible substitution cobalt acid lithium, has very big market application prospect.
Although nickle cobalt lithium manganate has the advantages that numerous, the specific discharge capacity of nickle cobalt lithium manganate is lower, and analysis lithium easily occurs
Phenomenon, currently, people solve this technical problem by improving nickel content.Exactly because however also nickelic substitution, cause
The mixing of nickel and lithium in material and to generate analysis lithium phenomenon serious, especially at high humidity, analyse lithium phenomenon than more serious, while material
Overall conductivity also decrease.Currently, have about the document for improving nickle cobalt lithium manganate composite property, such as:
1, patent application CN201310739997.8 discloses a kind of height ratio capacity graphene coated nickel-cobalt lithium manganate material
Preparation method, the specific discharge capacity for mainly solving nickle cobalt lithium manganate present in the prior art is lower, and nickelic nickel
In material internal the precipitation that mixing phenomenon causes lithium easily occurs for cobalt manganic acid lithium, nickel and lithium, when air humidity is larger, analyses lithium phenomenon
More serious equal technical problem.It is under the conditions of 180 DEG C that graphene is thin using nickel-cobalt lithium manganate material and graphene platelet
Piece is dissolved in the graphene DMF solution for being configured to that concentration is 100-1000ppm in DMF solution, under stirring conditions by DMF solution
It is added drop-wise in the nickel-cobalt lithium manganate material of preparation, then above-mentioned resulting materials is put into 110-140 DEG C of drying in vacuum oven, i.e.,
Obtain finished product.This method is increased by the way of liquid phase doping relative to powder doping contact area, but graphene and nickel cobalt
It is connected between lithium manganate material by Van der Waals force, the two contact action power is smaller, so that passing through graphene packet using this method
It is limited to cover improvement nickel-cobalt lithium manganate material ion mixing phenomenon effect.
2, patent application CN201711154582.9 discloses a kind of system of graphene coated nickle cobalt lithium manganate composite material
Preparation Method.This method comprises the following steps: in conjunction with water phase " intercalation-expansion-oxidation " method and γ-X ray irradiation x reduction technique,
Green high-efficient prepares graphene easily separated, that water dispersible is good, conductivity is high.Using high-temperature calcination, with spherical manganese dioxide
For template, the ingenious spherical ternary material for preparing hollow structure, being formed by nanometer nickel-cobalt LiMn2O4 primary granule, and it is carried out
Surface modification treatment.And then controlling suitable condition makes graphene uniform be coated on nickle cobalt lithium manganate surface securely to get mesh
Mark composite material.The prices of raw materials involved in the present invention are cheap, and preparation process controllability is strong, and water or alcohol solvent used are to environment
It is friendly.The composite material electrochemical performance, specific capacity are up to 265mAhg-1, recycled through 500 times, capacity retention ratio is
86%, thus can be widely applied to the electrochemical energy storing devices such as lithium ion battery.But this method operating procedure is relative complex, to setting
It is standby more demanding.
But above-mentioned document prepares graphene coated nickle cobalt lithium manganate composite material or preparation method technique is relatively multiple
Miscellaneous, equipment requirement is high, and the stability of material or electrical property of preparation need to be further increased.Therefore, it is badly in need of now a kind of simple
Preparation method further improves material property.
Summary of the invention
The present invention is in order to solve the above technical problems, providing a kind of nickle cobalt lithium manganate composite material and preparation method and answering
With.The method of the present invention is keyed graphene by chemistry by realizing in-situ deposition graphene in nickle cobalt lithium manganate particle surface
Clad and nickel-cobalt lithium manganate material more preferably realize the protection to nickel-cobalt lithium manganate material, Ke Yiti while simplifying technique
The electric conductivity of high nickle cobalt lithium manganate composite material, while lithium precipitation and nickel cobalt manganese heavy metal ion in material can be inhibited to be electrolysed
Dissolution in liquid further increases the cyclical stability of material and meets the requirement of material height ratio capacity；Nickel cobalt obtained
The electric conductivity that LiMn2O4 composite material has had, the more uncoated nickel-cobalt lithium manganate material of discharge platform is significantly increased, and multiplying power
Performance and cyclical stability have clear improvement, and meet high power, energy-density lithium ion battery development trend.
In order to reach purpose described above, the invention adopts the following technical scheme:
A kind of nickle cobalt lithium manganate composite material, the nickle cobalt lithium manganate composite material surface growth in situ go out one layer of graphene
Clad, the preparation method of the nickle cobalt lithium manganate composite material the following steps are included: by nickel-cobalt lithium manganate material ultrasonic disperse in
In ethyl alcohol, reproducibility acid is added and carries out disproportionation, nickel-cobalt lithium manganate material surface nickel ion is made to carry out nickel ion reduction in situ,
Then under atmosphere of inert gases protection, then after precalcining, calcining, sieving processing, obtained surface in situ grows one layer of stone
The nickle cobalt lithium manganate composite material of black alkene clad.
Further, a kind of preparation method of nickle cobalt lithium manganate composite material, comprising the following steps:
The preparation of step 1, material previously treated: dispersing nickel-cobalt lithium manganate material in ethanol solution by ultrasonic treatment,
Then reproducibility acid is slowly added dropwise under stirring and carries out disproportionation, then is filtered, dehydrated alcohol rinsing, drying, is made
Surface has the nickle cobalt lithium manganate material previously treated of reproducibility nickel；
Step 2, precalcining: nickle cobalt lithium manganate material previously treated made from step 1 is gone in calcining furnace, indifferent gas is passed through
10~30min of body empties furnace air, and then heat temperature raising carries out precalcining under inert gas protection；
Step 3, calcining: after to precalcining, continue heat temperature raising under inert gas protection, then pass to unsaturation
Hydrocarbon gas is calcined, so that nickel-cobalt lithium manganate material surface forms graphene coated layer；
Step 4, sieving: after calcining, under inert gas protection, after cooled to room temperature, sieving, system are taken out
Obtain the nickle cobalt lithium manganate composite material that surface in situ grows one layer of graphene coated layer.
Further, in step 1, the mass ratio of the nickel-cobalt lithium manganate material and ethanol solution is 1:10~50.
Further, in step 1, the mass ratio of the nickel-cobalt lithium manganate material and reproducibility acid is 1:0.5~100.
Further, in step 1, the reproducibility acid is H2S, one of tartaric acid, citric acid or more than one, and
Concentration is 1wt.%~5wt.%.
Further, in step 1, the rate of the stirring is 50~800r/min, and the time of the disproportionation is 0.5
~2h.
Further, in step 2, the temperature of the precalcining is 200~400 DEG C, and the time is 0.5~2h.
Further, in step 2, the inert gas is nitrogen or argon gas, and it is 10~80mL/ that inert gas, which is passed through rate,
min。
Further, in step 3, the temperature of the calcining is 450~1500 DEG C, and the time is 3~6h.
Further, in step 3, the unsaturation hydrocarbon gas is one of acetylene, ethylene, propylene gas or one kind
More than, and it is 20~120mL/min that unsaturated hydrocarbon gas, which is passed through rate,.
Further, nickle cobalt lithium manganate composite material made from a kind of method as described above.
Further, the nickle cobalt lithium manganate composite material contains the stone that nickle cobalt lithium manganate base and its surface in situ are grown
Black alkene clad, the graphene coated layer with a thickness of 10nm~50nm.
Further, application of a kind of nickle cobalt lithium manganate composite material as anode material of lithium battery.
Reaction principle of the present invention: the present invention allows nickel ion that disproportionated reaction easily occurs in an acidic solution, generates elemental nickel, raw
At nickel simple substance can be used as catalyst, unsaturated hydrocarbon gas decomposition-reduction can be catalyzed under the high temperature conditions into graphene.Using
Reproducibility acid carries out nickel ion reduction in situ to nickel-cobalt lithium manganate material surface nickel ion, obtains surface and is catalyzed with reproducibility nickel
The nickel-cobalt lithium manganate material of agent.It is handled by low temperature precalcining, the removal pretreatment remaining moisture of nickel-cobalt lithium manganate material, purification
Unsaturated hydro carbons gas reduction environment, while pretreated nickel-cobalt lithium manganate material lattice is finely adjusted；Further mentioned
High calcination temperature, reproducibility Raney nickel can be catalyzed unsaturated hydrocarbon gas and vapour phase reduction occur in nickle cobalt lithium manganate particle surface
Decomposition reaction, to deposit one layer of graphene protective layer in cobalt lithium manganate material surface in situ；Reproducibility Raney nickel promotes stone
The electric conductivity of nickle cobalt lithium manganate composite material can be improved in the generation of black alkene protective layer, improves composite material high rate capability, together
When can inhibit the precipitation of lithium and nickel cobalt manganese heavy metal, further improve the thermal stability of material and meet material height ratio capacity
Requirement.
Since present invention employs above technical schemes, have the advantages that
(1) the method for the present invention is connected by realizing in-situ deposition graphene in nickle cobalt lithium manganate particle surface by chemical bond
Graphene coated layer and nickel-cobalt lithium manganate material are connect, the guarantor to nickel-cobalt lithium manganate material is more preferably realized while simplifying technique
Shield, can be improved the electric conductivity of nickle cobalt lithium manganate composite material, while lithium in material can be inhibited to be precipitated and nickel cobalt manganese heavy metal
The dissolution of ion in the electrolytic solution further increases the cyclical stability of material and meets the requirement of material height ratio capacity.
(2) electric conductivity that nickle cobalt lithium manganate composite material has had made from the method for the present invention, discharge platform are more uncoated
Nickel-cobalt lithium manganate material is significantly increased, and high rate performance and cyclical stability have clear improvement, and meets high power, high specific energy
Measure lithium ion battery development trend.
(3) present invention process is simple, structure-controllable, can significantly improve the cycle performance of nickel-cobalt lithium manganate material and forthright again
Can, suitable for application of the nickel-cobalt lithium manganate material lithium ion battery.
Detailed description of the invention
In order to illustrate more clearly of present example or technical solution in the prior art, to embodiment or will show below
There is in technical description required attached drawing do simply to introduce, it should be apparent that, the accompanying drawings in the following description is only the present invention
Some examples to those skilled in the art, can also be attached according to these under the premise of not paying creativeness
Figure obtains other attached drawings:
Fig. 1 is the preparation technology flow chart of nickle cobalt lithium manganate composite material of the present invention；
Fig. 2 is the embodiment of the present invention 1, embodiment 2, comparative example 1, comparative example 2 are made material and form battery in 0.2C and 5C
Discharge curve under multiplying power.
In attached drawing: 1- No.1 battery；2- C-size battery；No. tri- batteries of 3-；No. tetra- batteries of 4-.
Specific embodiment
Specific embodiments of the present invention will be described in further detail below, but the invention is not limited to these realities
Mode is applied, it is claimed to still fall within the claims in the present invention for any improvement or replacement on the present embodiment essence spirit
Range.
Embodiment 1
A kind of nickle cobalt lithium manganate composite material, the nickle cobalt lithium manganate composite material surface growth in situ go out one layer of graphene
Clad.
A kind of preparation method of nickle cobalt lithium manganate composite material, comprising the following steps:
The preparation of step 1, material previously treated: dispersing nickel-cobalt lithium manganate material in ethanol solution by ultrasonic treatment,
Then reproducibility acid is slowly added dropwise under stirring and carries out disproportionation, then is filtered, dehydrated alcohol rinsing, drying, is made
Surface has the nickle cobalt lithium manganate material previously treated of reproducibility nickel；
The mass ratio of the nickel-cobalt lithium manganate material and ethanol solution is 1:10；The nickel-cobalt lithium manganate material and reproducibility
The mass ratio of acid is 1:0.5；The reproducibility acid is citric acid, tartaric acid, and concentration is 1wt.%；The rate of the stirring is
50r/min, the time of the disproportionation are 0.5h；
Step 2, precalcining: nickle cobalt lithium manganate material previously treated made from step 1 is gone in calcining furnace, indifferent gas is passed through
Body 10min empties furnace air, and then heat temperature raising carries out precalcining under inert gas protection；The temperature of the precalcining
It is 200 DEG C, time 0.5h；The inert gas is nitrogen or argon gas, and it is 10mL/min that inert gas, which is passed through rate,；
Step 3, calcining: after to precalcining, continue heat temperature raising under inert gas protection, then pass to unsaturation
Hydrocarbon gas is calcined, so that nickel-cobalt lithium manganate material surface forms graphene coated layer；
The temperature of the calcining is 450 DEG C, time 3h；The unsaturation hydrocarbon gas is acetylene gas, and gas is passed through
Rate is 20mL/min；
Step 4, sieving: after calcining, under inert gas protection, after cooled to room temperature, sieving, system are taken out
Obtain the nickle cobalt lithium manganate composite material that surface in situ grows one layer of graphene coated layer.
Nickle cobalt lithium manganate composite material made from a kind of preparation method as described above, including nickle cobalt lithium manganate base and its table
Face growth in situ go out graphene coated layer, the graphene coated layer with a thickness of 10nm；The nickle cobalt lithium manganate composite wood
Material can be used as positive electrode and apply in lithium battery.
Embodiment 2
A kind of nickle cobalt lithium manganate composite material, the nickle cobalt lithium manganate composite material surface growth in situ go out one layer of graphene
Clad.
A kind of preparation method of nickle cobalt lithium manganate composite material, comprising the following steps:
The preparation of step 1, material previously treated: dispersing nickel-cobalt lithium manganate material in ethanol solution by ultrasonic treatment,
Then reproducibility acid is slowly added dropwise under stirring and carries out disproportionation, then is filtered, dehydrated alcohol rinsing, drying, is made
Surface has the nickle cobalt lithium manganate material previously treated of reproducibility nickel；
The mass ratio of the nickel-cobalt lithium manganate material and ethanol solution is 1:50；The nickel-cobalt lithium manganate material and reproducibility
The mass ratio of acid is 1:100；The reproducibility acid is tartaric acid, and concentration is 5wt.%；The rate of the stirring is 800r/
Min, the time of the disproportionation are 2h；
Step 2, precalcining: nickle cobalt lithium manganate material previously treated made from step 1 is gone in calcining furnace, indifferent gas is passed through
Body 30min empties furnace air, and then heat temperature raising carries out precalcining under inert gas protection；The temperature of the precalcining
It is 400 DEG C, time 2h；The inert gas is nitrogen or argon gas, and it is 80mL/min that inert gas, which is passed through rate,；
Step 3, calcining: after to precalcining, continue heat temperature raising under inert gas protection, then pass to unsaturation
Hydrocarbon gas is calcined, so that nickel-cobalt lithium manganate material surface forms graphene coated layer；
The temperature of the calcining is 1500 DEG C, time 6h；The unsaturation hydrocarbon gas is ethylene gas, and gas is passed through
Rate is 120mL/min；
Step 4, sieving: after calcining, under inert gas protection, after cooled to room temperature, sieving, system are taken out
Obtain the nickle cobalt lithium manganate composite material that surface in situ grows one layer of graphene coated layer.
Nickle cobalt lithium manganate composite material made from a kind of preparation method as described above, including nickle cobalt lithium manganate base and its table
Face growth in situ go out graphene coated layer, the graphene coated layer with a thickness of 50nm；The nickle cobalt lithium manganate composite wood
Material can be used as positive electrode and apply in lithium battery.
Embodiment 3
A kind of nickle cobalt lithium manganate composite material, the nickle cobalt lithium manganate composite material surface growth in situ go out one layer of graphene
Clad.
A kind of preparation method of nickle cobalt lithium manganate composite material, comprising the following steps:
The preparation of step 1, material previously treated: dispersing nickel-cobalt lithium manganate material in ethanol solution by ultrasonic treatment,
Then reproducibility acid is slowly added dropwise under stirring and carries out disproportionation, then is filtered, dehydrated alcohol rinsing, drying, is made
Surface has the nickle cobalt lithium manganate material previously treated of reproducibility nickel；
The mass ratio of the nickel-cobalt lithium manganate material and ethanol solution is 1:20；The nickel-cobalt lithium manganate material and reproducibility
The mass ratio of acid is 1:10；The reproducibility acid is H2S, and concentration is 2wt.%；The rate of the stirring is 100r/min, institute
The time for stating disproportionation is 1h；
Step 2, precalcining: nickle cobalt lithium manganate material previously treated made from step 1 is gone in calcining furnace, indifferent gas is passed through
Body 15min empties furnace air, and then heat temperature raising carries out precalcining under inert gas protection；The temperature of the precalcining
It is 250 DEG C, time 1h；The inert gas is nitrogen or argon gas, and it is 30mL/min that inert gas, which is passed through rate,；
Step 3, calcining: after to precalcining, continue heat temperature raising under inert gas protection, then pass to unsaturation
Hydrocarbon gas is calcined, so that nickel-cobalt lithium manganate material surface forms graphene coated layer；
The temperature of the calcining is 600 DEG C, time 4h；The unsaturation hydrocarbon gas is propylene gas, is passed through rate
For 50mL/min；
Step 4, sieving: after calcining, under inert gas protection, after cooled to room temperature, sieving, system are taken out
Obtain the nickle cobalt lithium manganate composite material that surface in situ grows one layer of graphene coated layer.
Nickle cobalt lithium manganate composite material made from a kind of preparation method as described above, including nickle cobalt lithium manganate base and its table
Face growth in situ go out graphene coated layer, the graphene coated layer with a thickness of 20nm；The nickle cobalt lithium manganate composite wood
Material can be used as positive electrode and apply in lithium battery.
Embodiment 4
A kind of nickle cobalt lithium manganate composite material, the nickle cobalt lithium manganate composite material surface growth in situ go out one layer of graphene
Clad.
A kind of preparation method of nickle cobalt lithium manganate composite material, comprising the following steps:
The preparation of step 1, material previously treated: dispersing nickel-cobalt lithium manganate material in ethanol solution by ultrasonic treatment,
Then reproducibility acid is slowly added dropwise under stirring and carries out disproportionation, then is filtered, dehydrated alcohol rinsing, drying, is made
Surface has the nickle cobalt lithium manganate material previously treated of reproducibility nickel；
The mass ratio of the nickel-cobalt lithium manganate material and ethanol solution is 1:40；The nickel-cobalt lithium manganate material and reproducibility
The mass ratio of acid is 1:90；The reproducibility acid is H2S, citric acid, and concentration is 4wt.%；The rate of the stirring is
700r/min, the time of the disproportionation are 1.5h；
Step 2, precalcining: nickle cobalt lithium manganate material previously treated made from step 1 is gone in calcining furnace, indifferent gas is passed through
Body 25min empties furnace air, and then heat temperature raising carries out precalcining under inert gas protection；The temperature of the precalcining
It is 350 DEG C, time 1.5h；The inert gas is nitrogen or argon gas, and it is 60mL/min that inert gas, which is passed through rate,；
Step 3, calcining: after to precalcining, continue heat temperature raising under inert gas protection, then pass to unsaturation
Hydrocarbon gas is calcined, so that nickel-cobalt lithium manganate material surface forms graphene coated layer；
The temperature of the calcining is 1300 DEG C, time 5h；The unsaturation hydrocarbon gas is acetylene, ethylene, propylene gas
Body, being passed through rate is 100mL/min；
Step 4, sieving: after calcining, under inert gas protection, after cooled to room temperature, sieving, system are taken out
Obtain the nickle cobalt lithium manganate composite material that surface in situ grows one layer of graphene coated layer.
Nickle cobalt lithium manganate composite material made from a kind of preparation method as described above, including nickle cobalt lithium manganate base and its table
Face growth in situ go out graphene coated layer, the graphene coated layer with a thickness of 40nm；The nickle cobalt lithium manganate composite wood
Material can be used as positive electrode and apply in lithium battery.
Embodiment 5
A kind of nickle cobalt lithium manganate composite material, the nickle cobalt lithium manganate composite material surface growth in situ go out one layer of graphene
Clad.
A kind of preparation method of nickle cobalt lithium manganate composite material, comprising the following steps:
The preparation of step 1, material previously treated: dispersing nickel-cobalt lithium manganate material in ethanol solution by ultrasonic treatment,
Then reproducibility acid is slowly added dropwise under stirring and carries out disproportionation, then is filtered, dehydrated alcohol rinsing, drying, is made
Surface has the nickle cobalt lithium manganate material previously treated of reproducibility nickel；
The mass ratio of the nickel-cobalt lithium manganate material and ethanol solution is 1:30；The nickel-cobalt lithium manganate material and reproducibility
The mass ratio of acid is 1:50；The reproducibility acid is tartaric acid, citric acid, and concentration is 3wt.%；The rate of the stirring is
400r/min, the time of the disproportionation are 1.2h；
Step 2, precalcining: nickle cobalt lithium manganate material previously treated made from step 1 is gone in calcining furnace, indifferent gas is passed through
Body 20min empties furnace air, and then heat temperature raising carries out precalcining under inert gas protection；The temperature of the precalcining
It is 300 DEG C, time 1.2h；The inert gas is nitrogen or argon gas, and it is 40mL/min that inert gas, which is passed through rate,；
Step 3, calcining: after to precalcining, continue heat temperature raising under inert gas protection, then pass to unsaturation
Hydrocarbon gas is calcined, so that nickel-cobalt lithium manganate material surface forms graphene coated layer；
The temperature of the calcining is 1000 DEG C, time 4.5h；The unsaturation hydrocarbon gas is acetylene and ethylene gas
(volume ratio 1:1), it is 70mL/min that gas, which is passed through rate,；
Step 4, sieving: after calcining, under inert gas protection, after cooled to room temperature, sieving, system are taken out
Obtain the nickle cobalt lithium manganate composite material that surface in situ grows one layer of graphene coated layer.
Nickle cobalt lithium manganate composite material made from a kind of preparation method as described above, including nickle cobalt lithium manganate base and its table
Face growth in situ go out graphene coated layer, the graphene coated layer with a thickness of 30nm；The nickle cobalt lithium manganate composite wood
Material can be used as positive electrode and apply in lithium battery.
Comparative example 1
It is carried out according to the embodiment in patent application CN201310739997.8.
Comparative example 2
It is carried out according to the embodiment in patent application CN201711154582.9.
Use 1 method of the embodiment of the present invention prepare nickle cobalt lithium manganate composite material as positive electrode, SP and CNTS for
Conductive agent, PVDF are binder, and according to positive electrode: conductive agent: binder=80:10:10 mass ratio is uniformly mixed
Anode sizing agent is coated on aluminium foil, is dried under the conditions of 100 DEG C, and lithium metal carries out lithium electricity as negative electrode in drying shed
The assembling in pond obtains No.1 battery, then No. two electricity is made using material made from embodiment 2 as anode using same method
Pond；Meanwhile be respectively adopted material made from 2 method of comparative example 1 and comparative example as positive electrode, SP and CNTS be conductive agent,
PVDF is binder, carries out lithium battery assembling using the above method, obtains No. three batteries and No. four batteries.By No.1 battery and three
Number discharge test of battery under the conditions of 0.2C multiplying power surveys the electric discharge of C-size battery and No. four batteries under the conditions of 5C multiplying power
Examination, discharge curve are illustrated in fig. 2 shown below.
As shown in Figure 2, the nickle cobalt lithium manganate composite material of the method for the present invention preparation has preferable high-rate discharge ability,
With 0.2C multiplying power discharging, discharge capacity 203.01mAhg-1；With 5C multiplying power discharging, discharge capacity 170.16mAhg-1, relatively
0.2C capacity retention ratio is 85.08%.In contrast, the material as made from comparative example 1 is with 0.2C multiplying power discharging, discharge capacity
For 185.36mAhg-1；For the material as made from comparative example 2 with 5C multiplying power discharging, discharge capacity is only 148.49mAhg-1, therefore
Nickle cobalt lithium manganate composite material prepared by the present invention has superior high rate performance.
In conclusion the method for the present invention is by realizing in-situ deposition graphene, passing through in nickle cobalt lithium manganate particle surface
Key connection graphene coated layer and nickel-cobalt lithium manganate material are learned, is more preferably realized to nickel-cobalt lithium manganate material while simplifying technique
Protection, the electric conductivity of nickle cobalt lithium manganate composite material can be improved, while lithium can be inhibited in material to be precipitated and nickel cobalt manganese weight
The dissolution of metal ion in the electrolytic solution, the cyclical stability for further increasing material and the use for meeting material height ratio capacity are wanted
It asks；The electric conductivity that nickle cobalt lithium manganate composite material obtained has had, the more uncoated nickel-cobalt lithium manganate material of discharge platform have bright
It is aobvious to increase, and high rate performance and cyclical stability have clear improvement, and meet high power, energy-density lithium ion battery development becomes
Gesture；Simple process, structure-controllable can significantly improve the cycle performance and high rate performance of nickel-cobalt lithium manganate material, be suitable for nickel cobalt
Application of the lithium manganate material in lithium ion battery.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, nothing
By from the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended
Claim rather than above description limit, it is intended that by the institute in the meaning and scope for the equivalent loins for falling in claim
It changes and includes within protection scope of the present invention.
Claims (10)
1. a kind of nickle cobalt lithium manganate composite material, it is characterised in that: the nickle cobalt lithium manganate composite material surface growth in situ goes out
One layer of graphene coated layer, the preparation method of the nickle cobalt lithium manganate composite material is the following steps are included: by nickel-cobalt lithium manganate material
Ultrasonic disperse is added reproducibility acid and carries out disproportionation in ethyl alcohol, carries out nickel-cobalt lithium manganate material surface nickel ion in situ
Then under atmosphere of inert gases protection, then after precalcining, calcining, sieving processing, it is raw that surface in situ is made in nickel ion reduction
Grow the nickle cobalt lithium manganate composite material of one layer of graphene coated layer.
2. a kind of preparation method of nickle cobalt lithium manganate composite material, which comprises the following steps:
The preparation of step 1, material previously treated: it disperses nickel-cobalt lithium manganate material in ethanol solution by ultrasonic treatment, then
Reproducibility acid is slowly added dropwise under stirring and carries out disproportionation, then is filtered, dehydrated alcohol rinsing, drying, surface is made
Nickle cobalt lithium manganate material previously treated with reproducibility nickel；
Step 2, precalcining: nickle cobalt lithium manganate material previously treated made from step 1 is gone in calcining furnace, is passed through inert gas 10
~30min empties furnace air, and then heat temperature raising carries out precalcining under inert gas protection；
Step 3, calcining: after to precalcining, continue heat temperature raising under inert gas protection, then pass to unsaturated hydro carbons
Gas is calcined, so that nickel-cobalt lithium manganate material surface forms graphene coated layer；
Step 4, sieving: after calcining, under inert gas protection, after cooled to room temperature, sieving is taken out, table is made
Face growth in situ goes out the nickle cobalt lithium manganate composite material of one layer of graphene coated layer.
3. a kind of preparation method of nickle cobalt lithium manganate composite material according to claim 2, it is characterised in that: in step 1,
The mass ratio of the nickel-cobalt lithium manganate material and ethanol solution is 1:10~50；The nickel-cobalt lithium manganate material and reproducibility acid
Mass ratio is 1:0.5~100.
4. a kind of preparation method of nickle cobalt lithium manganate composite material according to claim 2, it is characterised in that: in step 1,
The reproducibility acid is H2S, one of tartaric acid, citric acid or more than one, and concentration be 1wt.%~5wt.%；It is described
The rate of stirring is 50~800r/min, and the time of the disproportionation is 0.5~2h.
5. a kind of preparation method of nickle cobalt lithium manganate composite material according to claim 2, it is characterised in that: in step 2,
The temperature of the precalcining is 200~400 DEG C, and the time is 0.5~2h；The inert gas is nitrogen or argon gas, inert gas
Being passed through rate is 10~80mL/min.
6. a kind of preparation method of nickle cobalt lithium manganate composite material according to claim 2, it is characterised in that: in step 3,
The temperature of the calcining is 450~1500 DEG C, and the time of calcining is 3~6h.
7. a kind of preparation method of nickle cobalt lithium manganate composite material according to claim 2, it is characterised in that: in step 3,
The unsaturation hydrocarbon gas be one of acetylene, ethylene, propylene gas or more than one, and unsaturated hydrocarbon gas is passed through
Rate is 20~120mL/min.
8. a kind of nickle cobalt lithium manganate composite material as made from any one of claim 1~7 the method.
9. a kind of nickle cobalt lithium manganate composite material according to claim 8, it is characterised in that: the nickle cobalt lithium manganate is compound
Material contains the graphene coated layer that nickle cobalt lithium manganate base and its surface in situ are grown, the graphene coated layer with a thickness of
10nm~50nm.
10. a kind of application of the nickle cobalt lithium manganate composite material according to claim 8 as anode material of lithium battery.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169986A (en) * | 2011-04-02 | 2011-08-31 | 江苏乐能电池股份有限公司 | Preparation method of lithium ferric phosphate / grapheme composite positive electrode material |
| CN102263239A (en) * | 2011-06-21 | 2011-11-30 | 刘剑洪 | Graphene-like clad and doped lithium manganate composite cathode material and preparation method |
| CN103346319A (en) * | 2013-07-04 | 2013-10-09 | 河北工业大学 | Preparation method of metal doped lithium manganese phosphate/graphene/carbon composite material |
| CN104157854A (en) * | 2014-07-31 | 2014-11-19 | 山东玉皇新能源科技有限公司 | Preparation method for ternary positive electrode material of graphene composite lithium ion battery |
| CN104538604A (en) * | 2015-01-20 | 2015-04-22 | 河北工业大学 | Surface modifying method for lithium nickel manganese oxide positive electrode material |
| CN104934608A (en) * | 2015-04-13 | 2015-09-23 | 青岛科技大学 | Preparation method of in-situ graphene coated lithium ion battery cathode material |
| CN105006376A (en) * | 2015-07-13 | 2015-10-28 | 华北电力大学 | Preparation method of carbon nanotube and nickel oxide composite material |
| CN105552360A (en) * | 2016-03-03 | 2016-05-04 | 四川浩普瑞新能源材料股份有限公司 | Modified lithium nickel cobalt manganese oxide cathode material and preparation method thereof |
| US20160240841A1 (en) * | 2015-02-18 | 2016-08-18 | Hui He | Pre-sulfurized cathode for alkali metal-sulfur secondary battery and production process |
| CN106450279A (en) * | 2016-10-28 | 2017-02-22 | 武汉理工大学 | Preparation method of graphene coated nickel cobalt manganese lithium ion battery cathode material |
| CN106450217A (en) * | 2016-11-07 | 2017-02-22 | 珠海格力电器股份有限公司 | Modification method of lithium nickelate, cobaltate and manganate ternary material |
| CN107845786A (en) * | 2017-09-27 | 2018-03-27 | 中国科学院过程工程研究所 | A kind of hud typed positive electrode, its preparation method and the purposes in lithium ion battery of composite cladding |
| US20180102543A1 (en) * | 2016-10-06 | 2018-04-12 | Nanotek Instruments, Inc. | Lithium Ion Battery Anode Containing Silicon Nanowires Grown in situ in Pores of Graphene Foam and Production Process |
| CN107910532A (en) * | 2017-11-20 | 2018-04-13 | 复旦大学 | A kind of preparation method of graphene coated nickle cobalt lithium manganate composite material |
| CN108288708A (en) * | 2018-03-07 | 2018-07-17 | 深圳市本征方程石墨烯技术股份有限公司 | A kind of graphene In-situ reaction phosphoric acid ferrimanganic nickel lithium anode material and preparation method thereof |
-
2019
- 2019-06-18 CN CN201910527164.2A patent/CN110137483B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169986A (en) * | 2011-04-02 | 2011-08-31 | 江苏乐能电池股份有限公司 | Preparation method of lithium ferric phosphate / grapheme composite positive electrode material |
| CN102263239A (en) * | 2011-06-21 | 2011-11-30 | 刘剑洪 | Graphene-like clad and doped lithium manganate composite cathode material and preparation method |
| CN103346319A (en) * | 2013-07-04 | 2013-10-09 | 河北工业大学 | Preparation method of metal doped lithium manganese phosphate/graphene/carbon composite material |
| CN104157854A (en) * | 2014-07-31 | 2014-11-19 | 山东玉皇新能源科技有限公司 | Preparation method for ternary positive electrode material of graphene composite lithium ion battery |
| CN104538604A (en) * | 2015-01-20 | 2015-04-22 | 河北工业大学 | Surface modifying method for lithium nickel manganese oxide positive electrode material |
| US20160240841A1 (en) * | 2015-02-18 | 2016-08-18 | Hui He | Pre-sulfurized cathode for alkali metal-sulfur secondary battery and production process |
| CN104934608A (en) * | 2015-04-13 | 2015-09-23 | 青岛科技大学 | Preparation method of in-situ graphene coated lithium ion battery cathode material |
| CN105006376A (en) * | 2015-07-13 | 2015-10-28 | 华北电力大学 | Preparation method of carbon nanotube and nickel oxide composite material |
| CN105552360A (en) * | 2016-03-03 | 2016-05-04 | 四川浩普瑞新能源材料股份有限公司 | Modified lithium nickel cobalt manganese oxide cathode material and preparation method thereof |
| US20180102543A1 (en) * | 2016-10-06 | 2018-04-12 | Nanotek Instruments, Inc. | Lithium Ion Battery Anode Containing Silicon Nanowires Grown in situ in Pores of Graphene Foam and Production Process |
| CN106450279A (en) * | 2016-10-28 | 2017-02-22 | 武汉理工大学 | Preparation method of graphene coated nickel cobalt manganese lithium ion battery cathode material |
| CN106450217A (en) * | 2016-11-07 | 2017-02-22 | 珠海格力电器股份有限公司 | Modification method of lithium nickelate, cobaltate and manganate ternary material |
| CN107845786A (en) * | 2017-09-27 | 2018-03-27 | 中国科学院过程工程研究所 | A kind of hud typed positive electrode, its preparation method and the purposes in lithium ion battery of composite cladding |
| CN107910532A (en) * | 2017-11-20 | 2018-04-13 | 复旦大学 | A kind of preparation method of graphene coated nickle cobalt lithium manganate composite material |
| CN108288708A (en) * | 2018-03-07 | 2018-07-17 | 深圳市本征方程石墨烯技术股份有限公司 | A kind of graphene In-situ reaction phosphoric acid ferrimanganic nickel lithium anode material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 周德凤，袁亚莉: "《无机化学（第二版）》", 31 July 2014, 华中科技大学出版社 * |
| 四川大学工科基础化学教学中心: "《近代化学基础下册》", 30 August 2002, 高等教育出版社 * |
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