CN109713240A - The nickel cobalt lithium aluminate cathode material and preparation method thereof of conducting polymer cladding - Google Patents
The nickel cobalt lithium aluminate cathode material and preparation method thereof of conducting polymer cladding Download PDFInfo
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Abstract
The invention discloses a kind of nickel cobalt lithium aluminate cathode material and preparation method thereof of conducting polymer cladding, chemical general formula Lib(NixCoyAlzRa)O2@e-polymer, wherein (x+y+z+a): b=1:(0.9~1.1), (x+y+z): a=1:(0.01~0.05), x > 0.33, R are at least one of rare earth element, and e-polymer is the conducting polymer with electro-chemical activity；In this way, the present invention is rear-earth-doped by carrying out to nickel cobalt lithium aluminate cathode material, to improve the structural stability of material；The cladding of conducting polymer, nickel cobalt lithium aluminate cathode material is isolated with electrolyte, nickel cobalt lithium aluminate cathode material is avoided directly to contact with electrolyte, is reducing the conductivity that can be improved material while the generation of side reaction, it can accelerate lithium ion conduction, improve cycle performance and high rate performance.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of nickel cobalt lithium aluminate of conducting polymer cladding is just
Pole material and preparation method thereof.
Background technique
In the prior art, nickel cobalt lithium aluminate (LNCA) positive electrode is due to energy density with higher and relatively simple
Single preparation process is widely used in 3C Product and new-energy automobile field；But in cyclic process, due to anode/
The structure of the positive electrode of electrolyte interface can change and positive electrode and electrolyte between side reaction can occur, from
And cause nickel cobalt lithium aluminate cathode material anode/electrolyte interface can there is a phenomenon where chemical properties to decay；In addition, by
It is slower in the electronics of existing nickel cobalt lithium aluminate cathode material, ionic conduction, cause nickel cobalt lithium aluminate cathode material under high magnification
Chemical property it is poor.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is intended to provide a kind of nickel cobalt aluminium of conducting polymer cladding
Sour lithium anode material and preparation method thereof.
The embodiment of the present invention provides a kind of nickel cobalt lithium aluminate cathode material of electric polymer cladding, chemical general formula Lib
(NixCoyAlzRa)O2@e-polymer, wherein (x+y+z+a): b=1:(0.9~1.1), (x+y+z): a=1:(0.01~
0.05), x > 0.33, R are at least one of rare earth element, and e-polymer is the conducting polymer with electro-chemical activity.
Wherein, e-polymer is specially poly- to benzene or poly- union II thiophene.
The nickel cobalt lithium aluminate cathode material for the conducting polymer cladding that the present invention also provides a kind of as described in above scheme
Preparation method, method are implemented by following steps:
Step 1, nickel cobalt aluminium presoma, lithium salts and rare earth dopant are mixed in molar ratio, is sintered after mixing evenly, obtained
Obtain rear-earth-doped LNCA positive electrode；
Step 2, it disperses the rear-earth-doped LNCA positive electrode and conducting polymer in solvent, it is molten to obtain mixing
Liquid, Xiang Suoshu mixed solution are added conductive agent and binder, stir evenly, and obtain the LNCA anode material for being coated with conducting polymer
Slurry material；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, is carried out
Freeze-drying obtains the LNCA positive electrode for being coated with conducting polymer.
In above scheme, the molar ratio of nickel cobalt aluminium presoma, lithium salts and rare earth dopant described in the step 1 is 100:
(90~110): (1~5).
In above scheme, lithium salts described in the step 1 is lithium hydroxide or lithium carbonate, rare earth described in the step 1
Dopant is at least one of scandium, yttrium, lanthanum, cerium, praseodymium, the compound of neodymium.
In above scheme, the technique being sintered in the step 1 is that sintering temperature is 700~900 DEG C, sintering time be 4~
12h, mixing speed are 100~500r/min.
In above scheme, the quality of conducting polymer described in the step 2 is the rear-earth-doped LNCA anode material
The 0.5%~5% of the quality of material.
In above scheme, rear-earth-doped LNCA positive electrode described in the step 2, conductive agent and binder rub
You are than being 80:(5~15): (5~15).
In above scheme, the reaction time of the step 2 is 4~8h, and mixing speed is 100~500r/min.
In above scheme, conducting polymer described in the step 2 is poly- to benzene or poly- union II thiophene.
In above scheme, conductive agent described in the step 2 be carbon black, Ketjen black or Super P Li conductive carbon black in extremely
Few one kind, the binder are at least one of Kynoar, polytetrafluoroethylene (PTFE), carboxymethyl cellulose or butadiene-styrene rubber, institute
Stating solvent is solvable conducting polymer but the solvent of insoluble LNCA, and the solvent is specially n,N-Dimethylformamide, N- methyl
At least one of pyrrolidones or chloroform.
In above scheme, freeze-drying is carried out at vacuum degree 5-50pa in the step 3, the temperature of the freeze-drying
It is -50~-10 DEG C.
Compared with prior art, the invention proposes a kind of conducting polymer cladding nickel cobalt lithium aluminate cathode material and its
Preparation method, chemical general formula Lib(NixCoyAlzRa)O2@e-polymer, wherein (x+y+z+a): b=1:(0.9~
1.1), (x+y+z): a=1:(0.01~0.05), x > 0.33, R are at least one of rare earth element, and e-polymer is with electricity
Chemically active conducting polymer；This method is by preparing rear-earth-doped LNCA positive electrode, then to described rear-earth-doped
LNCA positive electrode conducting polymer, conductive agent and binder is added, directly obtain the LNCA for being coated with conducting polymer
Positive electrode slurry, finally, freeze-drying, obtains the LNCA positive electrode for being coated with conducting polymer；In this way, the present invention passes through
It is rear-earth-doped to the progress of nickel cobalt lithium aluminate cathode material, to improve the structural stability of material；The cladding of conducting polymer, will
Nickel cobalt lithium aluminate cathode material is isolated with electrolyte, and nickel cobalt lithium aluminate cathode material is avoided directly to contact with electrolyte,
It can be improved the conductivity of material while reducing the generation of side reaction, while there is the conducting polymer of electro-chemical activity,
It can be improved the lithium ion conduction of material to a certain extent, to improve the high rate performance of nickel cobalt lithium aluminate cathode material；In addition,
Conductive agent is added while to nickel cobalt lithium aluminate cathode material coated with conductive polymer and binder directly modulates positive electrode
Slurry, and obtain slurry freeze-drying after can direct pressing pole piece is made, exempt from collector, the energy for improving battery is close
Degree, simplifies production technology, save the cost.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The embodiment of the present invention provides a kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, and chemical general formula is
Lib(NixCoyAlzRa)O2@e-polymer, wherein (x+y+z+a): b=1:(0.9~1.1), (x+y+z): a=1:(0.01
~0.05), x > 0.33, R are at least one of rare earth element, and e-polymer is the conducting polymer with electro-chemical activity.
Wherein, e-polymer is specially poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate anode of conducting polymer cladding as described in above scheme
The preparation method of material, method are implemented by following steps:
Step 1, it is 100:(90~110 according to the molar ratio of nickel cobalt aluminium presoma, lithium salts and rare earth dopant): (1~
5) nickel cobalt aluminium presoma, lithium salts and rare earth dopant are weighed, is uniformly mixed with the mixing speed of 100~500r/min, then
It is sintered 4-12h at 700-900 DEG C, it is rear cooling, obtain rear-earth-doped LNCA positive electrode；
Wherein, the lithium salts is lithium hydroxide or lithium carbonate, and the rare earth dopant is the change of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium
Close at least one of object；
Step 2, it disperses the rear-earth-doped LNCA positive electrode and conducting polymer in solvent, reacts 4~8h,
Mixed solution is obtained, Xiang Suoshu mixed solution is added conductive agent and binder, stirs evenly at 100~500r/min, obtains
It is coated with the LNCA positive electrode slurry of conducting polymer；
Wherein, the quality of the conducting polymer be the rear-earth-doped LNCA positive electrode quality 0.5%~
5%；
The molar ratio of the rear-earth-doped LNCA positive electrode, conductive agent and binder is 80:(5~15): (5~
15)；
The conducting polymer is poly- to benzene or poly- union II thiophene；
The conductive agent is at least one of carbon black, Ketjen black or Super P Li conductive carbon black, and the binder is poly-
At least one of vinylidene, polytetrafluoroethylene (PTFE), carboxymethyl cellulose or butadiene-styrene rubber, the solvent are solvable conducting polymer
But the solvent of insoluble LNCA, the solvent are specially at least one in n,N-Dimethylformamide, N-Methyl pyrrolidone or chloroform
Kind.
One layer of conducting polymer is coated in rear-earth-doped LNCA positive electrode, is capable of the structure of stabilizing material, completely cuts off material
Expect to contact with the direct of electrolyte, avoid the side reaction with electrolyte, to improve the conductivity of material, accelerates electronics conduction.
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, true
It is freeze-dried under 5~50pa of reciprocal of duty cycle with drying temperature -50~-10 DEG C, obtains the LNCA anode for being coated with conducting polymer
Material.
Using freeze-drying process, directly preparation is coated with the LNCA positive electrode of conducting polymer, and passes through compacting
The LNCA anode pole piece for being coated with conducting polymer can be directly obtained, is polymerize to nickel cobalt lithium aluminate cathode material coated with conductive
Conductive agent is added while object and binder directly modulates positive electrode slurry, and can be direct after the slurry freeze-drying obtained
Pole piece is made, simplifies production technology, save the cost, also, the pole piece obtained relative to traditional clad anode material, this
Invent the LNCA that is coated with conducting polymer of the obtained LNCA anode pole piece for being coated with conducting polymer due to forming pole piece
Positive electrode is connected as one, and conductivity can significantly improve, and has greatly facilitated the electronics conduction of pole piece；In addition, by cold
It is lyophilized dry, directly obtains the anode pole piece for exempting from collector, the energy density of battery can be effectively improved.
The invention proposes a kind of nickel cobalt lithium aluminate cathode material and preparation method thereof of conducting polymer cladding, chemistry
General formula is Lib(NixCoyAlzRa)O2@e-polymer, wherein (x+y+z+a): b=1:(0.9~1.1), (x+y+z): a=1:
(0.01~0.05), x > 0.33, R are at least one of rare earth element, and e-polymer is the conducting polymer with electro-chemical activity
Object；Then this method is added by preparing rear-earth-doped LNCA positive electrode to the rear-earth-doped LNCA positive electrode
Conducting polymer, conductive agent and binder directly obtain the LNCA positive electrode slurry for being coated with conducting polymer, finally,
Freeze-drying obtains the LNCA positive electrode for being coated with conducting polymer；In this way, the present invention passes through to nickel cobalt lithium aluminate anode material
Material progress is rear-earth-doped, to improve the structural stability of material；Conducting polymer cladding with electro-chemical activity, by nickel cobalt
Lithium aluminate cathode material is isolated with electrolyte, avoids nickel cobalt lithium aluminate cathode material from directly contacting with electrolyte, while energy
Electronics, the ionic conduction for enough improving material, to improve the high rate performance of nickel cobalt lithium aluminate cathode material；In addition, to nickel cobalt
Conductive agent is added while lithium aluminate cathode material coated with conductive polymer and binder directly modulates positive electrode slurry, and
Acquisition slurry freeze-drying after can direct pressing pole piece is made, simplify production technology, save the cost exempts from current collector structure
Pole piece can effectively improve the energy density of battery.
Embodiment 1
A kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, which is characterized in that its chemical general formula is Li
(Ni0.37Co0.3Al0.3La0.03)O2@e-polymer, wherein e-polymer is poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate anode of conducting polymer cladding as described in above scheme
The preparation method of material, method are implemented by following steps:
Step 1, the compound of 10mol nickel cobalt aluminium presoma, 10mol lithium carbonate and 0.3mol lanthanum is weighed, with 300r/min
It is uniformly mixed, Isothermal sinter 8h obtains rear-earth-doped LNCA positive electrode after cooling at 800 DEG C under oxygen atmosphere；
Step 2,1000g rear-earth-doped LNCA positive electrode and 20g are gathered and benzene is scattered in N- first pyrrolidones, instead
6h is answered, mixed solution is obtained, then 93.75g carbon black and 93.75g Kynoar is added to the mixed solution, in 300r/min
Under stir evenly, obtain and be coated with the LNCA positive electrode slurry of conducting polymer；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, true
It is freeze-dried under reciprocal of duty cycle 28pa with -30 DEG C of drying temperature, obtains the LNCA positive electrode for being coated with conducting polymer.
Conducting polymer is coated with by obtaining after the LNCA positive electrode compacting for being coated with conducting polymer after above-mentioned drying
The LNCA anode pole piece of object；The existing LNCA anode pole piece using uncoated conducting polymer is as anode, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, first discharge specific capacity reaches 180mAh/g under 0.5C multiplying power；100
Capacity retention ratio is reduced to 95.2% after secondary charge-discharge cycle；Under 2C multiplying power, specific discharge capacity is only 158.3mAh/g；With existing skill
Art is compared, and the LNCA anode pole piece obtained for being coated with conducting polymer is as anode using the above scheme, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, using the LNCA anode produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 178.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
96.7%；Under 2C multiplying power, specific discharge capacity reaches 164.3mAh/g.
Embodiment 2
A kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, which is characterized in that its chemical general formula is Li
(Ni0.34Co0.33Al0.3La0.03)O2@e-polymer, wherein e-polymer is poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate anode of conducting polymer cladding as described in above scheme
The preparation method of material, method are implemented by following steps:
Step 1, the compound of 10mol nickel cobalt aluminium presoma, 9mol lithium carbonate and 0.3mol lanthanum is weighed, it is mixed with 300r/min
It closes uniformly, Isothermal sinter 8h obtains rear-earth-doped LNCA positive electrode after cooling at 800 DEG C under oxygen atmosphere；
Step 2,1000g rear-earth-doped LNCA positive electrode and 20g are gathered and benzene is scattered in N- first pyrrolidones, instead
6h is answered, mixed solution is obtained, then 93.75g carbon black and 93.75g Kynoar is added to the mixed solution, in 300r/min
Under stir evenly, obtain and be coated with the LNCA positive electrode slurry of conducting polymer；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, true
It is freeze-dried under reciprocal of duty cycle 28pa with -30 DEG C of drying temperature, obtains the LNCA positive electrode for being coated with conducting polymer.
Conducting polymer is coated with by obtaining after the LNCA positive electrode compacting for being coated with conducting polymer after above-mentioned drying
The LNCA anode pole piece of object；The existing LNCA anode pole piece using uncoated conducting polymer is as anode, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, first discharge specific capacity reaches 180mAh/g under 0.5C multiplying power；100
Capacity retention ratio is reduced to 95.2% after secondary charge-discharge cycle；Under 2C multiplying power, specific discharge capacity is only 158.3mAh/g；With existing skill
Art is compared, and the LNCA anode pole piece obtained for being coated with conducting polymer is as anode using the above scheme, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, using the LNCA anode produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 178.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
96.7%；Under 2C multiplying power, specific discharge capacity reaches 164.3mAh/g.
Embodiment 3
A kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, which is characterized in that its chemical general formula is Li
(Ni0.34Co0.3Al0.33La0.03)O2@e-polymer, wherein e-polymer is poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate anode of conducting polymer cladding as described in above scheme
The preparation method of material, method are implemented by following steps:
Step 1, the compound of 10mol nickel cobalt aluminium presoma, 11mol lithium carbonate and 0.3mol lanthanum is weighed, with 300r/min
It is uniformly mixed, Isothermal sinter 8h obtains rear-earth-doped LNCA positive electrode after cooling at 800 DEG C under oxygen atmosphere；
Step 2,1000g rear-earth-doped LNCA positive electrode and 20g are gathered and benzene is scattered in N- first pyrrolidones, instead
6h is answered, mixed solution is obtained, then 93.75g carbon black and 93.75g Kynoar is added to the mixed solution, in 300r/min
Under stir evenly, obtain and be coated with the LNCA positive electrode slurry of conducting polymer；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, true
It is freeze-dried under reciprocal of duty cycle 28pa with -30 DEG C of drying temperature, obtains the LNCA positive electrode for being coated with conducting polymer.
Conducting polymer is coated with by obtaining after the LNCA positive electrode compacting for being coated with conducting polymer after above-mentioned drying
The LNCA anode pole piece of object；The existing LNCA anode pole piece using uncoated conducting polymer is as anode, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, first discharge specific capacity reaches 180mAh/g under 0.5C multiplying power；100
Capacity retention ratio is reduced to 95.2% after secondary charge-discharge cycle；Under 2C multiplying power, specific discharge capacity is only 158.3mAh/g；With existing skill
Art is compared, and the LNCA anode pole piece obtained for being coated with conducting polymer is as anode using the above scheme, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, using the LNCA anode produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 178.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
96.7%；Under 2C multiplying power, specific discharge capacity reaches 164.3mAh/g.
Embodiment 4
A kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, which is characterized in that its chemical general formula is Li
(Ni0.34Co0.33Al0.32Y0.01)O2@e-polymer, wherein e-polymer is poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate anode of conducting polymer cladding as described in above scheme
The preparation method of material, method are implemented by following steps:
Step 1, the compound of 10mol nickel cobalt aluminium presoma, 10mol lithium carbonate and 0.1mol yttrium is weighed, with 300r/min
It is uniformly mixed, Isothermal sinter 8h obtains rear-earth-doped LNCA positive electrode after cooling at 800 DEG C under oxygen atmosphere；
Step 2,1000g rear-earth-doped LNCA positive electrode and 20g are gathered and benzene is scattered in N- first pyrrolidones, instead
6h is answered, mixed solution is obtained, then 93.75g carbon black and 93.75g Kynoar is added to the mixed solution, in 300r/min
Under stir evenly, obtain and be coated with the LNCA positive electrode slurry of conducting polymer；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, true
It is freeze-dried under reciprocal of duty cycle 28pa with -30 DEG C of drying temperature, obtains the LNCA positive electrode for being coated with conducting polymer.
Conducting polymer is coated with by obtaining after the LNCA positive electrode compacting for being coated with conducting polymer after above-mentioned drying
The LNCA anode pole piece of object；The existing LNCA anode pole piece using uncoated conducting polymer is as anode, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, first discharge specific capacity reaches 180mAh/g under 0.5C multiplying power；100
Capacity retention ratio is reduced to 95.2% after secondary charge-discharge cycle；Under 2C multiplying power, specific discharge capacity is only 158.3mAh/g；With existing skill
Art is compared, and the LNCA anode pole piece obtained for being coated with conducting polymer is as anode using the above scheme, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, using the LNCA anode produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 178.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
96.7%；Under 2C multiplying power, specific discharge capacity reaches 164.3mAh/g.
Embodiment 5
A kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, which is characterized in that its chemical general formula is Li
(Ni0.34Co0.3Al0.31Y0.05)O2@polymer, wherein e-polymer is poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate anode of conducting polymer cladding as described in above scheme
The preparation method of material, method are implemented by following steps:
Step 1, the compound of 10mol nickel cobalt aluminium presoma, 10mol lithium carbonate and 0.5mol yttrium is weighed, with 300r/min
It is uniformly mixed, Isothermal sinter 8h obtains rear-earth-doped LNCA positive electrode after cooling at 800 DEG C under oxygen atmosphere；
Step 2,1000g rear-earth-doped LNCA positive electrode and 20g are gathered and benzene is scattered in N- first pyrrolidones, instead
6h is answered, mixed solution is obtained, then 93.75g carbon black and 93.75g Kynoar is added to the mixed solution, in 300r/min
Under stir evenly, obtain and be coated with the LNCA positive electrode slurry of conducting polymer；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, true
It is freeze-dried under reciprocal of duty cycle 28pa with -30 DEG C of drying temperature, obtains the LNCA positive electrode for being coated with conducting polymer.
Conducting polymer is coated with by obtaining after the LNCA positive electrode compacting for being coated with conducting polymer after above-mentioned drying
The LNCA anode pole piece of object；The existing LNCA anode pole piece using uncoated conducting polymer is as anode, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, first discharge specific capacity reaches 180mAh/g under 0.5C multiplying power；100
Capacity retention ratio is reduced to 95.2% after secondary charge-discharge cycle；Under 2C multiplying power, specific discharge capacity is only 158.3mAh/g；With existing skill
Art is compared, and the LNCA anode pole piece obtained for being coated with conducting polymer is as anode using the above scheme, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, using the LNCA anode produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 178.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
96.7%；Under 2C multiplying power, specific discharge capacity reaches 164.3mAh/g.
Embodiment 6
A kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, which is characterized in that its chemical general formula is Li
(Ni0.35Co0.32Al0.3Ce0.03)O2@e-polymer, wherein e-polymer is poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate anode of conducting polymer cladding as described in above scheme
The preparation method of material, method are implemented by following steps:
Step 1, the compound of 10mol nickel cobalt aluminium presoma, 10mol lithium carbonate and 0.3mol cerium is weighed, with 300r/min
It is uniformly mixed, Isothermal sinter 8h obtains rear-earth-doped LNCA positive electrode after cooling at 800 DEG C under oxygen atmosphere；
Step 2,1000g rear-earth-doped LNCA positive electrode and 5g are gathered and benzene is scattered in N- first pyrrolidones, instead
6h is answered, mixed solution is obtained, then 93.75g carbon black and 93.75g Kynoar is added to the mixed solution, in 300r/min
Under stir evenly, obtain and be coated with the LNCA positive electrode slurry of conducting polymer；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, true
It is freeze-dried under reciprocal of duty cycle 28pa with -30 DEG C of drying temperature, obtains the LNCA positive electrode for being coated with conducting polymer.
Conducting polymer is coated with by obtaining after the LNCA positive electrode compacting for being coated with conducting polymer after above-mentioned drying
The LNCA anode pole piece of object；The existing LNCA anode pole piece using uncoated conducting polymer is as anode, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, first discharge specific capacity reaches 180mAh/g under 0.5C multiplying power；100
Capacity retention ratio is reduced to 95.2% after secondary charge-discharge cycle；Under 2C multiplying power, specific discharge capacity is only 158.3mAh/g；With existing skill
Art is compared, and the LNCA anode pole piece obtained for being coated with conducting polymer is as anode using the above scheme, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, using the LNCA anode produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 178.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
96.7%；Under 2C multiplying power, specific discharge capacity reaches 164.3mAh/g.
Embodiment 7
A kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, which is characterized in that its chemical general formula is Li
(Ni0.37Co0.3Al0.3Ce0.03)O2@e-polymer, wherein e-polymer is poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate anode of conducting polymer cladding as described in above scheme
The preparation method of material, method are implemented by following steps:
Step 1, the compound of 10mol nickel cobalt aluminium presoma, 10mol lithium carbonate and 0.3mol cerium is weighed, with 300r/min
It is uniformly mixed, Isothermal sinter 8h obtains rear-earth-doped LNCA positive electrode after cooling at 800 DEG C under oxygen atmosphere；
Step 2,1000g rear-earth-doped LNCA positive electrode and 50g are gathered and benzene is scattered in N- first pyrrolidones, instead
6h is answered, mixed solution is obtained, then 93.75g carbon black and 93.75g Kynoar is added to the mixed solution, in 300r/min
Under stir evenly, obtain and be coated with the LNCA positive electrode slurry of conducting polymer；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, true
It is freeze-dried under reciprocal of duty cycle 28pa with -30 DEG C of drying temperature, obtains the LNCA positive electrode for being coated with conducting polymer.
Conducting polymer is coated with by obtaining after the LNCA positive electrode compacting for being coated with conducting polymer after above-mentioned drying
The LNCA anode pole piece of object；The existing LNCA anode pole piece using uncoated conducting polymer is as anode, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, first discharge specific capacity reaches 180mAh/g under 0.5C multiplying power；100
Capacity retention ratio is reduced to 95.2% after secondary charge-discharge cycle；Under 2C multiplying power, specific discharge capacity is only 158.3mAh/g；With existing skill
Art is compared, and the LNCA anode pole piece obtained for being coated with conducting polymer is as anode using the above scheme, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, using the LNCA anode produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 178.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
96.7%；Under 2C multiplying power, specific discharge capacity reaches 164.3mAh/g.
Embodiment 8
A kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, which is characterized in that its chemical general formula is Li
(Ni0.37Co0.3Al0.3La0.03)O2@e-polymer, wherein e-polymer is poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate anode of conducting polymer cladding as described in above scheme
The preparation method of material, method are implemented by following steps:
Step 1, the compound of 10mol nickel cobalt aluminium presoma, 10mol lithium carbonate and 0.3mol lanthanum is weighed, with 300r/min
It is uniformly mixed, Isothermal sinter 8h obtains rear-earth-doped LNCA positive electrode after cooling at 800 DEG C under oxygen atmosphere；
Step 2,1000g rear-earth-doped LNCA positive electrode and 20g are gathered and benzene is scattered in N- first pyrrolidones, instead
6h is answered, mixed solution is obtained, then 62.5g carbon black and 187.5g Kynoar is added to the mixed solution, in 300r/min
Under stir evenly, obtain and be coated with the LNCA positive electrode slurry of conducting polymer；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, true
It is freeze-dried under reciprocal of duty cycle 28pa with -30 DEG C of drying temperature, obtains the LNCA positive electrode for being coated with conducting polymer.
Conducting polymer is coated with by obtaining after the LNCA positive electrode compacting for being coated with conducting polymer after above-mentioned drying
The LNCA anode pole piece of object；The existing LNCA anode pole piece using uncoated conducting polymer is as anode, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, first discharge specific capacity reaches 180mAh/g under 0.5C multiplying power；100
Capacity retention ratio is reduced to 95.2% after secondary charge-discharge cycle；Under 2C multiplying power, specific discharge capacity is only 158.3mAh/g；With existing skill
Art is compared, and the LNCA anode pole piece obtained for being coated with conducting polymer is as anode using the above scheme, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, using the LNCA anode produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 178.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
96.7%；Under 2C multiplying power, specific discharge capacity reaches 164.3mAh/g.
Embodiment 9
A kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, which is characterized in that its chemical general formula is Li
(Ni0.37Co0.3Al0.3La0.03)O2@e-polymer, wherein e-polymer is poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate anode of conducting polymer cladding as described in above scheme
The preparation method of material, method are implemented by following steps:
Step 1, the compound of 10mol nickel cobalt aluminium presoma, 10mol lithium carbonate and 0.3mol lanthanum is weighed, with 300r/min
It is uniformly mixed, Isothermal sinter 8h obtains rear-earth-doped LNCA positive electrode after cooling at 800 DEG C under oxygen atmosphere；
Step 2,1000g rear-earth-doped LNCA positive electrode and 20g are gathered and benzene is scattered in N- first pyrrolidones, instead
6h is answered, mixed solution is obtained, then 187.5g carbon black and 62.5g Kynoar is added to the mixed solution, in 300r/min
Under stir evenly, obtain and be coated with the LNCA positive electrode slurry of conducting polymer；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, true
It is freeze-dried under reciprocal of duty cycle 28pa with -30 DEG C of drying temperature, obtains the LNCA positive electrode for being coated with conducting polymer.
Conducting polymer is coated with by obtaining after the LNCA positive electrode compacting for being coated with conducting polymer after above-mentioned drying
The LNCA anode pole piece of object；The existing LNCA anode pole piece using uncoated conducting polymer is as anode, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, first discharge specific capacity reaches 180mAh/g under 0.5C multiplying power；100
Capacity retention ratio is reduced to 95.2% after secondary charge-discharge cycle；Under 2C multiplying power, specific discharge capacity is only 158.3mAh/g；With existing skill
Art is compared, and the LNCA anode pole piece obtained for being coated with conducting polymer is as anode using the above scheme, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, using the LNCA anode produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 178.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
96.7%；Under 2C multiplying power, specific discharge capacity reaches 164.3mAh/g.
Embodiment 10
A kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, which is characterized in that its chemical general formula is Li
(Ni0.37Co0.3Al0.3Nd0.03)O2@e-polymer, wherein e-polymer is poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate anode of conducting polymer cladding as described in above scheme
Material, method are implemented by following steps:
Step 1, the compound of 10mol nickel cobalt aluminium presoma, 10mol lithium carbonate and 0.3mol neodymium is weighed, with 100r/min
It is uniformly mixed, Isothermal sinter 12h obtains rear-earth-doped LNCA positive electrode after cooling at 700 DEG C under oxygen atmosphere；
Step 2,1000g rear-earth-doped LNCA positive electrode and 20g are gathered and benzene is scattered in N- first pyrrolidones, instead
8h is answered, mixed solution is obtained, then 93.75g carbon black and 93.75g Kynoar is added to the mixed solution, in 100r/min
Under stir evenly, obtain and be coated with the LNCA positive electrode slurry of conducting polymer；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, true
It is freeze-dried under reciprocal of duty cycle 5pa with -50 DEG C of drying temperature, obtains the LNCA positive electrode for being coated with conducting polymer.
Conducting polymer is coated with by obtaining after the LNCA positive electrode compacting for being coated with conducting polymer after above-mentioned drying
The LNCA anode pole piece of object；The existing LNCA anode pole piece using uncoated conducting polymer is as anode, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, first discharge specific capacity reaches 180mAh/g under 0.5C multiplying power；100
Capacity retention ratio is reduced to 95.2% after secondary charge-discharge cycle；Under 2C multiplying power, specific discharge capacity is only 158.3mAh/g；With existing skill
Art is compared, and the LNCA anode pole piece obtained for being coated with conducting polymer is as anode using the above scheme, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, using the LNCA anode produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 178.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
96.7%；Under 2C multiplying power, specific discharge capacity reaches 164.3mAh/g.
Embodiment 11
A kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, which is characterized in that its chemical general formula is Li
(Ni0.37Co0.3Al0.3Nd0.03)O2@e-polymer, wherein e-polymer is poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate anode of conducting polymer cladding as described in above scheme
Material, method are implemented by following steps:
Step 1, the compound of 10mol nickel cobalt aluminium presoma, 10mol lithium carbonate and 0.3mol neodymium is weighed, with 500r/min
It is uniformly mixed, Isothermal sinter 4h obtains rear-earth-doped LNCA positive electrode after cooling at 900 DEG C under oxygen atmosphere；
Step 2,1000g rear-earth-doped LNCA positive electrode and 20g are gathered and benzene is scattered in N- first pyrrolidones, instead
4h is answered, mixed solution is obtained, then 93.75g carbon black and 93.75g Kynoar is added to the mixed solution, in 500r/min
Under stir evenly, obtain and be coated with the LNCA positive electrode slurry of conducting polymer；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, true
It is freeze-dried under reciprocal of duty cycle 50pa with -10 DEG C of drying temperature, obtains the LNCA positive electrode for being coated with conducting polymer.
Conducting polymer is coated with by obtaining after the LNCA positive electrode compacting for being coated with conducting polymer after above-mentioned drying
The LNCA anode pole piece of object；The existing LNCA anode pole piece using uncoated conducting polymer is as anode, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, first discharge specific capacity reaches 180mAh/g under 0.5C multiplying power；100
Capacity retention ratio is reduced to 95.2% after secondary charge-discharge cycle；Under 2C multiplying power, specific discharge capacity is only 158.3mAh/g；With existing skill
Art is compared, and the LNCA anode pole piece obtained for being coated with conducting polymer is as anode using the above scheme, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, using the LNCA anode produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 178.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
96.7%；Under 2C multiplying power, specific discharge capacity reaches 164.3mAh/g.
Embodiment 12
A kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, which is characterized in that its chemical general formula is Li
(Ni0.37Co0.3Al0.3Sc0.03)O2@e-polymer, wherein e-polymer is poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate anode of conducting polymer cladding as described in above scheme
Material, method are implemented by following steps:
Step 1, the compound of 10mol nickel cobalt aluminium presoma, 9mol lithium carbonate and 0.3mol scandium is weighed, it is mixed with 300r/min
It closes uniformly, Isothermal sinter 8h obtains rear-earth-doped LNCA positive electrode after cooling at 800 DEG C under oxygen atmosphere；
Step 2, N- first pyrrolidones is dispersed by 1000g rear-earth-doped LNCA positive electrode and the poly- union II thiophene of 20g
In, 6h is reacted, obtains mixed solution, then 93.75g Ketjen black and 93.75g polytetrafluoroethylene (PTFE) is added to the mixed solution,
It is stirred evenly under 300r/min, obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, true
It is freeze-dried under reciprocal of duty cycle 28pa with -30 DEG C of drying temperature, obtains the LNCA positive electrode for being coated with conducting polymer.
Conducting polymer is coated with by obtaining after the LNCA positive electrode compacting for being coated with conducting polymer after above-mentioned drying
The LNCA anode pole piece of object；The existing LNCA anode pole piece using uncoated conducting polymer is as anode, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, first discharge specific capacity reaches 180mAh/g under 0.5C multiplying power；100
Capacity retention ratio is reduced to 95.2% after secondary charge-discharge cycle；Under 2C multiplying power, specific discharge capacity is only 158.3mAh/g；With existing skill
Art is compared, and the LNCA anode pole piece obtained for being coated with conducting polymer is as anode using the above scheme, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, using the LNCA anode produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 178.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
96.7%；Under 2C multiplying power, specific discharge capacity reaches 164.3mAh/g.
Embodiment 13
A kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, which is characterized in that its chemical general formula is Li
(Ni0.37Co0.3Al0.3Sc0.03)O2@e-polymer, wherein e-polymer is poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate anode of conducting polymer cladding as described in above scheme
The preparation method of material, method are implemented by following steps:
Step 1, the compound of 10mol nickel cobalt aluminium presoma, 9mol lithium carbonate and 0.3mol scandium is weighed, it is mixed with 300r/min
It closes uniformly, Isothermal sinter 8h obtains rear-earth-doped LNCA positive electrode after cooling at 800 DEG C under oxygen atmosphere；
Step 2, N- first pyrrolidones is dispersed by 1000g rear-earth-doped LNCA positive electrode and the poly- union II thiophene of 20g
In, 6h is reacted, obtains mixed solution, then 93.75g Super P Li conductive carbon black and 93.75g is added to the mixed solution
Carboxymethyl cellulose is stirred evenly at 300r/min, obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, true
It is freeze-dried under reciprocal of duty cycle 28pa with -30 DEG C of drying temperature, obtains the LNCA positive electrode for being coated with conducting polymer.
Conducting polymer is coated with by obtaining after the LNCA positive electrode compacting for being coated with conducting polymer after above-mentioned drying
The LNCA anode pole piece of object；The existing LNCA anode pole piece using uncoated conducting polymer is as anode, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, first discharge specific capacity reaches 180mAh/g under 0.5C multiplying power；100
Capacity retention ratio is reduced to 95.2% after secondary charge-discharge cycle；Under 2C multiplying power, specific discharge capacity is only 158.3mAh/g；With existing skill
Art is compared, and the LNCA anode pole piece obtained for being coated with conducting polymer is as anode using the above scheme, using metal lithium sheet
Charge-discharge test is carried out as cathode assembly button cell, using the LNCA anode produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 178.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
96.7%；Under 2C multiplying power, specific discharge capacity reaches 164.3mAh/g.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.
Claims (10)
1. a kind of nickel cobalt lithium aluminate cathode material of conducting polymer cladding, which is characterized in that its chemical general formula is Lib
(NixCoyAlzRa)O2@e-polymer, wherein (x+y+z+a): b=1:(0.9~1.1), (x+y+z): a=1:(0.01~
0.05), x > 0.33, R are at least one of rare earth element, and e-polymer is the conducting polymer with electro-chemical activity.
2. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of conducting polymer cladding as described in claim 1, special
Sign is that method is implemented by following steps:
Step 1, nickel cobalt aluminium presoma, lithium salts and rare earth dopant are mixed in molar ratio, is sintered after mixing evenly, obtained dilute
The LNCA positive electrode of soil doping；
Step 2, it disperses the rear-earth-doped LNCA positive electrode and conducting polymer in solvent, obtains mixed solution,
Conductive agent and binder is added to the mixed solution, stirs evenly, obtains the LNCA positive electrode for being coated with conducting polymer
Slurry；
Step 3, the LNCA positive electrode slurry for being coated with conducting polymer is transferred in freeze-dryer, is freezed
It is dry, obtain the LNCA positive electrode for being coated with conducting polymer.
3. the nickel cobalt lithium aluminate cathode material of conducting polymer cladding as described in claim 1 according to claim 2
Preparation method, which is characterized in that the molar ratio of nickel cobalt aluminium presoma, lithium salts and rare earth dopant described in the step 1 is
100:(90~110): (1~5).
4. the nickel cobalt lithium aluminate cathode material of conducting polymer cladding as described in claim 1 according to claim 3
Preparation method, which is characterized in that lithium salts described in the step 1 be lithium hydroxide or lithium carbonate, it is dilute described in the step 1
Native dopant is at least one of scandium, yttrium, lanthanum, cerium, praseodymium, the compound of neodymium.
5. the nickel cobalt lithium aluminate cathode material of conducting polymer cladding as described in claim 1 according to claim 4
Preparation method, which is characterized in that the technique being sintered in the step 1 is that sintering temperature is 700~900 DEG C, sintering time 4
~12h, mixing speed are 100~500r/min.
6. the nickel cobalt aluminic acid of the cladding of the conducting polymer as described in claim 1 according to claim 2-5 any one
The preparation method of lithium anode material, which is characterized in that the quality of conducting polymer described in the step 2 is described rear-earth-doped
LNCA positive electrode quality 0.5%~5%.
7. the nickel cobalt lithium aluminate cathode material of conducting polymer cladding as described in claim 1 according to claim 6
Preparation method, which is characterized in that rear-earth-doped LNCA positive electrode, conductive agent and binder described in the step 2
Molar ratio be 80:(5~15): (5~15).
8. the nickel cobalt lithium aluminate cathode material of conducting polymer cladding as described in claim 1 according to claim 7
Preparation method, which is characterized in that the reaction time of the step 2 be 4~8h, mixing speed be 100~500r/min.
9. the nickel cobalt lithium aluminate cathode material of conducting polymer cladding as described in claim 1 according to claim 8
Preparation method, which is characterized in that be poly- be conducting polymer to benzene or poly- union II thiophene, the conductive agent in the step 2
At least one of carbon black, Ketjen black or Super P Li conductive carbon black, the binder be Kynoar, polytetrafluoroethylene (PTFE),
At least one of carboxymethyl cellulose or butadiene-styrene rubber, the solvent are solvable conducting polymer but the solvent of insoluble LNCA, institute
Stating solvent is specially at least one of N,N-dimethylformamide, N-Methyl pyrrolidone or chloroform.
10. the nickel cobalt lithium aluminate cathode material of conducting polymer cladding as described in claim 1 according to claim 9
Preparation method, which is characterized in that in the step 3 freeze-drying carried out at 5~50pa of vacuum degree, the freeze-drying
Temperature is -50~-10 DEG C.
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