CN109713241A - Nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer and preparation method thereof - Google Patents
Nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer and preparation method thereof Download PDFInfo
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- CN109713241A CN109713241A CN201711014791.3A CN201711014791A CN109713241A CN 109713241 A CN109713241 A CN 109713241A CN 201711014791 A CN201711014791 A CN 201711014791A CN 109713241 A CN109713241 A CN 109713241A
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Abstract
The invention discloses nickel cobalt lithium aluminate cathode material of a kind of in-stiu coating conducting polymer and preparation method thereof, 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 rare earth ion doped by carrying out to nickel cobalt lithium aluminate cathode material, the structural stability of material is improved；Coated with conductive polymer nickel cobalt lithium aluminate cathode material is isolated with electrolyte, nickel cobalt lithium aluminate cathode material is avoided directly to contact with electrolyte, the generation of side reaction is reduced, while can be improved the electronics of material, ionic conduction, to improve the high rate performance of nickel cobalt lithium aluminate cathode material.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of nickel cobalt aluminic acid of in-stiu coating conducting polymer
Lithium anode 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 of in-stiu coating conducting polymer
Cobalt lithium aluminate cathode material and preparation method thereof.
The embodiment of the present invention provides a kind of nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer, chemical general formula
For 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.
Wherein, e-polymer is poly- to benzene or poly- union II thiophene.
The nickel cobalt lithium aluminate anode material for the in-stiu coating conducting polymer that the present invention also provides a kind of as described in above scheme
The preparation method of material, 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, disperse the rear-earth-doped LNCA positive electrode and conducting polymer monomer in solvent, then plus
Enter initiator, to centrifuge washing after the reaction was completed, is finally dispersed using the solvent, acquisition is coated with conducting polymer
LNCA positive electrode solution；
Step 3, conductive agent and binder, stirring is added in the LNCA positive electrode solution that Xiang Suoshu is coated with conducting polymer
Uniformly, the LNCA positive electrode slurry for being coated with conducting polymer is obtained；
Step 4, 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 the nickel cobalt aluminium presoma, lithium salts and rare earth dopant is 100:(90~110):
(1~5).
In above scheme, lithium salts described in the step 1 is lithium hydroxide or lithium carbonate, and lithium salts is hydrogen in the step 1
Lithia or lithium carbonate, the rare earth dopant are 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 monomer is rear-earth-doped LNCA positive electrode in the step 2
The 0.01%~5% of quality, the quality of the initiator are the 30%~80% of the quality of rear-earth-doped LNCA positive electrode.
In above scheme, the step 2 addition initiator reaction temperature be -10~20 DEG C, the reaction time be 4~
8h。
In above scheme, conducting polymer monomer is at least one of benzene, union II thiophene, the initiation in the step 2
Agent is anhydrous FeCl3Or anhydrous CuCl2, the solvent is solvable conducting polymer but the solvent of insoluble LNCA, the solvent are specific
For at least one of N,N-dimethylformamide, N-Methyl pyrrolidone or chloroform.
In above scheme, conductive agent, binder in the step 3 and the rear-earth-doped LNCA anode material in step 2
The molar ratio of material is (5~15): (5~15): 80.
In above scheme, conductive agent is at least one in carbon black, Ketjen black or Super P Li conductive carbon black in the step 3
Kind, the binder is at least one of Kynoar, polytetrafluoroethylene (PTFE), carboxymethyl cellulose or butadiene-styrene rubber.
In above scheme, freeze-drying is carried out at 5~50pa of vacuum degree in the step 4, the temperature of the freeze-drying
Degree is -50~-10 DEG C.
Compared with prior art, the invention proposes a kind of nickel cobalt lithium aluminate cathode materials of in-stiu coating conducting polymer
And preparation method thereof, 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, e-polymer be with
The conducting polymer of electro-chemical activity；Then this method is mixed by preparing rear-earth-doped LNCA positive electrode to the rare earth
Conducting polymer monomer, initiator, conductive agent and binder is added in miscellaneous LNCA positive electrode, directly obtains and is coated with conduction
The LNCA positive electrode slurry of polymer, finally, freeze-drying, obtains the LNCA positive electrode for being coated with conducting polymer；This
Sample, the present invention is rare earth ion doped by carrying out to nickel cobalt lithium aluminate cathode material, to improve the structural stability of material；It leads
The cladding of electric polymer is isolated by nickel cobalt lithium aluminate cathode material with electrolyte, avoid nickel cobalt lithium aluminate cathode material with
Electrolyte directly contacts, and reduces the generation of side reaction, improves the cycle performance of material；Original flavor cladding has electro-chemical activity
After conducting polymer, electronics, the ionic conduction of positive electrode are accelerated, to improve the forthright again of nickel cobalt lithium aluminate cathode material
Energy；In addition, can be improved the energy density of battery using the pole piece for exempting from collector machine structure.
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 in-stiu coating conducting polymer, chemical general formula
For 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.
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 of in-stiu coating conducting polymer as described in above scheme
The preparation method of positive electrode, 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, disperse the rear-earth-doped LNCA positive electrode and conducting polymer monomer in solvent, then plus
Enter initiator, 4~8h reacted at -10~10 DEG C, after complete reaction centrifuge washing, is finally dispersed again using solvent,
Obtain the LNCA positive electrode solution for being coated with conducting polymer；
Wherein, the quality of conducting polymer monomer is the 0.01%~5% of the quality of rear-earth-doped LNCA positive electrode,
The quality of the initiator is the 30%~80% of the quality of rear-earth-doped LNCA positive electrode.
Conducting polymer monomer is at least one of benzene, union II thiophene, and the initiator is anhydrous FeCl3Or it is anhydrous
CuCl2, the solvent is solvable conducting polymer but the solvent of insoluble LNCA, and the solvent is specially N, N- dimethyl formyl
At least one of amine, N-Methyl pyrrolidone or chloroform.
Step 3, conductive agent and binder is added in the LNCA positive electrode solution that Xiang Suoshu is coated with conducting polymer, with
The mixing speed of 100~500r/min is uniformly mixed, and obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Wherein, the molar ratio of the rear-earth-doped LNCA positive electrode in the conductive agent in step 3, binder and step 2
For (5~15): (5~15): 80.
Conductive agent is at least one of carbon black, Ketjen black or Super P Li conductive carbon black, binder be Kynoar,
At least one of polytetrafluoroethylene (PTFE), carboxymethyl cellulose or butadiene-styrene rubber.
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 4, 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 after object, while washing away initiator and binder directly modulates positive electrode slurry, and the slurry obtained is cold
Be lyophilized it is dry after can direct pressing pole piece is made, simplify production technology, save the cost, also, relative to traditional clad anode material
Expect obtained pole piece, what the present invention obtained is coated with the LNCA anode pole piece of conducting polymer since being coated with for pole piece of composition is led
The LNCA positive electrode of electric polymer is connected as one, and conductivity can significantly improve, and the electronics for having greatly facilitated pole piece passes
It leads；In addition, directly obtaining the anode pole piece for exempting from collector by freeze-drying, the energy density of battery can be effectively improved.
The invention proposes nickel cobalt lithium aluminate cathode material of a kind of in-stiu coating conducting polymer and preparation method thereof,
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 poly- to benzene or poly- union II thiophene；
Then this method is added conductive by preparing rear-earth-doped LNCA positive electrode to the rear-earth-doped LNCA positive electrode
Polymer monomer, initiator, conductive agent and binder directly obtain the LNCA positive electrode slurry for being coated with conducting polymer
Material, 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 aluminic acid
Lithium anode material progress is rare earth ion doped, to improve the structural stability of material；The cladding of conducting polymer, by nickel cobalt aluminium
Sour lithium anode material is isolated with electrolyte, and nickel cobalt lithium aluminate cathode material is avoided directly to contact with electrolyte, is reduced secondary anti-
The generation answered, while improving the cycle performance of material；After original flavor cladding has the conducting polymer of electro-chemical activity, accelerate
The electronics of positive electrode, ionic conduction, to improve the high rate performance of nickel cobalt lithium aluminate cathode material.Using exempting from collector machine knot
The pole piece of structure can be improved the energy density of battery.
Embodiment 1
A kind of nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer, 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 of in-stiu coating conducting polymer as described in above scheme
The preparation method of positive electrode, 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, it disperses 1000g rear-earth-doped LNCA positive electrode and 20g benzene in N- first pyrrolidones, is added
The anhydrous FeCl of 500g3, 6h is reacted at -5 DEG C, after complete reaction centrifuge washing, finally carried out again using N- first pyrrolidones
Dispersion obtains the LNCA positive electrode solution for being coated with conducting polymer；
Step 3, Xiang Suoshu is coated with the LNCA positive electrode solution 93.75g carbon black of conducting polymer and 93.75g gathers partially
Vinyl fluoride is stirred evenly at 300r/min, obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Step 4, 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 155mAh/g；With the prior art
It compares, the LNCA anode pole piece obtained for being coated with conducting polymer is made as anode using metal lithium sheet using the above scheme
Button cell is assembled for cathode and carries out charge-discharge test, using the LNCA anode material produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 179.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
98.8%；Under 2C multiplying power, specific discharge capacity reaches 167mAh/g.
Embodiment 2
A kind of nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer, 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 of in-stiu coating conducting polymer as described in above scheme
The preparation method of positive electrode, 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, it disperses 1000g rear-earth-doped LNCA positive electrode and 20g benzene in N- first pyrrolidones, is added
The anhydrous FeCl of 500g3, 6h is reacted at -5 DEG C, after complete reaction centrifuge washing, finally carried out again using N- first pyrrolidones
Dispersion obtains the LNCA positive electrode solution for being coated with conducting polymer；
Step 3, Xiang Suoshu is coated with the LNCA positive electrode solution 93.75g carbon black of conducting polymer and 93.75g gathers partially
Vinyl fluoride is stirred evenly at 300r/min, obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Step 4, 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 155mAh/g；With the prior art
It compares, the LNCA anode pole piece obtained for being coated with conducting polymer is made as anode using metal lithium sheet using the above scheme
Button cell is assembled for cathode and carries out charge-discharge test, using the LNCA anode material produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 179.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
98.8%；Under 2C multiplying power, specific discharge capacity reaches 167mAh/g.
Embodiment 3
A kind of nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer, 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 of in-stiu coating conducting polymer as described in above scheme
The preparation method of positive electrode, 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, it disperses 1000g rear-earth-doped LNCA positive electrode and 20g benzene in N- first pyrrolidones, is added
The anhydrous FeCl of 500g3, 6h is reacted at -5 DEG C, after complete reaction centrifuge washing, finally carried out again using N- first pyrrolidones
Dispersion obtains the LNCA positive electrode solution for being coated with conducting polymer；
Step 3, Xiang Suoshu is coated with the LNCA positive electrode solution 93.75g carbon black of conducting polymer and 93.75g gathers partially
Vinyl fluoride is stirred evenly at 300r/min, obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Step 4, 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 155mAh/g；With the prior art
It compares, the LNCA anode pole piece obtained for being coated with conducting polymer is made as anode using metal lithium sheet using the above scheme
Button cell is assembled for cathode and carries out charge-discharge test, using the LNCA anode material produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 179.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
98.8%；Under 2C multiplying power, specific discharge capacity reaches 167mAh/g.
Embodiment 4
A kind of nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer, 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 of in-stiu coating conducting polymer as described in above scheme
The preparation method of positive electrode, 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, it disperses 1000g rear-earth-doped LNCA positive electrode and 20g benzene in N- first pyrrolidones, is added
The anhydrous FeCl of 500g3, 6h is reacted at -5 DEG C, after complete reaction centrifuge washing, finally carried out again using N- first pyrrolidones
Dispersion obtains the LNCA positive electrode solution for being coated with conducting polymer；
Step 3, Xiang Suoshu is coated with the LNCA positive electrode solution 93.75g carbon black of conducting polymer and 93.75g gathers partially
Vinyl fluoride is stirred evenly at 300r/min, obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Step 4, 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 155mAh/g；With the prior art
It compares, the LNCA anode pole piece obtained for being coated with conducting polymer is made as anode using metal lithium sheet using the above scheme
Button cell is assembled for cathode and carries out charge-discharge test, using the LNCA anode material produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 179.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
98.8%；Under 2C multiplying power, specific discharge capacity reaches 167mAh/g.
Embodiment 5
A kind of nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer, 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 of in-stiu coating conducting polymer as described in above scheme
The preparation method of positive electrode, 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, it disperses 1000g rear-earth-doped LNCA positive electrode and 20g benzene in N- first pyrrolidones, is added
The anhydrous FeCl of 500g3, 6h is reacted at -5 DEG C, after complete reaction centrifuge washing, finally carried out again using N- first pyrrolidones
Dispersion obtains the LNCA positive electrode solution for being coated with conducting polymer；
Step 3, Xiang Suoshu is coated with the LNCA positive electrode solution 93.75g carbon black of conducting polymer and 93.75g gathers partially
Vinyl fluoride is stirred evenly at 300r/min, obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Step 4, 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 155mAh/g；With the prior art
It compares, the LNCA anode pole piece obtained for being coated with conducting polymer is made as anode using metal lithium sheet using the above scheme
Button cell is assembled for cathode and carries out charge-discharge test, using the LNCA anode material produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 179.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
98.8%；Under 2C multiplying power, specific discharge capacity reaches 167mAh/g.
Embodiment 6
A kind of nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer, 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 of in-stiu coating conducting polymer as described in above scheme
The preparation method of positive electrode, 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, it disperses 1000g rear-earth-doped LNCA positive electrode and 5g benzene in N- first pyrrolidones, is added
The anhydrous FeCl of 300g3, 6h is reacted at -5 DEG C, after complete reaction centrifuge washing, finally carried out again using N- first pyrrolidones
Dispersion obtains the LNCA positive electrode solution for being coated with conducting polymer；
Step 3, Xiang Suoshu is coated with the LNCA positive electrode solution 93.75g carbon black of conducting polymer and 93.75g gathers partially
Vinyl fluoride is stirred evenly at 300r/min, obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Step 4, 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 155mAh/g；With the prior art
It compares, the LNCA anode pole piece obtained for being coated with conducting polymer is made as anode using metal lithium sheet using the above scheme
Button cell is assembled for cathode and carries out charge-discharge test, using the LNCA anode material produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 179.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
98.8%；Under 2C multiplying power, specific discharge capacity reaches 167mAh/g.
Embodiment 7
A kind of nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer, 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 of in-stiu coating conducting polymer as described in above scheme
The preparation method of positive electrode, 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, it disperses 1000g rear-earth-doped LNCA positive electrode and 50g benzene in N- first pyrrolidones, is added
The anhydrous FeCl of 800g3, 6h is reacted at -5 DEG C, after complete reaction centrifuge washing, finally carried out again using N- first pyrrolidones
Dispersion obtains the LNCA positive electrode solution for being coated with conducting polymer；
Step 3, Xiang Suoshu is coated with the LNCA positive electrode solution 93.75g carbon black of conducting polymer and 93.75g gathers partially
Vinyl fluoride is stirred evenly at 300r/min, obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Step 4, 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 155mAh/g；With the prior art
It compares, the LNCA anode pole piece obtained for being coated with conducting polymer is made as anode using metal lithium sheet using the above scheme
Button cell is assembled for cathode and carries out charge-discharge test, using the LNCA anode material produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 179.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
98.8%；Under 2C multiplying power, specific discharge capacity reaches 167mAh/g.
Embodiment 8
A kind of nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer, which is characterized in that its chemical general formula is Li
(Ni0.37Co0.3Al0.3La0.03)O2@e-polymer, wherein x > 0.33, e-polymer are poly- to benzene or poly- union II thiophene.
The embodiment of the present invention also provides a kind of nickel cobalt lithium aluminate of in-stiu coating conducting polymer as described in above scheme
The preparation method of positive electrode, 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, it disperses 1000g rear-earth-doped LNCA positive electrode and 20g benzene in N- first pyrrolidones, is added
The anhydrous FeCl of 500g3, 6h is reacted at -5 DEG C, after complete reaction centrifuge washing, finally carried out again using N- first pyrrolidones
Dispersion obtains the LNCA positive electrode solution for being coated with conducting polymer；
Step 3, Xiang Suoshu is coated with the LNCA positive electrode solution 62.5g carbon black of conducting polymer and 187.5g gathers inclined fluorine
Ethylene is stirred evenly at 300r/min, obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Step 4, 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 155mAh/g；With the prior art
It compares, the LNCA anode pole piece obtained for being coated with conducting polymer is made as anode using metal lithium sheet using the above scheme
Button cell is assembled for cathode and carries out charge-discharge test, using the LNCA anode material produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 179.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
98.8%；Under 2C multiplying power, specific discharge capacity reaches 167mAh/g.
Embodiment 9
A kind of nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer, 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 of in-stiu coating conducting polymer as described in above scheme
The preparation method of positive electrode, 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, it disperses 1000g rear-earth-doped LNCA positive electrode and 20g benzene in N- first pyrrolidones, is added
The anhydrous FeCl of 500g3, 6h is reacted at -5 DEG C, after complete reaction centrifuge washing, finally carried out again using N- first pyrrolidones
Dispersion obtains the LNCA positive electrode solution for being coated with conducting polymer；
Step 3, Xiang Suoshu is coated with the LNCA positive electrode solution 187.5g carbon black of conducting polymer and 62.5g gathers inclined fluorine
Ethylene is stirred evenly at 300r/min, obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Step 4, 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 155mAh/g；With the prior art
It compares, the LNCA anode pole piece obtained for being coated with conducting polymer is made as anode using metal lithium sheet using the above scheme
Button cell is assembled for cathode and carries out charge-discharge test, using the LNCA anode material produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 179.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
98.8%；Under 2C multiplying power, specific discharge capacity reaches 167mAh/g.
Embodiment 10
A kind of nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer, 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 of in-stiu coating conducting polymer as described in above scheme
The preparation method of positive electrode, 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, it disperses 1000g rear-earth-doped LNCA positive electrode and 20g union II thiophene in N- first pyrrolidones,
The anhydrous FeCl of 500g is added3, 8h is reacted at -10 DEG C, after complete reaction centrifuge washing, finally use N- first pyrrolidones again
Dispersed, obtains the LNCA positive electrode solution for being coated with conducting polymer；
Step 3, Xiang Suoshu is coated with the LNCA positive electrode solution 93.75g carbon black of conducting polymer and 93.75g gathers partially
Vinyl fluoride is stirred evenly at 100r/min, obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Step 4, 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 155mAh/g；With the prior art
It compares, the LNCA anode pole piece obtained for being coated with conducting polymer is made as anode using metal lithium sheet using the above scheme
Button cell is assembled for cathode and carries out charge-discharge test, using the LNCA anode material produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 179.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
98.8%；Under 2C multiplying power, specific discharge capacity reaches 167mAh/g.
Embodiment 11
A kind of nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer, 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 of in-stiu coating conducting polymer as described in above scheme
The preparation method of positive electrode, 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, it disperses 1000g rear-earth-doped LNCA positive electrode and 20g union II thiophene in N- first pyrrolidones,
The anhydrous FeCl of 500g is added3, 4h is reacted at 10 DEG C, after complete reaction centrifuge washing, finally use N- first pyrrolidones again
Dispersed, obtains the LNCA positive electrode solution for being coated with conducting polymer；
Step 3, Xiang Suoshu is coated with the LNCA positive electrode solution 93.75g carbon black of conducting polymer and 93.75g gathers partially
Vinyl fluoride is stirred evenly at 500r/min, obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Step 4, 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 155mAh/g；With the prior art
It compares, the LNCA anode pole piece obtained for being coated with conducting polymer is made as anode using metal lithium sheet using the above scheme
Button cell is assembled for cathode and carries out charge-discharge test, using the LNCA anode material produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 179.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
98.8%；Under 2C multiplying power, specific discharge capacity reaches 167mAh/g.
Embodiment 12
A kind of nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer, 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 of in-stiu coating conducting polymer as described in above scheme
The preparation method of positive electrode, 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, it disperses 1000g rear-earth-doped LNCA positive electrode and 20g union II thiophene in N- first pyrrolidones,
The anhydrous CuCl of 500g is added2, 6h is reacted at -5 DEG C, after complete reaction centrifuge washing, finally use N- first pyrrolidones again
Dispersed, obtains the LNCA positive electrode solution for being coated with conducting polymer；
Step 3, Xiang Suoshu is coated with the LNCA positive electrode solution 93.75g Ketjen black of conducting polymer and 93.75g gathers
Tetrafluoroethene is stirred evenly at 300r/min, obtains the LNCA positive electrode slurry for being coated with conducting polymer；
Step 4, 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 155mAh/g；With the prior art
It compares, the LNCA anode pole piece obtained for being coated with conducting polymer is made as anode using metal lithium sheet using the above scheme
Button cell is assembled for cathode and carries out charge-discharge test, using the LNCA anode material produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 179.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
98.8%；Under 2C multiplying power, specific discharge capacity reaches 167mAh/g.
Embodiment 13
A kind of nickel cobalt lithium aluminate cathode material of in-stiu coating conducting polymer, 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 of in-stiu coating conducting polymer as described in above scheme
The preparation method of positive electrode, 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, it disperses 1000g rear-earth-doped LNCA positive electrode and 20g union II thiophene in N- first pyrrolidones,
The anhydrous CuCl of 500g is added2, 6h is reacted at -5 DEG C, after complete reaction centrifuge washing, finally use N- first pyrrolidones again
Dispersed, obtains the LNCA positive electrode solution for being coated with conducting polymer；
Step 3, Xiang Suoshu is coated with the LNCA positive electrode solution 93.75g Super P Li conductive carbon of conducting polymer
Black and 93.75g carboxymethyl cellulose, stirs evenly at 300r/min, obtains the LNCA anode material for being coated with conducting polymer
Slurry material；
Step 4, 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 155mAh/g；With the prior art
It compares, the LNCA anode pole piece obtained for being coated with conducting polymer is made as anode using metal lithium sheet using the above scheme
Button cell is assembled for cathode and carries out charge-discharge test, using the LNCA anode material produced by the present invention for being coated with conducting polymer
Material first discharge specific capacity under 0.5C multiplying power reaches 179.5mAh/g；Capacity retention ratio is reachable after 100 charge-discharge cycles
98.8%；Under 2C multiplying power, specific discharge capacity reaches 167mAh/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 in-stiu coating conducting polymer, 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 in-stiu coating conducting polymer as described in claim 1,
It is characterized in that, its 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 monomer in solvent, is then added and draws
Agent is sent out, to centrifuge washing after the reaction was completed, is finally dispersed using the solvent, obtains the LNCA for being coated with conducting polymer
Positive electrode solution；
Step 3, conductive agent and binder is added in the LNCA positive electrode solution that Xiang Suoshu is coated with conducting polymer, and stirring is equal
It is even, obtain the LNCA positive electrode slurry for being coated with conducting polymer；
Step 4, 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 anode of in-stiu coating conducting polymer as described in claim 1 according to claim 2
The preparation method of material, which is characterized in that mole of nickel cobalt aluminium presoma described in the step 1, lithium salts and rare earth dopant
Than for 100:(90~110): (1~5), the rare earth dopant are at least one of scandium, yttrium, lanthanum, cerium, praseodymium, the compound of neodymium.
4. in-stiu coating conducting polymer as described in claim 1 according to claim 3
Nickel cobalt lithium aluminate cathode material 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 is 4~12h, and mixing speed is 100~500r/min.
5. the nickel cobalt of the in-stiu coating conducting polymer as described in claim 1 according to claim 2-4 any one
The preparation method of lithium aluminate cathode material, which is characterized in that the quality of conducting polymer monomer is rear-earth-doped in the step 2
LNCA positive electrode quality 0.01%~5%, the quality of the initiator is rear-earth-doped LNCA positive electrode
The 30%~80% of quality.
6. the nickel cobalt lithium aluminate anode of in-stiu coating conducting polymer as described in claim 1 according to claim 5
The preparation method of material, which is characterized in that reaction temperature is -10~20 DEG C in the step 2, and the reaction time is 4~8h.
7. the nickel cobalt lithium aluminate anode of in-stiu coating conducting polymer as described in claim 1 according to claim 6
The preparation method of material, which is characterized in that conducting polymer monomer is at least one of benzene, union II thiophene, institute in the step 2
Stating initiator is anhydrous FeCl3Or anhydrous CuCl2, the solvent is the solvent of solvable conducting polymer but insoluble LNCA, described molten
Agent is specially at least one of N,N-dimethylformamide, N-Methyl pyrrolidone or chloroform.
8. the nickel cobalt lithium aluminate anode of in-stiu coating conducting polymer as described in claim 1 according to claim 7
The preparation method of material, which is characterized in that conductive agent, binder in the step 3 and the rear-earth-doped LNCA in step 2
The molar ratio of positive electrode is (5~15): (5~15): 80.
9. the nickel cobalt lithium aluminate anode of in-stiu coating conducting polymer as described in claim 1 according to claim 8
The preparation method of material, which is characterized in that conductive agent is carbon black, Ketjen black or Super P Li conductive carbon black in the step 3
At least one of, the binder is at least one in Kynoar, polytetrafluoroethylene (PTFE), carboxymethyl cellulose or butadiene-styrene rubber
Kind.
10. the nickel cobalt lithium aluminate anode of in-stiu coating conducting polymer as described in claim 1 according to claim 9
The preparation method of material, which is characterized in that freeze-drying is carried out at 5~50pa of vacuum degree in the step 4, and the freezing is dry
Dry temperature is -50~-10 DEG C.
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Application publication date: 20190503 |