CN109148860A - A kind of nickelic positive electrode and preparation method thereof and lithium ion battery - Google Patents

A kind of nickelic positive electrode and preparation method thereof and lithium ion battery Download PDF

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CN109148860A
CN109148860A CN201810998065.8A CN201810998065A CN109148860A CN 109148860 A CN109148860 A CN 109148860A CN 201810998065 A CN201810998065 A CN 201810998065A CN 109148860 A CN109148860 A CN 109148860A
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positive electrode
nickelic positive
nickelic
oxide
rare earth
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叶柏青
刘妮娜
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Danfu Sichuan West Energy Science And Technology Ltd Co
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Danfu Sichuan West Energy Science And Technology Ltd Co
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to cell manufacturing techniques fields, more particularly to it is related to a kind of nickelic positive electrode and preparation method thereof and lithium ion battery, nickelic positive electrode includes the rear-earth-doped nickelic positive electrode being made of nickelic substrate and the rare earth compound being doped in nickelic substrate, rear-earth-doped nickelic positive electrode and aniline monomer form the tree-shaped electrically conductive polyaniline network of nanometer by in-situ polymerization between the hole of the offspring of rear-earth-doped nickelic positive electrode and obtain in-situ polymerization material, and the surface of in-situ polymerization material is coated with lithium ion conductor layer；Nickelic substrate is Li1+aNixCoyM1‑x‑yO2.Compared with the prior art, the present invention improves the cycle performance and high rate performance of material significantly.

Description

A kind of nickelic positive electrode and preparation method thereof and lithium ion battery
Technical field
The invention belongs to cell manufacturing techniques fields, more particularly to be related to a kind of nickelic positive electrode and preparation method thereof and Lithium ion battery.
Background technique
Nickelic transition metal oxide material is considered as most attractive positive electrode of new generation.Pass through nickel cobalt manganese The complementary synergistic effect of three kinds of ions, improves the defect of independent ion, to realize material capacity, cyclicity and security performance Regulation.
However, that there is also some problems is urgently to be resolved for high-nickel material.Ni2+With Li+Radius is close, is easy to cause nickel lithium mixed Row hinders Li+Channel, while intercrystalline crack easily occurs for offspring, causes material structure unstable, reduces the specific volume of material Amount, cycle performance and high rate performance.Easily with electrolyte side reaction occurs for transition metal ions, causes cycle performance poor, surface Residual alkali deposit causes surface transfer resistance to increase, and hinders Li+Diffusion.In addition, high-nickel material surface residual alkali deposit passes through Adsorb the moisture and CO in air2, lead to pulp gel.
For this purpose, patent CN201711241652 coats the modified nickelic positive material of fast-ionic conductor by washing and surface dry method Material, reduces the side reaction of material and electrolyte, improves the high-temperature stability and safety of material, is wrapped by doping and surface Fast-ionic conductor is covered, energy density, the high rate performance, cycle performance of material is improved, ultimately increases the long circulation life of battery. In addition, patent CN201510545968 provides a kind of nickelic positive electrode, matrix surface contains doped chemical, the element of doping Can stabilized matrix surface crystal structure, alleviate cleaning solution to substrate material surface structural damage, make nickelic positive electrode system Standby capacity of lithium ion battery and cycle performance is preferable；In addition, this nickelic positive electrode has clad, clad can make Positive electrode is isolated with anolyte portion, improves electrochemical stability and the safety of positive electrode.However both the above scheme There are deficiency, patent CN201711241652 increases washing in material preparation process, causes lithium ion battery to moisture Susceptibility increase, patent CN201510545968 is to improve the cycle performance of material, and there is no the multiplying powers for improving material Performance.
In view of this, it is necessory to provide a kind of new nickelic positive electrode with significantly improve the cycle performance of material and times Rate performance.
Summary of the invention
It is an object of the present invention to: in view of the deficiencies of the prior art, and a kind of nickelic positive electrode is provided, significantly mentioned The cycle performance and high rate performance of high material.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of nickelic positive electrode, including being made of nickelic substrate and the rare earth compound being doped in the nickelic substrate Rear-earth-doped nickelic positive electrode, the rear-earth-doped nickelic positive electrode and aniline monomer are by in-situ polymerization described dilute The tree-shaped electrically conductive polyaniline network of nanometer, which is formed, between the hole of the offspring of the nickelic positive electrode of soil doping obtains in-situ polymerization material Material, the surface of the in-situ polymerization material is coated with lithium ion conductor layer；
Wherein, the nickelic substrate is Li1+aNixCoyM1-x-yO2, M be Mn or Al, 0.05≤a≤0.15,0.8≤x < 1.0,0 < y≤0.1；Contain compound L i in the lithium ion conductor layer7La3Zr2O12、Li1.3Al0.7Ti1.7(PO4)3、 Li10GeLa3P2S12、Li3La2(PO4)3And LiLaAlO4One or more of.
Preferably, the porosity of the offspring of the rear-earth-doped nickelic positive electrode is 26~32%.Porosity mistake It will lead to material tap density greatly and compacted density reduce, further influence battery capacity；Porosity is too small, although material jolt ramming Density and compacted density increase, but will affect battery high rate performance.
Preferably, the quality of the rare earth compound is the 0.1%~3.0% of the nickelic substrate mass.
Preferably, the rare earth compound is rare earth oxide ReO2、Re2O3、Re4O7And Re6O11One or more of, Wherein Re is rare earth element.
Preferably, the quality of the lithium ion conductor layer is the 1%~5% of nickelic substrate mass.
Compared with the prior art, the beneficial effect of above-mentioned technical proposal is:
1) since the outer electronic structure of rare earth metal shows special electrical property, rare earth metal forms key in conjunction with oxygen The biggish Re-O key of energy, therefore, by rear-earth-doped mode, the big bond energy of Re-O key enhances metal in nickelic positive electrode With the binding force of oxygen, reduces charge and discharge process and analyse oxygen；Meanwhile rare earth doped reducing Ni/Li cation mixing, it is suppressed that material Structure changes in charge and discharge process.
2) on the one hand, the diameter of tree-shaped nano-conductive polyaniline is less than 100nm, not only with the conduction of electrically conductive polyaniline Property, there are also the effects such as the quantum tunneling of nano material, small size, hence it is evident that improves the chemical property of polyaniline；On the other hand, The branch interchain of tree-shaped electrically conductive polyaniline has strong interaction, can form stable spacial framework.The present invention passes through original The tree-shaped electrically conductive polyaniline network of nanometer is formed not only between the hole for the offspring that position is aggregated in rear-earth-doped nickelic positive electrode The electric conductivity of reinforcing material, while interparticle binding force is strengthened, material structure dusting is prevented, its structural stability is improved.
3) the surface coated lithium ion conductor layer of polymeric material in situ of the invention, on the one hand, the lattice of lithium ion conductor There are the tunnels that lithium ion fast transferring interpenetrates for inside, shorten the distance of lithium ion diffusive migration, promote lithium ion Migration rate, to improve high rate performance；On the other hand, lithium ion conductor clad realizes the surface guarantor to positive electrode Shield reduces surface lithium salts residual alkali, prevents electrolyte from side reaction occurs with it, be conducive to the promotion of material circulation stability.
The second object of the present invention is: providing a kind of preparation method of nickelic positive electrode, comprising the following steps:
Step 1), transition metal oxide, oxidate for lithium and rare earth oxide ball milling mixing is uniform, first 450~550 DEG C 5~7h of preroast is further crushed sieving then in 800~1000 DEG C of 10~15h of roasting, obtain it is rear-earth-doped it is nickelic just Pole material；
Rear-earth-doped nickelic positive electrode obtained in step 1) is mixed with Bronsted acid and ultrasonic wave disperses 15 by step 2) ~30min；
Step 3) first continuously stirs material made from step 2) under the conditions of high pressure low temperature, adds aniline monomer, and Continuous that oxidant is added dropwise, 1~3h of in-situ polymerization forms nanometer between the hole of the offspring of rear-earth-doped nickelic positive electrode Tree-shaped electrically conductive polyaniline network；
Step 4) is washed 15~30min of material high speed centrifugation in step 3) with detergent, at 150~200 DEG C Lower vacuum drying 10h, obtains in-situ polymerization material；
In-situ polymerization material, oxidate for lithium and rare earth oxide made from step 4) are poured slowly into and continuously stir by step 5) In the deionized water mixed, acid solution is added, continues to stir, is finally dried in vacuo, polymeric materials coat in situ Lithium ion conductor layer obtains nickelic positive electrode.
Preferably, in step 1), the D10 of the broken obtained rear-earth-doped nickelic positive electrode that is sieved is 5~8 μ M, D50 are 9~14 μm, and D90 is 15~23 μm.The purpose of sieving is the particle of different-grain diameter range in order to obtain, by different grains The particle of diameter is mixed to get rear-earth-doped nickelic positive electrode according to a certain percentage.
Preferably, in step 2), the Bronsted acid is one of hydrochloric acid, sulfuric acid, acetic acid, nitric acid and phosphoric acid, described The concentration of Bronsted acid is 0.1mol/L.
Preferably, in step 3), the high pressure is -0.1~20Mpa, and the low temperature is 5~10 DEG C.
Preferably, in step 3), the concentration of the aniline monomer is 0.1mol/L, and the oxidant is H2O2、(NH4)2S2O8、K2MnO4、KIO3、FeCl3、K2Cr2O7And MnO2One of, nAniline monomer:nOxidant=1:1.
Preferably, in step 3), the mass ratio of the aniline monomer and the rear-earth-doped nickelic positive electrode is 0.5%~2.0%.
Preferably, in step 4), the detergent is at least one in deionized water, dehydrated alcohol, propyl alcohol and acetone Kind.
Preferably, in step 5), the rare earth oxide is ReO2、Re2O3、Re4O7And Re6O11At least one of, The acid solution is H3PO4、H4AlO4、H2ZrO3And P2S5One or more of.
Compared with the prior art, the preparation method of the invention is easy to operate, and production process is easily controllable, energy consumption also compared with Low, suitable for material scale of mass production.
The third object of the present invention is: a kind of lithium ion battery is provided, including previously described nickelic positive electrode or Person's nickelic positive electrode as made from previously described preparation method.
Compared with the prior art, the lithium ion battery as made from nickelic positive electrode of the invention has better cyclicity Energy and high rate performance.
Detailed description of the invention
Fig. 1 is the sem analysis figure of nickelic positive electrode prepared by comparative example 1.
Fig. 2 is the sem analysis figure of nickelic positive electrode prepared by embodiment 1.
Fig. 3 is the cycle performance figure of button cell prepared by part comparative example and embodiment.
Fig. 4 is the high rate performance figure of button cell prepared by part comparative example and embodiment.
Specific embodiment
With reference to embodiment and Figure of description, the present invention is described in further detail, but the present invention Embodiment be not limited to this.
Comparative example 1
The preparation of nickelic positive electrode:
Cobalt oxide, nickel oxide, manganese oxide and lithia ball milling mixing is uniform, uniform powder is obtained, in uniformed powder Nickel, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05；Above-mentioned powder is placed in microwave horse Not in furnace, 500 DEG C of preroast 6h are further crushed sieving then in 900 DEG C of roasting 12h, and the granularity for being crushed sieving is 3~20 μ M obtains nickelic positive electrode.
The preparation of battery:
1) nickelic positive electrode obtained in comparative example 1 is assembled into button cell, the specific scheme is that nickelic by what is obtained Positive electrode is mixed according to 85:10:5 ratio with conductive agent acetylene black and binder PVDF, is added by being further ground up, sieved A certain amount of organic solvent NMP stirring 2h is mixed into uniform sizing material, and slurry is uniformly coated on aluminium foil, 120 DEG C of vacuum are placed in In drying box, taking-up slice after 12h is kept to be cut intoCylindrical pole piece.
2) assembled battery in high argon gas glove box is anode with the pole piece of above-mentioned preparation, using pour lithium slice as cathode (99.9%), 1mol/L LiPF6/ EC/DMC (volume ratio 1:1) is electrolyte, and diaphragm is 16+4 single side coated ceramic polypropylene Microporous barrier.
Comparative example 2
The preparation of this comparative example nickelic positive electrode unlike comparative example 1:
Cobalt oxide, nickel oxide, manganese oxide, lithia and lanthana ball milling mixing is uniform, uniform powder is obtained, uniformly Powder in nickel, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of lanthana It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, first 500 DEG C of preroast 6h are further crushed sieving then in 900 DEG C of roasting 12h, obtain the nickelic positive material of Doping with Rare Earth Lanthanum Material, the D10 of the nickelic positive electrode of Doping with Rare Earth Lanthanum are 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm；Doping with Rare Earth Lanthanum The porosity of the offspring of nickelic positive electrode is 26%.
Remaining is with comparative example 1, and which is not described herein again.
Comparative example 3
The preparation of this comparative example nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia ball milling mixing is uniform, obtain uniform powder, uniform powder Middle nickel, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05；Above-mentioned powder is placed in microwave In Muffle furnace, first 500 DEG C of preroast 6h obtain nickelic positive electrode then in 900 DEG C of roasting 12h, are further crushed sieving, Nickelic positive electrode after being sieved；
2) the nickelic positive electrode after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, slowly add Enter 0.1mol/L hydrochloric acid, is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, the company of holding under the conditions of -0.1Mpa, 5 DEG C of high pressure low temperature Continuous stirring, is added 0.1mol/L aniline monomer, opens precision metering pump and 0.1mol/L oxidant H is added2O2, nAniline monomer:nOxidant= 1:1, it is 5mL/min, H that speed, which is added, in aniline monomer solution2O2It is 1mL/min, H that speed, which is added, in solution2O2After solution completion of dropwise addition The reaction was continued 1h, controls 5 DEG C of reaction temperature, and the mass ratio of aniline monomer and nickelic positive electrode is 0.5%~2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, be to wash with dehydrated alcohol Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 150 DEG C 10h in vacuum oven, obtain offspring The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between hole.
Remaining is with comparative example 1, and which is not described herein again.
Comparative example 4
The preparation of this comparative example nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia ball milling mixing is uniform, obtain uniform powder, the homogeneous powder Nickel in body, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05.Above-mentioned powder is placed in micro- In wave Muffle furnace, first 500 DEG C of preroast 6h are further crushed sieving then in 900 DEG C of roasting 12h, nickelic after being sieved Positive electrode；
2) nickelic positive electrode, lithia and the lanthanum oxide powder after screening obtained above are uniformly mixed, are slowly fallen Enter in the deionized water continuously stirred, obtains unit for uniform suspension；H is added in above-mentioned unit for uniform suspension3PO4Solution is stirred continuously It is evaporated to moisture, keeps for 24 hours, obtaining cladding Li in 150 DEG C of vacuum ovens3La2(PO4)3Lithium ion conductor layer it is nickelic just Pole material.Li3La2(PO4)3The quality of lithium ion conductor layer is the 1%~5% of substrate mass.
Remaining is with comparative example 1, and which is not described herein again.
Comparative example 5
The preparation of this comparative example nickelic positive electrode unlike comparative example 2:
1) the nickelic positive electrode of Doping with Rare Earth Lanthanum is obtained according to comparative example 2；
2) it weighs the nickelic positive electrode of the Doping with Rare Earth Lanthanum after a certain amount of above-mentioned screening using precision electronic balance and is added and burn In cup, it is slowly added to 0.1mol/L sulfuric acid, ultrasound 30min in ultrasonic disperse instrument is placed in, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuously stirring under the conditions of 5Mpa, 5 DEG C of high pressure low temperature It mixes, 0.1mol/L aniline monomer is added, open precision metering pump and 0.1mol/L oxidant (NH is added4)2S2O8, nAniline monomer:nOxidant =1:1, it is 5mL/min, (NH that speed, which is added, in aniline monomer solution4)2S2O8It is 1mL/min, (NH that speed, which is added, in solution4)2S2O8It is molten The reaction was continued after drop adds 1h, 5 DEG C of reaction temperature of control, the quality of aniline monomer and the nickelic positive electrode of Doping with Rare Earth Lanthanum Than being 0.5%~2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, be to wash with dehydrated alcohol Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 150 DEG C 10h in vacuum oven, obtain doping La and two The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of secondary particle.
Remaining is with comparative example 2, and which is not described herein again.
Comparative example 6
The preparation of this comparative example nickelic positive electrode unlike comparative example 3:
1) according to comparative example 3 obtain being formed between the hole of offspring the tree-shaped electrically conductive polyaniline network of nanometer it is nickelic just Pole material；
2) material, lithia and lanthanum oxide powder after screening obtained above are uniformly mixed, are poured slowly into and continuously stir Deionized water in, obtain unit for uniform suspension；H is added in above-mentioned unit for uniform suspension3PO4Solution is stirred continuously to moisture and steams Hair, keeps being formed with the tree-shaped electrically conductive polyaniline net of nanometer between the hole for obtaining offspring for 24 hours in 150 DEG C of vacuum ovens Network, surface coat Li3La2(PO4)3The nickelic positive electrode of lithium ion conductor layer.Li3La2(PO4)3The quality of lithium ion conductor layer It is the 1%~5% of substrate mass.
Remaining is with comparative example 3, and which is not described herein again.
Embodiment 1
The preparation of the present embodiment nickelic positive electrode unlike comparative example 2:
1) the nickelic positive electrode of Doping with Rare Earth Lanthanum is obtained according to comparative example 2；
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L acetic acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuously stirring under the conditions of 1Mpa, 5 DEG C of high pressure low temperature It mixes, 0.1mol/L aniline monomer is added, open precision metering pump and 0.1mol/L oxidant K is added2MnO4, nAniline monomer:nOxidant=1: 1, it is 5mL/min, K that speed, which is added, in aniline monomer solution2MnO4It is 1mL/min, K that speed, which is added, in solution2MnO4Solution completion of dropwise addition The reaction was continued afterwards 1h, controls 5 DEG C of reaction temperature, and the mass ratio of aniline monomer and the nickelic positive electrode of Doping with Rare Earth Lanthanum is 0.5% ~2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, using acetone as detergent, It will be washed repeatedly three times after centrifugation solid compounds, be placed at 150 DEG C 10h in vacuum oven, obtain doping La and secondary grain The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of son；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping La obtained above and offspring Nickelic positive electrode, lithia and lanthanum oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, are obtained uniformly Suspension；H is added in above-mentioned unit for uniform suspension3PO4Solution is stirred continuously to moisture and evaporates, in 150 DEG C of vacuum oven It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface cladding Li between the hole for obtaining doping La, offspring for 24 hours3La2 (PO4)3The nickelic positive electrode of lithium ion conductor layer.Li3La2(PO4)3The quality of lithium ion conductor layer is the 1% of substrate mass ~5%.
Remaining is with comparative example 2, and which is not described herein again.
Embodiment 2
The preparation of the present embodiment nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia and cerium oxide ball milling are uniformly mixed, obtain uniform powder, Nickel in even powder, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of cerium oxide It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, 500 DEG C of preroast 6h are further crushed sieving then in 900 DEG C of roasting 12h, obtain the nickelic positive material of rare earth Ce doping Material；The D10 of the nickelic positive electrode of rare earth Ce doping is 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm；Rare earth Ce doping The porosity of the offspring of nickelic positive electrode is 27%；
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L nitric acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuous under the conditions of 5Mpa, 10 DEG C of high pressure low temperature 0.1mol/L aniline monomer is added in stirring, opens precision metering pump and 0.1mol/L oxidant KIO is added3, nAniline monomer:nOxidant=1: 1, it is 5mL/min, KIO that speed, which is added, in aniline monomer solution3It is 1mL/min, KIO that speed, which is added, in solution3Solution completion of dropwise addition is subsequent Continuous reaction 1h, controls 5 DEG C of reaction temperature, and the mass ratio of aniline monomer and the nickelic positive electrode of rare earth Ce doping is 0.5%~ 2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, be to wash with dehydrated alcohol Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 150 DEG C 10h in vacuum oven, obtain doping Ce and two The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of secondary particle；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping Ce obtained above and offspring Nickelic positive electrode, lithia and lanthanum oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, are obtained uniformly Suspension；H is added in above-mentioned unit for uniform suspension4AlO4Solution is stirred continuously to moisture and evaporates, in 150 DEG C of vacuum oven It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface cladding between the hole for obtaining doping Ce, offspring for 24 hours LiLaAlO4The nickelic positive electrode of lithium ion conductor layer.LiLaAlO4The quality of lithium ion conductor layer be substrate mass 1%~ 5%.
Remaining is with comparative example 1, and which is not described herein again.
Embodiment 3
The preparation of the present embodiment nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia and praseodymium oxide ball milling mixing is uniform, uniform powder is obtained, Nickel in even powder, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of praseodymium oxide It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, 450 DEG C of preroast 7h are further crushed sieving then in 1000 DEG C of roasting 10h, obtain the nickelic positive material of rare earth Pr doping Material；The D10 that rare earth Pr adulterates nickelic positive electrode is 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm；Rare earth Pr doping The porosity of the offspring of nickelic positive electrode is 28%；
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L phosphoric acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuous under the conditions of 20Mpa, 5 DEG C of high pressure low temperature 0.1mol/L aniline monomer is added in stirring, opens precision metering pump and 0.1mol/L oxidant FeCl is added3, nAniline monomer:nOxidant= 1:1, it is 5mL/min, FeCl that speed, which is added, in aniline monomer solution3It is 1mL/min, FeCl that speed, which is added, in solution3Solution completion of dropwise addition The reaction was continued afterwards 1h controls 5 DEG C of reaction temperature, and the mass ratio that aniline monomer and rare earth Pr adulterate nickelic positive electrode is 0.5% ~2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, using propyl alcohol as detergent, It will be washed repeatedly three times after centrifugation solid compounds, be placed at 150 DEG C 10h in vacuum oven, obtain doping Pr and secondary grain The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of son；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping Pr obtained above and offspring Nickelic positive electrode, lithia and lanthanum oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, are obtained uniformly Suspension；H is added in above-mentioned unit for uniform suspension2ZrO3Solution is stirred continuously to moisture and evaporates, in 150 DEG C of vacuum oven It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface cladding between the hole for obtaining doping Pr, offspring for 24 hours Li7La3Zr2O12The nickelic positive electrode of lithium ion conductor layer.Li7La3Zr2O12The quality of lithium ion conductor layer is substrate mass 1%~5%.
Remaining is with comparative example 1, and which is not described herein again.
Embodiment 4
The preparation of the present embodiment nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia and neodymia ball milling mixing is uniform, uniform powder is obtained, Nickel in even powder, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of neodymia It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, 550 DEG C of preroast 5h are further crushed sieving then in 800 DEG C of roasting 15h, obtain the nickelic positive material of rare earth Nd doping Material；The D10 that rare earth Nd adulterates nickelic positive electrode is 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm；Rare earth Nd doping The porosity of the offspring of nickelic positive electrode is 29%；
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L hydrochloric acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuous under the conditions of 15Mpa, 5 DEG C of high pressure low temperature 0.1mol/L aniline monomer is added in stirring, opens precision metering pump and 0.1mol/L oxidant K is added2Cr2O7, nAniline monomer:nOxidant= 1:1, it is 5mL/min, K that speed, which is added, in aniline monomer solution2Cr2O7It is 1mL/min, K that speed, which is added, in solution2Cr2O7Solution is added dropwise After the reaction was continued 1h, control 5 DEG C of reaction temperature, the mass ratio that aniline monomer adulterates nickelic positive electrode with rare earth Nd is 0.5%~2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, be to wash with deionized water Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 200 DEG C 10h in vacuum oven, obtain doping Nd and two The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of secondary particle；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping Nd obtained above and offspring Nickelic positive electrode, lithia, aluminium oxide and titanium oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, Obtain unit for uniform suspension；H is added in above-mentioned unit for uniform suspension3PO4Solution is stirred continuously to moisture and evaporates, in 150 DEG C of vacuum It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface between the hole for obtaining doping Nd, offspring for 24 hours in drying box Coat Li1.3Al0.7Ti1.7(PO4)3The nickelic positive electrode of lithium ion conductor layer.Li1.3Al0.7Ti1.7(PO4)3Lithium ion conductor The quality of layer is the 1%~5% of substrate mass.
Remaining is with comparative example 1, and which is not described herein again.
Embodiment 5
The preparation of the present embodiment nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia and lanthana ball milling mixing is uniform, uniform powder is obtained, Nickel in even powder, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of lanthana It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, 500 DEG C of preroast 6h are further crushed sieving then in 900 DEG C of roasting 12h, obtain the nickelic positive material of Doping with Rare Earth Lanthanum Material；The D10 of the nickelic positive electrode of Doping with Rare Earth Lanthanum is 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm；Doping with Rare Earth Lanthanum The porosity of the offspring of nickelic positive electrode is 30%；
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L hydrochloric acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuous under the conditions of 10Mpa, 10 DEG C of high pressure low temperature 0.1mol/L aniline monomer is added in stirring, opens precision metering pump and 0.1mol/L oxidant MnO is added2, nAniline monomer:nOxidant=1: 1, it is 5mL/min, MnO that speed, which is added, in aniline monomer solution2It is 1mL/min, MnO that speed, which is added, in solution2Solution completion of dropwise addition is subsequent Continuous reaction 1h, controls 5 DEG C of reaction temperature, and the mass ratio of aniline monomer and the nickelic positive electrode of Doping with Rare Earth Lanthanum is 0.5%~ 2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, be to wash with dehydrated alcohol Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 150 DEG C 10h in vacuum oven, obtain doping La and two The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of secondary particle；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping La obtained above and offspring Nickelic positive electrode, lithia and lanthanum oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, are obtained uniformly Suspension；H is added in above-mentioned unit for uniform suspension3PO4And H4AlO4Solution is stirred continuously to moisture and evaporates, in 150 DEG C of vacuum It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface between the hole for obtaining doping La, offspring for 24 hours in drying box Cladding contains Li3La2(PO4)3And LiLaAlO4Lithium ion conductor layer nickelic positive electrode.Contain Li3La2(PO4)3With LiLaAlO4Lithium ion conductor layer quality be substrate mass 1%~5%.
Remaining is with comparative example 1, and which is not described herein again.
Embodiment 6
The preparation of the present embodiment nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia and cerium oxide ball milling are uniformly mixed, obtain uniform powder, Nickel in even powder, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of cerium oxide It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, 500 DEG C of preroast 6h are further crushed sieving then in 900 DEG C of roasting 12h, obtain the nickelic positive material of rare earth Ce doping Material；The D10 of the nickelic positive electrode of rare earth Ce doping is 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm；Rare earth Ce doping The porosity of the offspring of nickelic positive electrode is 31%；
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L nitric acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuous under the conditions of 20Mpa, 10 DEG C of high pressure low temperature 0.1mol/L aniline monomer is added in stirring, opens precision metering pump and 0.1mol/L oxidant KIO is added3, nAniline monomer:nOxidant=1: 1, it is 5mL/min, KIO that speed, which is added, in aniline monomer solution3It is 1mL/min, KIO that speed, which is added, in solution3Solution completion of dropwise addition is subsequent Continuous reaction 1h, controls 5 DEG C of reaction temperature, and the mass ratio of aniline monomer and the nickelic positive electrode of rare earth Ce doping is 0.5%~ 2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, be to wash with dehydrated alcohol Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 150 DEG C 10h in vacuum oven, obtain doping Ce and two The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of secondary particle；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping Ce obtained above and offspring Nickelic positive electrode, lithia, germanium oxide and lanthanum oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, Obtain unit for uniform suspension；P is added in above-mentioned unit for uniform suspension2S5Solution is stirred continuously to moisture and evaporates, dry in 150 DEG C of vacuum It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface packet between the hole for obtaining doping Ce, offspring for 24 hours in dry case Cover Li10GeLa3P2S12The nickelic positive electrode of lithium ion conductor layer.Li10GeLa3P2S12The quality of lithium ion conductor layer is substrate The 1%~5% of quality.
Remaining is with comparative example 1, and which is not described herein again.
Embodiment 7
The preparation of the present embodiment nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia and luteium oxide ball milling mixing is uniform, uniform powder is obtained, Nickel in even powder, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of luteium oxide It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, 500 DEG C of preroast 6h are further crushed sieving then in 900 DEG C of roasting 12h, obtain the nickelic positive material of rare earth Lu doping Material；The D10 that rare earth Lu adulterates nickelic positive electrode is 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm；Rare earth Lu doping The porosity of the offspring of nickelic positive electrode is 32%；
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L nitric acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuous under the conditions of 20Mpa, 10 DEG C of high pressure low temperature 0.1mol/L aniline monomer is added in stirring, opens precision metering pump and 0.1mol/L oxidant H is added2O2, nAniline monomer:nOxidant=1: 1, it is 5mL/min, H that speed, which is added, in aniline monomer solution2O2It is 1mL/min, H that speed, which is added, in solution2O2Solution completion of dropwise addition is subsequent Continuous reaction 1h, controls 5 DEG C of reaction temperature, aniline monomer and rare earth Lu adulterate the mass ratio of nickelic positive electrode be 0.5%~ 2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, be to wash with dehydrated alcohol Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 150 DEG C 10h in vacuum oven, obtain doping Lu and two The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of secondary particle；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping Lu obtained above and offspring Nickelic positive electrode, lithia, germanium oxide and lanthanum oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, Obtain unit for uniform suspension；P is added in above-mentioned unit for uniform suspension2S5Solution is stirred continuously to moisture and evaporates, dry in 150 DEG C of vacuum It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface packet between the hole for obtaining doping Lu, offspring for 24 hours in dry case Cover Li10GeLa3P2S12The nickelic positive electrode of lithium ion conductor layer.Li10GeLa3P2S12The quality of lithium ion conductor layer is substrate The 1%~5% of quality.
Remaining is with comparative example 1, and which is not described herein again.
Embodiment 8
The preparation of the present embodiment nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia and scandium oxide ball milling mixing is uniform, uniform powder is obtained, Nickel in even powder, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of scandium oxide It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, 500 DEG C of preroast 6h are further crushed sieving then in 900 DEG C of roasting 12h, obtain the nickelic positive material of rare earth Sc doping Material；The D10 that rare earth Sc adulterates nickelic positive electrode is 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm；Rare earth Sc doping The porosity of the offspring of nickelic positive electrode is 32%；
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L nitric acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuous under the conditions of 15Mpa, 10 DEG C of high pressure low temperature 0.1mol/L aniline monomer is added in stirring, opens precision metering pump and 0.1mol/L oxidant KIO is added3, nAniline monomer:nOxidant=1: 1, it is 5mL/min, KIO that speed, which is added, in aniline monomer solution3It is 1mL/min, KIO that speed, which is added, in solution3Solution completion of dropwise addition is subsequent Continuous reaction 1h, controls 5 DEG C of reaction temperature, aniline monomer and rare earth Sc adulterate the mass ratio of nickelic positive electrode be 0.5%~ 2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, be to wash with dehydrated alcohol Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 150 DEG C 10h in vacuum oven, obtain doping Sc and two The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of secondary particle；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping Sc obtained above and offspring Nickelic positive electrode, lithia, germanium oxide and lanthanum oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, Obtain unit for uniform suspension；P is added in above-mentioned unit for uniform suspension2S5Solution is stirred continuously to moisture and evaporates, dry in 150 DEG C of vacuum It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface packet between the hole for obtaining doping Sc, offspring for 24 hours in dry case Cover Li10GeLa3P2S12The nickelic positive electrode of lithium ion conductor layer.Li10GeLa3P2S12The quality of lithium ion conductor layer is substrate The 1%~5% of quality.
Remaining is with comparative example 1, and which is not described herein again.
Embodiment 9
The preparation of the present embodiment nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia and dysprosia ball milling mixing is uniform, uniform powder is obtained, Nickel in even powder, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of dysprosia It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, 550 DEG C of preroast 5h are further crushed sieving then in 900 DEG C of roasting 12h, obtain the nickelic positive material of rare earth β-diketone complex doping Material；The D10 that rare earth β-diketone complex adulterates nickelic positive electrode is 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm；Rare earth β-diketone complex doping The porosity of the offspring of nickelic positive electrode is 31%；
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L nitric acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuous under the conditions of 20Mpa, 5 DEG C of high pressure low temperature 0.1mol/L aniline monomer is added in stirring, opens precision metering pump and 0.1mol/L oxidant H is added2O2, nAniline monomer:nOxidant=1: 1, it is 5mL/min, H that speed, which is added, in aniline monomer solution2O2It is 1mL/min, H that speed, which is added, in solution2O2Solution completion of dropwise addition is subsequent Continuous reaction 1h, controls 5 DEG C of reaction temperature, aniline monomer and rare earth β-diketone complex adulterate the mass ratio of nickelic positive electrode be 0.5%~ 2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, be to wash with dehydrated alcohol Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 150 DEG C 10h in vacuum oven, obtain doping Dy and two The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of secondary particle；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping Dy obtained above and offspring Nickelic positive electrode, lithia, germanium oxide and lanthanum oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, Obtain unit for uniform suspension；P is added in above-mentioned unit for uniform suspension2S5Solution is stirred continuously to moisture and evaporates, dry in 150 DEG C of vacuum It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface packet between the hole for obtaining doping Dy, offspring for 24 hours in dry case Cover Li10GeLa3P2S12The nickelic positive electrode of lithium ion conductor layer.Li10GeLa3P2S12The quality of lithium ion conductor layer is substrate The 1%~5% of quality.
Remaining is with comparative example 1, and which is not described herein again.
Embodiment 10
The preparation of the present embodiment nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia and lanthana ball milling mixing is uniform, uniform powder is obtained, Nickel in even powder, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of lanthana It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, 500 DEG C of preroast 6h are further crushed sieving then in 1000 DEG C of roasting 10h, obtain the nickelic positive material of Doping with Rare Earth Lanthanum Material；The D10 of the nickelic positive electrode of Doping with Rare Earth Lanthanum is 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm；Doping with Rare Earth Lanthanum The porosity of the offspring of nickelic positive electrode is 30%；
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L nitric acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuous under the conditions of 5Mpa, 10 DEG C of high pressure low temperature 0.1mol/L aniline monomer is added in stirring, opens precision metering pump and 0.1mol/L oxidant H is added2O2, nAniline monomer:nOxidant=1: 1, it is 5mL/min, H that speed, which is added, in aniline monomer solution2O2It is 1mL/min, H that speed, which is added, in solution2O2Solution completion of dropwise addition is subsequent Continuous reaction 1h, controls 5 DEG C of reaction temperature, and the mass ratio of aniline monomer and the nickelic positive electrode of Doping with Rare Earth Lanthanum is 0.5%~ 2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, be to wash with dehydrated alcohol Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 150 DEG C 10h in vacuum oven, obtain doping La and two The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of secondary particle；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping La obtained above and offspring Nickelic positive electrode, lithia, germanium oxide and lanthanum oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, Obtain unit for uniform suspension；P is added in above-mentioned unit for uniform suspension2S5Solution is stirred continuously to moisture and evaporates, dry in 150 DEG C of vacuum It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface packet between the hole for obtaining doping La, offspring for 24 hours in dry case Cover Li10GeLa3P2S12The nickelic positive electrode of lithium ion conductor layer.Li10GeLa3P2S12The quality of lithium ion conductor layer is substrate The 1%~5% of quality.
Remaining is with comparative example 1, and which is not described herein again.
Embodiment 11
The preparation of the present embodiment nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia and luteium oxide ball milling mixing is uniform, uniform powder is obtained, Nickel in even powder, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of luteium oxide It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, 500 DEG C of preroast 6h are further crushed sieving then in 900 DEG C of roasting 12h, obtain the nickelic positive material of rare earth Lu doping Material；The D10 that rare earth Lu adulterates nickelic positive electrode is 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm；Rare earth Lu doping The porosity of the offspring of nickelic positive electrode is 29%；
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L nitric acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuous under the conditions of 20Mpa, 10 DEG C of high pressure low temperature 0.1mol/L aniline monomer is added in stirring, opens precision metering pump and 0.1mol/L oxidant H is added2O2, nAniline monomer:nOxidant=1: 1, it is 5mL/min, H that speed, which is added, in aniline monomer solution2O2It is 1mL/min, H that speed, which is added, in solution2O2Solution completion of dropwise addition is subsequent Continuous reaction 1h, controls 5 DEG C of reaction temperature, aniline monomer and rare earth Lu adulterate the mass ratio of nickelic positive electrode be 0.5%~ 2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, be to wash with dehydrated alcohol Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 180 DEG C 10h in vacuum oven, obtain doping Lu and two The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of secondary particle；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping Lu obtained above and offspring Nickelic positive electrode, lithia, germanium oxide and lanthanum oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, Obtain unit for uniform suspension；P is added in above-mentioned unit for uniform suspension2S5Solution is stirred continuously to moisture and evaporates, dry in 150 DEG C of vacuum It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface packet between the hole for obtaining doping Lu, offspring for 24 hours in dry case Cover Li10GeLa3P2S12The nickelic positive electrode of lithium ion conductor layer.Li10GeLa3P2S12The quality of lithium ion conductor layer is substrate The 1%~5% of quality.
Remaining is with comparative example 1, and which is not described herein again.
Embodiment 12
The preparation of the present embodiment nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia and luteium oxide ball milling mixing is uniform, uniform powder is obtained, Nickel in even powder, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of luteium oxide It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, 450 DEG C of preroast 7h are further crushed sieving then in 900 DEG C of roasting 12h, obtain the nickelic positive material of rare earth Lu doping Material；The D10 of the nickelic positive electrode of rare earth Ce doping is 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm；Rare earth Ce doping The porosity of the offspring of nickelic positive electrode is 28%；
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L nitric acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuous under the conditions of 20Mpa, 10 DEG C of high pressure low temperature 0.1mol/L aniline monomer is added in stirring, opens precision metering pump and 0.1mol/L oxidant H is added2O2, nAniline monomer:nOxidant=1: 1, it is 5mL/min, H that speed, which is added, in aniline monomer solution2O2It is 1mL/min, H that speed, which is added, in solution2O2Solution completion of dropwise addition is subsequent Continuous reaction 1h, controls 5 DEG C of reaction temperature, aniline monomer and rare earth Lu adulterate the mass ratio of nickelic positive electrode be 0.5%~ 2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, be to wash with dehydrated alcohol Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 175 DEG C 10h in vacuum oven, obtain doping Lu and two The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of secondary particle；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping Lu obtained above and offspring Nickelic positive electrode, lithia, germanium oxide and lanthanum oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, Obtain unit for uniform suspension；P is added in above-mentioned unit for uniform suspension2S5Solution is stirred continuously to moisture and evaporates, dry in 150 DEG C of vacuum It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface packet between the hole for obtaining doping Lu, offspring for 24 hours in dry case Cover Li10GeLa3P2S12The nickelic positive electrode of lithium ion conductor layer.Li10GeLa3P2S12The quality of lithium ion conductor layer is substrate The 1%~5% of quality.
Remaining is with comparative example 1, and which is not described herein again.
Embodiment 13
The preparation of the present embodiment nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia and luteium oxide ball milling mixing is uniform, uniform powder is obtained, Nickel in even powder, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of luteium oxide It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, 450 DEG C of preroast 6h are further crushed sieving then in 800 DEG C of roasting 14h, obtain the nickelic positive material of rare earth Lu doping Material；The D10 that rare earth Lu adulterates nickelic positive electrode is 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm；Rare earth Lu doping The porosity of the offspring of nickelic positive electrode is 27%；
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L nitric acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuous under the conditions of 20Mpa, 10 DEG C of high pressure low temperature 0.1mol/L aniline monomer is added in stirring, opens precision metering pump and 0.1mol/L oxidant H is added2O2, nAniline monomer:nOxidant=1: 1, it is 5mL/min, H that speed, which is added, in aniline monomer solution2O2It is 1mL/min, H that speed, which is added, in solution2O2Solution completion of dropwise addition is subsequent Continuous reaction 1h, controls 5 DEG C of reaction temperature, aniline monomer and rare earth Lu adulterate the mass ratio of nickelic positive electrode be 0.5%~ 2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 15min, be to wash with dehydrated alcohol Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 150 DEG C 10h in vacuum oven, obtain doping Lu and two The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of secondary particle；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping Lu obtained above and offspring Nickelic positive electrode, lithia, germanium oxide and lanthanum oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, Obtain unit for uniform suspension；P is added in above-mentioned unit for uniform suspension2S5Solution is stirred continuously to moisture and evaporates, dry in 150 DEG C of vacuum It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface packet between the hole for obtaining doping Lu, offspring for 24 hours in dry case Cover Li10GeLa3P2S12The nickelic positive electrode of lithium ion conductor layer.Li10GeLa3P2S12The quality of lithium ion conductor layer is substrate The 1%~5% of quality.
Remaining is with comparative example 1, and which is not described herein again.
Embodiment 14
The preparation of the present embodiment nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia and lanthana ball milling mixing is uniform, uniform powder is obtained, Nickel in even powder, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of lanthana It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, 450 DEG C of preroast 7h are further crushed sieving then in 1000 DEG C of roasting 10h, obtain the nickelic positive material of Doping with Rare Earth Lanthanum Material；The porosity of the offspring of the nickelic positive electrode of Doping with Rare Earth Lanthanum is 85%；The D10 of the nickelic positive electrode of Doping with Rare Earth Lanthanum It is 5~8 μm, D50 is 9~14 μm, and D90 is 15~23 μm；The porosity of the offspring of the nickelic positive electrode of Doping with Rare Earth Lanthanum It is 26%.
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L hydrochloric acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuous under the conditions of 10Mpa, 10 DEG C of high pressure low temperature 0.1mol/L aniline monomer is added in stirring, opens precision metering pump and 0.1mol/L oxidant H is added2O2, nAniline monomer:nOxidant=1: 1, it is 5mL/min, H that speed, which is added, in aniline monomer solution2O2It is 1mL/min, H that speed, which is added, in solution2O2Solution completion of dropwise addition is subsequent Continuous reaction 1h, controls 5 DEG C of reaction temperature, and the mass ratio of aniline monomer and the nickelic positive electrode of Doping with Rare Earth Lanthanum is 0.5%~ 2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 30min, be to wash with dehydrated alcohol Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 150 DEG C 10h in vacuum oven, obtain doping La and two The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of secondary particle；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping La obtained above and offspring Nickelic positive electrode, lithia and lanthanum oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, are obtained uniformly Suspension；H is added in above-mentioned unit for uniform suspension3PO4And H4AlO4Solution is stirred continuously to moisture and evaporates, in 150 DEG C of vacuum It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface between the hole for obtaining doping La, offspring for 24 hours in drying box Cladding contains Li3La2(PO4)3And LiLaAlO4Lithium ion conductor layer nickelic positive electrode.Contain Li3La2(PO4)3With LiLaAlO4Lithium ion conductor layer quality be substrate mass 1%~5%.
Remaining is with comparative example 1, and which is not described herein again.
Embodiment 15
The preparation of the present embodiment nickelic positive electrode unlike comparative example 1:
1) cobalt oxide, nickel oxide, manganese oxide, lithia and lanthana ball milling mixing is uniform, uniform powder is obtained, Nickel in even powder, cobalt, manganese molar ratio be 0.8:0.1:0.1, the molar ratio of nickel cobalt manganese and lithium is 1:1.05, the quality of lanthana It is the 0.1%~3.0% of cobalt oxide, nickel oxide, manganese oxide and lithia quality summation；Above-mentioned powder is placed in microwave Muffle furnace In, 500 DEG C of preroast 6h are further crushed sieving then in 800 DEG C of roasting 15h, obtain the nickelic positive material of Doping with Rare Earth Lanthanum Material；The D10 of the nickelic positive electrode of Doping with Rare Earth Lanthanum is 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm；Doping with Rare Earth Lanthanum The porosity of the offspring of nickelic positive electrode is 26%；
2) material after a certain amount of above-mentioned screening is weighed using precision electronic balance to be added in beaker, be slowly added to 0.1mol/L hydrochloric acid is placed in ultrasound 30min in ultrasonic disperse instrument, obtains homogeneous solution；
3) above-mentioned solution is slowly added in autoclave, keeps continuous under the conditions of 15Mpa, 10 DEG C of high pressure low temperature 0.1mol/L aniline monomer is added in stirring, opens precision metering pump and 0.1mol/L oxidant MnO is added2, nAniline monomer:nOxidant=1: 1, it is 5mL/min, MnO that speed, which is added, in aniline monomer solution2It is 1mL/min, MnO that speed, which is added, in solution2Solution completion of dropwise addition is subsequent Continuous reaction 1h, controls 5 DEG C of reaction temperature, and the mass ratio of aniline monomer and the nickelic positive electrode of Doping with Rare Earth Lanthanum is 0.5%~ 2.0%；
4) mixing suspension that above-mentioned reaction obtains is placed in supercentrifuge and is centrifuged 20min, be to wash with dehydrated alcohol Agent is washed, will be washed repeatedly three times after centrifugation solid compounds, be placed at 150 DEG C 10h in vacuum oven, obtain doping La and two The nickelic positive electrode of the tree-shaped electrically conductive polyaniline network of nanometer is formed between the hole of secondary particle；
5) the tree-shaped electrically conductive polyaniline network of nanometer will be formed between the hole of doping La obtained above and offspring Nickelic positive electrode, lithia and lanthanum oxide powder are uniformly mixed, and are poured slowly into the deionized water continuously stirred, are obtained uniformly Suspension；H is added in above-mentioned unit for uniform suspension3PO4And H4AlO4Solution is stirred continuously to moisture and evaporates, in 150 DEG C of vacuum It keeps being formed with the tree-shaped electrically conductive polyaniline network of nanometer, surface between the hole for obtaining doping La, offspring for 24 hours in drying box Cladding contains Li3La2(PO4)3And LiLaAlO4Lithium ion conductor layer nickelic positive electrode.Contain Li3La2(PO4)3With LiLaAlO4Lithium ion conductor layer quality be substrate mass 1%~5%.
Remaining is with comparative example 1, and which is not described herein again.
Performance test
1) surface topography of the nickelic positive electrode using scanning electron microscope prepared by comparative example 1 and embodiment 1 into Row observation, respectively obtains scanning figure, as shown in Fig. 1~2.
2) the nickelic positive electrode prepared using PHSJ-SF type Accurate pH measurement examination comparative example 1~6 and embodiment 1~15 PH value, test result is shown in Table 1.
3) it uses and is titrated with dilute hydrochloric acid, methyl orange is the acid-base titration test comparison example 1~6 and embodiment 1 of indicator The nickelic positive electrode remained on surface lithium salt content of~15 preparations, test result are shown in Table 1.
4) battery test system (CT2001A) is used, in the voltage range of 2.5~4.5V, 25 DEG C, 0.1C charge and discharge item Under part, test comparison example 1~6 and embodiment 1~15 prepare the cycle performance and high rate performance of button cell, and test result is shown in Table 1, in addition, the cycle performance figure and high rate performance figure of part comparative example and the button cell of embodiment preparation are respectively such as Fig. 3 and Fig. 4 It is shown.
Table 1: the chemical property of embodiment and the nickelic positive electrode of comparative example compares
As seen from the above table: 1) pH of the embodiment of the present invention is reduced, while residual impurity lithium content is significantly lower；2) of the invention The tree-shaped electrically conductive polyaniline network of nanometer is formed between rear-earth-doped, offspring the hole of preparation and surface coated lithium ion is led The gram volume of the nickelic positive electrode of the triple modifications of body (embodiment 1) is 204.7mAh/g, and 200 capacity retention ratios are recycled at 1C Up to 89.8%, the capacity retention ratio of not modified nickelic positive (comparative example 1) is only 65.8% under same test condition；3) The present invention prepare be formed between rear-earth-doped, offspring gap the tree-shaped electrically conductive polyaniline network of nanometer and surface cladding lithium from The nickelic positive electrode of the sub- triple modifications of conductor (embodiment 1) has optimal high rate performance at 3C/0.1C, up to 87.3%, And comparative example be no more than 75.6%.It can be seen that the chemical property of nickelic positive electrode of the invention is significantly improved.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula is changed and is modified.Therefore, the invention is not limited to above-mentioned specific embodiment, all those skilled in the art exist Made any conspicuous improvement, replacement or modification all belong to the scope of protection of the present invention on the basis of the present invention.This Outside, although using some specific terms in this specification, these terms are merely for convenience of description, not to the present invention Constitute any restrictions.

Claims (14)

1. a kind of nickelic positive electrode, it is characterised in that: including by nickelic substrate and the rare earth being doped in the nickelic substrate The rear-earth-doped nickelic positive electrode of compound composition, the rear-earth-doped nickelic positive electrode and aniline monomer pass through in situ poly- The formation tree-shaped electrically conductive polyaniline network of nanometer between the hole of the offspring of the rear-earth-doped nickelic positive electrode is closed to obtain The surface of in-situ polymerization material, the in-situ polymerization material is coated with lithium ion conductor layer；
Wherein, the nickelic substrate is Li1+aNixCoyM1-x-yO2, M is Mn or Al, 0.05≤a≤0.15,0.8≤x < 1.0,0 < y ≤0.1；Contain compound L i in the lithium ion conductor layer7La3Zr2O12、Li1.3Al0.7Ti1.7(PO4)3、Li10GeLa3P2S12、 Li3La2(PO4)3And LiLaAlO4One or more of.
2. nickelic positive electrode according to claim 1, it is characterised in that: the two of the rear-earth-doped nickelic positive electrode The porosity of secondary particle is 26-32%.
3. nickelic positive electrode according to claim 1, it is characterised in that: the quality of the rare earth compound is the height The 0.1%~3.0% of nickel substrate mass.
4. nickelic positive electrode according to claim 1, it is characterised in that: the rare earth compound is rare earth oxide ReO2、Re2O3、Re4O7And Re6O11One or more of, wherein Re is rare earth element.
5. nickelic positive electrode according to claim 1, it is characterised in that: the quality of the lithium ion conductor layer is nickelic The 1%~5% of substrate mass.
6. a kind of preparation method of nickelic positive electrode, which comprises the following steps:
Step 1), transition metal oxide, oxidate for lithium and rare earth oxide ball milling mixing is uniform, it is first pre- at 450~550 DEG C 5~7h is roasted, then in 800~1000 DEG C of 10~15h of roasting, is further crushed sieving, obtains rear-earth-doped nickelic positive material Material；
Step 2), rear-earth-doped nickelic positive electrode obtained in step 1) is mixed with Bronsted acid and ultrasonic wave dispersion 15~ 30min；
Step 3) first continuously stirs material made from step 2) under the conditions of high pressure low temperature, adds aniline monomer, and continuous Oxidant is added dropwise, it is tree-shaped to form nanometer between the hole of the offspring of rear-earth-doped nickelic positive electrode by 1~3h of in-situ polymerization Electrically conductive polyaniline network；
Step 4) is washed 15~30min of material high speed centrifugation in step 3) with detergent, true at 150~200 DEG C The dry 10h of sky, obtains in-situ polymerization material；
In-situ polymerization material, oxidate for lithium and rare earth oxide made from step 4) are poured slowly into and to continuously stir by step 5) In deionized water, add acid solution, continue to stir, be finally dried in vacuo, in situ polymeric materials cladding lithium from Sub- conductor layer obtains the described in any item nickelic positive electrodes of Claims 1 to 5.
7. the preparation method of nickelic positive electrode according to claim 6, it is characterised in that: described broken in step 1) The D10 of the broken obtained rear-earth-doped nickelic positive electrode that is sieved is 5~8 μm, and D50 is 9~14 μm, and D90 is 15~23 μm.
8. the preparation method of nickelic positive electrode according to claim 6, it is characterised in that: in step 2), the matter Sub- acid is one of hydrochloric acid, sulfuric acid, acetic acid, nitric acid and phosphoric acid, and the concentration of the Bronsted acid is 0.1mol/L.
9. the preparation method of nickelic positive electrode according to claim 6, it is characterised in that: in step 3), the height Pressure is -0.1~20Mpa, and the low temperature is 5~10 DEG C.
10. the preparation method of nickelic positive electrode according to claim 6, it is characterised in that: in step 3), the benzene The concentration of amine monomers is 0.1mol/L, and the oxidant is H2O2、(NH4)2S2O8、K2MnO4、KIO3、FeCl3、K2Cr2O7And MnO2 One of, nAniline monomer:nOxidant=1:1.
11. the preparation method of nickelic positive electrode according to claim 6, it is characterised in that: in step 3), the benzene The mass ratio of amine monomers and the rear-earth-doped nickelic positive electrode is 0.5%~2.0%.
12. the preparation method of nickelic positive electrode according to claim 6, it is characterised in that: described to wash in step 4) Washing agent is at least one of deionized water, dehydrated alcohol, propyl alcohol and acetone.
13. the preparation method of nickelic positive electrode according to claim 6, it is characterised in that: described dilute in step 5) Native oxide is ReO2、Re2O3、Re4O7And Re6O11At least one of, the acid solution is H3PO4、H4AlO4、H2ZrO3With P2S5One or more of.
14. a kind of lithium ion battery, it is characterised in that: including the described in any item nickelic positive electrodes of Claims 1 to 5 or The nickelic positive electrode as made from the described in any item preparation methods of claim 6~13.
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