CN108269998A - A kind of preparation method of polynary positive pole material of lithium ion cell - Google Patents
A kind of preparation method of polynary positive pole material of lithium ion cell Download PDFInfo
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- CN108269998A CN108269998A CN201710028307.6A CN201710028307A CN108269998A CN 108269998 A CN108269998 A CN 108269998A CN 201710028307 A CN201710028307 A CN 201710028307A CN 108269998 A CN108269998 A CN 108269998A
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 229910003684 NixCoyMnz Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 238000007792 addition Methods 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910021311 NaFeO2 Inorganic materials 0.000 claims description 2
- 229910003618 NixCoyMn1-x-y(OH)2 Inorganic materials 0.000 claims description 2
- 229910003690 NixCoyMnzM1-x-y-z(OH)2 Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000013021 overheating Methods 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 4
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910016722 Ni0.5Co0.2Mn0.3 Inorganic materials 0.000 description 1
- 229910015150 Ni1/3Co1/3Mn1/3(OH)2 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- -1 nickel cobalt lithium aluminates Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- 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
- H01M4/362—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
- 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
-
- 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 discloses a kind of preparation method of polynary positive pole material of lithium ion cell, the positive electrode average chemical composition being prepared is：Li[NixCoyMnzMm]O2·n[M´wO],x+y+z+m=1,0.0005≤m≤ 0.03,0.0005≤nOne or more in≤0.05, M Al, Y, Si, Zr, Ti, Mg element, M ' is one or more in Al, Ce, Zr, Y, Yb, W, Ti, Si, B, Mg, La element.The present invention stablizes crystal grain layer structure by optimizing element doping, improves the high rate performance of polynary positive pole material；The oxide skin(coating) adhered to by surface avoids corrosion of the electrolyte to multicomponent material matrix, improves cycle performance and hot storage performance.This preparation process equipment requirement is low, simple for process, relative inexpensiveness, suitable for industrialized production.
Description
Technical field
The invention belongs to lithium ion secondary battery anode material technical fields, and in particular to a kind of lithium ion battery is polynary just
The preparation method of pole material.
Background technology
As the lithium ion battery key components being concerned in recent years, the exploitation of positive electrode is from cobalt acid
Lithium, LiMn2O4 develop to multicomponent materials directions such as nickle cobalt lithium manganate, nickel cobalt lithium aluminates, and have been successfully applied in IT, electronic
The fields such as automobile, energy accumulating device.In application scenarios such as PHEV/HEV electric vehicles, model plane, start and stop power supplys, lithium ion is needed
Secondary cell high current fast charging and discharging, is provided simultaneously with the characteristics such as high power capacity, high temperature resistant, long-life.
However, irreversible destruction can be caused during high current charge-discharge to cathode material structure.In order to stablize positive electrode material
Crystal structure, it usually needs material is modified by adulterating and coating, i.e., it is more stable to prepare crystal structure first
Adulterate kernel, then service life, stability and the reliability for improving material by coating.Doped chemical can stablize positive electrode
Layer structure, but stabilizing power is poor when doping is few, can interfere Li when doping is more instead+Movement, cause material multiplying power
It reduces.Therefore, need chosen doping element and optimize doping, with improve positive electrode material form improve multiplying power property.In addition,
Clad can influence Li in positive electrode+Abjection and insertion, select suitable cladding element and method for coating, optimization cladding
Amount can reduce the influence to material multiplying power property while improving and recycling.
At present, the polynary positive pole material used in above-mentioned field is mainly LiNi1/3Co1/3Mn1/3O2, other systems it is more
First positive electrode is because there are big multiplying power discharging is poor, Cycle Difference, safety are low etc., reasons do not use generally.Have in the prior art
Scheme attempts to solve the above problems.Chinese patent literature CN102938459A prepares powerful lithium ion battery using template
Polynary positive pole material improves positive electrode multiplying power, but this method step is more by shortening lithium ion abjection/insertion, and technique is multiple
It is miscellaneous.Chinese patent literature CN105680015A uses rare earth oxide La2O3Coat polynary positive pole material LiNi1/3Co1/3Mn1/ 3O2, the high-temperature behavior of material is improved, but the multiplying power of material is not improved by increasing coating thickness.
Invention content
To solve the above problems, the present invention provides a kind of preparation method of polynary positive pole material of lithium ion cell, it is prepared into
To positive electrode can reach LiNi1/3Co1/3Mn1/3O2Multiplying power, cycle performance, while the specific capacity of material can be promoted, dropped
Low cost, available for markets such as PHEV/HEV electric vehicles, model plane, start and stop power supplys.
To achieve the above object, the invention discloses a kind of polynary positive pole material of lithium ion cell, which includes：
Adulterate kernel and oxide skin(coating).
Above-mentioned polynary positive pole material has α ~ NaFeO2Layer structure, average chemical composition are：
Li[NixCoyMnzMm]O2·n[M´wO]
Wherein, doping kernel is Li [NixCoyMnzM m]O2, one or more, the M ' in M Al, Y, Si, Zr, Ti, Mg element
It is one or more in Al, Ce, Zr, Y, Yb, W, Ti, Si, B, Mg, La element；
Wherein,x+y+z+m=1,0.0005≤m≤ 0.03,0.0005≤n≤0.05；
Wherein, the meso-position radius D of the polynary positive pole material50It is 3 ~ 9 μm.
On the other hand, purpose to realize the present invention, the present invention also provides a kind of sides for preparing the polynary positive pole material
Method, specific technical solution include the following steps：
（1）Method one：By NixCoyMn1-x-y(OH)2Polynary presoma, lithium source and M element compound are abundant by certain mol proportion
Uniformly mixing, the addition of lithium source is Li：（Ni+Co+Mn+M）Molar ratio=0.95 ~ 1.10；
Method two：By NixCoyMnzM1-x-y-z(OH)2Polynary presoma and lithium source are by the full and uniform mixing of certain mol proportion, lithium source
Addition be Li：（Ni+Co+Mn+M）Molar ratio=0.95 ~ 1.10；
（2）By step（1）Obtained mixture is sintered under dry air atmosphere, and temperature is 800 ~ 1000 DEG C, the time 5
~ 20 hours, doping kernel is obtained after cooling, broken, sieving；
（3）The compound powder of M ' elements is uniformly mixed by a certain percentage with doping kernel；Or by M ' element compound solution
After uniformly mixing dispersion with deionized water, a certain proportion of doping kernel is added in, quick stirring, drying；
（4）By step（3）Obtained mixture after cooling, sieving, obtains final products through Overheating Treatment.
In above-mentioned preparation method, step（1）Described in polynary presoma meso-position radius D50It it is 2 ~ 8 μm, it is preferred that described more
The meso-position radius D of first presoma50It is 3.5-6 μm；
In above-mentioned preparation method, step（1）Described in M element addition control in M：（Ni+Co+Mn）Molar ratio be 0
.0005~0.03：1；Preferably, the M elements addition control is in M：（Ni+Co+Mn）Molar ratio=0.001 ~ 0.02：1.
In above-mentioned preparation method, step（1）Described in M element compound be the nano-oxide of M element, oxalates,
It is one or more in carbonate or oxyhydroxide.
In above-mentioned preparation method, step（3）Described in the control of M ' elements additions in M ' oxides and doping kernel
Molar ratio is 0.0005 ~ 0.05:1；Preferably, the molar ratio of M ' oxides and doping kernel is 0.001 ~ 0.03:1.
In above-mentioned preparation method, step（3）Described in M ' element compounds for M ' elements nano-oxide, fluorination
It is one or more in object, phosphate, carbonate or oxyhydroxide.
In above-mentioned preparation method, step（3）Described in M ' elements introduce form be powder, solution, colloidal sol or suspension
In it is one or more.
In above-mentioned preparation method, step（4）Described in heat treatment temperature for 100-600 DEG C, the time is 2 ~ 15 hours.
The present invention has the advantage that：
1st, the preparation method of polynary positive pole material provided by the invention realizes and stablizes crystal grain stratiform knot by element doping
Structure improves the high rate performance of polynary positive pole material.
2nd, the oxide skin(coating) that the preparation method of polynary positive pole material provided by the invention is adhered to by surface, partly with Louis
This alkali form is reacted with HF remaining in electrolyte, avoids the corrosion of multicomponent material matrix, improves cycle performance and heat stores
Performance.
3rd, the preparation method of multicomponent material positive electrode provided by the invention is low for equipment requirements, simple for process, cost phase
To cheap, suitable for industrialized production.
Description of the drawings
Fig. 1 is the XRD test charts of embodiment 1.
Fig. 2 is the polynary positive pole material SEM figures obtained in embodiment 1.
It is embodiment 1 and comparative example 1, the high temperature circulation comparison diagram of comparative example 2 that Fig. 3, which is,.
Specific implementation method
Embodiment 1
Use 4.1 μm of Ni0.5Co0.2Mn0.3(OH)2Presoma, Li2CO3, nanometer ZrO2Powder, in molar ratio Li/（Ni+Co+
Mn+ Zr）=1.03, Zr/（Ni+Co+Mn）=0.002 uniformly mixing, mixture is sintered 10 hours in 910 DEG C of air atmospheres, cold
But it, crushes, being sieved obtains doping kernel.Doping 1000 g of kernel is taken, adds in nanometer Al2O3Powder 10.5g is sufficiently mixed uniformly,
Then 7h is heat-treated at 400 DEG C, 5.3 μm of Li (Ni are obtained after cooling sieving0.499Co0.200Mn0.299Zr0.002)O2·
0.03Al2/3O polynary positive pole materials.
Embodiment 2
Use 3.5 μm of Ni0.5Co0.2Mn0.3(OH)2Presoma, Li2CO3, nano-TiO2Powder, nanometer MgCO3Powder, massage
You compare Li/（Ni+Co+Mn+ Ti+Mg）=1.05、Ti/（Ni+Co+Mn）=0.01、Mg/（Ni+Co+Mn）=0.01 uniformly mixing,
Mixture is sintered 15 hours in 880 DEG C of air atmospheres, and cooling, broken, sieving obtain doping kernel.Take doping kernel 1000g,
Nano-meter SiO_22Powder 2.5g is uniformly mixed, and 10h is then heat-treated at 500 DEG C, and cooling, sieving obtain 4.3 μm of Li
(Ni0.490Co0.196Mn0.294Ti0.010Mg0.010)O2·0.008Si0.5The polynary positive pole material of O.
Embodiment 3
Using 5.5 μm of Ni0.6Co0.2Mn0.19Al0.01（OH)2Presoma and Li2CO3Li/ in molar ratio（Ni+Co+ Mn+ Al）
=1.02 uniformly mixing, mixture are sintered 15 hours in 850 DEG C of air atmospheres, and cooling, broken, sieving obtain doping kernel.It takes
500mL deionized waters add in Al colloidal sols（Convert Al2O3For 2.1g）It is stirred evenly with nano-MgO powder 1.3g, adds doping
Kernel 1000g, is dried while stirring.Drying material is heat-treated 6h at 300 DEG C, obtains 7.6 μm of Li [Ni0.6Co0.2Mn0.19Al0.01]
O2·0.006Al2/3O0.003MgO polynary positive pole materials.
Comparative example 1
Use 5.3 μm of Ni1/3Co1/3Mn1/3(OH)2Presoma, Li2CO3, Li/ in molar ratio（Ni+Co+Mn）=1.03 is uniformly mixed
It closes, mixture is sintered 10h in 950 DEG C of air atmospheres, and cooling, broken sieving obtain Li [Ni1/3Co1/3Mn1/3] O2It is polynary just
Pole material.
Comparative example 2
Use 4.1 μm of Ni0.5Co0.2Mn0.3(OH)2Presoma, Li2CO3, molar ratio Li/（Ni+Co+Mn）=1.03 is uniformly mixed
It closes, mixture is sintered 10 hours in 910 DEG C of air atmospheres, and cooling, broken, sieving obtain Li [Ni0.5Co0.2Mn0.3] O2It is more
First positive electrode.
Test
Material phase analysis is carried out to polynary positive pole material with XRD, embodiment 1 and the test result of comparative example 2 are shown in Fig. 1.Pass through comparison
As it can be seen that there is Al in 2 θ=67.00 ° in the XRD spectrum of embodiment 12O3(440) object phase peak.
Sem test
Polynary positive pole material surface is characterized with scanning electron microscope.Fig. 2 is the multielement cathode material obtained in embodiment 1
The SEM figures of material, it can be seen that be attached to the uniform dotted oxide particle of white in material surface.
Button cell is tested
According to positive electrode, conductive carbon black, PVDF=95%:2.5%:2.5% mass ratio weighs quantitative material, and it is fixed that PVDF is dissolved in
It measures in NMP, adds in positive electrode and conductive agent, be put into blender and stir 30min, be uniformly mixed above-mentioned material, be made
Even anode sizing agent.Anode sizing agent is coated uniformly on aluminium foil and is fabricated to pole piece, dries, is fabricated to just in 120 DEG C of baking ovens
Pole piece is for use；Positive plate and diaphragm, lithium piece, electrolyte etc. are assembled into CR2025 type button half-cells.
The button half-cell of making places 2h, after open-circuit voltage is stablized, battery is charged to current density 17mA/g and is cut
Only voltage 4.3V, then constant-voltage charge 30min, are then discharged to blanking voltage 3.0V with same current density.By same side
Formula carries out 1 time again, using battery at this time as active cell.
High rate performance test is as follows：Using active cell, in the voltage range of 3.0~4.3V, with 34mA/g（0.2C）
Current density charging, then respectively with 85 mA/g（0.5C）、170 mA/g（1C）、340mA/g（2C）With 680mA/g（4C）
Current density is discharged, and tests the high rate performance of battery；
Cycle performance test is as follows：Using active cell, with the current density of 1C in the voltage range of 3.0~4.4V, temperature
Under the conditions of 45 DEG C, the high temperature capacity of 50 test materials is recycled.
Table 1 is the capacity of embodiment 1 ~ 3 and comparative example 1 ~ 2 and the correction data of multiplying power.The result shows that embodiment 1 ~ 3
Capacity and multiplying power are better than comparative example 1 and comparative example 2.
The capacity multiplying power table of 1 embodiment 1 ~ 3 of table and Comparative Examples 1 and 2
Claims (8)
1. a kind of preparation method of polynary positive pole material of lithium ion cell, it is characterised in that include the following steps：
（1）By NixCoyMn1-x-y(OH)2Polynary presoma, lithium source and M element compound press the full and uniform mixing of certain mol proportion,
Or by NixCoyMnzM1-x-y-z(OH)2Polynary presoma and lithium source press the full and uniform mixing of certain mol proportion；Wherein, lithium source
Addition is Li：（Ni+Co+Mn+ M）Molar ratio=0.95 ~ 1.10；
（2）By step（1）Mixture is obtained to be sintered under dry air atmosphere, temperature is 800 ~ 1000 DEG C, the time for 5 ~
20 hours, doping kernel is obtained after cooling, broken, sieving；
（3）The compound powder of M ' elements is uniformly mixed by a certain percentage with doping kernel；Or by M ' element compound solution
After uniformly mixing dispersion with deionized water, add in a certain proportion of doping kernel and quickly stir, dry；
（4）By step（3）Obtained mixture obtains positive electrode through Overheating Treatment after cooling, sieving；
Gained positive electrode includes：Kernel and oxide skin(coating) are adulterated, there is α ~ NaFeO2Layer structure, meso-position radius D50It is 3 ~ 9 μm,
Average chemical forms：
Li[NixCoyMnzMm]O2·n[M´wO]
Wherein, doping kernel is Li [NixCoyMnzM m]O2, one or more, the M ' in M Al, Y, Si, Zr, Ti, Mg element
It is one or more in Al, Ce, Zr, Y, Yb, W, Ti, Si, B, Mg, La element；
Wherein,x+y+z+m=1,0.0005≤m≤ 0.03,0.0005≤n≤0.05。
2. the preparation method of polynary positive pole material of lithium ion cell according to claim 1, it is characterised in that step（1）Institute
State the meso-position radius D of polynary presoma50It it is 2 ~ 8 μm, it is preferred that the meso-position radius D of the polynary presoma50It is 3.5-6 μm.
3. the preparation method of polynary positive pole material of lithium ion cell according to claim 1, it is characterised in that step（1）
Described in M element addition control in M：（Ni+Co+Mn）Molar ratio be 0 .0005 ~ 0.03：1；Preferably, it is described
M elements addition is controlled in M：（Ni+Co+Mn）Molar ratio=0.001 ~ 0.02：1.
4. the preparation method of polynary positive pole material of lithium ion cell according to claim 1, it is characterised in that step（1）In
The M element compound is one or more in the nano-oxide of M element, oxalates, carbonate or oxyhydroxide.
5. the preparation method of polynary positive pole material of lithium ion cell according to claim 1, it is characterised in that step（3）In
M ' elements addition the control is 0.0005 ~ 0.05 in the molar ratio of M ' oxides and doping kernel:1；Preferably, M ' oxygen
Compound and the molar ratio of doping kernel are 0.001 ~ 0.03:1.
6. the preparation method of polynary positive pole material of lithium ion cell according to claim 1, it is characterised in that（3）Described in
M ' element compounds be the nano-oxides of M ' elements, fluoride, phosphate, carbonate or one kind in oxyhydroxide or
It is a variety of.
7. the preparation method of polynary positive pole material of lithium ion cell according to claim 1, it is characterised in that step（3）In
It is one or more in powder, solution, colloidal sol or suspension that the M ' elements, which are introduced into form,.
8. the preparation method of polynary positive pole material of lithium ion cell according to claim 1, it is characterised in that step（4）In
The heat treatment temperature is 100-600 DEG C, and the time is 2 ~ 15 hours.
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