CN106558697A - A kind of preparation method of the nickel cobalt lithium aluminate cathode material of doping Mg - Google Patents
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of doping Mg Download PDFInfo
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- CN106558697A CN106558697A CN201510632110.4A CN201510632110A CN106558697A CN 106558697 A CN106558697 A CN 106558697A CN 201510632110 A CN201510632110 A CN 201510632110A CN 106558697 A CN106558697 A CN 106558697A
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- doping
- nickel cobalt
- cathode material
- nickel
- lithium
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- 239000010406 cathode material Substances 0.000 title claims abstract description 30
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 30
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- ACKHWUITNXEGEP-UHFFFAOYSA-N aluminum cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Co+2].[Ni+2] ACKHWUITNXEGEP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 5
- 239000006104 solid solution Substances 0.000 claims abstract description 5
- 239000011777 magnesium Substances 0.000 claims description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910019421 CoxAly Inorganic materials 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical group [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- DETKHEZXMOBNHJ-UHFFFAOYSA-N [Co].[Ni].[Li].[Li] Chemical compound [Co].[Ni].[Li].[Li] DETKHEZXMOBNHJ-UHFFFAOYSA-N 0.000 abstract 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 abstract 1
- -1 nickel cobalt aluminum Chemical compound 0.000 description 13
- 238000012360 testing method Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of preparation method of the nickel cobalt lithium aluminate cathode material of doping Mg, comprises the following steps：(1) the spherical nickel-cobalt aluminium hydroxide presoma of doping Mg is prepared in the method being co-precipitated；(2) the spherical nickel-cobalt aluminium hydroxide presoma of the doping Mg is individually carried out into pre-oxidation calcination processing, obtains the nickel cobalt aluminum oxide homogenous solid solution of the spherical doping Mg of high-valence state；The nickel cobalt aluminum oxide of the doping Mg of high-valence state is uniformly mixed with lithium source, is calcined in oxygen atmosphere high temperature, break process obtains a kind of lithium nickel cobalt lithium aluminate cathode material of doping Mg after cooling.Nickel cobalt lithium aluminate cathode material prepared by the method, with high-energy-density, low cost, preparation process is simple, be easily achieved industrialization the features such as, and compared to the material of the Mg that do not adulterate, all it is greatly improved in terms of the battery performance such as battery specific capacity and multiplying power.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, more particularly to it is a kind of
The preparation method of nickel cobalt lithium aluminate cathode material.
Background technology
Lithium ion battery due to the advantages of its energy density height, good cycle, environmental protection,
It has been widely used in 3C, power and energy storage field.But with the fast development of society, people
Demand high to energy density, the lithium ion battery that volume is less it is also more urgent.Lithium ion
The lifting of battery energy density depends primarily on positive electrode and negative material, at present, lithium ion
The specific capacity of negative material is high compared to positive electrode, therefore, positive electrode is
Jing becomes the Main Bottleneck of restriction lithium ion battery energy lift.
Synthesis nickel cobalt lithium aluminate cathode material method include solid phase method, coprecipitation, thermosetting
Phase reaction, complexometry and sol-gel process.Solid phase method process is simple, low cost, but the party
It is poor to there is electrochemistry stability in method synthetic material, aluminium element skewness, and crystal morphology is not
Regular the shortcomings of；Sol-gel method craft is complicated, and high cost is not suitable for heavy industrialization
Production；Coprecipitation process is relatively easy, and the material electrochemical performance of synthesis is excellent, is currently
The important method of synthesis nickel cobalt lithium aluminate cathode material.But due in presoma manufacturing process
In, nickel, cobalt, aluminium ion can not be while precipitation from homogeneous solution, presoma lattice order variation, balls
Shape degree is bad, real density step-down, the final electrochemistry for affecting nickel cobalt lithium aluminate cathode material
Energy.It is therefore desirable to further developing the preparation method of the positive electrode of nickel cobalt lithium aluminate.
The content of the invention
The invention aims to overcome above-mentioned problem, there is provided a kind of doping Mg's
The preparation method of nickel cobalt lithium aluminate cathode material.
In order to achieve the above object, the present invention has following technical scheme：
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of doping Mg, comprises the following steps：
(1) method molten altogether is taken to be configured in nickel source, cobalt source, silicon source, magnesium source certain dense
The solution of degree, and aqueous slkali, ammonia is used together dosing pump and pumps into special reaction by a certain percentage
In kettle, while ensureing constant mixing speed and temperature, doping is prepared in the method being co-precipitated
The spherical nickel-cobalt aluminium hydroxide presoma of Mg；
(2) by the spherical nickel-cobalt aluminium hydroxide presoma of the doping Mg at 300 DEG C
～1000 DEG C, pre-oxidation calcination processing in oxygen atmosphere, is carried out, process time is 0.5～10h, is obtained
To the nickel cobalt aluminum oxide homogenous solid solution of the spherical doping Mg of high-valence state；
(3) the nickel cobalt aluminum oxide of the doping Mg of high-valence state is uniformly mixed with lithium source,
500 DEG C～1000 DEG C, 1～20h of calcining at constant temperature in oxygen atmosphere, after cooling, break process obtains one
Plant the nickel cobalt lithium aluminate cathode material of doping Mg.
Preferably, the magnesium source is magnesium sulfate, magnesium acetate, magnesium nitrate, the one kind in magnesium chloride
Or it is several.
Preferably, a kind of chemical formula of the nickel cobalt lithium aluminate cathode material of doping Mg is
LimNi(1-x-y)CoxAlyO2, wherein 0.05<x<0.25,0.02<y<0.05,0.96<m<1.3.
Preferably, before the spherical nickel-cobalt aluminium hydroxide of the doping Mg in the step (1)
The doping ratio for driving Mg in body is 0.02～0.3wt%.
Preferably, source of aluminium be aluminum sulfate, aluminum chloride, one or more in sodium metaaluminate.
Preferably, the spherical nickel-cobalt aluminium hydroxide of doping Mg is prepared in the step (1)
The Ni adopted by presoma：Co：The mol ratio of Al is (0.73～0.92)：(0.05～0.25)：
(0.02～0.05).
Preferably, the atmosphere of the pre-oxidation calcining in the step (2) is oxygen.
Preferably, the programming rate of the pre-oxidation calcination processing in the step (2) is
0.5～5 DEG C/min.
Preferably, in the step (3), the nickel cobalt aluminum oxide of doping Mg presses original with lithium source
Son compares nLi：(nNi+nCo+nAl)=(1.10～1.20)：The ratio mixing of (0.80～1.20), with
Ethanol is ball-milling medium, and 1～10h of ball milling, ball milling post-drying are placed in resistance furnace in oxygen
In gas atmosphere, after being warmed up to 500 DEG C～1000 DEG C, 1～20h of constant temperature, natural cooling are crushed,
Product is obtained after classification.
Preferably, described lithium source is Lithium hydrate, lithium carbonate, lithium nitrate, lithium chloride, grass
One or more in sour lithium, lithium acetate.
Compared with prior art, it is an advantage of the current invention that：
(1) adulterate in forerunner's production procedure Mg, makes aluminium element be evenly distributed, increases nickel
Monocrystal particle size in cobalt lithium aluminate cathode material granule, improves the compactness extent of granule, from
And the compacted density of raising nickel cobalt lithium aluminate cathode material, effectively increase nickel cobalt lithium aluminate positive pole
The cycle performance of material, high rate performance and security performance, the reversible appearance between 2.80-4.3V
Amount is more than 185mAh/g；
(2) present invention first carries out aoxidizing pre- to nickel cobalt aluminium hydroxide presoma with certain temperature
Process, decompose precursor in advance, aoxidize, form the uniform solid solution of high-valence state oxide of nickel cobalt
Body, then pretreated presoma is mixed with lithium source, when carrying out high-temperature calcination, due to front
Drive in body preprocessing process, nickel cobalt has become high-valence state oxide, and makes nickel cobalt by pre-burning
And doped chemical Mg diffuses into one another the solid solution defined relative to presoma evenly, so
During mixing lithium source high-temperature calcination, lithium ion is easier to make for the reaction of nickel cobalt, material property meeting
It is more excellent.
Description of the drawings
Fig. 1 is a kind of SEM spectrum of the nickel cobalt aluminum complex hydroxide presoma of doping Mg；
SEM spectrums of the Fig. 2 for the product of embodiment 1；
XRD spectrums of the Fig. 3 for the product of embodiment 1；
First charge-discharge curves of the Fig. 4 for the product of embodiment 1；
Cycle performance figures of the Fig. 5 for the product of embodiment 1；
SEM spectrums of the Fig. 6 for the product of embodiment 2；
XRD spectrums of the Fig. 7 for the product of embodiment 2；
First charge-discharge curves of the Fig. 8 for the product of embodiment 2；
Cycle performance figures of the Fig. 9 for the product of embodiment 2；
SEM spectrums of the Figure 10 for the product of embodiment 3；
XRD spectrums of the Figure 11 for the product of embodiment 3；
First charge-discharge curves of the Figure 12 for the product of embodiment 3；
Cycle performance figures of the Figure 13 for the product of embodiment 3.
Specific embodiment
With reference to Fig. 1-13, the present invention will be further described.
Embodiment 1
(1) with nickel sulfate, cobaltous sulfate, sodium metaaluminate, magnesium acetate as raw material, according to Ni:
Co: Al mol ratio 0.92: 0.5: 0.03, the doping ratio of Mg is 0.3%, by altogether
The sedimentation method prepare the complex hydroxide presoma of the spherical nickel-cobalt aluminum of doping Mg, the compound hydrogen
The SEM figures of oxide precursor are as shown in Figure 1；
(2) the complex hydroxide presoma of the nickel cobalt aluminum of doping Mg is placed in resistance furnace,
With the ramp of 5 DEG C/min to 800 DEG C, 10 hours are incubated, are pre-oxidized in oxygen atmosphere
Obtain the composite oxides Ni of nickel cobalt aluminum1-x-yCoxAlyO2, x=0.05, y=0.03；
(3) composite oxides of nickel cobalt aluminum and Lithium hydrate are pressed into atomic ratio nLi：
(nNi+nCo+nAl)=1.20：1 ratio mixing, with ethanol as ball-milling medium, ball milling 10
Hour is uniform, is placed in after being slowly warmed up to 850 DEG C in oxygen atmosphere in resistance furnace after drying, permanent
Temperature 20 hours, natural cooling are crushed, classification, that is, obtain a kind of doping as shown in Figure 2
The nickel cobalt lithium aluminate cathode material of Mg, Fig. 3 are the XRD figure of the positive electrode.
Above product is fabricated to into button cell and 186502600mAh battery testing specific capacities
And cycle life test, normal temperature condition test, first charge-discharge curve is as shown in figure 4,0.2C
Specific capacity is 205mAh/g first, and cycle performance test is as shown in figure 5,1C/1C circulations
Capability retention is 77% within 700 weeks.
Embodiment 2
(1) with nickel sulfate, cobaltous sulfate, aluminum chloride, magnesium chloride as raw material, according to Ni:
Co: Al mol ratio 0.80: 0.15: 0.05, the doping ratio of Mg is 0.2%, is led to
Cross the complex hydroxide presoma that coprecipitation prepares the spherical nickel-cobalt aluminum of doping Mg；
(2) the complex hydroxide presoma of the nickel cobalt aluminum of doping Mg is placed in resistance furnace,
With the ramp of 3 DEG C/min to 500 DEG C, 5 hours are incubated, are pre-oxidized in oxygen atmosphere
Obtain the composite oxides Ni1-x-yCoxAlyO2 of nickel cobalt aluminum, x=0.15, y=0.05；
(3) composite oxides of nickel cobalt aluminum and Lithium hydrate are pressed into atomic ratio nLi：
(nNi+nCo+nAl)=1.11: 1.0 ratio mixing, with ethanol as ball-milling medium, ball
Mill is uniformly placed in after drying after being slowly warmed up to 650 DEG C in oxygen atmosphere in resistance furnace for 6 hours,
Constant temperature 15 hours, natural cooling are crushed, and classification obtains one kind as shown in Figure 6 and mix
The nickel cobalt lithium aluminate cathode material of miscellaneous Mg, Fig. 7 are the XRD figure of the positive electrode.
Above product is fabricated to into button cell and 186502600mAh battery testing specific capacities
And cycle life test, normal temperature condition test, first charge-discharge curve is as shown in figure 8,0.2C
Specific capacity is 198mAh/g first, and cycle performance test is as shown in figure 9,1C/1C circulations
Capability retention is 85% within 700 weeks.
Embodiment 3
(1) with nickel sulfate, cobaltous sulfate, aluminum sulfate and magnesium sulfate as raw material, according to Ni:
Co: Al mol ratio 0.73: 0.25: 0.02, the doping ratio of Mg is 0.02%,
The complex hydroxide presoma of the spherical nickel-cobalt aluminum of doping Mg is prepared by coprecipitation；
(2) the complex hydroxide presoma of the nickel cobalt aluminum of doping Mg is placed in resistance furnace,
With the ramp of 1 DEG C/min to 300 DEG C, 1 hour is incubated, is pre-oxidized in oxygen atmosphere
Obtain the composite oxides Ni1-x-yCoxAlyO2 of nickel cobalt aluminum, x=0.25, y=0.02；
(3) composite oxides of nickel cobalt aluminum and Lithium hydrate are pressed into atomic ratio nLi：
(nNi+nCo+nAl)=1.10: 0.80 ratio mixing, with ethanol as ball-milling medium, ball
Mill is uniformly placed in after drying in resistance furnace and is slowly warmed up to 500 DEG C in oxygen atmosphere for 3 hours
Afterwards, constant temperature 10 hours, natural cooling crush, and classification obtains as shown in Figure 10
A kind of nickel cobalt lithium aluminate cathode material of doping Mg, Figure 11 is the XRD figure of the positive electrode.
Above product is fabricated to into button cell and 186502600mAh battery testing specific capacities
And cycle life test, normal temperature condition test, first charge-discharge curve is as shown in figure 8,0.2C
Specific capacity is 189mAh/g first, and cycle performance test is as shown in figure 9,1C/1C circulations
Capability retention is 92% within 700 weeks.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate what the present invention was made
Citing, and it is not the restriction to embodiments of the present invention.For the common skill of art
For art personnel, can also make on the basis of the above description other multi-forms change or
Change.Here all of embodiment cannot be exhaustive.Every technology for belonging to the present invention
Scheme it is extended obvious change or change still in protection scope of the present invention it
Row.
Claims (10)
1. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of doping Mg, it is characterised in that the party
Method is comprised the following steps：
(1) method molten altogether is taken to be configured in nickel source, cobalt source, silicon source, magnesium source certain density
Solution, and aqueous slkali, ammonia is used together dosing pump and pumps into by a certain percentage in special reactor, together
When ensure constant mixing speed and temperature, be co-precipitated method prepare doping Mg spherical nickel-cobalt
Aluminium hydroxide presoma；
(2) by the spherical nickel-cobalt aluminium hydroxide presoma of the doping Mg at 300 DEG C
～1000 DEG C, pre-oxidation calcination processing in oxygen atmosphere, is carried out, process time is 0.5～10h, obtains height
The nickel cobalt aluminum oxide homogenous solid solution of the spherical doping Mg of valence state；
(3) the nickel cobalt aluminum oxide of the doping Mg of high-valence state is uniformly mixed with lithium source, at 500 DEG C
～1000 DEG C, 1～20h of calcining at constant temperature in oxygen atmosphere, after cooling, break process obtains a kind of doping Mg
Nickel cobalt lithium aluminate cathode material.
2. the preparation of the nickel cobalt lithium aluminate cathode material of a kind of doping Mg according to claim 1
Method, it is characterised in that the magnesium source is magnesium acetate, magnesium sulfate, magnesium nitrate, the one kind in magnesium chloride
Or it is several.
3. the preparation of the nickel cobalt lithium aluminate cathode material of a kind of doping Mg according to claim 1
Method, it is characterised in that the chemical formula of the nickel cobalt lithium aluminate cathode material of the doping Mg is LimNi(1-x-y)CoxAlyO2, wherein 0.05<x<0.25,0.02<y<0.05,0.96<m<1.3.
4. the preparation of the nickel cobalt lithium aluminate cathode material of a kind of doping Mg according to claim 1
Method, it is characterised in that：Before the spherical nickel-cobalt aluminium hydroxide of the doping Mg in the step (1)
The doping ratio for driving Mg in body is 0.02～0.3wt%.
5. the preparation of the nickel cobalt lithium aluminate cathode material of a kind of doping Mg according to claim 1
Method, it is characterised in that：Source of aluminium is aluminum sulfate, aluminum chloride, the one kind or several in sodium metaaluminate
Kind.
6. the preparation of the nickel cobalt lithium aluminate cathode material of a kind of doping Mg according to claim 1
Method, it is characterised in that：The spherical nickel-cobalt aluminium hydroxide of doping Mg is prepared in the step (1)
The Ni adopted by presoma：Co：The mol ratio of Al is (0.73～0.92)：(0.05～0.25)：
(0.02～0.05).
7. the preparation of the nickel cobalt lithium aluminate cathode material of a kind of doping Mg according to claim 1
Method, it is characterised in that：The atmosphere of the pre-oxidation calcining in the step (2) is oxygen.
8. the preparation of the nickel cobalt lithium aluminate cathode material of a kind of doping Mg according to claim 1
Method, it is characterised in that：The programming rate of the pre-oxidation calcination processing in the step (2) is 0.5～5 DEG C
/min。
9. the preparation of the nickel cobalt lithium aluminate cathode material of a kind of doping Mg according to claim 1
Method, it is characterised in that：In the step (3), the nickel cobalt aluminum oxide of doping Mg presses original with lithium source
Son compares nLi：(nNi+nCo+nAl)=(1.10～1.20)：The ratio mixing of (0.80～1.20), with ethanol
For ball-milling medium, 1～10h of ball milling, ball milling post-drying, it is placed in resistance furnace in oxygen atmosphere,
After being warmed up to 500 DEG C～1000 DEG C, 1～20h of constant temperature, natural cooling are crushed, product are obtained after classification.
10. the preparation of the nickel cobalt lithium aluminate cathode material of a kind of doping Mg according to claim 1
Method, it is characterised in that：Described lithium source be Lithium hydrate, lithium carbonate, lithium nitrate, lithium chloride,
One or more in lithium oxalate, lithium acetate.
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| CN109037669A (en) * | 2018-07-06 | 2018-12-18 | 乳源东阳光磁性材料有限公司 | Modified nickel-cobalt lithium aluminate anode material and preparation method and application thereof |
| CN109037649A (en) * | 2018-08-13 | 2018-12-18 | 河北省科学院能源研究所 | It is a kind of to be mixed with modified nickel cobalt lithium aluminate cathode material and preparation method thereof |
| CN109273688A (en) * | 2018-09-17 | 2019-01-25 | 国联汽车动力电池研究院有限责任公司 | High-nickel cathode material with surface rich rock salt phase and preparation method and application thereof |
| CN110752362A (en) * | 2019-10-31 | 2020-02-04 | 贵州中伟资源循环产业发展有限公司 | Ternary precursor coated with magnesium and preparation method thereof |
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| CN109037649A (en) * | 2018-08-13 | 2018-12-18 | 河北省科学院能源研究所 | It is a kind of to be mixed with modified nickel cobalt lithium aluminate cathode material and preparation method thereof |
| CN109273688A (en) * | 2018-09-17 | 2019-01-25 | 国联汽车动力电池研究院有限责任公司 | High-nickel cathode material with surface rich rock salt phase and preparation method and application thereof |
| CN110752362A (en) * | 2019-10-31 | 2020-02-04 | 贵州中伟资源循环产业发展有限公司 | Ternary precursor coated with magnesium and preparation method thereof |
| CN115667154A (en) * | 2020-01-07 | 2023-01-31 | Ev金属英国有限公司 | Method for preparing lithium transition metal oxides |
| CN113651373A (en) * | 2021-10-19 | 2021-11-16 | 河南科隆新能源股份有限公司 | Anode material with uniform porous structure and preparation method thereof |
| CN114426313A (en) * | 2022-01-07 | 2022-05-03 | 云南大学 | High-energy-density ternary cathode material and preparation method and application thereof |
| CN117525333A (en) * | 2023-11-16 | 2024-02-06 | 南开大学 | Titanium molten salt-assisted cladding doped monocrystal cobalt-free lithium nickel oxide positive electrode material, and preparation method and application thereof |
| CN117525333B (en) * | 2023-11-16 | 2024-05-28 | 南开大学 | Titanium molten salt-assisted cladding doped monocrystal cobalt-free lithium nickel oxide positive electrode material, and preparation method and application thereof |
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Application publication date: 20170405 |