CN104409723B - A kind of electrochemical preparation method of tertiary cathode material - Google Patents
A kind of electrochemical preparation method of tertiary cathode material Download PDFInfo
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- CN104409723B CN104409723B CN201410826843.7A CN201410826843A CN104409723B CN 104409723 B CN104409723 B CN 104409723B CN 201410826843 A CN201410826843 A CN 201410826843A CN 104409723 B CN104409723 B CN 104409723B
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- 239000010406 cathode material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 32
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 31
- 239000010941 cobalt Substances 0.000 claims abstract description 26
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 239000011572 manganese Substances 0.000 claims abstract description 12
- 239000010405 anode material Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 34
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims description 22
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 21
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 21
- 229910001453 nickel ion Inorganic materials 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 238000000518 rheometry Methods 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 abstract description 18
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- -1 manganese salt compound Chemical class 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- 238000009388 chemical precipitation Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000004886 process control Methods 0.000 description 4
- 229910012653 LiNi0.5Co0.2Mn0.3 Inorganic materials 0.000 description 3
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910018434 Mn0.5O2 Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- QNLVXLJTOLHAMA-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(O)(O)=O Chemical compound N=NC=NN.N=NC=NN.C(O)(O)=O QNLVXLJTOLHAMA-UHFFFAOYSA-N 0.000 description 1
- 229910015150 Ni1/3Co1/3Mn1/3(OH)2 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 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
- 239000012528 membrane Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- H01M4/52—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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses the electrochemical preparation method of a kind of tertiary cathode material, directly use nickel, cobalt, manganese simple metal and electric energy as raw material, use Green Electrochemical synthetic method, electrolytic synthesis nickel, cobalt, manganese salt compound under normal pressure and temperature, through add lithium reaction, be spray-dried, high-temperature process obtain tertiary cathode material LiNixCoyMnzO2, wherein, 0 < x < 1,0 < y < 0.8,0 < z < 1, and x+y+z=1.Compared with prior art, the electrochemical preparation method that the present invention provides reduces the cost of raw material and energy consumption, simplifies technique, reduces environmental pollution simultaneously, improve properties of product.The electrochemical synthesis technology of this method is a kind of environment amenable Green Chemistry process; use simple metal to make anode material, do not introduce any impurity, it is ensured that nickel, cobalt, the controlled and high-purity of manganese ion concentration; realize the waste water zero-emission to environment simultaneously, continuous way large-scale production can be realized.
Description
Technical field
The present invention relates to the preparation method of ternary cathode material of lithium ion battery, be specifically related to one
The electrochemical preparation method of tertiary cathode material.
Background technology
The positive electrode that lithium ion battery uses at present mainly has cobalt acid lithium, LiFePO4, mangaic acid
Lithium and tertiary cathode material etc..Nickle cobalt lithium manganate tertiary cathode material has specific capacity height, safety
Performance and multiplying power discharging property are good, are the lithium ion power battery cathode materials of a kind of great potential
Material, has wide application at dynamic field such as electronic car and boat, electronic spacecraft, electric tools
Prospect.
The preparation method of tertiary cathode material mainly has high temperature solid-phase sintering method and liquid phase at present
Learn the sedimentation method.High temperature solid-state method method is simple, but smashes ball milling and be difficult to control to, and exists each former
The defect that material compound mixing is uneven, and sintering temperature is high, energy consumption is big, it is difficult to extensively carry out.
Chemical precipitation method can be divided into the indirect chemical sedimentation method and direct chemical precipitation method.Close with conventional solid
One-tenth method is compared, and chemical precipitation method can make material reach the mixing in molecule or atomic level, it is easy to
Obtaining that particle diameter is little, the presoma of mix homogeneously, and sintering temperature is relatively low, synthetic product component is equal
Even.But LITHIUM BATTERY nickel source, cobalt source, manganese source material price height used by chemical precipitation method, purity is not
Ternary mixing co-precipitation easy to control, that obtain, needs multiple times of filtration to wash, produces a large amount of waste water,
To environment.
Summary of the invention
In order to solve problems of the prior art, the present invention provides a kind of tertiary cathode material
Electrochemical preparation method, the method directly uses nickel, cobalt, manganese simple metal and electric energy as former
Material, low cost, technique is simple, and reduces environmental pollution, enhances product performance.
The electrochemical preparation method of a kind of tertiary cathode material that the present invention provides, mainly include with
Lower step:
(1), respectively using pure metallic nickel, cobalt, manganese as anode material, the moon is made with inert electrode
Pole, with acetic acid, citric acid mixed solution as electrolyte, logical unidirectional current in undivided cell
Electrolysis, respectively obtains nickel ion solution, cobalt ion solution and manganese ion solution；
(2) nickel ion solution, cobalt ion solution and the manganese ion, step (1) prepared are molten
After liquid mixes by a certain percentage, by certain mole with nickel ion, cobalt ion and manganese ion total amount
Than adding lithium ion, heated and stirred is reacted, and obtains rheology phase suspension；
(3) the rheology phase suspension high-speed centrifugal, step (2) obtained is spray-dried
Machine is spray-dried, and obtains ternary material precursor, then through height in inert atmosphere high temperature furnace
Temperature processes, and obtains nickel-cobalt-manganternary ternary anode material.
In step (1), the current intensity of electrolysis is 0.1-10A/dm2, described electrolyte is
0.1-4.0mol/L acetic acid, citric acid mixed solution, wherein citric acid and the mol ratio of acetic acid
For 1:1～5；The nickel ion solution, cobalt ion solution and the manganese ion solution concentration that obtain are
0.1-3.0mol/L。
Nickel ion solution in step (2), cobalt ion solution and the mixing of manganese ion solution mole
Ratio is for nickel ion: cobalt ion: manganese ion=x:y:z, and wherein 0 < x < 1,0 < y < 0.8,0 < z < 1,
And x+y+z=1；The lithium ion of nickel ion, cobalt ion and manganese ion total amount and addition mole
Ratio is 1:1～1.4；Described lithium ion is selected from Lithium hydrate, lithium oxide, Quilonorm (SKB)
Plant or several；Described stirring reaction, condition is: be 30-80 DEG C in temperature, pH 7-9 condition
Lower stirring reaction 6-28h.
In step (3), spray drying condition control is: feeding flow velocity is 0.2～10L/min,
Inlet temperature is 160 DEG C～320 DEG C, and export environment temperature is 90 DEG C～150 DEG C；Described height
Temperature is processed as high-temperature process 2-11h of 400-900 DEG C；Prepared tertiary cathode material molecule
Formula is LiNixCoyMnzO2, wherein, 0 < x < 1,0 < y < 0.8,0 < z < 1, and x+y+z=1.
Compared with prior art, the invention provides one and directly use pure metallic nickel, cobalt, manganese
As nickel source, cobalt source, manganese source material, electrolytic synthesis nickel, cobalt, manganese salinization under normal pressure and temperature
Compound, through adding lithium reaction, is spray-dried, and high-temperature process obtains the electrochemistry of tertiary cathode material
Technology of preparing, reduces the cost of raw material and energy consumption, simplifies technique, reduces environment dirty simultaneously
Dye, improves properties of product.The electrochemical synthesis technology of this method is a kind of environment amenable
Green Chemistry process, uses simple metal to make anode material, does not introduce any impurity, it is ensured that nickel,
Cobalt, the controlled and high-purity of manganese ion concentration, realize the waste water zero-emission to environment simultaneously, can
Realize continuous way large-scale production.This method realizes the reaction of molecule, ionic level, can be any
Add surface modifier；Product component is uniform, and concordance is good, the tertiary cathode of this method synthesis
The electric discharge gram volume of material product is high, and multiplying power discharging property is good, and cyclical stability is high.
Accompanying drawing explanation
Fig. 1 is the process chart of the electrochemical synthesis tertiary cathode material that the present invention provides；
Fig. 2 is the charge-discharge performance figure of nickel-cobalt-manganternary ternary anode material prepared by the present invention
Detailed description of the invention
In order to be more fully understood that present disclosure, make furtherly below in conjunction with specific embodiment
Bright.Should be understood that these embodiments are only used for that the present invention is further described, rather than limit
The scope of the present invention.
Embodiment 1
The preparation method of a kind of tertiary cathode material, comprises the following steps:
(1), 100L 1.0mol/L acetic acid, citric acid electrolyte are prepared, wherein containing acetic acid
0.8mol/L, citric acid 0.2mol/L, do anode with pure metallic nickel, cobalt, manganese respectively, with
Inert electrode titanium is negative electrode, controls electric current 3A electrolysis, and electrolysis electricity is to 160F (farad
Younger brother, 1F=26.8Ah) stop electrolysis, obtaining concentration, to be 0.8mol/L nickel, cobalt, manganese ion molten
Liquid.
(2), nickel, cobalt, manganese ion solution are pressed nickel ion: cobalt ion: manganese ion=0.5:
The mixed in molar ratio of 0.2:0.3, is slowly added dropwise the Lithium hydrate of 1.0mol/L to continuous stirring
Reactor in, lithium ion in molar ratio: (nickel ion+cobalt ion+manganese ion)=1.1:
The mol ratio metering of 1, whole process control temp, at about 50 DEG C stirring reaction 18h, controls
PH 7.5, obtains rheology phase suspension.
(3) the rheology phase suspension high-speed centrifugal, step (2) obtained is spray-dried
Machine is spray-dried, and feeding flow velocity is 1L/min, and inlet temperature is 240 DEG C, leaving air temp
It is 110 DEG C, the spray-dried powdery ternary material quickly obtaining high degree of dispersion of rheology phase suspension
Material precursor, by ternary material precursor in nitrogen atmosphere high temperature furnace, with 5 DEG C/min's
Programming rate heats up and is incubated 3 hours, then with the programming rate of 5 DEG C/min at 400 DEG C
Heating up and obtain nickel-cobalt-manganternary ternary anode material 800 DEG C of high-temperature process 8h, its molecular formula is
LiNi0.5Co0.2Mn0.3O2。
Embodiment 2
The preparation method of a kind of tertiary cathode material, comprises the following steps:
(1), 100L 2.0mol/L acetic acid, citric acid electrolyte are prepared, wherein containing acetic acid
1.2mol/L, citric acid 0.8mol/L, do anode with pure metallic nickel, cobalt, manganese respectively, with
Inert electrode rustless steel is negative electrode, controls electric current 6A electrolysis, and electrolysis electricity to 240F stops electricity
Solve, obtain concentration and be 1.2mol/L nickel, cobalt, manganese ion solution.
(2), nickel, cobalt, manganese ion solution are pressed nickel ion: cobalt ion: manganese ion=1/3:
The mixed in molar ratio of 1/3:1/3, is slowly added dropwise the Lithium hydrate of 1.0mol/L to stirring continuously
In the reactor mixed, lithium ion in molar ratio: (nickel ion+cobalt ion+manganese ion)=1.2:1
Mol ratio metering, whole process control temp about 60 DEG C stirring reaction 18h, control
PH 8.5, obtains rheology phase suspension.
(3) the rheology phase suspension high-speed centrifugal, step (2) obtained is spray-dried
Machine is spray-dried, and feeding flow velocity is 1L/min, and inlet temperature is 238 DEG C, leaving air temp
It is 106 DEG C, the spray-dried powdery ternary material quickly obtaining high degree of dispersion of rheology phase suspension
Material precursor, in nitrogen atmosphere high temperature furnace, heats up with the programming rate of 5 DEG C/min
300 DEG C are incubated 4 hours, then heat up high at 850 DEG C with the programming rate of 5 DEG C/min
Temperature processes 7h and obtains nickel-cobalt-manganternary ternary anode material, and its molecular formula is LiNi1/3Co1/3Mn1/3O2。
Embodiment 3
The preparation method of a kind of tertiary cathode material, comprises the following steps:
(1), 100L 2.6mol/L acetic acid, citric acid electrolyte are prepared, wherein containing acetic acid
1.6mol/L, citric acid 1.0mol/L, do anode with pure metallic nickel, cobalt, manganese respectively, with
Inert electrode rustless steel is negative electrode, controls electric current 6A electrolysis, electrolysis electricity to 320F, stops
Electrolysis, obtains concentration and is 1.6mol/L nickel, cobalt, manganese ion solution.
(2), nickel, cobalt, manganese ion solution are pressed nickel ion: cobalt ion: manganese ion=1/3:
The mixed in molar ratio of 1/3:1/3, is slowly added dropwise the Lithium hydrate of 1.0mol/L to stirring continuously
In the reactor mixed, by lithium ion: (nickel ion+cobalt ion+manganese ion)=1.15:1's
Mol ratio is measured, and whole process control temp, at about 50 DEG C stirring reaction 18h, controls pH
8, obtain rheology phase suspension.
(3) the rheology phase suspension high-speed centrifugal, step (2) obtained is spray-dried
Machine is spray-dried, and feeding flow velocity is 1L/min, and inlet temperature is 230 DEG C, goes out pathogenic wind-warm
Degree is 102 DEG C, the spray-dried powdery three quickly obtaining high degree of dispersion of rheology phase suspension
Unit's material precursor, by ternary material precursor in nitrogen atmosphere high temperature furnace, with 5 DEG C/min
Programming rate heat up and be incubated 3 hours at 400 DEG C, then with the intensification of 5 DEG C/min speed
Degree heats up and obtains nickel-cobalt-manganternary ternary anode material 850 DEG C of high-temperature process 8h, and its molecular formula is
LiNi1/3Co1/3Mn1/3O2。
Embodiment 4
The preparation method of a kind of tertiary cathode material, comprises the following steps:
(1), 100L 3.0mol/L acetic acid, citric acid electrolyte are prepared, wherein containing acetic acid
1.8mol/L, citric acid 1.2mol/L, do anode with pure metallic nickel, cobalt, manganese respectively, with
Inert electrode rustless steel is negative electrode, controls electric current 6A electrolysis, and electrolysis electricity to 360F stops electricity
Solve, obtain concentration and be 1.8mol/L nickel, cobalt, manganese ion solution.
(2), nickel, cobalt, manganese ion solution are pressed nickel ion: cobalt ion: manganese ion=0.8:
The mixed in molar ratio of 0.2:1, is slowly added dropwise the Lithium hydrate of 1.0mol/L to continuous stirring
Reactor in, by lithium ion: (nickel ion+cobalt ion+manganese ion)=1.1:1 rubs
You measure by ratio, and whole process control temp, at about 50 DEG C stirring reaction 18h, controls pH 7.5,
Obtain rheology phase suspension.
(3) the rheology phase suspension high-speed centrifugal, step (2) obtained is spray-dried
Machine is spray-dried, and feeding flow velocity is 1L/min, and inlet temperature is 235 DEG C, leaving air temp
It is 102 DEG C, the spray-dried powdery ternary material quickly obtaining high degree of dispersion of rheology phase suspension
Material precursor, by ternary material precursor in nitrogen atmosphere high temperature furnace, with 5 DEG C/min's
Programming rate heats up and is incubated 3 hours, then with the programming rate of 5 DEG C/min at 400 DEG C
Heat up and obtain nickel-cobalt-manganternary ternary anode material 850 DEG C of high-temperature process 8h.Its molecular formula is
LiNi0.4Co0.1Mn0.5O2。
Comparative example 1
(1) nickel that weighs by the molar ratio of 5:2:3, cobalt, manganese nitrate are dissolved in solution,
Utilize 1mol/L sodium hydroxide solution regulation pH value between 8-11, sustained response 20 hours；
Reaction carries out solid-liquid separation after terminating, and cleans, and is dried final acquisition hydroxide nickel cobalt manganese presoma
LiNi0.5Co0.2Mn0.3(OH)2。
(2) mol ratio of 1.1:1 is pressed by CH3COOLi·2H20 and LiNi0.5Co0.2Mn0.3(OH)2
Mix by the mode of ball milling, by this mixture with the programming rate of 5 DEG C/min at 500 DEG C
It is incubated 4 hours and removes acetate, be then warming up to 920 DEG C with the programming rate of 5 DEG C/min
Carry out double sintering, and furnace cooling is just finally obtaining ternary after insulation 8 hours at this temperature
Pole material LiNi0.5Co0.2Mn0.3O2
Comparative example 2
(1) nickel that weighs by the molar ratio of 1:1:1, cobalt, manganese nitrate are dissolved in solution, profit
With the sodium hydroxide solution regulation pH value of 1mol/L between 8-11, sustained response 20 hours；Instead
Solid-liquid separation should be carried out after terminating, clean, be dried final acquisition hydroxide nickel cobalt manganese presoma
Ni1/3Co1/3Mn1/3(OH)2。
(2) mol ratio of 1.2:1 is pressed by CH3COOLi·2H20 and LiNi0.5Co0.2Mn0.3(OH)2
Mix by the mode of ball milling, by this mixture with the programming rate of 5 DEG C/min at 500 DEG C
It is incubated 4 lab scales and removes acetate, be then warming up to 920 DEG C with the programming rate of 5 DEG C/min
Carry out double sintering, and furnace cooling finally obtains nickel cobalt manganese after insulation 8 hours at this temperature
Tertiary cathode material LiNi1/3Co1/3Mn1/3O2。
Respectively by present example 1-4, tertiary cathode material that comparative example 1 and 2 obtains, poly-partially
Difluoroethylene, acetylene black mix according to the ratio of mass percent 80:12:8, and stir into mud
Shape, is coated uniformly on aluminium foil surface, then vacuum drying at 80 DEG C, after tabletted
Vacuum drying again at 90 DEG C, thus prepare based lithium-ion battery positive plate.
This based lithium-ion battery positive plate and lithium ion battery negative (metal reason sheet) are assembled into lithium
Ion battery, with microporous polypropylene membrane (cellgard2000) as lithium ion battery separator, with body
The long-pending ethylene carbonate vinegar (EC) than 1:1 is solvent with carbonic acid diformazan vinegar (DMC), by 1mol/L LiPF6
Electrolyte as lithium ion battery.The lithium ion battery assembled at room temperature places 24
Carrying out charge-discharge test after hour, the voltage range of discharge and recharge is 2.75V～4.5V, in room temperature
The embedding lithium reversible capacity of lithium ion battery, charge-discharge performance are measured in lower circulation.
With the lithium ion battery of the tertiary cathode material making of this method synthesis head under 0.2C
Secondary discharge capacity reaches 195mAh/g, and after 100 circulations, discharge capacity still has 172mAh/g,
And high rate performance highlights, reach 185mAh/g and 166mAh/g at 1C and 10C discharge capacity.
Electric discharge gram volume contrast is shown in Table 1, and charge-discharge performance is shown in Fig. 2.
Table 1 discharge gram volume contrast
In addition, it is to be understood that in the range of without departing from the most described objective, the enforcement of change is all wrapped
It is contained in the technical scope of the present invention.After having read content of the present invention, this field
The present invention is made some nonessential change or adjustment by technical staff, still falls within the guarantor of the present invention
Protect scope.
Claims (10)
1. the electrochemical preparation method of a tertiary cathode material, it is characterised in that described preparation method comprises the following steps:
(1), respectively using pure metallic nickel, cobalt, manganese as anode material, negative electrode is made with inert electrode, with acetic acid, citric acid mixed solution as electrolyte, in undivided cell, logical unidirectional current electrolysis, respectively obtains nickel ion solution, cobalt ion solution and manganese ion solution；
(2) after nickel ion solution, cobalt ion solution and the mixing of manganese ion solution, by step (1) prepared, adding lithium ion, heated and stirred is reacted, and obtains rheology phase suspension；
(3) the rheology phase suspension high-speed centrifugal spray dryer, by step (2) obtained is spray-dried, and obtains ternary material precursor, then through high-temperature process in inert atmosphere high temperature furnace, obtains nickel-cobalt-manganternary ternary anode material.
Preparation method the most according to claim 1, it is characterised in that in step (1), the electric current density of electrolysis is 0.1-10A/dm2, the nickel ion solution, cobalt ion solution and the manganese ion solution concentration that obtain are 0.1-3.0
mol/L。
Preparation method the most according to claim 1, it is characterised in that described in step (1), electrolyte is 0.1-4.0
Mol/L acetic acid, citric acid mixed solution, wherein the mol ratio of citric acid and acetic acid is 1:1 ~ 5.
Preparation method the most according to claim 1, it is characterised in that in step (2), the mol ratio of nickel ion solution, cobalt ion solution and the mixing of manganese ion solution is
Nickel ion: cobalt ion: manganese ion=x:y:z, wherein 0 < x < 1,0 < y < 0.8,0 < z < 1, and x+y+z=1.
Preparation method the most according to claim 1, it is characterised in that the mol ratio 1 of the lithium ion of nickel ion, cobalt ion and manganese ion total amount and addition in step (2)
: 1~1.4。
Preparation method the most according to claim 1, it is characterised in that one or more in Lithium hydrate, lithium oxide, Quilonorm (SKB) of lithium ion described in step (2).
Preparation method the most according to claim 1, it is characterised in that heated and stirred described in step (2) is reacted, and condition is: be 30-80 DEG C in temperature, stirring reaction 6-28h under the conditions of pH 7-9.
Preparation method the most according to claim 1, it is characterised in that in step (3) spray drying condition control be: feeding flow velocity is 0.2 ~ 10L/min, inlet temperature is 160 DEG C ~
320 DEG C, export environment temperature is 90 DEG C ~ 150 DEG C.
Preparation method the most according to claim 1, it is characterised in that described in step (3), high-temperature process is high-temperature process 2-11h of 400-900 DEG C.
Preparation method the most according to claim 1, it is characterised in that the tertiary cathode material molecular formula prepared is
LiNixCoyMnzO2, wherein, 0 < x < 1,
0 < y < 0.8,0 < z < 1, and x+y+z=1.
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