CN105336932A - Preparation method of nickel cobalt lithium manganate and lithium-rich composite material - Google Patents
Preparation method of nickel cobalt lithium manganate and lithium-rich composite material Download PDFInfo
- Publication number
- CN105336932A CN105336932A CN201510753076.6A CN201510753076A CN105336932A CN 105336932 A CN105336932 A CN 105336932A CN 201510753076 A CN201510753076 A CN 201510753076A CN 105336932 A CN105336932 A CN 105336932A
- Authority
- CN
- China
- Prior art keywords
- lithium
- lithium manganate
- rich
- nickle cobalt
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 5
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 150000002696 manganese Chemical class 0.000 claims abstract description 5
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 17
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910013716 LiNi Inorganic materials 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 239000011268 mixed slurry Substances 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 238000005204 segregation Methods 0.000 abstract description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 abstract 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical class [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 7
- 239000002002 slurry Substances 0.000 description 5
- 229910052493 LiFePO4 Inorganic materials 0.000 description 4
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910012516 LiNi0.4Co0.2Mn0.4O2 Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- -1 cobalt lithium manganate compound Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 1
- LTUDISCZKZHRMJ-UHFFFAOYSA-N potassium;hydrate Chemical compound O.[K] LTUDISCZKZHRMJ-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 239000002904 solvent 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
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a lithium nickel cobalt manganese oxide and lithium-rich composite material, which comprises the following steps: dissolving manganese salt, cobalt salt, nickel salt and lithium salt in water, adding a complexing agent to form a sol, adding a nickel cobalt lithium manganate material into the sol, ultrasonically mixing the nickel cobalt lithium manganate and the sol uniformly, heating to form gel, and preparing the composite material with lithium-rich material uniformly distributed around the nickel cobalt lithium manganate by a high-temperature solid phase method. The invention improves the cycling stability, the safety performance and the overcharge problem of the nickel cobalt lithium manganate, especially the lithium-rich ternary material. Because the selected materials have the same or similar elements and have equivalent tap density, the phenomenon of segregation of the nickel cobalt lithium manganate and lithium iron phosphate series composite material due to long-term storage or transportation vibration is not easy to occur, so the safety performance is better, and the volume energy density is higher.
Description
Technical field
The present invention relates to the preparation method of a kind of nickle cobalt lithium manganate and rich lithium composite material, belong to Green Chemistry field of power supplies.
Background technology
Lithium ion battery just by the Portable power source of consumer electronics product to power source cells convert, domestic current lithium ion battery is main or for consumer electronics power supply, but the growth rate of electrokinetic cell makes it too far behind to catch up really.The positive electrode that can be used as electrokinetic cell has three kinds at present: LiFePO4, LiMn2O4, ternary material (i.e. nickle cobalt lithium manganate).The positive electrode that domestic current use is maximum or LiFePO4, the security performance of LiFePO4 is very good, but energy density is low, and this just determines ferric phosphate lithium cell and is suitable for big bus or city scooter.Its shorter course continuation mileage still causes " mileage is worried ".And although lithium manganate battery has good high rate performance, can as the alternative power source of fast punching, but its energy density is also not high, make its high temperature cyclic performance very poor because Jahn-Teller and manganese dissolve simultaneously, be difficult to separately for pure electric automobile, but due to cost low at present in electric bicycle development good greatly.Due to the natural defect of this bi-material, domestic major cell manufacturer starts Devoting Major Efforts To Developing ternary battery.But the thermal stability of ternary material, security performance are all bad, be difficult to by safety tests such as acupunctures.Mainly strengthen controlling to realize to battery by doing baby battery at present simultaneously.Also has other positive electrode of compound, as ferric phosphate lithium or LiMn2O4, this bi-material can improve the fail safe of ternary really, but also has other problem, as low jolt ramming, the low energy densities of LiFePO4, LiMn2O4 then has the problems such as manganese dissolving, structural aberration, high temperature circulation difference.
The present invention adopts rich lithium material and nickle cobalt lithium manganate compound, due to the jolt ramming of rich lithium material and the suitable of nickle cobalt lithium manganate, can not segregation, when voltage lower (4.3V or 4.2V), Mn is in inertia simultaneously, and also can not be oxidized in a large number, this spline structure stablizes very much.Although energy density can be sacrificed to some extent but rock-steady structure makes it safer, high-pressure solid can improve its volume energy density, and what the energy density of material was declined can not be too many.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of nickle cobalt lithium manganate and rich lithium composite material, to solve the problem proposed in above-mentioned background technology.
For achieving the above object, the invention provides following technology example:
A preparation method for nickle cobalt lithium manganate and rich lithium composite material, composite positive pole is by Li [Li
1/3-2x/3-y/3ni
xco
ymn
2/3-x/3-2y/3] O
2.LiNi
1-p-qco
pmn
qo
2(0≤x≤0.428,0≤x+0.5y≤0.428,0≤p≤0.333,0.1≤q≤0.5) form, the mass percent of rich lithium material is 1-40%, and the mass percent of nickle cobalt lithium manganate is 60-99%, and rich lithium material is evenly distributed on nickle cobalt lithium manganate particle surrounding;
Comprise following preparation process:
(1) rich lithium colloidal sol preparation: be dissolved in water by manganese salt, cobalt salt, nickel salt and lithium salts, after fully stirring, add complexing agent, fully stirs at 60-90 DEG C and forms colloidal sol in water-bath;
(2) add nickle cobalt lithium manganate: a certain amount of nickel-cobalt lithium manganate material is added above-mentioned colloidal sol, then ultrasonic vibration and stirring arm stir and carry out simultaneously, obtain more homogeneous mixed slurry;
(3) solid gel preparation: above-mentioned mixed slurry is heated at 80-120 DEG C, makes it form solid gel;
(4) high-temp combustion: be placed in Muffle furnace by above-mentioned gel mixture, burns under 400-500 DEG C of ignition temperature, then is incubated at 600-1000 DEG C, obtains the composite positive pole that rich lithium material is evenly distributed on nickle cobalt lithium manganate particle surrounding after cooling.
Preferably, manganese salt is one or more mixing in manganese nitrate, manganese sulfate, manganese chloride; Cobalt salt is one or more mixing in cobalt nitrate, cobaltous sulfate, cobalt chloride; Nickel salt is one or more mixing in nickel nitrate, nickelous sulfate, nickel chloride; Lithium salts is one or more mixing in lithium nitrate, lithium sulfate, lithium chloride.
Preferably, complexing agent is one or more mixing in citric acid, EDTA, urea, ammoniacal liquor, sucrose.
Preferably, rich lithium material is Li [Li
1/3-2x/3-y/3ni
xco
ymn
2/3-x/3-2y/3] O
2(0≤x≤0.428,0≤x+0.5y≤0.428).
Preferably, nickle cobalt lithium manganate is LiNi
1-p-qco
pmn
qo
2, wherein 0≤p≤0.333,0.1≤q≤0.5.
Preferably, rich lithium material accounts for the 1-40% of material gross mass.
Preferably, bath temperature prepared by colloidal sol is 60-90 DEG C, and temperature retention time is 3-10h.
Preferably, when adding nickel-cobalt lithium manganate material, ultrasonic vibration and stirring arm stir and carry out simultaneously, and the time is 0.5h-1h.
Preferably, ignition temperature is 400-500 DEG C, and burning time is 5-30min; The temperature of high-temperature process is 600-1000 DEG C, and temperature retention time is 2-15h.
Compared with prior art, the invention has the beneficial effects as follows:
It is high that the composite material of nickle cobalt lithium manganate of the present invention and rich lithium has energy density, and security performance is high, and circulation is long, and the close not easily segregation of jolt ramming is with low cost, can be continuously produced.
Accompanying drawing explanation
Fig. 1 is that the nickle cobalt lithium manganate SEM before compound schemes;
Fig. 2 is that composite material SEM prepared by embodiment 1 schemes;
Fig. 3 is LiNi
0.8co
0.1mn
0.1o
2with the circulation figure of the half-cell of the composite material of embodiment 1 preparation.
Embodiment
Below by embodiment, the present invention will be further described, but embodiment does not limit the scope of the invention.
Embodiment 1
The preparation method of a kind of nickle cobalt lithium manganate of the present invention and rich lithium composite material, comprises the following steps:
(1) rich lithium colloidal sol preparation: the manganese nitrate of 34.0148g50wt%, 6.6537g six water nickel nitrate, 6.6592g cobalt nitrate hexahydrate and 14.5622g lithium nitrate are dissolved in 300mL water, stirring makes it to dissolve completely, adds 73.969g monohydrate potassium.Above-mentioned solution is placed in 80 DEG C of water-baths, after fully dissolving, adds ammoniacal liquor and be transferred to 8 to pH value.Be placed in water-bath again and stir 8h, form vitreosol.
(2) nickle cobalt lithium manganate is added: by 85gLiNi
0.8co
0.1mn
0.1o
2add in above-mentioned colloidal sol, in ultrasonic device, carry out ultrasonic and stir process 1h, form uniform sizing material;
(3) solid gel preparation: above-mentioned slurry is stirred to into solid gel in the oil bath pan of 100 DEG C;
(4) high-temp combustion: Muffle furnace solid gel being placed in 500 DEG C burns 10min, then is warming up to 800 DEG C of insulation 8h, namely obtains LiNi
0.8co
0.1mn
0.1o
2and Li
1.2mo
0.54ni
0.13co
0.13o
2the composite material of even compound, wherein, in the present embodiment, rich lithium material quality accounts for 15% of material gross mass.
Take composite material 1.6g, 0.2gSP (carbon black conductive agent) prepared by the present embodiment, 0.2gPVDF (Kynoar), stir 2h with NMP (1-METHYLPYRROLIDONE) for solvent closes slurry, prepare half-cell.Above-mentioned composite material and graphite are prepared into square battery (wherein length is respectively 140mm, 65mm and 18mm), wherein, positive electrode compacted density is 3g/cm
3, surface density is 170g/m
2(one side); Negative material compacted density 1.46g/cm
3, the thickness of pole piece is 104 μm.
Fig. 1 is that the nickle cobalt lithium manganate SEM before compound schemes, and Fig. 2 is that composite material SEM prepared by the present embodiment schemes, and Quantitative Assessment of Particle Distribution prepared by the present embodiment is even.
Fig. 3 is LiNi
0.8co
0.1mn
0.1o
2the circulation figure of the half-cell of the composite material prepared with the present embodiment, although can find out the relative nickel-cobalt lithium manganate material initial capacity reduction of composite material, cyclical stability increases.
Embodiment 2
The preparation method of a kind of nickle cobalt lithium manganate of the present invention and rich lithium composite material, comprises the following steps:
(1) rich lithium colloidal sol preparation: 32.536g Manganous sulfate monohydrate, 32.199g six water nickel nitrate and 21.163g lithium nitrate are dissolved in 500mL ethanol, stirring makes it to dissolve completely, the ammoniacal liquor of 28wt% is added water and to dilute by 1:4, getting 102gEDTA (ethylenediamine tetra-acetic acid) adds in the weak ammonia of 72mL, after abundant dissolving, mix with above-mentioned solion, at 60 DEG C, stir 5h form colloidal sol;
(2) nickle cobalt lithium manganate is added: by the LiNi of 70g
0.6co
0.2mn
0.2o
2add in above-mentioned colloidal sol, in ultrasonic device, carry out ultrasonic and stir process 1h, form uniform sizing material;
(3) solid gel preparation: above-mentioned slurry is stirred to into solid gel in 100 DEG C in oil bath pan;
(4) high-temp combustion: Muffle furnace solid gel being placed in 500 DEG C processes 30min, then be warming up to 1000 DEG C of process 3h, namely obtain LiNi
0.6co
0.2mn
0.2o
2and Li
1.1mo
0.55ni
0.35o
2the composite material of even compound, wherein rich lithium material quality accounts for 30% of material gross mass.
Embodiment 3
The preparation method of a kind of nickle cobalt lithium manganate of the present invention and rich lithium composite material, comprises the following steps:
(1) rich lithium colloidal sol preparation: be dissolved in 300mL water by the manganese nitrate of 11.334g50wt%, 2.215g six water nickel nitrate, 2.217g cobalt nitrate hexahydrate and 4.852g lithium nitrate, stirs after making it to dissolve completely, adds 75.24g sucrose.Above-mentioned solution is placed in 60 DEG C of water-baths, fully dissolves, add ammoniacal liquor and be transferred to 8 to pH value, then stir 8h in water-bath, form vitreosol;
(2) nickle cobalt lithium manganate is added: by the LiNi of 95g
0.4co
0.2mn
0.4o
2add in above-mentioned colloidal sol, in ultrasonic device, carry out ultrasonic and stir process 1h, form uniform sizing material.
(3) solid gel preparation: and then above-mentioned slurry is stirred to into solid gel in 100 DEG C in oil bath pan;
(4) high-temp combustion: Muffle furnace solid gel being placed in 500 DEG C processes 10min, then be warming up to 800 DEG C of process 8h, namely obtain LiNi
0.4co
0.2mn
0.4o
2and Li
1.2mo
0.54ni
0.13co
0.13o
2the composite material of even compound, wherein rich lithium material quality accounts for 5% of material gross mass.
Embodiment 4
The preparation method of a kind of nickle cobalt lithium manganate of the present invention and rich lithium composite material, comprises the following steps:
(1) manganese nitrate of 34.0148g50wt%, 6.6537g six water nickel nitrate, 6.6592g cobalt nitrate hexahydrate and 14.5622g lithium nitrate are dissolved in 300mL water, stir after making it to dissolve completely, add 44.381g Citric Acid Mono and 8.448g urea.Above-mentioned solution is placed in 80 DEG C of water-baths, after fully dissolving, adds ammoniacal liquor and be transferred to 8 to pH value.In water-bath, stir 8h again, form vitreosol;
(2) nickle cobalt lithium manganate is added: by the LiNi of 85g
0.8co
0.1mn
0.1o
2add in above-mentioned colloidal sol, in ultrasonic device, carry out ultrasonic and stir process 1h, form uniform sizing material,
(3) solid gel preparation: above-mentioned slurry is stirred to into solid gel in 100 DEG C in oil bath pan,
High-temp combustion: Muffle furnace solid gel being placed in 500 DEG C processes 10min, then be warming up to 800 DEG C of process 8h, namely obtain LiNi
0.8co
0.1mn
0.1o
2and Li
1.2mo
0.54ni
0.13co
0.13o
2the composite material of even compound, wherein rich lithium material quality accounts for 15% of material gross mass.
Claims (9)
1. a preparation method for nickle cobalt lithium manganate and rich lithium composite material, is characterized in that, composite positive pole is by Li [Li
1/3-2x/3-y/3ni
xco
ymn
2/3-x/3-2y/3] O
2.LiNi
1-p-qco
pmn
qo
2(0≤x≤0.428,0≤x+0.5y≤0.428,0≤p≤0.333,0.1≤q≤0.5) form, the mass percent of rich lithium material is 1-40%, and the mass percent of nickle cobalt lithium manganate is 60-99%, and rich lithium material is evenly distributed on nickle cobalt lithium manganate particle surrounding;
Comprise following preparation process:
(1) rich lithium colloidal sol preparation: be dissolved in water by manganese salt, cobalt salt, nickel salt and lithium salts, after fully stirring, add complexing agent, fully stirs at 60-90 DEG C and forms colloidal sol in water-bath;
(2) add nickle cobalt lithium manganate: a certain amount of nickel-cobalt lithium manganate material is added above-mentioned colloidal sol, then ultrasonic vibration and stirring arm stir and carry out simultaneously, obtain more homogeneous mixed slurry;
(3) solid gel preparation: above-mentioned mixed slurry is heated at 80-120 DEG C, makes it form solid gel;
(4) high-temp combustion: be placed in Muffle furnace by above-mentioned gel mixture, burns under 400-500 DEG C of ignition temperature, then is incubated at 600-1000 DEG C, obtains the composite positive pole that rich lithium material is evenly distributed on nickle cobalt lithium manganate particle surrounding after cooling.
2. the nickle cobalt lithium manganate according to claims 1 and rich lithium composite preparation method for material, is characterized in that, manganese salt is one or more mixing in manganese nitrate, manganese sulfate, manganese chloride; Cobalt salt is one or more mixing in cobalt nitrate, cobaltous sulfate, cobalt chloride; Nickel salt is one or more mixing in nickel nitrate, nickelous sulfate, nickel chloride; Lithium salts is one or more mixing in lithium nitrate, lithium sulfate, lithium chloride.
3. the nickle cobalt lithium manganate according to claims 1 and rich lithium composite preparation method for material, is characterized in that, complexing agent is one or more mixing in citric acid, EDTA, urea, ammoniacal liquor, sucrose.
4. nickle cobalt lithium manganate according to claim 1 and rich lithium composite preparation method for material, is characterized in that, rich lithium material is Li [Li
1/3-2x/3-y/3ni
xco
ymn
2/3-x/3-2y/3] O
2(0≤x≤0.428,0≤x+0.5y≤0.428).
5. nickle cobalt lithium manganate according to claim 1 and rich lithium composite preparation method for material, is characterized in that, nickle cobalt lithium manganate is LiNi
1-p-qco
pmn
qo
2, wherein 0≤p≤0.333,0.1≤q≤0.5.
6. nickle cobalt lithium manganate according to claim 1 and rich lithium composite preparation method for material, it is characterized in that, rich lithium material accounts for the 1-40% of material gross mass.
7. nickle cobalt lithium manganate according to claim 1 and rich lithium composite preparation method for material, is characterized in that, bath temperature prepared by colloidal sol is 60-90 DEG C, and temperature retention time is 3-10h.
8. nickle cobalt lithium manganate according to claim 1 and rich lithium composite preparation method for material, is characterized in that, when adding nickel-cobalt lithium manganate material, ultrasonic vibration and stirring arm stir and carry out simultaneously, and the time is 0.5h-1h.
9. nickle cobalt lithium manganate according to claim 1 and rich lithium composite preparation method for material, is characterized in that, ignition temperature is 400-500 DEG C, and burning time is 5-30min; The temperature of high-temperature process is 600-1000 DEG C, and temperature retention time is 2-15h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510753076.6A CN105336932B (en) | 2015-11-07 | 2015-11-07 | Preparation method of nickel cobalt lithium manganate and lithium-rich composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510753076.6A CN105336932B (en) | 2015-11-07 | 2015-11-07 | Preparation method of nickel cobalt lithium manganate and lithium-rich composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105336932A true CN105336932A (en) | 2016-02-17 |
| CN105336932B CN105336932B (en) | 2018-12-14 |
Family
ID=55287332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510753076.6A Active CN105336932B (en) | 2015-11-07 | 2015-11-07 | Preparation method of nickel cobalt lithium manganate and lithium-rich composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105336932B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106442047A (en) * | 2016-08-31 | 2017-02-22 | 合肥国轩高科动力能源有限公司 | Pretreatment method for detecting metal ions in graphite |
| CN106450276A (en) * | 2016-10-14 | 2017-02-22 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery electrode modified material, preparation method thereof and lithium ion battery |
| CN107180955A (en) * | 2017-05-25 | 2017-09-19 | 西藏杭能新能源科技有限公司 | A kind of preparation method of the rich lithium metal oxide anode composite electrodes of nickle cobalt lithium manganate NCM |
| CN107665988A (en) * | 2016-07-27 | 2018-02-06 | 南通亨利锂电新材料有限公司 | A kind of lithium metal oxide stratified material and preparation method thereof |
| CN107910511A (en) * | 2017-10-31 | 2018-04-13 | 多氟多（焦作）新能源科技有限公司 | A kind of stratiform lithium-rich anode material and preparation method thereof, lithium ion battery |
| CN109167039A (en) * | 2018-08-27 | 2019-01-08 | 山东理工大学 | The method of microstage nucleocapsid tertiary cathode material is received in a kind of preparation of low-temperature self-propagating method |
| CN110364703A (en) * | 2019-06-11 | 2019-10-22 | 浙江吉利控股集团有限公司 | A kind of composite material and preparation method thereof, anode, battery and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023539087A (en) * | 2020-10-06 | 2023-09-13 | エルジー・ケム・リミテッド | Method for producing positive electrode active material for lithium secondary batteries and positive electrode active material produced thereby |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102201573A (en) * | 2011-04-13 | 2011-09-28 | 北京工业大学 | Rich-lithium positive electrode material of lithium ion battery having coreshell structure and preparation method of rich-lithium positive electrode material |
| CN103474625A (en) * | 2013-08-05 | 2013-12-25 | 合肥国轩高科动力能源股份公司 | Coating method for core-shell novel positive electrode material for lithium ion battery |
| CN104409685A (en) * | 2014-11-28 | 2015-03-11 | 东莞市迈科科技有限公司 | Lithium ion cell cathode material with core shell structure and preparation method thereof |
-
2015
- 2015-11-07 CN CN201510753076.6A patent/CN105336932B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102201573A (en) * | 2011-04-13 | 2011-09-28 | 北京工业大学 | Rich-lithium positive electrode material of lithium ion battery having coreshell structure and preparation method of rich-lithium positive electrode material |
| CN103474625A (en) * | 2013-08-05 | 2013-12-25 | 合肥国轩高科动力能源股份公司 | Coating method for core-shell novel positive electrode material for lithium ion battery |
| CN104409685A (en) * | 2014-11-28 | 2015-03-11 | 东莞市迈科科技有限公司 | Lithium ion cell cathode material with core shell structure and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107665988A (en) * | 2016-07-27 | 2018-02-06 | 南通亨利锂电新材料有限公司 | A kind of lithium metal oxide stratified material and preparation method thereof |
| CN106442047A (en) * | 2016-08-31 | 2017-02-22 | 合肥国轩高科动力能源有限公司 | Pretreatment method for detecting metal ions in graphite |
| CN106450276A (en) * | 2016-10-14 | 2017-02-22 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery electrode modified material, preparation method thereof and lithium ion battery |
| CN106450276B (en) * | 2016-10-14 | 2019-09-24 | 中国科学院宁波材料技术与工程研究所 | Lithium ion cell electrode modified material, preparation method and lithium ion battery |
| CN107180955A (en) * | 2017-05-25 | 2017-09-19 | 西藏杭能新能源科技有限公司 | A kind of preparation method of the rich lithium metal oxide anode composite electrodes of nickle cobalt lithium manganate NCM |
| CN107910511A (en) * | 2017-10-31 | 2018-04-13 | 多氟多（焦作）新能源科技有限公司 | A kind of stratiform lithium-rich anode material and preparation method thereof, lithium ion battery |
| CN109167039A (en) * | 2018-08-27 | 2019-01-08 | 山东理工大学 | The method of microstage nucleocapsid tertiary cathode material is received in a kind of preparation of low-temperature self-propagating method |
| CN110364703A (en) * | 2019-06-11 | 2019-10-22 | 浙江吉利控股集团有限公司 | A kind of composite material and preparation method thereof, anode, battery and preparation method thereof |
| CN110364703B (en) * | 2019-06-11 | 2021-02-26 | 浙江吉利控股集团有限公司 | Composite material preparation method, battery anode, battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105336932B (en) | 2018-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105336932B (en) | Preparation method of nickel cobalt lithium manganate and lithium-rich composite material | |
| CN105742622A (en) | Olivine-structured LiMPO<4> surface modification layered lithium-rich manganese-based positive electrode material and preparation method therefor | |
| CN104362333B (en) | A kind of lithium ion battery preparation method of spherical lithium-rich anode material | |
| CN103236512A (en) | Ceramic diaphragm and application of same to lithium ion battery | |
| CN102790209B (en) | Positive pole material of lithium ion battery and preparation method thereof | |
| CN106299282B (en) | Nitrogen-doped carbon nanotube sulfur composite material and preparation method thereof | |
| CN105244492A (en) | Cathode material for boracic lithium ion battery and preparation method thereof | |
| CN105428637A (en) | Lithium ion battery, positive electrode material of lithium ion battery and preparation method for positive electrode material | |
| CN107394190A (en) | The preparation method of the spherical lithium-rich manganese-based anode material of high-tap density | |
| CN107732193A (en) | It is a kind of using solid lithium battery of the nickelic positive electrode of core shell structure and preparation method thereof | |
| CN104091941B (en) | A kind of lithium-rich manganese-based Layered Lithium cell positive material and preparation method thereof | |
| CN105280910A (en) | Phosphorus-contained lithium ion battery positive electrode material and preparation method therefor | |
| CN110233261A (en) | A kind of preparation method and lithium ion battery of monocrystalline ternary anode material of lithium battery | |
| CN102275890A (en) | Microwave-assisted synthesis method of nanometer lithium iron phosphate | |
| CN106340621A (en) | Ferric negative electrode material for lithium battery and preparation method thereof | |
| CN105826568A (en) | Lithium-rich positive electrode material with hypoxic metallic oxide coating layer structure, preparation method and application | |
| CN104766969B (en) | Method for preparing cathode material of lithium ion battery | |
| CN104009221B (en) | Method for preparing positive electrode material rich in lithium via sol-gel self-propagating combustion method | |
| CN103413945A (en) | Manufacturing method of positive material for lithium ion battery | |
| CN108847481A (en) | A kind of preparation and application of the porous manganese sesquioxide managnic oxide cube negative electrode material of high performance lithium ion battery carbon coating | |
| CN107834063A (en) | A kind of monocrystalline type one-dimentional structure lithium-rich manganese-based anode material and preparation method thereof | |
| CN103390751A (en) | Method of preparing lithium battery vanadate positive materials by utilizing hydrothermal method | |
| CN110438557A (en) | A kind of preparation method of sharpening monocrystalline high-voltage spinel nickel lithium manganate cathode material | |
| CN103326021B (en) | The preparation method of lithium iron phosphate cathode material | |
| CN104347873B (en) | Preparation method of sphere-like lithium ion battery positive pole material lithium iron phosphate (LiFePO4) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |