CN104103825A - Rich lithium ternary lithium ion battery cathode materials and production method thereof - Google Patents
Rich lithium ternary lithium ion battery cathode materials and production method thereof Download PDFInfo
- Publication number
- CN104103825A CN104103825A CN201410382840.9A CN201410382840A CN104103825A CN 104103825 A CN104103825 A CN 104103825A CN 201410382840 A CN201410382840 A CN 201410382840A CN 104103825 A CN104103825 A CN 104103825A
- Authority
- CN
- China
- Prior art keywords
- lithium
- rich
- anode material
- ion batteries
- rich lithium
- 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.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000010406 cathode material Substances 0.000 title abstract 7
- 238000004519 manufacturing process Methods 0.000 title abstract 6
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract 3
- 238000003756 stirring Methods 0.000 claims abstract 2
- 238000005406 washing Methods 0.000 claims abstract 2
- 239000010405 anode material Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003483 aging Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 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 4
- 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 4
- 150000002696 manganese Chemical class 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000008187 granular material Substances 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
- 235000007079 manganese sulphate Nutrition 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
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 claims 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 229940011182 cobalt acetate Drugs 0.000 claims 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 229910052808 lithium carbonate Inorganic materials 0.000 claims 1
- 229940071125 manganese acetate Drugs 0.000 claims 1
- 239000011565 manganese chloride Substances 0.000 claims 1
- 235000002867 manganese chloride Nutrition 0.000 claims 1
- 229940099607 manganese chloride Drugs 0.000 claims 1
- 229940099596 manganese sulfate Drugs 0.000 claims 1
- 239000011702 manganese sulphate Substances 0.000 claims 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims 1
- 229940078494 nickel acetate Drugs 0.000 claims 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000011206 ternary composite Substances 0.000 abstract description 3
- -1 transition metal salt Chemical class 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 2
- 229910016536 Ni0.2Co0.1Mn0.7(OH)2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910016533 Ni0.2Co0.2Mn0.6(OH)2 Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses rich lithium ternary lithium ion battery cathode materials and a production method thereof. The production method comprises enabling transition metal salt to be dissolved in the water to obtain a solution which is mixed through different metal ions; enabling precipitant to be dissolved in the water to obtain a precipitant solution; enabling a complexing agent to be mixed with the water to obtain a complexing agent solution; enabling the three solutions to be mixed slowly under the protection and stirring of the inert gas; obtaining a precursor of ternary composite cathode materials through growth, aging, filtration, washing and drying of obtained precipitates; performing sintering after the precursor is fully mixed with the lithium salt to obtain the ternary composite cathode materials, wherein the formula as follows. According to the production method of the rich lithium ternary lithium ion battery cathode materials, the shape of the rich lithium ternary lithium ion battery cathode materials can be effectively controlled and accordingly the electrochemical performance of the rich lithium ternary lithium ion battery cathode materials which serve as a cathode lithium ion battery is improved and meanwhile the production process is free of pollution and accordingly the production method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of rich lithium ternary anode material for lithium-ion batteries and preparation method thereof, particularly rich lithium nickel cobalt manganese tri compound positive electrode and preparation method thereof.
Background technology
Since first commercialization lithium battery (claiming again lithium ion battery) of Sony in 1991 comes out, lithium battery is subject to the extensive concern of academia and industrial quarters.Than lead-acid battery, nickel-cadmium cell, Ni-MH battery, it remains the most promising in the secondary chemical sources of electric energy that commercialization uses so far, and its advantage comprises: specific energy is high, have extended cycle life, memory-less effect etc.Exactly because these advantages, lithium ion battery has been used to the electrical source of power of electric automobile and hybrid-electric car.
In lithium ion battery, developing excellent positive electrode is one of key technology of development high power lithium battery.Wherein, LiCoO
2as most widely used positive electrode, because it has α-NaFeO
2two-dimensional layered structure, be suitable for Li embedding betwixt with deviate from; But because it is under the condition of overcharging, the stability of structure reduces, and the cost compare of Co is high simultaneously, becomes the development bottleneck of this material.LiMn
2o
4there is cubic spinel structure, due to its cheapness, stable and good electric conductivity, can finely avoid the danger such as burning, blast; But its maximum shortcoming is at high temperature, and capacity attenuation is very serious.And LiFePO
4there is olivine structural, and due to its excellent security performance, wider Applicable temperature and longer useful life, received very large concern, but its maximum shortcoming is that electronic conductivity is poor.
Be similar to LiCoO
2structure, after Co is replaced by Ni, Mn part, its structure still can keep original α-NaFeO
2two-dimensional layered structure, rich its capacity of lithium ternary anode material for lithium-ion batteries obtaining is about 2 times of left and right of cobalt acid lithium.This material combines LiCoO
2, LiMnO
2, LiNiO
2the advantage of three kinds of materials, has good fail safe, higher energy density, environmentally friendly, cheap etc., has wide market prospects.At present, on market, more common tri compound positive electrode has NCM-333, NCM-424, NCM-523, NCM-262, NCM-811 etc.
Summary of the invention
The object of the invention is in order to obtain a kind of novel tri compound positive electrode and preparation method thereof, its chemical formula is Li
1+m(Ni
xco
ymn
z) O
2, 0.15≤x≤0.3,0≤y≤0.3,0.4≤z≤1,0≤m≤0.3, x+y+z=1-m.To achieve these goals, the technical solution used in the present invention: a kind of preparation method of rich lithium ternary anode material for lithium-ion batteries: concrete steps are as follows:
1) nickel salt, cobalt salt and manganese salt are mixed, and be dissolved in deionized water.Complexing agent and precipitation reagent are dissolved in respectively in deionized water, and wherein the ratio of the amount of substance of complexing agent and the amount of total metal ion species is 2-6:1; The amount of substance of precipitation reagent is 2-4:1 with the ratio of the amount of total metal ion species;
2) under the protection of nitrogen atmosphere, mix above-mentioned three kinds of solution, and keep reacting liquid temperature at 40-80 ° of C, mixing speed is 200-1000rpm, control the pH of reactant liquor at 8-14, through outgrowth, ageing, filtration, the sediment obtaining washs with deionized water, under 80-100 ° of C environment, be dried afterwards, obtain the presoma of tri compound positive electrode;
3) by the presoma obtaining with lithium salts after ball milling mixes, carry out thermal sintering, obtain a kind of rich lithium tri compound positive electrode Li
1+m(Ni
xco
ymn
z) O
2, 0.15≤x≤0.3,0≤y≤0.3,0≤z≤1,0≤m≤0.3.Wherein, the ratio that adds the amount of substance of metal ion total in the amount of substance of lithium ion in lithium salts and the presoma of tri compound positive electrode is 1.5-1:1; When sintering, maintain the temperature at 400-1100 ° of C sintering 15-25 hour, obtain above-mentioned rich lithium ternary anode material for lithium-ion batteries.
Brief description of the drawings
Fig. 1 is obtained ternary material XRD figure;
Fig. 2 is obtained ternary material SEM figure;
Fig. 3 is the front 30 circle discharge capacity curves of obtained ternary material;
Fig. 4 is obtained ternary material first circle and the tenth circle charging and discharging curve.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is elaborated; but be not limited to this; every technical solution of the present invention is modified or is equal to replacement, and not departing from spirit and the category of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1
4.64 g nickelous sulfates, 1.55 g cobaltous sulfates and 9.06 g manganese sulfates are mixed, and be dissolved in 50 mL deionized waters.14 g KOH are dissolved in 50 mL deionized waters, ammoniacal liquor is diluted to 5 mol/L with deionized water.Under the protection of nitrogen atmosphere; mix above-mentioned three kinds of solution; and keep reacting liquid temperature at 60 ° of C; mixing speed is 400 rpm, controls the pH of reactant liquor at 11-12, through outgrowth, ageing, filtration; the sediment obtaining washs with deionized water; under 100 ° of C environment, be dried afterwards, obtain the presoma of tri compound positive electrode, chemical formula is Ni
0.3co
0.1mn
0.6(OH)
2.By the presoma obtaining with 3.6 g lithium hydroxides after ball milling mixes, 400 ° of C thermal sinterings 5 hours, then improve temperature to 1000 ° C sintering 20 hours, obtain the rich lithium ternary of one described in the present invention anode material for lithium-ion batteries.
Fig. 1 is the XRD figure of described material, and wherein cell parameter a is 2.8506, and cell parameter c is 14.2410; Near peak 2 θ=22 ° is the characteristic peak of rich lithium, peak (003) with the intensity rate at peak (104) up to 1.36; The appearance at (006), (102), (108), (110) these several groups of peaks simultaneously, has proved that this material is the nickel-cobalt-manganese ternary composite material of a rich lithium.Concrete testing result is summarized in following table:
Measure through EDX and AES-ICP, this rich lithium tri compound positive electrode consist of Li
1.15(Ni
0.26co
0.08mn
0.51) O
2.
Fig. 2 is morphology characterization above-mentioned material being carried out by SEM.From SEM result, the tri compound positive electrode major part obtaining is spherical in shape, and integral particle size is at 5 microns-500 microns, is specifically made up of the granule of 100 nanometer-5 micron, and granular size is homogeneous relatively.
Key in herein summary of the invention and describe paragraph.Described material is assembled into button cell to be tested.Wherein negative material is lithium metal, and electrolyte is EC-DEC or EC-DMC, and barrier film is Celgard2501 or Celgard3500, and tester is Arbin.Fig. 3 is the front 30 circle discharge capacity curves of obtained rich lithium ternary material: as we can see from the figure, through the discharge process of 30 circles, battery capacity still remains on 195 mAh/g left and right, and cycle performance is very good.Fig. 4 is obtained ternary material first circle and the tenth circle charging and discharging curve: by the activation to this material, the efficiency for charge-discharge of first circle reaches 80% left and right.Through the circulation of 10 circles, the electric discharge average voltage of this material maintains 3.7V left and right, has very good cyclical stability.
Embodiment 2
2.42 g nickel nitrates, 1.21 g cobalt nitrates and 8.19 g manganese nitrates are mixed, and be dissolved in 100 mL deionized waters.16 g KOH are dissolved in 100 mL deionized waters, ammoniacal liquor is diluted to 5 mol/L with deionized water.Under the protection of nitrogen atmosphere; mix above-mentioned three kinds of solution; and keep reacting liquid temperature at 50 ° of C; mixing speed is 600 rpm, controls the pH of reactant liquor at 11-12, through outgrowth, ageing, filtration; the sediment obtaining washs with deionized water; under 100 ° of C environment, be dried afterwards, obtain the presoma of tri compound positive electrode, chemical formula is Ni
0.2co
0.1mn
0.7(OH)
2.By the presoma obtaining with 5.5 g lithium carbonates after ball milling mixes, 600 ° of C thermal sinterings 5 hours, then improve temperature to 1100 ° C sintering 15 hours, obtain the rich lithium ternary of one described in the present invention anode material for lithium-ion batteries.Through identical characterizing method, obtain with embodiment 1 in the similar crystal morphology of rich lithium ternary anode material for lithium-ion batteries and the crystal parameter of gained, its chemical composition is Li
1.20(Ni
0.16co
0.08mn
0.56) O
2.Described material is assembled into button cell and similarly characterizes, prove the discharge process through 30 circles, battery capacity is in 200 mAh/g left and right, and the efficiency for charge-discharge of first circle is in 75% left and right.Through the circulation of 10 circles, the electric discharge average voltage of this material maintains 3.7V left and right, has good cycle performance.
Embodiment 3
2.42 g nickel nitrates, 1.21 g cobalt nitrates and 8.19 g manganese nitrates are mixed, and be dissolved in 100 mL deionized waters.16 g KOH are dissolved in 100 mL deionized waters, ammoniacal liquor is diluted to 3 mol/L with deionized water.Under the protection of nitrogen atmosphere; mix above-mentioned three kinds of solution; and keep reacting liquid temperature at 55 ° of C; mixing speed is 700 rpm, controls the pH of reactant liquor at 11-12, through outgrowth, ageing, filtration; the sediment obtaining washs with deionized water; under 100 ° of C environment, be dried afterwards, obtain the presoma of tri compound positive electrode, chemical formula is Ni
0.2co
0.1mn
0.7(OH)
2.By the presoma obtaining with 3.3 g lithium hydroxides after ball milling mixes, 450 ° of C thermal sinterings 5 hours, then improve temperature to 900 ° C sintering 20 hours, obtain the rich lithium ternary of one described in the present invention anode material for lithium-ion batteries.Through identical characterizing method, obtain with embodiment 1 in the similar crystal morphology of rich lithium ternary anode material for lithium-ion batteries and the crystal parameter of gained, its chemical composition is Li
1.20(Ni
0.16co
0.08mn
0.56) O
2.Described material is assembled into button cell and similarly characterizes, prove the discharge process through 30 circles, battery capacity is in 190 mAh/g left and right, and the efficiency for charge-discharge of first circle is in 83% left and right.Through the circulation of 10 circles, the electric discharge average voltage of this material maintains 3.8V left and right, has good cycle performance.
Embodiment 4
2.42g nickel nitrate, 2.42 g cobalt nitrates and 7.02 g manganese nitrates are mixed, and be dissolved in 50 mL deionized waters.9.6 g LiOH are dissolved in 100 mL deionized waters, carbonic hydroammonium are made into the aqueous solution of 3 mol/L.Under the protection of nitrogen atmosphere; mix above-mentioned three kinds of solution; and keep reacting liquid temperature at 60 ° of C; mixing speed is 500 rpm, controls the pH of reactant liquor at 9-10, through outgrowth, ageing, filtration; the sediment obtaining washs with deionized water; under 100 ° of C environment, be dried afterwards, obtain the presoma of tri compound positive electrode, chemical formula is Ni
0.2co
0.2mn
0.6(OH)
2.By the presoma obtaining with 3.3 g lithium hydroxides after ball milling mixes, 500 ° of C thermal sinterings 5 hours, then improve temperature to 1100 ° C sintering 15 hours, obtain the rich lithium ternary of one described in the present invention anode material for lithium-ion batteries.Through identical characterizing method, obtain with embodiment 1 in the similar crystal morphology of rich lithium ternary anode material for lithium-ion batteries and the crystal parameter of gained, its chemical composition is Li
1.18(Ni
0.16co
0.16mn
0.50) O
2.Described material is assembled into button cell and similarly characterizes, prove the discharge process through 30 circles, battery capacity is in 190 mAh/g left and right, and the efficiency for charge-discharge of first circle is in 85% left and right.Through the circulation of 10 circles, the electric discharge average voltage of this material maintains 3.7V left and right, has good cycle performance.
Claims (14)
1. a rich lithium ternary anode material for lithium-ion batteries, is characterized in that: the chemical composition of described rich lithium ternary anode material for lithium-ion batteries is Li
1+m(Ni
xco
ymn
z) O
2, 0.15≤x≤0.3,0≤y≤0.3,0.4≤z≤1,0≤m≤0.3, x+y+z=1-m.
2. the preparation method of a kind of rich lithium ternary anode material for lithium-ion batteries as claimed in claim 1, is characterized in that comprising the following steps:
The nickel of solubility, cobalt and manganese salt are made into the aqueous solution of metal ion; Respectively precipitation reagent, complexing agent are made into the aqueous solution;
At the temperature of 40-80 ° of C, under stirring and inert gas shielding, the aqueous solution of metal ion, the precipitation reagent aqueous solution, complexing agent aqueous solution are mixed, obtain reactant liquor, control the pH value of reactant liquor between 8-14, through outgrowth, ageing, filtration, washing, dry, obtain the presoma of tri compound positive electrode;
After the presoma obtaining mixes with lithium salts, carry out thermal sintering, obtain a kind of rich lithium tri compound positive electrode Li
1+m(Ni
xco
ymn
z) O
2, 0.15≤x≤0.3,0≤y≤0.3,0.4≤z≤1,0≤m≤0.3, x+y+z=1-m.
3. the preparation method of a kind of rich lithium ternary anode material for lithium-ion batteries according to claim 2, is characterized in that: step 1) described in the nickel salt of solubility be at least one in nickel chloride, nickel oxalate, nickelous sulfate, nickel nitrate or nickel acetate; The cobalt salt of solubility is at least one in cobalt chloride, cobalt oxalate, cobaltous sulfate, cobalt nitrate or cobalt acetate; The manganese salt of solubility is at least one in manganese chloride, manganese oxalate, manganese sulfate, manganese nitrate or manganese acetate.
4. the preparation method of a kind of rich lithium ternary anode material for lithium-ion batteries according to claim 2, is characterized in that: step 1) described in precipitation reagent be at least one in potassium hydroxide, NaOH or lithium hydroxide; Step 1) described in complexing agent be at least one in ammoniacal liquor or carbonic hydroammonium.
5. the preparation method of a kind of rich lithium ternary anode material for lithium-ion batteries according to claim 2, is characterized in that: step 1) described in the concentration of amount of substance of slaine of solubility be 0.1-2 mol/L; The concentration of the amount of substance of precipitation reagent is 1-10 mol/L; The concentration of the amount of substance of complexing agent is 1-10 mol/L.
6. the preparation method of a kind of rich lithium ternary anode material for lithium-ion batteries according to claim 2, is characterized in that: step 2) in reaction remain on 40-80 ° of C; Inert gas is nitrogen or argon gas; Reactant liquor pH is controlled at 8-14; Mixing speed is 200-1000rpm; After having washed, remain on 80-100 ° of C dry.
7. the preparation method of a kind of rich lithium ternary anode material for lithium-ion batteries according to claim 2, is characterized in that: step 3) described in lithium salts be at least one in lithium hydroxide or lithium carbonate.
8. the preparation method of a kind of rich lithium ternary anode material for lithium-ion batteries according to claim 2, is characterized in that: step 3) described in add the amount of substance of metal ion total in the amount of substance of Li in lithium salts and the presoma of tri compound positive electrode ratio be 1.5-1:1.
9. the preparation method of a kind of rich lithium ternary anode material for lithium-ion batteries according to claim 2, is characterized in that: step 3) described in mixing refer to by ball milling and fully mix.
10. the preparation method of a kind of rich lithium ternary anode material for lithium-ion batteries according to claim 2, is characterized in that: step 3) described in thermal sintering refer at 400-1100 ° of C sintering 15-25 hour.
The preparation method of 11. a kind of rich lithium ternary anode material for lithium-ion batteries according to claim 2, it is characterized in that: the tri compound positive electrode major part obtaining is spherical in shape, integral particle size is at 5 microns-500 microns, is specifically made up of the granule of 100 nanometer-5 micron.
12. a kind of rich lithium ternary lithium ion cell positive materials claimed in claim 1 are in the application of preparing in lithium ion battery, electronic product energy storage, industrial electric power storage energy storage, electric automobile or electric bicycle power supply.
13. application according to claim 12, wherein electronic product is mobile phone, camera, notebook computer, panel computer.
14. application according to claim 12, wherein industrial electric power storage energy storage is wind energy, solar energy storage, stand-by power supply.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410382840.9A CN104103825A (en) | 2014-08-06 | 2014-08-06 | Rich lithium ternary lithium ion battery cathode materials and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410382840.9A CN104103825A (en) | 2014-08-06 | 2014-08-06 | Rich lithium ternary lithium ion battery cathode materials and production method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104103825A true CN104103825A (en) | 2014-10-15 |
Family
ID=51671780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410382840.9A Pending CN104103825A (en) | 2014-08-06 | 2014-08-06 | Rich lithium ternary lithium ion battery cathode materials and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104103825A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409721A (en) * | 2014-12-05 | 2015-03-11 | 上海空间电源研究所 | Lithium-rich ternary cathode material for lithium-ion battery and preparation method of lithium-rich ternary cathode material |
| CN104701524A (en) * | 2015-03-03 | 2015-06-10 | 中南大学 | Method for directly preparing nickel-cobalt-manganese ternary cathode material precursor from nickel electrolyte |
| CN104934591A (en) * | 2015-05-08 | 2015-09-23 | 天津理工大学 | High-volume-energy-density spherical Li-rich cathode material and preparing method of high-volume-energy-density spherical Li-rich cathode material |
| TWI781427B (en) * | 2020-07-28 | 2022-10-21 | 明志科技大學 | Preparation method of nickel-rich hydroxide precursor and nickel-rich cathode composite material using continuous Taylor flow reactor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101356671A (en) * | 2006-06-09 | 2009-01-28 | Agc清美化学股份有限公司 | Positive electrode active material for rechargeable battery with nonaqueous electrolyte, and method for manufacturing the same |
| CN102148373A (en) * | 2011-03-02 | 2011-08-10 | 中国科学院化学研究所 | Cathode material of lithium ion battery and preparation method thereof |
| US20110291043A1 (en) * | 2008-09-24 | 2011-12-01 | The Regents Of The University Of California | Aluminum Substituted Mixed Transition Metal Oxide Cathode Materials for Lithium Ion Batteries |
| CN103682311A (en) * | 2013-12-04 | 2014-03-26 | 浙江大学 | Preparation method of ternary composite cathode material of lithium ion battery |
-
2014
- 2014-08-06 CN CN201410382840.9A patent/CN104103825A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101356671A (en) * | 2006-06-09 | 2009-01-28 | Agc清美化学股份有限公司 | Positive electrode active material for rechargeable battery with nonaqueous electrolyte, and method for manufacturing the same |
| US20110291043A1 (en) * | 2008-09-24 | 2011-12-01 | The Regents Of The University Of California | Aluminum Substituted Mixed Transition Metal Oxide Cathode Materials for Lithium Ion Batteries |
| CN102148373A (en) * | 2011-03-02 | 2011-08-10 | 中国科学院化学研究所 | Cathode material of lithium ion battery and preparation method thereof |
| CN103682311A (en) * | 2013-12-04 | 2014-03-26 | 浙江大学 | Preparation method of ternary composite cathode material of lithium ion battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409721A (en) * | 2014-12-05 | 2015-03-11 | 上海空间电源研究所 | Lithium-rich ternary cathode material for lithium-ion battery and preparation method of lithium-rich ternary cathode material |
| CN104701524A (en) * | 2015-03-03 | 2015-06-10 | 中南大学 | Method for directly preparing nickel-cobalt-manganese ternary cathode material precursor from nickel electrolyte |
| CN104934591A (en) * | 2015-05-08 | 2015-09-23 | 天津理工大学 | High-volume-energy-density spherical Li-rich cathode material and preparing method of high-volume-energy-density spherical Li-rich cathode material |
| TWI781427B (en) * | 2020-07-28 | 2022-10-21 | 明志科技大學 | Preparation method of nickel-rich hydroxide precursor and nickel-rich cathode composite material using continuous Taylor flow reactor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109980219B (en) | Full-gradient nickel-cobalt-manganese positive electrode material, ruthenium oxide coating material and preparation method thereof | |
| CN104157831B (en) | Lithium-rich manganese-based composite positive pole of the spinel nickel LiMn2O4 of a kind of core shell structure, stratiform and preparation method thereof | |
| US20190386293A1 (en) | Ternary material and preparation method thereof, battery slurry, positive electrode and lithium battery | |
| CN103227323B (en) | Preparation method of positive pole material (spinel type lithium nickel manganese oxide) of high-voltage lithium ion battery | |
| CN106340638B (en) | A kind of high-rate lithium-rich manganese-based anode material of double layer hollow structure and preparation method thereof | |
| CN103762353B (en) | A kind of heterogeneous nucleocapsid structure high-capacity lithium ion battery electricity positive electrode with and preparation method thereof | |
| CN102983326B (en) | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method | |
| CN104852038A (en) | Preparation method of high-capacity quickly-chargeable/dischargeable lithium ion battery ternary anode material | |
| CN102437323A (en) | Anode material of lithium ion battery and preparation method thereof | |
| CN104241630B (en) | Lithium nickel cobalt manganate hollow sphere as well as preparation method and application thereof | |
| CN105576233A (en) | Nickel base trinary positive electrode material and preparation method thereof | |
| CN104638227A (en) | Method for modifying positive electrode material of lithium ion battery | |
| CN102569773B (en) | Anode material for lithium-ion secondary battery and preparation method thereof | |
| CN104835957B (en) | Preparation method of high-nickel ternary material used for lithium ion battery | |
| CN103413926B (en) | Preparation method of lithium nickel cobalt manganese oxide precursor | |
| CN103441263B (en) | The method of a kind of collosol and gel-solid sintering technology synthesis nickle cobalt lithium manganate | |
| CN102368547A (en) | Lithium ion battery and anode active material thereof | |
| CN105161693A (en) | High-cycle lithium ion battery multi-element anode material NCM and preparation method thereof | |
| CN106058238A (en) | Modified spherical nickel cobalt lithium manganate NCM622 anode material and preparation method thereof | |
| CN104037401A (en) | Nickel-cobalt-lithium manganate ternary anode material suitable for application under high voltage | |
| CN102655232A (en) | Preparation method of lithium manganese base-enriched ternary composite anode material | |
| CN104157844A (en) | High magnifying power lithium-rich manganese-based cathode material with nano/microstructure | |
| CN105280898A (en) | Vanadium-doped lithium nickel cobalt manganese oxide nanometer material and preparation method and application thereof | |
| CN103078099A (en) | Anode material for lithium ion cell and preparation method thereof | |
| CN104218241A (en) | Lithium ion battery anode lithium-rich material modification method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180528 Address after: 313100 No. 118 Nanzhuang Road, Changxing County Economic Development Zone, Huzhou, Zhejiang Applicant after: Zhejiang Lin Naixin Energy Co. Ltd. Address before: 211505 Jiangsu Zhongshan Nanjing science and Technology Park, Liuhe science and Technology Park, Zhongshan, science and Technology Park No. 9, Science Park, F2 3. Applicant before: Yu Yingchao |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141015 |
|
| RJ01 | Rejection of invention patent application after publication |