CN107342402A - One kind prepares LiNi1/3Co1/3Mn1/3O2The method of tertiary cathode material - Google Patents
One kind prepares LiNi1/3Co1/3Mn1/3O2The method of tertiary cathode material Download PDFInfo
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- CN107342402A CN107342402A CN201710414860.3A CN201710414860A CN107342402A CN 107342402 A CN107342402 A CN 107342402A CN 201710414860 A CN201710414860 A CN 201710414860A CN 107342402 A CN107342402 A CN 107342402A
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- 239000010406 cathode material Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 13
- 229910016104 LiNi1 Inorganic materials 0.000 title description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 238000007873 sieving Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 6
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- 238000009413 insulation Methods 0.000 claims abstract description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 6
- 150000002696 manganese Chemical class 0.000 claims abstract description 6
- 150000002815 nickel Chemical class 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims description 15
- 229910013716 LiNi Inorganic materials 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 229910001437 manganese ion Inorganic materials 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 2
- 239000008367 deionised water Substances 0.000 claims 2
- 229910021641 deionized water Inorganic materials 0.000 claims 2
- 229910001868 water Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000975 co-precipitation Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 23
- 239000003643 water by type Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 230000004087 circulation Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 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
- H01M4/364—Composites as mixtures
-
- 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
Abstract
The present invention provides one kind and prepares LiNi1/3Co1/3Mn1/3O2The method of tertiary cathode material, specifically include and the mixed solution of nickel salt, cobalt salt, manganese salt is added drop-wise in NaOH solution, and add ammoniacal liquor as complexing agent, stirring, insulation reaction 10 12 hours, obtains black suspension, stands, filters, washs, is dried to obtain presoma；By presoma and Li2CO3After using absolute ethyl alcohol as medium ball milling 46 hours, dry, sintered 36 hours at 400 500 DEG C, 10 14 hours, sieving are then sintered at 850 950 DEG C, obtains LiNi1/3Co1/3Mn1/ 3O2Tertiary cathode material.Compared to traditional coprecipitation, the preparation method used in the present invention need not be passed through nitrogen, and greatly reduce production cost；The preparation method used in the present invention is not required to the strict pH value for controlling reaction system during driving body before the synthesis, i.e., is not required to adjust pH value by being continuously added into ammoniacal liquor during driving body before the synthesis.
Description
Technical field
The present invention relates to a kind of easy and effective preparation high-performance LiNi1/3Co1/3Mn1/3O2The method of tertiary cathode material, category
In field of electrochemical power source.
Background technology
Since Ohzuku and Makimura in 2001 proposes LiNi first1/3Co1/3Mn1/3O2Ternary material can be used as lithium from
Since sub- cell positive material, the material just receives the extensive concern of people.LiNi1/3Co1/3Mn1/3O2Combine LiCoO2、
LiNiO2、LiMnO2The advantages of three kinds of stratified materials, Co can reduce cation mixing, stabilizing material stratiform structure, and Ni can be carried
High material capacity, Mn can not only reduce material cost, can also improve the safety and stability of material.Therefore, LiNi1/ 3Co1/3Mn1/3O2Tertiary cathode material has a variety of advantages such as specific capacity is high, cycle performance and heat endurance are good, cost is low, is one
The preferable anode material for lithium-ion batteries of kind.Numerous studies show that the synthetic method of material has important shadow to chemical property
Ring, because the preparation technology of material decides the cation mixing of ternary material, particle diameter and pattern etc..So far, it is a variety of
Various synthetic method has been successfully applied to LiNi1/3Co1/3Mn1/3O2The synthesis of ternary material, including hydro-thermal method, solid phase method,
Sol-gel process, spray drying process, coprecipitation etc..Wherein, coprecipitation is because it can control the crystallization of presoma
Journey, the pattern of particle and size and be considered as one of optimal synthetic method.It is but traditional used in synthesis of ternary material
Coprecipitation is stricter to technological requirement, such as：Need constantly to be passed through nitrogen or argon gas, the pH value of strict control reaction system
Deng.These conditions can undoubtedly increase the difficulty and cost of ternary material production.And during the body of drive before the synthesis of the invention not
The pH value of strict control reaction system is needed, presoma is directly synthesized in air atmosphere, and be prepared by the presoma
The LiNi of electrochemical performance1/3Co1/3Mn1/3O2Tertiary cathode material, it enormously simplify the production technology of ternary material.
The content of the invention
It is an object of the invention to provide a kind of LiNi prepared using straightforward procedure1/3Co1/3Mn1/3O2Tertiary cathode material
Material, involved LiNi1/3Co1/3Mn1/3O2Its synthesis material of tertiary cathode material is lithium salts（Li2CO3）, Ni salt（NiSO4·
6H2O）, Co salt（CoSO4·7H2O）, Mn salt（MnSO4·H2O）.
Described lithium salts, nickel salt, cobalt salt, the mol ratio of manganese salt are 1.03-1.12:0.333:0.333:0.333.
Described lithium salts, nickel salt, cobalt salt, the purity of manganese salt are all higher than 98 %.
Simple synthesis LiNi of the present invention1/3Co1/3Mn1/3O2The method of tertiary cathode material has following advantage：（1）
Compared to traditional coprecipitation, the preparation method used in the present invention need not be passed through nitrogen, and production operation is easier, and greatly
Reduce production cost greatly；（2）The preparation method used in the present invention is not required to strict control reaction during driving body before the synthesis
The pH value of system, i.e., it is not required to adjust pH value by being continuously added into ammoniacal liquor during driving body before the synthesis, makes synthesis technique more
Simply.
Another object of the present invention is to provide a kind of simple and effective preparation high-performance LiNi1/3Co1/3Mn1/3O2Ternary
The method of positive electrode.Lithium salts after the presoma synthesized in atmosphere is dried with excess mixes, and carries out high temperature sintering and obtains
The LiNi of electrochemical performance1/3Co1/3Mn1/3O2Tertiary cathode material.
Specifically preparation method is：
The well mixed solution containing nickel ion, cobalt ions, manganese ion is added drop-wise in NaOH solution,（Uniform stirring is simultaneously incubated
12 hours）Obtain the suspension of black.After suspension is stood into 6-8 hours, filtering, washing, dry, obtain presoma.By before
Drive body and Li2CO3The ball milling 4-6 hours in anhydrous ethanol medium, dry, sintering 3-6 is small at 400-500 DEG C in air atmosphere
When, 10-14 hours are then sintered at 850-950 DEG C, after cooling, grinding sieving, obtain LiNi1/3Co1/3Mn1/3O2Ternary is just
Pole material.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of sample：（a）Comparative example,（b）Embodiment 1,（c）Embodiment 2,（d）Embodiment 3.
Fig. 2 is embodiment 2 and the chemical property figure of the sample of comparative example 1：（a）Charging and discharging curve,（b）Cycle performance is bent
Line.
Embodiment
Below by the description of embodiment, substantive distinguishing features of the invention and advantage is expanded on further.For convenience of description, it is first
First comparative example is described, embodiment is then described again, compares therewith, shows the effect of the present invention.
Comparative example 1
By 1.7515 g NiSO4·6H2O、1.8731 g CoSO4·7H2O、1.1266 g MnSO4·H2O is with mol ratio 1：1：
1 is dissolved in 80 mL deionized waters successively, and stirring is completely dissolved it in 30 minutes, while 1.6109 g NaOH are added into 80
In mL deionized waters.Then, the mixed solution containing nickel ion, cobalt ions, manganese ion is added drop-wise in NaOH solution, and adds 15
ML concentration is 3.35 mol L-1Ammoniacal liquor as complexing agent, with 400 r min-1Rotating speed be stirred, in reaction system
Nitrogen is filled with as protective gas, insulation reaction 12 hours at 50-55 DEG C, obtains pink suspension, stands 6-8 hours
After filter, washing for several times, in 90 DEG C of baking ovens dry 9 hours, obtain presoma.In presoma（1.8 g）It is middle to add 0.7265
g Li2CO3, using absolute ethyl alcohol as medium ball milling 6 hours after, dry, and after being sintered 5 hours at 450 DEG C again at 900 DEG C
Sintering 12 hours, cooling, sieving, obtains LiNi1/3Co1/3Mn1/3O2Tertiary cathode material.By LiNi1/3Co1/3Mn1/3O2Ternary is just
Pole material and acetylene black, Kynoar（PVdF）It is 75 in mass ratio:15:10 are mixed into slurry, are coated on aluminium foil, pass through
Dry, rush film and LiNi is made in press mold1/3Co1/3Mn1/3O2Tertiary cathode material electrode slice.Using metallic lithium foil as to electrode,
Celgard 2400 is barrier film, 1M LiPF6/(EC+DMC) (1:1) it is electrolyte, is assembled into R2025 button cells and carries out perseverance
Charge-discharge test is flowed, voltage range is between 2.8-4.5 V.First discharge specific capacity of the material in 0.5 C is 182.7 mAh
g-1, its specific discharge capacity is 146.3 mAh g after 50 circulations-1。
Embodiment 1
By 1.7515 g NiSO4·6H2O、1.8731 g CoSO4·7H2O、1.1266 g MnSO4·H2O is with mol ratio 1:1:
1 is dissolved in 40 mL deionized waters successively, and stirring is completely dissolved it in 30 minutes, while 1.6109 g NaOH are added into 80
In mL deionized waters.Then, the mixed solution containing nickel ion, cobalt ions, manganese ion is added drop-wise in NaOH solution, and adds 15
ML concentration is 3.35 mol L-1Ammoniacal liquor as complexing agent, with 400 r min-1Rotating speed be stirred, at 50-55 DEG C
Insulation reaction 12 hours, black suspension is obtained, filtered after standing 6-8 hours, washing for several times, it is small to dry 9 in 90 DEG C of baking ovens
When, obtain presoma.In presoma（1.8 g）0.7265 g Li of middle addition2CO3, using absolute ethyl alcohol as medium ball milling 6 hours
Afterwards, dry, and sintered 12 hours at 900 DEG C again after being sintered 5 hours at 450 DEG C, cooling, sieving, obtain LiNi1/ 3Co1/3Mn1/3O2Tertiary cathode material.By LiNi1/3Co1/3Mn1/3O2Tertiary cathode material and acetylene black, Kynoar
（PVdF）It is 75 in mass ratio:15:10 are mixed into slurry, are coated on aluminium foil, by drying, rush film and LiNi is made in press mold1/ 3Co1/3Mn1/3O2Tertiary cathode material electrode slice.Using metallic lithium foil as to electrode, Celgard 2400 is barrier film, 1M LiPF6/
(EC+DMC) (1:1) it is electrolyte, is assembled into R2025 button cells and carries out constant current charge-discharge test, voltage range is in 2.8-
Between 4.5 V.First discharge specific capacity of the ternary material in 0.5 C is 189.2 mAh g-1, by 50 times circulation after its
Specific discharge capacity is 150.8 mAh g-1。
Embodiment 2
By 1.7515 g NiSO4·6H2O、1.8731 g CoSO4·7H2O、1.1266 g MnSO4·H2O is with mol ratio 1:1:
1 is dissolved in 80 mL deionized waters successively, and stirring is completely dissolved it in 30 minutes, while 1.6109 g NaOH are added into 80
In mL deionized waters.Then, the mixed solution containing nickel ion, cobalt ions, manganese ion is slowly dropped in NaOH solution, and added
It is 3.35 mol L to enter 15 mL concentration-1Ammoniacal liquor as complexing agent, be stirred with 400 r min-1 rotating speed, in 50-55
Insulation reaction 12 hours at DEG C, black suspension is obtained, filtered after standing 6-8 hours, washing for several times, is done in 90 DEG C of baking ovens
Dry 9 hours, obtain presoma.In presoma（1.8 g）0.7265 g Li of middle addition2CO3, using absolute ethyl alcohol as medium ball milling 6
After hour, dry, and sintered 12 hours at 900 DEG C again after being sintered 5 hours at 450 DEG C, cooling, sieving, obtained
LiNi1/3Co1/3Mn1/3O2Tertiary cathode material.By LiNi1/3Co1/3Mn1/3O2Tertiary cathode material and acetylene black, Kynoar
（PVdF）It is 75 in mass ratio:15:10 are mixed into slurry, are coated on aluminium foil, by drying, rush film and LiNi is made in press mold1/ 3Co1/3Mn1/3O2Tertiary cathode material electrode slice.Using metallic lithium foil as to electrode, Celgard 2400 is barrier film, 1M LiPF6/
(EC+DMC) (1:1) it is electrolyte, is assembled into R2025 button cells and carries out constant current charge-discharge test, voltage range is in 2.8-
Between 4.5 V.First discharge specific capacity of the ternary material in 0.5 C is 187.8 mAh g-1, by 50 times circulation after its
Specific discharge capacity is 160.2 mAh g-1。
Embodiment 3
By 1.7515 g NiSO4·6H2O、1.8731 g CoSO4·7H2O、1.1266 g MnSO4·H2O is with mol ratio 1:1:
1 is dissolved in 200 mL deionized waters successively, and stirring is completely dissolved it in 30 minutes, while 1.6109 g NaOH are added to
In 80 mL deionized waters.Then, the mixed solution containing nickel ion, cobalt ions, manganese ion is slowly dropped in NaOH solution,
And it is 3.35 mol L to add 15 mL concentration-1Ammoniacal liquor as complexing agent, be stirred with 400 r min-1 rotating speed,
Insulation reaction 12 hours at 50-55 DEG C, black suspension is obtained, filtered after standing 6-8 hours, washing for several times, is dried at 90 DEG C
Dried 9 hours in case, obtain presoma.In presoma（1.8 g）0.7265 g Li of middle addition2CO3, using absolute ethyl alcohol as medium
After ball milling 6 hours, dry, and sintered 12 hours at 900 DEG C again after being sintered 5 hours at 450 DEG C, cooling, sieving, obtained
LiNi1/3Co1/3Mn1/3O2Tertiary cathode material.By LiNi1/3Co1/3Mn1/3O2Tertiary cathode material and acetylene black, Kynoar
（PVdF）It is 75 in mass ratio:15:10 are mixed into slurry, are coated on aluminium foil, by drying, rush film and LiNi is made in press mold1/ 3Co1/3Mn1/3O2Tertiary cathode material electrode slice.Using metallic lithium foil as to electrode, Celgard 2400 is barrier film, 1M LiPF6/
(EC+DMC) (1:1) it is electrolyte, is assembled into R2025 button cells and carries out constant current charge-discharge test, voltage range is in 2.8-
Between 4.5 V.First discharge specific capacity of the ternary material in 0.5 C is 195.3mAh g-1, it is put after 50 circulations
Electric specific capacity is 160.1 mAh g-1。
Claims (4)
1. one kind prepares LiNi1/3Co1/3Mn1/3O2The method of tertiary cathode material, it is characterised in that comprise the following steps：
(1) nickel salt, cobalt salt, manganese salt are added in deionized water, stir 0.5-1 hours, be completely dissolved it, obtaining concentration is
0.1-0.5 mol L-1Mixed solution, while by NaOH dissolving in deionized water, it is 0.1-0.3 mol L to obtain concentration-1
NaOH solution；
（2）To be added drop-wise to concentration be 0.1-0.3 mol L to mixed solution containing nickel ion, cobalt ions, manganese ion in will be above-mentioned-1's
In NaOH solution, and it is 3.30-3.70 mol L to add concentration-1Ammoniacal liquor as complexing agent, with 300-500r min-1Turn
Speed is stirred, the insulation reaction 10-12 hours at 50-55 DEG C, obtains black suspension, is filtered, is washed after standing 6-8 hours
Wash, and 7-10 hours are dried at 90 DEG C, obtain presoma；
（3）By presoma and Li2CO3After using absolute ethyl alcohol as medium ball milling 4-6 hours, dry, and the 400- in air atmosphere
3-6 hours are sintered at 500 DEG C, 10-14 hours, sieving are then sintered at 850-950 DEG C, obtains LiNi1/3Co1/3Mn1/3O2Three
First positive electrode.
2. the preparation high-performance LiNi described in claim 11/3Co1/3Mn1/3O2The method of tertiary cathode material, it is characterised in that
Described lithium salts is Li2CO3Or LiOH；Ni salt is NiSO4·6H2O；Co salt is CoSO4·7H2O；Mn salt is MnSO4·H2O。
3. the preparation high-performance LiNi described in claim 11/3Co1/3Mn1/3O2The method of tertiary cathode material, it is characterised in that
Lithium salts, nickel salt, cobalt salt, the mol ratio of manganese salt are 1.01-1.15：0.333：0.333：0.333.
4. the preparation high-performance LiNi described in claim 11/3Co1/3Mn1/3O2The method of tertiary cathode material, it is characterised in that
Lithium salts, nickel salt, cobalt salt, the purity of manganese salt are all higher than 98 %.
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| CN201710414860.3A CN107342402B (en) | 2017-06-05 | 2017-06-05 | Preparation of LiNi1/3Co1/3Mn1/3O2Method for preparing ternary cathode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108172818A (en) * | 2017-12-18 | 2018-06-15 | 佛山市德方纳米科技有限公司 | The method that inert free gas protects synthesis of ternary presoma |
| CN113782722A (en) * | 2021-08-31 | 2021-12-10 | 深圳市泽塔电源系统有限公司 | Preparation process of spherical lithium manganate cathode material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102723475A (en) * | 2012-06-06 | 2012-10-10 | 株洲泰和高科技有限公司 | Preparation method of ternary layered lithium-ion battery anode material |
| CN103117380A (en) * | 2013-01-31 | 2013-05-22 | 中信大锰矿业有限责任公司 | Preparation method of manganese Li-NiCoMn ternary material for lithium ion battery |
| CN104319388A (en) * | 2014-09-19 | 2015-01-28 | 青岛乾运高科新材料股份有限公司 | Preparation method of spherical ternary cathode material |
| CN106006762A (en) * | 2016-05-18 | 2016-10-12 | 西北师范大学 | Preparation of pedal-layered Ni-Co-Mn ternary material precursor and application of precursor as cathode material for lithium ion cell |
| CN106159251A (en) * | 2015-03-31 | 2016-11-23 | 河南科隆新能源有限公司 | One kind monocrystalline lithium battery tertiary cathode material and preparation method thereof |
-
2017
- 2017-06-05 CN CN201710414860.3A patent/CN107342402B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102723475A (en) * | 2012-06-06 | 2012-10-10 | 株洲泰和高科技有限公司 | Preparation method of ternary layered lithium-ion battery anode material |
| CN103117380A (en) * | 2013-01-31 | 2013-05-22 | 中信大锰矿业有限责任公司 | Preparation method of manganese Li-NiCoMn ternary material for lithium ion battery |
| CN104319388A (en) * | 2014-09-19 | 2015-01-28 | 青岛乾运高科新材料股份有限公司 | Preparation method of spherical ternary cathode material |
| CN106159251A (en) * | 2015-03-31 | 2016-11-23 | 河南科隆新能源有限公司 | One kind monocrystalline lithium battery tertiary cathode material and preparation method thereof |
| CN106006762A (en) * | 2016-05-18 | 2016-10-12 | 西北师范大学 | Preparation of pedal-layered Ni-Co-Mn ternary material precursor and application of precursor as cathode material for lithium ion cell |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108172818A (en) * | 2017-12-18 | 2018-06-15 | 佛山市德方纳米科技有限公司 | The method that inert free gas protects synthesis of ternary presoma |
| CN108172818B (en) * | 2017-12-18 | 2020-12-18 | 佛山市德方纳米科技有限公司 | Method for synthesizing ternary precursor without inert gas protection |
| CN113782722A (en) * | 2021-08-31 | 2021-12-10 | 深圳市泽塔电源系统有限公司 | Preparation process of spherical lithium manganate cathode material |
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