CN104934594A - Coating modified nickel-cobalt binary material, and preparation method and application of material - Google Patents
Coating modified nickel-cobalt binary material, and preparation method and application of material Download PDFInfo
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- CN104934594A CN104934594A CN201510208962.0A CN201510208962A CN104934594A CN 104934594 A CN104934594 A CN 104934594A CN 201510208962 A CN201510208962 A CN 201510208962A CN 104934594 A CN104934594 A CN 104934594A
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- nickel cobalt
- cobalt binary
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- sintering
- coating
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- 239000000463 material Substances 0.000 title claims abstract description 204
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical class [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000011248 coating agent Substances 0.000 title claims abstract description 42
- 238000000576 coating method Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011247 coating layer Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 44
- 230000004048 modification Effects 0.000 claims description 34
- 238000012986 modification Methods 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 238000000975 co-precipitation Methods 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910013716 LiNi Inorganic materials 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 238000007599 discharging Methods 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 25
- 239000000203 mixture Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 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 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910011695 LiNi0.7Co0.3O2 Inorganic materials 0.000 description 1
- 229910015915 LiNi0.8Co0.2O2 Inorganic materials 0.000 description 1
- 229910016222 LiNi0.9Co0.1O2 Inorganic materials 0.000 description 1
- 229910017095 Ni0.6Mn0.2Co0.2 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical class [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000013589 supplement 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
- H01M4/52—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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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 provides a coating modified nickel-cobalt binary material, and a preparation method and an application of the material. The material comprises a core area and a coating layer, wherein the coating layer coats the surface of a core area material; the core area material is a nickel-cobalt binary material; a coating layer material is LiN; N is Ni<o>Co<p>Mn<q>M'; o+p+q is equal to 1; a mole ratio of the mole number of Li to the sum of the mole numbers of metal elements contained in N is 1:(0.95-1.25); M' is O<2->, OH<->, CO3<2->, MO, MOH or MCO3; and M is one or more of Zr, Mg, Ti, La, Nb and Tb. After a battery is prepared with the coating modified nickel-cobalt binary material, the specific capacity of first charging and discharging can reach above 190mAh/g, and a capacity retention rate of the battery after 200 cycles is above 90%.
Description
Technical field
The present invention relates to field of lithium ion battery, especially, relate to a kind of coating modification nickel cobalt binary material, its preparation method and application thereof.
Background technology
In recent years, new-energy automobile is developed rapidly, and especially Development of Electric Vehicles is comparatively rapid, in order to adapt to the development need of electric automobile, lithium-ion-power cell is had higher requirement, particularly also more comes also high to the requirement of anode material for lithium-ion batteries.Nickel cobalt-based binary material, modified lithium manganate, LiFePO4 and ternary material are developed rapidly, and are progressively applied in lithium-ion-power cell field.
Because nickel cobalt-based binary material charging/discharging voltage is high, specific energy is high, is one of the most promising lithium ion power battery cathode material, but due to this material circulation less stable, limits the large-scale application of this material in electric automobile.Having report more is at present the chemical property being improved nickel cobalt binary material by doping, for at nickel cobalt binary material Surface coating other materials, prior art is as disclosed a kind of preparation method wrapping the nickel cobalt binary material of Al in CN201210292760.5, the method, by improving existing dry method is coated, adopts the nickel cobalt binary material of wet-layer preparation Surface coating Al.With simplification of flowsheet, be convenient to control reaction, thus reach the object improving Al distributing homogeneity and homogeneity of product in nickel brill binary material, thus improve the electric performance stablity of the battery that resulting materials prepares.Any explanation is not provided to the cyclical stability how improving existing nickel cobalt binary material.And the charge/discharge capacity of nickel cobalt binary material after coated Al reduces.
Summary of the invention
The present invention aims to provide and a kind ofly realizes coating modification nickel cobalt binary material that matrix and coating concentration gradient change, its preparation method and application thereof, to solve the technical problem that in prior art, nickel cobalt binary material cyclical stability is poor.
According to an aspect of the present invention, provide a kind of coating modification nickel cobalt binary material, comprise core space and coating layer, described coating layer is coated on the material surface of core space, and core space is nickel cobalt binary material; Coating layer material therefor is LiN, and wherein N is Ni
oco
pmn
qin the molal quantity of M ', o+p+q=1, Li and N, the mol ratio of contained metallic element molal quantity summation is 1:0.95 ~ 1.25, and M ' is O
2-, OH
-, CO
3 2-, MO, MOH or MCO
3, wherein M is one or more in Zr, Mg, Ti, La, Nb, Tb.
Further, in Li and N, the mol ratio of contained metallic element molal quantity summation is 1:1.05 ~ 1.1.
Further, in Li and N, the mol ratio of contained metallic element molal quantity summation is 1:1.1.
Further, total volume of coating layer material is 0.01 ~ 20wt.% of core space material.
Further, total volume of coating layer material is 0.3 ~ 15wt.% of core space material.
Further, the D of coating modification nickel cobalt binary material
50it is 3 ~ 25 μm; The D of coating layer material
50it is 0.01 ~ 5 μm; The volume of M ' accounts for the 0.01 ~ 10wt.% of material N.
Additionally provide a kind of above-mentioned application of coating modification nickel cobalt binary material in lithium ion battery according to a further aspect in the invention.
Additionally provide a kind of above-mentioned coating modification nickel cobalt binary material preparation method according to a further aspect in the invention, comprise the following steps: after being mixed with coating layer material by core space material, obtain coating modification nickel cobalt binary material through coated sintering; Coated sintering condition is at 300 ~ 800 DEG C, and sinter 3 ~ 20 hours, the throughput in sintering process is 2 ~ 20m
3/ hour.
Further, core space material obtains according to the following steps: a) by LiNi
xco
yo
2stoichiometric proportion mixing nickel salt and cobalt salt obtain nickel cobalt mixed liquor, complexing agent, nickel cobalt mixed liquor and alkali lye are pumped in liquid at the bottom of pure water simultaneously, and continue to pass into inert gas, carry out coprecipitation reaction and obtain nickel cobalt binary presoma, wherein x+y=1; B) by nickel cobalt binary presoma and the mole of lithium salts by Li element: the mol ratio that Ni and Co mole neutralizes is obtain core space material after carrying out core sintering after 1:0.95 ~ 1.25 mix.
Further, coprecipitation reaction condition is: at 30 ~ 85 DEG C, speed of agitator is 300 ~ 800rpm, and the pH value of reaction system is 10.0 ~ 12.0, and gas intake is 0.5 ~ 3.0m
3/ hour; Concentration of metal ions total in coprecipitation reaction solution is 0.5 ~ 3.5mol/L; The condition of core sintering step is at 500 ~ 1200 DEG C, and sinter 5 ~ 40 hours, in sintering process, throughput is 2 ~ 30m
3/ hour.
The present invention has following beneficial effect:
Modified Nickel cobalt binary material provided by the invention, using unmodified nickel cobalt binary material as core space, is the coating layer of material with LiN in its surface setting.Wherein N is Ni
oco
pmn
qin M ', o+p+q=1, Li and N, the mol ratio of contained metallic element molal quantity summation is 1:0.95 ~ 1.25, and M ' is O
2-, OH
-, CO
3 2-, MO, MOH or MCO
3, wherein M is one or more in Zr, Mg, Ti, La, Nb, Tb.With LiNi
oco
pmn
qm ' is clad material, the nickel cobalt binary material on this material and core space surface can be made to interpenetrate fusion, nickel cobalt concentration gradient transition zone is formed on core space nickel cobalt binary material surface, utilize this concentration gradient transition region, cycle performance and the cyclical stability of gained nickel cobalt binary material can be improved.By arranging this concentration gradient transition region, also can realize the mutual supplement with each other's advantages between core space nickel cobalt binary material and coating layer material, every premium properties of coating layer material is embodied on core space material.Give full play to the effect of coating layer material, stabilized the structure of material, improve the chemical properties such as the capacity of gained coating modification nickel cobalt binary material, cycle performance and application security.After making battery with coating modification nickel cobalt binary material, first charge-discharge specific capacity can reach more than 190mAh/g, through 200 cycle battery capability retentions more than 90%.
Coating modification nickel cobalt binary material provided by the invention is used for, in field of lithium ion battery, improving capacity, the specific energy of gained lithium ion battery, improving cyclical stability and application security.
The preparation method of coating modification nickel cobalt binary material provided by the invention is by being formed at nickel cobalt binary material Surface coating with LiNi
oco
pmn
qthe coating layer that M ' is material, can improve the chemical property of resulting materials, reduces the generation of heterotypic material.
Except object described above, feature and advantage, the present invention also has other object, feature and advantage.Below with reference to figure, the present invention is further detailed explanation.
Accompanying drawing explanation
The accompanying drawing forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Gained nickel cobalt binary positive material electron microscope scanning result figure when Fig. 1 is not coated; And
Fig. 2 is the binary positive material electron microscope scanning result figure of the preferred embodiment of the present invention.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are described in detail, but the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
If do not specialize, the conventional means that technological means used in embodiment is well known to those skilled in the art.
The percentage sign " % " related to herein, if not specified, refers to mass percent; But the percentage of solution, unless otherwise specified, refers in solution 100m1 containing solute some grams; Percentage between liquid, refers to the ratio of capacity 20 DEG C time.
Nickel cobalt binary material molecular formula is LiNi herein
xco
yo
2, wherein x+y=1.The not coated other materials in its surface, other metallic elements but can adulterate in its inside.This material also can be commercially available nickel cobalt binary material.
The present invention, using unmodified nickel cobalt binary material as core space, is the coating layer of material with LiN in its surface setting.Wherein N is Ni
oco
pmn
qin the molal quantity of M ', o+p+q=1, Li and N, the mol ratio of contained metallic element molal quantity summation is 1:0.95 ~ 1.25, and M ' is O
2-, OH
-, C
3o
2-, MO, MOH or MCO
3, wherein M is one or more in Zr, Mg, Ti, La, Nb, Tb.With LiNi
oco
pmn
qm ' is clad material, the nickel cobalt binary material on this material and core space surface can be made to interpenetrate fusion, nickel cobalt concentration gradient transition zone is formed on core space nickel cobalt binary material surface, utilize this concentration gradient transition region, cycle performance and the cyclical stability of gained nickel cobalt binary material can be improved.After making battery with coating modification nickel cobalt binary material, first charge-discharge specific capacity can reach more than 190mAh/g, through 200 cycle battery capability retentions more than 90%.
Preferred M ' is O
2-or OH now cycle performance reach optimum.When M ' is CO
3 2-, MO time, the preparation method of this clad material and M ' are O
2-or OH
-shi Xiangtong.When M ' is MO, MOH or MCO
3, wherein M is one or more in Zr, Mg, Ti, La, Nb, Tb.Now the preparation method of coating layer material is with reference to method disclosed in embodiment 1 in CN201410508982.5.
Preferably, in Li and N, the mol ratio of contained metallic element molal quantity summation is 1:1.05 ~ 1.1.In the coating layer material that this ratio prepares, better can merge with core space material, form more reasonably nickel cobalt element concentration gradient conversion, avoid the excessive coating layer material character caused of concentration gradient cannot produce the problem appearance of beneficial effect to core space material character.Preferred, in Li and N, the mol ratio of contained metallic element molal quantity summation is 1:1.1.Now the properties of resulting materials reaches optimum.
The volume of preferred M ' accounts for the 0.01 ~ 10wt.% of material N.The coating layer material cyclical stability obtained by this doping is better.
Preferably, total volume of coating layer is 0.01 ~ 20wt.% of core space material.Too much or very few coating layer material not only can not form stable nickel cobalt element concentration gradient district, makes it give play to synergy.
Preferred, total volume of coating layer material is 0.3 ~ 15wt.% of core space material.Carry out protecting doping the properties of the nickel cobalt concentration gradient zones formed of adulterating can better be shown outward in this ratio, ensure that the original properties just had of core space material can realize simultaneously.
The D of coating modification nickel cobalt binary material
50it is 3 ~ 25 μm.Gained, after coating modification process, has higher tap density, when being conducive to for the preparation of battery, obtains good performance.
Another aspect of the present invention additionally provides the application of a kind of above-mentioned coating modification nickel cobalt binary material in lithium ion battery.This material uses as the positive electrode of lithium ion battery.This material can reach more than 190mAh/g, through 200 circulation volume conservation rates more than 90% for the preparation of the lithium ion battery first charge-discharge specific capacity obtained.Obviously the purposes of this material is not limited to this.Any needs have in the device of better cycle performance all can use this this material.
The method for coating that method for coating used can be that dry type is coated, wet type is coated or co-precipitation cladding process etc. is conventional.
Preferred the present invention additionally provides the preparation method of above-mentioned coating modification nickel cobalt binary material on the other hand, and the method comprises the following steps: obtain coating modification nickel cobalt binary material through coated sintering after being mixed with coating layer material by core space material; Coated sintering condition is at 300 ~ 800 DEG C, and sinter 3 ~ 20 hours, the throughput in sintering process is 2 ~ 20m
3/ hour.Carry out with this understanding sintering can improve coating layer material and core space material interpenetrate the degree of depth, be conducive to obtaining the Modified Nickel cobalt binary material with better cyclical stability.
Preferred core space material obtains according to the following steps:
A) by LiNi
xco
yo
2stoichiometric proportion mixing nickel salt and cobalt salt obtain nickel cobalt mixed liquor, complexing agent, nickel cobalt mixed liquor and alkali lye are pumped in liquid at the bottom of pure water simultaneously, and continue to pass into inert gas, carry out coprecipitation reaction and obtain nickel cobalt binary presoma, wherein x+y=1;
Carry out reacting under this condition first generating nucleus, be then grown to required sphere material, control the above-mentioned condition of reaction system, the D of gained sphere material product can be regulated and controled
50.
Preferred coprecipitation reaction condition is: at 30 ~ 85 DEG C, speed of agitator is 300 ~ 800rpm, and the pH value of reaction system is 10.0 ~ 12.0, and gas intake is 0.5 ~ 3.0m
3/ hour; Concentration of metal ions total in coprecipitation reaction solution is 0.5 ~ 3.5mol/L.Carry out the tap density that coprecipitation reaction can improve gained presoma with this understanding.
B) by nickel cobalt binary presoma and the mole of lithium salts by Li element: the mol ratio of Ni and Co mole summation is obtain core space material after sintering after 1:0.95 ~ 1.25 mix.
The condition of core sintering step is at 500 ~ 1200 DEG C, and sinter 5 ~ 40 hours, in sintering process, throughput is 2 ~ 30m
3/ hour.Sinter with this understanding, every chemical property of gained core space material can be improved, make it after coated, better chemical property can be had.
In order to improve the chemical property of resulting materials, the D of preferred coating layer material therefor
50be 0.01 ~ 5 μm, the depth & wideth that the coating layer material under this particle diameter infiltrates in core space material is higher, forms stable concentration gradient district.
Be below specific targets process, above non-detailed portion is determined with reference to following content.
A, nickel cobalt binary material (LiNi
xco
yo
2, wherein x+y=1) preparation:
1. be end liquid with pure water in reactor, add complexing agent and alkali lye regulates end liquid pH value to be 10.0 ~ 12.0, and continue to pass into inert protective gas in reactor, gas intake is 0.5 ~ 3.0m
3/ hour;
2. the preparation of nickel cobalt binary precursor: nickel salt is become mixed aqueous solution with salt solubility, mixing concentration of metal ions total in rear solution controls between 0.5 ~ 3.5mol/L, complex liquid, alkali lye continuous also stream together with nickel cobalt mixed aqueous solution is pumped in reactor, coprecipitation reaction is there is at 30 ~ 85 DEG C, control speed of agitator is 300 ~ 800rpm, control the pH value of reaction system between 10.0 ~ 12.0, and pass into inert gas continuously, gas intake is 0.5 ~ 3.0m
3/ hour, after reaction, feed liquid is flowed out continuously by the top overfall of reactor and enters in aging reactor, and feed liquid, through centrifuge and vacuum drier drying, obtains the compound of spherical nickel-cobalt binary precursor-nickel cobalt;
3. batch mixing: the compound of spherical nickel-cobalt 2. and LITHIUM BATTERY lithium source substance are mixed according to certain ratio, mixed method is wet mixed or dry type mixing.Wherein Li:(Ni+Co) mol ratio be 0.95 ~ 1.25, mixing apparatus does not limit, as dry-mixed machine or batch mixer etc.;
4. sintering processes: the material after 3. processing carries out sintering processes, sintering takes the different warm area sintering of multisection type, sintering main temperature controls between 500 ~ 1200 DEG C, main warm area sintering time is 5 ~ 40 hours, need the gas passed into be air or oxygen in sintering process, throughput control range is 2 ~ 30m
3/ hour, by the material after sintering through broken, pulverize, sieve, the PROCESS FOR TREATMENT such as deironing, obtain required nickel cobalt binary;
B, coated process: the nickel cobalt binary in steps A is carried out coated, clad material be N material (NioCopMnqM ', wherein o+p+q=1) and the mixture of LITHIUM BATTERY lithium source substance, wherein, in Li and N, the mol ratio of contained metallic element molal quantity summation is 0.95 ~ 1.25, and total volume of clad material is 0.01 ~ 20wt.% of nickel cobalt binary;
C, sintering processes: the material after B process carries out sintering experiment, sintering takes the different warm area sintering of multisection type, and sintering main temperature controls between 300 ~ 800 DEG C, and main warm area sintering time is 3 ~ 20 hours, need in sintering process to pass into air or oxygen, throughput control range is 2 ~ 20m
3/ hour, by the material after sintering through broken, pulverize, sieve, the PROCESS FOR TREATMENT such as deironing, obtain required nickel cobalt-based binary anode material for lithium-ion batteries.
Nickel source material in steps A can be selected from one or more mixture of nickelous sulfate, nickel chloride, nickel nitrate.
Cobalt source material in steps A can be selected from one or more mixture of cobaltous sulfate, cobalt chloride, cobalt nitrate.
Complexing agent in steps A can be selected from one or more the mixture of ammoniacal liquor, ammonium chloride, ammonium sulfate, ammonium nitrate, EDTA.
Alkali lye in steps A can be selected from one or more mixture of NaOH, sodium carbonate, sodium acid carbonate.
Lithium source substance in steps A and B can be one or more the mixture in lithium hydroxide, lithium carbonate, lithium oxalate.
In reaction system, continue the inert protective gas that passes in steps A can for the one in helium, nitrogen, argon gas, and as preferably, the inert protective gas continuing to pass in steps A in reaction system generally elects nitrogen as.
Embodiment
In following examples, material used and instrument are commercially available.Coated process is if any not detailed part below, please refer to the encapsulation steps in CN201410325663.0 in embodiment and operating parameter thereof.
Embodiment 1
(1) using pure water as end liquid, temperature is set as 50 DEG C, control speed of agitator is 500rpm, the sodium hydroxide solution of the ammonium sulfate and 30wt.% that add 15wt.% regulates the acidity of end liquid in reactor, pH value is 11.5 ~ 11.6, continue in reaction system to pass into nitrogen, intake is 2.5m
3/ hour;
(2) by nickelous sulfate and cobalt chloride in molar ratio 4:1 be dissolved into mixed aqueous solution, after mixing, in solution, total concentration of metal ions is 2.5mol/L;
(3) sodium hydroxide solution of 30wt.%, the ammonium sulfate of 15wt.% continuous also stream together with mixed Ni cobalt liquor is pumped in reactor, controlling reacting liquid temperature is 50 DEG C, control mixing speed is 500rpm, and the pH value controlling reaction system is 11.5 ~ 11.6
(4) reaction generates nucleus, and is grown to sphere material, and after reaction, the overfall Continuous Flow of feed liquid through reactor top enters in aging reactor, through centrifuge and vacuum drying chamber drying, obtains spherical nickel-cobalt hydroxide.The pH value of the water after centrifuge washing controls between 7.2 ~ 8.2, and it is 90 ~ 100 DEG C that vacuum drying chamber temperature controls;
(5) by spherical nickel-cobalt hydroxide in (4) and battery-level lithium carbonate according to Li:(Ni+Co) mol ratio be that 1:1.05 prepares burden, and fully mix in dry-mixed machine, then material after mixing is carried out sintering processes, sintering main temperature is 800 DEG C, the sintering time of main warm area is 15 hours, pass into air in sintering process, the throughput of air is 25m
3/ hour, by the material after sintering through broken, pulverize, sieve, the PROCESS FOR TREATMENT such as deironing, obtain required nickel cobalt binary material, its molecular formula is LiNi
0.8co
0.2o
2;
(6) material in step (5) is carried out dry type coated, coated material used is Ni
0.6mn
0.2co
0.2the mixture of O and battery-level lithium carbonate, wherein the mol ratio of Li and metallic element Ni, Co, Mn molal quantity summation is 1.1, and total volume of clad material accounts for the 3.0wt.% of nickel cobalt binary;
(7) material after coated for step (6) is carried out sintering experiment, sintering main temperature is 600 DEG C, and the sintering time of main warm area is 10 hours, passes into air in sintering process, and the throughput of air is 15m
3/ hour, by the material after sintering through broken, pulverize, sieve, the PROCESS FOR TREATMENT such as deironing, obtain required nickel cobalt-based binary finished product.
Embodiment 2
(1) using pure water as end liquid, temperature is set as 70 DEG C, and control speed of agitator is 300rpm, the sodium carbonate liquor of the EDTA solution and 10wt.% that add 5wt.% regulates the acidity of end liquid in reactor, pH value is 10.0 ~ 10.1, continues to pass into nitrogen in reaction system, and intake is 2.0m
3/ hour;
(2) by nickelous sulfate and cobaltous sulfate in molar ratio 7:3 be dissolved into mixed aqueous solution, after mixing, in solution, total concentration of metal ions is 2.0mol/L;
(3) the EDTA solution of the sodium carbonate liquor of 10wt.%, 5wt.% continuous also stream together with mixed Ni cobalt liquor is pumped in reactor, controlling reacting liquid temperature is 70 DEG C, control mixing speed is 300rpm, and the pH value controlling reaction system is 10.0 ~ 10.1
(4) reaction generates nucleus, and is grown to sphere material, and after reaction, the overfall Continuous Flow of feed liquid through reactor top enters in aging reactor, through centrifuge and vacuum drying chamber drying, obtains spherical nickel-cobalt carbonated.The pH value of the water after centrifuge washing controls between 7.2 ~ 8.2, and it is 90 ~ 100 DEG C that vacuum drying chamber temperature controls;
(5) by spherical nickel-cobalt carbonated in (4) and battery-level lithium carbonate according to Li:(Ni+Co) mol ratio be that 1:1.02 prepares burden, and mix fully in dry-mixed machine, then material after mixing is carried out sintering processes, sintering main temperature is 700 DEG C, the sintering time of main warm area is 20 hours, pass into air in sintering process, the throughput of air is 20m
3/ hour, by the material after sintering through broken, pulverize, sieve, the PROCESS FOR TREATMENT such as deironing, obtain required nickel cobalt binary material, its molecular formula is LiNi
0.7co
0.3o
2;
(6) material in step (5) is carried out dry type coated, coated material used is Ni
0.2mn
0.5co
0.3(OH)
2with the mixture of battery-level lithium carbonate, wherein the mol ratio of Li and metallic element Ni, Co, Mn molal quantity summation is 1.05, and total volume of clad material accounts for the 10.0wt.% of nickel cobalt binary;
(7) material after coated for step (6) is carried out sintering experiment, sintering main temperature is 500 DEG C, and the sintering time of main warm area is 12 hours, passes into air in sintering process, and the throughput of air is 15m
3/ hour, by the material after sintering through broken, pulverize, sieve, the PROCESS FOR TREATMENT such as deironing, obtain required nickel cobalt-based binary finished product.
Embodiment 3
(1) using pure water as end liquid, temperature is set as 40 DEG C, control speed of agitator is 600rpm, the sodium hydroxide solution of the ammoniacal liquor and 20wt.% that add 15wt.% concentration regulates the acidity of end liquid in reactor, pH value is 10.5 ~ 10.6, continue in reaction system to pass into nitrogen, intake is 1.0m3/ hour;
(2) by nickelous sulfate and cobaltous sulfate in molar ratio 9:1 be dissolved into mixed aqueous solution, after mixing, in solution, total concentration of metal ions is 3.0mol/L;
(3) sodium hydroxide solution of 20wt.%, the ammoniacal liquor of 15wt.% continuous also stream together with mixed Ni cobalt liquor is pumped in reactor, controlling reacting liquid temperature is 40 DEG C, control mixing speed is 600rpm, and the pH value controlling reaction system is 10.5 ~ 10.6;
(4) reaction generates nucleus, and is grown to sphere material, and the overfall Continuous Flow of reacted feed liquid through reactor top enters in aging reactor, through centrifuge and vacuum drying chamber drying, obtains spherical nickel-cobalt hydroxide.The pH value of the water after centrifuge washing controls between 7.2 ~ 8.2, and it is 90 ~ 100 DEG C that vacuum drying chamber temperature controls;
(5) by spherical nickel-cobalt hydroxide in (4) and LITHIUM BATTERY lithium hydroxide according to Li:(Ni+Co) mol ratio be that 1:1.04 prepares burden, and mix fully in dry-mixed machine, then material after mixing is carried out sintering processes, sintering main temperature is 1100 DEG C, the sintering time of main warm area is 10 hours, pass into air in sintering process, the throughput of air is 35m
3/ hour, by the material after sintering through broken, pulverize, sieve, the PROCESS FOR TREATMENT such as deironing, obtain required nickel cobalt binary material, its molecular formula is LiNi
0.9co
0.1o
2;
(6) material in step (5) is carried out wet type coated, adopt spirit solvent, coated material used is Ni
0.4mn
0.4co
0.3the mixture of O and LITHIUM BATTERY lithium hydroxide, wherein the mol ratio of Li and metallic element Ni, Co, Mn molal quantity summation is 1.10, and total volume of clad material accounts for the 15.0wt.% of nickel cobalt binary;
(7) material after coated for step (6) is carried out sintering experiment, sintering main temperature is 700 DEG C, and the sintering time of main warm area is 8 hours, passes into air in sintering process, and the throughput of air is 5m
3/ hour, by the material after sintering through broken, pulverize, sieve, the PROCESS FOR TREATMENT such as deironing, obtain required nickel cobalt-based binary finished product.
Embodiment 4
Be with the difference of embodiment 1: in coating layer material therefor, in Li and N, the mol ratio of contained metallic element molal quantity summation is 1:0.95.
Embodiment 5
Be with the difference of embodiment 1: in coating layer material therefor, in Li and N, the mol ratio of contained metallic element molal quantity summation is 1:1.25, and total volume of coating layer material is the 0.01wt.% of core space material, the D of coating layer material
50it is 5 μm; The volume of M ' accounts for the 0.01wt.% of material N.
Embodiment 6
Be with the difference of embodiment 1: total volume of coating layer material is the 20wt.% of core space material, the D of coating layer material
50be 0.01 μm, the volume of M ' accounts for the 10wt.% of material N.
Embodiment 7
Be with the difference of embodiment 1: M ' is MO, wherein M is Zr.Now the preparation method of coating layer material is with reference to method disclosed in embodiment 1 in CN201410508982.5.
Embodiment 8
Be with the difference of embodiment 1: when M ' is MOH, wherein M is Mg and Ti.Now the preparation method of coating layer material is with reference to method disclosed in embodiment 1 in CN201410508982.5.
Coating modification nickel cobalt binary material obtained in embodiment 1 ~ 8 is prepared battery by method disclosed in CN200710124332.The battery that each embodiment resulting materials is obtained, mean first charging and discharging capacity >=190mAh/g, through 200 circulation volume conservation rate >=90%.As can be seen here, by coating layer material on nickel cobalt binary material Surface coating, can effectively obtain the positive electrode with nickel cobalt element concentration gradient, thus improve the cycle performance of nickel cobalt binary material.
Gained coating modification nickel cobalt binary material see Fig. 2, the D of resulting materials
50it is 3 ~ 25 μm.Fig. 1 is the nickel cobalt binary material of uncoated modification, contrasted from Fig. 1 and 2, after coated, coating layer material is coated on nickel cobalt binary material surface, and form the structure with gradient concentration, core space and coated district have complementary advantages, and can improve the chemical property such as capacity and cyclical stability of the cobalt of nickel shown in Fig. 1 binary material.。
These are only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a coating modification nickel cobalt binary material, comprises core space and coating layer, it is characterized in that, described coating layer is coated on the material surface of described core space, and described core space is nickel cobalt binary material;
Described coating layer material therefor is LiN, and wherein N is Ni
oco
pmn
qin the molal quantity of M ', o+p+q=1, Li and N, the mol ratio of contained metallic element molal quantity summation is 1:0.95 ~ 1.25, and M ' is O
2-, OH
-, CO
3 2-, MO, MOH or MCO
3, wherein M is one or more in Zr, Mg, Ti, La, Nb, Tb.
2. coating modification nickel cobalt binary material according to claim 1, is characterized in that, in Li and N, the mol ratio of contained metallic element molal quantity summation is 1:1.05 ~ 1.1.
3. coating modification nickel cobalt binary material according to claim 2, is characterized in that, in Li and N, the mol ratio of contained metallic element molal quantity summation is 1:1.1.
4. the coating modification nickel cobalt binary material according to any one of claims 1 to 3, is characterized in that, total volume of described coating layer material is 0.01 ~ 20wt.% of described core space material.
5. coating modification nickel cobalt binary material according to claim 4, is characterized in that, total volume of described coating layer material is 0.3 ~ 15wt.% of described core space material.
6. coating modification nickel cobalt binary material according to claim 5, is characterized in that, the D of described coating modification nickel cobalt binary material
50it is 3 ~ 25 μm; The D of coating layer material
50it is 0.01 ~ 5 μm; The volume of M ' accounts for the 0.01 ~ 10wt.% of material N.
7. the application of coating modification nickel cobalt binary material in lithium ion battery according to any one of claim 1 ~ 6.
8. the coating modification nickel cobalt binary material preparation method according to any one of claim 1 ~ 6, is characterized in that, comprise the following steps: obtain described coating modification nickel cobalt binary material through coated sintering after being mixed with coating layer material by core space material; Described coated sintering condition is at 300 ~ 800 DEG C, and sinter 3 ~ 20 hours, the throughput in sintering process is 2 ~ 20m
3/ hour.
9. coating modification nickel cobalt binary material preparation method according to claim 8, it is characterized in that, described core space material obtains according to the following steps:
A) by LiNi
xco
yo
2stoichiometric proportion mixing nickel salt and cobalt salt obtain nickel cobalt mixed liquor, complexing agent, described nickel cobalt mixed liquor and alkali lye are pumped in liquid at the bottom of pure water simultaneously, and continue to pass into inert gas, carry out coprecipitation reaction and obtain nickel cobalt binary presoma, wherein x+y=1;
B) by described nickel cobalt binary presoma and the mole of lithium salts by Li element: the mol ratio of Ni and Co mole summation is obtain described core space material after carrying out core sintering after 1:0.95 ~ 1.25 mix.
10. coating modification nickel cobalt binary material preparation method according to claim 8 or claim 9, it is characterized in that, described coprecipitation reaction condition is: at 30 ~ 85 DEG C, speed of agitator is 300 ~ 800rpm, and the pH value of reaction system is 10.0 ~ 12.0, and gas intake is 0.5 ~ 3.0m
3/ hour; Concentration of metal ions total in described coprecipitation reaction solution is 0.5 ~ 3.5mol/L; The condition of described core sintering step is at 500 ~ 1200 DEG C, and sinter 5 ~ 40 hours, in sintering process, throughput is 2 ~ 30m
3/ hour.
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