CN1870330A - Multicomponent oxide containing cobalt nickel and preparation and application thereof - Google Patents
Multicomponent oxide containing cobalt nickel and preparation and application thereof Download PDFInfo
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- CN1870330A CN1870330A CNA2005100210142A CN200510021014A CN1870330A CN 1870330 A CN1870330 A CN 1870330A CN A2005100210142 A CNA2005100210142 A CN A2005100210142A CN 200510021014 A CN200510021014 A CN 200510021014A CN 1870330 A CN1870330 A CN 1870330A
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- cobalt nickel
- component oxide
- contains cobalt
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- 238000002360 preparation method Methods 0.000 title claims description 29
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 title claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000000975 co-precipitation Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910018198 Ni—Co—M Inorganic materials 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- 239000011572 manganese Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 238000003483 aging Methods 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- -1 amine salt Chemical class 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 239000006183 anode active material Substances 0.000 claims description 5
- 239000002253 acid Substances 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
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- 239000000243 solution Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000007853 buffer solution Substances 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 37
- 238000012360 testing method Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000012545 processing Methods 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 6
- 229910013716 LiNi Inorganic materials 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 230000002950 deficient Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- QDWNJWYHGDYFOG-UHFFFAOYSA-N [N+](=O)(O)[O-].[Li] Chemical compound [N+](=O)(O)[O-].[Li] QDWNJWYHGDYFOG-UHFFFAOYSA-N 0.000 description 3
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentoxide Inorganic materials [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 229910018146 Ni—Co—Al—Mn Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical compound [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 244000050510 Cunninghamia lanceolata Species 0.000 description 1
- 229910002593 Fe-Ti Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910018058 Ni-Co-Al Inorganic materials 0.000 description 1
- 229910018144 Ni—Co—Al Inorganic materials 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Images
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
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A method for preparing multicomponent oxide containing Ni and Co includes preparing mixed ammonia complex solution by materials of Ni and Co as well as the other metal M in buffer solution; adding prepared ammonia complex solution and aqueous alkali slowly into reactor simultaneously to generate Ni-Co-M composite hydroxide by coprecipitation then obtaining forerunner after aging, separating, washing and drying; mix-grinding forerunner and lithium hydroxide to obtain final product of Lia(NibCoc) M1-b-cO2 after heat treatment.
Description
[technical field]
The present invention relates to the high energy electrochemical field, the multi-component oxide and preparation method thereof that is specifically related to contain cobalt nickel with and application in lithium rechargeable battery.
[background technology]
Lithium cobalt oxygen is with its good performance over past ten years, and as the specific capacity height, good cycle, processing behavior excellence etc. are always as the first-selection of commercial li-ion cell positive material, but cobalt is a rare metal, natural resources shortage, and supply falls short of demand in recent years, and price continues to soar.On the other hand, develop rapidly along with IT industry mobile communication electronic equipment and electric automobile, lithium ion battery is being proposed new requirement aspect high cycle performance, the high-energy-density, so, the research of anode material for lithium-ion batteries that with new forms of energy and new material technology is background seeks to substitute novel low cost, high-energy-density, environmental friendliness, long-life novel anode material of lithium cobalt oxygen also in the continuous new direction of developing.
At present, high nickel-base material is being studied, produced in the more existing manufacturers in home and abroad, domestic as auspicious auspicious, China fir Taxodiaceae skill of CITIC Guoan, Hunan etc., external as day written or printed documents village, SANYO GS, Korea S's three magnitudes, its production method all is mainly solid reaction process, solid reaction process is about to reaction mass to be mixed by machine mill, then with the process of its sintering.Outstanding advantage of this method promptly is that industrialization is simple, and the production technology cost is not high, and its shortcoming promptly is that the presoma material is difficult to mix, and the product component, performance heterogeneity, particularly reactive component that cause generation are more for a long time, and be all the more so.Material very easily freezes when slurrying, and it is short that slurry is deposited the time of not freezing; The pole piece compacted density is lower, and the pole piece of making is harder, crisp especially, easy fracture, thus make the volumetric specific energy of material lower, the processing behavior is poor.
[summary of the invention]
Deficiency at above-mentioned prior art exists the object of the present invention is to provide a kind of material granule size distribution even, the multi-component oxide Li that contains cobalt nickel that the volumetric specific energy of material is higher
a(Ni
bCo
c) M
1-b-cO
2
Another object of the present invention provides that a kind of preparation technology is simple, the multi-component oxide Li that contains cobalt nickel of strong operability
a(Ni
bCo
c) M
1-b-cO
2The preparation method, make its with the above-mentioned multi-component oxide that makes as positive electrode, it is long that the flowability of made slurry and good uniformity, slurry are deposited the time of freezing, the processing behavior that makes pole piece is good, can improve the cycle performance and the capacity retentivity of battery.
Realize the technical scheme of above-mentioned purpose:
A kind of multi-component oxide Li that contains cobalt nickel
a(Ni
bCo
c) M
1-b-cO
2(M is the metallic atom of at least a chosen from Fe (Fe), aluminium (Al), manganese (Mn), titanium (Ti), copper (Cu) and calcium (Ca) in the formula, a=0.97-1.07,0.3≤b＜1,0＜c≤0.5,0.8＜b+c＜1).
The multi-component oxide Li that contains cobalt nickel
a(Ni
bCo
c) M
1-b-cO
2The preparation method, may further comprise the steps:
(a) in cushioning liquid, preparation nickel, cobalt and other metal M are closed solution (Ni with the ammino that mixes of ammonia
bCo
cM
1-b-c) (NH
3)
n(0＜n≤6);
(b) will mix ammino and close solution (Ni
bCo
cM
1-b-c) (NH
3)
nAnd in the slow simultaneously adding reactor of aqueous slkali, co-precipitation generates the Ni-Co-M complex hydroxide, makes presoma after ageing, separation, washing, the drying;
(c) presoma that (b) step is made and lithium hydroxide or lithium salts carry out mix grinding, and
(d) mixture that makes behind the heat treatment mix grinding is removed adsorbed water and constitution water; And
(e) product of gained makes lithium composite xoide in the heat treatment step (d).
Described metal M salt is metal oxide or its slaine of at least a chosen from Fe (Fe), aluminium (Al), manganese (Mn), titanium (Ti), copper (Cu) and calcium (Ca).
Described cushioning liquid is made up of ammonia and amine salt or ammonia and weak acid are made into.
The pH of cushioning liquid is 8～11 in the described step (a).
The temperature of coprecipitation reaction is 40-80 ℃ in the described step (b), and the mixing speed of blender is 240-1000rpm during reaction, and the pH value of solution is 10-12 during reaction, and the time of coprecipitation reaction is 4-10 hour.
Heat treated temperature is 240-550 ℃ in the described step (d), and heat treatment period is 3-7 hour.
Heat treated temperature is 650-850 ℃ in the described step (e), and heat treatment period is 5-18 hour.
The above-mentioned application that contains the multi-component oxide of cobalt nickel as the positive electrode of lithium rechargeable battery.
A kind of lithium ion battery comprises positive plate, and the positive electrode active materials on the described positive plate contains the described multi-component oxide that contains cobalt nickel of claim 9.
Adopt technique scheme, in conjunction with the following embodiment that will describe in detail, otherwise effective technique effect of the present invention is: 1, a kind of multi-component oxide Li that contains cobalt nickel is provided
a(Ni
bCo
c) M
1-b-cO
2(M is at least a chosen from Fe (Fe) in the formula, the metallic atom of aluminium (Al), manganese (Mn), titanium (Ti), copper (Cu) and calcium (Ca), a=0.97-1.07,0.3≤b＜1,0＜c≤0.5,0.8＜b+c＜1), this multi-component oxide is as the lithium positive electrode active materials, and the processing behavior of the cycle performance of battery, capacity retentivity and pole piece all improves a lot than prior art.2, because preparation method of the present invention adopts coprecipitation reaction, each elemental constituent that has realized material mixes by atomic level, generate the ellipsoidal particle of uniform particle diameter, and be easy to separate, an elliposoidal similar particle that generates in the time of can obtaining to coprecipitation reaction behind washing precipitation, sintering, the material homogeneity is good.Shown in embodiment and Comparative Examples in the embodiment, show through the XRD test result: this active material is a layer structure, and crystalline form physically well develops, and does not have other impurity peaks appearance, and promptly the ion distribution of Can Zaing is in layered crystal structure; SEM test result display material particle size distribution is even, is the elliposoidal structure, and average grain diameter is at 5-16 μ m, and tap density is 2.15-2.35g/cm
3Employing contains the flowability and the good uniformity of the made slurry of multi-component oxide of cobalt nickel, and it is long that slurry is deposited the time of freezing, and the processing behavior that makes pole piece is good; Electrochemical property test shows: the processing behavior of the cycle performance of material, capacity retentivity and pole piece all improves a lot, and specific capacity also improves; 3, not only process is simple for this preparation method, and it is workable to have technology, produces good reproducibility, and characteristics such as product good uniformity are easy to realize industrialization, and cost is relatively low.
[description of drawings]
Fig. 1 is the X diffraction pattern (XRD) of the anode active material of lithium ion secondary battery of embodiment 1 preparation.
Fig. 2 is the sem photograph (SEM) of the anode active material of lithium ion secondary battery of embodiment 1 preparation.
Fig. 3 is the first charge-discharge curve chart of the anode active material of lithium ion secondary battery of embodiment 1 preparation.
Fig. 4 is the charge-discharge performance figure of the anode active material of lithium ion secondary battery of embodiment 1 preparation.
[embodiment]
The preparation method who contains the multi-component oxide of cobalt nickel, be earlier in the pH value is 8～11 ammoniacal liquor-amine salt or ammoniacal liquor-weak acid cushioning liquid, the complex solution that mixes of preparation nickel cobalt and metal M and ammonia, then slowly add in the reactor simultaneously and carry out coprecipitation reaction with alkali lye, wherein, the coprecipitation reaction time is 4-10 hour, reaction temperature is 40-80 ℃, mixing speed is 240-1000rpm, generate the Ni-Co-M complex hydroxide, ageing separates, washing Ni-Co-M complex hydroxide, it is even to make particle diameter, density is bigger, an elliposoidal Ni-Co-M complex hydroxide material of chemical property excellence; At baking temperature is that a dry Ni-Co-M complex hydroxide material carried out mix grinding with lithium hydroxide or lithium salts after 16-36 hour under 60-120 ℃ air atmosphere or the vacuum environment, and in 240-550 ℃ of this mixture of following heat treatment 3-7 hour; And then, promptly get the multi-component oxide that contains cobalt nickel in 650-850 ℃ of this mixture of following heat treatment 5-18 hour.
In the above-mentioned experimental condition, when dosing pH value is lower than 8, need adding more saline solution, is ammonium ion in the ammoniacal liquor and we will utilize, and the purpose of its adding just is used for balance pH value, on the other hand, and as more adding of amine salt into the more alkali lye of needs consumption; When the pH value was higher than 11, precipitation appearred when joining complex solution easily.The scope of synthesis condition (reaction time, temperature, pH value, mixing speed) and heat-treat condition is granularity and the density that is used for controlling the product particle, and in conjunction with cost consideration, if outside scope, may cause the physics of synthetic material, chemical property to worsen.Reaction time too short (＜4h) reaction not exclusively, overlong time (＞10h) reaction is finished, prolong the reaction time to have reduced production efficiency.Mixing speed slow excessively (＜240rpm), stir inhomogeneously, reaction is not exclusively; Mixing speed too fast (＞1000rpm), will make the material particle of generation meticulous, influence the structure of product.If temperature is lower than 650 ℃ during sintering, material meeting sintering is incomplete, and crystallization is imperfect, if be higher than 850 ℃, then for this material, its structure will be damaged.
Embodiment 1: positive electrode active materials LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2Preparation and performance structure test
Got nickel (Ni) in 0.75: 0.1 in molar ratio, the sulfate of cobalt (Co) amounts to 8.5 moles, and slowly to add the pH values of being prepared by ammoniacal liquor and sulfuric acid amine under continuous stirring condition be in 10 the cushioning liquid, make nickel cobalt ammino and close solution 10L, under continuous stirring state, with itself and 10L, 2.2M NaOH and 0.1M Al
2(SO4)
3Mixed aqueous solution slowly splash into simultaneously and fill the 7L aqueous solution and regulate in the reactor of its pH value to 11 with the pure NaOH solution of 2.2M, reaction temperature is 40 ℃, mixing speed is 400rpm.Isolate the Ni-Co-Al complex hydroxide after 6 hours, ageing after 2 hours with behind the distilled water washing several times in 80 ℃ of dryings 16 hours, grind, make presoma after sieving, be placed in the Based Intelligent Control Muffle furnace with manganese carbonate and 1: 0.053: 1.06 in molar ratio mix grinding of monohydrate lithium hydroxide (LiOHH2O) after accurately measuring its moisture content, in dry air, be warming up to 320 ℃ and constant temperature and carried out the heat treatment first time in 6 hours with 2 ℃/min, then be warming up to 750 ℃ and constant temperature and carried out clinkering in 16 hours with 2 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.
The structure of present embodiment products therefrom, pattern test result: XRD figure is composed as shown in Figure 1a, with LiCoO
2XRD figure spectrum similar, the peak of I003/I104 is strong than up to more than 1.9, structure peak 006 with 102 and peak 008 and 110 all trend towards the existence of independent peak, thereby can think that synthetic product has layer structure and the crystal formation growth is fine, structural integrity, defective is few.The SEM collection of illustrative plates shows that the grain shape of synthetic product is an elliposoidal, and size is than homogeneous, and average grain diameter is 5-16 μ m, and the tap density of powder is 2.19g/cm
3The chemical property of product is tested its button cell made from the little current tester of new prestige.The negative pole of button cell is a lithium metal, barrier film is a glass fiber filter paper, positive pole is made by synthetic product, the method for making of its positive plate is similar to macrocell pole piece method for making, be about to 92 parts of products of the present invention, 4 parts of conductive agents, 4 parts of binding agent PVdF and an amount of solvent NMP mixing stirring and make slurry, it is thick then it to be coated with the about 160um of single face on aluminium foil, oven dry, compacting into about 110um after, get the disk of the about 18mm of diameter with puncher, its vacuumize was assembled into 2430 model button cells in 8～12 hours in glove box.Lie prostrate with 0.1C constant current charge to 4.3, behind the 4.3V constant voltage charge, lie prostrate with 0.1C constant-current discharge to 2.75, the initial charge specific capacity that records positive electrode of the present invention is 196.2258mAh/g, and first discharge specific capacity is 167.2495mAh/g, and coulombic efficiency was 85.23% (as shown in Figure 3); The reversible specific capacity that circulates after 100 times is 160.2937mAh/g, and capability retention is 97.00%, electrochemistry cycle performance very excellent (as shown in Figure 4).The slurrying of pole piece, the processing behavior of filming are good, and slurry is placed after 48 hours and gelatin phenomenon all do not occurred, and the material phenomenon does not appear falling in the pole piece smooth surface of making.
Embodiment 2: positive electrode active materials LiNi
0.85Co
0.1Mn
0.02Ti
0.02Cu
0.01O
2Preparation and performance structure test
0.85: 0.1: 0.02 in molar ratio: 0.01 sulfate of getting nickel (Ni), cobalt (Co), manganese (Mn), copper (Cu) amounts to 9.8 moles, and slowly to add the pH values of being prepared by ammoniacal liquor and sulfuric acid amine under continuous stirring condition be in 9 the cushioning liquid, make nickel cobalt copper-manganese ammonia mixing complex solution 10L, under continuous stirring state, with itself and 10L, 2.2M the NaOH mixed aqueous solution slowly splashes into simultaneously and fills the 7L aqueous solution and regulate in the reactor of its pH value to 10 with the pure NaOH solution of 2.2M, reaction temperature is 50 ℃, and mixing speed is 600rpm.Isolate the Ni-Co-Mn-Cu complex hydroxide after 7 hours, ageing after 1 hour with behind the distilled water washing several times in 100 ℃ of dryings 10 hours, grind, make presoma after sieving, be placed in the Based Intelligent Control Muffle furnace with titanium dioxide and 1: 0.02: 0.53 in molar ratio mix grinding of lithium carbonate after accurately measuring its moisture content, in dry air, be warming up to 200 ℃ and constant temperature and carried out the heat treatment first time in 4 hours with 5 ℃/min, then be warming up to 800 ℃ and constant temperature and carried out clinkering in 12 hours with 2 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.
The structure of present embodiment products therefrom, pattern test result: the XRD figure spectrum is similar to the XRD figure spectrum of embodiment 1, the peak of I003/I104 is by force than up to more than 1.6, structure peak 006 and 102 and peak 008 and 110 all trend towards independent peak and exist, thereby can think that synthetic product has layer structure and crystal formation is grown fine, structural integrity, defective is few.The SEM collection of illustrative plates is similar to the SEM collection of illustrative plates of embodiment 1, shows that the grain shape of synthetic product is an elliposoidal, and size is than homogeneous, and average grain diameter is 6-12 μ m, and the tap density of powder is 2.24g/cm
3The chemical property of product is tested its button cell made from the little current tester of new prestige, and material initial charge specific capacity is 192.4837mAh/g, and first discharge specific capacity is 173.5134mAh/g, and coulombic efficiency is 90.14%; Circulating, capability retention is 98.13% after 100 times, and reversible capacity reaches 170.2687mAh/g, and the slurrying of pole piece, the processing behavior of filming are good, and slurry is placed after 48 hours and gelatin phenomenon all do not occurred, and the material phenomenon does not appear falling in the pole piece smooth surface of making.
Embodiment 3: positive electrode active materials LiNi
0.75Co
0.15Fe
0.03Ti
0.02Mn
0.05O
2Preparation and performance structure test
0.75: 0.15: 0.03 in molar ratio: the sulfate of getting nickel (Ni), cobalt (Co), iron (Fe), titanium (Ti), manganese (Mn) at 0.02: 0.05 amounts to 10 moles, and slowly to add the pH values of being prepared by ammoniacal liquor and boric acid under continuous stirring condition be in 8 the cushioning liquid, make and mix complex solution 10L, under continuous stirring state, with itself and 10L, 2.2M the NaOH mixed aqueous solution slowly splashes into simultaneously and fills the 7L aqueous solution and regulate in the reactor of its pH value to 10.5 with the pure NaOH solution of 2.2M, reaction temperature is 60 ℃, and mixing speed is 800rpm.Isolate the Ni-Co-Mn-Fe-Ti complex hydroxide after 9 hours, ageing after 3 hours with behind the distilled water washing several times in 60 ℃ of dryings 24 hours, make presoma after grinding, sieving, be placed in the Based Intelligent Control Muffle furnace with 1: 1.04 in molar ratio mix grinding of anhydrous nitric acid lithium after accurately measuring its moisture content, in dry air, be warming up to 500 ℃ and constant temperature and carried out the heat treatment first time in 3 hours with 5 ℃/min, then be warming up to 780 ℃ and constant temperature and carried out clinkering in 16 hours with 5 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.
The structure of present embodiment products therefrom, pattern test result: the XRD figure spectrum is similar (also with LiCoO to the XRD figure spectrum of embodiment 1
2XRD figure spectrum similar), the peak of I003/I104 is strong than being about 1.7, structure peak 006 with 102 and peak 008 and 110 all trend towards the existence of independent peak, thereby can think that synthetic product has layer structure and the crystal formation growth is fine, structural integrity, defective is few.The SEM collection of illustrative plates is similar to the SEM collection of illustrative plates of embodiment 1, and the SEM collection of illustrative plates shows that the grain shape of synthetic product is an elliposoidal, and size is than homogeneous, and average grain diameter is 4-13 μ m, and the tap density of powder is 2.26g/cm
3The chemical property of product is tested its button cell made from the little current tester of new prestige, and material initial charge specific capacity is 193.7749mAh/g, and first discharge specific capacity is 164.7483mAh/g, and coulombic efficiency is 85.02%; Circulating, capability retention is 96.47% after 100 times, and reversible capacity reaches 158.9327mAh/g, and the slurrying of pole piece, the processing behavior of filming are good, and slurry is placed after 48 hours and gelatin phenomenon all do not occurred, and the material phenomenon does not appear falling in the pole piece smooth surface of making.
Embodiment 4: positive electrode active materials LiNi
0.65Co
0.2Al
0.1Mn
0.05O
2Preparation and performance structure test:
0.65: 0.2: 0.1 in molar ratio: 0.05 got nickel (Ni), the sulfate of cobalt (Co), aluminium (Al), manganese (Mn) amounts to 10 moles, and slowly to add the pH values of being prepared by ammoniacal liquor and sulfuric acid amine under continuous stirring condition be in 8.5 the cushioning liquid, make the mixing ammino and close solution 10L, under continuous stirring state, with itself and 10L, 2.2M the NaOH aqueous solution slowly splashes into simultaneously and fills the 7L aqueous solution and regulate in the reactor of its pH value to 11.5 with the pure NaOH solution of 2.2M, reaction temperature is 70 ℃, and mixing speed is 300rpm.Isolate the Ni-Co-Al-Mn complex hydroxide after 5 hours, ageing after 4 hours with behind the distilled water washing several times in 120 ℃ of dryings 8 hours, make presoma after grinding, sieving, accurately measure monohydrate lithium hydroxide (LiOHH behind its moisture content
2O) 1: 1.07 in molar ratio mix grinding is placed in the Based Intelligent Control Muffle furnace, in dry air, be warming up to 400 ℃ and constant temperature and carried out the heat treatment first time in 6 hours with 2 ℃/min, then be warming up to 770 ℃ and constant temperature and carried out clinkering in 24 hours with 2 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.
The structure of present embodiment products therefrom, pattern test result: the XRD figure spectrum is similar (also with LiCoO to the XRD figure spectrum of embodiment 1
2XRD figure spectrum similar), the peak of I003/I104 is strong than being about 1.4, structure peak 006 with 102 and peak 008 and 110 all trend towards the existence of independent peak, thereby can think that synthetic product has layer structure and the crystal formation growth is fine, structural integrity, defective is few.The SEM collection of illustrative plates is similar to the SEM collection of illustrative plates of embodiment 1, shows that the grain shape of synthetic product is an elliposoidal, and size is than homogeneous, and average grain diameter is 4-18 μ m, and the tap density of powder is 2.17g/cm
3The chemical property of product is tested its button cell made from the little current tester of new prestige, and material initial charge specific capacity is 189.6044mAh/g, and first discharge specific capacity is 165.2592mAh/g, and coulombic efficiency is 87.16%; Circulating, capability retention is 96.13% after 100 times, and reversible capacity reaches 158.8637mAh/g, and the slurrying of pole piece, the processing behavior of filming are good, and slurry is placed after 48 hours and gelatin phenomenon all do not occurred, and the material phenomenon does not appear falling in the pole piece smooth surface of making.
Embodiment 5: positive electrode active materials LiNi
0.65Co
0.3Al
0.02Mn
0.01Cu
0.01Ca
0.01O
2Preparation and performance structure test
0.65: 0.3: 0.02 in molar ratio: get nickel (Ni) at 0.01: 0.01: 0.01, cobalt (Co), aluminium (Al), manganese (Mn), the sulfate of copper (Cu) and calcium (Ca) amounts to 10 moles, and slowly to add the pH values of being prepared by ammoniacal liquor and oxamide under continuous stirring condition be in 11 the cushioning liquid, make the mixing ammino and close solution 10L, under continuous stirring state, with itself and 10L, 2.2MNaOH the aqueous solution slowly splashes into simultaneously and fills the 7L aqueous solution and regulate in the reactor of its pH value to 11.0 with the pure NaOH solution of 2.2M, reaction temperature is 55 ℃, and mixing speed is 900rpm.Isolate the Ni-Co-Al-Mn-Cu-Ca complex hydroxide after 10 hours, ageing after 3 hours with behind the distilled water washing several times in 50 ℃ of dryings 30 hours, make presoma after grinding, sieving, 1: 1.07 in molar ratio mix grinding of anhydrous nitric acid lithium is placed in the Based Intelligent Control Muffle furnace after accurately measuring its moisture content, in dry air, be warming up to 550 ℃ and constant temperature and carried out the heat treatment first time in 8 hours with 2 ℃/min, then be warming up to 770 ℃ and constant temperature and carried out clinkering in 20 hours with 2 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.
The structure of present embodiment products therefrom, pattern test result: the XRD figure spectrum is similar to the XRD figure spectrum of embodiment 1, the peak of I003/I104 is by force than being about 1.4, structure peak 006 and 102 and peak 008 and 110 all trend towards independent peak and exist, thereby can think that synthetic product has layer structure and crystal formation is grown fine, structural integrity, defective is few.The SEM collection of illustrative plates is similar to the SEM collection of illustrative plates of embodiment 1, shows that the grain shape of synthetic product is an elliposoidal, and size is than homogeneous, and average grain diameter is 5-17 μ m, and the tap density of powder is 2.21g/cm
3The chemical property of product is tested its button cell made from the little current tester of new prestige, and material initial charge specific capacity is 191.6174mAh/g, and first discharge specific capacity is 166.7329mAh/g, and coulombic efficiency is 87.01%; Circulating, capability retention is 94.88% after 100 times, and reversible capacity reaches 158.1962mAh/g, and the slurrying of pole piece, the processing behavior of filming are good, and slurry is placed after 48 hours and gelatin phenomenon all do not occurred, and the material phenomenon does not appear falling in the pole piece smooth surface of making.
Embodiment 6: positive electrode active materials LiNi
0.3Co
0.5Al
0.1Mn
0.1O
2Preparation and performance structure test
0.3: 0.5: 0.1 in molar ratio: 0.1 got nickel (Ni), the sulfate of cobalt (Co), aluminium (Al), manganese (Mn) amounts to 10 moles, and slowly to add the pH values of being prepared by ammoniacal liquor and amine carbonate under continuous stirring condition be in 8 the cushioning liquid, make the mixing ammino and close solution 10L, under continuous stirring state, with itself and 10L, 2.2M the NaOH aqueous solution slowly splashes into simultaneously and fills the 7L aqueous solution and regulate in the reactor of its pH value to 11.5 with the pure NaOH solution of 2.2M, reaction temperature is 70 ℃, and mixing speed is 950rpm.Isolate the Ni-Co-Al-Mn complex hydroxide after 10 hours, ageing after 3 hours with behind the distilled water washing several times in 80 ℃ of dryings 24 hours, make presoma after grinding, sieving, 1: 1.05 in molar ratio mix grinding of anhydrous nitric acid lithium is placed in the Based Intelligent Control Muffle furnace after accurately measuring its moisture content, in dry air, be warming up to 550 ℃ and constant temperature and carried out the heat treatment first time in 8 hours with 5 ℃/min, then be warming up to 770 ℃ and constant temperature and carried out clinkering in 16 hours with 2 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.
The structure of present embodiment products therefrom, pattern test result: the XRD figure spectrum is similar to the XRD figure spectrum of embodiment 1, the peak of I003/I104 is by force than being about 1.53, structure peak 006 and 102 and peak 008 and 110 all trend towards independent peak and exist, thereby can think that synthetic product has layer structure and crystal formation is grown fine, structural integrity, defective is few.The SEM collection of illustrative plates is similar to the SEM collection of illustrative plates of embodiment 1, shows that the grain shape of synthetic product is an elliposoidal, and size is than homogeneous, and average grain diameter is 7-15 μ m, and the tap density of powder is 2.34g/cm
3The chemical property of product is tested its button cell made from the little current tester of new prestige, and material initial charge specific capacity is 192.7129mAh/g, and first discharge specific capacity is 172.6642mAh/g, and coulombic efficiency is 89.60%; Circulating, capability retention is 96.21% after 100 times, and reversible capacity reaches 166.1202mAh/g, and the slurrying of pole piece, the processing behavior of filming are good, and slurry is placed after 96 hours and gelatin phenomenon all do not occurred, and the material phenomenon does not appear falling in the pole piece smooth surface of making.
Claims (10)
1, the multi-component oxide Li that contains cobalt nickel
a(Ni
bCo
c) M
1-b-cO
2, M is the metallic atom of at least a chosen from Fe (Fe), aluminium (Al), manganese (Mn), titanium (Ti), copper (Cu) and calcium (Ca) in the formula, a=0.97-1.07,0.3≤b＜1,0＜c≤0.5,0.8≤b+c＜1.
2, the multi-component oxide Li that contains cobalt nickel
a(Ni
bCo
c) M
1-b-cO
2The preparation method, may further comprise the steps:
(a) in cushioning liquid, preparation nickel, cobalt and other metal M are closed solution (Ni with the ammino that mixes of ammonia
bCo
cM
1-b-c) (NH
3)
n(0＜n≤6);
(b) will mix ammino and close solution (Ni
bCo
cM
1-b-c) (NH
3)
nAnd in the slow simultaneously adding reactor of aqueous slkali, co-precipitation generates the Ni-Co-M complex hydroxide, makes presoma after ageing, separation, washing, the drying;
(c) presoma that (b) step is made and lithium hydroxide or lithium salts carry out mix grinding, and
(d) mixture that makes behind the heat treatment mix grinding is removed adsorbed water and constitution water; And
(e) product of gained makes lithium composite xoide in the heat treatment step (d).
3, the multi-component oxide Li that contains cobalt nickel according to claim 2
a(Ni
bCo
c) M
1-b-cO
2The preparation method, it is characterized in that described metal M is the metal M oxide or the metal M salt of at least a chosen from Fe (Fe), aluminium (Al), manganese (Mn), titanium (Ti), copper (Cu) and calcium (Ca).
4, the multi-component oxide Li that contains cobalt nickel according to claim 2
a(Ni
bCo
c) M
1-b-cO
2The preparation method, it is characterized in that described cushioning liquid is made up of ammonia and amine salt or ammonia and weak acid are made into.
5, the multi-component oxide Li that contains cobalt nickel according to claim 4
a(Ni
bCo
c) M
1-b-cO
2The preparation method, the pH that it is characterized in that described cushioning liquid is 8～11.
6, the multi-component oxide Li that contains cobalt nickel according to claim 2
a(Ni
bCo
c) M
1-b-cO
2The preparation method, it is characterized in that the temperature of coprecipitation reaction is 40-80 ℃ in the step (b), the mixing speed of blender is 240-1000rpm during reaction, the pH value of solution is 10-12 during reaction, the time of coprecipitation reaction is 4-11 hour.
7, the multi-component oxide Li that contains cobalt nickel according to claim 2
a(Ni
bCo
c) M
1-b-cO
2The preparation method, it is characterized in that heat treated temperature is 240-550 ℃ in the step (d), heat treatment period is 3-7 hour.
8, the multi-component oxide Li that contains cobalt nickel according to claim 2
a(Ni
bCo
c) M
1-b-cO
2The preparation method, it is characterized in that heat treated temperature is 650-850 ℃ in the step (e), heat treatment period is 5-18 hour.
9, any described application that contains the multi-component oxide of cobalt nickel as anode active material of lithium ion secondary battery of claim 1-8.
10, a kind of lithium ion battery comprises positive plate, it is characterized in that: the positive electrode active materials on the described positive plate contains the described multi-component oxide that contains cobalt nickel of claim 9.
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| CNA2005100210142A CN1870330A (en) | 2005-05-27 | 2005-05-27 | Multicomponent oxide containing cobalt nickel and preparation and application thereof |
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|---|---|---|---|
| CNA2005100210142A CN1870330A (en) | 2005-05-27 | 2005-05-27 | Multicomponent oxide containing cobalt nickel and preparation and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102334220A (en) * | 2009-02-27 | 2012-01-25 | 住友化学株式会社 | Lithium composite metal oxide and positive electrode active material |
| CN102362377A (en) * | 2009-03-23 | 2012-02-22 | 住友化学株式会社 | Lithium composite metal oxide and positive electrode active material |
| US8703335B2 (en) | 2007-09-28 | 2014-04-22 | Sumitomo Chemical Company, Limited | Lithium mixed metal oxide and nonaqueous electrolyte secondary battery |
| CN104157854A (en) * | 2014-07-31 | 2014-11-19 | 山东玉皇新能源科技有限公司 | Preparation method for ternary positive electrode material of graphene composite lithium ion battery |
| CN104157872A (en) * | 2014-08-26 | 2014-11-19 | 宁波金和新材料股份有限公司 | Low-cost high-capacity multiple-type nickel-manganese precursor, preparation method thereof and cathode material |
| CN104925846A (en) * | 2014-03-17 | 2015-09-23 | 北京化工大学 | Preparation method of nano copper oxide and application of nano copper oxide in lithium ion battery |
| CN105375020A (en) * | 2015-11-28 | 2016-03-02 | 中信大锰矿业有限责任公司大新锰矿分公司 | Preparation method of spherical lithium nickel cobalt manganese oxide precursor mixture |
| CN105406058A (en) * | 2015-12-28 | 2016-03-16 | 浙江华友钴业股份有限公司 | Preparation method for nickel-cobalt-aluminium oxide having super-large particle diameter |
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2005
- 2005-05-27 CN CNA2005100210142A patent/CN1870330A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8703335B2 (en) | 2007-09-28 | 2014-04-22 | Sumitomo Chemical Company, Limited | Lithium mixed metal oxide and nonaqueous electrolyte secondary battery |
| CN102334220A (en) * | 2009-02-27 | 2012-01-25 | 住友化学株式会社 | Lithium composite metal oxide and positive electrode active material |
| US9023524B2 (en) | 2009-02-27 | 2015-05-05 | Sumitomo Chemical Company, Limted | Lithium mixed metal oxide and positive electrode active material |
| CN102362377A (en) * | 2009-03-23 | 2012-02-22 | 住友化学株式会社 | Lithium composite metal oxide and positive electrode active material |
| CN102362377B (en) * | 2009-03-23 | 2013-01-30 | 住友化学株式会社 | Lithium composite metal oxide and positive electrode active material |
| CN104925846A (en) * | 2014-03-17 | 2015-09-23 | 北京化工大学 | Preparation method of nano copper oxide and application of nano copper oxide in lithium ion battery |
| CN104157854A (en) * | 2014-07-31 | 2014-11-19 | 山东玉皇新能源科技有限公司 | Preparation method for ternary positive electrode material of graphene composite lithium ion battery |
| CN104157854B (en) * | 2014-07-31 | 2016-05-04 | 山东玉皇新能源科技有限公司 | A kind of preparation method of Graphene composite lithium ion cell tertiary cathode material |
| CN104157872A (en) * | 2014-08-26 | 2014-11-19 | 宁波金和新材料股份有限公司 | Low-cost high-capacity multiple-type nickel-manganese precursor, preparation method thereof and cathode material |
| CN105375020A (en) * | 2015-11-28 | 2016-03-02 | 中信大锰矿业有限责任公司大新锰矿分公司 | Preparation method of spherical lithium nickel cobalt manganese oxide precursor mixture |
| CN105406058A (en) * | 2015-12-28 | 2016-03-16 | 浙江华友钴业股份有限公司 | Preparation method for nickel-cobalt-aluminium oxide having super-large particle diameter |
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