CN109524659A - The preparation method of nickelic ternary material, nickelic ternary material and battery - Google Patents
The preparation method of nickelic ternary material, nickelic ternary material and battery Download PDFInfo
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- CN109524659A CN109524659A CN201811529108.4A CN201811529108A CN109524659A CN 109524659 A CN109524659 A CN 109524659A CN 201811529108 A CN201811529108 A CN 201811529108A CN 109524659 A CN109524659 A CN 109524659A
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- 239000000463 material Substances 0.000 title claims abstract description 171
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 238000005245 sintering Methods 0.000 claims abstract description 107
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 239000010936 titanium Substances 0.000 claims abstract description 34
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 36
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 28
- 239000004408 titanium dioxide Substances 0.000 claims description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 6
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 5
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000037396 body weight Effects 0.000 description 14
- 238000001816 cooling Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000005253 cladding Methods 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 6
- 229910019775 (Ni0.6CO0.2Mn0.2)(OH)2 Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910019769 (Ni0.8Co0.1Mn0.1)(OH)2 Inorganic materials 0.000 description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000004087 circulation Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000009432 framing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910020084 (NixCoyMnz)O2 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910004403 Li(Ni0.6Co0.2Mn0.2)O2 Inorganic materials 0.000 description 1
- 229910002999 Li(Ni0.8Co0.1Mn0.1)O2 Inorganic materials 0.000 description 1
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to field of batteries, and the preparation method of in particular to nickelic ternary material, nickelic ternary material and battery；This method, which is included in ternary precursor, mixes lithium raw material, zirconium raw material and the first titanium material, obtains the first mixture；First sintering is carried out to the first mixture, obtains first sintering material；The second titanium material and covering are mixed in first sintering material, obtain the second mixture；Second is carried out to the second mixture to be sintered；The nickelic ternary material prepared by this method is more stable, and the performances such as gram volume and cyclicity are improved.
Description
Technical field
The present invention relates to field of batteries, and the preparation method of in particular to nickelic ternary material, nickelic ternary material and electricity
Pond.
Background technique
Tertiary cathode material LiNi1-x-yCoxMnyO2(NCM) there is high electrode current potential, good electron conduction, be high energy
One of metric density lithium battery applications direction.Li(Ni0.6Co0.2Mn0.2)O2With Li (Ni0.8Co0.1Mn0.1)O2As nickelic lithium ion
Cell positive material has the characteristics that specific discharge capacity is high, energy density is high.In addition, having good association between three kinds of elements
Same effect.But the defects of that there is cycle performances is bad for existing ternary material, and capacity retention ratio is low, and thermal stability is poor.Material
Surface side reaction and surface phase transformation are typically considered the reason of causing capacity to reduce, and the fracture that prevents positive electrode particle, dusting are still
So it is to maintain the key of capacity.
Summary of the invention
The first purpose of this invention is to provide a kind of preparation method of nickelic ternary material, this method simple process,
The material metal structural framing prepared is more stable, and the performances such as stability, gram volume and cyclicity of material are improved.
Second object of the present invention is to provide a kind of nickelic ternary material, and the material metal structural framing is more steady
It is fixed, and the performances such as the stability of the material, gram volume and cyclicity are improved.
Third object of the present invention is to provide a kind of battery, and performance is preferable, and capacity and cycle performance are improved.
What the present invention adopts the following technical solutions to realize.
The present invention proposes a kind of preparation method of nickelic ternary material comprising in ternary precursor mix lithium raw material,
Zirconium raw material and the first titanium material, obtain the first mixture；First sintering is carried out to the first mixture, obtains first sintering material
Material；The second titanium material and covering are mixed in first sintering material, obtain the second mixture；The is carried out to the second mixture
Double sintering.
The present invention proposes a kind of nickelic ternary material, is prepared by the preparation method of above-mentioned nickelic ternary material.
The present invention proposes that a kind of battery, the positive electrode active materials of the battery include above-mentioned nickelic ternary material.
The beneficial effect of the preparation method of the nickelic ternary material of the embodiment of the present invention is: the preparation of the nickelic ternary material
Method is by doping metals zirconium and titanium in ternary precursor, so that ternary material metal structure frame is more stable, to increase
The stability of the nickelic ternary material of preparation is added, and has carried out cladding processing with covering and titanium, so that the ternary material of preparation
Gram volume and cycle performance promoted, i.e., the preparation method allows titanium and material to form the solid solution of gradient distribution, and covering is equal
Even cladding on the surface of the material, that is, improves material itself crystal framework stability, while improving material again after cladding
External stability, to obtain preferable cycle performance.
The beneficial effect of nickelic ternary material of the invention is: the nickelic ternary material is prepared by above-mentioned preparation method
So that the crystal inside frame stability of the nickelic ternary material is preferable, and external stability is also preferable, thus have compared with
Good cycle performance.
The beneficial effect of battery of the invention is: the positive electrode active materials of the battery include above-mentioned nickelic ternary material,
To which the battery performance is preferable, capacity and cycle performance are improved.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is that cycle-index-specific discharge capacity of the battery for the nickelic ternary material preparation that the embodiment of the present invention 1 provides follows
Ring figure；
Fig. 2 is that cycle-index-specific discharge capacity of the battery for the nickelic ternary material preparation that the embodiment of the present invention 2 provides follows
Ring figure.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
The preparation method of the nickelic ternary material of the embodiment of the present invention, nickelic ternary material and battery are carried out below specific
Explanation.
The preparation method of nickelic ternary material of the invention include: in ternary precursor mix lithium raw material, zirconium raw material and
First titanium material obtains the first mixture；First sintering is carried out to the first mixture, obtains first sintering material；?
The second titanium material and covering are mixed in once sintered material, obtain the second mixture；Second is carried out to the second mixture to burn
Knot.
The preparation method of nickelic ternary material of the invention passes through the doping zirconium (Zr) and titanium in ternary precursor
(Ti), to improve the metal framework of ternary material, then mixed with covering and the second titanium material with first sintering material,
Sintering, to form relatively stable cladding outside ternary material, so as to improve the stability of material outer, to improve preparation
Stability, gram volume and the cycle performance of nickelic ternary material etc..
In detail, the ternary precursor of the present embodiment includes the ternary precursor prepared by hydroxide coprecipitation step
(Ni0.6Co0.2Mn0.2)(OH)2Or (Ni0.8Co0.1Mn0.1)(OH)2At least one of；By ternary precursor and lithium raw material and zirconium
After raw material mixing carries out the first sintering, sinter can be crushed, to obtain first sintering material；By first sintering material
It is mixed with the second titanium material and covering second of progress after being sintered, crushes, nickelic ternary material (Li can be obtained
(NixCoyMnz)O2, X >=0.6).It should be noted that the sinter that first sintering is obtained crush again with the second titanium material
And covering mixing, uniformly to be mixed, thus uniformly improve the stability of nickelic ternary material, gram volume and
Cycle performance etc..
It should be noted that the hydroxide coprecipitation step for preparing ternary precursor can refer to prior art progress, herein
It repeats no more.
Further, first sintering includes: to heat up according to 1-20 DEG C per minute of heating rate in the present invention,
1-5h is sintered in the environment of 200-500 DEG C；Then it heats up according still further to 1-20 DEG C per minute of heating rate, in 760-900
6-12h is sintered in the environment of DEG C.First sintering is carried out using two sintering stages, can further be improved in ternary material
The stability of portion's crystal framework.
Still further, second of sintering includes: to heat up according to 1-20 DEG C per minute of heating rate in the present invention,
1-5h is sintered in the environment of 200-500 DEG C；Then it heats up according still further to 1-20 DEG C per minute of heating rate, in 660-
6-12h is sintered in the environment of 800 DEG C.Second is carried out using two sintering stages to be sintered, and can further improve ternary material
The external stability of material.
It should be noted that being all made of two for first sintering and second of sintering when preparing nickelic ternary material
The sintering in stage can improve the stability of the crystal inside frame of ternary material, additionally it is possible to improve steady outside ternary material
It is qualitative, to improve the gram volume and cycle performance of ternary material.
Lithium raw material of the invention includes at least one of lithium carbonate and lithium hydroxide, it is preferable that lithium carbonate and hydroxide
Lithium is LITHIUM BATTERY material.It should be noted that in other embodiments, can also select other can be used in preparing battery
Lithium raw material prepares nickelic ternary material of the invention.
Further, ternary precursor can be mixed with lithium raw material according to the molar ratio of 1:1.06-1.08.
Zirconium raw material of the invention includes zirconium dioxide (ZrO2), zirconium silicate (ZrSiO4) and zirconium chloride (ZrCl4) at least
It is a kind of；Further, make an addition to the zirconium raw material of ternary precursor weight be ternary precursor weight 0.01%-10%.
It should be noted that in other embodiments, other zirconium raw material preparation present invention that can be used in preparing battery can also be selected
Nickelic ternary material.
First titanium material and the second titanium material of the invention may each comprise titanium dioxide (TiO2), wherein the first titanium is former
The weight of material is the 0.00%-10% of the weight of ternary precursor, and the weight of the second titanium material is first sintering material weight
0.01%-10%.Optionally, in other embodiments, the first titanium material or the second titanium material can also select other energy
It is enough in the titanium material for preparing battery, such as: metatitanic acid etc..
Covering of the invention includes aluminium isopropoxide (C9H21AlO3), aluminum oxide (Al2O3) and aluminium hydroxide (Al
(OH)3At least one of)；Further, the weight of covering is the weight 0.01%-10% of first sintering material.
It should be noted that the mixing in the present invention can use mixing device completion, and such as: batch mixer；Sintering can
To select sintering equipment to carry out, such as: sintering furnace；It should be further noted that the time mixed every time is not especially limited,
As long as can be uniformly mixed.
It should be noted that first sintering material prepared by the present invention and nickelic ternary material after being pulverized can be with
It is screened, the mesh number of screening is preferable in 300 mesh or so.
The present invention is prepared in the method for nickelic ternary material, is first mixed in ternary precursor before carrying out first sintering
Lithium raw material, zirconium raw material and the first titanium material can use the stability for the crystal framework that Zr and Ti is improved inside ternary material, then
It mixed, be sintered with the second titanium material and covering with the first sintering material of crushing, can be improved outside ternary material
Stability, to improve the gram volume and cycle performance of ternary material.
The nickelic ternary material of the preparation method preparation of nickelic ternary material of the invention can be used in preparing battery, battery
The method of battery is similar, and this will not be repeated here with using ternary material to prepare in the prior art for specific preparation method.
With reference to embodiments to the preparation method of nickelic ternary material of the invention, nickelic ternary material and battery make into
The detailed description of one step.
Embodiment 1
To ternary precursor (Ni0.6Co0.2Mn0.2)(OH)2The lithium carbonate of middle addition LITHIUM BATTERY, ternary precursor and carbonic acid
The molar ratio of lithium is 1:1.06, is then adding zirconium dioxide according to the 0.6% of forerunner's body weight, and according to forerunner's body weight
0.06% addition titanium dioxide, mix 20min in a high speed mixer.
The first mixture mixed is placed in sintering furnace and is sintered, is that 20 DEG C/min is risen according to heating rate
Temperature, until the temperature in sintering furnace reaches 500 DEG C, pre-burning 6h under the conditions of 500 DEG C, then according still further to heating rate be 20 DEG C/
Min heats up, and until the temperature in sintering furnace reaches 800 DEG C, 10h is sintered under conditions of 800 DEG C, then cold with furnace
But, sinter is taken out, is crushed, 300 mesh is crossed, obtains first sintering material.
Aluminum oxide is added according to the 0.03% of first sintering material weight, and according to first sintering material weight
0.01% addition titanium dioxide of amount, mixes 30min in ultrasonic batch mixer.
The second mixture mixed is placed in sintering furnace and is sintered, is that 20 DEG C/min is risen according to heating rate
Temperature is sintered 6h under the conditions of 400 DEG C until the temperature in sintering furnace reaches 400 DEG C, then according still further to heating rate be 20 DEG C/
Min heats up, and until the temperature in sintering furnace reaches 770 DEG C, is sintered 10h under the conditions of 770 DEG C, then in furnace cooling,
Sinter is taken out, is crushed, 300 mesh is crossed, nickelic ternary material can be obtained.
Embodiment 2
To ternary precursor (Ni0.8Co0.1Mn0.1)(OH)2The lithium carbonate of middle addition LITHIUM BATTERY, ternary precursor and carbonic acid
The molar ratio of lithium is 1:1.08, is then adding zirconium dioxide according to the 0.5% of forerunner's body weight, and according to forerunner's body weight
0.05% addition titanium dioxide, mix 20min in a high speed mixer.
The first mixture mixed is placed in sintering furnace and is sintered, is that 15 DEG C/min is risen according to heating rate
Temperature, until the temperature in sintering furnace reaches 500 DEG C, pre-burning 6h under the conditions of 500 DEG C, then according still further to heating rate be 15 DEG C/
Min heats up, and until the temperature in sintering furnace reaches 800 DEG C, 10h is sintered under conditions of 800 DEG C, then cold with furnace
But, sinter is taken out, is crushed, 300 mesh is crossed, obtains first sintering material.
Aluminum oxide is added according to the 0.02% of first sintering material weight, and according to first sintering material weight
0.05% addition titanium dioxide of amount, mixes 30min in ultrasonic batch mixer.
The second mixture mixed is placed in sintering furnace and is sintered, is that 12 DEG C/min is risen according to heating rate
Temperature is sintered 6h under the conditions of 400 DEG C until the temperature in sintering furnace reaches 400 DEG C, then according still further to heating rate be 1 DEG C/
Min heats up, and until the temperature in sintering furnace reaches 770 DEG C, is sintered 10h under the conditions of 770 DEG C, then in furnace cooling,
Sinter is taken out, is crushed, 300 mesh is crossed, nickelic ternary material can be obtained.
Embodiment 3
To ternary precursor (Ni0.6Co0.2Mn0.2)(OH)2The lithium hydroxide of middle addition LITHIUM BATTERY, ternary precursor and hydrogen
The molar ratio of lithia is 1:1.07, is then adding zirconium silicate according to the 10% of forerunner's body weight, and according to forerunner's weight
0.01% addition titanium dioxide of amount, mixes in a high speed mixer.
The first mixture mixed is placed in sintering furnace and is sintered, is that 1 DEG C/min is risen according to heating rate
Temperature, until the temperature in sintering furnace reaches 200 DEG C, pre-burning 5h under the conditions of 200 DEG C, then according still further to heating rate be 5 DEG C/
Min heats up, and until the temperature in sintering furnace reaches 760 DEG C, 12h is sintered under conditions of 760 DEG C, then cold with furnace
But, sinter is taken out, crushes, obtains first sintering material.
Aluminium isopropoxide is added according to the 10% of first sintering material weight, and according to first sintering material weight
10% addition titanium dioxide, mixes in ultrasonic batch mixer.
The second mixture mixed is placed in sintering furnace and is sintered, is that 12 DEG C/min is risen according to heating rate
Temperature is sintered 1h under the conditions of 300 DEG C until the temperature in sintering furnace reaches 300 DEG C, then according still further to heating rate be 20 DEG C/
Min heats up, and until the temperature in sintering furnace reaches 660 DEG C, is sintered 12h under the conditions of 660 DEG C, then in furnace cooling,
Sinter is taken out, crushes, nickelic ternary material can be obtained.
Embodiment 4
To ternary precursor (Ni0.8Co0.1Mn0.1)(OH)2The lithium hydroxide of middle addition LITHIUM BATTERY, ternary precursor and hydrogen
The molar ratio of lithia is 1:1.08, is then adding zirconium chloride according to the 0.01% of forerunner's body weight, and according to presoma
10% addition titanium dioxide of weight, mixes 30min in a high speed mixer.
The first mixture mixed is placed in sintering furnace and is sintered, is that 10 DEG C/min is risen according to heating rate
Temperature, until the temperature in sintering furnace reaches 400 DEG C, pre-burning 1h under the conditions of 400 DEG C, then according still further to heating rate be 1 DEG C/
Min heats up, and until the temperature in sintering furnace reaches 900 DEG C, is sintered 6h under conditions of 900 DEG C, then in furnace cooling,
Sinter is taken out, crushes, obtains first sintering material.
Aluminium hydroxide is added according to the 0.01% of first sintering material weight, and according to first sintering material weight
10% addition titanium dioxide, mixed in ultrasonic batch mixer.
The second mixture mixed is placed in sintering furnace and is sintered, is that 6 DEG C/min is risen according to heating rate
Temperature is sintered 1h under the conditions of 500 DEG C until the temperature in sintering furnace reaches 500 DEG C, then according still further to heating rate be 10 DEG C/
Min heats up, and until the temperature in sintering furnace reaches 800 DEG C, is sintered 6h under the conditions of 800 DEG C, then in furnace cooling, takes
Sinter out crushes, nickelic ternary material can be obtained.
Embodiment 5
To ternary precursor (Ni0.6Co0.2Mn0.2)(OH)2The lithium carbonate of middle addition LITHIUM BATTERY, ternary precursor and carbonic acid
The molar ratio of lithium is 1:1.07, then in the mixing of 5% the addition zirconium dioxide, zirconium silicate and zirconium chloride according to forerunner's body weight
Object, and titanium dioxide is added according to the 4% of forerunner's body weight, 30min is mixed in a high speed mixer.
The first mixture mixed is placed in sintering furnace and is sintered, is that 18 DEG C/min is risen according to heating rate
Temperature, until the temperature in sintering furnace reaches 350 DEG C, pre-burning 3h under the conditions of 350 DEG C, then according still further to heating rate be 13 DEG C/
Min heats up, and until the temperature in sintering furnace reaches 850 DEG C, is sintered 8h under conditions of 850 DEG C, then in furnace cooling,
Sinter is taken out, crushes, obtains first sintering material.
The mixture of aluminum oxide, aluminium isopropoxide and aluminium hydroxide is added according to the 3% of first sintering material weight,
And titanium dioxide is added according to the 7.2% of first sintering material weight, 20min is mixed in ultrasonic batch mixer.
The second mixture mixed is placed in sintering furnace and is sintered, is that 13 DEG C/min is risen according to heating rate
Temperature is sintered 3h under the conditions of 420 DEG C until the temperature in sintering furnace reaches 420 DEG C, then according still further to heating rate be 12 DEG C/
Min heats up, and until the temperature in sintering furnace reaches 700 DEG C, is sintered 8h under the conditions of 700 DEG C, then in furnace cooling, takes
Sinter out crushes, nickelic ternary material can be obtained.
Embodiment 6
To ternary precursor (Ni0.8Co0.1Mn0.1)(OH)2The lithium hydroxide of middle addition LITHIUM BATTERY, ternary precursor and carbon
The molar ratio of sour lithium be 1:1.06, then according to forerunner's body weight 0.8% addition zirconium silicate and zirconium chloride mixture, with
And titanium dioxide is added according to the 0.03% of forerunner's body weight, in a high speed mixer.
The first mixture mixed is placed in sintering furnace and is sintered, is that 16 DEG C/min is risen according to heating rate
Temperature, until the temperature in sintering furnace reaches 250 DEG C, pre-burning 4h under the conditions of 250 DEG C, then according still further to heating rate be 9 DEG C/
Min heats up, and until the temperature in sintering furnace reaches 750 DEG C, 11h is sintered under conditions of 750 DEG C, then cold with furnace
But, sinter is taken out, is crushed, 300 mesh is crossed, obtains first sintering material.
According to the mixture of 4% addition aluminum oxide and aluminium hydroxide of first sintering material weight, and according to
2.1% addition titanium dioxide of first sintering material weight, mixes 30min in ultrasonic batch mixer.
The second mixture mixed is placed in sintering furnace and is sintered, is that 1 DEG C/min is risen according to heating rate
Temperature is sintered 5h under the conditions of 200 DEG C until the temperature in sintering furnace reaches 200 DEG C, then according still further to heating rate be 13 DEG C/
Min heats up, and until the temperature in sintering furnace reaches 720 DEG C, is sintered 11h under the conditions of 720 DEG C, then in furnace cooling,
Sinter is taken out, is crushed, 300 mesh is crossed, nickelic ternary material can be obtained.
Embodiment 7
To ternary precursor (Ni0.6Co0.2Mn0.2)(OH)2The lithium carbonate of middle addition LITHIUM BATTERY, ternary precursor and carbonic acid
The molar ratio of lithium is 1:1.06, is then adding zirconium dioxide according to the 0.6% of forerunner's body weight, and according to forerunner's body weight
0.06% addition titanium dioxide, mix 20min in a high speed mixer.
The first mixture mixed is placed in sintering furnace and is sintered, sintering temperature control is 800 DEG C, sintering time
Sinter is taken out then in furnace cooling for 15h, is crushed, is crossed 300 mesh, obtain first sintering material.
Aluminum oxide is added according to the 0.03% of first sintering material weight, and according to first sintering material weight
0.01% addition titanium dioxide of amount, mixes 30min in ultrasonic batch mixer.
The second mixture mixed is placed in sintering furnace and is sintered, sintering temperature is 700 DEG C, and sintering time is
15h takes out sinter then in furnace cooling, crushes, and crosses 300 mesh, nickelic ternary material can be obtained.
Comparative example 1
The method of ternary material prepared by comparative example 1 is similar with the preparation method that embodiment 3 prepares nickelic ternary material, no
It is with place, comparative example 1 is added to lithium hydroxide in ternary precursor, and the molar ratio of ternary precursor and lithium hydroxide is
Then 1:1.07 is adding zirconium silicate according to the 10% of forerunner's body weight, and is adding two according to the 0.01% of forerunner's body weight
Titanium oxide, and mixture is placed in sintering furnace and is sintered, it is that 20 DEG C/min heats up according to heating rate, until sintering
Temperature in furnace reaches 500 DEG C, pre-burning 6h under the conditions of 500 DEG C, is then that 20 DEG C/min heats up according still further to heating rate,
Until the temperature in sintering furnace reaches 800 DEG C, it is sintered 10h under conditions of 800 DEG C, then in furnace cooling, takes out sinter,
It crushes.
Comparative example 2
The method of ternary material prepared by comparative example 2 is similar to Example 3, the difference is that, comparative example 2 is before ternary
It drives and is added to lithium hydroxide in body, the molar ratio of ternary precursor and lithium hydroxide is 1:1.07, then according to ternary precursor
10% addition aluminium isopropoxide of weight, and titanium dioxide is added according to the 10% of ternary precursor weight, and mixture is set
It is sintered in sintering furnace, is that 12 DEG C/min heats up according to heating rate, until the temperature in sintering furnace reaches 300
DEG C, it is sintered 1h under the conditions of 300 DEG C, is then that 20 DEG C/min heats up according still further to heating rate, until the temperature in sintering furnace
Degree reaches 660 DEG C, is sintered 12h under the conditions of 660 DEG C, then in furnace cooling, takes out sinter.
The ternary material prepared with the nickelic ternary material and comparative example 1,2 of embodiment 1-7 is as a positive electrode active material
Battery is prepared, the capacity retention ratio after comparing the battery over multiple cycles prepared.
The preparation method of battery is equal are as follows: selects the nickelic ternary material of a selection example 1-7 or the ternary material of comparative example 1,2
As a positive electrode active material, acetylene black is conductive agent to material, and Kynoar is binder, and three's mass is 90:5:5, is added
NMP is uniformly mixed and slurry is made, and applies Al foil collector, anode is made.Lithium titanate is that cathode is assembled into button cell, conductive agent,
Binder is as above, and mass ratio is constant, is applied in copper foil current collector after slurry is made, obtains battery cathode.Using 1mol/L's
LiPF6 conductive salt and DMC:DEC:EC (wt%)=1:1:1 solvent.The other steps for preparing battery can refer to the prior art.
The test method of circulation electric discharge specific volume conservation rate: under conditions of 0.5C/0.5C, 2.75-4.4V charge and discharge, measuring electricity
Capacity under the multiplying power, surveys capacity retention ratio after 50 circulations, the results are shown in Table 1.
The discharging efficiency of 1 each group battery of table
Result and Fig. 1, Fig. 2 of consolidated statement 1 are it is found that preparation method provided by the invention, the nickelic ternary material of preparation
It is coated, the stability of nickelic ternary material can be effectively improved and is followed by adulterating Zr and Ti, and using Al and Ti
Ring performance, repeatedly still then higher capacity retention ratio after circulation.
In conclusion the beneficial effect of the preparation method of the nickelic ternary material of the embodiment of the present invention is: the nickelic ternary
The preparation method of material is by doping metals zirconium and titanium in ternary precursor, so that ternary material metal structure frame is more steady
It is fixed, to increase the stability of the nickelic ternary material of preparation, and cladding processing is carried out with covering and titanium, so that preparation
The gram volume and cycle performance of ternary material are promoted, i.e., the preparation method allows titanium and material to form the solid solution of gradient distribution,
Covering is evenly coated at material surface, that is, improves material itself crystal framework stability, while mentioning again after cladding
The high external stability of material, to obtain preferable cycle performance.
The beneficial effect of nickelic ternary material of the invention is: the nickelic ternary material is prepared by above-mentioned preparation method
So that the crystal inside frame stability of the nickelic ternary material is preferable, and external stability is also preferable, thus have compared with
Good cycle performance.
The beneficial effect of battery of the invention is: the positive electrode active materials of the battery include above-mentioned nickelic ternary material,
To which the battery performance is preferable, capacity and cycle performance are improved.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nickelic ternary material characterized by comprising mix lithium raw material, zirconium in ternary precursor
Raw material and the first titanium material, obtain the first mixture；
First sintering is carried out to first mixture, obtains first sintering material；
The second titanium material and covering are mixed in the first sintering material, obtains the second mixture；
Second is carried out to the second mixture to be sintered.
2. the preparation method of nickelic ternary material according to claim 1, which is characterized in that the first sintering packet
It includes: heating up according to 1-20 DEG C per minute of heating rate, be sintered 1-5h in the environment of 200-500 DEG C；Then according still further to
1-20 DEG C of heating rate heats up per minute, is sintered 6-12h in the environment of 760-900 DEG C.
3. the preparation method of nickelic ternary material according to claim 1, which is characterized in that second of sintering packet
It includes: heating up according to 1-20 DEG C per minute of heating rate, be sintered 1-5h in the environment of 200-500 DEG C；Then according still further to
1-20 DEG C of heating rate heats up per minute, is sintered 6-12h in the environment of 660-800 DEG C.
4. the preparation method of nickelic ternary material according to claim 1, which is characterized in that the lithium raw material includes carbonic acid
At least one of lithium or lithium hydroxide.
5. the preparation method of nickelic ternary material according to claim 1, which is characterized in that the zirconium raw material includes dioxy
Change at least one of zirconium, zirconium silicate and zirconium chloride.
6. the preparation method of nickelic ternary material according to claim 1, which is characterized in that first titanium material includes
Titanium dioxide；And/or second titanium material includes titanium dioxide.
7. the preparation method of nickelic ternary material according to claim 1, which is characterized in that the covering includes isopropyl
At least one of aluminium alcoholates, aluminum oxide and aluminium hydroxide.
8. the preparation method of nickelic ternary material according to claim 1, which is characterized in that the ternary precursor and institute
The molar ratio for stating lithium raw material is 1:1.06-1.08；And/or
The weight of the zirconium raw material is the 0.01%-10% of the weight of the ternary precursor；And/or
The weight of first titanium material is the 0.00%-10% of the weight of the ternary precursor；And/or
The weight of second titanium material is the 0.01%-10% of the first sintering material weight；And/or
The weight of the covering is the weight 0.01%-10% of the first sintering material.
9. a kind of nickelic ternary material, which is characterized in that it is by the described in any item nickelic ternary materials of claim 1-8
Preparation method preparation.
10. a kind of battery, which is characterized in that the positive active material of the battery includes nickelic ternary as claimed in claim 9
Material.
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| CN113113590A (en) * | 2021-04-13 | 2021-07-13 | 湖南长远锂科股份有限公司 | Single crystal anode material with core-shell structure and preparation method thereof |
| CN113437289A (en) * | 2021-06-29 | 2021-09-24 | 中钢天源股份有限公司 | High-capacity single crystal cathode material and preparation method thereof |
| CN114725371A (en) * | 2022-04-20 | 2022-07-08 | 天津巴莫科技有限责任公司 | High-nickel single crystal positive electrode material, preparation method thereof, lithium ion battery and all-solid-state battery |
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| CN113437289A (en) * | 2021-06-29 | 2021-09-24 | 中钢天源股份有限公司 | High-capacity single crystal cathode material and preparation method thereof |
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