CN110970601B - Double-gradient coated high-nickel ternary cathode material and preparation method thereof - Google Patents
Double-gradient coated high-nickel ternary cathode material and preparation method thereof Download PDFInfo
- Publication number
- CN110970601B CN110970601B CN201811142276.8A CN201811142276A CN110970601B CN 110970601 B CN110970601 B CN 110970601B CN 201811142276 A CN201811142276 A CN 201811142276A CN 110970601 B CN110970601 B CN 110970601B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- electrode material
- aluminum
- nickel ternary
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 50
- 239000010406 cathode material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 33
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000010410 layer Substances 0.000 claims abstract description 28
- 239000011247 coating layer Substances 0.000 claims abstract description 21
- 239000012792 core layer Substances 0.000 claims abstract description 16
- 239000012466 permeate Substances 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 40
- 239000010936 titanium Substances 0.000 claims description 37
- 239000006185 dispersion Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- 239000011162 core material Substances 0.000 claims description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 15
- 229910010199 LiAl Inorganic materials 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- -1 aluminum ion Chemical class 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 9
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 9
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 9
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 7
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 6
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 5
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 238000007792 addition Methods 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910017698 Ni 1-x-y Co Inorganic materials 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000010405 anode material Substances 0.000 description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 229910013716 LiNi Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229910010093 LiAlO Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910015118 LiMO Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NJNFCDQQEIAOIF-UHFFFAOYSA-N 2-(3,4-dimethoxy-2-methylsulfanylphenyl)ethanamine Chemical compound COC1=CC=C(CCN)C(SC)=C1OC NJNFCDQQEIAOIF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QCGPWGVCUWLMJF-UHFFFAOYSA-N [Al+3].CCO.CC(C)[O-].CC(C)[O-].CC(C)[O-] Chemical compound [Al+3].CCO.CC(C)[O-].CC(C)[O-].CC(C)[O-] QCGPWGVCUWLMJF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910001868 water Inorganic materials 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
- H01M4/362—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
- H01M4/485—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
-
- 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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a double-gradient coated high-nickel ternary cathode material and a preparation method thereof, wherein the cathode material comprises an inner core layer and a coating layer, wherein the inner core layer is the high-nickel ternary cathode material; the coating material of the coating layer permeates into the inner core layer to form a first concentration gradient, and the concentration of the coating material of the inner core layer is gradually increased from the inner layer to the outer layer; the coating material of the coating layer forms a second concentration gradient, the concentration of Al of the coating layer from the inner layer to the outer layer is gradually reduced, and the concentration of Ti is gradually increased. The high-nickel ternary cathode material has high conductivity, high capacity, high rate performance and excellent cycle stability.
Description
Technical Field
The invention belongs to the field of lithium ion battery anode materials, and relates to a double-gradient coated high-nickel ternary anode material and a preparation method thereof.
Background
The lithium ion battery has the advantages of high working voltage, long cycle service life, no memory effect, small self-discharge, environmental friendliness and the like, is widely applied to portable electronic products and electric automobiles, and the conventional anode material cannot meet the requirements of the lithium ion battery on quick charge and discharge and high energy density along with the pursuit of people on quick charge and discharge and ultrahigh endurance mileage. Therefore, the high-nickel ternary cathode material has higher energyThe mass density is concerned, and the mass density is more and more applied to a power system; however, the high-nickel ternary cathode material still has a plurality of problems to be solved, namely Ni 2+ And Li + A large degree of cation mixing therebetween is unavoidable, and it is difficult to maintain all of Ni in flowing oxygen 3+ ，Ni 2+ The lithium ion battery is arranged on a lithium battery, and an effective diffusion path of Li ions in the operation process of the battery is prevented; and Ni formed under electric charge 4+ Tend to react violently with organic electrolytes, producing undesirable side reaction products; these reactions are carried out at higher temperatures and higher operating voltages (> 4.3Vvs. Li/Li) + ) The case of (2) is more deteriorated; in addition, due to highly oxidized Ni 4+ The side reaction of crystal grains and electrolyte and the formation of NiO rock salt phase caused by the chemical instability of the lithium ion battery can reduce the diffusion kinetics of Li ions in the circulation process, and lead to capacity attenuation; therefore, improving the effective diffusion of Li ions and the stability of the nickel-rich layered oxide surface is essential to achieve long-term cyclability.
CN 103236537A discloses a lithium ion battery gradient core-shell anode material and a synthesis method thereof, the invention adopts a coprecipitation method to coat a binary material and/or a unitary material precursor on the outer layer of a ternary precursor, then a lithium source is added to mix and then high-temperature sintering is carried out, the core is a ternary material, the first layer of shell is a binary material and the structural formula is LiNi x Mn y O 2 Wherein x: y is 0.5:0.5 or 0.5: 1.5. The second shell is a unitary material of LiMn 2 O 4 Or lithium cobaltate, the rate capability and the cycle performance of the obtained material are good, but the material prepared by the method has thicker coating layer, gram capacity is not well exerted, and energy density is lower.
CN 103928673A discloses a composite multi-element lithium ion battery anode material and a preparation method thereof, wherein the outer layer of a precursor is coated with hydroxide or carbonate nano-particles of metal M to obtain a coated composite precursor, and then a lithium source is added to mix and then sintered at high temperature to form layered LiNi 1-x-y Co x Mn y O 2 Coating a LiMO layer with the same layered structure as the core 2 Part of the LiMO 2 Infiltration ofTo LiNi 1-x-y Co x Mn y O 2 In the structure, gradient doping from less to more is formed from inside to outside, the obtained material has good cycle performance under high charge cut-off voltage, but the material coating layer prepared by the method has poor electrochemical stability and is decomposed under a high-voltage full-current state, so that the diffusion dynamics of Li ions in the cycle process is reduced.
Therefore, the research and development of a high-nickel ternary cathode material with high conductivity, high capacity, high rate performance and good cycle stability is a technical problem in the field of lithium ion batteries.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a double-gradient coated high-nickel ternary cathode material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
one purpose of the invention is to provide a double-gradient coated high-nickel ternary cathode material, which comprises a core layer and a coating layer, wherein the core layer is the high-nickel ternary cathode material; the coating material of the coating layer permeates into the inner core layer to form a first concentration gradient, and the concentration of the coating material of the inner core layer is gradually increased from the inner layer to the outer layer; and the coating material of the coating layer forms a second concentration gradient, the Al concentration of the coating layer is gradually reduced from the inner layer to the outer layer, and the Ti concentration is gradually increased.
As the preferable technical scheme of the invention, the structural formula of the high-nickel ternary cathode material is Li 1±z Ni 1-x- y Co x M y O 2 Wherein M is Al and/or Mn, x is more than or equal to 0.02 and less than or equal to 0.20, y is more than or equal to 0.02 and less than or equal to 0.20, and z is more than or equal to 0 and less than or equal to 0.20.
Where x may be 0.02, 0.03, 0.05, 0.08, 0.10, 0.12, 0.15, 0.18 or 0.20, y may be 0.02, 0.03, 0.05, 0.08, 0.10, 0.12, 0.15, 0.18 or 0.20, etc., and z may be 0.02, 0.03, 0.05, 0.08, 0.10, 0.12, 0.15, 0.18 or 0.20, etc., but is not limited to the values recited, and other values not recited in the above numerical ranges are equally applicable.
As a preferable technical scheme of the invention, the coating material is Ti m :LiAl n O 2 Wherein m is more than 0 and less than 1, and n is more than 0 and less than 1.
In the above, m may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, etc., and n may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, etc., but is not limited to the values listed, and other values not listed in the above numerical ranges are also applicable.
In a preferred embodiment of the present invention, the mass percentage of the coating material in the positive electrode material is 0 to 5wt%, excluding 0, such as 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5wt%, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
In the dual-gradient coated high-nickel ternary cathode material, the mass percent of the core material is obtained by subtracting the mass percent of the coating material from 100 wt%.
In the invention, the coating layer in the cathode material can permeate into the inner core layer in the process of coating the inner core layer, the concentration of the coating material at the outermost layer of the inner core layer is highest, and the concentration of the coating material is gradually reduced along with the increase of the depth of the coating material permeating into the inner core layer to form a first concentration gradient.
In the present invention, a clad layer of the same chemical composition can be regarded as one layer, i.e., the clad layer is made of Ti m :LiAl n O 2 The second concentration gradient is that the chemical composition of the coating layer is constantly changed from the inner layer to the outer layer, and Ti in the innermost layer m :LiAl n O 2 N is the maximum value and m is the minimum value, Ti in the outermost layer m :LiAl n O 2 N is the minimum value, m is the maximum value, wherein m is more than 0 and less than 1, and n is more than 0 and less than 1.
The invention also aims to provide a preparation method of the dual-gradient coated high-nickel ternary cathode material, which comprises the following steps:
(1) mixing and pretreating a high-nickel ternary positive electrode material hydroxide precursor with a lithium source, and sintering to obtain a core material;
(2) dispersing the core material obtained in the step (1) in deionized water to form a positive electrode material dispersion liquid, inputting a prepared titanium solution into an aluminum solution to form a titanium mixed solution, inputting the aluminum-titanium mixed solution into the positive electrode material dispersion liquid, simultaneously adding a precipitator into the positive electrode material dispersion liquid, stirring, drying and carrying out heat treatment to obtain the dual-gradient coated high-nickel ternary positive electrode material.
In the invention, the input in the step (2) is a dynamic addition process, the titanium ion concentration and the aluminum ion concentration in the aluminum-titanium mixed solution are constantly changed, the aluminum ion concentration is gradually reduced, and the titanium ion concentration is gradually increased; and in the process of inputting the titanium solution into the aluminum solution, inputting the titanium-aluminum mixed solution into the positive electrode material dispersion liquid, and adding a precipitator to form a gradient coating layer in which the aluminum element is gradually reduced from inside to outside and the titanium element is gradually increased. The operation is shown in fig. 6.
As a preferred embodiment of the present invention, the temperature of the pretreatment in the step (1) is 300 to 600 ℃, for example, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the temperature of the pretreatment in step (1) is 3-10 h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the sintering temperature in step (1) is 700-1000 ℃, such as 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the sintering time in step (1) is 6-15 h, such as 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h or 15h, but is not limited to the recited values, and other unrecited values in the range of the recited values are also applicable.
Preferably, the lithium source in step (1) comprises any one of lithium carbonate, lithium hydroxide monohydrate, lithium acetate or lithium nitrate, or a combination of at least two of these, typical but non-limiting examples being: a combination of lithium carbonate and lithium hydroxide monohydrate, a combination of lithium hydroxide monohydrate and lithium acetate, a combination of lithium acetate and lithium nitrate, a combination of lithium nitrate and lithium carbonate, or a combination of lithium carbonate, lithium acetate and lithium nitrate, and the like.
As a preferred embodiment of the present invention, the aluminum solution in step (2) includes a solution of any one or a combination of at least two of aluminum nitrate, aluminum chloride, aluminum fluoride, and aluminum isopropoxide, and typical but non-limiting examples of the combination are: combinations of aluminum nitrate and aluminum chloride, aluminum chloride and aluminum fluoride, aluminum fluoride heat exchange aluminum isopropoxide, aluminum isopropoxide and aluminum nitrate, or aluminum nitrate, aluminum chloride and aluminum fluoride, and the like.
Preferably, the titanium solution of step (2) comprises a solution of any one of or a combination of at least two of tetrabutyl titanate, methyl titanate, ethyl titanate, titanium sulfate or titanyl sulfate, typical but non-limiting examples of which are: a combination of tetrabutyl titanate and methyl titanate, a combination of methyl titanate and ethyl titanate, a combination of ethyl titanate and titanium sulfate, a combination of titanium sulfate and titanyl sulfate, a combination of titanyl sulfate and tetrabutyl titanate, or a combination of tetrabutyl titanate, methyl titanate and titanium sulfate, and the like.
The solvent of the aluminum solution and the titanium solution may be deionized water or ethanol, but is not limited to the above solvent.
As a preferred technical scheme of the invention, the precipitant in the step (2) is any one or a combination of at least two of lithium hydroxide monohydrate, sodium hydroxide or ammonia water, and typical but non-limiting examples of the combination are as follows: combinations of lithium hydroxide monohydrate and sodium hydroxide, combinations of sodium hydroxide and ammonia, combinations of ammonia and lithium hydroxide monohydrate, or combinations of lithium hydroxide monohydrate, sodium hydroxide and ammonia, and the like.
In a preferred embodiment of the present invention, the temperature of the heat treatment in the step (2) is 300 to 800 ℃, for example, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Preferably, the heat treatment time in step (2) is 2 to 10 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the heat treatment in step (2) is performed under a protective atmosphere, and the protective atmosphere is oxygen.
The conditions of stirring and drying in step (2) have almost no influence on the performance of the positive electrode material of the present invention, and therefore, the conditions are not specifically limited herein.
As a preferable technical scheme of the invention, the method comprises the following steps:
(1) mixing a high-nickel ternary positive electrode material hydroxide precursor with a lithium source, pretreating for 3-10 hours at 300-600 ℃, and sintering for 6-15 hours at 700-1000 ℃ to obtain a core material;
(2) dispersing the core material obtained in the step (1) in deionized water to form a positive electrode material dispersion liquid, inputting a prepared titanium solution into an aluminum solution to form a titanium mixed solution, inputting the aluminum-titanium mixed solution into the positive electrode material dispersion liquid, simultaneously adding a precipitator into the positive electrode material dispersion liquid, stirring, drying, and carrying out heat treatment at 300-800 ℃ for 2-10 h to obtain the dual-gradient coated high-nickel ternary positive electrode material.
Compared with the prior art, the double-gradient-coated high-nickel ternary cathode material and the preparation method thereof successfully prepare the double-gradient-coated high-nickel ternary cathode material by coprecipitation m :LiAl n O 2 Gradient coating of Ti doped with titanium m :LiAl n O 2 The gradient lithium ion conductor solves the problem of LiAlO 2 Has poor electrochemical stability and is easy to decompose to form Li 2 O reacts with the electrolyte to generate gas, Ti is a safety problem 4+ Incorporation of substituted moieties Al 3+ The lithium vacancy in the crystal is increased, so that the diffusion and instability of Li are solved, and the structure is more stable; having LiAlO 2 Good lithium ion conductivity, improved multiplying power performance of the material, more stable structure, and enhanced LiAlO 2 Electrochemical and thermal stability, Ti m :LiAl n O 2 The gradient coating of the material inhibits the dissolution of metal elements, reduces the side reaction between the active material and the electrolyte, and improves the charge-discharge capacity and the cycle performance of the material; the dual-gradient coating enables the layers to be combined more tightly, solves the problems of structural instability of single-layer or multi-layer coating materials and too fast attenuation of the circulating capacity of the high-nickel material, and enables the high-nickel ternary cathode material to be circulated more stably.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention provides a dual-gradient coated high-nickel ternary cathode material, which has the advantages of high conductivity, high capacity, high rate performance and excellent cycle stability, wherein the first coulombic efficiency can reach more than 88%, and the 1C 50-cycle retention rate can reach more than 95%;
(2) the invention provides a preparation method of a double-gradient coated high-nickel ternary cathode material, which is simple in process and suitable for industrial production.
Drawings
FIG. 1 is a schematic diagram of the effect of a dual-gradient coated high-nickel ternary cathode material provided in example 1 of the present invention;
FIG. 2 is an SEM image of a dual-gradient coated high-nickel ternary cathode material of example 1 of the invention;
FIG. 3 is an EDX diagram of a dual gradient coated high nickel ternary cathode material of example 1 of the present invention;
fig. 4 is a loop curve for the button half cell of comparative example 1 of the present invention;
fig. 5 is a button half cell cycling curve in example 1 of the present invention;
FIG. 6 is a schematic operation process diagram of step (2) of the preparation method of the dual-gradient-coated high-nickel ternary cathode material provided by the invention;
in the figure: 1-high nickel ternary anode material, 2-Tim: LiAlnO2 coating layer.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a preparation method of a double-gradient coated high-nickel ternary cathode material, which comprises the following steps:
(1) mixing Ni 0.88 Co 0.09 Al 0.03 (OH) 2 Precursor and lithium source LiOH H 2 Mixing the ingredients with O according to the molar ratio of Li/(Ni + Co + Al) of 1.05, pretreating at 600 ℃ for 5 hours, and sintering at 750 ℃ for 10 hours to obtain a core material;
(2) dispersing the core material obtained in the step (1) in deionized water, inputting the prepared titanium sulfate aqueous solution into an aluminum nitrate aqueous solution, inputting an aluminum-titanium mixed solution into a positive electrode material dispersion liquid in the process of inputting a titanium solution into an aluminum solution, and simultaneously adding LiOH & H & lt/EN & gt into the positive electrode material dispersion liquid 2 O, stirring to make the coating amount be Ti 0.25 :LiAl 0.75 O 2 /Li 1.05 Ni 0.88 Co 0.09 Al 0.03 O 2 2.5 wt%, vacuum drying in a vacuum drying oven at 200 ℃ for 12.0h, introducing oxygen, heating to 600 ℃, preserving heat for 10h, and naturally cooling to room temperature to obtain the dual-gradient coated high-nickel ternary cathode material.
Example 2
The embodiment provides a preparation method of a double-gradient coated high-nickel ternary cathode material, which comprises the following steps:
(1) mix Ni 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor and lithium source LiOH H 2 Mixing the ingredients with O according to the molar ratio of Li/(Ni + Co + Mn) of 1.08, pretreating for 5 hours at 600 ℃, and sintering for 10 hours at 900 ℃ to obtain a core material;
(2) dispersing the core material obtained in the step (1) in deionized water, inputting the prepared ethanol solution of tetrabutyl titanate into the ethanol solution of aluminum isopropoxide, inputting the aluminum-titanium mixed solution into the dispersion liquid of the anode material in the process of inputting the titanium solution into the aluminum solution, and simultaneously adding LiOH. H into the dispersion liquid of the anode material 2 O, stirring to make the coating amount be Ti 0.25 :LiAl 0.75 O 2 /Li 1.08 Ni 0.88 Co 0.09 Mn 0.03 O 2 And (2.5) performing vacuum drying for 12.0h in a vacuum drying oven at 200 ℃, introducing oxygen, heating to 600 ℃, preserving heat for 10h, and naturally cooling to room temperature to obtain the dual-gradient coated high-nickel ternary cathode material.
Example 3
The embodiment provides a preparation method of a double-gradient coated high-nickel ternary cathode material, which comprises the following steps:
(1) mixing Ni 0.6 Co 0.2 Al 0.2 (OH) 2 Precursor and Li source 2 CO 3 Mixing the materials according to the molar ratio of Li/(Ni + Co + Al) of 0.8, pretreating at 300 ℃ for 10 hours, and sintering at 700 ℃ for 15 hours to obtain a core material;
(2) dispersing the core material obtained in the step (1) in deionized water, inputting the prepared titanyl sulfate aqueous solution into an aluminum chloride aqueous solution, inputting an aluminum-titanium mixed solution into the anode material dispersion liquid in the process of inputting a titanium solution into an aluminum solution, simultaneously adding NaOH into the anode material dispersion liquid, and stirring to ensure that the coating amount is Ti 0.5 :LiAl 0.5 O 2 /Li 0.8 Ni 0.6 Co 0.2 Al 0.2 O 2 5wt%, vacuum drying in a vacuum drying oven at 200 deg.C for 12.0h, introducing oxygen, heating to 700 deg.C, maintaining for 10h, and naturally cooling to room temperature to obtain the double-gradient coated high-nickel-content tri-nickelAnd (3) a meta-anode material.
Example 4
The embodiment provides a preparation method of a double-gradient coated high-nickel ternary cathode material, which comprises the following steps:
(1) mixing Ni 0.96 Co 0.02 Mn 0.02 (OH) 2 Precursor and lithium source LiOH H 2 Mixing the ingredients with O according to the molar ratio of Li/(Ni + Co + Mn) of 1.2, pretreating for 3 hours at 600 ℃, and sintering for 6 hours at 1000 ℃ to obtain a core material;
(2) dispersing the core material obtained in the step (1) in deionized water, inputting the prepared ethyl alcohol solution of methyl titanate into the ethyl alcohol solution of aluminum isopropoxide, inputting the aluminum-titanium mixed solution into the positive electrode material dispersion liquid in the process of inputting the titanium solution into the aluminum solution, simultaneously adding ammonia water into the positive electrode material dispersion liquid, and stirring to ensure that the coating amount is Ti 0.8 :LiAl 0.2 O 2 /Li 1.2 Ni 0.96 Co 0.02 Mn 0.02 O 2 And (2) 0.5 wt%, vacuum drying in a vacuum drying oven at 200 ℃ for 12.0h, introducing oxygen, heating to 800 ℃, preserving heat for 2h, and naturally cooling to room temperature to obtain the dual-gradient coated high-nickel ternary cathode material.
Example 5
The embodiment provides a preparation method of a double-gradient coated high-nickel ternary cathode material, which comprises the following steps:
(1) mixing Ni 0.89 Co 0.05 Al 0.06 (OH) 2 Precursor and lithium source CH 3 Mixing COOLi with the molar ratio Li/(Ni + Co + Al) of 1.1, pretreating at 550 ℃ for 4h, and sintering at 800 ℃ for 8h to obtain a core material;
(2) dispersing the core material obtained in the step (1) in deionized water, inputting the prepared titanium sulfate aqueous solution into the aluminum fluoride aqueous solution, inputting the aluminum-titanium mixed solution into the anode material dispersion liquid in the process of inputting the titanium solution into the aluminum solution, and simultaneously adding LiOH. H. into the anode material dispersion liquid 2 O, stirring to make the coating amount be Ti 0.65 :LiAl 0.35 O 2 /Li 1.1 Ni 0.89 Co 0.05 Al 0.06 O 2 And (3) putting the mixture into a vacuum drying oven at 200 ℃, performing vacuum drying for 12.0h, introducing oxygen, heating to 600 ℃, preserving the heat for 5h, and naturally cooling to room temperature to obtain the dual-gradient coated high-nickel ternary cathode material.
Example 6
The embodiment provides a preparation method of a double-gradient coated high-nickel ternary cathode material, which comprises the following steps:
(1) mixing Ni 0.73 Co 0.12 Mn 0.15 (OH) 2 Precursor and lithium source LiNO 3 Mixing the ingredients according to the molar ratio of Li/(Ni + Co + Mn) of 1.0, pretreating at 500 ℃ for 5 hours, and sintering at 800 ℃ for 8 hours to obtain a core material;
(2) dispersing the core material obtained in the step (1) in deionized water, inputting the prepared ethyl titanate ethanol solution into the aluminum isopropoxide ethanol solution, inputting the aluminum-titanium mixed solution into the anode material dispersion liquid in the process of inputting the titanium solution into the aluminum solution, and simultaneously adding LiOH & H into the anode material dispersion liquid 2 O, stirring to make the coating amount be Ti 0.7 :LiAl 0.3 O 2 /LiNi 0.73 Co 0.12 Mn 0.15 O 2 1.5 wt%, vacuum drying in a vacuum drying oven at 200 ℃ for 12.0h, introducing oxygen, heating to 700 ℃, preserving heat for 5h, and naturally cooling to room temperature to obtain the dual-gradient coated high-nickel ternary cathode material.
Comparative example 1
In this comparative example, step (2), i.e., coating of the core material, was not performed, and step (1) was the same as step (1) of example 1.
Comparative example 2
In this comparative example, the same conditions as in example 1 were used except that in step (2), the titanium-containing compound was not added and the aluminum-containing compound was directly used for coating.
Comparative example 3
In this comparative example, the same conditions as in example 1 were used except that in step (2), the aluminum-containing compound was not added and the titanium-containing compound was directly used for coating.
The sample morphology and the element composition of the cathode materials prepared in examples 1 to 6 were tested by a scanning electron microscope (S4800 scanning electron microscope, spectrographic analysis and transmission electron microscope (ri) corporation, and as shown in the SEM picture of example 1 in fig. 2 and the EDX picture of example 1 in fig. 3, it can be seen that the coating layer is obviously coated, and the element concentration of the coating layer is: the Al concentration is gradually reduced from the inner layer to the outer layer, and the Ti concentration is gradually increased.
The positive electrode materials obtained in examples 1-6 and comparative examples 1-3, an adhesive and a conductive agent are uniformly mixed according to a ratio of 96:2:2, then the mixture is coated on a current collector, dried and cut into a positive plate, assembly is started under the condition that the concentrations of H2O and O2 in a glove box are lower than 0.1ppm, a negative electrode shell, a top ring, a gasket, a metal lithium plate, a diaphragm, a pole piece and a positive electrode shell are sequentially placed in a battery shell, electrolyte is added when the diaphragm is placed in the battery shell, the assembled battery is sealed by a sealing machine to be assembled into a button type half battery, a blue test cabinet is used for testing the rate capability, the cycle performance and the charge-discharge capacity of the button type half battery, and the electrochemical data are shown in Table 1.
TABLE 1
As can be seen from table 1, the positive electrode materials prepared in examples 1 to 6 of the present invention have excellent rate capability, cycle performance, and charge/discharge capacity, and the retention rate at 50 weeks can reach 98%. While comparative example 1 is not coated with a coating layer, comparative examples 2 and 3 are not added with a titanium-containing compound and an aluminum-containing compound respectively during coating, i.e., a titanium element concentration gradient and an aluminum element concentration gradient are not formed, so that the 50-week retention rate of the positive electrode materials prepared in comparative examples 1 to 3 is about 90%.
The applicant states that the present invention is described by the above embodiments to explain the detailed structural features of the present invention, but the present invention is not limited to the above detailed structural features, that is, it is not meant to imply that the present invention must be implemented by relying on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that, in the above embodiments, the various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present invention does not separately describe various possible combinations.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.
Claims (14)
1. The double-gradient coated high-nickel ternary cathode material is characterized by comprising an inner core layer and a coating layer, wherein the inner core layer is the high-nickel ternary cathode material; the coating material of the coating layer permeates into the inner core layer to form a first concentration gradient, and the concentration of the coating material of the inner core layer is gradually increased from the inner layer to the outer layer; the coating material of the coating layer forms a second concentration gradient, the Al concentration of the coating layer is gradually reduced from the inner layer to the outer layer, and the Ti concentration is gradually increased;
the coating material is Ti m :LiAl n O 2 Wherein m is more than 0 and less than 1, and n is more than 0 and less than 1;
the preparation method of the double-gradient coated high-nickel ternary cathode material comprises the following steps of:
(1) mixing and pretreating a high-nickel ternary positive electrode material hydroxide precursor with a lithium source, and sintering to obtain a core material;
(2) dispersing the core material obtained in the step (1) in deionized water to form a positive electrode material dispersion liquid, inputting a prepared titanium solution into an aluminum solution to form an aluminum-titanium mixed solution, inputting the aluminum-titanium mixed solution into the positive electrode material dispersion liquid, simultaneously adding a precipitator into the positive electrode material dispersion liquid, stirring, drying and carrying out heat treatment to obtain the double-gradient coated high-nickel ternary positive electrode material;
and (3) the input in the step (2) is a dynamic addition process, the titanium ion concentration and the aluminum ion concentration in the aluminum-titanium mixed solution are constantly changed, the aluminum ion concentration is gradually reduced, and the titanium ion concentration is gradually increased.
2. The positive electrode material according to claim 1, wherein the high-nickel ternary positive electrode material has a chemical formula of Li 1±z Ni 1-x-y Co x M y O 2 Wherein M is Al and/or Mn, x is more than or equal to 0.02 and less than or equal to 0.2, y is more than or equal to 0.02 and less than or equal to 0.2, and z is more than or equal to 0 and less than or equal to 0.2.
3. The positive electrode material according to claim 1, wherein the mass percentage of the coating material in the positive electrode material is 0 to 5wt%, excluding 0.
4. The positive electrode material as claimed in claim 1, wherein the temperature of the pretreatment in step (1) is 300 to 600 ℃.
5. The cathode material according to claim 1, wherein the temperature of the pretreatment in the step (1) is 3-10 h.
6. The positive electrode material according to claim 1, wherein the sintering temperature in the step (1) is 700 to 1000 ℃.
7. The cathode material according to claim 1, wherein the sintering time in the step (1) is 6-15 h.
8. The positive electrode material according to claim 1, wherein the lithium source in step (1) comprises any one of lithium carbonate, lithium hydroxide monohydrate, lithium acetate, or lithium nitrate, or a combination of at least two thereof.
9. The positive electrode material as claimed in claim 1, wherein the aluminum solution of step (2) comprises a solution of any one of aluminum nitrate, aluminum chloride, aluminum fluoride or aluminum isopropoxide or a combination of at least two thereof.
10. The positive electrode material as claimed in claim 1, wherein the titanium solution of step (2) comprises a solution of any one of or a combination of at least two of tetrabutyl titanate, methyl titanate, ethyl titanate, titanium sulfate, or titanyl sulfate.
11. The cathode material according to claim 1, wherein the precipitant in step (2) is one or a combination of at least two of lithium hydroxide monohydrate, sodium hydroxide, and ammonia water.
12. The positive electrode material according to claim 1, wherein the temperature of the heat treatment in the step (2) is 300 to 800 ℃.
13. The positive electrode material according to claim 1, wherein the heat treatment time in the step (2) is 2 to 10 hours.
14. The positive electrode material as claimed in claim 1, wherein the method comprises the steps of:
(1) mixing a high-nickel ternary positive electrode material hydroxide precursor with a lithium source, pretreating for 3-10 hours at 300-600 ℃, and sintering for 6-15 hours at 700-1000 ℃ to obtain a core material;
(2) dispersing the core material obtained in the step (1) in deionized water to form a positive electrode material dispersion liquid, inputting a prepared titanium solution into an aluminum solution to form an aluminum-titanium mixed solution, inputting the aluminum-titanium mixed solution into the positive electrode material dispersion liquid, simultaneously adding a precipitator into the positive electrode material dispersion liquid, stirring, drying, and carrying out heat treatment at 300-800 ℃ for 2-10 h to obtain the dual-gradient coated high-nickel ternary positive electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811142276.8A CN110970601B (en) | 2018-09-28 | 2018-09-28 | Double-gradient coated high-nickel ternary cathode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811142276.8A CN110970601B (en) | 2018-09-28 | 2018-09-28 | Double-gradient coated high-nickel ternary cathode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110970601A CN110970601A (en) | 2020-04-07 |
| CN110970601B true CN110970601B (en) | 2022-09-06 |
Family
ID=70027017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811142276.8A Active CN110970601B (en) | 2018-09-28 | 2018-09-28 | Double-gradient coated high-nickel ternary cathode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110970601B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111900364B (en) * | 2020-08-28 | 2022-08-30 | 蜂巢能源科技有限公司 | Coated ternary cathode material and preparation method and application thereof |
| CN114388779B (en) * | 2022-01-12 | 2024-02-02 | 万华化学(四川)有限公司 | Composite ternary positive electrode material, preparation method thereof and lithium ion battery |
| CN115472817A (en) * | 2022-08-26 | 2022-12-13 | 天津巴莫科技有限责任公司 | Ternary positive electrode material, preparation method thereof, positive electrode plate, secondary battery and electronic equipment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022467A (en) * | 2011-09-28 | 2013-04-03 | 北京当升材料科技股份有限公司 | Lithium manganate material for surface treatment and preparation method thereof |
| CN103325996A (en) * | 2013-06-06 | 2013-09-25 | 南通瑞翔新材料有限公司 | Lithium ion battery positive electrode material aluminum-titanium coating preparation method |
| CN103367704A (en) * | 2012-04-06 | 2013-10-23 | 协鑫动力新材料（盐城）有限公司 | Gradient distribution multivariate composite material precursor as well as preparation method and application thereof |
| CN105070896A (en) * | 2015-07-03 | 2015-11-18 | 湖南杉杉新能源有限公司 | High-nickel multi-element positive electrode material for lithium secondary battery, and preparation method thereof |
| CN107910542A (en) * | 2017-12-11 | 2018-04-13 | 广东工业大学 | A kind of lithium-rich manganese-based composite positive pole and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101573421B1 (en) * | 2012-07-23 | 2015-12-02 | 국립대학법인 울산과학기술대학교 산학협력단 | Positive active material for rechargeable lithium battery, method prepareing the same, and rechargeable lithium battery including the same |
| KR20140142172A (en) * | 2013-05-31 | 2014-12-11 | 한양대학교 산학협력단 | Manufacturing method of cathod active material for lithium rechargeable battery and cathod active material made by the same |
| US20170077496A1 (en) * | 2015-09-11 | 2017-03-16 | Fu Jen Catholic University | Metal gradient-doped cathode material for lithium batteries and its production method |
| CN108039481A (en) * | 2017-12-25 | 2018-05-15 | 湖北环天高科新能源有限公司 | A kind of fluorine-containing power battery positive electrode |
-
2018
- 2018-09-28 CN CN201811142276.8A patent/CN110970601B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022467A (en) * | 2011-09-28 | 2013-04-03 | 北京当升材料科技股份有限公司 | Lithium manganate material for surface treatment and preparation method thereof |
| CN103367704A (en) * | 2012-04-06 | 2013-10-23 | 协鑫动力新材料（盐城）有限公司 | Gradient distribution multivariate composite material precursor as well as preparation method and application thereof |
| CN103325996A (en) * | 2013-06-06 | 2013-09-25 | 南通瑞翔新材料有限公司 | Lithium ion battery positive electrode material aluminum-titanium coating preparation method |
| CN105070896A (en) * | 2015-07-03 | 2015-11-18 | 湖南杉杉新能源有限公司 | High-nickel multi-element positive electrode material for lithium secondary battery, and preparation method thereof |
| CN107910542A (en) * | 2017-12-11 | 2018-04-13 | 广东工业大学 | A kind of lithium-rich manganese-based composite positive pole and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110970601A (en) | 2020-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113955809B (en) | Nickel-cobalt-manganese-lithium aluminate positive electrode material with shell-core structure and preparation method thereof | |
| CN107403913B (en) | Surface-modified nickel-cobalt lithium aluminate cathode material and preparation method thereof | |
| CN112018341A (en) | High-capacity high-nickel cathode material and preparation method thereof | |
| CN110112388B (en) | Porous tungsten trioxide coated modified positive electrode material and preparation method thereof | |
| CN114005978B (en) | Cobalt-free cathode material and preparation method and application thereof | |
| CN108899480A (en) | A kind of long circulation life height ratio capacity nickel cobalt aluminium positive electrode and preparation method thereof | |
| CN110890535A (en) | Cathode material, preparation method thereof and application of cathode material in lithium ion battery | |
| CN110970601B (en) | Double-gradient coated high-nickel ternary cathode material and preparation method thereof | |
| CN112349885B (en) | Modified lithium ion battery positive electrode material and preparation method thereof | |
| CN114520318B (en) | High-nickel cobalt-free nickel tungsten lithium manganate positive electrode material for power battery and preparation method | |
| CN111799457A (en) | Pre-lithiation-treated lithium ion positive electrode material and preparation method and application thereof | |
| EP4194406A1 (en) | Environment-friendly precursor and preparation method therefor, and composite oxide powder and preparation method therefor, and application | |
| Paulus et al. | An in-depth study of Sn substitution in Li-rich/Mn-rich NMC as a cathode material for Li-ion batteries | |
| CN110112387B (en) | Titanium suboxide coated and modified cathode material and preparation method thereof | |
| WO2023071336A1 (en) | Nitride/graphitized carbon nanosheet-coated ternary positive electrode material and preparation method therefor | |
| CN113745487A (en) | Positive electrode material and preparation method and application thereof | |
| WO2019104948A1 (en) | Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery | |
| EP4113660A1 (en) | Method for preparing material having composition gradient characteristic, and application in battery | |
| CN113764630A (en) | Positive electrode material and preparation method and application thereof | |
| WO2023179613A1 (en) | Composite positive electrode material, preparation method therefor, and application thereof | |
| CN115520911A (en) | Lithium-nickel composite oxide positive electrode material and preparation method thereof | |
| CN116022859A (en) | Method for preparing positive electrode material and positive electrode material | |
| CN114976197B (en) | Method for improving interface between high nickel material and LATP solid electrolyte and battery | |
| CN117276535B (en) | High-nickel positive electrode material, and preparation method and application thereof | |
| WO2023056635A1 (en) | Positive electrode material for lithium-ion battery, preparation method therefor, and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |