CN110649252A - Ternary material LiNi of lithium battery0.8Co0.1Mn0.1O2Surface coated with Li2ZrO3Method (2) - Google Patents
Ternary material LiNi of lithium battery0.8Co0.1Mn0.1O2Surface coated with Li2ZrO3Method (2) Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 87
- 229910013716 LiNi Inorganic materials 0.000 title claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 55
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 44
- 229910007822 Li2ZrO3 Inorganic materials 0.000 claims abstract description 36
- 239000007774 positive electrode material Substances 0.000 claims abstract description 28
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 26
- 238000002161 passivation Methods 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 42
- 239000011572 manganese Substances 0.000 claims description 32
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims description 28
- 150000004706 metal oxides Chemical class 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 17
- 239000002585 base Substances 0.000 claims description 15
- 239000011812 mixed powder Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000010406 cathode material Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000003980 solgel method Methods 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 229910018671 Lix(NiaCobMnc)O2 Inorganic materials 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 9
- 238000012546 transfer Methods 0.000 abstract description 5
- 235000015110 jellies Nutrition 0.000 abstract description 4
- 239000008274 jelly Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000011247 coating layer Substances 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 229910052759 nickel Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000005253 cladding Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910005518 NiaCobMnc Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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
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- 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
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- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
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- 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 invention discloses a ternary material LiNi of a lithium battery0.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method comprises the LiNi which is the ternary positive electrode material of the lithium ion battery0.8Co0.1Mn0.1O2The invention adopts the LiNi as the ternary anode material of the lithium ion battery0.8Co0.1Mn0.1O2Surface passivation coating of Li by wet chemical method2ZrO3Substantially reduce the lithium ionTernary positive electrode material LiNi of sub-battery0.8Co0.1Mn0.1O2Soluble salts such as lithium carbonate and lithium hydroxide formed on the surface also reduce the pH value of the material, so that the material can not absorb water in the mixing process to be in a jelly shape, subsequent coating can not be influenced, moisture control is more perfect, and the processing performance is reduced, so that the loss of gram capacity of the material is reduced on the basis of reducing the pH value, the energy density and the corresponding cycle performance of the material are further ensured, and meanwhile, the material can pass through Li and the like2ZrO3The coating layer inhibits side reaction between the anode material and electrolyte, and reduces the charge transfer resistance of the material in the circulation process, thereby improving the electrochemical performance of the material.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a ternary material LiNi of a lithium battery0.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method of (1).
Background
The chemical general formula of the high nickel layered anode material is Lix(NiaCobMnc)O2Wherein x is more than or equal to 1.00 and less than or equal to 1.09, a + b + c is 1, a is more than or equal to 0.8, particularly when the content of Ni element is more than 80%, the material shows the high-capacity characteristic of more than 180mAh/g, and the lithium ion battery ternary cathode material LiNi must be taken as a high-nickel route in the whole industry chain due to the fact that the current policy and market demand are both driven0.8Co0.1Mn0.1O2Because of the advantages of high reversible specific capacity, low cost and the like, the material has wide application prospect, is regarded as the first choice of the next generation of high specific energy anode material, but the residual LiOH and Li on the surface of the material2CO3When the electrode is prepared, the electrode reacts with a binder, (PVDF) and an organic solvent (NMP) to cause a jelly phenomenon in a slurry mixing process, so that LiNi is enabled to be generated0.8Co0.1Mn0.1O2The NCM622 cannot be skipped directly, and rapidly under the power battery positive electrode field, the following reasons are mainly used: in the aspect of process difficulty, the separation of lithium is caused due to serious cation mixing caused by high Ni content of the material, soluble salts such as lithium carbonate and lithium hydroxide are formed on the surface of the material, so that the pH value of the material is alkaline, water is easily absorbed in the mixing process to form a jelly shape, coating is influenced, the water control is not good, and the processing performance is difficultAttempts have previously been made to prevent further reaction of the precipitated lithium by surface coating, e.g. by coating the material surface with Li2ZrO3Surface passivation or attempts to strengthen the structure of the material by cationic doping are still not well established in the industry and even if some enterprises improve it, it is still impossible to put an end to the industry.
The invention content is as follows:
the present invention is directed to solving the above problems by providing a lithium battery ternary material LiNi0.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method of (1) solves the problems mentioned in the background art.
In order to solve the above problems, the present invention provides a technical solution:
ternary material LiNi of lithium battery0.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method comprises the LiNi which is the ternary positive electrode material of the lithium ion battery0.8Co0.1Mn0.1O2The lithium ion battery ternary positive electrode material LiNi0.8Co0.1Mn0.1O2The matrix material is Lix(NiaCobMnc)O2A type NCM ternary material, wherein x is more than or equal to 1.00 and less than or equal to 1.09, a + b + c is 1, and a is more than or equal to 0.8, in the Lix(NiaCobMnc)O2The NCM ternary material is coated with a surface modified nano metal oxide passivation layer, the surface modification adopts low-melting-point inorganic salt, and the nano metal oxide passivation layer is Li2ZrO3。
Preferably, the lithium ion battery ternary cathode material LiNi0.8Co0.1Mn0.1O2The surface of the base material contains LiOH with a residual alkali content of 0.5-0.6 wt% and Li with a residual alkali content of 0.2-0.3 wt%2CO3。
Preferably, the lithium ion battery ternary cathode material LiNi0.8Co0.1Mn0.1O2The surface residual alkali content of (A) is 0.1-0.2 wt% of LiOH and 0.1-0.03 wt% of Li2CO3。
Preferably, the nano metal oxide passivation layer Li2ZrO3Is a ternary positive electrode material LiNi of a lithium ion battery0.8Co0.1Mn0.1O20.05-0.1 wt% of the base material of (1), the nano metal oxide passivation layer Li2ZrO3Is prepared by adopting a sol-gel method.
Preferably, the low-melting-point inorganic salt is AlCl3。
Preferably, the method comprises the following steps:
a. putting a nickel-cobalt-manganese hydroxide precursor and a lithium source into a mixer for mixing to obtain mixed powder, then putting the mixed powder into a bowl, putting the bowl into a kiln for sintering to obtain the lithium ion battery ternary cathode material LiNi0.8Co0.1Mn0.1O2The base material of (1);
b. the lithium ion battery ternary positive electrode material LiNi0.8Co0.1Mn0.1O2The substrate material and the nano metal oxide are uniformly mixed by a dry method to obtain primary mixed powder, and then the primary mixed powder is annealed to obtain modified powder;
c. washing the modified powder with water, and then mixing with low-melting-point inorganic salt AlCl3Uniformly mixing by a dry method, and performing secondary annealing treatment to obtain new modified powder, namely the ternary cathode material of the lithium ion battery, namely LiNi0.8Co0.1Mn0.1O2；
d. Preparing nano metal oxide passivation layer Li by sol-gel method2ZrO3；
e. With Zr (NO)3)4·5H2O and CH3COOLi·2H2O is used as raw material, and a wet chemical method is adopted to passivate the Li layer of the nano metal oxide passivation layer2ZrO3LiNi coated on ternary positive electrode material of lithium ion battery0.8Co0.1Mn0.1O2Of (2) is provided.
Preferably, in the step a, firstly, a metal ion mixed solution with a certain concentration is prepared according to a stoichiometric ratio, meanwhile, an ammonia-alkali mixed solution with a certain concentration is prepared as a precipitator and a complexing agent, nitrogen is continuously introduced to enable the atmosphere of the reaction kettle to be nitrogen, then, the reaction is carried out, a composite precipitate is produced by adjusting the pH value of the solution, and the nickel-cobalt-manganese hydroxide precursor is directly obtained after filtration, washing and vacuum drying.
Preferably, the molar ratio between the nickel cobalt manganese hydroxide precursor and the lithium source is 1 to 1.04; the sintering is carried out in a pure oxygen atmosphere, and the feeding quantity and the proportion are accurately mastered, so that the materials are uniformly mixed and the color is normal.
Preferably, in both steps b and c, after the annealing treatment, the powder is first crushed to a particle size as required, then crushed again to a usable size, and then classified to distribute the powder according to particle size.
Preferably, in the step c, the new modified powder needs to be subjected to an iron removal operation, magnetic impurities doped in the new modified powder are removed through a special iron removal device, then the new modified powder is subjected to a sieving operation, the operation is performed through a special standard screen so that the new modified powder can reach corresponding physical and chemical indexes, and finally the new modified powder is packaged to complete the final coating of the nano metal oxide passivation layer.
The invention has the beneficial effects that: the invention relates to a ternary material LiNi of a lithium battery0.8Co0.1Mn0.1O2Surface coated with Li2ZrO3By using LiNi as the ternary positive electrode material of lithium ion battery0.8Co0.1Mn0.1O2Surface coated with Li2ZrO3And the LiNi serving as the ternary cathode material of the lithium ion battery is fully reduced0.8Co0.1Mn0.1O2Soluble salts such as lithium carbonate and lithium hydroxide formed on the surface also reduce the pH value of the material, so that the material can not absorb water in the process of mixing materials to be in a jelly shape, subsequent coating can not be influenced, the moisture control is more perfect, the processing performance is also reduced, and the loss of gram capacity of the material is reduced on the basis of reducing the pH valueThereby ensuring the energy density and corresponding cycle performance of the material, and simultaneously passing through Li2ZrO3The coating layer inhibits side reaction between the anode material and electrolyte, and reduces the charge transfer resistance of the material in the circulation process, thereby improving the electrochemical performance of the material.
Description of the drawings:
for ease of illustration, the invention is described in detail by the following detailed description and the accompanying drawings.
FIG. 1 shows a base material, a high nickel material and Li cladding in the present invention2ZrO3Rear LiNi0.8Co0.1Mn0.1O2A bar graph of pH versus pH;
FIG. 2 shows a base material, a high nickel material and Li cladding in the present invention2ZrO3Rear LiNi0.8Co0.1Mn0.1O2Surface residual alkali map of (1);
FIG. 3 shows a base material, a high nickel material and Li cladding in the present invention2ZrO3Rear LiNi0.8Co0.1Mn0.1O2Graphs of cycle performance of the respectively prepared half cells.
The specific implementation mode is as follows:
as shown in fig. 1 to 3, the following technical solutions are adopted in the present embodiment:
example (b):
ternary material LiNi of lithium battery0.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method comprises the LiNi which is the ternary positive electrode material of the lithium ion battery0.8Co0.1Mn0.1O2Ternary positive electrode material LiNi of lithium ion battery0.8Co0.1Mn0.1O2The matrix material is Lix(NiaCobMnc)O2The NCM ternary material is characterized in that x is more than or equal to 1.00 and less than or equal to 1.09, a + b + c is 1, a is more than or equal to 0.8, and Li isx(NiaCobMnc)O2The NCM ternary material is coated with a surface modified nano metal oxide passivation layer, and the surface modification adopts low-melting-point inorganic saltThe nano metal oxide passivation layer is Li2ZrO3。
Wherein, the lithium ion battery ternary anode material LiNi0.8Co0.1Mn0.1O2The surface of the base material contains LiOH with a residual alkali content of 0.5-0.6 wt% and Li with a residual alkali content of 0.2-0.3 wt%2CO3And strictly controlling the lithium ion battery ternary positive electrode material LiNi while preparing the matrix material0.8Co0.1Mn0.1O2The residual alkali content on the surface of the base material is beneficial to subsequent tests or subsequent coating processes, so that the whole preparation process is simpler and faster, the difficulty of subsequent operation is reduced, the step of changing the residual alkali content on the surface of the base material in the subsequent operation is reduced, and the speed of the coating preparation process is greatly increased.
Wherein, the lithium ion battery ternary anode material LiNi0.8Co0.1Mn0.1O2The surface residual alkali content of (A) is 0.1-0.2 wt% of LiOH and 0.1-0.03 wt% of Li2CO3By strictly controlling the ternary positive electrode material LiNi of the lithium ion battery0.8Co0.1Mn0.1O2The method comprises the following steps of preparing a lithium ion battery ternary positive electrode material, preparing a half battery by using the lithium ion battery ternary positive electrode material, and then observing the residual alkali content on the surfaces of a base material and the lithium ion battery ternary positive electrode material to determine the precipitation content of lithium in the half battery.
Wherein, the nanometer metal oxide passivation layer Li2ZrO3Is a ternary positive electrode material LiNi of a lithium ion battery0.8Co0.1Mn0.1O20.05-0.1 wt% of the base material, and a nano metal oxide passivation layer Li2ZrO3Is prepared by a sol-gel method, Li2ZrO3Is a lithium ion material with wider application in industry, and contains Li with more monoclinic phase crystal grains2ZrO3Has high lithium atom density and shows physical propertiesGood thermal stability and electrical conductivity therefore Li2ZrO3Has a plurality of applications in the field of lithium ion batteries, and synthesizes Li2ZrO3The method mainly comprises a high-temperature solid phase method, a soft chemical method, a sol-gel method and the like, wherein the high-temperature solid phase method needs to be roasted at high temperature for a long time to obtain a good crystal form, but impurities are easily introduced in the preparation process, the synthesized material has large particle size and poor uniformity, and the spray drying soft chemical method is adopted to prepare Li2ZrO3The particle size is about 13nm, the uniformity is good, but the spraying temperature is high, the material amount synthesized at one time is small, and the practical application is limited, so the sol-gel method is the most common method for preparing nano-grade lithium zirconate, and the Li prepared by the sol-gel method is the most common method for preparing nano-grade lithium zirconate2ZrO3The grain size is small and uniform, and the method is simple.
Wherein the low-melting-point inorganic salt is AlCl3The modified powder after washing is convenient to be better and uniformly mixed with the modified powder obtained for the first time by a dry method, and the subsequent use is convenient.
The method comprises the following steps:
a. putting a nickel-cobalt-manganese hydroxide precursor and a lithium source into a mixer for mixing to obtain mixed powder, then putting the mixed powder into a bowl, putting the bowl into a kiln for sintering to obtain the lithium ion battery ternary cathode material LiNi0.8Co0.1Mn0.1O2The base material of (1);
b. the ternary positive electrode material LiNi of the lithium ion battery0.8Co0.1Mn0.1O2The substrate material and the nano metal oxide are uniformly mixed by a dry method to obtain primary mixed powder, and then the primary mixed powder is annealed to obtain modified powder;
c. washing the modified powder with water and then mixing with low-melting-point inorganic salt AlCl3Uniformly mixing by a dry method, and performing secondary annealing treatment to obtain new modified powder, namely the ternary cathode material of the lithium ion battery, namely LiNi0.8Co0.1Mn0.1O2；
d. Preparing nano metal oxide passivation layer Li by sol-gel method2ZrO3；
e. With Zr (NO)3)4·5H2O and CH3COOLi·2H2O is used as raw material, and a wet chemical method is adopted to passivate the Li layer of the nano metal oxide passivation layer2ZrO3LiNi coated on ternary positive electrode material of lithium ion battery0.8Co0.1Mn0.1O2The wet chemical method is to use various zinc-containing materials as raw materials, leach zinc by acid leaching, remove impurities in the raw materials by multiple purification, then precipitate to obtain basic zinc carbonate, finally calcine and the like to obtain nano zinc oxide, and the wet chemical method is adopted to conveniently combine a reaction kinetics principle with an enhanced heat transfer technology under a balanced condition to quickly complete the calcine of the basic zinc carbonate.
In the step a, firstly, preparing a metal ion mixed solution with a certain concentration according to a stoichiometric ratio, preparing an ammonia-alkali mixed solution with a certain concentration as a precipitator and a complexing agent, continuously introducing nitrogen to make the atmosphere of a reaction kettle be nitrogen, then carrying out reaction, adjusting the pH value of the solution to produce a composite precipitate, filtering, washing and vacuum drying the composite precipitate to directly obtain a nickel-cobalt-manganese hydroxide precursor, wherein the nickel-cobalt-manganese hydroxide precursor is a necessary condition for preparing a good lithium ion battery ternary positive electrode material, and the nickel-cobalt-manganese hydroxide precursor obtained by filtering, washing and vacuum drying is a precursor which is more compounded in the whole preparation process.
In the step a, the molar ratio of the nickel-cobalt-manganese hydroxide precursor to the lithium source is 1: 1.04; sintering is carried out in a pure oxygen atmosphere, the feeding quantity and the proportion are accurately mastered, so that the materials are uniformly mixed, the color is normal, the feeding quantity and the proportion are accurately mastered, so that the materials are uniformly mixed, a specific molar ratio can be ensured between a nickel-cobalt-manganese hydroxide precursor and a lithium source in the preparation process, and unqualified products are prevented from being prepared.
In the steps b and c, after annealing treatment, firstly crushing according to requirements to enable the powder to reach the particle size, then crushing the powder to enable the powder to reach the usable size degree, then grading the crushed powder, distributing according to the particle size, crushing and screening the primarily obtained powder through necessary procedures, and obtaining the powder most suitable for the preparation process in a distinguishing manner.
In the step c, the new modified powder needs to be subjected to iron removal operation, the magnetic impurities doped in the new modified powder are removed through a special iron removal device, then the new modified powder is subjected to sieving operation, the new modified powder is operated through a special standard screen, so that the new modified powder can reach corresponding physical and chemical indexes, and finally the new modified powder is packaged to complete the coating of the final nano metal oxide passivation layer.
The using state of the invention is as follows: firstly, preparing a metal ion mixed solution with a certain concentration according to a stoichiometric ratio, simultaneously preparing an ammonia-alkali mixed solution with a certain concentration as a precipitator and a complexing agent, continuously introducing nitrogen to ensure that the atmosphere of a reaction kettle is nitrogen, then carrying out reaction, producing a composite precipitate by adjusting the pH value of the solution, directly obtaining a nickel-cobalt-manganese hydroxide precursor after filtering, washing and vacuum drying, then putting the nickel-cobalt-manganese hydroxide precursor and a lithium source into a mixer for mixing to obtain mixed powder, then carrying out pot loading, then putting into a kiln, sintering the mixture for 3-10 hours at 720-0.8Co0.1Mn0.1O2The lithium ion battery ternary positive electrode material LiNi0.8Co0.1Mn0.1O2The substrate material and the nano metal oxide are evenly mixed by a dry method to obtain primary mixed powder, then the primary mixed powder is placed in a pure oxygen atmosphere to be annealed at the temperature of 500-750 ℃ for 3-6 hours to obtain modified powder, the modified powder and deionized water are mixed and stirred for 5-20 minutes, then the mixture is filtered and dried, nitrogen is introduced for replacement while drying, and then the modified powder after being washed by water and low-melting-point inorganic salt AlCl are added3Uniformly mixing by a dry method, and then performingSecondary annealing treatment, namely placing the material in a pure oxygen atmosphere and preserving heat for 3-6 hours at the temperature of 400-700 ℃, and then obtaining new modified powder, namely the ternary anode material of the lithium ion battery, namely LiNi0.8Co0.1Mn0.1O2Then preparing nano metal oxide passivation layer Li by sol-gel method2ZrO3Li prepared by sol-gel method2ZrO3The grain diameter is small and uniform, and the method is simple, convenient to operate, suitable for practical application, and capable of obtaining Li most suitable for the whole preparation process2ZrO3Thereby greatly increasing the reliability and practicability of the preparation, and finally taking Zr (NO)3)4·5H2O and CH3COOLi·2H2O is used as raw material, and a wet chemical method is adopted to passivate the Li layer of the nano metal oxide passivation layer2ZrO3LiNi coated on ternary positive electrode material of lithium ion battery0.8Co0.1Mn0.1O2The surface of (1) the wet chemical method is to use various zinc-containing materials as raw materials, adopt acid leaching to leach zinc, remove impurities in the raw materials through multiple purification, then precipitate to obtain basic zinc carbonate, finally calcine and the like to obtain nano zinc oxide, adopt the wet chemical method to combine the reaction kinetics principle with the enhanced heat transfer technology under the equilibrium condition to rapidly complete the calcine of the basic zinc carbonate, compare with figure 3, although the nickel-rich NCM811 material has the advantages of high capacity, low price and the like, but because of the short plates of the structure, chemical characteristics and the like, the problems of circulation, thermal stability, safety and the like need to be further optimized and stabilized, when a battery core manufacturer introduces the NCM811, the problems need to be fully evaluated, can not be blindly taken, the popularization and application of the high-nickel NCM811 material need a systematic solution, not only the innovation progress of the material, but also need to be applied (field process technology) Product structure, environmental control, BMS, etc.) has a profound understanding of the materials, so that the advantages of NCM811 are exploited sufficiently, while Li with a thickness of about 8nm is used2ZrO3LiNi coated on ternary positive electrode material of lithium ion battery0.8Co0.1Mn0.1O2As shown in FIG. 3, 1% mass fraction of Li as compared with the pure phase2ZrO3Coated LiNi0.8Co0.1Mn0.1O2The first discharge specific capacity of the composite material, the matrix material and the high-nickel material at 1.0C is 184.7mAh/g, but the discharge specific capacity is Li after 100 cycles2ZrO3Coated LiNi0.8Co0.1Mn0.1O2169.5mAh/g of composite material, 159.5mAh/g of matrix material and 164.6mAh/g of high-nickel material, which are all lower than Li2ZrO3Coated LiNi0.8Co0.1Mn0.1O2Composite materials, i.e. proving Li2ZrO3Coated LiNi0.8Co0.1Mn0.1O2Less lithium is precipitated in the composite material, less soluble salts such as lithium carbonate and lithium hydroxide are formed on the surface of the material, and Li2ZrO3Coated LiNi0.8Co0.1Mn0.1O2Composite after 100 cycles, Li2ZrO3The coating layer inhibits side reaction between the anode material and electrolyte, and reduces charge transfer resistance of the material in the circulation process, thereby improving the electrochemical performance of the material.
While there have been shown and described what are at present considered to be the fundamental principles of the invention and its essential features and advantages, it will be understood by those skilled in the art that the invention is not limited by the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (10)
1. Ternary material LiNi of lithium battery0.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method is characterized by comprising a lithium ion battery ternary cathode material LiNi0.8Co0.1Mn0.1O2The lithium ion battery ternary positive electrode material LiNi0.8Co0.1Mn0.1O2The matrix material is Lix(NiaCobMnc)O2A type NCM ternary material, wherein x is more than or equal to 1.00 and less than or equal to 1.09, a + b + c is 1, and a is more than or equal to 0.8, in the Lix(NiaCobMnc)O2The NCM ternary material is coated with a surface modified nano metal oxide passivation layer, the surface modification adopts low-melting-point inorganic salt, and the nano metal oxide passivation layer is Li2ZrO3。
2. The lithium battery ternary material LiNi according to claim 10.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method of (2), characterized by: the lithium ion battery ternary positive electrode material LiNi0.8Co0.1Mn0.1O2The surface of the base material contains LiOH with a residual alkali content of 0.5-0.6 wt% and Li with a residual alkali content of 0.2-0.3 wt%2CO3。
3. The lithium battery ternary material LiNi according to claim 10.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method of (2), characterized by: the lithium ion battery ternary positive electrode material LiNi0.8Co0.1Mn0.1O2The surface residual alkali content of (A) is 0.1-0.2 wt% of LiOH and 0.1-0.03 wt% of Li2CO3。
4. The lithium battery ternary material LiNi according to claim 10.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method of (2), characterized by: the nano metal oxide passivation layer Li2ZrO3Is a ternary positive electrode material LiNi of a lithium ion battery0.8Co0.1Mn0.1O20.05-0.1 wt% of the base material of (1), the nano metal oxide passivation layer Li2ZrO3Is prepared by adopting a sol-gel method.
5. The lithium battery ternary material LiNi according to claim 10.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method of (2), characterized by: the low-melting-point inorganic salt is AlCl3。
6. The lithium battery ternary material LiNi according to claim 10.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method of (2), characterized by: the method comprises the following steps:
a. putting a nickel-cobalt-manganese hydroxide precursor and a lithium source into a mixer for mixing to obtain mixed powder, then putting the mixed powder into a bowl, putting the bowl into a kiln for sintering to obtain the lithium ion battery ternary cathode material LiNi0.8Co0.1Mn0.1O2The base material of (1);
b. the lithium ion battery ternary positive electrode material LiNi0.8Co0.1Mn0.1O2The substrate material and the nano metal oxide are uniformly mixed by a dry method to obtain primary mixed powder, and then the primary mixed powder is annealed to obtain modified powder;
c. washing the modified powder with water, and then mixing with low-melting-point inorganic salt AlCl3Uniformly mixing by a dry method, and performing secondary annealing treatment to obtain new modified powder, namely the ternary cathode material of the lithium ion battery, namely LiNi0.8Co0.1Mn0.1O2；
d. Preparing nano metal oxide passivation layer Li by sol-gel method2ZrO3；
e. With Zr (NO)3)4·5H2O and CH3COOLi·2H2O is used as raw material, and a wet chemical method is adopted to passivate the Li layer of the nano metal oxide passivation layer2ZrO3LiNi coated on ternary positive electrode material of lithium ion battery0.8Co0.1Mn0.1O2Of (2) is provided.
7. The method of claim 6The lithium battery ternary material LiNi0.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method of (2), characterized by: in the step a, firstly, preparing a metal ion mixed solution with a certain concentration according to a stoichiometric ratio, simultaneously preparing an ammonia-alkali mixed solution with a certain concentration as a precipitator and a complexing agent, continuously introducing nitrogen to enable the atmosphere of a reaction kettle to be nitrogen, then carrying out reaction, adjusting the pH value of the solution to produce a composite precipitate, and directly obtaining the nickel-cobalt-manganese hydroxide precursor after filtering, washing and vacuum drying.
8. The lithium battery ternary material LiNi according to claim 60.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method of (2), characterized by: in the step a, the molar ratio of the nickel-cobalt-manganese hydroxide precursor to the lithium source is 1: 1.04; the sintering is carried out in a pure oxygen atmosphere, and the feeding quantity and the proportion are accurately mastered, so that the materials are uniformly mixed and the color is normal.
9. The lithium battery ternary material LiNi according to claim 60.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method of (2), characterized by: in the steps b and c, after the annealing treatment, firstly crushing the powder to reach the particle size according to the requirements, then crushing the powder to reach the usable size, and then grading the crushed powder and distributing the powder according to the particle size.
10. The lithium battery ternary material LiNi according to claim 60.8Co0.1Mn0.1O2Surface coated with Li2ZrO3The method of (2), characterized by: in the step c, the new modified powder needs to be subjected to iron removal operation, magnetic impurities doped in the new modified powder are removed through a special iron removal device, then the new modified powder is subjected to sieving operation, and the new modified powder is operated through a special standard screen so as to reach the corresponding physical propertyAnd finally packaging the nano metal oxide and the chemical indexes to finish the final coating of the nano metal oxide passivation layer.
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