CN113178560B - Metal oxide coated NCM ternary electrode material, preparation method thereof and lithium ion battery - Google Patents
Metal oxide coated NCM ternary electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 66
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 53
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 53
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000010406 cathode material Substances 0.000 claims abstract description 20
- 238000001694 spray drying Methods 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 21
- 239000011343 solid material Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 14
- 230000010355 oscillation Effects 0.000 claims description 14
- ZUGAOYSWHHGDJY-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-aluminabicyclo[3.3.2]decane-3,7,10-trione Chemical compound [Al+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZUGAOYSWHHGDJY-UHFFFAOYSA-K 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 108010064470 polyaspartate Proteins 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 claims description 6
- 229940068475 zinc citrate Drugs 0.000 claims description 6
- 235000006076 zinc citrate Nutrition 0.000 claims description 6
- 239000011746 zinc citrate Substances 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- 229920000578 graft copolymer Polymers 0.000 claims description 3
- -1 polysuccinimide Polymers 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims 1
- 239000011247 coating layer Substances 0.000 abstract description 28
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000000576 coating method Methods 0.000 abstract description 13
- 238000001704 evaporation Methods 0.000 abstract description 8
- 230000008020 evaporation Effects 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000609 methyl cellulose Polymers 0.000 description 6
- 239000001923 methylcellulose Substances 0.000 description 6
- 235000010981 methylcellulose Nutrition 0.000 description 6
- 238000005336 cracking Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000002632 lipids Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 150000003482 tantalum compounds Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
Classifications
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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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a metal oxide coated NCM ternary electrode material, a preparation method thereof and a lithium ion battery. The preparation method comprises the following steps: (1) Mixing organic metal salt solution and a binder, and stirring to obtain gel; (2) Mixing graphene and the gel obtained in the step (1) under a stirring condition, and standing to obtain graphene gel; (3) Mixing the ternary cathode material and the graphene gel obtained in the step (2), and oscillating and stirring to obtain a suspension; (4) And (4) sieving the suspension obtained in the step (3), and sequentially performing spray drying and heat treatment on the sieved material to obtain the metal oxide coated NCM ternary electrode material. The invention adopts a sol-gel method to realize controllable uniform coating of the coating layer, regulates the water evaporation rate of the coating layer by a spray drying method to form a compact coating layer, improves the electrochemical performance, has short preparation flow, simple and convenient operation and low preparation cost, and is beneficial to industrial production.
Description
Technical Field
The invention belongs to the field of battery electrode materials, relates to an NCM ternary electrode material, and particularly relates to a metal oxide-coated NCM ternary electrode material and a preparation method and application thereof.
Background
Ternary materials (LiNi) x Co y Mn z O 2 ) Has both LiCoO and LiCoO 2 、LiNiO 2 And LiMn z O 2 The advantages of (1). In ternary materials, nickel is the main active element. In general, the higher the relative content of nickel, the higher the theoretical discharge capacity of the ternary material.
The ternary material has higher specific capacity, energy density and power density and more stable performance, thereby becoming a popular material for a commercial anode. However, the electrochemical performance, thermal stability and structural stability of the ternary material need to be further improved. The ternary material is coated, so that a protective layer can be provided for the ternary active electrode material, the ternary active electrode material is prevented from being in direct contact with electrolyte, a series of side reactions are reduced to a great extent, for example, precipitation of transition metals is reduced, a thinner SEI film is formed, precipitation of oxygen atoms is reduced, and the like, and the charged chemical stability is improved. In addition, by screening a proper coating material, the conductivity and the thermal stability of the lithium ion electron are remarkably improved, so that good multiplying power and cycle performance are obtained.
CN 110416491A discloses a modified ternary nickel-cobalt-manganese electrode coated with graphene and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Mixing ternary nickel cobalt lithium manganate powder, a conductive additive and a binder, grinding the mixture into slurry, coating the slurry on a current collector, and drying to obtain a ternary nickel cobalt manganese electrode; (2) Dissolving graphene in absolute ethyl alcohol to obtain a coating solution; (3) Immersing the ternary nickel-cobalt-manganese electrode into a coating solution, stirring and coating, and taking out to obtain a coated electrode; (4) And (3) putting the coated electrode into a forced air drying oven for drying, and then putting the dried electrode into a vacuum drying oven for drying to obtain the graphene coated modified ternary nickel cobalt manganese electrode. According to the method, the graphene-coated modified ternary nickel-cobalt-manganese electrode is prepared by a wet chemical method, the operation process of the preparation method is complex, and the coated electrode is placed into an air-blast drying oven for drying, so that the coating layer is easy to crack, and the performance of the graphene-coated modified ternary nickel-cobalt-manganese electrode is influenced.
CN 110648860A discloses a preparation method of a ternary material coated with polyaluminium-graphene, which comprises the following steps: (1) Mixing polyvinylpyrrolidone with a liquid medium, adding graphene powder while stirring, and performing ultrasonic oscillation treatment to obtain a graphene solution; (2) Mixing the graphene solution with the diluted solution to obtain a polyaluminium-graphene solution; (3) Uniformly mixing the ternary material and a liquid medium to obtain a mixed solution 2; (4) Uniformly mixing the polyaluminium-graphene solution and the mixed solution 2 to obtain a mixed solution 3, under the condition of continuous stirring, dropwise adding ammonia water until the acidity of the mixed solution 3 is within the range of pH8-12, and aging to obtain a precursor 1; (5) Sequentially carrying out vacuum treatment on the precursor 1Drying or spray drying, and roasting to obtain the layered alpha-NaFeO 2 The structure is coated with the ternary cathode material of the polyaluminium chloride-graphene. The preparation method is complex to operate, and the liquid medium and the diluted solution cannot be effectively recycled in the preparation process, thereby causing resource waste.
CN 110970604A discloses a coated ternary cathode material, a preparation method and an application thereof, wherein the coated ternary cathode material comprises a ternary cathode material and a coating layer containing lithium and tantalum, and the coating layer is coated on the surface of the ternary cathode material. The preparation method comprises the steps of coating a ternary material with residual alkali on the surface by using a tantalum compound as a coating raw material, and reacting the residual alkali with the tantalum compound to form a coating layer containing lithium and tantalum on the surface of the ternary cathode material, so as to obtain the coated ternary cathode material. The preparation method comprises the steps of firstly processing the ternary cathode material, and then coating the processed ternary cathode material, wherein the processing method is complex. Alkali liquor and precursors can not be effectively recovered in the preparation process, so that waste of resources is caused; and the ternary cathode material is directly roasted without a drying process, so that the cracking of a coating layer is easily caused, and the performance of the ternary cathode material is influenced.
In summary, the preparation process of the coated ternary cathode material provided at present is complicated, high in cost and difficult to operate. Therefore, the preparation method of the coated ternary cathode material is simple, the cost is low, the conductivity and the thermal stability of the lithium ion battery are obviously improved, and the coated ternary cathode material becomes one of the problems to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a metal oxide coated NCM ternary electrode material. The preparation process of the metal oxide-coated NCM ternary electrode material provided by the invention is short, the operation is simple and convenient, harsh reaction conditions are not required, the operation is safe, the implementation is easy, the preparation cost is low, and the industrial production is facilitated.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a metal oxide-coated NCM ternary electrode material, comprising the steps of:
(1) Mixing organic metal salt solution and a binder, and stirring to obtain gel;
(2) Mixing graphene and the gel obtained in the step (1) under a stirring condition, and standing to obtain graphene gel;
(3) Mixing the NCM ternary positive electrode material and the graphene gel obtained in the step (2), and shaking and stirring to obtain a suspension;
(4) And (4) processing the suspension liquid obtained in the step (3) to obtain the NCM ternary electrode material coated with the metal oxide.
The preparation process of the metal oxide-coated NCM ternary electrode material provided by the invention is short, the operation is simple and convenient, harsh reaction conditions are not required, the operation is safe, the implementation is easy, and the preparation cost is low. The invention adopts a liquid phase sol-gel method to realize controllable uniform coating of the coating layer by controlling the quality and temperature of the coating layer material; the spray drying method is adopted to regulate the water evaporation rate of the coating layer, so that a compact coating layer is formed, the electrochemical performance of the lithium ion battery is effectively improved, and the cracking of the coating layer caused by the traditional capillary evaporation process is avoided.
Preferably, the concentration of the organometallic salt solution in step (1) is 200-1000mg/L, such as 200mg/L, 250mg/L, 300mg/L, 350mg/L, 400mg/L, 450mg/L, 500mg/L, 550mg/L, 600mg/L, 650mg/L, 700mg/L, 750mg/L, 800mg/L, 850mg/L, 900mg/L, 950mg/L or 1000mg/L, but is not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the organometallic salts in the organometallic salt solution of step (1) include any one of, or a combination of at least two of, aluminum citrate, zinc citrate, or titanium-containing lipid metal salts, with typical, but non-limiting combinations including, combinations of aluminum citrate and zinc citrate, aluminum citrate and titanium-containing lipid metal salts, zinc citrate and titanium-containing lipid metal salts, or aluminum citrate, zinc citrate and titanium-containing lipid metal salts.
Preferably, the binder of step (1) comprises any one or a combination of at least two of sodium carboxymethylcellulose, carboxymethylcellulose-acrylamide graft copolymer, polysuccinimide, polyaspartic acid, or polyacrylamide, and typical but non-limiting combinations include a combination of sodium carboxymethylcellulose and carboxymethylcellulose-acrylamide graft copolymer, a combination of sodium carboxymethylcellulose and polysuccinimide, a combination of sodium carboxymethylcellulose and polyaspartic acid, a combination of polyaspartic acid and polyacrylamide, and a combination of polysuccinimide, polyaspartic acid, and polyacrylamide; preferably polyacrylamide.
Preferably, the concentration of the binder in step (1) is 500-2000mg/L, such as 500mg/L, 600mg/L, 700mg/L, 800mg/L, 900mg/L, 1000mg/L, 1100mg/L, 1200mg/L, 1300mg/L, 1400mg/L, 1500mg/L, 1600mg/L, 1700mg/L, 1800mg/L, 1900mg/L or 2000mg/L, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the mixing of step (1) is carried out in a reaction vessel.
Preferably, the stirring process in step (1) further comprises ultrasonic oscillation treatment.
Preferably, the frequency of the ultrasonic oscillations is in the range of 80 to 100kHz, and may be, for example, 80kHz, 82kHz, 84kHz, 86kHz, 88kHz, 90kHz, 92kHz, 94kHz, 96kHz, 98kHz or 100kHz, but is not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the time of the ultrasonic oscillation is 30-90min, such as 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min or 90min, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the stirring of step (1) is vacuum stirring.
Preferably, the stirring rate in step (1) is 120-600rpm, for example 120rpm,150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm or 600rpm, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the stirring temperature in step (1) is 20-60 ℃, for example, 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃ or 60 ℃, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the stirring time in step (1) is 30-90min, such as 30min, 33min, 36min, 39min, 42min, 45min, 48min, 51min, 54min, 57min, 60min, 63min, 66min, 69min, 72min, 75min, 78min, 81min, 84min, 87min or 90min, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the degree of vacuum during the stirring in step (1) is 20 to 80kPa, and may be, for example, 20kPa, 25kPa, 30kPa, 35kPa, 40kPa, 45kPa, 50kPa, 55kPa, 60kPa, 65kPa, 70kPa, 75kPa, or 80kPa, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the graphene of step (2) comprises graphene oxide or reduced graphene oxide.
Preferably, the stirring of step (2) is vacuum stirring.
Preferably, the degree of vacuum during the stirring in step (2) is 20 to 80kPa, and may be, for example, 20kPa, 25kPa, 30kPa, 35kPa, 40kPa, 45kPa, 50kPa, 55kPa, 60kPa, 65kPa, 70kPa, 75kPa, or 80kPa, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the stirring rate of the stirring in step (2) is 120-600rpm, for example 120rpm,150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm or 600rpm, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the stirring temperature in step (2) is 20-60 ℃, for example, 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃ or 60 ℃, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the stirring time in step (2) is 60-120min, such as 60min, 65min, 70min, 75min, 80min, 85min, 90min, 95min, 100min, 105min, 110min, 115min or 120min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the end point of the standing in step (2) is that the graphene gel has a viscosity of 1 to 10Pa · s, and may be, for example, 1Pa · s, 1.5Pa · s, 2Pa · s, 2.5Pa · s, 3Pa · s, 3.5Pa · s, 4Pa · s, 4.5Pa · s, 5Pa · s, 5.5Pa · s, 6Pa · s, 6.5Pa · s, 7Pa · s, 7.5Pa · s, 8Pa · s, 8.5Pa · s, 9Pa · s, 9.5Pa · s, or 10Pa · s, but is not limited to the recited values, and other values in the range of values are also applicable.
Preferably, the ternary cathode material of step (3) is used in an amount of 500-1000g/L, such as 500g/L, 550g/L, 600g/L, 650g/L, 700g/L, 750g/L, 800g/L, 850g/L, 900g/L, 950g/L or 1000g/L, but not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the stirring rate in step (3) is 800-2000rpm, such as 800rpm, 850rpm, 900rpm, 950rpm, 1000rpm, 1050rpm, 1100rpm, 1150rpm, 1200rpm, 1250rpm, 1300rpm, 1350rpm, 1400rpm, 1450rpm, 1500rpm, 1550rpm, 1600rpm, 1650rpm, 1700rpm, 1750rpm, 1800rpm, 1850rpm, 1900rpm, 1950rpm or 2000rpm, but is not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the stirring time in step (3) is 30-90min, such as 30min, 35min, 40min, 45min, 50min, 60min, 65min, 70min, 75min, 80min, 85min or 90min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the stirring temperature in step (3) is 20-50 ℃, for example, 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃ or 50 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the stirring process of step (3) is accompanied by ultrasonic vibration.
Preferably, the treatment of step (4) comprises sieving, drying and heat treatment.
Preferably, the drying comprises spray drying.
In the spray drying process of the invention, the solvent is simultaneously condensed and recovered. The solvent recovered by condensation comprises a solvent for preparing an organic metal salt solution and a binder.
Preferably, the screened mesh size is 150-300 mesh, such as 150 mesh, 180 mesh, 190 mesh, 200 mesh, 210 mesh, 220 mesh, 230 mesh, 240 mesh, 250 mesh, 260 mesh, 270 mesh, 280 mesh, 290 mesh or 300 mesh, but not limited to the listed values, and other non-listed values within the range of values are equally applicable.
Preferably, the spray drying time is from 0.5 to 3.0h, for example 0.5h, 1.0h, 1.5h, 2.0h, 2.5h or 3.0h, but is not limited to the values listed, and other values not listed in the range of values are equally suitable.
Preferably, the temperature of the spray drying is 80-110 ℃, for example 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃ or 110 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
According to the invention, the evaporation rate of the water in the coating layer is regulated and controlled by adopting a spray drying method, a compact coating layer is formed, the possibility of cracking of the coating layer is avoided, and the electrochemical performance of the ternary electrode material is improved.
Preferably, the heat treatment is carried out on the sieved material in an oxygen and/or air atmosphere.
Preferably, the heat treatment comprises the steps of:
(a) Heating to 105-150 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 2-5h,gas flow rate of O 2 Meter, control at 5m 3 H/kg solid material;
(b) Heating to 600-900 deg.C at a rate of 5-10 deg.C/min, maintaining for 3-6h, and maintaining the gas flow rate at O 2 Meter, control at 5m 3 H/kg solid material;
(c) Cooling to below 100 deg.C at a cooling rate of not more than 10 deg.C/min, and introducing gas at a flow rate of O 2 Meter, control at 20m 3 The volume per hour per kg of solid material.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) Mixing an organic metal salt solution and a binder in a reaction kettle, and carrying out vacuum stirring for 30-90min at the conditions of 120-600rpm, 20-60 ℃ and 20-80kPa vacuum degree to obtain gel, wherein the vacuum stirring process comprises ultrasonic oscillation treatment;
(2) Stirring and mixing graphene and the gel obtained in the step (1) under the conditions of 120-600rpm, 20-60 ℃ and 20-80kPa vacuum degree, stirring for 60-120min, and standing to obtain graphene gel with the viscosity of 1-10Pa & s;
(3) Mixing the NCM ternary positive electrode material and the graphene gel obtained in the step (2), stirring for 30-90min in vacuum at 800-2000rpm and 20-50 ℃ to obtain a suspension, and carrying out ultrasonic oscillation in the stirring process;
(4) Sieving the suspension obtained in the step (3) by a sieve of 150-300 meshes, and sequentially performing spray drying and heat treatment on the sieved material to obtain the NCM ternary electrode material coated with the metal oxide;
the heat treatment of the step (4) comprises the following steps:
(a) Heating to 105-150 deg.C at a rate of 5-10 deg.C/min, maintaining for 2-5h at a gas flow rate of O 2 Meter, control at 5m 3 H/kg solid material;
(b) Heating to 600-900 deg.C at a rate of 5-10 deg.C/min, maintaining for 3-6h, and maintaining the gas flow rate at O 2 Meter, control at 5m 3 H/kg solid material;
(c) Cooling to below 100 deg.C at a cooling rate of not more than 10 deg.C/min, and introducing gas at a flow rate of O 2 Meter, control at 20m 3 The volume per hour per kg of solid material.
In a second aspect, the invention provides a metal oxide coated NCM ternary electrode material prepared by the preparation method of the first aspect.
The coating layer of the NCM ternary electrode material coated with the metal oxide can effectively inhibit the structural change of the ternary electrode material in the charging and discharging processes, reduce the direct contact between the ternary electrode material and electrolyte and the dissolution of surface transition metal in the electrolyte, reduce the occurrence of side reactions and effectively improve the electrochemical cycle performance of the ternary electrode material.
In a third aspect, the invention provides a lithium ion battery, which comprises the metal oxide-coated NCM ternary electrode material prepared by the preparation method of the first aspect.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) The metal oxide-coated NCM ternary electrode material provided by the invention has the advantages of short preparation process, simple and convenient operation, no need of harsh reaction conditions, safe operation and easy realization;
(2) The NCM ternary electrode material coated with the metal oxide has the advantages of wide sources of coating raw materials, low price, solvent recovery in the preparation process, low processing cost and no introduction of impurity anions into the ternary cathode material in the preparation process;
(3) The coating layer of the NCM ternary electrode material coated with the metal oxide can effectively inhibit the structural change of the ternary electrode material in the charging and discharging processes, reduces the direct contact between the ternary electrode material and electrolyte and the dissolution of surface transition metal in the electrolyte, simultaneously reduces the occurrence of side reaction, and effectively improves the electrochemical cycle performance of the ternary electrode material;
(4) The NCM ternary electrode material coated with the metal oxide provided by the invention adopts a spray drying method to regulate and control the water evaporation rate of the coating layer, so that a compact coating layer is formed, the electrochemical performance of the material is improved, and the cracking of the coating layer caused by the traditional capillary evaporation process is avoided.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a metal oxide-coated NCM ternary electrode material, and a preparation method of the ternary electrode material comprises the following steps:
(1) Mixing 200mg/L of aluminum citrate and 500mg/L of sodium methyl cellulose in a reaction kettle, and carrying out vacuum stirring for 90min at the conditions of 120rpm, 20 ℃ and 20kPa vacuum degree to obtain gel, wherein the vacuum stirring process comprises ultrasonic oscillation treatment;
(2) Stirring and mixing graphene oxide and the gel obtained in the step (1) under the conditions of 120rpm, 20 ℃ and 20kPa vacuum degree, stirring for 120min, and standing to obtain graphene gel with the viscosity of 1Pa & s;
(3) Mixing the NCM ternary positive electrode material and the graphene gel obtained in the step (2), stirring for 90min in vacuum at 800rpm and 20 ℃ to obtain a suspension, and carrying out ultrasonic oscillation in the stirring process;
(4) Sieving the suspension obtained in the step (3) by a 150-mesh sieve, and sequentially performing spray drying and heat treatment on the sieved material to obtain a metal oxide coated NCM ternary electrode material;
the heat treatment of the step (4) comprises the following steps:
(a) Heating to 105 deg.C at a rate of 5 deg.C/min, maintaining for 5 hr at a gas flow rate of O 2 Meter, control at 6m 3 H/kg solid material;
(b) Heating to 600 deg.C at a rate of 5 deg.C/min, maintaining for 6 hr, and maintaining at a gas flow rate of O 2 Meter, control at 10m 3 H/kg solid material;
(c) Cooling to 100 ℃ at a cooling rate of 10 ℃/min, and using the gas flow rate of O 2 Meter, control at 20m 3 H/kg solid material.
The lithium ion battery prepared from the NCM ternary electrode material coated with metal oxide provided in this embodiment is subjected to charge and discharge tests, and has a voltage range of 3.0-4.3V and a current range of 0.5-2C. Electrochemical performance data of the lithium ion battery provided in this example is shown in table 1.
Example 2
The embodiment provides a metal oxide-coated NCM ternary electrode material, and a preparation method of the ternary electrode material comprises the following steps:
(1) Mixing 200mg/L aluminum citrate and 500mg/L sodium methylcellulose in a reaction kettle, and stirring at 600rpm, 60 deg.C and 80kPa vacuum degree for 30min to obtain gel, wherein the vacuum stirring process comprises ultrasonic vibration treatment;
(2) Stirring and mixing the redox graphene and the gel obtained in the step (1) at the conditions of 600rpm, 60 ℃ and 80kPa vacuum degree, stirring for 60min, and standing to obtain graphene gel with the viscosity of 10Pa & s;
(3) Mixing the NCM ternary positive electrode material and the graphene gel obtained in the step (2), stirring for 30min in vacuum at 2000rpm and 50 ℃ to obtain a suspension, and carrying out ultrasonic oscillation in the stirring process;
(4) Sieving the suspension obtained in the step (3) by a 300-mesh sieve, and sequentially performing spray drying and heat treatment on the sieved material to obtain a metal oxide coated NCM ternary electrode material;
the heat treatment of the step (4) comprises the following steps:
(a) Heating to 150 deg.C at a heating rate of 10 deg.C/min, maintaining for 2 hr at a gas flow rate of O 2 Meter, control at 10m 3 H/kg solid material;
(b) Heating to 900 deg.C at a heating rate of 10 deg.C/min, maintaining for 3 hr, and maintaining at a gas flow rate of O 2 Meter, control at 10m 3 H/kg solid material;
(c) Cooling to 80 ℃ at a cooling rate of 8 ℃/min, and controlling the gas flow rate to be O 2 Meter, control at 30m 3 H/kg solid material.
The lithium ion battery prepared from the NCM ternary electrode material coated with metal oxide provided in this embodiment is subjected to charge and discharge tests, and has a voltage range of 3.0-4.3V and a current range of 0.5-2C. The electrochemical performance data of the lithium ion battery provided in this example are shown in table 1.
Example 3
The embodiment provides a metal oxide-coated NCM ternary electrode material, and a preparation method of the ternary electrode material comprises the following steps:
(1) Mixing 200mg/L of aluminum citrate and 500mg/L of sodium methyl cellulose in a reaction kettle, and carrying out vacuum stirring for 50min at the conditions of 300rpm, 45 ℃ and 60kPa vacuum degree to obtain gel, wherein the vacuum stirring process comprises ultrasonic oscillation treatment;
(2) Stirring and mixing graphene oxide and the gel obtained in the step (1) at the conditions of 300rpm, 45 ℃ and 60kPa vacuum degree, stirring for 80min, and standing to obtain graphene gel with the viscosity of 5Pa & s;
(3) Mixing the NCM ternary positive electrode material and the graphene gel obtained in the step (2), stirring for 60min in vacuum at 1200rpm and 40 ℃ to obtain a suspension, and carrying out ultrasonic oscillation in the stirring process;
(4) Sieving the suspension obtained in the step (3) by a 230-mesh sieve, and sequentially performing spray drying and heat treatment on the sieved material to obtain a metal oxide coated NCM ternary electrode material;
the heat treatment of the step (4) comprises the following steps:
(a) Heating to 120 ℃ at a heating rate of 8 ℃/min, and keeping the temperature for 3.5h, wherein the gas flow rate is O 2 Meter, control at 6m 3 H/kg solid material;
(b) Heating to 780 deg.C at a heating rate of 6 deg.C/min, maintaining for 4.5h, and maintaining the gas flow rate at O 2 Meter, control at 6.8m 3 H/kg solid material;
(c) Cooling to 90 deg.C at a cooling rate of 7 deg.C/min, and introducing a gas at a flow rate of O 2 Meter, control at 22m 3 H/kg solid material.
The lithium ion battery prepared from the NCM ternary electrode material coated with metal oxide provided in this embodiment is subjected to charge and discharge tests, and has a voltage range of 3.0-4.3V and a current range of 0.5-2C. The electrochemical performance data of the lithium ion battery provided in this example are shown in table 1.
Example 4
The embodiment provides a metal oxide-coated NCM ternary electrode material, and a preparation method of the ternary electrode material comprises the following steps:
(1) Mixing 200mg/L of aluminum citrate and 500mg/L of sodium methyl cellulose in a reaction kettle, and carrying out vacuum stirring for 30-90min at the conditions of 500rpm, 50 ℃ and 60kPa vacuum degree to obtain gel, wherein the vacuum stirring process comprises ultrasonic oscillation treatment;
(2) Stirring and mixing the redox graphene and the gel obtained in the step (1) under the conditions of 500rpm, 50 ℃ and 60kPa vacuum degree, stirring for 100min, and standing to obtain graphene gel with the viscosity of 4.6Pa & s;
(3) Mixing the NCM ternary positive electrode material and the graphene gel obtained in the step (2), stirring for 70min in vacuum at 1600rpm and 38 ℃ to obtain a suspension, and carrying out ultrasonic oscillation in the stirring process;
(4) Sieving the suspension obtained in the step (3) by a 200-mesh sieve, and sequentially performing spray drying and heat treatment on the sieved material to obtain a metal oxide coated NCM ternary electrode material;
the heat treatment of the step (4) comprises the following steps:
(a) Heating to 140 deg.C at a heating rate of 9 deg.C/min, maintaining for 2.5h, and maintaining the gas flow rate at O 2 Meter, control at 7m 3 H/kg solid material;
(b) Heating to 860 deg.C at a rate of 9 deg.C/min, maintaining for 5.4h, and introducing O into the gas at a flow rate 2 Meter, control at 7m 3 H/kg solid material;
(c) Cooling to 90 deg.C at a cooling rate of 6 deg.C/min, and introducing a gas at a flow rate of O 2 Meter, control at 26m 3 H/kg solid material.
The lithium ion battery prepared from the NCM ternary electrode material coated with metal oxide provided in this embodiment is subjected to charge and discharge tests, and has a voltage range of 3.0-4.3V and a current range of 0.5-2C. The electrochemical performance data of the lithium ion battery provided in this example are shown in table 1.
Example 5
This example provides a metal oxide-coated NCM ternary electrode material, which was prepared in the same manner as in example 3, except that 200mg/L of aluminum citrate in step (1) was replaced with 200mg/L of zinc citrate.
The lithium ion battery prepared from the NCM ternary electrode material coated with metal oxide provided in this embodiment is subjected to charge and discharge tests, and has a voltage range of 3.0-4.3V and a current range of 0.5-2C. The electrochemical performance data of the lithium ion battery provided in this example are shown in table 1.
Example 6
This example provides a metal oxide-coated NCM ternary electrode material prepared in the same manner as in example 3, except that 200mg/L of aluminum citrate in step (1) was replaced with 200mg/L of a titanium-containing metal salt.
The lithium ion battery prepared from the NCM ternary electrode material coated with metal oxide provided in this embodiment is subjected to charge and discharge tests, and has a voltage range of 3.0-4.3V and a current range of 0.5-2C. The electrochemical performance data of the lithium ion battery provided in this example are shown in table 1.
Example 7
This example provides a metal oxide-coated NCM ternary electrode material, which was prepared in the same manner as in example 3, except that 500mg/L of sodium methylcellulose in step (1) was replaced with 500mg/L of polyacrylamide.
The lithium ion battery prepared from the NCM ternary electrode material coated with metal oxide provided in this embodiment is subjected to charge and discharge tests, and has a voltage range of 3.0-4.3V and a current range of 0.5-2C. The electrochemical performance data of the lithium ion battery provided in this example are shown in table 1.
Example 8
This example provides a metal oxide-coated NCM ternary electrode material, which was prepared in the same manner as in example 7, except that 500mg/L of polyacrylamide was replaced with 2000mg/L of polyacryl in step (1).
The lithium ion battery prepared from the NCM ternary electrode material coated with metal oxide provided in this embodiment is subjected to charge and discharge tests, and has a voltage range of 3.0-4.3V and a current range of 0.5-2C. The electrochemical performance data of the lithium ion battery provided in this example are shown in table 1.
Example 9
This example provides a metal oxide-coated NCM ternary electrode material, which was prepared in the same manner as in example 7, except that 500mg/L of sodium methyl cellulose in step (1) was replaced with a combination of 1000mg/L of polyacryl and polyaspartic acid.
The lithium ion battery prepared from the NCM ternary electrode material coated with metal oxide provided in this embodiment is subjected to charge and discharge tests, and has a voltage range of 3.0-4.3V and a current range of 0.5-2C. The electrochemical performance data of the lithium ion battery provided in this example are shown in table 1.
Example 10
This example provides a metal oxide coated NCM ternary electrode material prepared by the same method as in example 3 except that the spray drying in step (4) was changed to capillary evaporation.
Compared with example 3, the coating layer of the NCM ternary electrode material coated with metal oxide of this example cracks during the preparation process.
The lithium ion battery prepared from the NCM ternary electrode material coated with metal oxide provided in this embodiment is subjected to charge and discharge tests, and has a voltage range of 3.0-4.3V and a current range of 0.5-2C. Electrochemical performance data of the lithium ion battery provided in this example is shown in table 1.
Comparative example 1
This comparative example provides a ternary positive electrode material of surface-coated metal oxide as described in example 1 of CN 108258224A.
Compared with the embodiment 3, the ternary cathode material with the surface coated with the metal oxide prepared by the ball milling method in the comparative example is easy to have the phenomenon of uneven coating of the coating layer in the preparation process, and the electrochemical cycle performance of the electrode material is influenced.
The lithium ion battery prepared by the NCM ternary electrode material coated with the metal oxide provided by the comparative example is subjected to charge and discharge tests, wherein the voltage range is 3.0-4.3V, and the current range is 0.5-2C. The electrochemical performance data of the lithium ion battery provided by the comparative example is shown in table 1.
TABLE 1
Analysis table 1 shows that the metal oxide-coated NCM ternary electrode material provided by the invention has the advantages of good discharge rate performance and high cycle capacity retention rate, and the capacity retention rate of a lithium ion battery prepared from the metal oxide-coated NCM ternary electrode material for 100 cycles is more than or equal to 99.03%, which is obviously superior to that of the lithium ion battery prepared by the method of comparative example 1 and the currently disclosed ternary cathode material with the surface coated with the metal oxide.
In conclusion, the invention realizes the controllable and uniform coating of the coating layer by controlling the quality and temperature of the coating layer material by adopting the sol-gel method, and the spray drying method regulates and controls the water evaporation rate of the coating layer to form a compact coating layer, thereby improving the electrochemical performance, avoiding the possibility of cracking of the coating layer, having short preparation flow, simple and convenient operation and low preparation cost, and being beneficial to industrial production.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (30)
1. A preparation method of a metal oxide coated NCM ternary electrode material comprises the following steps:
(1) Mixing organic metal salt solution and a binder, and stirring to obtain gel;
(2) Mixing graphene and the gel obtained in the step (1) under a stirring condition, and standing to obtain graphene gel;
(3) Mixing the NCM ternary positive electrode material and the graphene gel obtained in the step (2), and oscillating and stirring to obtain a suspension;
(4) Processing the suspension obtained in the step (3) to obtain a metal oxide coated NCM ternary electrode material;
the concentration of the organic metal salt solution in the step (1) is 200-1000mg/L;
the organic metal salt in the organic metal salt solution in the step (1) comprises any one or the combination of at least two of aluminum citrate, zinc citrate or titanium-containing metal salt;
the binder in the step (1) comprises any one or a combination of at least two of sodium carboxymethyl cellulose, carboxymethyl cellulose-acrylamide graft copolymer, polysuccinimide, polyaspartic acid or polyacrylamide;
the concentration of the binder in the step (1) is 500-2000mg/L;
the treatment in the step (4) comprises sieving, drying and heat treatment;
the drying comprises spray drying.
2. The method according to claim 1, wherein the binder in step (1) is polyacrylamide.
3. The method according to claim 1, wherein the mixing in step (1) is carried out in a reaction vessel.
4. The method according to claim 1, wherein the stirring process in step (1) further comprises ultrasonic vibration treatment.
5. The method according to claim 4, wherein the frequency of the ultrasonic oscillation is 80-100kHz.
6. The method according to claim 4, wherein the time of the ultrasonic vibration is 30-90min.
7. The method according to claim 1, wherein the stirring in step (1) is vacuum stirring.
8. The method according to claim 1, wherein the stirring rate in the step (1) is 120 to 600rpm.
9. The method according to claim 1, wherein the stirring temperature in the step (1) is 20 to 60 ℃.
10. The method according to claim 1, wherein the stirring time in the step (1) is 30 to 90min.
11. The production method according to claim 1, wherein the degree of vacuum during the stirring in step (1) is 20 to 80kPa.
12. The method according to claim 1, wherein the graphene of step (2) comprises graphene oxide or reduced graphene oxide.
13. The method according to claim 1, wherein the stirring in the step (2) is vacuum stirring.
14. The production method according to claim 1, wherein the degree of vacuum during the stirring in step (2) is 20 to 80kPa.
15. The method according to claim 1, wherein the stirring rate in the step (2) is 120 to 600rpm.
16. The method according to claim 1, wherein the stirring temperature in the step (2) is 20 to 60 ℃.
17. The method according to claim 1, wherein the stirring time in the step (2) is 60 to 120min.
18. The production method according to claim 1, wherein the end point of the standing in the step (2) is that the viscosity of the graphene gel is 1 to 10Pa · s.
19. The preparation method according to claim 1, wherein the ternary cathode material in the step (3) is used in an amount of 500 to 1000g/L.
20. The method according to claim 1, wherein the stirring rate in the step (3) is 800 to 2000rpm.
21. The method according to claim 1, wherein the stirring time in the step (3) is 30 to 90min.
22. The method according to claim 1, wherein the stirring temperature in the step (3) is 20 to 50 ℃.
23. The method according to claim 1, wherein the stirring in step (3) is accompanied by ultrasonic vibration.
24. The method of claim 1, wherein the mesh size of the screen is 150 to 300 mesh.
25. The method of claim 1, wherein the spray drying time is 0.5 to 3.0 hours.
26. The method of claim 1, wherein the temperature of the spray drying is 80-110 ℃.
27. The method according to claim 1, wherein the heat treatment is a heat treatment of the sieved material in an oxygen and/or air atmosphere.
28. The method for preparing according to claim 1, wherein the heat treatment comprises the steps of:
(a) Heating to 105-150 deg.C at a rate of 5-10 deg.C/min, maintaining for 2-5h at a gas flow rate of O 2 Meter, control at 5m 3 H/kg solid material;
(b) Heating to 600-900 deg.C at a rate of 5-10 deg.C/min, maintaining for 3-6h at a gas flow rate of O 2 Meter, control at 5m 3 H/kg solid material;
(c) Cooling to below 100 deg.C at a cooling rate of not more than 10 deg.C/min, and introducing gas at a flow rate of O 2 Meter, control at 20m 3 The volume per hour per kg of solid material.
29. A metal oxide coated NCM ternary electrode material prepared according to the preparation method of any one of claims 1 to 28.
30. A lithium ion battery comprising the metal oxide coated NCM ternary electrode material of claim 29.
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| CN106299320B (en) * | 2016-11-07 | 2018-11-30 | 珠海格力电器股份有限公司 | Modified nickel cobalt lithium manganate ternary material and preparation method thereof |
| US10586982B2 (en) * | 2017-08-01 | 2020-03-10 | Global Graphene Group, Inc. | Alkali metal-sulfur secondary battery containing a hybrid anode |
| CN108539152A (en) * | 2018-03-27 | 2018-09-14 | 宁夏汉尧石墨烯储能材料科技有限公司 | Spray drying process prepares the positive electrode that graphene is modified the method for nickelic system's positive electrode and is prepared by this method |
| CN112151742A (en) * | 2020-09-25 | 2020-12-29 | 福建师范大学 | Preparation method of ternary cathode material modified by metal oxide and graphene and used for improving performance of full battery |
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