CN114927658B - Device and method for modifying surface of positive electrode material based on ion exchange membrane - Google Patents
Device and method for modifying surface of positive electrode material based on ion exchange membrane Download PDFInfo
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- CN114927658B CN114927658B CN202210485883.4A CN202210485883A CN114927658B CN 114927658 B CN114927658 B CN 114927658B CN 202210485883 A CN202210485883 A CN 202210485883A CN 114927658 B CN114927658 B CN 114927658B
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 33
- 150000001450 anions Chemical class 0.000 claims abstract description 90
- 150000001768 cations Chemical class 0.000 claims abstract description 71
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 16
- 238000005341 cation exchange Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 85
- 238000000576 coating method Methods 0.000 claims description 84
- 239000011248 coating agent Substances 0.000 claims description 82
- 239000002243 precursor Substances 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 44
- 230000004048 modification Effects 0.000 claims description 44
- 238000012986 modification Methods 0.000 claims description 44
- 238000005245 sintering Methods 0.000 claims description 43
- 239000011259 mixed solution Substances 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 36
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 26
- 238000004321 preservation Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 125000002091 cationic group Chemical group 0.000 claims description 21
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- 125000000129 anionic group Chemical group 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 230000000630 rising effect Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- 229910017119 AlPO Inorganic materials 0.000 claims description 3
- 229910010093 LiAlO Inorganic materials 0.000 claims description 3
- 238000002715 modification method Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 2
- 229910018071 Li 2 O 2 Inorganic materials 0.000 claims description 2
- 229910013553 LiNO Inorganic materials 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims 2
- 239000013590 bulk material Substances 0.000 claims 1
- 239000003011 anion exchange membrane Substances 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000010405 anode material Substances 0.000 description 17
- 239000011572 manganese Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007784 solid electrolyte Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
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- 239000000203 mixture Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000011343 solid material Substances 0.000 description 7
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- 238000005119 centrifugation Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
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- 230000000694 effects Effects 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
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- 230000009471 action Effects 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
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- 230000007704 transition Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
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- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
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- 238000010008 shearing Methods 0.000 description 1
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- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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 relates to a device for modifying the surface of a positive electrode material based on an ion exchange membrane and a method for modifying the surface of the positive electrode material. The device for modifying the surface of the positive electrode material based on the ion exchange membrane comprises: a cation chamber containing a cation solution therein; an anion chamber containing an anion solution therein; an ion exchange membrane for physically separating the anion chamber and the cation chamber, the ion exchange membrane comprising a cation exchange membrane and an anion exchange membrane; and the stirring system is respectively arranged at the bottom of the cation chamber and the bottom of the anion chamber or/and the flowing system is respectively communicated and connected with the cation chamber and the anion chamber.
Description
Technical Field
The invention relates to surface modification of a lithium ion electrode material, in particular to a device for surface modification of a lithium ion positive electrode material and a method for surface modification of the positive electrode material, and belongs to the field of chemical energy storage batteries.
Background
The rapid development of new energy automobiles puts higher demands on the specific capacity and safety of the positive electrode materials used for the power batteries. Among the current commercialized spinel-type, olivine-type and layered cathode materials, the ternary layered cathode material has been receiving a great deal of attention because of its excellent specific capacity, and although the increase of nickel content can increase the specific capacity and reduce the cost of the ternary cathode, the cycle performance, thermal stability and safety of the ternary cathode material are drastically deteriorated with the increase of nickel content, severely restricting its practical application. The root cause of the problems is derived from the material properties of the high nickel ternary positive electrode, including dissolution of metal elements and Ni with strong oxidizing property under the state of charge 4+ With electrolyte solutionSide reactions and surface reconstruction occur, and a high-impedance NiO phase is generated and active oxygen is released, so that gas production and thermal runaway of the battery are caused. At present, scholars at home and abroad mainly coat the surface of the ternary material to inhibit the dissolution of transition metal and isolate high-activity Ni 4+ Direct contact with the electrolyte solves the above drawbacks.
The existing methods for coating the surface of the positive electrode material mainly comprise a coprecipitation method, a sol-gel method, a hydrothermal method, a chemical vapor deposition method, an atomic deposition method, a solid-phase ball milling method and the like, but still have the problems of high cost, uneven coating and the like. Precursor salts of the sol-gel method and the hydrothermal method are expensive, and the yield is low; the chemical vapor deposition method and the atomic deposition method have long processing time, strong toxicity and complex process, and the solid-phase ball milling method is difficult to obtain a uniform coating layer. The key point of uniform coating is the regulation of the coating layer, the key point of the regulation of the coating layer is the slow deposition of the coating substance on the surface of the coated substance, and the formation of separated two phases is avoided through diffusion control. The current uniform regulation strategies of the coating layer mainly comprise buffer solution, precipitation slow release, catalyst assistance, charge interaction and the like. The strategy can effectively realize accurate regulation and control of the coating layer, and can obviously improve the performance of the anode material, but also has the problems of low universality, complex operation and the like. Therefore, the development of a method for uniformly coating the anode material has important significance and is convenient to operate.
Disclosure of Invention
In order to solve the problems, the invention provides a device for modifying the surface of a positive electrode material based on an ion exchange membrane and a method for modifying the surface of the positive electrode material.
In a first aspect, the present invention provides an apparatus for surface modification of an ion exchange membrane-based cathode material, comprising:
a cation chamber containing a cation solution therein;
an anion chamber containing an anion solution therein;
an ion exchange membrane for physically separating the anion chamber and the cation chamber, the ion exchange membrane comprising a cation exchange membrane and an anion exchange membrane;
and the stirring system is respectively arranged at the bottom of the cation chamber and the bottom of the anion chamber or/and the flowing system is respectively communicated and connected with the cation chamber and the anion chamber.
According to the invention, based on the ion exchange effect of the ion exchange membrane, the surface modification is carried out on the lithium ion anode material, so that the electrochemical performance and safety of the lithium ion anode material are improved, the modification cost is reduced, and the coating uniformity is improved. The method has the advantages of convenient operation, uniform coating and easy expanded production.
Preferably, the flow system comprises:
a flow pump and a flow pipeline for communicating the cation chamber with the cation solution storage tank;
and the anion solution storage tank is communicated with the anion chamber, the flow pump of the anion solution storage tank and the flow pipeline.
Preferably, stirring devices are arranged in the cation chamber and the anion chamber, wherein the stirring devices comprise at least one of a magnetic stirring device, a mechanical stirring device, an ultrasonic stirring device and other stirring devices.
Preferably, the active group in the cation exchange membrane comprises at least one of sulfonic acid group, phosphoric acid group, carboxylic acid group, phenol group, arsenic group and selenium group; the active group in the anion exchange membrane comprises at least one of amino groups and aromatic amino groups of primary, secondary, tertiary and quaternary amines.
Preferably, the positive electrode material comprises a positive electrode material after lithiation and a positive electrode precursor material;
the positive electrode material after lithiation comprises LiNi b Co c Mn 1-b-c O 2 (wherein b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1); liNi m Co n Al 1-m-n O 2 (0≤m≤1，0≤n≤1)；
The positive electrode precursor material comprises Ni (1-y-z) Co y Mn z (OH) 2 (wherein y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1) and Ni (1-a-d) Co a Al d (OH) 2 (wherein a is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1).
Preferably, in the cationic solutionThe solute is selected from Al (NO) 3 ) 3 、Al 2 (SO 4 ) 3 、AlCl 3 、MnCl 3 、 Co(NO 3 ) 3 、Co 2 (SO 4 ) 3 、Fe(NO 3 ) 3 、Fe 2 (SO 4 ) 3 、FeCl 3 、Cr(NO 3 ) 3 、Cr 2 (SO 4 ) 3 、CrCl 3 、 Zr(NO 3 ) 4 、ZrCl 4 、Zn(NO 3 ) 3 、TiBr 4 At least one of them.
Preferably, the solvent in the cationic solution comprises at least one of distilled water, methanol, ethanol, isopropanol, n-butanol, isobutanol, cyclic ethanol, acetone, cyclohexanone, glycerol and ethyl acetate.
Preferably, the concentration of the cationic solution is 0.01mol/L to 10mol/L.
Preferably, the solute in the anionic solution is selected from KOH, naOH, liOH, (NH) 4 ) 2 HPO 4 、NH 4 H 2 PO 4 、H 3 PO 4 、NH 3 ·H 2 O, liF, naF, at least one of KF.
Preferably, the solvent in the anionic solution comprises at least one of distilled water, methanol, ethanol, isopropanol, n-butanol, isobutanol, cyclic ethanol, acetone, cyclohexanone, glycerol and ethyl acetate. The concentration of the anionic solution is 0.01mol/L to 10mol/L.
Preferably, the device for modifying the surface of the positive electrode material based on the ion exchange membrane further comprises an external power supply connected to the cation chamber and the anion chamber.
In a second aspect, the present invention provides a surface modification method of a positive electrode material, including:
(1) Dispersing the positive electrode material in a cation solution or an anion solution in the device for modifying the surface of the positive electrode material based on the ion exchange membrane, combining the anion solution with the cation solution through a stirring system or a flowing system, generating precipitation through precipitation reaction or redox reaction, forming coating substances on the surface of the positive electrode material or at particle pores of the positive electrode material, and separating and drying to obtain the positive electrode material with the coating substances distributed on the surface;
(4) And carrying out heat treatment on the positive electrode material with the coating substances distributed on the surface to obtain the surface modified positive electrode material.
In the invention, the anion and the cation of the coating or filling material are isolated by the unique device structure and the ion exchange membrane, so that the anion and the cation are slowly combined to generate precipitation reaction or oxidation-reduction reaction to generate precipitation without an external power supply, thereby obtaining the coating material. Of course, the external power source can also be used, namely, the charge ions under the concentration diffusion and the electric field can be transferred faster. The process of generating the precipitate is controlled by the diffusion rate of ions in the ion exchange membrane, so that the supersaturation degree of the coating substance in the anode material mixed solution system is always kept at a lower level, the process of forming separation particles by the coating substance and the anode material is inhibited, heterogeneous nucleation and growth on the surface of the anode material are promoted, and uniform coating or filling of the coating substance on the surface of the anode material particles is realized under the stirring effect. The surface coating of the positive electrode material is realized through subsequent heat treatment, primary particle grain boundary filling, surface element doping and other multiple surface modifications are realized, and the stability of the positive electrode material is improved.
Preferably, when the ion exchange membrane is a cation exchange membrane, the positive electrode material is dispersed in the anion chamber; when the ion exchange membrane is an anion exchange membrane, dispersing the positive electrode material in a cation chamber; the particle size of the positive electrode material is 1-100 mu m.
Preferably, the cation solution or the anion solution is mixed with the positive electrode material to obtain a mixed solution; the solid content of the positive electrode material in the mixed solution is 2-20wt%.
Preferably, the temperature of the precipitation reaction or the oxidation-reduction reaction is 20-100 ℃ and the time is 0.5-36 hours.
Preferably, the coating substance in the positive electrode material with the coating substance distributed on the surface comprises Mn (OH) 2 、Co(OH) 2 、 AlPO 4 、Mn 3 (PO 4 ) 2 、FePO 4 、Li 3 PO 4 、AlF 3 、LiAlO 2 、Li 2 ZrO 3 、Li 4 Ti 5 O1 2 、Al 2 O 3 、TiO 2 、 ZrO 2 、ZnO、Al(OH) 3 And Zr (OH) 4 One or more of the following; the mass of the coating substance is 0.1-10% of the mass of the positive electrode material (before modification). Wherein the drying is natural drying, drying and vacuum drying, the drying temperature is 20-150 ℃ and the drying time is 24-48 h.
Preferably, when the positive electrode material is a lithiated positive electrode material, the heat treatment temperature is 600-800 ℃, the heat treatment time is 2-10 h, and the heat treatment atmosphere is pure oxygen or air. Or when the positive electrode material is a positive electrode precursor material, mixing the obtained positive electrode material with the coating substances distributed on the surface with lithium oxide, and performing sintering treatment to obtain a surface modified positive electrode material; the lithium-containing oxide comprises LiOH.H 2 O、LiNO 3 、Li 2 CO 3 、Li 2 O and Li 2 O 2 The molar ratio of the positive electrode material with the coating substance distributed on the surface to the lithium-containing oxide is 1: (1.01-1.10).
Preferably, the sintering process includes: one-step sintering or two-step sintering; the sintering treatment atmosphere is pure oxygen or air
Wherein the one-step sintering comprises: the sintering temperature is 600-850 ℃, the heat preservation time is 10-20 h, and the heating rate of one-step sintering is 2-5 ℃/min;
the two-step sintering comprises: the sintering temperature in the first step is 300-500 ℃, and the heat preservation time is 2-4 hours; the sintering temperature is 700-850 ℃ and the heat preservation time is 10-20 h; preferably, the temperature rising rate of the two-step sintering is 2-5 ℃/min.
In a third aspect, the present invention provides a surface-modified cathode material prepared according to the surface-modifying method described above.
In a fourth aspect, the present invention provides a lithium ion battery comprising: a negative electrode material, the surface-modified positive electrode material, and a separator or a solid electrolyte separating the surface-modified positive electrode material and the negative electrode material; preferably, the separator comprises a polypropylene separator (PP), a celgard separator, the solid electrolyte comprises a garnet-type solid electrolyte, a NASICON-type solid electrolyte, a sulfide-type solid electrolyte, and a perovskite-type solid electrolyte; preferably, the negative electrode material is graphite, silicon carbon, silicon dioxide, a silicon alloy, tin oxide, metallic lithium or a lithium alloy.
The beneficial effects are that:
the invention uses ion exchange membrane to diffuse anion or cation selectively, to combine anion and cation slowly to generate precipitation reaction or generate oxidation-reduction reaction to generate precipitation, to obtain coating material. The device and the method keep the supersaturation degree of the coating substance in the mixed solution system of the anode material at a lower level all the time, inhibit the process that the coating substance forms particles separated from the precursor material due to homogeneous nucleation and growth, promote heterogeneous nucleation and growth of the coating substance on the surface of the precursor material, and realize uniform coating of the surface of the anode material under the action of solid-liquid phase shearing force provided by stirring action;
the method realizes uniform coating by in-situ reaction on the surface of the precursor, and realizes surface coating of the positive electrode material through a heat treatment step, and multiple surface modifications such as primary particle grain boundary filling, surface element doping and the like are realized, so that the stability of the active material is further improved under various synergistic effects;
the basic driving force of the coating is derived from ion diffusion, no extra energy is needed, the principle is simple, and the required medicines and solvents are cheap and easy to obtain and are environment-friendly. Therefore, the invention has strong universality, convenient operation, environmental protection and higher industrialized application value
Drawings
FIG. 1 is a schematic diagram of a device for modifying the surface of a cathode material according to the present invention, wherein: 1-cation chamber, 2-anion chamber, 3-ion exchange membrane, 4-stirrer;
FIG. 2 is an X-ray diffraction (XRD) pattern of a positive electrode material including example 1 with surface modification and comparative example 1 without surface modification;
FIG. 3 is a plot of dQ/dV for a positive electrode material at various cycles, the material including surface modified example 1 (B) and non-surface modified comparative example 1 (A);
FIGS. 4A and 4B are graphs comparing the cyclic stability of examples 1-3 with surface modification and comparative example 1 without surface modification;
FIG. 5 is a graph comparing the rate performance of example 1 with surface modification and comparative example 1 without surface modification;
fig. 6 is a Scanning Electron Micrograph (SEM) of a cross-section of positive electrode particles before and after cycling of a positive electrode material comprising example 1 with surface modification and comparative example 1 without surface modification (both scales are 5 μm).
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
In the present disclosure, an apparatus for surface modification of an ion exchange membrane-based cathode material: a cation exchange membrane comprising a cation chamber and an anion chamber, separating the anion chamber from the cation chamber; wherein the inside of the cation chamber and the inside of the anion chamber are both provided with stirring devices. When the device is used, the positive electrode material mixed solution and the provided cationic substance solution are prepared, and then the positive electrode material mixed solution and the provided cationic substance solution are respectively injected into the anion chamber and the cation chamber, so that stirring is always kept on when coating is carried out.
In the present invention, providing an anionic substance solution and providing a cationic substance solution, placing anions and cations constituting the coating substance in an anion chamber and a cation chamber, respectively, and optionally placing a positive electrode material in the anion chamber or the cation chamber to obtain a positive electrode material mixed solution. And isolating anions and cations of the coating substance by adopting an ion exchange membrane, controlling the diffusion of the anions or the cations, and slowly combining the anions and the cations to generate precipitation reaction or redox reaction to generate precipitation, thereby obtaining the coating substance on the surface of the positive electrode material or at the particle pores. And separating, drying and heat-treating the obtained modified positive electrode material to obtain the surface modified positive electrode material. The method for modifying the surface of the positive electrode material by using the device will be described in detail below
An anionic solution is prepared. A soluble substance which provides anions of the coating substance is dissolved in a solvent to obtain an anion solution. Optionally, the positive electrode material is dispersed into an anionic solution to obtain a positive electrode material mixed solution. More preferably, the positive electrode material mixture is injected into the anion chamber, and the cation solution is injected into the cation chamber. And coating the anode material, and centrifuging and drying the mixed solution of the anion chamber after coating to obtain the coated anode material. During the coating process, the anion and cation chambers were always stirred. The centrifugal speed can be 3000-8000 rpm, and the centrifugal time can be 3-5 min. Drying is carried out or vacuum drying is carried out, the drying temperature is 20-150 ℃, and the drying time is 24-48 h.
Preparing a cationic solution. A soluble material that provides the cations of the coating material is dissolved in a solvent, an anionic solution. Optionally, the positive electrode material is dispersed into a cationic solution to obtain a positive electrode material mixed solution. More preferably, the positive electrode material mixture is injected into the cation chamber, and the anion solution is injected into the anion chamber. And then to the pair. And coating the anode material, and centrifuging and drying the mixed solution of the anion chamber after coating to obtain the coated anode material. During the coating process, the anion and cation chambers were always stirred. The centrifugal speed can be 3000-8000 rpm, and the centrifugal time can be 3-5 min. Drying is carried out or vacuum drying is carried out, the drying temperature is 20-150 ℃, and the drying time is 24-48 h.
When the coated material is a lithiated positive electrode material, the obtained coated positive electrode material is subjected to heat treatment, the electrochemical activity of the positive electrode material is recovered, and the coating substance coated on the surface of the positive electrode material can realize surface coating and/or element doping of the positive electrode material through heat treatment.
When the coated material is a positive electrode precursor material, the obtained coated positive electrode precursor material is mixed with LiOH H 2 Mixing (such as ball milling mixing is complete) lithium-containing compounds such as O and the like according to a molar ratio of 1:x (1.01-1.10), and sintering, wherein the sintering process is carried out in the process, and the anode is in front of the cathodeThe precursor material and the lithium-containing oxide are subjected to high-temperature solid-phase reaction to form the positive electrode material, and the coating substance coated on the surface of the positive electrode precursor material can realize surface coating and/or element doping of the positive electrode material at high temperature.
In the invention, the positive electrode material comprises a positive electrode material after lithiation and a positive electrode precursor material. The particle size of the positive electrode material is 1-100 mu m. In an alternative embodiment, the positive electrode material is dispersed into the cationic solution or the anionic solution to obtain the positive electrode material mixed solution in an ultrasonic dispersion mode, the ultrasonic power is 100-500W, and the ultrasonic time is 1-180 min.
In the present invention, a lithium ion battery includes: a positive electrode, a negative electrode, and a separator or a solid electrolyte separating the positive and negative electrode materials. The positive electrode material of the battery is the surface modified positive electrode material based on the surface modification of the ion exchange membrane. The separator or the solid electrolyte includes PP, celgard, garnet-type solid electrolyte, NASICON-type solid electrolyte, sulfide-type solid electrolyte, and perovskite-type solid electrolyte. The negative electrode is graphite, silicon carbon, silicon dioxide, silicon alloy, tin oxide, metallic lithium or lithium alloy.
Specifically, the surface-modified positive electrode material, conductive carbon and a binder are uniformly mixed to prepare slurry, the slurry is coated on an aluminum foil, and the dried aluminum foil loaded with the slurry is cut into small wafers by a cutter to be used as a positive electrode. Full cells were composed and subjected to test characterization.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
A device diagram as shown in fig. 1 is assembled. Device and method for controlling the sameThe ion exchange membrane is Nafion 117 produced by DuPont company, and before use, the Nafion 117 membrane is treated with 5wt% of H at 80deg.C 2 O 2 Boiling in water solution for 1 hr to remove organic impurities in the membrane. Repeatedly washing the membrane with deionized water, soaking in 80deg.C deionized water, and decocting for 1 hr to completely remove residual H 2 O 2 . Soaking the membrane again in 5wt% H at 80deg.C 2 SO 4 Boiling in the solution for 1h. Finally, repeatedly washing the membrane with deionized water, soaking the membrane in the deionized water at 80 ℃ for heat treatment for 1H to completely remove residual H in the membrane 2 SO 4 . The purpose of the proton exchange membrane Nafion 117 treatment is to activate the proton exchange membrane to have cation exchange effect.
Step 1): naOH is weighed and dissolved in the water solution, and the water solution of NaOH with the concentration of 0.1mol/L is prepared as the anion solution. 4g of a ternary nickel cobalt manganese precursor material (Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 ) Mixing the cathode material with the obtained anion solution according to the mass ratio of 1:20, dispersing the mixed solution by utilizing ultrasonic, wherein the ultrasonic time is 10min, and obtaining the mixed solution of the cathode material.
Step 2): taking MnCl 2 Dissolving in water to prepare MnCl of 0.1mol/L 2 The solution (80 mL) was used as the cationic solution.
Step 3): injecting the positive electrode material mixed solution obtained in the step 1) and the cationic solution obtained in the step 2) into an anion chamber and a cation chamber respectively, keeping stirring of the anion chamber and the cation chamber always on, and coating the surface of the precursor for 4 hours at a coating temperature of 25 ℃. After the coating, the anion chamber mixture was centrifuged at 3000rpm for 3min. The solid material obtained by centrifugation was dried in a vacuum oven at 80℃for 24 hours. Obtaining surface Mn (OH) 2 And (3) a coated ternary positive electrode precursor material.
Step 4): coating the ternary precursor material obtained in the step 3) with LiOH H 2 O is fully ball-milled and mixed according to the mol ratio of 1:1.05, and then is sintered in two steps under pure oxygen atmosphere: the sintering temperature in the first step is 400 ℃ and the heat preservation time is long2h; the sintering temperature in the second step is 750 ℃, and the heat preservation time is 12 hours; the temperature rising rate is 3 ℃/min. And obtaining the surface modified cathode material.
And preparing the obtained surface modified positive electrode material as a positive electrode active material into an electrode and assembling the button cell. Assembly and testing of CR2025 button cells: preparing a surface modified cathode material, conductive carbon (Super P: VGCF=1:1), polyvinylidene fluoride (PVDF) into slurry according to the mass ratio of 8:1:1, coating the slurry on an aluminum foil, cutting the dried aluminum foil loaded with the slurry into small discs with the diameter of 1.2cm by a sheet cutting machine to be used as a cathode, taking a metal lithium sheet as a cathode, celgard as a diaphragm, taking a 1M carbonate solution as an electrolyte (wherein the solvent is a mixed solution of Ethylene Carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) in the volume ratio of 1:1:1), and taking a solute of LiPF as a solute 6 ) The CR2025 button cell was assembled in an argon glove box.
Example 2
Step 1): naOH is weighed and dissolved in water solution to prepare 0.1mol/L anion solution. 4g of a ternary nickel cobalt manganese precursor material (Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 ) Mixing the cathode material with the obtained anion solution according to the mass ratio of 1:20, dispersing the mixed solution by utilizing ultrasonic waves for 10min to obtain a mixed solution of the cathode material;
step 2): mn (C) 2 O 2 H 3 ) 2 Dissolving in water to obtain Mn (C) with concentration of 0.2mol/L 2 O 2 H 3 ) 2 Solution (80 mL) as cationic solution;
step 3): injecting the precursor mixed solution obtained in the step 1) and the cation solution obtained in the step 2) into an anion chamber and a cation chamber respectively, keeping the stirring of the anion chamber and the cation chamber always on, and coating the surface of the precursor for 4 hours at a coating temperature of 25 ℃. After the coating, the anion chamber mixture was centrifuged at 3000rpm for 3min. The solid material obtained by centrifugation was dried in a vacuum oven at 80℃for 24 hours. Obtaining surface Mn (OH) 2 A coated ternary positive electrode precursor material;
step 4): coating the ternary precursor material obtained in the step 3) with LiOH H 2 O is fully ball-milled and mixed according to the mol ratio of 1:1.05, and then is sintered in two steps under pure oxygen atmosphere: the sintering temperature in the first step is 400 ℃, and the heat preservation time is 2 hours; the sintering temperature in the second step is 750 ℃, and the heat preservation time is 12 hours; the temperature rising rate is 3 ℃/min. Obtaining a surface modified anode material; the resulting surface-modified cathode material was prepared into an electrode and a button cell was assembled, and the preparation process was the same as in example 1.
Example 3
Step 1): naOH is weighed and dissolved in water solution to prepare 0.1mol/L anion solution. 4g of a ternary nickel cobalt manganese precursor material (Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 ) Mixing the cathode material with the obtained anion solution according to the mass ratio of 1:20, dispersing the mixed solution by utilizing ultrasonic waves for 10min to obtain a mixed solution of the cathode material;
step 2): co (C) 2 O 2 H 3 ) 2 Dissolving in water to obtain Co (C) with concentration of 0.2mol/L 2 O 2 H 3 ) 2 Solution (80 mL) as cationic solution;
step 3): injecting the precursor mixed solution obtained in the step 1) and the cation solution obtained in the step 2) into an anion chamber and a cation chamber respectively, keeping the stirring of the anion chamber and the cation chamber always on, and coating the surface of the precursor for 4 hours at a coating temperature of 25 ℃. After the coating, the anion chamber mixture was centrifuged at 3000rpm for 3min. The solid material obtained by centrifugation was dried in a vacuum oven at 80℃for 24 hours. Obtaining surface Co (OH) 2 A coated ternary positive electrode precursor material;
step 4): coating the ternary precursor material obtained in the step 3) with LiOH H 2 O is fully ball-milled and mixed according to the mol ratio of 1:1.05, and then is sintered in two steps under pure oxygen atmosphere: the sintering temperature in the first step is 400 ℃, and the heat preservation time is 2 hours; the sintering temperature in the second step is 750 ℃, and the heat preservation time is 12 hours; the temperature rising rate is 3 ℃/min. Obtaining the surface modified positiveA polar material; the resulting surface-modified cathode material was prepared into an electrode and a button cell was assembled, and the preparation process was the same as in example 1.
Example 4
Step 1): naOH is weighed and dissolved in water solution to prepare 0.1mol/L anion solution. 4g of a ternary nickel cobalt manganese precursor material (Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 ) Mixing the solution with the obtained anionic salt solution according to the mass ratio of 1:20, dispersing the mixed solution by utilizing ultrasonic, wherein the ultrasonic time is 10min, and obtaining the mixed solution of the positive electrode material.
Step 2): taking MnCl 2 And Co (NO) 3 ) 2 A cationic solution (80 mL) was prepared by dissolving the cationic solution in water in a molar ratio of 1:1.
Step 3): injecting the precursor mixed solution obtained in the step 1) and the cation solution obtained in the step 2) into an anion chamber and a cation chamber respectively, keeping the stirring of the anion chamber and the cation chamber always on, and coating the surface of the precursor for 4 hours at a coating temperature of 25 ℃. After the coating, the anion chamber mixture was centrifuged at 3000rpm for 3min. The solid material obtained by centrifugation was dried in a vacuum oven at 80℃for 24 hours. Obtaining surface Mn f Co g (OH) 2 (f+g=1) coated ternary positive electrode precursor material.
Step 4): coating the ternary precursor material obtained in the step 3) with LiOH H 2 O is fully ball-milled and mixed according to the mol ratio of 1:1.05, and then is sintered in two steps under pure oxygen atmosphere: the sintering temperature in the first step is 400 ℃, and the heat preservation time is 2 hours; the sintering temperature in the second step is 750 ℃, and the heat preservation time is 12 hours; the temperature rising rate is 3 ℃/min. And obtaining the surface modified cathode material.
The resulting surface-modified cathode material was prepared into an electrode and a button cell was assembled, in the same manner as in example 1.
Example 5
Step 1): weighing (NH) 4 ) 2 HPO 4 Dissolving in water solution to prepare 0.1mol/L anionic solution. 4g of nickel-cobalt-manganese ternary precursor materialMaterial (Ni) 0.83 Co 0.12 Mn 0.05 (OH) 2 ) Mixing the cathode material with the obtained anion solution according to the mass ratio of 1:20, dispersing the mixed solution by utilizing ultrasonic waves for 10min to obtain a mixed solution of the cathode material;
step 2): taking Al (NO) 3 ) 3 ·9H 2 O was dissolved in water to prepare a cationic solution (80 mL) of 0.1 mol/L;
step 3): injecting the precursor mixed solution obtained in the step 1) and the cation solution obtained in the step 2) into an anion chamber and a cation chamber respectively, keeping the stirring of the anion chamber and the cation chamber always on, and coating the precursor for 4 hours at a coating temperature of 25 ℃. After the coating, the anion chamber mixture was centrifuged at 3000rpm for 3min. The solid material obtained by centrifugation was dried in a vacuum oven at 80℃for 24 hours. Obtaining AlPO 4 A coated ternary positive electrode precursor material;
step 4): coating the ternary precursor material obtained in the step 3) with LiOH H 2 O is fully ball-milled and mixed according to the mol ratio of 1:1.05, and then is sintered in two steps under pure oxygen atmosphere: the sintering temperature in the first step is 400 ℃, and the heat preservation time is 2 hours; the sintering temperature in the second step is 750 ℃, and the heat preservation time is 12 hours; the temperature rising rate is 3 ℃/min. And obtaining the surface modified cathode material.
The surface-modified cathode material was prepared into an electrode and a button cell was assembled, in the same manner as in example 1.
Example 6
Step 1): weighing LiOH H 2 O was dissolved in an aqueous solution to prepare a 0.1mol/L anionic solution. 4g of a ternary nickel cobalt manganese precursor material (Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 ) Mixing the cathode material with the obtained anion solution according to the mass ratio of 1:20, dispersing the mixed solution by utilizing ultrasonic waves for 10min to obtain a mixed solution of the cathode material;
step 2): taking Al (NO) 3 ) 3 ·9H 2 O was dissolved in water to prepare a cationic solution (80 mL) of 0.1 mol/L;
step 3): injecting the precursor mixed solution obtained in the step 1) and the cation solution obtained in the step 2) into an anion chamber and a cation chamber respectively, keeping the stirring of the anion chamber and the cation chamber always on, and coating the precursor for 4 hours at a coating temperature of 25 ℃. After the coating time is over, the mixed solution in the anion chamber is centrifuged at 3000rpm for 3min. The solid material obtained by centrifugation was dried in a vacuum oven at 80℃for 24 hours. Obtaining LiAlO 2 A coated ternary positive electrode precursor material;
step 4): coating the ternary precursor material obtained in the step 3) with LiOH H 2 Fully ball-milling and mixing O according to a molar ratio of 1:1.05, and then sintering in two steps under pure oxygen atmosphere, wherein the sintering temperature in the first step is 400 ℃, and the heat preservation time is 2 hours; the sintering temperature in the second step is 750 ℃, and the heat preservation time is 12 hours; the temperature rising rate is 3 ℃/min. And obtaining the surface modified cathode material.
The resulting surface-modified cathode material was prepared into an electrode and a button cell was assembled, in the same manner as in example 1.
Example 7
Step 1): weighing LiOH H 2 O was dissolved in an aqueous solution to prepare a 0.1mol/L anionic solution. 4g of a ternary nickel cobalt manganese precursor material (Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 ) Mixing the cathode material with the obtained anion solution according to the mass ratio of 1:20, dispersing the mixed solution by utilizing ultrasonic waves for 10min to obtain a mixed solution of the cathode material;
step 2): 0.49g of ZrO (NO) 3 ) 2 ·5H 2 O was dissolved in water to prepare a cationic solution (80 mL) of 0.1 mol/L;
step 3): injecting the precursor mixed solution obtained in the step 1) and the cation solution obtained in the step 2) into an anion chamber and a cation chamber respectively, keeping the stirring of the anion chamber and the cation chamber always on, and carrying out ZrO on the precursor 2 Coating, wherein the coating time is 4 hours, and the coating temperature is 25 ℃. After the coating time is over, the mixed solution in the anion chamber is centrifuged at 3000rpm for 3min. Separation ofThe solid material obtained from the core was dried in a vacuum oven at 80℃for 24 hours. Obtaining ZrO 2 A coated ternary positive electrode precursor material;
step 4): coating the ternary precursor material obtained in the step 3) with LiOH H 2 O is fully ball-milled and mixed according to the mol ratio of 1:1.05, and then is sintered in two steps under pure oxygen atmosphere: the sintering temperature in the first step is 400 ℃, and the heat preservation time is 2 hours; the sintering temperature in the second step is 750 ℃, and the heat preservation time is 12 hours; the temperature rising rate is 3 ℃/min. And obtaining the surface modified cathode material.
The obtained surface-modified cathode material was prepared into an electrode and a button cell was assembled, and the procedure was the same as in example 1.
Comparative example 1
A nickel cobalt manganese ternary precursor material (Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 ) Directly with LiOH H 2 O is fully ball-milled and mixed according to the mol ratio of 1:1.05, and then is sintered in two steps under pure oxygen atmosphere: the sintering temperature in the first step is 400 ℃, and the heat preservation time is 2 hours; the sintering temperature in the second step is 750 ℃, and the heat preservation time is 12 hours; the temperature rising rate is 3 ℃/min. And obtaining the surface modified cathode material.
The resulting surface-modified cathode material was prepared into an electrode and a button cell was assembled, the procedure of which was the same as in example 1.
Fig. 1 shows a device for modifying the surface of a positive electrode, respectively. The device is largely divided into a cation chamber, an anion chamber, an ion exchange membrane, and a stirring or flow system. When in use, anions and cations which form the coating substance are respectively arranged in the anion chamber and the cation chamber, and the anode material is optionally arranged in the anion chamber or the cation chamber according to the type of the ion exchange membrane to obtain the anode material mixed solution. The components in the drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the embodiments, embodiments and devices. It is to be understood that the application is not limited to the details or methodology set forth in the description or illustrated in the drawings. It is also to be understood that the terminology used in the present disclosure is for the purpose of description only and should not be regarded as limiting.
FIG. 2 shows a positive electrodeThe positive electrode material includes example 1 with surface modification and comparative example 1 without surface modification. All diffraction peaks are equal to those of typical hexagonal a-NaFeO 2 The structure (JCDF card number 01-089-4533, space group R-3 m) matches well, which represents the major phase of NCM. a-NaFeO 2 The type crystal structure is of ordered rock salt type, with Li and Me ions occupying alternating (111) layers. NCM has layered NaFeO 2 Structure, R-3m space group, is composed of LiO 6 And MO (metal oxide semiconductor) 6 The octahedra form alternating layers. As can be seen from fig. 1, the main diffraction peaks of all samples match well with JCPDF cards with R-3m space group. It is demonstrated that surface modification by the method of the present invention does not alter the layered structure of the NCM material.
Fig. 3 shows the dQ/dV curves of the positive electrode material at different cycles, including surface modified example 1 (B) and non-surface modified comparative example 1 (a). The dQ/dV curve shows that after circulation, the peak position of the dQ/dV curve of the comparative example 1 is severely shifted, and the charging peak moves rightwards, which indicates that the material is severely polarized in the circulation process; the phase transition peaks H2-H3 gradually disappear under high voltage, which indicates that the high-voltage positive electrode material undergoes serious phase transition. In contrast, the position of the peak of example 1 was not significantly shifted, indicating that the polarization and phase change of the positive electrode material during cycling were smaller. The surface modification method of the nickel-cobalt-manganese ternary positive electrode material based on the ammonolysis reaction is fully shown to be beneficial to inhibiting polarization and phase change in the circulation process of the positive electrode material.
Fig. 4A and 4B compare the cycle performance of the positive electrode materials obtained in example 1, example 2 and example 3, which were surface-modified, and comparative example 1, which was not surface-modified. The result shows that the cycle performance of the positive electrode material subjected to surface modification by the method is obviously improved, and after the positive electrode material subjected to surface modification is cycled under the same conditions, the capacity retention rate of the positive electrode material subjected to surface modification is obviously higher than that of the positive electrode material not subjected to surface modification, which shows that the cycle stability of the positive electrode material can be obviously improved by the surface modification implemented by the method. The effectiveness of the device and method for surface modification of the positive electrode material based on the ion exchange membrane is fully demonstrated.
Fig. 5 shows a ratio-to-ratio graph of a positive electrode material including example 1 with surface modification and comparative example 1 without surface modification. The result shows that the device and the method for modifying the surface of the positive electrode material based on the ion exchange membrane can obviously improve the multiplying power performance of the nickel-cobalt-manganese positive electrode material after the surface modification, and can release more capacity in a high multiplying power state, and fully show that the device and the method for modifying the surface of the positive electrode material based on the ion exchange membrane can improve the multiplying power performance of the positive electrode material.
Fig. 6 shows SEM images of cross-sections of positive electrode particles before and after cycling of positive electrode materials, including surface modified example 1 and unmodified comparative example 1. The results show that the example 1 and the comparative example 1 are both secondary particles formed by agglomerating primary particles, the primary particles are tightly combined before circulation, and no obvious cracks exist between the secondary particles. Whereas example 1 maintained the morphology of the intact spherical secondary particles after 150 cycles at 1C, the positive electrode particles of comparative example 1 had been significantly crushed. The device and the method for modifying the surface of the positive electrode material based on the ion exchange membrane can inhibit the particle breakage of the positive electrode material in the circulating process.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (12)
1. A method for modifying a surface of a positive electrode material, comprising:
(1) Dispersing the positive electrode material in an anion solution in an anion chamber in a device based on surface modification of the positive electrode material of an ion exchange membrane, combining the anion solution and the cation solution through a stirring system or a flowing system, generating precipitation through precipitation reaction, forming coating substances on the surface of the positive electrode material or at particle pores of the positive electrode material, and separating and drying to obtain the positive electrode material with the coating substances distributed on the surface; the positive electrode material is a positive electrode precursorA bulk material; the positive electrode precursor material is Ni (1-y-z) Co y Mn z (OH) 2 Wherein y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1; the coating substance in the positive electrode material with the coating substance distributed on the surface is Mn (OH) 2 、Co(OH) 2 、AlPO 4 、LiAlO 2 And ZrO(s) 2 One of the following; the device for modifying the surface of the positive electrode material based on the ion exchange membrane comprises: a cation chamber containing a cation solution therein; an anion chamber containing an anion solution having a solute selected from the group consisting of NaOH, liOH and (NH) 4 ) 2 HPO 4 The method comprises the steps of carrying out a first treatment on the surface of the The positive electrode material is dispersed in an anionic solution; the ion exchange membrane is used for physically separating the anion chamber from the cation chamber, and is a cation exchange membrane; the active group in the cation exchange membrane is a sulfonic group; and stirring systems respectively arranged at the bottom of the cation chamber and the bottom of the anion chamber or/and flow systems respectively communicated with the cation chamber and the anion chamber; the flow system includes: a flow pump and a flow pipeline for communicating the cation chamber with the cation solution storage tank; a flow pump and a flow pipeline which are communicated with the anion chamber and the anion solution storage tank;
(2) Mixing the obtained positive electrode material with the surface distributed with the coating substance and lithium oxide, and performing sintering treatment to obtain a surface modified positive electrode material; the lithium oxide is LiOH.H 2 O、LiNO 3 、Li 2 CO 3 、Li 2 O and Li 2 O 2 At least one of them.
2. The method for surface modification of a positive electrode material according to claim 1, wherein the positive electrode material has a particle diameter of 1 to 100 μm.
3. The method for surface modification of a positive electrode material according to claim 1, wherein the anionic solution and the positive electrode material are mixed to obtain a mixed solution; the solid content of the positive electrode material in the mixed solution is 2-20wt%;
the temperature of the precipitation reaction is 20-100 ℃ and the time is 0.5-36 hours.
4. The method for modifying the surface of a positive electrode material according to claim 1, wherein the mass of the coating substance is 0.1 to 10% of the mass of the positive electrode material.
5. The method for surface modification of a positive electrode material according to any one of claims 1 to 4, wherein the solute in the cationic solution is selected from Al (NO 3 ) 3 、MnCl 2 And Co (NO) 3 ) 2 。
6. The method for surface modification of a positive electrode material according to any one of claims 1 to 4, wherein the molar ratio of the positive electrode material having the coating substance distributed on the surface thereof to the lithium oxide is 1: (1.01-1.10).
7. The method for surface modification of a positive electrode material according to claim 6, wherein the sintering treatment comprises: one-step sintering or two-step sintering; the sintering treatment atmosphere is pure oxygen or air
Wherein the one-step sintering comprises: the sintering temperature is 600-850 ℃, and the heat preservation time is 10-20 hours;
the two-step sintering comprises: the sintering temperature in the first step is 300-500 ℃, and the heat preservation time is 2-4 hours; the sintering temperature in the second step is 700-850 ℃, and the heat preservation time is 10-20 h.
8. The surface modification method of a positive electrode material according to claim 7, wherein the one-step sintering has a temperature rise rate of 2 to 5 ℃/min; the temperature rising rate of the two-step sintering is 2-5 ℃/min.
9. The method for surface modification of a positive electrode material according to any one of claims 1 to 4, wherein the stirring system comprises at least one of a magnetic stirring device, a mechanical stirring device and an ultrasonic stirring device, which are provided at the bottom of the anion chamber and the bottom of the anion chamber, respectively.
10. The method for surface modification of a positive electrode material according to any one of claims 1 to 4, wherein the solvent in the cationic solution is at least one of distilled water, methanol, ethanol, isopropanol, n-butanol, isobutanol, cyclo-ethanol, acetone, cyclohexanone, glycerin, and ethyl acetate;
the concentration of the cationic solution is 0.01mol/L to 10mol/L.
11. The method for surface modification of a positive electrode material according to any one of claims 1 to 4, wherein the solvent in the anionic solution is at least one of distilled water, methanol, ethanol, isopropanol, n-butanol, isobutanol, cyclo-ethanol, acetone, cyclohexanone, glycerin and ethyl acetate;
the concentration of the anionic solution is 0.01mol/L to 10mol/L.
12. The method for surface modification of a positive electrode material according to claim 11, wherein the device for surface modification of a positive electrode material based on an ion exchange membrane further comprises an external power source connected to the cation chamber and the anion chamber.
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