CN116230878A - Sodium ion positive electrode material, preparation method and sodium ion positive electrode plate - Google Patents
Sodium ion positive electrode material, preparation method and sodium ion positive electrode plate Download PDFInfo
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- CN116230878A CN116230878A CN202211526579.6A CN202211526579A CN116230878A CN 116230878 A CN116230878 A CN 116230878A CN 202211526579 A CN202211526579 A CN 202211526579A CN 116230878 A CN116230878 A CN 116230878A
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 70
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000006258 conductive agent Substances 0.000 claims abstract description 38
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 35
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 18
- WFSRWJJESXWWSH-UHFFFAOYSA-N [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] Chemical compound [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] WFSRWJJESXWWSH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005056 compaction Methods 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 71
- 239000006185 dispersion Substances 0.000 claims description 66
- 239000011572 manganese Substances 0.000 claims description 60
- 239000003960 organic solvent Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000498 ball milling Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000006230 acetylene black Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011267 electrode slurry Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000006256 anode slurry Substances 0.000 claims description 7
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- UQXKXGWGFRWILX-UHFFFAOYSA-N ethylene glycol dinitrate Chemical compound O=N(=O)OCCON(=O)=O UQXKXGWGFRWILX-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 abstract description 20
- 239000011888 foil Substances 0.000 abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- -1 nickel iron sodium manganate Chemical compound 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000227 grinding Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000000630 rising effect Effects 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 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 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/624—Electric conductive fillers
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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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion positive electrode material, a preparation method and a sodium ion positive electrode plate, wherein the sodium ion positive electrode material comprises a sodium nickel iron manganese oxide matrix and an organic conductive coating, and the organic conductive coating is coated on the sodium nickel iron manganese oxide matrix; the organic conductive coating includes polyacrylonitrile and a conductive agent. The sodium ion positive electrode material is coated with the organic conductive coating on the surface of the nickel iron sodium manganate material, the organic conductive coating comprises polyacrylonitrile and a conductive agent, and the polyacrylonitrile can effectively prevent chemical reaction between the positive electrode material and the aluminum foilThe method comprises the steps of carrying out a first treatment on the surface of the The conductive agent connects the positive electrode material and the aluminum foil, and reduces the resistance of the positive electrode plate. Compared with the alumina coated positive electrode material, the compaction density of the sodium ion positive electrode plate prepared by the sodium ion positive electrode material is improved by 0.1g/cm 3 ‑0.2g/cm 3 The capacity of the prepared sodium ion battery is improved by 14-25%, and the cycle life is improved by 40-80%.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion positive electrode material, a preparation method and a sodium ion positive electrode plate.
Background
The sodium source is wide, the reserve is rich, and the price is far lower than that of lithium. In recent years, along with the crazy rise of lithium price, the sodium ion battery is expected to be lower than the lithium ion battery by 30% -50% in cost, and is widely concerned, and particularly has attractive application prospects in the fields of energy storage, hybrid power and lead-acid battery replacement.
At present, the sodium ion positive electrode material has strong practical value and is a nickel iron sodium manganate material. In the preparation process of the positive electrode material, excessive Na is required to be added to obtain the positive electrode material with good crystallinity, so that the material has a small amount of Na remaining (Na is used at high temperature 2 O in the form of O), na after the temperature is reduced to room temperature 2 O adsorbs CO in the air 2 And H 2 O to form NaOH and Na 2 CO 3 The positive electrode material is rendered alkaline. And the alkalinity of Na is stronger than Li, so that the alkalinity of the sodium ion nickel iron sodium manganate positive electrode material is far higher than that of the corresponding lithium ion nickel cobalt manganese ternary positive electrode material.
The lithium ion nickel cobalt manganese ternary anode material is generally coated with a layer of nano aluminum oxide coating on the surface of the lithium ion nickel cobalt manganese ternary anode material to isolate the contact between the lithium ion nickel cobalt manganese ternary anode material and an aluminum foil and electrolyte, and the cycle life of a corresponding lithium battery is greatly prolonged because of relatively weak alkalinity; however, for the sodium ion sodium nickel iron manganese oxide positive electrode material, the surface residual alkali is very strong, and for the alumina coating, the sodium ion sodium nickel iron manganese oxide positive electrode material and the alumina coating are easy to react, and the positive electrode material is likely to react with the aluminum foil after reacting with the alumina. Therefore, after the traditional aluminum oxide coating coats the nickel iron sodium manganate material, the compaction density of the positive electrode plate is not obviously improved, and the corresponding battery cycle life is not obviously improved.
Disclosure of Invention
The invention provides a sodium ion positive electrode material, a preparation method and a sodium ion positive electrode plate, which are used for solving the technical problems in the prior art.
In a first aspect, the invention provides a sodium ion positive electrode material, which comprises a sodium nickel iron manganese oxide matrix and an organic conductive coating, wherein the organic conductive coating is coated on the sodium nickel iron manganese oxide matrix; the organic conductive coating includes polyacrylonitrile and a conductive agent.
In the scheme, aiming at the problems that the existing sodium ion sodium nickel iron manganese oxide anode material has strong residual alkali alkalinity on the surface, the compaction density of an anode plate is not obviously improved after the traditional aluminum oxide coating coats the sodium nickel iron manganese oxide material, and the corresponding battery cycle life is not obviously improved, the sodium ion anode material disclosed by the invention is coated with an organic conductive coating on the surface of the sodium nickel iron manganese oxide material, and the organic conductive coating comprises polyacrylonitrile and a conductive agent, wherein the polyacrylonitrile can effectively prevent the contact between the anode material and an aluminum foil, and the chemical reaction between the anode material and the aluminum foil is prevented; meanwhile, the conductive agent in the organic conductive coating is communicated with the anode material and the aluminum foil, so that the resistance of the anode plate is reduced. The compaction density of the positive electrode plate of the sodium ion secondary battery prepared by the sodium ion positive electrode material is improved by 0.1g/cm relative to that of the sodium ion secondary battery corresponding to the alumina-coated positive electrode material 3 -0.2g/cm 3 The capacity of the prepared sodium ion battery is improved by 14% -25%, and the cycle life is improved by 40% -80%.
In a second aspect of the present invention, the present invention provides a method for preparing the sodium ion positive electrode material, comprising the steps of:
(1) Preparing NaNi by solid phase synthesis method x Fe y Mn z O 2 A material; wherein x is more than 0 and less than or equal to 0.9, y is more than 0 and less than or equal to 0.5, and z is more than 0 and less than or equal to 0.3;
(2) Dissolving the polyacrylonitrile in an organic solvent in a high-speed dispersing machine; adding the conductive agent for first dispersion to prepare conductive organic slurry;
(3) Subjecting the NaNi obtained in step (1) x Fe y Mn z O 2 Adding the material into the conductive organic slurry obtained in the step (2) for secondary dispersion to prepare a positive electrodeA slurry;
(4) And (3) performing first drying treatment on the positive electrode slurry obtained in the step (3) to obtain the sodium ion positive electrode material.
In the above scheme, in the preparation method of the sodium ion positive electrode material, polyacrylonitrile is effectively dissolved in an organic solvent in a high-speed dispersion mode, then a conductive agent is added for carrying out first dispersion to prepare uniformly dispersed conductive organic slurry, and then the conductive organic slurry and NaNi are mixed x Fe y Mn z O 2 The material is dispersed for the second time to prepare evenly dispersed positive electrode slurry, and finally the positive electrode slurry is dried for the first time to remove the organic solvent, so that NaNi is obtained x Fe y Mn z O 2 The uniform and compact organic conductive coating containing polyacrylonitrile and a conductive agent is formed on the surface of the material, so that the contact between the anode material and the aluminum foil can be effectively prevented, and the occurrence of chemical reaction between the anode material and the aluminum foil is prevented; meanwhile, the resistance of the positive pole piece can be effectively reduced.
In one possible design, the polyacrylonitrile and the NaNi x Fe y Mn z O 2 The mass ratio of the materials is (0.1-3): 100.
Optionally, the polyacrylonitrile and the NaNi x Fe y Mn z O 2 The mass ratio of the materials may be 0.1:100, 0.5:100, 1:100, 1.5:100, 2:100, 2.5:100, or 3:100, etc., but may be other values within the above range, and is not limited thereto.
Understandably, by combining the polyacrylonitrile with the NaNi x Fe y Mn z O 2 The mass ratio of the materials is limited within a reasonable range, so that the contact between the anode material and the aluminum foil can be prevented more effectively, and the occurrence of chemical reaction between the anode material and the aluminum foil can be prevented more effectively.
In one possible design, the conductive agent is in contact with the NaNi x Fe y Mn z O 2 The mass ratio of the materials is (0.1-2): 100.
Optionally, the conductive agent and the NaNi x Fe y Mn z O 2 The mass ratio of the materials may be 0.1:100, 0.2:100, 0.3:100, 0.4:100, 0.5:100, 0.6:100, 0.7:100, 0.8:100, 0.9:100, 1:100, 1.2:100, 1.4:100, 1.5:100, 1.6:100, 1.8:100, or 2:100, etc., but other values within the above range are also possible, and the present invention is not limited thereto.
Understandably, by combining the conductive agent with the NaNi x Fe y Mn z O 2 The mass ratio of the materials is limited in a reasonable range value, so that the anode material and the aluminum foil can be more effectively communicated, and the resistance of the anode plate can be more effectively reduced.
In one possible design, the organic solvent is mixed with the NaNi x Fe y Mn z O 2 The mass ratio of the materials is (25-80): 100.
Optionally, the organic solvent and the NaNi x Fe y Mn z O 2 The mass ratio of the materials may be 25:100, 30:100, 35:100, 40:100, 45:100, 50:100, 55:100, 60:100, 65:100, 70:100, 75:100, or 80:100, etc., but other values within the above range are also possible, and are not limited thereto.
Understandably, by combining the organic solvent with the NaNi x Fe y Mn z O 2 The mass ratio of the materials is limited within a reasonable range, so that the organic solvent can more effectively dissolve the polyacrylonitrile in the preparation process, thereby leading the NaNi to be x Fe y Mn z O 2 The material surface can form a more uniform and compact organic conductive coating containing polyacrylonitrile and a conductive agent, so that the contact between the positive electrode material and the aluminum foil can be more effectively prevented, and the occurrence of chemical reaction between the positive electrode material and the aluminum foil can be prevented; meanwhile, the resistance of the positive pole piece can be effectively reduced.
In one possible design, the molecular weight of the polyacrylonitrile is 20000 to 200000, preferably 50000 to 150000.
In the scheme, the polyacrylonitrile with proper molecular weight is selected to be beneficial to the formation of conductive organic slurry, thereby leading NaNi to be formed x Fe y Mn z O 2 The surface of the material being capable of formingA more uniform, dense organic conductive coating.
In one possible design, in the step (2), the linear velocity of the first dispersion is 10m/min to 200m/min; the dispersion time of the first dispersion is 120min-240min.
Optionally, in the step (2), the linear velocity of the first dispersion may be 10m/min, 20m/min, 30m/min, 40m/min, 50m/min, 60m/min, 70m/min, 80m/min, 90m/min, 100m/min, 120m/min, 140m/min, 160m/min, 180m/min or 200m/min, or the like, but may be other values within the above range, which is not limited thereto, and is preferably 30m/min to 70m/min. The dispersion time of the first dispersion may be 120min, 140min, 160min, 180min, 200min, 220min, 240min, or the like, but may be other values within the above range, and is not limited thereto.
In the scheme, the linear speed and the dispersing time of the first dispersion are limited within reasonable range values, so that the polyacrylonitrile and the conductive agent are fully dispersed in the organic solvent, and meanwhile, the conductive agent is prevented from being damaged. If the linear velocity of the first dispersion is too low, it is difficult to sufficiently disperse, and if the linear velocity of the first dispersion is too high, the conductive agent is easily broken.
In one possible design, in the step (3), the linear velocity of the second dispersion is 10m/min to 100m/min; the dispersion time of the second dispersion is 60min-180min.
Optionally, in the step (3), the linear velocity of the second dispersion may be 10m/min, 20m/min, 30m/min, 40m/min, 50m/min, 60m/min, 70m/min, 80m/min, 90m/min, 100m/min, or the like, but may be other values within the above range, which is not limited herein, and preferably 20m/min to 40m/min. The dispersion time of the second dispersion may be 60min, 80min, 100min, 120min, 140min, 160min, 180min, or the like, but may be other values within the above range, and is not limited thereto.
By limiting the linear velocity and dispersion time of the second dispersion to reasonable range values, naNi can be obtained x Fe y Mn z O 2 The material is fully and electrically conductive with organic matterSlurry contact is favorable for NaNi x Fe y Mn z O 2 And forming an organic conductive coating on the surface of the material.
In one possible design, in the step (4), the first drying treatment is vacuum drying; the temperature of the first drying treatment is 60-80 ℃ and the time is 1-2 h.
Alternatively, the temperature of the first drying process may be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or the like, and the time may be 1h, 1.2h, 1.4h, 1.5h, 1.8h, 2h or the like, but may be other values within the above range, which is not limited thereto.
By limiting the temperature and time of the first drying treatment to a reasonable range, the removal of the organic solvent is facilitated, and the organic conductive coating is simultaneously facilitated in NaNi x Fe y Mn z O 2 The surface of the material is uniformly and effectively formed.
In one possible design, the organic solvent is one or both of dimethyl sulfoxide, sulfolane, and ethylene nitrate.
By selecting a reasonable type of organic solvent, the dispersion of polyacrylonitrile and a conductive agent is facilitated, and the organic conductive coating is further facilitated on NaNi x Fe y Mn z O 2 The surface of the material is uniformly and effectively formed.
In one possible design, the conductive agent is selected from one or more of carbon black, acetylene black, carbon nanotubes, ketjen black and carbon fibers, preferably acetylene black and carbon nanotubes.
Through selecting proper type of conductive agent, the purpose of effectively communicating the anode material with the aluminum foil can be achieved, and then the resistance of the anode plate is effectively reduced.
In one possible design, in the step (1), the NaNi x Fe y Mn z O 2 The preparation method of the material comprises the following steps:
NiO, fe 2 O 3 、MnO 2 、Na 2 CO 3 Adding into ball milling tank according to the required stoichiometric ratio, adding ethanol solvent, and ball millingBall milling is carried out on the medium; performing second drying treatment on the ball-milled material to obtain a precursor; sintering the obtained precursor in air atmosphere to obtain the NaNi x Fe y Mn z O 2 A material.
In one possible design, the total mass of the ethanol solvent is NiO, fe 2 O 3 、MnO 2 、Na 2 CO 3 60% -80% of the total mass.
Alternatively, the total mass of the ethanol solvent can be NiO or Fe 2 O 3 、MnO 2 、Na 2 CO 3 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78% or 80% of the total mass, etc., of course, may be other values within the above range, and are not limited thereto.
By limiting the total mass of the ethanol solvent to NiO and Fe 2 O 3 、MnO 2 、Na 2 CO 3 60% -80% of the total mass, and can achieve the purpose of effectively ball milling NiO and Fe 2 O 3 、MnO 2 、Na 2 CO 3 Is a target of (a).
In one possible design, the ball milling medium has a mass of NiO, fe 2 O 3 、MnO 2 、Na 2 CO 3 One half of the total mass.
By limiting the mass of the ball milling medium to NiO and Fe 2 O 3 、MnO 2 、Na 2 CO 3 One half of the total mass can achieve the purpose of effectively ball milling NiO and Fe 2 O 3 、MnO 2 、Na 2 CO 3 Is a target of (a).
In one possible design, the ball milling is performed at a speed of 100rpm to 200rpm for a period of 8 hours to 16 hours.
Alternatively, the rotation speed of the ball mill may be 100rpm, 120rpm, 140rpm, 150rpm, 180rpm, 200rpm, etc., and the time may be 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, etc., but may be other values within the above range, which is not limited thereto.
By limiting the rotation speed and time of ball milling to reasonable range valuesCan achieve the purpose of effectively ball milling NiO and Fe 2 O 3 、MnO 2 、Na 2 CO 3 Is a target of (a).
In one possible design, the second drying process is vacuum drying.
In one possible design, the second drying process is at a temperature of 80 ℃ to 120 ℃ for a time of 1h to 2h.
Alternatively, the temperature of the second drying process may be 80 ℃, 85 ℃, 90 ℃,95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ or the like, and the time may be 1h, 1.2h, 1.5h, 1.8h or 2h or the like, but may be other values within the above range, and the second drying process is not limited thereto.
The temperature and time of the second drying treatment are limited within reasonable range values, so that the ethanol solvent can be effectively removed, and a high-quality precursor can be obtained.
In one possible design, the specific process of sintering is: raising the temperature to 350-500 ℃ at the heating rate of 5-15 ℃/min, sintering for 0.5-1 h, and raising the temperature to 700-900 ℃ for sintering for 5-10 h. Preferably, the rate of temperature increase is 10deg.C/min.
By limiting the temperature rising rate, temperature and time in the sintering process, the sintering effect can be improved, and the NaNi can be improved x Fe y Mn z O 2 Properties of the material.
In a third aspect, the invention provides a sodium ion positive electrode sheet, which comprises the sodium ion positive electrode material or the sodium ion positive electrode material prepared by the preparation method; the maximum compaction density of the sodium ion positive plate is 2.7g/cm 3 -2.9g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The impedance of the sodium ion positive electrode plate is 1 omega-2 omega.
According to the sodium ion positive electrode material provided by the invention, the surface of the sodium nickel iron manganese oxide material is coated with the organic conductive coating, the organic conductive coating comprises polyacrylonitrile and a conductive agent, and the polyacrylonitrile can effectively prevent the positive electrode material from being contacted with the aluminum foil, so that the occurrence of chemical reaction between the positive electrode material and the aluminum foil is prevented; meanwhile, the conductive agent in the organic conductive coating is communicated with the anode material and the aluminum foil, so that the resistance of the anode plate is reduced.The compaction density of the positive electrode plate of the sodium ion secondary battery prepared by the sodium ion positive electrode material is improved by 0.1g/cm relative to that of the sodium ion secondary battery corresponding to the alumina-coated positive electrode material 3 -0.2g/cm 3 The capacity of the prepared sodium ion battery is improved by 14% -25%, and the cycle life is improved by 40% -80%.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the sodium ion positive electrode material comprises the following steps:
(1) 20mol NiO and 10mol Fe 2 O 3 、20molMnO 2 、30molNa 2 CO 3 Adding the mixture into a ball milling tank according to the required stoichiometric ratio, and adding an ethanol solvent, wherein the total mass of the ethanol solvent is 70% of the total mass of the materials.
Then adding a ball grinding medium into the ball grinding tank for ball grinding; wherein the mass of the ball milling medium is one half of the weight of the solid material, the ball milling rotating speed is 150rpm, and the ball milling time is 10 hours.
And (3) placing the ball-milled material in a vacuum oven for drying at 90 ℃ for 2 hours to obtain a precursor.
Sintering the obtained precursor for 1h at the temperature rising rate of 10 ℃/min to 450 ℃ in air atmosphere, and then sintering the precursor for 8h at the temperature rising rate of 850 ℃ to obtain the NaNi powder 1/3 Fe 1/3 Mn 1/3 O 2 A material.
(2) In a high-speed dispersing machine, a certain amount of polyacrylonitrile is dissolved in an organic solvent, and then a conductive agent is added for first dispersion, so that the conductive organic slurry is prepared. Wherein, the linear velocity of the first dispersion is 45m/min, and the dispersion time is 180min.
Polyacrylonitrile and NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The mass ratio is 1.5:100, and the molecular weight of the polyacrylonitrile is 80000; conductive agent and NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The mass ratio is 1.2:100; the conductive agent is a mixture of acetylene black and carbon nano tubes, and the ratio of the acetylene black to the carbon nano tubes is 1:1. Organic solvent and NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The mass ratio is 65:100, and the organic solvent is dimethyl sulfoxide.
(3) NaNi obtained in step (1) 1/3 Fe 1/3 Mn 1/3 O 2 And (3) adding the material into the conductive organic slurry obtained in the step (2) for secondary dispersion, and preparing the anode slurry. Wherein, the linear velocity of the second dispersion is 35m/min, and the dispersion time is 120min.
(4) And (3) carrying out vacuum drying on the positive electrode slurry obtained in the step (3) to obtain the sodium ion positive electrode material. Wherein the vacuum drying temperature is 75 ℃, and the drying time is 2h.
Example 2
The preparation method of the sodium ion positive electrode material comprises the following steps:
(1) 10mol NiO and 1mol Fe 2 O 3 、2molMnO 2 、16molNa 2 CO 3 Adding the mixture into a ball milling tank according to the required stoichiometric ratio, and adding an ethanol solvent, wherein the total mass of the ethanol solvent is 75% of the total mass of the materials.
Then adding a ball grinding medium into the ball grinding tank for ball grinding; wherein the mass of the ball milling medium is one half of the weight of the solid material; the rotation speed of the ball milling is 150rpm, and the ball milling time is 10 hours.
And (3) placing the ball-milled material in a vacuum oven for drying at 88 ℃ for 2 hours to obtain a precursor.
Sintering the obtained precursor for 1.5h at the temperature rising rate of 10 ℃/min to 420 ℃ in air atmosphere, and then sintering the precursor for 10h at the temperature rising rate of 880 ℃ to obtain the NaNi powder 0.8 Fe 0.1 Mn 0.1 O 2 A material.
(2) In a high-speed dispersing machine, a certain amount of polyacrylonitrile is dissolved in an organic solvent, and then a conductive agent is added for first dispersion, so that the conductive organic slurry is prepared. Wherein, the linear velocity of the first dispersion is 40m/min, and the dispersion time is 180min.
Above, polyacrylonitrile and NaNi 0.8 Fe 0.1 Mn 0.1 O 2 The mass ratio is 1.8:100, and the molecular weight of the polyacrylonitrile is 120000; conductive agent and NaNi 0.8 Fe 0.1 Mn 0.1 O 2 The mass ratio is 1.9:100; the conductive agent is a carbon nanotube mixture; organic solvent and NaNi 0.8 Fe 0.1 Mn 0.1 O 2 The mass ratio is 65:100; the organic solvent is sulfolane.
(3) NaNi obtained in step (1) 0.8 Fe 0.1 Mn 0.1 O 2 And (3) adding the material into the conductive organic slurry obtained in the step (2) for secondary dispersion, and preparing the anode slurry. Wherein, the linear velocity of the second dispersion is 35m/min, and the dispersion time is 120min.
(4) And (3) carrying out vacuum drying on the positive electrode slurry obtained in the step (3) to obtain the sodium ion positive electrode material. Wherein the vacuum drying temperature is 75 ℃, and the drying time is 2h.
Example 3
The preparation method of the sodium ion positive electrode material comprises the following steps:
(1) 10mol NiO and 2mol Fe 2 O 3 、6molMnO 2 、10molNa 2 CO 3 Adding the mixture into a ball milling tank according to the required stoichiometric ratio, and adding an ethanol solvent, wherein the total mass of the ethanol solvent is 80% of the total mass of the materials.
Then adding a ball grinding medium into the ball grinding tank for ball grinding; wherein the mass of the ball milling medium is one half of the weight of the solid material; the ball milling speed was 150rpm and the ball milling time was 10 hours.
And (3) placing the ball-milled material in a vacuum oven for drying at 88 ℃ for 2 hours to obtain a precursor.
Sintering the obtained precursor for 1.5h at the temperature rising rate of 10 ℃/min to 410 ℃ in air atmosphere, and then sintering for 10h at the temperature rising rate of 880 ℃ to obtain the NaNi powder 0.5 Fe 0.2 Mn 0.3 O 2 A material.
(2) In a high-speed dispersing machine, a certain amount of polyacrylonitrile is dissolved in an organic solvent, and then a conductive agent is added for first dispersion, so that the conductive organic slurry is prepared. Wherein, in the linear velocity of 40m/min of the first dispersion, the dispersion time is 180min.
Above, polyacrylonitrile and NaNi 0.5 Fe 0.2 Mn 0.3 O 2 The mass ratio is 1.7:100, and the molecular weight of the polyacrylonitrile is 100000; conductive agent and NaNi 0.5 Fe 0.2 Mn 0.3 O 2 The mass ratio is 1.6:100; the conductive agent can be a mixture of acetylene black and carbon nano tubes, and the ratio of the acetylene black to the carbon nano tubes is 1:2; organic solvent and NaNi 0.5 Fe 0.2 Mn 0.3 O 2 The mass ratio is 60:100; the organic solvent is dimethyl sulfoxide.
(3) NaNi obtained in step (1) 0.5 Fe 0.2 Mn 0.3 O 2 And (3) adding the material into the conductive organic slurry obtained in the step (2) for secondary dispersion, and preparing the anode slurry. Wherein, the linear velocity of the second dispersion is 35m/min, and the dispersion time is 120min.
(4) And (3) carrying out vacuum drying on the positive electrode slurry obtained in the step (3) to obtain the sodium ion positive electrode material. Wherein the vacuum drying temperature is 75 ℃, and the drying time is 2h.
Example 4
A method for preparing a sodium ion positive electrode material is different from example 1 in that polyacrylonitrile and NaNi 1/ 3 Fe 1/3 Mn 1/3 O 2 The mass ratio of the conductive agent to NaNi is 3:100 1/3 Fe 1/3 Mn 1/3 O 2 The mass ratio is 2:100; organic solvent and NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The mass ratio is 80:100.
Example 5
A method for preparing a sodium ion positive electrode material is different from example 1 in that polyacrylonitrile and NaNi 1/ 3 Fe 1/3 Mn 1/3 O 2 The mass ratio of the conductive agent to NaNi is 0.1:100 1/3 Fe 1/3 Mn 1/3 O 2 The mass ratio is 0.1:100; organic solvent and NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The mass ratio is 20:100.
Comparative example 1
Compared to example 1, the difference is that step (2) and step (3):
step (2): in a high-speed dispersing machine, a certain amount of nano alumina powder is placed in an organic solvent for first dispersion, and organic slurry is prepared. Wherein, the linear velocity of the first dispersion is 40m/min, and the dispersion time is 180min.
The nano alumina powder and NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The mass ratio is 1.8:100; organic solvent and NaNi 1/ 3 Fe 1/3 Mn 1/3 O 2 The mass ratio is 65:100; the organic solvent is dimethyl sulfoxide.
Step (3): the NaNi obtained is then processed 1/3 Fe 1/3 Mn 1/3 O 2 And (3) adding the material into the organic slurry obtained in the step (2) for secondary dispersion, and preparing the anode slurry. Wherein, the linear velocity of the second dispersion is 35m/min, and the dispersion time is 120min.
Comparative example 2
Compared to example 2, the difference is that step (2) and step (3):
step (2): in a high-speed dispersing machine, a certain amount of nano alumina powder is placed in an organic solvent for first dispersion, and organic slurry is prepared. Wherein, the linear velocity of the first dispersion is 40m/min, and the dispersion time is 180min.
The nano alumina powder and NaNi 0.8 Fe 0.1 Mn 0.1 O 2 The mass ratio is 1.8:100;
the organic solvent and NaNi 0.8 Fe 0.1 Mn 0.1 O 2 The mass ratio is 65:100; the organic solvent is sulfolane.
Step (3): the NaNi obtained is then processed 0.8 Fe 0.1 Mn 0.1 O 2 Adding the material into the organic slurry obtained in the step (2)And performing secondary dispersion to prepare the anode slurry. Wherein, the linear velocity of the second dispersion is 35m/min, and the dispersion time is 120min.
Comparative example 3
Compared to example 3, the difference is that step (2) and step (3):
step (2): in a high-speed dispersing machine, a certain amount of nano alumina powder is placed in an organic solvent for first dispersion, and organic slurry is prepared. Wherein, the linear velocity of the first dispersion is 40m/min, and the dispersion time is 180min.
The nano alumina powder and NaNi 0.5 Fe 0.2 Mn 0.3 O 2 The mass ratio is 1.8:100;
the organic solvent and NaNi 0.5 Fe 0.2 Mn 0.3 O 2 The mass ratio is 60:100; the organic solvent is dimethyl sulfoxide.
Step (3): the NaNi obtained is then processed 0.5 Fe 0.2 Mn 0.3 O 2 And (3) adding the material into the organic slurry obtained in the step (2) for secondary dispersion, and preparing the anode slurry. Wherein, the linear velocity of the second dispersion is 35m/min, and the dispersion time is 120min.
Comparative example 4
Compared with comparative example 1, the difference is that the conductive agent is added in the step (2), the conductive agent is a mixture of acetylene black and carbon nano tube, the ratio of the conductive agent to NaNi is 1:1 1/3 Fe 1/3 Mn 1/3 O 2 The mass ratio is 1.2:100.
Comparative example 5
The difference from example 1 is that the present comparative example eliminates step (2), step (3) and step (4).
The positive electrode materials prepared in examples 1 to 3 and comparative examples 1 to 5 were prepared into slurry with Super P, PVDF and NMP, coated on a 15 μm thick aluminum foil (1060 aluminum foil of Guangzhou Nanoz New Material technology Co., ltd.), dried at 95℃and rolled to obtain a positive electrode sheet, and further slit and wound to obtain a 26650 cylindrical sodium ion secondary battery. The proportion of the positive electrode slurry is as follows in percentage by mass: 94% of positive electrode material, 3% of Super P, 3% of PVDF and 60% of NMP.
The method for testing the maximum compaction density of the pole piece comprises the following steps: cutting the coated pole piece into 200mm, setting the pressure of a roller press to be 30-60 tons, rolling, folding the rolled pole piece in half, and compacting the pole piece which is provided with a gap in half but is not broken, namely the maximum compaction of the pole piece.
The pole piece impedance testing method comprises the following steps: cutting the rolled pole piece into square size of 4cm x 8cm, placing the cut pole piece between probes of BER2200 tester, applying 5MPa pressure, and reading the value.
The method for testing the internal resistance of the battery comprises the following steps: the internal resistance of the battery was measured at 1000Hz using an RJ3563 internal resistance meter.
And (3) carrying out cyclic test on the prepared battery at 25 ℃, cycling for N times, recording the discharge capacity of the N-th and 1-th batteries, and calculating the discharge retention rate. Discharge retention = nth discharge capacity/1 st discharge capacity 100%, and when the cyclic discharge retention was 80%, the cyclic test was terminated, and the number of cycles was recorded.
Table 1 comparison of properties of examples and comparative examples
As can be seen from table 1 above, the positive electrode sheet of the sodium ion secondary battery prepared by using the sodium ion positive electrode material of the present invention has a large compacted density, low impedance, large battery capacity and excellent cycle life. As can be seen from the comparison results of example 1 and comparative example 5, compared with the sodium ion positive electrode material without the organic conductive coating, the sodium ion positive electrode material of the present invention has the organic conductive coating of specific components added, which can significantly improve the compaction density of the sodium ion positive electrode sheet, reduce the impedance of the sodium ion positive electrode sheet, and improve the battery capacity and cycle performance of the sodium ion battery. Further, examples 1 to 5The sodium ion positive electrode materials of the preferred examples 1-4, the compaction density of the sodium ion secondary battery positive electrode plate prepared by the sodium ion positive electrode materials obtained in the examples is improved by 0.1g/cm compared with that of the sodium ion secondary battery positive electrode plate corresponding to the alumina coated positive electrode materials of the comparative examples 1-4 3 -0.2g/cm 3 The capacity of the prepared sodium ion battery is improved by 14-25%, and the cycle life is improved by 40-80%.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The sodium ion positive electrode material is characterized by comprising a sodium nickel iron manganese oxide matrix and an organic conductive coating, wherein the organic conductive coating is coated on the sodium nickel iron manganese oxide matrix; the organic conductive coating includes polyacrylonitrile and a conductive agent.
2. The method for preparing the sodium ion positive electrode material according to claim 1, comprising the steps of:
(1) Preparing NaNi by solid phase synthesis method x Fe y Mn z O 2 A material; wherein x is more than 0 and less than or equal to 0.9, y is more than 0 and less than or equal to 0.5, and z is more than 0 and less than or equal to 0.3;
(2) Dissolving the polyacrylonitrile in an organic solvent in a high-speed dispersing machine; adding the conductive agent for first dispersion to prepare conductive organic slurry;
(3) Subjecting the NaNi obtained in step (1) x Fe y Mn z O 2 Adding the material into the conductive organic slurry obtained in the step (2) for secondary dispersion to prepare anode slurry;
(4) And (3) performing first drying treatment on the positive electrode slurry obtained in the step (3) to obtain the sodium ion positive electrode material.
3. The method according to claim 2, wherein the polyacrylonitrile and the NaNi x Fe y Mn z O 2 The mass ratio of the materials is (0.1-3) 100;
and/or the conductive agent and the NaNi x Fe y Mn z O 2 The mass ratio of the materials is (0.1-2) 100;
and/or the organic solvent and the NaNi x Fe y Mn z O 2 The mass ratio of the materials is (25-80): 100.
4. The preparation method according to claim 2, characterized in that the molecular weight of the polyacrylonitrile is 20000-200000, preferably 50000-150000.
5. The method according to claim 2, wherein in step (2), the linear velocity of the first dispersion is 10m/min to 200m/min, preferably 30m/min to 70m/min; the dispersion time of the first dispersion is 120min-240min;
and/or, in the step (3), the linear velocity of the second dispersion is 10m/min to 100m/min, preferably 20m/min to 40m/min; the dispersion time of the second dispersion is 60min-180min.
6. The method according to claim 2, wherein in the step (4), the first drying treatment is vacuum drying; the temperature of the first drying treatment is 60-80 ℃ and the time is 1-2 h.
7. The preparation method according to claim 2, wherein the organic solvent is one or two of dimethyl sulfoxide, sulfolane and ethylene nitrate;
and/or the electric conduction is selected from one or more of carbon black, acetylene black, carbon nano tube, ketjen black and carbon fiber, preferably acetylene black and carbon nano tube.
8. The method according to claim 2, wherein in the step (1), the NaNi is x Fe y Mn z O 2 The preparation method of the material comprises the following steps:
NiO, fe 2 O 3 、MnO 2 、Na 2 CO 3 Adding the mixture into a ball milling tank according to the required stoichiometric ratio, adding an ethanol solvent, and then adding a ball milling medium for ball milling; performing second drying treatment on the ball-milled material to obtain a precursor; sintering the obtained precursor in air atmosphere to obtain the NaNi x Fe y Mn z O 2 A material.
9. The preparation method according to claim 8, wherein the total mass of the ethanol solvent is NiO or Fe 2 O 3 、MnO 2 、Na 2 CO 3 60% -80% of the total mass;
and/or the mass of the ball milling medium is NiO and Fe 2 O 3 、MnO 2 、Na 2 CO 3 One half of the total mass;
and/or the rotation speed of the ball milling is 100rpm-200rpm, and the time is 8h-16h;
and/or, the second drying treatment is vacuum drying;
and/or the temperature of the second drying treatment is 80-120 ℃ and the time is 1-2 h;
and/or, the specific process of sintering is as follows: raising the temperature to 350-500 ℃ at the heating rate of 5-15 ℃/min, sintering for 0.5-1 h, and raising the temperature to 700-900 ℃ for sintering for 5-10 h.
10. A sodium ion positive electrode sheet, characterized by comprising the sodium ion positive electrode material of claim 1 or prepared by the preparation method of any one of claims 2 to 9; the maximum compaction density of the sodium ion positive plate is 2.7g/cm 3 -2.9g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The impedance of the sodium ion positive electrode plate is 1 omega-2 omega.
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| CN116404117A (en) * | 2023-06-07 | 2023-07-07 | 四川富临新能源科技有限公司 | Method for improving capacity of sodium ion positive electrode material |
| CN117342630A (en) * | 2023-12-04 | 2024-01-05 | 宜宾锂宝新材料有限公司 | Sodium ion positive electrode material, preparation method thereof, positive electrode plate and sodium battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116404117A (en) * | 2023-06-07 | 2023-07-07 | 四川富临新能源科技有限公司 | Method for improving capacity of sodium ion positive electrode material |
| CN116404117B (en) * | 2023-06-07 | 2023-08-11 | 四川富临新能源科技有限公司 | Method for improving capacity of sodium ion positive electrode material |
| CN117342630A (en) * | 2023-12-04 | 2024-01-05 | 宜宾锂宝新材料有限公司 | Sodium ion positive electrode material, preparation method thereof, positive electrode plate and sodium battery |
| CN117342630B (en) * | 2023-12-04 | 2024-02-23 | 宜宾锂宝新材料有限公司 | Sodium ion positive electrode material, preparation method thereof, positive electrode plate and sodium battery |
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