CN115771915B - Method for improving residual alkali on surface of sodium ion layered anode material - Google Patents
Method for improving residual alkali on surface of sodium ion layered anode material Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 70
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000010405 anode material Substances 0.000 title claims abstract description 33
- 239000003513 alkali Substances 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 98
- 239000002243 precursor Substances 0.000 claims abstract description 40
- 239000011734 sodium Substances 0.000 claims abstract description 30
- 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 claims abstract description 28
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims description 35
- 239000010406 cathode material Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- IREHHCMIJCTSKK-UHFFFAOYSA-H [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] IREHHCMIJCTSKK-UHFFFAOYSA-H 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 14
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 14
- 238000011049 filling Methods 0.000 description 13
- 229910052863 mullite Inorganic materials 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000001508 eye Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
Classifications
-
- 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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- Compositions Of Oxide Ceramics (AREA)
Abstract
The application discloses a method for improving residual alkali on the surface of a sodium ion layered anode material. The nano oxide has a large metal ion radius, the interlayer spacing of the precursor can be increased in the presintering process, so that the pre-sintered precursor has stronger reaction activity, and the sodium source material can fully react with the pre-sintered precursor, so that the residual alkali on the surface of the material is greatly reduced, and the method is simple to operate, economical and environment-friendly and easier to industrialize.
Description
Technical Field
The application relates to the field of battery preparation methods, in particular to a method for improving residual alkali on the surface of a sodium ion layered anode material.
Background
Compared with lithium element, the earth sodium element has abundant reserves in the crust, and the earth sodium element and the lithium element belong to the same main group element, and the earth sodium element has similar physical and chemical properties and working principles as the lithium element, so that the problem of limited development of a new energy battery caused by shortage of lithium resources can be relieved. In the sintering process of the sodium ion layered anode material by adopting a high-temperature solid phase method, after the sodium salt and the metal oxide are broken and recombined through chemical bonds to form a layered structure, part of the sodium salt does not enter the bulk structure of the material, but remains on the surface of the material to form alkaline substances, so that the processing of the material and the performance of a battery are affected.
In order to reduce the residual alkali content on the surface of the layered anode material, the layered anode material of the sodium ion battery to be treated can be put into an atmosphere rotary furnace at present; and under the condition of constant temperature, introducing volatile acid gas into the atmosphere rotary furnace, removing residual alkali on the surface of the layered positive electrode material of the sodium ion battery through the volatile acid gas, and cooling to room temperature to obtain the layered positive electrode material with reduced residual alkali on the surface.
However, hydrochloric acid with high corrosiveness is used in the method, and the hydrochloric acid and acid mist can corrode human tissues and possibly irreversibly damage respiratory organs, eyes, skin, stomach intestine and the like, and the strong corrosiveness of the hydrochloric acid can have higher requirements on production equipment, so that the hydrochloric acid and the acid mist are difficult to realize large-scale industrial production and utilization.
Disclosure of Invention
The application aims to provide a method for improving residual alkali on the surface of a sodium ion layered positive electrode material, which can improve the problems.
Embodiments of the present application are implemented as follows:
the application provides a method for improving residual alkali on the surface of a sodium ion layered anode material, which comprises the following steps:
S1, weighing a precursor of the sodium ion layered anode material and the nano oxide, and fully mixing to obtain a first mixed material. Wherein the precursor of the sodium ion layered cathode material does not contain sodium element;
S2, presintering the first mixed material to obtain a sintered first block-shaped material;
s3, after the first block-shaped material is crushed, adding a sodium source material for fully mixing to obtain a second mixed material;
S4, sintering the second mixed material again to obtain a sintered second block material;
s5, crushing the second block material to obtain target powder;
and S6, sieving the target powder, and obtaining the powder with the particle diameter smaller than a preset standard as the sodium ion layered anode material.
The residual alkali of the layered oxide material mainly comes from the fact that after the sodium salt and the metal oxide are broken and recombined through chemical bonds to form a layered structure, part of the sodium salt does not enter the bulk structure of the material due to the fact that the ionic radius of the sodium is large.
It can be understood that the application discloses a method for improving residual alkali on the surface of a sodium ion layered anode material, which comprises the steps of fully mixing a precursor without sodium element and nano oxide, pre-sintering, adding a sodium source material, and re-sintering to obtain a small amount of residual alkali. The pre-sintering can increase the interlayer spacing of the precursor, so that the pre-sintered precursor has stronger reactivity, and the sodium source material can fully react with the pre-sintered precursor, so that the residual alkali on the surface of the material is greatly reduced, and the method is simple to operate, economical and environment-friendly and is easier to industrialize.
In an alternative embodiment of the present application, the particle radius of the sodium ion layered cathode material precursor is in the range of 4 micrometers to 7 micrometers.
In an alternative embodiment of the present application, step S1 includes: the molar ratio of the nano oxide to the sodium ion layered cathode material precursor is 0.001:1 to 0.01:1, and fully mixing to obtain a first mixed material.
Wherein the nano oxide is one or more of metal oxides of copper (Cu), zinc (Zn), strontium (Sr), aluminum (Al), boron (B), chromium (Cr), zirconium (Zr), titanium (Ti), tin (Sn), vanadium (V), molybdenum (Mo), ruthenium (Ru), niobium (Nb), antimony (Sb), calcium (Ca) and yttrium (Y); the precursor of the sodium ion layered cathode material is nickel iron manganese hydroxide Ni x1Fey1Mnz1Mb1(OH)2, wherein M represents copper element, zinc element, titanium element or tin element, x1+y1+z1+b1=1, the value range of x1 is 0-0.35, the value range of y1 is 0-0.35, the value range of z1 is 0-0.35, and the value range of b1 is 0-0.2.
Wherein, the value range of x1 can be 0.2-0.35, the value range of y1 can be 0.2-0.35, and the value range of z1 can be 0.2-0.35.
In an alternative embodiment of the present application, step S2 includes: placing the first mixed material into a box furnace, heating to 500-800 ℃ at a speed of 1-3 ℃/min, and then preserving heat for 4-10 hours to obtain a sintered first block material; wherein the sintering atmosphere is an air atmosphere; the step S4 includes: placing the second mixed material into a box-type furnace, heating to 400-600 ℃ at a speed of 1-3 ℃/min, preserving heat for 2-4 hours, heating to 800-1000 ℃ at a speed of 1-3 ℃/min, and preserving heat for 10-14 hours; wherein the sintering atmosphere is an air atmosphere.
In an alternative embodiment of the present application, step S4 includes: the molar ratio of the sodium source material to the crushed first block material is 0.87:1 to 1.04:1, and fully mixing to obtain a second mixed material.
Wherein the sodium source material comprises one or more of sodium carbonate, sodium hydroxide, sodium phosphate and sodium chloride.
In an alternative embodiment of the present application, the chemical formula of the sodium ion layered cathode material prepared by the method for improving the residual alkali on the surface of the sodium ion layered cathode material is Na a2Nix2Fey2Mnz2Mb2Nc2O2;
Wherein M represents copper element, zinc element, titanium element or tin element; n represents copper (Cu) element, zinc (Zn) element, strontium (Sr) element, aluminum (Al) element, boron (B) element, chromium (Cr) element, zirconium (Zr) element, titanium (Ti) element, tin (Sn) element, vanadium (V) element, molybdenum (Mo) element, ruthenium (Ru) element, niobium (Nb) element, antimony (Sb) element, calcium (Ca) element, yttrium (Y) element;
In the case of c2=0, x2+y2+z2=1; in the case of c2+.0, x2+y2+z2+b2=1;
The value range of x2 is 0-0.35, the value range of y2 is 0-0.35, the value range of z2 is 0-0.35, the value range of a2 is 0.67-1.1, the value range of b2 is 0-0.2, and the value range of c2 is 0-0.2.
Wherein, the value range of x2 can be 0.2-0.35, the value range of y2 can be 0.2-0.35, and the value range of z2 can be 0.2-0.35.
The beneficial effects are that:
the application discloses a method for improving residual alkali on the surface of a sodium ion layered anode material.
The nano oxide has a large metal ion radius, can be doped into a bulk phase structure of a precursor in the presintering process, increases the interlayer spacing of the precursor, and ensures that the precursor after presintering has stronger reaction activity, so that a sodium source material can fully react with the precursor after presintering, thereby greatly reducing residual alkali on the surface of the material, and the method has the advantages of simple operation, economy, environmental protection and easiness in industrialization.
The doping element with large radius ions can enlarge the interlayer spacing of the layered metal oxide, and the large interlayer spacing is beneficial to the diffusion of sodium ions, so that the multiplying power performance of the material is improved; meanwhile, the doped ions can stabilize the space structure of the material in the process of sodium ion deintercalation, and the structural stability of the material is improved, so that the cycle performance of the material is enhanced.
In order to make the above objects, features and advantages of the present application more comprehensible, alternative embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic structural diagram of a method for improving residual alkali on the surface of a sodium ion layered positive electrode material;
FIG. 2 is an SEM image of a layered positive electrode material of sodium ions obtained in experiment 1 provided by the present application;
FIG. 3 is an X-ray diffraction pattern of the sodium ion layered cathode material obtained in experiment 1;
FIG. 4 is a schematic diagram of 0.1C discharge capacity of a battery prepared by taking a sodium ion layered positive electrode material obtained in experiment 1 as a negative electrode at different voltages;
Fig. 5 is an SEM image of the sodium ion layered cathode material obtained in comparative example 1 provided by the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
As shown in fig. 1, the present application provides a method for improving residual alkali on the surface of a sodium ion layered cathode material, which comprises:
S1, weighing a precursor of the sodium ion layered anode material and the nano oxide, and fully mixing to obtain a first mixed material. Wherein the precursor of the sodium ion layered cathode material does not contain sodium element.
In an alternative embodiment of the application, the particle radius of the sodium ion layered cathode material precursor is in the range of 4 micrometers to 7 micrometers.
In the step S1, the precursor of the sodium ion layered cathode material and the nano oxide are weighed according to a certain proportion, then are added into a high-speed mixer to be mixed according to a certain rotating speed and time, and after the materials are uniformly mixed, the materials are taken out.
S2, presintering the first mixed material to obtain a sintered first block-shaped material.
The step S2 comprises the following steps: placing the first mixed material into a box furnace, heating to 500-800 ℃ at a speed of 1-3 ℃/min, and then preserving heat for 4-10 hours to obtain a sintered first block material; wherein the sintering atmosphere is an air atmosphere.
S3, after the first block-shaped material is crushed, adding the sodium source material for full mixing, and obtaining a second mixed material.
In the step S3, the material obtained by pre-sintering is crushed to obtain powder, a sodium source with a certain proportion is added, then the powder is transferred into a high-speed mixer to be mixed according to a certain rotating speed and time, and after the material is uniformly mixed, the material is taken out.
Among them, the preferable high-speed mixer mixing time is 15 to 30 minutes, and the mixing speed is 600rpm to 900rpm.
S4, sintering the second mixed material again to obtain a sintered second block material.
The step S4 includes: placing the second mixed material into a box-type furnace, heating to 400-600 ℃ at a speed of 1-3 ℃/min, preserving heat for 2-4 hours, heating to 800-1000 ℃ at a speed of 1-3 ℃/min, and preserving heat for 10-14 hours; wherein the sintering atmosphere is an air atmosphere.
S5, crushing the second block material to obtain target powder.
In step S5, the material obtained by sintering is crushed by a roller machine to obtain powder.
And S6, sieving the target powder, and taking the powder with the particle diameter smaller than a preset standard as a sodium ion layered anode material.
The residual alkali of the layered oxide material mainly comes from the fact that after the sodium salt and the metal oxide are broken and recombined through chemical bonds to form a layered structure, part of the sodium salt does not enter the bulk structure of the material due to the fact that the ionic radius of the sodium is large.
It can be understood that the application discloses a method for improving residual alkali on the surface of a sodium ion layered anode material, which comprises the steps of fully mixing a precursor without sodium element and nano oxide, pre-sintering, adding a sodium source material, and re-sintering to obtain a small amount of residual alkali. The pre-sintering can increase the interlayer spacing of the precursor, so that the pre-sintered precursor has stronger reactivity, and the sodium source material can fully react with the pre-sintered precursor, so that the residual alkali on the surface of the material is greatly reduced, and the method is simple to operate, economical and environment-friendly and is easier to industrialize.
In an alternative embodiment of the present application, step S1 includes: the molar ratio of the nano oxide to the sodium ion layered cathode material precursor is 0.001:1 to 0.01:1, and fully mixing to obtain a first mixed material.
Wherein the nano oxide is one or more of metal oxides of copper (Cu), zinc (Zn), strontium (Sr), aluminum (Al), boron (B), chromium (Cr), zirconium (Zr), titanium (Ti), tin (Sn), vanadium (V), molybdenum (Mo), ruthenium (Ru), niobium (Nb), antimony (Sb), calcium (Ca) and yttrium (Y); the precursor of the sodium ion layered cathode material is nickel iron manganese hydroxide Ni x1Fey1Mnz1Mb1(OH)2, wherein M represents copper element, zinc element, titanium element or tin element, x1+y1+z1+b1=1, the value range of x1 is 0-0.35, the value range of y1 is 0-0.35, the value range of z1 is 0-0.35, and the value range of b1 is 0-0.2.
Wherein, the value range of x1 can be 0.2-0.35, the value range of y1 can be 0.2-0.35, and the value range of z1 can be 0.2-0.35.
In an alternative embodiment of the present application, step S4 includes: the molar ratio of the sodium source material to the crushed first block material is 0.87:1 to 1.04:1, and fully mixing to obtain a second mixed material.
Wherein the sodium source material comprises one or more of sodium carbonate, sodium hydroxide, sodium phosphate and sodium chloride.
In an alternative embodiment of the application, the chemical formula of the sodium ion layered cathode material prepared by the method for improving the residual alkali on the surface of the sodium ion layered cathode material is Na a2Nix2Fey2Mnz2Mb2Nc2O2;
Wherein M represents copper element, zinc element, titanium element or tin element; n represents copper (Cu) element, zinc (Zn) element, strontium (Sr) element, aluminum (Al) element, boron (B) element, chromium (Cr) element, zirconium (Zr) element, titanium (Ti) element, tin (Sn) element, vanadium (V) element, molybdenum (Mo) element, ruthenium (Ru) element, niobium (Nb) element, antimony (Sb) element, calcium (Ca) element, yttrium (Y) element;
In the case of c2=0, x2+y2+z2=1; in the case of c2+.0, x2+y2+z2+b2=1;
The value range of x2 is 0-0.35, the value range of y2 is 0-0.35, the value range of z2 is 0-0.35, the value range of a2 is 0.67-1.1, the value range of b2 is 0-0.2, and the value range of c2 is 0-0.2.
Wherein, the value range of x2 can be 0.2-0.35, the value range of y2 can be 0.2-0.35, and the value range of z2 can be 0.2-0.35.
In order to better illustrate the effect of the method for improving the residual alkali on the surface of the sodium ion layered cathode material, the application provides a plurality of groups of experiments as follows.
Experiment 1: a preparation method of a sodium ion layered anode material comprises the following steps:
1.5 kg of Ni 0.33Fe0.28Mn0.33Cu0.06(OH)2, a precursor with a particle size D50 of 5.3 μm, and 11.8g of nano strontium oxide were weighed into a high-speed mixer and mixed for 30 minutes at a rotation speed of 750 rpm.
2. And (2) filling the mixture obtained in the step (1) into a cordierite-mullite sagger, placing the sagger into a box furnace, heating to 750 ℃ according to 3 ℃/min, preserving heat for 6 hours, taking the sintering atmosphere as air, cooling, discharging from the furnace, and sieving to obtain a powder material.
3. 2.91Kg of sodium carbonate is weighed and mixed with the powder material in the step 2 in a high-speed mixer for 30 minutes according to the rotating speed of 750 rpm.
4. And (3) filling the mixture obtained in the step (3) into a cordierite-mullite sagger, placing the sagger into a box furnace, heating to 500 ℃ at 2 ℃/min, preserving heat for 2 hours, heating to 970 ℃ at 1.5 ℃/min, preserving heat for 12 hours, taking the sintering atmosphere as air, cooling, taking out, and crushing by a pair of rollers to obtain the sodium ion layered anode material.
Fig. 2 shows a scanning electron microscope (Scanning Electron Microscope, SEM) image of the sodium ion layered cathode material obtained in experiment 1. FIG. 3 is an X-ray diffraction pattern of the sodium ion layered cathode material obtained in experiment 1. Fig. 4 is a schematic diagram of 0.1C discharge capacity of a battery prepared with the sodium ion layered cathode material obtained in experiment 1 as a negative electrode at different voltages.
Experiment 2: a preparation method of a sodium ion layered anode material comprises the following steps:
1.5 kg of Ni 0.33Fe0.28Mn0.33Cu0.06(OH)2, a precursor with a particle size D50 of 5.3 μm, 11.8g of nano strontium oxide and 12.4g of titanium dioxide are weighed into a high-speed mixer and mixed for 30 minutes according to a rotation speed of 750 rpm.
2. And (2) filling the mixture obtained in the step (1) into a cordierite-mullite sagger, placing the sagger into a box furnace, heating to 750 ℃ according to 3 ℃/min, preserving heat for 6 hours, taking the sintering atmosphere as air, cooling, discharging from the furnace, and sieving to obtain a powder material.
3. 2.91Kg of sodium carbonate is weighed and mixed with the powder material in the step 2 in a high-speed mixer for 30 minutes according to the rotating speed of 750 rpm.
4. And (3) filling the mixture obtained in the step (3) into a cordierite-mullite sagger, placing the sagger into a box furnace, heating to 500 ℃ at 2 ℃/min, preserving heat for 2 hours, heating to 970 ℃ at 1.5 ℃/min, preserving heat for 12 hours, taking the sintering atmosphere as air, cooling, taking out, and crushing by a pair of rollers to obtain the sodium ion layered anode material.
Experiment 3: a preparation method of a sodium ion layered anode material comprises the following steps:
1.5 kg of Ni 0.33Fe0.28Mn0.33Cu0.06(OH)2, a precursor with a particle size D50 of 5.3 μm, 11.8g of nano strontium oxide and 12.4g of titanium dioxide are weighed into a high-speed mixer and mixed for 30 minutes according to a rotation speed of 750 rpm.
2. And (2) filling the mixture obtained in the step (1) into a cordierite-mullite sagger, placing the sagger into a box furnace, heating to 750 ℃ according to 3 ℃/min, preserving heat for 6 hours, taking the sintering atmosphere as air, cooling, discharging from the furnace, and sieving to obtain a powder material.
3. 2.53Kg of sodium carbonate is weighed and mixed with the powder material in the step 2 in a high-speed mixer for 30 minutes according to the rotating speed of 750 rpm.
4. And (3) filling the mixture obtained in the step (3) into a cordierite-mullite sagger, placing the sagger into a box furnace, heating to 500 ℃ at 2 ℃/min, preserving heat for 2 hours, heating to 970 ℃ at 1.5 ℃/min, preserving heat for 12 hours, taking the sintering atmosphere as air, cooling, taking out of the furnace, and crushing by a pair of rollers to obtain the sodium ion layered anode material.
Experiment 4: a preparation method of a sodium ion layered anode material comprises the following steps:
1. 5.0kg of precursor Ni 0.33Fe0.28Mn0.33Cu0.06(OH)2 with the granularity D50 of 5.3 mu m and 11.8g of nanometer strontium oxide are weighed and added into a high-speed mixer to be mixed for 30 minutes according to the rotating speed of 750 rpm.
2. And (2) filling the mixture obtained in the step (1) into a cordierite-mullite sagger, placing the sagger into a box furnace, heating to 750 ℃ according to 3 ℃/min, preserving heat for 6 hours, taking the sintering atmosphere as air, cooling, discharging from the furnace, and sieving to obtain a powder material.
3. 2.53Kg of sodium carbonate is weighed and mixed with the powder material in the step 2 in a high-speed mixer for 30 minutes according to the rotating speed of 750 rpm.
4. And (3) filling the mixture obtained in the step (3) into a cordierite-mullite sagger, placing the sagger into a box furnace, heating to 500 ℃ at 2 ℃/min, preserving heat for 2 hours, heating to 970 ℃ at 1.5 ℃/min, preserving heat for 12 hours, taking the sintering atmosphere as air, cooling, taking out, and crushing by a pair of rollers to obtain the sodium ion layered anode material.
Comparative example 1: a preparation method of a sodium ion layered anode material comprises the following steps:
1. 5kg of precursor Ni 0.33Fe0.28Mn0.33Cu0.06(OH)2 having a particle size D50 of 5.3 μm were weighed out.
2. And (3) filling the materials in the step (1) into a cordierite-mullite sagger, placing the sagger into a box furnace, heating to 750 ℃ according to 3 ℃/min, preserving heat for 6 hours, taking the sintering atmosphere as air, cooling, discharging from the furnace, and sieving to obtain powder materials.
3. 2.91Kg of sodium carbonate is weighed and mixed with the powder material in the step 2 in a high-speed mixer for 30 minutes according to the rotating speed of 750 rpm.
4. And (3) filling the mixture obtained in the step (3) into a cordierite-mullite sagger, placing the sagger into a box furnace, heating to 500 ℃ at 2 ℃/min, preserving heat for 2 hours, heating to 970 ℃ at 1.5 ℃/min, preserving heat for 12 hours, taking the sintering atmosphere as air, cooling, taking out, and crushing by a pair of rollers to obtain the sodium ion layered anode material.
Fig. 5 is a scanning electron microscope SEM image of the sodium ion layered cathode material obtained in comparative example 1.
Comparative example 2: a preparation method of a sodium ion layered anode material comprises the following steps:
1.5 kg of Ni 0.33Fe0.28Mn0.33Cu0.06(OH)2, a precursor with a particle size D50 of 5.3 μm, 11.8g of nano strontium oxide and 2.91kg of sodium carbonate are weighed into a high-speed mixer and mixed for 30 minutes at a rotation speed of 750 rpm.
2. And (2) filling the mixture obtained in the step (1) into a cordierite-mullite sagger, placing the sagger into a box furnace, heating to 500 ℃ at 2 ℃/min, preserving heat for 2 hours, heating to 970 ℃ at 1.5 ℃/min, preserving heat for 12 hours, taking the sintering atmosphere as air, cooling, taking out, and crushing by a pair of rollers to obtain the sodium ion layered anode material.
Comparative example 3: a preparation method of a sodium ion layered anode material comprises the following steps:
1.5 kg of Ni 0.33Fe0.28Mn0.33Cu0.06(OH)2, a precursor with a particle size D50 of 5.3 μm, 11.8g of nano strontium oxide, 12.4g of titanium dioxide and 2.91kg of sodium carbonate are weighed into a high-speed mixer and mixed for 30 minutes at a rotation speed of 750 rpm.
2. And (2) filling the mixture obtained in the step (1) into a cordierite-mullite sagger, placing the sagger into a box furnace, heating to 500 ℃ at 2 ℃/min, preserving heat for 2 hours, heating to 970 ℃ at 1.5 ℃/min, preserving heat for 12 hours, taking the sintering atmosphere as air, cooling, taking out, and crushing by a pair of rollers to obtain the sodium ion layered anode material.
Comparative example 4: a preparation method of a sodium ion layered anode material comprises the following steps:
1. 5.0kg of precursor Ni 0.33Fe0.28Mn0.33Cu0.06(OH)2 with the granularity D50 of 5.3 mu m, 11.8g of nanometer strontium oxide and 2.53kg of sodium carbonate are weighed into a high-speed mixer and mixed for 30 minutes according to the rotating speed of 750 rpm.
2. And (2) filling the mixture obtained in the step (1) into a cordierite-mullite sagger, placing the sagger into a box furnace, heating to 500 ℃ at 2 ℃/min, preserving heat for 2 hours, heating to 970 ℃ at 1.5 ℃/min, preserving heat for 12 hours, taking the sintering atmosphere as air, cooling, taking out, and crushing by a pair of rollers to obtain the sodium ion layered anode material.
The sodium ion layered cathode materials prepared in experimental examples 1to 4 and comparative examples 1to 4 were subjected to residual alkali test, and the test results are shown in table 1. It can be seen that the sodium ion layered cathode material surface residual alkali in experimental examples 1to 4 is greatly reduced compared with comparative examples 1to 4.
TABLE 1 residual alkali content comparison results
The samples above use sodium sheets as negative electrodes to prepare CR2025 button cells, and the 0.1C discharge capacity is tested in the voltage range of 2.0-4.0V, and specific data are shown in Table 1. It can be seen that the high nickel ternary material prepared by adopting the experimental example scheme has better capacity than the comparative example under the voltage of 4.0V; therefore, by adopting the scheme, the residual alkali on the surface of the sodium ion layered cathode material can be greatly reduced, and excellent performance can be obtained.
The terms "first," "second," "the first," or "the second," as used in various embodiments of the present disclosure, may modify various components without regard to order and/or importance, but these terms do not limit the corresponding components. The above description is only configured for the purpose of distinguishing an element from other elements. For example, the first user device and the second user device represent different user devices, although both are user devices. For example, a first element could be termed a second element, and, similarly, a second element could be termed a first element, without departing from the scope of the present disclosure.
When an element (e.g., a first element) is referred to as being "coupled" (operatively or communicatively) to "another element (e.g., a second element) or" connected "to another element (e.g., a second element), it is understood that the one element is directly connected to the other element or the one element is indirectly connected to the other element via yet another element (e.g., a third element). In contrast, it will be understood that when an element (e.g., a first element) is referred to as being "directly connected" or "directly coupled" to another element (a second element), then no element (e.g., a third element) is interposed therebetween.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, the element defined by the phrase "comprising one … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element, and furthermore, elements having the same name in different embodiments of the application may have the same meaning or may have different meanings, the particular meaning of which is to be determined by its interpretation in this particular embodiment or by further combining the context of this particular embodiment.
The above description is only of alternative embodiments of the application and of illustrations of the technical principles applied. It will be appreciated by persons skilled in the art that the scope of the application referred to in the present application is not limited to the specific combinations of the technical features described above, but also covers other technical features formed by any combination of the technical features described above or their equivalents without departing from the inventive concept described above. Such as the above-mentioned features and the technical features disclosed in the present application (but not limited to) having similar functions are replaced with each other.
The words "if", as used herein, may be interpreted as "at … …" or "at … …" or "in response to a determination" or "in response to a detection", depending on the context. Similarly, the phrase "if determined" or "if detected (stated condition or event)" may be interpreted as "when determined" or "in response to determination" or "when detected (stated condition or event)" or "in response to detection (stated condition or event), depending on the context.
The above description is only of alternative embodiments of the application and of illustrations of the technical principles applied. It will be appreciated by persons skilled in the art that the scope of the application referred to in the present application is not limited to the specific combinations of the technical features described above, but also covers other technical features formed by any combination of the technical features described above or their equivalents without departing from the inventive concept described above. Such as the above-mentioned features and the technical features disclosed in the present application (but not limited to) having similar functions are replaced with each other.
The above description is only of alternative embodiments of the present application and is not intended to limit the present application, and various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (2)
1. The method for improving the residual alkali on the surface of the sodium ion layered cathode material is characterized by comprising the following steps of:
weighing a sodium ion layered cathode material precursor and nano oxides, and fully mixing to obtain a first mixed material, wherein the sodium ion layered cathode material precursor does not contain sodium element;
Pre-sintering the first mixed material to obtain a sintered first block-shaped material;
after the first block-shaped material is crushed, adding a sodium source material for fully mixing to obtain a second mixed material; the sodium source material comprises one or more of sodium carbonate, sodium hydroxide, sodium phosphate and sodium chloride;
After the first block-shaped material is crushed, adding a sodium source material for full mixing to obtain a second mixed material, wherein the method comprises the following steps of:
The molar ratio of the sodium source material to the crushed first block material is 0.87: weighing in a range of 1 to 1.04:1, and fully mixing to obtain a second mixed material;
Re-sintering the second mixed material to obtain a sintered second block material;
crushing the second block material to obtain target powder;
Sieving the target powder, and taking the powder with the particle diameter smaller than a preset standard as the sodium ion layered anode material;
The particle radius of the sodium ion layered cathode material precursor is in the range of 4-7 microns;
The method comprises the steps of weighing a precursor of a sodium ion layered anode material and nano oxides, fully mixing to obtain a first mixed material, and comprises the following steps:
the molar ratio of the nano oxide to the sodium ion layered cathode material precursor is 0.001: weighing in a range of 1 to 0.01:1, and fully mixing to obtain a first mixed material;
The nano oxide is one or more of metal oxides of copper (Cu), zinc (Zn), strontium (Sr), aluminum (Al), boron (B), chromium (Cr), zirconium (Zr), titanium (Ti), tin (Sn), vanadium (V), molybdenum (Mo), ruthenium (Ru), niobium (Nb), antimony (Sb), calcium (Ca) and yttrium (Y);
The precursor of the sodium ion layered cathode material is nickel iron manganese hydroxide Ni x1Fey1Mnz1Mb1(OH)2, wherein M represents copper element, zinc element, titanium element or tin element, x1+y1+z1+b1=1, the value range of x1 is 0.2-0.35, the value range of y1 is 0.2-0.35, the value range of z1 is 0.2-0.35, and the value range of b1 is 0-0.2;
the step of pre-sintering the first mixed material to obtain a sintered first block-shaped material comprises the following steps:
placing the first mixed material into a box furnace, heating to 500-800 ℃ at a speed of 1-3 ℃/min, and then preserving heat for 4-10 hours to obtain a sintered first block material; wherein the sintering atmosphere is an air atmosphere.
2. The method for improving the residual alkali on the surface of the sodium ion layered cathode material according to claim 1, wherein,
And sintering the second mixed material again to obtain a sintered second block material, wherein the sintering process comprises the following steps of:
Placing the second mixed material into a box-type furnace, heating to 400-600 ℃ at a speed of 1-3 ℃/min, preserving heat for 2-4 hours, heating to 800-1000 ℃ at a speed of 1-3 ℃/min, and preserving heat for 10-14 hours; wherein the sintering atmosphere is an air atmosphere.
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