CN117254007A - Layered anode material of battery, preparation method and application thereof - Google Patents
Layered anode material of battery, preparation method and application thereof Download PDFInfo
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- CN117254007A CN117254007A CN202311274274.5A CN202311274274A CN117254007A CN 117254007 A CN117254007 A CN 117254007A CN 202311274274 A CN202311274274 A CN 202311274274A CN 117254007 A CN117254007 A CN 117254007A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000010405 anode material Substances 0.000 title abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 62
- 238000005245 sintering Methods 0.000 claims abstract description 57
- 239000011734 sodium Substances 0.000 claims abstract description 42
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 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 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 239000007774 positive electrode material Substances 0.000 claims description 28
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 26
- 239000010406 cathode material Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910002706 AlOOH Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910018626 Al(OH) Inorganic materials 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 38
- 239000011248 coating agent Substances 0.000 abstract description 36
- 239000003513 alkali Substances 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 18
- 239000011159 matrix material Substances 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 238000005253 cladding Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000009768 microwave sintering Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
- 238000005303 weighing 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of battery preparation, in particular to a battery layered anode material and a preparation method and application thereof. The preparation method comprises the following steps: coating the positive electrode matrix material (Li/Na) with alkali residue on the surface a MO 2 Mixing with an aluminum source to obtain a mixed material, and heating the mixed material to 1200 at a heating rate of 50-100 ℃ per minute1800 ℃; wherein M represents one or more transition metals, and a is more than or equal to 0.5 and less than or equal to 1.0. According to the invention, the sodium source/lithium source of the coating substance is the residual alkali on the surface of the layered material, so that the residual alkali content of the material can be reduced, and the air stability of the material can be improved; meanwhile, the invention can realize Na-beta' -Al of the sodium/lithium battery layered anode material by optimizing the sintering method during cladding 2 O 3 In-situ coating, the coating effect is better, and the cycle performance of the material is improved.
Description
Technical Field
The invention relates to the technical field of battery preparation, in particular to a battery layered anode material and a preparation method and application thereof.
Background
In recent years, with the increase of electric and large-scale energy storage demands, the secondary battery market is further excited, and particularly, a high-nickel ternary battery and a sodium ion battery are developed vigorously, but the layered positive electrode materials in the high-nickel ternary positive electrode material and the sodium ion battery at present also have the defects of high residual alkali content and poor stability, so that the cycle performance is poor, and meanwhile, the battery core of the battery is also subjected to the safety challenges such as gas production.
At present, the prior art solves the problems of high residual alkali and poor stability of layered positive electrode materials of lithium ion batteries and sodium ion batteries, and adopts the main operation mode of using Al 2 O 3 、ZrO 2 The coating is performed by an oxide, a carbon material such as carbon nanotubes and graphene, and a solid electrolyte material such as LATP and LLZO. The specific cladding mode mainly comprises the following steps: the positive electrode material is mixed with a coating material synthesized in advance, and then subjected to operations such as secondary heat treatment. However, the above-mentioned ex-situ coating method is limited by the particle size, melting point, reaction temperature, etc. of the coating material, so that it is difficult to obtain a uniform coating effect, and the production cost is high. Patent CN 115425200A discloses a sodium ion positive electrode material and a preparation method thereof, wherein the sodium ion positive electrode material is prepared by utilizing Na-beta' -Al synthesized in advance 2 O 3 Coating the sodium-electricity layered anode material at 400-600 ℃ improves the material performance, but the sodium-electricity layered anode material belongs to ex-situ coating, and still has room for further improvement in the coating effect and the battery performance.
In view of this, the present invention has been made.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a battery layered anode material, a preparation method and application thereof, so as to improve the coating effect and the cycle performance of a battery.
The invention firstly provides a preparation method of a battery layered anode material, which comprises the following steps: the positive electrode base material (Li/Na) to be coated a MO 2 Mixing the mixture with an aluminum source to obtain a mixed material, and heating the mixed material to 1200-1800 ℃ at a heating rate of 50-100 ℃ per minute;
wherein M represents one or more transition metals, and a is more than or equal to 0.5 and less than or equal to 1.0.
According to the preparation method of the battery layered anode material provided by the invention, the mixed material is heated to 1200-1800 ℃ and then is subjected to heat preservation, and the heat preservation time is 5-60 minutes.
The preparation method of the battery layered anode material provided by the invention comprises the following steps: coating the positive electrode matrix material (Li/Na) with alkali residue on the surface a MO 2 Mixing with an aluminum source to obtain a mixed material; the temperature of the mixture is raised from room temperature to 600-800 ℃ at a temperature raising rate of 3-10 ℃ per minute, and then is raised to 1200-1800 ℃ at a temperature raising rate of 50-100 ℃ per minute.
According to the preparation method of the battery layered anode material provided by the invention, the aluminum source comprises nano Al 2 O 3 、AlOOH、Al(OH) 3 And Al (NO) 3 ) 3 One or more of the following; in the way described (Li/Na) a MO 2 The amount of the aluminum source is 0.01 to 3wt% based on the mass of the aluminum source.
According to the preparation method of the battery layered positive electrode material provided by the invention, the surface of the battery layered positive electrode material has alkali residues and is used for coating the positive electrode matrix material (Li/Na) a MO 2 The preparation method of (2) comprises the following steps: mixing a sodium source or a lithium source with an M source, and then performing primary sintering treatment; wherein the M source is oxide of transition metal or hydroxide precursor of transition metal, and the transition metal is one or more of Fe, ni, mn, co, cu, ti.
According to the preparation method of the battery layered anode material provided by the invention, the primary sintering temperature is 750-1000 ℃, and the sintering time is 8-22 hours.
The preparation method of the battery layered anode material provided by the invention comprises the following steps:
s1: mixing a sodium source or a lithium source with an M source, and then performing primary sintering treatment at 750-1000 ℃ for 8-22 hours to obtain a primary sintering raw material;
s1: mixing the primary sintering raw material with an aluminum source to obtain a mixed material, and performing secondary sintering on the mixed material; the temperature rise curve of the secondary sintering comprises: the temperature is raised from room temperature to 700-900 ℃ at a temperature raising rate of 3-10 ℃ per minute, then raised to 1200-1800 ℃ at a temperature raising rate of 50-100 ℃ per minute, and then kept at 1200-1800 ℃ for 5-60 minutes.
The invention further provides a battery layered positive electrode material, which is prepared by the preparation method.
The battery layered positive electrode material provided by the invention has the molecular formula as follows: (Li/Na) a MO 2 @Na-β”-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The inner layer material of the battery layered positive electrode material is (Li/Na) a MO 2 The coating layer is made of Na-beta' -Al 2 O 3 。
The invention also provides a battery, which contains the battery layered positive electrode material.
Based on the technical scheme, the invention has the beneficial effects that:
according to the invention, the sodium source/lithium source of the coating substance is the residual alkali on the surface of the layered material, so that the residual alkali content of the material can be reduced, and the air stability of the material can be improved; meanwhile, the invention can realize Na-beta' -Al of the sodium/lithium battery layered anode material by optimizing the sintering method during cladding 2 O 3 In-situ coating, the coating effect is better, and the cycle performance of the material is improved.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 shows the Na-. Beta. -Al produced in example 1 provided by the present invention 2 O 3 SEM image of coated single crystal morphology sodium-electricity layered anode material;
FIG. 2 shows the Na-. Beta. -Al produced in example 2 according to the present invention 2 O 3 SEM image of coated polycrystalline morphology sodium-electricity layered anode material;
FIG. 3 shows the Na-. Beta. -Al produced in example 3 provided by the present invention 2 O 3 SEM image of coated polycrystalline morphology sodium-electricity layered anode material;
fig. 4 is a graph showing the retention of capacity of the battery in the comparative example and the example according to the present invention.
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.
In order to achieve a more uniform coating effect, researchers have been trying to use in-situ coating, but since high temperature may damage the structure of the coated material, affect the performance of the coated material, and the treatment is not good and may have adverse effects, the sintering temperature adopted in the in-situ coating is generally lower than 800 ℃, however, at the temperature, the material such as Na-beta' -Al cannot be obtained 2 O 3 And Na (Na) 3 Zr 2 (SiO 4 ) 2 PO 4 And some special coatings. The invention is tried to be in the positive electrode matrix material (Li/Na) in the early stage of development a MO 2 Coating Na-beta' -Al on surface in situ 2 O 3 Conventional high temperature processing operations have been foundThe loss of Li/Na element of the positive electrode material is very easy to cause, and the capacity is reduced.
After a great deal of researches, the invention discovers that the uniform in-situ coating of Na-beta' -Al can be realized by controlling the temperature rising rate of high temperature during coating 2 O 3 And meanwhile, the loss of Li/Na element of the positive electrode material is avoided to the greatest extent.
Based on this, the invention has the following technical scheme:
the invention firstly provides a preparation method of a battery layered anode material, which comprises the following steps: the positive electrode base material (Li/Na) to be coated a MO 2 Mixing the mixture with an aluminum source to obtain a mixed material, and heating the mixed material to 1200-1800 ℃ at a heating rate of 50-100 ℃ per minute;
wherein M represents one or more transition metals, and a is more than or equal to 0.5 and less than or equal to 1.0.
The invention discovers that Na-beta' -Al can be satisfied by controlling the temperature rising rate 2 O 3 The method can lead the coating raw material to react on the surface of the anode substrate material to be coated to generate a coating Na-beta' -Al 2 O 3 A uniform coating effect is obtained. Meanwhile, the residual alkali on the surface of the positive electrode matrix material to be coated is used as a coating Li/Na source, and the Na-beta' -Al is obtained by sintering after adding an Al source 2 O 3 The coated lithium battery/sodium battery layered anode material has lower residual alkali content, less gas production in the charge and discharge process and better cycle performance.
Preferably, the invention adopts a microwave sintering furnace to realize the heating rate for sintering and coating.
As a preferred embodiment of the invention, the mixed material is heated to 1200-1800 ℃ and then is subjected to heat preservation, and the heat preservation time is 5-60 minutes.
The invention further discovers that the heat preservation is carried out within the time range, so that the problems of melting, decomposition and the like of the coated material can be avoided while the coating effect is ensured.
As a preferred embodiment of the present invention, the battery layerThe preparation method of the positive electrode material comprises the following steps: coating the positive electrode matrix material (Li/Na) with alkali residue on the surface a MO 2 Mixing with an aluminum source to obtain a mixed material; the temperature of the mixture is raised from room temperature to 600-800 ℃ at a temperature raising rate of 3-10 ℃ per minute, and then is raised to 1200-1800 ℃ at a temperature raising rate of 50-100 ℃ per minute.
The invention discovers that the heating curve can lead the aluminum source to be decomposed in advance in the slower heating process, thereby optimizing the coating effect; meanwhile, the service life of the equipment can be prolonged, and the cracking caused by thermal expansion and cold contraction of material particles possibly caused by rapid temperature rise in a low-temperature section is avoided.
As a preferred embodiment of the present invention, the aluminum source comprises nano Al 2 O 3 、AlOOH、Al(OH) 3 And Al (NO) 3 ) 3 One or more of the following; in the way described (Li/Na) a MO 2 The amount of the aluminum source is 0.01 to 3wt% based on the mass of the aluminum source.
As a preferred embodiment of the present invention, the positive electrode base material (Li/Na) to be coated a MO 2 The preparation method of (2) comprises the following steps: mixing a sodium source or a lithium source with an M source, and then performing primary sintering treatment; wherein the M source is oxide of transition metal or hydroxide precursor of transition metal, and the transition metal is one or more of Fe, ni, mn, co, cu, ti, V and Cr.
In the invention, the positive electrode matrix material Na to be coated a MO 2 The surface residual alkali is mainly sodium carbonate and/or sodium hydroxide; li (Li) a MO 2 The residual alkali on the surface is lithium carbonate and/or lithium hydroxide.
As a preferred embodiment of the present invention, the primary sintering temperature is 750-1000 ℃ and the sintering time is 8-22 hours.
In the specific implementation process, the person skilled in the art can choose to adopt gradient heating or other heating modes known in the art to heat to 750-1000 ℃ for primary sintering according to actual conditions, and the method is not limited herein.
As a preferred embodiment of the present invention, the method for preparing a layered cathode material for a battery includes:
s1: mixing a sodium source or a lithium source with an M source, and then performing primary sintering treatment at 750-1000 ℃ to obtain a primary sintering raw material;
s1: mixing the primary sintering raw material with an aluminum source to obtain a mixed material, and performing secondary sintering on the mixed material; the temperature rise curve of the secondary sintering comprises: the temperature is raised from room temperature to 700-900 ℃ at a temperature raising rate of 3-10 ℃ per minute, then raised to 1200-1800 ℃ at a temperature raising rate of 50-100 ℃ per minute, and then kept at 1200-1800 ℃ for 5-60 minutes.
The invention further provides a battery layered positive electrode material, which is prepared by the preparation method.
As a preferred embodiment of the present invention, the molecular formula of the battery layered cathode material is: (Li/Na) a MO 2 @Na-β”-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The inner layer material of the battery layered positive electrode material is (Li/Na) a MO 2 The coating layer is made of Na-beta' -Al 2 O 3 。
The invention further provides a battery, which contains the battery layered positive electrode material.
Unless otherwise indicated, all of the starting materials used in the examples were commercially available conventional starting materials, and the technical means used were conventional means well known to those skilled in the art.
Example 1
The embodiment provides a battery layered cathode material, and the preparation method thereof comprises the following steps:
in this example, two-step sintering process is used to synthesize Na-beta' -Al 2 O 3 Coated sodium-electricity layered positive electrode material NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 @Na-β”-Al 2 O 3 . The method comprises the following specific steps: weighing anhydrous sodium carbonate (5% excess), niO and Fe according to stoichiometric ratio 2 O 3 And MnO 2 Mixing the weighed raw materials by a high-speed mixer, and packaging the mixed powderAfter entering the sagger, sintering treatment is carried out in a muffle furnace in air atmosphere, the sintering temperature is 950 ℃, and the temperature is kept for 20 hours. Crushing and sieving the primary sintering raw material, and adding nano Al 2 O 3 Mixing Al 2 O 3 The dosage is 0.5% of the mass of the primary sintering raw material, and then the primary sintering raw material is put into a microwave sintering furnace for secondary sintering, wherein the secondary sintering comprises the following steps: heating to 800 ℃ at a heating rate of 5 ℃ per minute, heating to 1500 ℃ at a heating rate of 100 ℃ per minute, preserving heat at 1500 ℃ for 10 minutes, naturally cooling, crushing and sieving the secondary sintering material to obtain Na-beta' -Al 2 O 3 The SEM image of the coated single crystal morphology sodium-electricity layered anode material is shown in figure 1.
The NaNi is treated by 1/3 Fe 1/3 Mn 1/3 O 2 @Na-β”-Al 2 O 3 As an active substance of a layered positive electrode material of the sodium ion battery, the proportion of positive electrode slurry is as follows: PVDF: super p=94:3:3, the slurry was uniformly coated on carbon coated aluminum foil with a 300 micron doctor blade, dried for 3 hours in an 80 degree celsius forced air drying oven, transferred to a 120 degree celsius vacuum oven for 12 hours, and then cut into 12 millimeter diameter pole pieces. The counter electrode is commercial sodium tablet (Shenzhen Ke Jing) and the membrane is glass fiber membrane, and the electrolyte is 1 mol/L NaPF 6 Dissolved in 1:1EC:DMC+5wt% FEC. And assembling the battery in a glove box to form a 2032 button battery, and performing constant-current charge and discharge test by adopting a Rayleigh energy battery test system at a current density of 0.5C, wherein the voltage range is 2-4 volts. Through tests, the first-turn discharge specific capacity of the material coated in the embodiment is 134.5 milliampere hours/gram, the first effect is 95.7%, and the 50-turn charge-discharge cycle retention rate is 97%.
Example 2
The embodiment provides a battery layered cathode material, and the preparation method thereof comprises the following steps:
in this example, two-step sintering process is used to synthesize Na-beta' -Al 2 O 3 Coated sodium-electricity layered positive electrode material NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 @Na-β”-Al 2 O 3 . The method comprises the following specific steps: stoichiometric in volumeThe anhydrous sodium carbonate (5% excess) and (Ni) were weighed in proportion 1/3 Fe 1/ 3 Mn 1/3 )(OH) 2 The precursor is placed in a mixer to be uniformly mixed, the mixed powder is put in a sagger and then is sintered in a muffle furnace for one time in air atmosphere, the sintering temperature is 900 ℃, and the heat preservation is carried out for 20 hours. Crushing and sieving the primary sintering raw material, and adding nano Al 2 O 3 Mixing Al 2 O 3 The dosage is 0.5% of the mass of the primary sintering raw material, and then the primary sintering raw material is put into a microwave sintering furnace for secondary sintering, wherein the secondary sintering comprises the following steps: heating to 750 ℃ at a heating rate of 10 ℃ per minute, heating to 1500 ℃ at a heating rate of 100 ℃ per minute, preserving heat at 1500 ℃ for 10 minutes, naturally cooling, crushing and sieving the secondary sintering material to obtain Na-beta' -Al 2 O 3 The SEM diagram of the coated polycrystalline morphology sodium-electricity layered anode material is shown in figure 2.
The current example was made as the same as example 1 for the battery test. Through testing, the first-circle discharge specific capacity of the coated material is 135.7 milliampere hours/gram, the first effect is 96.1%, and the 50-circle charge-discharge cycle retention rate is 97.5%.
Example 3:
this example provides a layered cathode material for a battery, which is different from example 2 only in that Al is added during secondary sintering 2 O 3 The mixture is replaced by AlOOH with the same Al content to finally obtain Na-beta' -Al 2 O 3 The SEM image of the coated polycrystalline morphology sodium-electricity layered anode material is shown in figure 3.
The current example was made as the same as example 1 for the battery test. Through testing, the first-circle discharge specific capacity of the coated material is 136.2 milliampere hours/gram, the first effect is 97.0%, and the 50-circle charge-discharge cycle retention rate is 97.2%.
Example 4
This example provides a layered cathode material for a battery, which differs from example 2 only in the preparation method: during secondary sintering, nano Al is added 2 O 3 And the primary sintering raw material is heated from room temperature to 1500 ℃ at a heating rate of 100 ℃ per minute, and the mostFinally obtain Na-beta' -Al 2 O 3 Coated polycrystalline morphology sodium-electricity layered anode material.
The current example was made as the same as example 1 for the battery test. Through testing, the first-circle discharge specific capacity of the coated material is 136.0 milliampere hour/gram, the first effect is 94.7%, and the 50-circle charge-discharge cycle retention rate is 95.3%.
Example 5
This example provides a layered cathode material for a battery, which differs from example 1 only in the preparation method: after the secondary sintering is finished, preserving heat for 10 minutes, and replacing the heat for 2 hours to finally obtain Na-beta' -Al 2 O 3 Coated polycrystalline morphology sodium-electricity layered anode material. The current example was made as the same as example 1 for the battery test. Through testing, the first-circle discharge specific capacity of the coated material is 128.4 milliampere hours/gram, the first effect is 90.1%, and the 50-circle charge-discharge cycle retention rate is 93.7%. The Na element loss can be caused by long-time heat preservation during the high-temperature secondary sintering in the comparative example, and the specific capacity of the material is reduced.
Comparative example 1
This comparative example provides a battery layered cathode material whose preparation method differs from that of example 1 only in that no secondary sintering coating is performed. Through testing, the initial-circle discharge specific capacity of the uncoated material is 136.8 milliampere hours/gram, the initial effect is 92.3%, and the 50-circle charge-discharge cycle retention rate is 85%. This comparative example demonstrates that coating can significantly improve the cycle performance of the material.
Comparative example 2
This comparative example provides a battery layered cathode material whose preparation method differs from example 2 only in that no secondary sintering coating is performed. Through testing, the first-circle discharge specific capacity of the uncoated material is 138.4 milliampere hours/gram, the first effect is 93.2%, and the 50-circle charge-discharge cycle retention rate is 87%. This comparative example demonstrates that coating can significantly improve the cycle performance of the material.
Comparative example 3
This comparative example provides a battery layered cathode material, which is prepared by a method differing from example 1 only in that: nano Al 2 O 3 And sintering the raw materials in a muffle furnace at 5 DEG CThe temperature rise rate per minute is raised from room temperature to 1500 ℃ and kept for 10min, and then the room temperature is naturally raised. Through tests, the first-cycle discharge specific capacity of the comparative example material is 119.8 milliampere hours/gram, the first effect is 91.6%, and the 50-cycle charge-discharge cycle retention rate is 92.0%. The specific capacity of this comparative example was greatly reduced because of the serious loss of Na element during the slow temperature rise.
The retention rate graphs of the power cycle capacity of the batteries in the examples and comparative examples are shown in fig. 4.
Test examples
The residual alkali content of the battery layered cathode materials in the examples and the comparative examples is further tested, and the results are shown in table 1:
10g of the materials obtained in examples 1 to 5 and comparative examples 1 to 3 were weighed respectively, stirred in 100mL of water for 30min, and 10mL of filtrate was collected after suction filtration and subjected to potentiometric titration for testing residual alkali (Na 2 CO 3 And NaOH) content, and the filtrate pH was tested with a pH meter. It is clear from the table that examples 1 to 3 can significantly reduce the residual alkali content and the pH value of the materials; in contrast, in example 4, the coating effect is relatively poor due to the adoption of the strategy of rapid temperature rise in the whole course of secondary sintering, and the residual alkali and the pH value are slightly increased; as is clear from comparative example 3 and example 5, the residual alkali can be reduced by reducing the rate of temperature rise in the secondary sintering and by extending the holding time, but the Na element loss caused by this is not negligible.
TABLE 1
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 preparation method of the battery layered cathode material is characterized by comprising the following steps: the positive electrode base material (Li/Na) to be coated a MO 2 Mixing the mixture with an aluminum source to obtain a mixed material, and heating the mixed material to 1200-1800 ℃ at a heating rate of 50-100 ℃ per minute;
wherein M represents one or more transition metals, and a is more than or equal to 0.5 and less than or equal to 1.0.
2. The method for preparing a layered positive electrode material for a battery according to claim 1, wherein the mixed material is heated to 1200 to 1800 ℃ and then is subjected to heat preservation for 5 to 60 minutes.
3. The method for producing a layered cathode material for a battery according to claim 1 or 2, comprising: the positive electrode base material (Li/Na) to be coated a MO 2 Mixing with an aluminum source to obtain a mixed material; the temperature of the mixture is raised from room temperature to 600-800 ℃ at a temperature raising rate of 3-10 ℃ per minute, and then is raised to 1200-1800 ℃ at a temperature raising rate of 50-100 ℃ per minute.
4. The method for producing a layered positive electrode material for a battery according to any one of claims 1 to 3, wherein the aluminum source comprises nano Al 2 O 3 、AlOOH、Al(OH) 3 And Al (NO) 3 ) 3 One or more of the following; in the way described (Li/Na) a MO 2 The amount of the aluminum source is 0.01 to 3wt% based on the mass of the aluminum source.
5. The method for producing a layered positive electrode material for a battery according to any one of claims 1 to 4, wherein the positive electrode base material (Li/Na) to be coated a MO 2 The preparation method of (2) comprises the following steps: mixing a sodium source or a lithium source with an M source, and then performing primary sintering treatment; wherein the M source is an oxide or hydroxide precursor of a transition metalThe transition metal is one or more of Fe, ni, mn, co, cu, ti.
6. The method for producing a layered positive electrode material for a battery according to any one of claims 1 to 5, wherein the primary sintering temperature is 750 to 1000 degrees celsius and the sintering time is 8 to 22 hours.
7. The method for producing a layered positive electrode material for a battery according to any one of claims 1 to 6, comprising:
s1: mixing a sodium source or a lithium source with an M source, and then performing primary sintering treatment at 750-1000 ℃ to obtain primary sintering raw materials, wherein M is one or more of Fe, ni, mn, co, cu, ti, V and Cr;
s1: mixing the primary sintering raw material with an aluminum source to obtain a mixed material, and performing secondary sintering on the mixed material; the temperature rise curve of the secondary sintering comprises: the temperature is raised from room temperature to 600-800 ℃ at a temperature raising rate of 3-10 ℃ per minute, then raised to 1200-1800 ℃ at a temperature raising rate of 50-100 ℃ per minute, and then kept at 1200-1800 ℃ for 5-60 minutes.
8. A layered cathode material for a battery, characterized in that it is produced by the production method according to any one of claims 1 to 7.
9. The layered cathode material for a battery according to claim 8, which has a molecular formula: (Li/Na) a MO 2 @Na-β”-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The inner layer material of the battery layered positive electrode material is (Li/Na) a MO 2 The coating layer is made of Na-beta' -Al 2 O 3 。
10. A battery comprising the layered positive electrode material for a battery according to claim 8 or 9.
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| CN116154128A (en) * | 2023-02-15 | 2023-05-23 | 三一红象电池有限公司 | Sodium ion battery positive electrode material, preparation method thereof, sodium ion battery and application |
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