CN117855420A - Atomic layer deposition modified sodium ion battery anode material and preparation method and application thereof - Google Patents
Atomic layer deposition modified sodium ion battery anode material and preparation method and application thereof Download PDFInfo
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical class [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000231 atomic layer deposition Methods 0.000 title claims abstract description 30
- 239000010405 anode material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 claims abstract description 43
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 239000011247 coating layer Substances 0.000 claims abstract description 28
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 238000000151 deposition Methods 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 239000010937 tungsten Substances 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 36
- 238000004140 cleaning Methods 0.000 claims description 25
- 230000008021 deposition Effects 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 11
- 239000012159 carrier gas Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- -1 ethylmethylamino) group Chemical group 0.000 claims description 2
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- MJGBSWYLJLDVAG-UHFFFAOYSA-N copper;1,1,1-trifluoropentane-2,4-dione Chemical compound [Cu].CC(=O)CC(=O)C(F)(F)F MJGBSWYLJLDVAG-UHFFFAOYSA-N 0.000 claims 1
- BIRTWROHEBFSNP-UHFFFAOYSA-N dimethylazanide;tungsten(2+) Chemical compound [W+2].C[N-]C.C[N-]C BIRTWROHEBFSNP-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 6
- 150000004706 metal oxides Chemical class 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 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 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000011572 manganese Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 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
Abstract
The invention discloses an atomic layer deposition modified sodium ion battery anode material, a preparation method and application thereof. Wherein, the atomic layer deposition technology is used for depositing Na in the inner core n Ni a Fe b Mn c Cu d O 2 Depositing coating layer precursor containing titanium, zinc, aluminum, zirconium, tungsten and copper elements on the surface, and sintering to obtain sodium with surface coated with metal oxide coating layer with continuous structure and small thicknessAn ion battery positive electrode material. The preparation method is simple and easy to operate, and the prepared atomic layer deposition modified sodium ion battery anode material is coated with stable metal oxide on the surface of the inner core, so that the interface stability of the material is enhanced when the material contacts with electrolyte, the circulation stability is enhanced, the gas production is reduced, and the air stability of the material is improved. Meanwhile, the metal oxide coating layer can inhibit phase change of the material during charge and discharge, so that the material has higher mechanical strength.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to an atomic layer deposition modified sodium ion battery anode material, a preparation method and application thereof.
Background
The positive electrode material of the sodium ion battery is one of key materials of the sodium ion battery, wherein the layered structure transition metal oxide with higher specific capacity is one of materials of the positive electrode material of the sodium ion battery, which has potential to be commercially produced. However, the layered anode material still has the problems of poor circulation stability, air sensitivity and the like in practical application. The surface-coated modified sodium ion battery anode material is obtained through atomic layer deposition and has a modified surface layer, so that the surface-coated modified sodium ion battery anode material has better interface stability when being contacted with electrolyte or air, and better cycle stability, safety and air stability are obtained.
Atomic layer deposition (Atomic Layer Deposition, ALD) is a method by which substances can be plated layer by layer on a substrate surface in the form of monoatomic films. The deposited film is formed by alternately introducing pulses of a vapor precursor into the reactor to chemisorb and react on the deposited substrate. The atomic layer deposition technology has wide application potential in the fields of micro-nano electronics, nano materials and the like due to the high controllability (thickness, composition and structure) of deposition parameters and excellent deposition uniformity and consistency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an atomic layer deposition modified sodium ion battery anode material.
The invention also aims to provide a preparation method of the atomic layer deposition modified sodium ion battery anode material.
The invention also aims to provide an application of the atomic layer deposition modified sodium ion battery anode material.
The technical scheme of the invention is as follows:
the preparation method of the atomic layer deposition modified sodium ion battery anode material is characterized by comprising the following steps of:
(1) The inner core of the positive electrode material of the sodium ion battery is arranged in a reaction cavity of an atomic layer deposition device, the reaction cavity is cleaned, the air pressure in the reaction cavity is regulated to be 10hPa-20hPa under a non-oxidizing atmosphere, the temperature is 80 ℃ to 150 ℃, wherein the inner core is Na n Ni a Fe b Mn c Cu d O 2 N is more than or equal to 0 and less than or equal to 1.2, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1, and n and a, b, c, d are valued so that the chemical formula is electrically neutral and at least two values in a, b, c, d are not 0;
(2) Introducing a coating layer precursor into a reaction cavity, depositing the coating layer precursor on the ferronickel manganese ternary oxide, cleaning the reaction cavity, and removing the coating layer precursor which is not deposited on the inner core, and performing the operation for 1 to 1000 times to obtain a positive electrode material precursor, wherein the coating layer precursor is at least one of titanium n-butoxide, titanium ethoxide, aluminum triisopropoxide, titanium tetra (dimethylamino) group, titanium tetra (diethylamino) group, titanium tri (dimethylamino) cyclopentadienyl group, titanium tetrabutyl titanate, diethyl zinc, trimethylaluminum, aluminum triisopropoxide, zirconium tetra (dimethylamino) group, zirconium tetra (ethylmethylamino) group, zirconium tri (dimethylamino) cyclopentadienyl group, (tertiary Ding Yaan group) tungsten, copper bis (hexafluoroacetylacetone), copper bis (hexafluorodimethylpropionyl acrylate) and copper trifluoroacetyl acetonate;
(3) And placing the precursor of the positive electrode material in an oxygen-containing atmosphere for sintering to obtain the positive electrode material of the sodium ion battery.
In one possible implementation, the total content of titanium, zinc, aluminum, zirconium, tungsten, and copper in the coating precursor is 1000ppm to 2000ppm.
In one possible implementation, the operation of introducing the coating precursor into the reaction chamber in the step (2) is as follows: and conveying the coating precursor to the reaction cavity through a non-oxidizing atmosphere under the condition that the carrier gas flow is 1ml/min-100ml/min, and the conveying time is 0.1s-1s.
In one possible implementation, the sintering in step (3) is performed at a temperature of 100-700 ℃ for a time of 1-10 hours.
In one possible implementation, the carrier gas flow rate for cleaning the reaction chamber in the step (1) and the step (2) is 1ml/min-100ml/min, and the cleaning time is 1s-10s.
The ternary positive electrode material of the sodium ion battery comprises a core and a coating layer deposited on the surface of the core by an atomic deposition technology;
the inner core is transition metal oxide Na n Ni a Fe b Mn c Cu d O 2 N is more than or equal to 0 and less than or equal to 1.2, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1, and n and a, b, c, d are valued so that the chemical formula is electrically neutral and at least two values in a, b, c, d are not 0;
the coating layer is an oxide of at least one element of titanium, zinc, aluminum, zirconium, tungsten and copper.
In one possible implementation, the thickness of the cladding layer is 1nm-10nm.
In one possible implementation, the total mass of titanium, zinc, aluminum, zirconium, tungsten, and copper in the coating layer is 0.2% -2% of the sodium ion positive electrode cell material.
The raw materials for preparing the positive electrode of the sodium ion battery comprise the positive electrode material of the sodium ion battery prepared by the preparation method.
The raw materials for preparing the positive electrode of the sodium ion battery comprise the positive electrode material of the sodium ion battery prepared by the preparation method.
The invention has the following beneficial effects:
1. the invention forms a thinner metal oxide coating layer with continuous structure on the surface of the inner core through atomic layer deposition and sintering, and is simple and easy to operate.
2. The atomic layer deposition modified sodium ion battery anode material prepared by the invention has the advantages that the stable metal oxide is coated on the surface of the inner core, so that the interface stability is enhanced when the material contacts with electrolyte, the circulation stability is enhanced, the gas production is reduced, and the air stability of the material is improved. Meanwhile, the metal oxide coating layer can inhibit phase change of the material during charge and discharge, so that the material has higher mechanical strength.
Drawings
FIG. 1 is a scanning electron microscope image of example 1;
FIG. 2 is a graph of the cycling stability of example 1 and comparative example;
fig. 3 is a first-round charge-discharge graph of example 1 and example 3.
Detailed Description
The technical scheme of the invention is further illustrated and described through the following specific embodiments.
In the following examples, the water used may be one or more of distilled water, purified water, and drinking water; unless otherwise specified, the detection methods in the following embodiments are all conventional detection methods; the reagents in the examples described below were purchased commercially unless otherwise specified.
The non-oxidizing atmosphere used in the present invention is nitrogen or an inert gas, and in the following examples, the non-oxidizing atmosphere used is high purity nitrogen having a purity of 99.999%.
The atomic layer deposition modified sodium ion battery anode material provided by the invention comprises a core and a coating layer deposited on the surface of the core, wherein metal elements in the coating layer generally partially permeate into the core in the actual preparation and use processes. Therefore, the selection of the coating layer and the inner core and the preparation method are the same as the technical scheme of the invention, and only part of metal elements in the coating layer penetrate into the sodium ion battery anode material of the inner core and are not excluded from the protection scope of the invention.
Example 1
NaNi is processed by 1/3 Fe 1/3 Mn 1/3 O 2 And (3) placing the reaction chamber of the atomic layer deposition equipment, closing the chamber, and cleaning the reaction chamber by using high-purity nitrogen with the purity of 99.999 percent. Vacuum pump is used for pumping the reaction cavityPumping to low vacuum of 10hPa, heating to 120 ℃, introducing tetrabutyl titanate into a reaction cavity for 0.1s under the condition of carrier gas flow of 5ml/min, cleaning for 5s by using high-purity nitrogen, cleaning redundant tetrabutyl titanate, and repeating the deposition cycle for 4 times (introducing the coating layer precursor, and then cleaning the reaction cavity for 1 deposition cycle) to obtain the anode material precursor. And sintering the precursor of the positive electrode material in an oxygen atmosphere for 3 hours at the sintering temperature of 400 ℃ to obtain the positive electrode material of the sodium ion battery.
The elements of the positive electrode material of the sodium ion battery prepared in example 1 are shown in table 1:
TABLE 1 elemental ratios of sodium ion batteries cathode materials
| Element(s) | Weight percent | Atomic percent |
| O | 25.78 | 50.37 |
| Mn | 20.45 | 11.64 |
| Fe | 20.06 | 11.23 |
| Ni | 21.88 | 11.64 |
| Ti | 1.38 | 0.90 |
| Na | 10.45 | 14.21 |
| Total amount of | 100.00 | 100.00 |
Example 2
NaNi is processed by 1/3 Fe 1/3 Mn 1/3 O 2 And (3) placing the reaction chamber of the atomic layer deposition equipment, closing the chamber, and cleaning the reaction chamber by using high-purity nitrogen with the purity of 99.999 percent. Pumping the reaction cavity to low vacuum of 10hPa by a vacuum pump, heating to 120 ℃, introducing tetrabutyl titanate into the reaction cavity for 0.1s under the condition of carrier gas flow of 5ml/min, cleaning for 5s by high-purity nitrogen, cleaning off redundant tetrabutyl titanate, and repeating the deposition cycle for 1 time to obtain the precursor of the positive electrode material. And sintering the precursor of the positive electrode material in an oxygen atmosphere for 3 hours at the sintering temperature of 400 ℃ to obtain the positive electrode material of the sodium ion battery.
Example 3
NaNi is processed by 1/3 Fe 1/3 Mn 1/3 O 2 And (3) placing the reaction chamber of the atomic layer deposition equipment, closing the chamber, and cleaning the reaction chamber by using high-purity nitrogen with the purity of 99.999 percent. Pumping the reaction cavity to low vacuum of 10hPa by a vacuum pump, heating to 120 ℃, introducing tetrabutyl titanate into the reaction cavity for 0.1s under the condition that the carrier gas flow is 5ml/min, cleaning for 5s by high-purity nitrogen, cleaning off redundant tetrabutyl titanate, and repeating the deposition cycle for 8 times to obtain the precursor of the positive electrode material. And sintering the precursor of the positive electrode material in an oxygen atmosphere for 3 hours at the sintering temperature of 400 ℃ to obtain the positive electrode material of the sodium ion battery.
Example 4
NaNi is processed by 1/3 Fe 1/3 Mn 1/3 O 2 And (3) placing the reaction chamber of the atomic layer deposition equipment, closing the chamber, and cleaning the reaction chamber by using high-purity nitrogen with the purity of 99.999 percent. Pumping the reaction cavity to low vacuum of 10hPa by a vacuum pump, heating to 120 ℃, introducing tetrabutyl titanate into the reaction cavity for 0.1s under the condition that the carrier gas flow is 5ml/min, cleaning for 5s by high-purity nitrogen, cleaning off redundant tetrabutyl titanate, and repeating the deposition cycle for 4 times to obtain the precursor of the positive electrode material. And sintering the precursor of the positive electrode material in an oxygen atmosphere for 3 hours at the sintering temperature of 250 ℃ to obtain the positive electrode material of the sodium ion battery.
Example 5
NaNi is processed by 1/3 Fe 1/3 Mn 1/3 O 2 And (3) placing the reaction chamber of the atomic layer deposition equipment, closing the chamber, and cleaning the reaction chamber by using high-purity nitrogen with the purity of 99.999 percent. Pumping the reaction cavity to a low vacuum of 10hPa by a vacuum pump, heating to 120 ℃, introducing diethyl zinc into the reaction cavity for 0.1s under the condition that the carrier gas flow is 5ml/min, cleaning for 5s by high-purity nitrogen, cleaning off redundant diethyl zinc, and repeating the deposition cycle for 4 times to obtain the precursor of the positive electrode material. And sintering the precursor of the positive electrode material in an oxygen atmosphere for 3 hours at the sintering temperature of 400 ℃ to obtain the positive electrode material of the sodium ion battery.
Example 6
NaNi is processed by 1/3 Fe 1/3 Mn 1/3 O 2 And (3) placing the reaction chamber of the atomic layer deposition equipment, closing the chamber, and cleaning the reaction chamber by using high-purity nitrogen with the purity of 99.999 percent. Pumping the reaction cavity to a low vacuum of 10hPa by a vacuum pump, heating to 120 ℃, introducing aluminum triisopropoxide into the reaction cavity for 0.1s under the condition that the carrier gas flow is 5ml/min, cleaning for 5s by high-purity nitrogen, cleaning away the redundant aluminum triisopropoxide, and repeating the deposition cycle for 4 times to obtain a positive electrode material precursor. And sintering the precursor of the positive electrode material in an oxygen atmosphere for 3 hours at the sintering temperature of 400 ℃ to obtain the positive electrode material of the sodium ion battery.
Comparative example 1
Comparative example 1 is NaNi without atomic layer deposition coating modification 1/3 Fe 1/3 Mn 1/3 O 2 。
Performance testing
1. Scanning electron microscopy was performed on example 1 and the results are shown in figure 1. It can be seen that the particles of the sodium ion positive electrode material prepared in example 1 have a polycrystalline structure, and a thin and uniform coating layer is formed on the surface of the material.
2. The positive electrode materials of sodium ion batteries prepared in examples 1 to 6 and the comparative positive electrode material of comparative example 1 were respectively mixed with acetylene black and polyvinylidene fluoride according to the following ratio of 8:1: mixing the 1 proportion with N-methyl pyrrolidone to prepare positive electrode slurry, then coating the positive electrode slurry on carbon-coated aluminum foil, and drying and rolling the positive electrode slurry to obtain the positive electrode plate. And assembling the positive electrode plate and sodium metal into a button cell, and performing electrochemical performance test.
The testing method comprises the following steps: the charge and discharge test was carried out at a 1C rate in a voltage range of 2.0V-4.0V with a current density of 150mA/g.
Test results: the electrochemical properties of examples 1 to 6 and comparative example 1 are shown in table 2, and fig. 2 shows the cycle performance after 100 cycles of example 1, and fig. 3 is a first cycle charge-discharge graph of examples 1 and 3.
Table 2 electrochemical properties of examples 1-6 and comparative example 1
As can be seen from Table 2 and FIG. 2, examples 1 to 6, which used tetrabutyl titanate, diethyl zinc and aluminum triisopropoxide all had good cycle retention rates of 90% or more after atomic layer deposition modification, compared with comparative example 1, which was poor in cycle performance because of the absence of the coating layer, difficulty in suppressing phase transition of the material and reducing internal defects of the material.
The sintering temperatures and the choice of coating precursor for examples 1-3 were the same, except that the number of deposition layers was different. As can be seen from comparative example 1, example 2, example 1 and example 3, the cycle retention of the battery increases significantly from 0 layer to 1 layer and from 1 layer to 4 layers, while the cycle retention of the battery increases relatively little although there is an increase from 4 layers to 8 layers.
FIG. 3 is a graph showing the first-turn charge and discharge curves of examples 1 and 3, and it can be seen that the specific first-turn discharge capacities of examples 1 and 3 reach 130mAhg -1 The above. Wherein, compared with example 1 and example 3, the number of deposition layers is smaller, the first-turn discharge specific capacity is larger, which shows that the increase of the coating layer may have a certain negative effect on the specific capacity of the electrode material.
In view of the test data, the invention controls the deposition layer number to be 1-10, and the positive electrode material of the sodium ion battery has higher specific capacity and cycle retention rate.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, i.e., the invention is not to be limited to the details of the invention.
Claims (10)
1. The preparation method of the atomic layer deposition modified sodium ion battery anode material is characterized by comprising the following steps of:
(1) The inner core of the positive electrode material of the sodium ion battery is arranged in a reaction cavity of an atomic layer deposition device, the reaction cavity is cleaned, the air pressure in the reaction cavity is regulated to be 5hPa-20hPa under a non-oxidizing atmosphere, the temperature is 80 ℃ to 150 ℃, wherein the inner core is Na n Ni a Fe b Mn c Cu d O 2 N is more than or equal to 0 and less than or equal to 1.2, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1, and n and a, b, c, d are valued so that the chemical formula is electrically neutral and at least two values in a, b, c, d are not 0; ；
(2) Introducing a coating layer precursor into the reaction cavity, depositing the coating layer precursor on the inner core, cleaning the reaction cavity, removing the coating layer precursor which is not deposited on the inner core, and executing the operation for 1 to 1000 times to obtain a positive electrode material precursor with 1 to 10 layers of deposited layers, wherein the coating layer precursor is at least one of titanium n-butoxide, titanium ethoxide, aluminum triisopropoxide, titanium tetra (dimethylamino) group, titanium tetra (diethylamino) group, titanium tri (dimethylamino) cyclopentadienyl group, titanium tetrabutyl titanate, diethyl zinc, trimethylaluminum, aluminum triisopropoxide, zirconium tetra (dimethylamino) group, zirconium tetra (ethylmethylamino) group, zirconium tri (dimethylamino) cyclopentadienyl group, (tertiary Ding Yaan groups) bis (dimethylamino) tungsten, copper bis (hexafluoroacetylacetone), copper bis (hexafluorodimethylpropionyl acrylate) and copper trifluoroacetylacetone;
(3) And placing the positive electrode material precursor in an oxygen-containing atmosphere for sintering to obtain the positive electrode material of the sodium ion battery.
2. The method of claim 1, wherein the total content of titanium, zinc, aluminum, zirconium, tungsten, and copper in the coating precursor is 1000ppm to 2000ppm.
3. The method of claim 1 or 2, wherein the operation of introducing the coating precursor into the reaction chamber in step (2) is: and conveying the coating precursor to the reaction cavity through a non-oxidizing atmosphere under the condition that the carrier gas flow is 1ml/min-100ml/min, and the conveying time is 0.1s-1s.
4. The method of claim 1, wherein the sintering in step (3) is performed at a temperature of 100 ℃ to 700 ℃ for a time of 1h to 10h.
5. The method according to claim 1, wherein the carrier gas flow rate of the cleaning reaction chamber in step (1) and step (2) is 1ml/min to 100ml/min, and the cleaning time is 1s to 10s.
6. An atomic layer deposition modified sodium ion battery positive electrode material, which is characterized by being prepared by the preparation method of claims 1-7, wherein the sodium ion battery ternary positive electrode material comprises a core and a coating layer deposited on the surface of the core through an atomic deposition technology;
the inner core is Na n Ni a Fe b Mn c Cu d O 2 N is more than or equal to 0 and less than or equal to 1.2, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1, and n and a, b, c, d are valued so that the chemical formula is electrically neutral and at least two values in a, b, c, d are not 0; ；
the coating layer is an oxide of at least one element of titanium, zinc, aluminum, zirconium, tungsten and copper.
7. The positive electrode material for sodium ion battery according to claim 6, wherein the thickness of the coating layer is 1nm to 10nm.
8. The positive electrode material of sodium ion battery according to claim 6, wherein the total mass of titanium, zinc, aluminum, zirconium, tungsten and copper in the coating layer is 0.2% -2% of the positive electrode material of sodium ion battery.
9. A sodium ion battery positive electrode, characterized in that the raw materials for preparing the sodium ion battery positive electrode comprise the sodium ion battery positive electrode material prepared by the preparation method according to any one of claims 1-5.
10. A sodium ion battery, characterized in that the raw materials for preparing the positive electrode of the sodium ion battery comprise the positive electrode material of the sodium ion battery prepared by the preparation method according to any one of claims 1-5.
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