CN117317168A - Metal atom doped layered oxide positive electrode material and preparation method and application thereof - Google Patents
Metal atom doped layered oxide positive electrode material and preparation method and application thereof Download PDFInfo
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- CN117317168A CN117317168A CN202311272149.0A CN202311272149A CN117317168A CN 117317168 A CN117317168 A CN 117317168A CN 202311272149 A CN202311272149 A CN 202311272149A CN 117317168 A CN117317168 A CN 117317168A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 65
- 239000002184 metal Substances 0.000 title claims abstract description 65
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 33
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 25
- 229910001415 sodium ion Inorganic materials 0.000 claims description 25
- 239000011734 sodium Substances 0.000 claims description 19
- 239000010406 cathode material Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- 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 description 7
- 230000001351 cycling effect Effects 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 8
- 125000004429 atom Chemical group 0.000 description 49
- 239000001301 oxygen Substances 0.000 description 25
- 229910052760 oxygen Inorganic materials 0.000 description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000011883 electrode binding agent Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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Abstract
The invention discloses a metal atom doped layered oxide positive electrode material, a preparation method and application thereof, wherein the metal atom doped layered oxide positive electrode material comprises a layered oxide layer and a coating material layer, and the structural general formula of the positive electrode material is A-TiO 2 @Na x N y M 1‑y O 2 Wherein 0 is<x≤2，0<y is less than or equal to 0.5, and a coating material layerComprising TiO 2 And is doped with TiO 2 Metal atom a on the metal atom a. The layered oxide positive electrode material obtained by doping single metal atoms has the advantages of high gram capacity, stable structure, good safety performance and the like, wherein TiO 2 As a stable oxide, the coating of the layered oxide can improve the capacity of the battery, improve the capacity retention rate, stabilize the structure of the layered oxide and avoid damaging the structure of the material when doping single metal atoms.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a metal atom doped layered oxide positive electrode material, and a preparation method and application thereof.
Background
New energy automobiles have been rapidly developed in recent years, and at the same time, the demand for energy storage devices is increasing. The scale of lithium ion batteries is gradually expanding, and researchers are widely researching the batteries. However, lithium resources are limited, and the price of the lithium source is currently increased to 480000 yuan/ton, which severely limits the development of the lithium battery industry. Sodium has a radius close to that of lithium, and is abundant in resources and low in cost, so that sodium batteries are considered to be the most potential alternatives to lithium batteries.
Among positive electrode materials of sodium batteries, layered oxides are receiving great attention because of their high specific capacity, similar to lithium ion battery structures. However, when the layered oxide is used as a positive electrode material, it has been found that the cycle stability and cycle life thereof need to be improved. Based on the method, the invention provides a method for doping the layered oxide by coating the surface with metal atoms, and aims to improve the structural stability of the layered oxide anode material in the circulating process.
Therefore, it is urgent to provide a metal atom doped layered oxide positive electrode material with high gram capacity, stable structure and good safety performance.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a metal atom doped layered oxide positive electrode material, the layered oxide positive electrode material obtained by doping single metal atom has the advantages of high gram capacity, stable structure, good safety performance and the like, wherein TiO 2 As a stable oxide, coating the layered oxide can increase the capacity of the battery, improve the capacity retention rate, stabilize the structure of the layered oxide and avoid dopingThe structure of the material itself is broken when the metal atoms are mixed.
The invention also provides a preparation method of the metal atom doped layered oxide cathode material.
The invention also provides a sodium ion battery, and the positive electrode material of the sodium ion battery is prepared from the raw materials.
According to a first aspect of the present invention, there is provided a metal atom doped layered oxide cathode material comprising a layered oxide layer and a coating material layer, wherein the cathode material has a general structural formula of A-TiO 2 @Na x N y M 1-y O 2 ，
Wherein x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 0.5,
the coating material layer comprises TiO 2 And is doped with TiO 2 Metal atom a on the metal atom a.
According to a first aspect of the invention, embodiments have at least the following advantageous effects:
the invention is realized by the method that the catalyst is prepared by the method of preparing the catalyst in TiO 2 Metal atoms of the above, where TiO 2 The oxide is more stable, and the coating of the oxide outside the layered oxide can improve the capacity of the battery, improve the capacity retention rate, stabilize the structure of the layered oxide and avoid damaging the structure of the material when the metal atoms are electrochemically doped. In TiO 2 The metal atoms are added to improve the battery performance and improve the capacity and the capacity retention rate. TiO (titanium dioxide) 2 Is a relatively stable oxide but has a relatively low capacity. By forming a metal oxide layer on TiO 2 The surface is coated with metal atoms, so that the conductivity of the material can be increased, the charge transmission rate can be improved, and the number of reversible intercalation/deintercalation lithium ions can be increased, thereby improving the capacity of the battery. In addition, the coating of the metal atoms can also stabilize the structure of the layered oxide. Layered oxides are materials with excellent ionic conductivity and structural stability that help alleviate the problem of volume expansion of lithium ions during electrochemical reactions. The coating of metal atoms can further stabilize the structure of the layered oxide and avoid damaging the layered structure of the material due to electrochemical doping of the metal atoms.
In summary, byTiO 2 The metal atoms are added for coating, so that the capacity and capacity retention rate of the battery can be improved, the structure of the layered oxide is stabilized, the damage of the material structure is avoided, and the performance of the battery is improved.
According to some embodiments of the invention, the TiO 2 The thickness of the layer is 3-7 nm.
TiO 2 Too thin layer thickness can not play a role in protecting layers and stabilizing material structures, too thick protective layers can increase the transmission path of lithium ions, influence battery performance, and the thickness of the coating layer can be adjusted through calcination temperature and time.
According to some embodiments of the invention, the M and the N are each independently selected from at least one of Al, mg, mo, fe, co and Ni; m and N are not the same.
According to some embodiments of the invention, the metal atom a comprises one of Mg, ti, cr, mn, fe, ni, cu, zn, ga, and Zr.
According to some embodiments of the invention, the number of metal atoms is 1.2% to 3%.
According to a second aspect of the present invention, there is provided a method for preparing the metal atom doped layered oxide cathode material, comprising the steps of:
s1, mixing a sodium source and a metal oxide, and then performing primary sintering, crushing, secondary sintering and titanium powder mixed sintering in an ammonia atmosphere to obtain a precursor;
s2, doping metal atoms A on the surface of the precursor.
Embodiments according to the second aspect of the invention have at least the following advantageous effects:
in the ammonia atmosphere, oxygen holes are generated in the material, and the ammonia can react with oxygen at high temperature to generate nitrogen and water, so that the reaction can effectively inhibit oxygen precipitation in the high-voltage circulation process. Under the ammonia atmosphere, oxygen molecules react with hydrogen ions in the ammonia gas to generate oxygen holes (O vacuum). These oxygen vacancies occupy oxygen sites in the material lattice, thereby reducing the precipitation of free oxygen atoms. Since oxygen precipitation under high voltage conditions is one of the main causes of safety problems of the battery, oxygen precipitation can be effectively suppressed by generating oxygen holes by oxygen, and thus safety performance of the battery can be improved. In addition, the formation of oxygen vacancies may also improve the ionic conductivity of the material. Oxygen acts as a carrier for ions in the material, and ion conduction of the cell is achieved by oxygen ion migration. The formation of oxygen vacancies increases the rate of oxygen ion migration, thereby increasing the ionic conductivity of the material. This is particularly important for high power batteries, as they require the transport of large amounts of ions to be achieved in a short time. The formation of oxygen vacancies may also increase the stability of the material. During high voltage cycling, oxygen evolution and reduction reactions often occur, resulting in structural changes and degradation of material properties. By generating oxygen holes by oxygen, the precipitation of oxygen can be suppressed, the structural change of the material can be reduced, and the stability of the battery can be improved.
According to some embodiments of the invention, in step S1, the mass ratio of the sodium source to the metal oxide is 0.8 to 1.5.
According to some embodiments of the invention, the temperature of the first sintering is 700-900 ℃ and the time of the first sintering is 12-24 hours.
According to some embodiments of the invention, the crushing comprises ball milling.
According to some embodiments of the invention, the temperature of the second sintering is 350-500 ℃, and the time of the first sintering is 5-8 hours.
According to some embodiments of the invention, the second sintering is sintering under an oxygen atmosphere.
According to some embodiments of the invention, the precursor is a titanium oxide coated layered oxide.
According to some embodiments of the invention, the precursor has a general structural formula of TiO 2 @Na x N y M 1-y O 2 。
According to some embodiments of the invention, in step S2, the sodium source comprises at least one of sodium carbonate, sodium nitrate, sodium peroxide, sodium hydroxide and sodium oxalate.
According to some embodiments of the invention, in step S2, the method of doping the metal atom a on the precursor surface is an electrochemical cycling method.
According to some embodiments of the invention, in step S2, in the electrochemical cycling method, the scanning speed is 5-10 mv/S, the scanning range is-1-0.5V, and the scanning number of turns is 500-1000.
According to some embodiments of the invention, in step S2, the number of doped metal atoms is 1.2% -3%.
According to some embodiments of the invention, in step S2, when the metal atom a is Al, the reference electrode is Ag/AgCl, the counter electrode is a carbon rod, the AlCl 3 The solution is a neutral electrolyte.
According to an embodiment of the third aspect of the present invention, the preparation raw material of the sodium ion battery includes the positive electrode material.
According to some embodiments of the invention, the preparation raw materials of the sodium ion battery further comprise: a positive electrode binder and a conductive agent.
According to some embodiments of the invention, the positive electrode binder comprises polyvinylidene fluoride.
According to some embodiments of the invention, the conductive agent comprises conductive carbon black.
According to some embodiments of the invention, the positive electrode material, the conductive agent, the binder have a weight ratio of 96.8:1:2.2.
according to some embodiments of the invention, the raw materials for preparing the sodium ion battery further comprise a negative electrode and a negative electrode binder.
According to some embodiments of the invention, the negative electrode comprises graphite.
According to some embodiments of the invention, the negative electrode bond comprises styrene-butadiene rubber.
According to some embodiments of the invention, the method for preparing a sodium ion battery comprises: and selecting a negative electrode material and a negative electrode binder, and winding the negative electrode material and the negative electrode binder with the separator in the middle after the stirring coating process. And then placing the battery core in an aluminum-plastic packaging bag, injecting the electrolyte, and performing procedures such as packaging, formation, capacity division and the like to prepare the sodium ion battery.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1:
the embodiment provides a metal atom doped layered oxide positive electrode material, a preparation method and a sodium ion battery, which specifically comprises the following steps:
TiO 2 @Na 0.43 Ni 0.33 Mo 0.33 O 2 preparing a precursor:
s1, grinding and mixing the sodium carbonate Ni/Mo oxide according to the mass ratio of 1:1. After the mixing is completed, placing the mixture into a tube furnace, starting primary sintering, introducing ammonia gas, and calcining at 800 ℃ for 18 hours; na is mixed with 0.43 Ni 0.33 Mo 0.33 O 2 Ball milling and crushing the particles, secondary sintering the crushed particles in an oxygen atmosphere, and mixing titanium powder and Na 0.43 Ni 0.33 Mo 0.33 O 2 Mixing and sintering to obtain layered oxide coated with titanium oxide, called TiO for short 2 @Na 0.43 Ni 0.33 Mo 0.33 O 2 Wherein TiO 2 The thickness of the layer was 5nm,
al-doped TiO 2 @Na x Ni y Mo 1-y O 2 Preparation of materials:
s2, preparing 1mol/L AlCl 3 The solution is used as neutral electrolyte, ag/AgCl is used as reference electrode, carbon rod is used as counter electrode, tiO 2 @Na 0.43 Ni 0.33 Mo 0.33 O 2 As a working electrode, the scanning range is-1-0.5V at the scanning speed of 5mv/s, and the scanning turns are 1000. Doping Al atoms into TiO by electrochemical cycling 2 @Na 0.43 Ni 0.33 Mo 0.33 O 2 Surface, al-TiO for short 2 @Na 0.43 Ni 0.33 Mo 0.33 O 2 。
Preparation of a battery:
s3, firstly obtaining the Al-TiO according to the preparation method of the material 2 @Na x Ni y Mo 1-y O 2 As the positive electrode active material, polyvinylidene fluoride (PVDF) is used as a positive electrode binder, conductive carbon black is used as a conductive agent, and the Al-TiO is 2 @Na x Ni y Mo 1-y O 2 And the weight ratio of the conductive agent to the binder is 96.8:1:2.2. the negative electrode material adopts graphite, the binder adopts Styrene Butadiene Rubber (SBR), the solvent adopts deionized water, and after the stirring coating process, the diaphragm is arranged in the middle and is wound with the positive and negative electrode materials. And then placing the battery core in an aluminum-plastic packaging bag, injecting the electrolyte, and performing procedures such as packaging, formation, capacity division and the like to prepare the sodium ion battery.
Example 2
The present embodiment provides a metal atom doped layered oxide cathode material, a method for preparing the same, and a sodium ion battery, and is different from embodiment 1 in that the metal atom doped TiO 2 @Na x Ni y Mo 1-y O 2 Preparation of materials in which the metal atom is Mg and the electrolyte is MgCl 3 . The remaining conditions were the same.
Example 3
The present embodiment provides a metal atom doped layered oxide cathode material, a method for preparing the same, and a sodium ion battery, and is different from embodiment 1 in that the metal atom doped TiO 2 @Na x Ni y Mo 1-y O 2 Preparation of materials, wherein the metal atom is Zr and the electrolyte is ZrCl 3 。
Example 4
The present embodiment provides a metal atom doped layered oxideCathode material, preparation method and sodium ion battery, and the difference between the embodiment and the embodiment 1 is that TiO 2 The thickness of the layer was 3nm.
Example 5
The present embodiment provides a metal atom doped layered oxide cathode material, a method for preparing the same, and a sodium ion battery, and is different from embodiment 1 in that TiO 2 The thickness of the layer was 7nm.
Comparative example 1
This comparative example provides a metal atom doped layered oxide cathode material, a method for preparing the same and a sodium ion battery, and is different from example 1 in that there is no metal doping step, and only TiO is prepared 2 @Na 0.43 Ni 0.33 Mo 0.33 O 2 。
The sodium ion battery was prepared in the same manner as in example 1.
Comparative example 2
The comparative example provides a metal atom doped layered oxide cathode material, a preparation method and a sodium ion battery, and the comparative example is different from the example 1 in that no titanium oxide coating step is adopted, specifically:
al doped with Na x Ni y Mo 1-y O 2 Preparation of materials: preparation of 1mol/L AlCl 3 The solution is used as neutral electrolyte, ag/AgCl is used as reference electrode, carbon rod is used as counter electrode, na 0.43 Ni 0.33 Mo 0.33 O 2 As a working electrode, the scanning range is-1-0.5V at the scanning speed of 5mv/s, and the scanning turns are 1000. Doping Al atoms to Na by electrochemical cycling 0.43 Ni 0.33 Mo 0.33 O 2 Surface, abbreviated as Al-Na 0.43 Ni 0.33 Mo 0.33 O 2 。
The sodium ion battery was prepared in the same manner as in example 1.
Comparative example 3
The comparative example provides a metal atom doped layered oxide cathode material, a preparation method and a sodium ion battery, and the comparative example is different from the example 1 in that metal atoms are doped firstly and then an oxide layer is coated, specifically:
al doped with Na x Ni y Mo 1-y O 2 Preparation of materials:
s1, preparing 1mol/L AlCl 3 The solution is used as neutral electrolyte, ag/AgCl is used as reference electrode, carbon rod is used as counter electrode, na 0.43 Ni 0.33 Mo 0.33 O 2 As a working electrode, the scanning range is-1-0.5V at the scanning speed of 5mv/s, and the scanning turns are 1000. Doping Al atoms to Na by electrochemical cycling 0.43 Ni 0.33 Mo 0.33 O 2 Surface, abbreviated as Al-Na 0.43 Ni 0.33 Mo 0.33 O 2 。
TiO 2 @Al-Na 0.43 Ni 0.33 Mo 0.33 O 2 Preparing a precursor:
s2, grinding and mixing the sodium carbonate Ni/Mo oxide according to the mass ratio of 1:1. After the mixing is completed, placing the mixture into a tube furnace, starting primary sintering, introducing ammonia gas, and calcining at 800 ℃ for 18 hours; al-Na 0.43 Ni 0.33 Mo 0.33 O 2 Ball milling and crushing the particles, secondary sintering the crushed particles in an oxygen atmosphere, and mixing titanium powder with Al-Na 0.43 Ni 0.33 Mo 0.33 O 2 Mixing and sintering to obtain layered oxide coated with titanium oxide, called TiO for short 2 @Al-Na 0.43 Ni 0.33 Mo 0.33 O 2 。
The sodium ion battery was prepared in the same manner as in example 1.
Comparative example 4
The comparative example provides a metal atom doped layered oxide positive electrode material, a preparation method and a sodium ion battery, which specifically comprises the following steps:
grinding the sodium carbonate Ni/Mo oxide according to the mass fraction of 1:1, and mixing. After the mixing is completed, placing the mixture into a tube furnace, and starting primary sintering, wherein the sintering temperature is 800 ℃ and the sintering time is 18 hours; na is mixed with 0.43 Ni 0.33 Mo 0.33 O 2 Ball milling and crushing the particles, secondary sintering the crushed particles in an oxygen atmosphere, and carrying out Na (sodium carbonate) sintering 0.43 Ni 0.33 Mo 0.33 O 2 Sintering again to obtain layered oxide, na 0.43 Ni 0.33 Mo 0.33 O 2 。
The sodium ion battery was prepared in the same manner as in example 1.
Comparative example 5
The comparative example provides a metal atom doped layered oxide positive electrode material, a preparation method and a sodium ion battery, which specifically comprises the following steps:
the comparative example differs from example 1 in that the Al-doped TiO 2 @Na x Ni y Mo 1-y O 2 Preparation of materials:
s2, preparing 1mol/L AlCl 3 Adding TiO into a reaction kettle as a doping solution 2 @Na 0.43 Ni 0.33 Mo 0.33 O 2 And ethanol (as solvent), sintering at 350deg.C for 6 hr, doping Al atoms into TiO by the chemical doping method 2 @Na 0.43 Ni 0.33 Mo 0.33 O 2 Surface, abbreviated as Al-TiO 2 @Na 0.43 Ni 0.33 Mo 0.33 O 2 。
The sodium ion battery was prepared in the same manner as in example 1.
Test example 1
The following performance tests were performed for the above examples and comparative examples:
1) Discharging at a multiplying power of 0.2C, and testing the gram capacity of the first discharge;
2) At normal temperature (25 ℃), calculating capacity retention rate after 200 weeks of 0.5C/0.5C cyclic charge and discharge;
3) At high temperature (45 ℃), calculating capacity retention rate after 200 weeks of 0.5C/0.5C cyclic charge and discharge;
4) Testing the thermal shock performance at 128 ℃ under 4.45V;
the test results are shown in Table 1:
TABLE 1 Performance test results
From the above data, it can be seen that the metal atoms are doped with TiO 2 @Na 0.43 Ni 0.33 Mo 0.33 O 2 The prepared battery core made of the positive electrode material has more excellent safety performance, and the doping of the metal atoms can promote the electronic conductivity of the material, increase the phase change reversibility and have higher discharge gram capacity and cycle capacity retention rate. The positive electrode material without metal doping has low gram capacity exertion, unstable system phase change and poor safety performance; the non-coated positive electrode material has no protective layer on the surface in the long-term circulation process, and the electrolyte is easy to produce side reaction and has poor high-temperature circulation. The metal atoms are doped firstly, then the oxide layer is coated, and under the condition that the bulk phase of the anode material is unstable, the electrochemical circulation method is utilized to dope the metal atoms, so that the material structure is easy to be damaged, and the final circulation performance and the safety performance are poor.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A metal atom doped layered oxide positive electrode material is characterized by comprising a layered oxide layer and a coating material layer, wherein the structural general formula of the positive electrode material is A-TiO 2 @Na x N y M 1-y O 2 ，
Wherein x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 0.5,
the coating material layer comprises TiO 2 Layer and doping in TiO 2 Metal atom a on the layer.
2. The metal atom doped layered oxide cathode material according to claim 1, wherein the TiO 2 The thickness of the layer is 3-7 nm.
3. The metal atom doped layered oxide cathode material according to claim 1, wherein M and N are each independently selected from at least one of Al, mg, mo, fe, co and Ni; m and N are not the same.
4. The metal atom doped layered oxide cathode material according to claim 1, wherein the metal atom a includes one of Mg, ti, cr, mn, fe, ni, cu, zn, ga, and Zr.
5. The metal atom doped layered oxide cathode material according to claim 1, wherein the number of the metal atoms is 1.2% to 3%.
6. A method for producing the metal atom-doped layered oxide cathode material according to any one of claims 1 to 5, comprising the steps of:
s1, mixing a sodium source and a metal oxide, and then performing primary sintering, crushing, secondary sintering and titanium powder mixed sintering in an ammonia atmosphere to obtain a precursor;
s2, doping metal atoms A on the surface of the precursor.
7. The method according to claim 6, wherein the temperature of the first sintering is 700 to 900 ℃, and the time of the first sintering is 12 to 24 hours; preferably, the temperature of the second sintering is 350-500 ℃, and the time of the first sintering is 5-8 h.
8. The method according to claim 6, wherein in step S2, the method of doping the metal atom a on the surface of the precursor is an electrochemical cycling method.
9. The method according to claim 8, wherein in the step S2, the electrochemical cycle method has a scanning speed of 5-10 mv/S, a scanning range of-1-0.5V, and a scanning number of 500-1000 cycles.
10. A sodium ion battery, characterized in that the preparation raw material of the sodium ion battery comprises the positive electrode material according to any one of claims 1 to 5.
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