CN117894931A - Nanocrystalline dispersion-strengthened sodium ion battery positive electrode material, and preparation method and application thereof - Google Patents
Nanocrystalline dispersion-strengthened sodium ion battery positive electrode material, and preparation method and application thereof Download PDFInfo
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- CN117894931A CN117894931A CN202311500564.7A CN202311500564A CN117894931A CN 117894931 A CN117894931 A CN 117894931A CN 202311500564 A CN202311500564 A CN 202311500564A CN 117894931 A CN117894931 A CN 117894931A
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 54
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 62
- 238000005245 sintering Methods 0.000 claims abstract description 49
- 239000010405 anode material Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000013081 microcrystal Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 92
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 74
- 239000011572 manganese Substances 0.000 claims description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 229910005565 NiaMnb Inorganic materials 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000010406 cathode material Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000009768 microwave sintering Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 13
- 238000003860 storage Methods 0.000 abstract description 11
- 229910002551 Fe-Mn Inorganic materials 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000007790 solid phase Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 239000012071 phase Substances 0.000 description 22
- 230000008859 change Effects 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 11
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 230000001351 cycling effect Effects 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 230000000087 stabilizing effect Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000001427 coherent effect Effects 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910003069 TeO2 Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002345 surface coating layer Substances 0.000 description 3
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 3
- 230000005536 Jahn Teller effect Effects 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/008—Salts of oxyacids of selenium or tellurium
-
- 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
-
- 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
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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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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention provides a nano-crystallite dispersion-strengthened sodium ion battery anode material and a preparation method and application thereof, belonging to the technical field of sodium ion battery anode materials; the invention utilizes the advantages of similar synthesis conditions and temperature of the layered structure Na 2M2TeO6 and Ni-Fe-Mn-based oxide, and realizes the synthesis of a matrix material and the coating of Na 2M2TeO6 by a simple solid-phase sintering reaction to prepare the nano microcrystal dispersion-strengthened sodium ion battery anode material; the nano-crystallite dispersion-strengthened sodium ion battery is a honeycomb Na 2M2TeO6 (M is Ni, mg, cu, zn, co) modified Ni-Fe-Mn base layered oxide anode material with a P2/O3 layered interlocking structure, and can effectively improve the storage property, safety and practicability of the anode material; the process flow of the positive electrode material has the advantages of easily available raw materials, simple preparation method, high controllability and the like, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of layered oxide positive electrodes of sodium ion batteries, and particularly relates to a nano-crystallite dispersion-strengthened positive electrode material of a sodium ion battery, a preparation method and application thereof.
Background
In recent years, the defect of lack of domestic lithium resources is increasingly remarkable, and the requirement of large-scale energy storage cannot be met in the future, so that a new material system capable of partially replacing lithium ion batteries needs to be developed. Sodium ion batteries have the advantages of higher energy density, better safety and stability, higher similarity with Li, high abundance and the like, and have been widely studied in recent years. Therefore, there is a need to develop sodium ion batteries with higher energy densities and cycle life.
At present, the cobalt-free Ni-Fe-Mn base layered oxide positive electrode material has the advantages of high specific capacity, low cost, environmental friendliness and the like, and is considered to be one of the most promising positive electrode materials of sodium ion batteries. However, the materials still have the problems of unstable structure and poor electrochemical performance: on one hand, transition metal ions migrate and a transition metal layer slides in the charge and discharge process and initiates a series of phase changes, so that lattice distortion stress is generated to cause unstable structure; on the other hand, upon storage in air, na in the crystal lattice escapes to the grain surface and forms fibrous Na 2CO3, resulting in serious capacity fade and polarization. Making the material difficult to store and transport, thereby impeding its practical use.
The traditional modification means such as inert element doping, surface coating and the like can effectively improve the structural stability and air stability of the anode material, but the means usually sacrifice part of capacity and are difficult to improve the problem of poor rate performance in the circulation process. Therefore, there is a need to develop a new modification strategy that can simultaneously neutralize the problems of capacity sacrifice and dynamic performance decline.
Disclosure of Invention
Aiming at the problems of capacity attenuation, poor multiplying power performance, poor air stability and the like in the circulation process of the layered oxide cathode material in the prior art, the invention provides a nano-crystallite dispersion-strengthened sodium ion battery cathode material, a preparation method and application thereof; according to the invention, the synthesis of a matrix material and the coating of Na 2M2TeO6 are realized through a simple solid-phase sintering reaction by utilizing the advantages of the layered structure Na 2M2TeO6 and the Ni-Fe-Mn-based oxide that the synthesis conditions and the temperature are similar, so that the nano microcrystal dispersion-strengthened sodium ion battery is prepared; the nano-crystallite dispersion-strengthened sodium ion battery is a honeycomb-structure Na 2M2TeO6 modified Ni-Fe-Mn base layered oxide positive electrode material, and can effectively improve the storage property, safety and practicability of the positive electrode material; the process flow of the positive electrode material has the advantages of easily available raw materials, simple preparation method, high controllability and the like, and has good application prospect.
In order to solve the technical purpose, the invention adopts the following technical means:
The invention firstly provides a nano-crystallite dispersion-strengthened sodium ion battery anode material, which takes Na xNiaMnbFe1-a-bO2 as a matrix material and Na 2M2TeO6 as a modified substance; in Na xNiaMnbFe1-a-bO2, x is more than or equal to 0.66 and less than or equal to 1, a is more than or equal to 0.01 and less than or equal to 0.33, b is more than or equal to 0.33 and less than or equal to 0.75,0 and less than or equal to 1-a-b is less than or equal to 0.33, and M in Na 2M2TeO6 comprises one or more of Cu, ni, co, mg, zn; the positive electrode material of the sodium ion battery is formed by stacking nano flaky particles; in the sodium ion battery anode material, na 2M2TeO6 of a honeycomb lamellar structure is coated on the outer side of a matrix material Na xNiaMnbFe1-a-bO2, and is also dispersed in Na xNiaMnbFe1-a-bO2 nano particles to form a P2/O3 lamellar interlocking structure with the Na xNiaMnbFe1-a-bO2 nano particles.
Preferably, the space group of the positive electrode material of the sodium ion battery is P6 3/mmc、P63/mcm or R-3m.
Preferably, the mass ratio of Na 2M2TeO6 to Na xNiaMnbFe1-a-bO2 is (0.5% to 1) to (20% to 1).
The invention also provides a preparation method of the nano-crystallite dispersion-strengthened sodium ion battery anode material, which specifically comprises the following steps:
(1) Under the protection of inert atmosphere, dissolving a nickel source, an iron source and a manganese source in distilled water, adding a coprecipitation agent into the distilled water for reaction, and washing, filtering and drying after the reaction is finished to obtain a Ni aMnbFe1-a-b(OH)2 precursor;
(2) Mixing a Ni aMnbFe1-a-b(OH)2 precursor with a sodium salt, an M compound and a Te compound, adding a ball grinding agent, and uniformly mixing by ball milling to obtain a mixture; the M comprises one or more of Cu, ni, co, mg, zn;
(3) And (3) carrying out multi-step sintering reaction on the mixture, and cooling after the reaction is finished to obtain the nano-crystallite dispersion-strengthened sodium ion battery anode material.
Preferably, in the step (1), the inert gas includes any one of argon and nitrogen;
the nickel source, the manganese source and the iron source are one or more of corresponding acetate, chloride, nitrate and sulfate;
The coprecipitation agent comprises one or more of NaOH solution, NH 4 OH solution and NaHCO 3 solution;
NaOH in the coprecipitate: the mole ratio of NH 4OH：NaHCO3 is 0-100%: 0-15%: 0-35%, and the molar ratio of the three is 0 at the same time.
Preferably, in the step (1), the addition amounts of the nickel source, the iron source, the manganese source and the coprecipitation agent are calculated according to the stoichiometric ratio of the precursor of the product Ni aMnbFe1-a-b(OH)2, wherein x is more than or equal to 0.66 and less than or equal to 1, a is more than or equal to 0.01 and less than or equal to 0.33, b is more than or equal to 0.33 and less than or equal to 0.75,0 and less than or equal to 1-a-b is more than or equal to 0.33.
Preferably, in the step (2), the molar ratio of the Ni aMnbFe1-a-b(OH)2 precursor to the sodium salt is 1:0.68-1:1.15;
The molar ratio of Na, M and Te in the sodium salt, M compound and Te compound is 2:2:1-2.15:2:1.
Preferably, in step (2), the sodium salt comprises one or more of Na 2CO3、NaNO3、NaHCO3;
the M compound comprises one or more of oxide, nitrate, acetate, carbonate and hydroxide;
the Te compound comprises one or more of oxide, nitrate, acetate, carbonate and hydroxide;
the ball milling agent comprises any one of methanol, ethanol, propanol and diethyl ether;
Ball milling, ball milling: and (3) material: the mass ratio of the ball grinding agent is 1-2:1:0.5-0.618.
Preferably, in step (3), in the multi-step sintering reaction, the sintering atmosphere is one or more of oxygen or air; the sintering method is one or more of microwave sintering, normal pressure sintering, hot pressing sintering, reaction sintering and self-sintering.
Preferably, in step (3), the multi-step sintering step comprises two stages:
the first stage is presintering at 400-600 ℃ for 0.5-12 h, and then sintering at 700-1000 ℃ for 0.1-2 h;
The second stage is pre-sintering for 4-12 h at 500-650 ℃, and then sintering for 4-12 h at 700-950 ℃;
in the multi-step sintering step, the heating rate is 3-10 ℃/min.
The invention also provides application of the nano-crystallite dispersion strengthening sodium ion battery anode material in preparation of sodium ion batteries.
Compared with the prior art, the invention has the beneficial effects that:
(1) The modified material Na 2M2TeO6 (M= Cu, ni, co, zn, mg) in the nano-crystallite dispersion-strengthened sodium ion battery anode material is a P2-phase layered sodium ion solid electrolyte material with stable structure, and the room-temperature ion conductivity (about 1.1 mS/cm) is basically equivalent to the levels of Al 2O3 and NASICON electrolytes. In addition, the P2 phase Na 2M2TeO6 has the advantages of stable structure and higher ionic conductivity, and can reduce the concentration of manganese ions, thereby inhibiting the Jahn-Teller effect. The Na 2M2TeO6 solid electrolyte has strong Te-O bond and Te 6+ induction effect, so that the solid electrolyte has good structural stability under high working voltage.
According to the invention, the Na 2M2TeO6 nano microcrystalline phase doping and surface coating are realized simultaneously by utilizing simple multi-step sintering reaction, so that the Na 2M2TeO6 and Na xNiaMnbFe1-a-bO2 mixed phase anode material is formed, and the formed composite phase epitaxial interface can well inhibit the stress and volume expansion of the material in the circulation process on the premise that the specific capacity of the anode material is not obviously influenced after coating, thereby improving the structure and interface stability of the material and finally improving the electrochemical performance of the material.
(2) The invention forms a protective layer with stable structure on the surface of the Ni-Fe-Mn base anode material by utilizing strong Te-O bond, and the protective layer can effectively isolate the contact between active substances and air and electrolyte, thereby improving the storage performance of the anode material; the Na 2M2TeO6 on the surface has a rapid Na ion conduction rate, and can effectively reduce the impedance of Na + transmitted between the electrolyte and the positive electrode material.
In addition, a two-phase composite layered structure epitaxial interface is formed on the surface of the positive electrode material Na xNiaMnbFe1-a-bO2, and the composite phase coupling structure can effectively buffer lattice distortion stress generated by the change of the phase structure of the material in circulation, so that the circulation stability of the material in the process of charging and discharging in a wider electrochemical window is improved; meanwhile, the surface coating layer Na 2M2TeO6 reduces the contact between the electrode and air and electrolyte, so that the positive electrode material combines the high specific capacity of Na xNiaMnbFe1-a-bO2 and the rapid ion conduction characteristic of the honeycomb structure Na 2M2TeO6, and the air stability and the cycle performance of the layered oxide positive electrode material are greatly improved.
A small amount of Na 2M2TeO6 microcrystalline disperse phase also exists in the Na xNiaMnbFe1-a-bO2 bulk phase structure, and the disperse phase reduces the concentration of Mn ions in the material so as to inhibit Jahn-Teller effect and prevent phase change. And finally, the comprehensive electrochemical performance of the Ni-Fe-Mn-based positive electrode material is improved.
(3) The invention has the advantages of easily obtained raw materials, simple preparation, low cost and high controllability, and the obtained sodium ion battery anode material has good storage performance and long cycle life, can obviously improve the practicability of the anode material, and is suitable for mass production and application.
Drawings
Fig. 1 is an XRD pattern of nanocrystalline dispersion-strengthened sodium ion battery cathode material (a) and material (b) in comparative examples 1 to 2.
Fig. 2 is an SEM image of original NaNi 1/3Fe1/3Mn1/3O2 positive electrode material (a) and nano-crystallite dispersion-strengthened sodium ion battery positive electrode material (b) in example 1.
Fig. 3 is a TEM image of the original NaNi 1/3Fe1/3Mn1/3O2 positive electrode material (a) and the sodium ion battery positive electrode material (b) in example 2.
Fig. 4 is a graph of the initial charge and discharge of a coin cell assembled from the materials provided in comparative examples 1 and 2 over a 2-4.2V voltage.
Fig. 5 is a graph of the initial charge and discharge of the assembled coin cell of examples 1-3 over 2-4.2V.
Fig. 6 is a graph of the cycling performance of the positive electrode material assembled button cell provided in examples 1-3 over 2-4.2V.
Fig. 7 is a graph of the rate performance of the positive electrode material assembled button cell provided in example 2 over 2-4.2V.
Fig. 8 is a graph showing the cycle performance of the material obtained in example 2 after air storage to prepare a battery.
In the figure: the pristine is an original material, 1% of NaNTO@O3-NaNFMO is a NaNi 1/ 3Fe1/3Mn1/3O2 material coated with 1% of Na 2Ni2TeO6, 1% of NaMgTO@O3-NaNFMO is a NaNi 1/3Fe1/3Mn1/3O2 material coated with 1% of Na 2Mg2TeO6, and 1% of NaNMgTO is a NaNi 1/3Fe1/3Mn1/3O2 material coated with 1% of Na 2NiMgTeO6.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are provided for the purpose of illustrating the invention in further detail, but are not to be construed as limiting the invention. Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
In the following examples, na xNiaMnbFe1-a-bO2 is described as Na xNi1/3Mn1/3Fe1/3O2, but the scope of protection is not limited thereto, and all materials falling within the scope of NaxNiaMnbFe1-a-bO2(0.66≤x≤1,0.01≤a≤0.33,0.33≤b≤0.75,0≤1-a-b≤0.33) can implement the present invention.
Example 1. Preparation of nanocrystalline dispersion-strengthened sodium ion battery cathode material:
(1) Under the protection of argon atmosphere, solid NiSO 4·6H2O、MnSO4·4H2 O and FeCl 3·6H2 O are dissolved in 50ml of distilled water in an equimolar ratio (1:1:1) to prepare a solution A, and then the solution A is slowly added into a beaker containing an NaOH coprecipitate, so that the molar ratio of NiSO 4·6H2O、MnSO4·4H2 O and FeCl 3·6H2 O to NaOH in the solution A is 1:1:1:6. Stirring at about 60 ℃ for 3 hours, performing coprecipitation reaction, obtaining powder after the reaction is finished, washing, filtering, and drying at 80 ℃ for 12-24 hours to obtain the Ni 1/3Mn1/3Fe1/3(OH)2 precursor.
(2) According to the mass ratio of NaNi 1/3Fe1/3Mn1/3O2 to Na 2Ni2TeO6 of 1:0.01, calculating and weighing the required mass of Ni 1/ 3Mn1/3Fe1/3(OH)2、Na2CO3、NiO、TeO2, dispersing in ethanol (ball milling agent), stirring uniformly, and transferring to a ball mill for ball milling to obtain a mixture.
(3) The mixture is sintered at high temperature at a heating rate of 5 ℃/min under an oxygen atmosphere, wherein the high temperature sintering comprises two stages, wherein the first stage is performed for 1h through microwave sintering at 500 ℃ and then is performed for 0.5h at 800 ℃, and the second stage is performed for 4h through tubular furnace reaction sintering at 650 ℃ and then is performed for 12h at normal pressure and then is performed at 900 ℃. And naturally cooling after sintering, and grinding to obtain the NaNi 1/3Fe1/3Mn1/3O2 anode material coated with 1% Na 2Ni2TeO6, namely the nano-crystallite dispersion-strengthened sodium ion battery anode material.
Fig. 1a is an XRD pattern of the nanocrystalline dispersion-strengthened sodium ion battery cathode material (1% Na 2Ni2TeO6 -coated NaNi 1/3Fe1/3Mn1/3O2 layered oxide cathode material) prepared in this example, and it can be seen from the figure that the diffraction peak thereof includes a strong diffraction peak of O3 phase NaNi 1/3Fe1/3Mn1/3O2, but no significant diffraction peak of P2 phase Na 2Ni2TeO6 is observed, probably because the ratio of coated Na 2Ni2TeO6 is small and difficult to observe. XRD results show that the crystal structure of the matrix material is not changed obviously before and after coating, which shows that the coating process does not affect the structure of the material.
Fig. 2 is an SEM morphology graph of an original NaNi 1/3Fe1/3Mn1/3O2 positive electrode material and a NaNi 1/3Fe1/3Mn1/3O2 positive electrode material modified by 1% Na 2Ni2TeO6, the positive electrode material prepared by a coprecipitation method combined with a solid phase method is approximately spherical, and is formed by stacking nano lamellar particles, and the morphology of particles does not change significantly before and after modification of Na 2Ni2TeO6.
Example 2. Preparation of nanocrystalline dispersion-strengthened sodium ion battery cathode material:
(1) Step (1) was performed as in example 1.
(2) The mass of Ni 1/3Mn1/3Fe1/3(OH)2、Na2CO3、MgCO3、TeO2 required is calculated according to the mass ratio of NaNi 1/3Fe1/3Mn1/3O2 to Na 2Mg2TeO6 of 1:0.01, dispersed in ethanol (ball milling agent), stirred uniformly, and then transferred to a ball mill for ball milling, thus obtaining a mixture. (3) Sintering the mixture at a high temperature at a heating rate of 5 ℃/min under an oxygen atmosphere, wherein the high temperature sintering comprises two stages, and the first stage of microwave sintering is pre-sintered at 500 ℃ for 0.5h and then sintered at 1000 ℃ for 0.1h; the second stage tube furnace sintering is performed at 650 ℃ under normal pressure for 12 hours, and then sintering is performed at 950 ℃ for 4 hours. And naturally cooling after sintering, and grinding to obtain the NaNi 1/3Fe1/3Mn1/3O2 anode material coated with 1% Na 2Mg2TeO6, namely the nano-crystallite dispersion-strengthened sodium ion battery anode material.
Fig. 3 is a TEM image of a NaNi 1/3Fe1/3Mn1/3O2 positive electrode material modified with 1% Na 2Mg2TeO6 at different magnifications. After modified coating, a coating layer with the thickness of about 2-8nm is formed on the surface of the substrate, and a local P2/O3 coupling structure is formed on the surface of the substrate.
Example 3 preparation of nanocrystalline dispersion-strengthened sodium ion battery cathode material:
(1) Step (1) was performed as in example 1.
(2) The required mass of Ni1/3Mn1/3Fe1/3(OH)2、Na2CO3、MgCO3、NiO、TeO2 is calculated according to the mass ratio of NaNi 1/3Fe1/3Mn1/3O2 to Na 2Mg2TeO6 of 1:0.01, dispersed in ethanol (ball milling agent), stirred uniformly, and then transferred to a ball mill for ball milling, thus obtaining a mixture. (3) Sintering the mixture at a high temperature at a heating rate of 5 ℃/min under an oxygen atmosphere, wherein the high temperature sintering comprises two stages, and the first stage of microwave sintering is pre-sintered at 600 ℃ for 2 hours and then sintered at 800 ℃ for 2 hours; the second stage tube furnace is sintered at normal pressure at 500 ℃ for 6 hours, and then sintered at 900 ℃ for 10 hours. And naturally cooling after sintering, and grinding to obtain the NaNi 1/3Fe1/3Mn1/3O2 anode material coated with 1% Na 2MgNiTeO6, namely the nano-crystallite dispersion-strengthened sodium ion battery anode material.
Comparative example 1 preparation of nani 1/3Fe1/3Mn1/3O2:
in this comparative example, the original layered oxide material NaNi 1/3Fe1/3Mn1/3O2 was synthesized by a one-step sintering method.
(1) Step (1) was performed as in example 1.
(2) Mixing the obtained Ni 1/3Mn1/3Fe1/3(OH)2 precursor with Na 2CO3 in a stoichiometric ratio of 2:1.05, adding a ball grinding agent (ethanol), stirring uniformly, and then transferring to a ball mill for ball milling to obtain a mixture;
(3) And heating the mixture to 900 ℃ at a heating rate of 5 ℃/min in an O 2 atmosphere, sintering for 12 hours, naturally cooling after the sintering is finished, and grinding to obtain the original layered oxide material NaNi 1/3Fe1/3Mn1/3O2.
Comparative example 2 preparation of nani 1/3Fe1/3Mn1/3O2:
The original layered oxide material NaNi 1/3Fe1/3Mn1/3O2 was synthesized using a multi-step sintering process in this comparative example.
Steps (1) and (2) are the same as in example 1.
(3) The mixture is preheated for 4 hours at 900 ℃ after being heated to 650 ℃ for 12 hours at a heating rate of 5 ℃/min under the O 2 atmosphere, naturally cooled after sintering is finished, and then ground to obtain the original layered oxide material NaNi 1/3Fe1/3Mn1/3O2.
Fig. 1 (b) is an XRD pattern of the layered oxide material NaNi 1/3Fe1/3Mn1/3O2 prepared in comparative examples 1 and 2, from which it can be seen that the crystal structure of the original NaNi 1/3Fe1/3Mn1/3O2 layered oxide obtained in comparative example 1 is O3 phase, and the X-ray diffraction peak of the material obtained after the one-step sintering to the two-step sintering in comparative example 2 is almost identical to that of comparative example 1, and it is seen that the change of the reaction conditions does not affect the material structure.
Button cells were assembled using the above comparative examples 1 and 2 and examples 1 to 3 as positive electrode materials, respectively, and the specific steps were as follows:
S1, manufacturing a pole piece:
The products prepared in comparative examples 1 and2 and examples 1 to 3 are used for the positive electrode of a sodium ion battery, are mixed with acetylene black and PVDF (polyvinylidene fluoride) in a mass ratio of 8:1:1, are added with a proper amount of NMP (N-methylpyrrolidone) solution, are uniformly coated on aluminum foil after being prepared into slurry, are dried for 3 hours in a vacuum drying oven at 80 ℃ and are cut into pole pieces, and the pole pieces are continuously dried for 12 hours in the vacuum drying oven at 60 ℃ and are transferred into an argon glove box for standby.
S2. Assembly of cr2032 coin cell (the entire assembly process is performed in a glove box):
The above-mentioned pole piece is used as positive electrode, sodium piece is used as counter electrode, naClO 4/diethyl carbonate (EC: DEC) solution is used as electrolyte, and assembled into button cell, and the button cell is respectively activated in the voltage range of 2-4.2V by means of current density of 0.1C, and circulated for 200 circles under 1C, and its electrochemical properties are tested.
Button cells assembled from comparative examples 1 and 2 and examples 1 to 3 as positive electrode materials were activated at a current density of 0.1C in a voltage range of 2 to 4.2V and cycled at 1C for 200 cycles.
The materials obtained in comparative example 1 and comparative example 2 are assembled to form a battery, and the shape of the first-turn charge-discharge curve (shown in fig. 4) is basically consistent, so that the change of the reaction conditions has little influence on the charge-discharge performance of O3-NaNi 1/3Fe1/3Mn1/3O2, the first-turn coulomb efficiency of the material prepared in comparative example 2 is higher, and the discharge capacity is slightly improved. It can be seen that varying the sintering temperature is beneficial for improving the electrochemical properties of the material.
The charge-discharge curve comparison and the cycle curve comparison distribution obtained by the test conditions corresponding to comparative example 1 and example 1 are shown in fig. 5: the charge-discharge curve shapes of the materials before and after coating are basically consistent, the original charge-discharge specific capacities of NaNi 1/3Fe1/3Mn1/3O2 under the current density of 0.1C are 158.95mAh/g and 151.4mAh/g respectively, the first charge-discharge specific capacities of the materials after coating are 160.09mAh/g and 145.06mAh/g, the change of the charge specific capacities of the materials before and after surface modification is small, but the discharge specific capacities are partially lost, and the whole capacity of the materials is reduced due to the addition of the materials of the coating layer. However, from the cycling data of fig. 6, the capacity loss is replaced by an improvement in cycling stability, which indicates that the existence of the epitaxial interface, which replaces the substrate material to be corroded by the electrolyte and coherent phase growth, suppresses the volume change of the material during cycling, thereby stabilizing the structure of the substrate material and improving the cycling performance.
The charge-discharge curve comparison and the cycle curve comparison distribution obtained by the test conditions corresponding to comparative example 1 and example 2 are shown in fig. 5: the charge-discharge curve shapes of the materials before and after coating are basically consistent, the charge-discharge specific capacities of the original NaNi 1/3Fe1/3Mn1/3 O2 under the current density of 0.1C are 169.60mAh/g and 150.52mAh/g respectively, the first charge-discharge specific capacities of the materials after coating are 173.30mAh/g and 154.02mAh/g, and the charge specific capacities of the materials before and after surface modification are improved. From the cyclic data of fig. 6, the cyclic stability of the coated material is improved, probably because Mg 2+ at the interface of the surface coating stabilizes the structure, and the existence of the epitaxial interface, which replaces the matrix material to be corroded by electrolyte and coherent phase growth during the cycle, suppresses the stress generated by the volume change of the material during the cycle, thus stabilizing the structure of the matrix material, and improving the cycle performance.
Comparison of the circulation curves corresponding to comparative example 1 and example 3 and comparison distribution of constant current charge and discharge curves at different multiplying powers in the voltage range of 2-4.2V are shown in fig. 6 and 7: the multiplying power performance of the coated material is improved, which indicates that the structural stability of the modified material under different current densities is improved. The specific charge and discharge capacities of the original material at 0.1C are 171.01mAh/g and 149.53mAh/g respectively, and the specific charge and discharge capacities of the coated material are 181.14mAh/g and 152.36mAh/g, namely the specific charge and discharge capacities of the modified material are improved. The method shows that the interface stability of the positive electrode material after treatment is obviously improved, and the irreversible electrochemical reaction at the interface in the first charge and discharge process is effectively inhibited. From the cyclic data in fig. 6, the co-existence of Ni 2+、Mg2+ in the coating layer can further improve the capacity and the cyclic performance of the material, and the synergistic effect of Ni 2+、Mg2+ in the surface coating layer and the existence of an epitaxial interface coupling P2 and O3 phases inhibit the volume change of the material and the contact of the electrolyte during the cyclic process, so that the structure of the matrix material is stabilized, and the capacity and the cyclic performance of the modified material are improved.
To verify the storage performance of the materials in the invention, the original material obtained in the comparative example 1 and the material coated in the example 2 are simultaneously exposed to air with the temperature of 25 ℃ and the humidity of 45% for 4 hours and then assembled into a battery according to the battery assembling step, the cycle performance characterization of the obtained battery after being cycled for 200 weeks at 2-4.2V and 1C is shown in figure 8, the discharge specific capacity of the original material is attenuated from 117.43mAh/g to 74.93mAh/g, and the capacity retention rate is 63.81%; the cycling stability of the modified material in example 2 is obviously better than that of the original material, the specific discharge capacity is only reduced to 91.77mAh/g from the original capacity 124.26mAh/g, and the capacity retention rate is 73.85%. This is attributed to the air-insulating effect of the dense and uniform cellular-structured Na 2Mg2TeO6 coating layer, thereby significantly improving the storage properties of the positive electrode material.
Fig. 4 to 6 are graphs of initial charge and discharge and cycle performance of button cells assembled from the products of comparative examples 1 to 2 and examples 1 to 3, respectively, within 2 to 4.2V. As can be seen from fig. 3, the materials obtained in comparative example 1 and comparative example 2 are assembled to form a battery, and the shape of the first-turn charge-discharge curve (as shown in fig. 4) is basically consistent, so that the change of the reaction conditions has little influence on the charge-discharge performance of O3-NaNi 1/3Fe1/3Mn1/ 3O2, and the first-turn coulomb efficiency of the material prepared in comparative example 2 is higher, and the discharge capacity is slightly improved. It can be seen that varying the sintering temperature is beneficial for improving the electrochemical properties of the material.
As can be seen from fig. 4 and 5, the charge-discharge curves of the materials before and after NaNTO coating are basically consistent in shape, the charge-discharge specific capacities of the original NaNi 1/3Fe1/3Mn1/3O2 under the current density of 0.1C are 158.95mAh/g and 151.4mAh/g respectively, the first charge-discharge specific capacities of the materials after coating are 160.09mAh/g and 145.06mAh/g, the change of the charge specific capacities of the materials before and after surface modification is small, but the discharge specific capacities are partially lost, and the whole capacity of the materials is reduced due to the addition of the materials of the coating. However, from the cycle data of fig. 5, the capacity loss is replaced by an improvement in cycle stability, which indicates that the existence of the epitaxial interface, which replaces the matrix material to be corroded by the electrolyte and coherent phase growth, suppresses the volume change of the material during the cycle, thereby stabilizing the structure of the matrix material and improving the cycle performance.
As can be seen from fig. 5 and 6, the charge-discharge curves of the materials before and after NaMgTO coating are basically consistent, the charge-discharge specific capacities of the original NaNi 1/3Fe1/3Mn1/3 O2 under the current density of 0.1C are 169.60mAh/g and 150.52mAh/g respectively, the first charge-discharge specific capacities of the materials after coating are 173.30mAh/g and 154.02mAh/g, and the charge specific capacities of the materials before and after surface modification are improved. From the view of cycle data, the cycle stability of the coated material is improved, probably because Mg 2+ at the interface of the surface coating stabilizes the structure, and the existence of the epitaxial interface, which replaces the base material corroded by electrolyte and coherent phase growth during the cycle, inhibits the stress generated by the volume change of the material during the cycle, thereby stabilizing the structure of the base material, and improving the cycle performance.
As can be seen from fig. 7, the shapes of the rate performance curves of the materials before and after NaNMgTO coating are basically consistent, and the rate performance of the coated materials is improved. The specific discharge capacity of the coated material at 5C is 105mAh/g, and the retention rate is about 73% at 0.1C (corresponding to 145 mAh/g). The specific discharge capacity of the original material 5C is only 95.4mAh/g, and is 72.1% of the corresponding capacity when the original material is 0.1C, the specific discharge capacities of the first circle of the material before and after coating are 145.32mAh/g and 152.36mAh/g, and the specific charge capacity of the material after surface modification is improved. The method shows that the interface stability of the positive electrode material after treatment is obviously improved, and the irreversible electrochemical reaction at the interface in the first charge and discharge process is effectively inhibited. From the cycle data, the capacity retention of the modified material after 200 weeks of cycling is improved by about 8% over that before coating. This is probably due to the fact that the capacity and cycle performance of the material are further improved when Ni 2+、Mg2+ is co-present in the coating layer, the synergistic effect of Ni 2+、Mg2+ in the surface coating layer and the existence of the epitaxial interface of the P2 and O3 two-phase coupling inhibit the volume change of the material and the contact of the electrolyte during the cycle, thereby stabilizing the structure of the matrix material and improving the capacity and cycle performance of the modified material.
To verify the storage performance of the materials, the original material obtained in comparative example 1 and the material coated in example 2 are simultaneously exposed to air with the temperature of 25 ℃ and the humidity of 45% for 4 hours and then assembled into a battery according to the battery assembly step, the cycle performance characterization of the obtained battery after the battery is cycled for 200 weeks at 2-4.2V and 1C is shown in FIG. 8, the discharge specific capacity of the original material is attenuated from 117.43mAh/g to 74.93mAh/g, and the capacity retention rate is 63.81%; the cycling stability of the modified material in example 2 is obviously better than that of the original material, the specific discharge capacity is only reduced to 91.77mAh/g from the original capacity 124.26mAh/g, and the capacity retention rate is 73.85%. This is attributed to the air-insulating effect of the dense and uniform cellular-structured Na 2Mg2TeO6 coating layer, thereby significantly improving the storage properties of the positive electrode material.
In conclusion, the storage property, the safety and the practicability of the nano-crystallite dispersion-strengthened sodium ion battery anode material are improved; the process flow of the sodium ion battery anode material has the advantages of easily available raw materials, simple preparation method, high controllability and the like, and has good application prospect.
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.
Claims (10)
1. The nano microcrystal dispersion-strengthened sodium ion battery anode material is characterized in that Na xNiaMnbFe1-a-bO2 is used as a matrix material, and Na 2M2TeO6 is used as a modified substance; in Na xNiaMnbFe1-a-bO2, x is more than or equal to 0.66 and less than or equal to 1, a is more than or equal to 0.01 and less than or equal to 0.33, b is more than or equal to 0.33 and less than or equal to 0.75,0 and less than or equal to 1-a-b is less than or equal to 0.33, and M in Na 2M2TeO6 comprises one or more of Cu, ni, co, mg, zn; the positive electrode material of the sodium ion battery is formed by stacking nano flaky particles; in the sodium ion battery anode material, na 2M2TeO6 of a honeycomb lamellar structure is coated on the outer side of a matrix material Na xNiaMnbFe1-a-bO2, and is also dispersed in Na xNiaMnbFe1-a-bO2 nano particles to form a P2/O3 lamellar interlocking structure with the Na xNiaMnbFe1-a-bO2 nano particles.
2. The nano-crystallite dispersion strengthened sodium ion battery positive electrode material according to claim 1, wherein the space group of the sodium ion battery positive electrode material is P6 3/mmc、P63/mcm or R-3m.
3. The nanocrystalline dispersion strengthened sodium ion battery positive electrode material according to claim 1, wherein the mass ratio of Na 2M2TeO6 to Na xNiaMnbFe1-a-bO2 is (0.5%: 1) to (20%: 1).
4. A method for preparing the nano-crystallite dispersion-strengthened sodium ion battery anode material according to any one of claims 1 to 3, which is characterized by comprising the following steps:
1) Under the protection of inert atmosphere, dissolving a nickel source, an iron source and a manganese source in distilled water, adding a coprecipitation agent into the distilled water for reaction, and washing, filtering and drying after the reaction is finished to obtain a Ni aMnbFe1-a-b(OH)2 precursor;
(2) Mixing a Ni aMnbFe1-a-b(OH)2 precursor with a sodium salt, an M compound and a Te compound, adding a ball grinding agent, and uniformly mixing by ball milling to obtain a mixture; the M comprises one or more of Cu, ni, co, mg, zn;
(3) And (3) carrying out multi-step sintering reaction on the mixture, and cooling after the reaction is finished to obtain the nano-crystallite dispersion-strengthened sodium ion battery anode material.
5. The method for preparing a nano-crystallite dispersion-strengthened sodium ion battery cathode material according to claim 4, wherein in the step (1), the inert gas comprises any one of argon and nitrogen;
the nickel source, the manganese source and the iron source are one or more of corresponding acetate, chloride, nitrate and sulfate;
The coprecipitation agent comprises one or more of NaOH solution, NH 4 OH solution and NaHCO 3 solution;
NaOH in the coprecipitate: the mole ratio of NH 4OH：NaHCO3 is 0-100%: 0-15%: 0-35%, and the molar ratio of the three is 0 at different times;
The addition amount of the nickel source, the iron source, the manganese source and the coprecipitation agent is calculated according to the stoichiometric ratio of the precursor of the product Ni aMnbFe1-a-b(OH)2, wherein x is more than or equal to 0.66 and less than or equal to 1, a is more than or equal to 0.01 and less than or equal to 0.33, b is more than or equal to 0.33 and less than or equal to 0.75,0 and less than or equal to 1-a-b is more than or equal to 0.33.
6. The method for preparing nano-crystallite dispersion-strengthened sodium ion battery anode material according to claim 4, wherein in the step (2), the molar ratio of the Ni aMnbFe1-a-b(OH)2 precursor to the sodium salt is 1:0.68-1:1.15;
The molar ratio of Na, M and Te in the sodium salt, M compound and Te compound is 2:2:1-2.15:2:1.
7. The method of preparing a nanocrystalline dispersion-strengthened sodium ion battery positive electrode material according to claim 4, wherein in step (2), the sodium salt includes one or more of Na 2CO3、NaNO3、NaHCO3;
the M compound comprises one or more of oxide, nitrate, acetate, carbonate and hydroxide;
the Te compound comprises one or more of oxide, nitrate, acetate, carbonate and hydroxide;
the ball milling agent comprises any one of methanol, ethanol, propanol and diethyl ether;
Ball milling, ball milling: and (3) material: the mass ratio of the ball grinding agent is 1-2:1:0.5-0.618.
8. The method for preparing nano-crystallite dispersion-strengthened sodium ion battery positive electrode material according to claim 4, wherein in the step (3), the sintering atmosphere is one or more of oxygen or air in the multi-step sintering reaction; the sintering method is one or more of microwave sintering, normal pressure sintering, hot pressing sintering, reaction sintering and self-sintering.
9. The method for preparing a nano-crystallite dispersion strengthened sodium ion battery positive electrode material according to claim 8, wherein the multi-step sintering step comprises two stages:
the first stage is presintering at 400-600 ℃ for 0.5-12 h, and then sintering at 700-1000 ℃ for 0.1-2 h;
The second stage is pre-sintering for 4-12 h at 500-650 ℃, and then sintering for 4-12 h at 700-950 ℃;
in the multi-step sintering step, the heating rate is 3-10 ℃/min.
10. Use of the nano-crystallite dispersion-strengthened sodium ion battery anode material according to any one of claims 1-3 in the preparation of sodium ion batteries.
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