CN113921809A - P2 type layered sodium-ion battery positive electrode material and preparation method thereof - Google Patents
P2 type layered sodium-ion battery positive electrode material and preparation method thereof Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 51
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000011734 sodium Substances 0.000 claims abstract description 56
- 239000011572 manganese Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 93
- 239000000243 solution Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000010791 quenching Methods 0.000 claims description 18
- 230000000171 quenching effect Effects 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000010405 anode material Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 9
- 239000010406 cathode material Substances 0.000 claims description 8
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 26
- 150000002500 ions Chemical class 0.000 abstract description 18
- 239000010410 layer Substances 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 239000011229 interlayer Substances 0.000 abstract description 3
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 3
- 230000008093 supporting effect Effects 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910020784 Co0.2O2 Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-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
- 241000764238 Isis Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021271 NaCrO2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 241000234314 Zingiber Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229940093956 potassium carbonate Drugs 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a P2 type layered positive electrode material of a sodium ion battery, which is modified by co-doping of Na site and transition metal site, wherein the chemical formula of the positive electrode material of the sodium ion battery is Na0.67‑xMxMn1‑ yNyO2Wherein M = Zn, Al, Mg, K, Ca, Li; n = Fe, Cr, V, Ni, Ti, Cu, Nb, Co; 0<x≤0.1,0<y is less than or equal to 0.3. N ions are used for replacing part of trivalent manganese ions to inhibit the Jahn-Taller effect, so that the circulation stability of the material is improved, M ions are doped to enlarge the interlayer spacing of a sodium ion layer, and a certain supporting effect is achieved during circulation, so that the material structure is further stable, the circulation stability of the material is further improved, and the electrochemical performance of the material is greatly improved. The invention adopts liquid phase synthesis of precursor combined with high-temperature calcinationThe method has the advantages that the whole surface of the prepared positive electrode material of the sodium-ion battery is smooth, the particles are uniform, and the structure is compact.
Description
Technical Field
The invention belongs to the field of preparation of electrode materials of sodium-ion batteries, and particularly relates to a Na-site and transition metal-site co-doped modified P2-type laminar positive electrode material of a sodium-ion battery and a preparation method thereof.
Background
Advances in technology require new renewable energy sources to supply power. Currently, mobile phones, computers, automobiles and most equipment require batteries to supply power. In recent years, the use of lithium ion batteries has entered large-scale applications, such as electric vehicles and power grid applications. The lithium ion battery has the advantages of large energy, long charge-discharge cycle, less pollution and the like. Because of these advantages, lithium ion batteries are considered to be key devices for electrical energy storage. Lithium ion batteries have begun to be used in the automotive industry, which may reduce the use of mineral oil in the near future. The demand for lithium is increasing due to insufficient reserves in the crust, which requires the search for other materials. Therefore, sodium ion batteries have received much attention from researchers. The sodium ion battery has the advantages of low production cost, high safety and abundant raw materials, so the sodium ion battery is considered to be an ideal large-scale energy storage device.
The layered metal oxide has the general formula of NaxMO2(M is a transition metal, x is between 0.67 and 1) and belongs to the hexagonal system. The layered metal oxide is a layered structure formed by alternately arranging transition metal layers and alkali metal layers, wherein the transition metal layers are formed by repeated MO6 octahedral connection in a common edge manner, and Na is+Between the transition metal layers, an alkali metal layer is formed. The layered transition metal oxide sodium ion battery positive electrode material can be divided into a P2 type and an O3 type according to the stacking sequence of the arrangement of oxygen atoms, wherein Na+Occupying sodium layer (NaO)2) The triangular prism position and the octahedral position distinguish between P-type and O-type. Compared with the P2 type layered cathode material, the electrochemical performance of the P2 type layered cathode material is better than that of the O3 type because the P2 phase structure has a lower diffusion barrier and higher ion conductivity than that of O3 phase. In addition, the P2 phase structure can not generate the oxide layer slip phenomenon in the process of Na ion de-intercalation, and the structure is more stable, so the method has better commercial application prospect.
But for P2-Na0.67MnO2In other words, when the material is exposed to air, water molecules will occupy Na+Resulting in increased layer spacing and reduced overall cell performance. Passerini et al have systematically studied in NaxMO2The ratio of (M ═ Mn, Fe, Cr, V, Ni, Ti, Cu, Nb, Co, etc.) Ni and Fe in the material influences the suppression of elution of Mn and the improvement of stability, and Na having a high Ni content is indicated0.6 Ni0.22Fe0.11Mn0.66O2Has better electrochemical performance. Research shows that P2-Na is synthesized by doping Te element2/3Ni2/3Te1/3O2The structural transformation of the P2 phase to the O2 phase also occurs during high voltage charging, so that the performance of the material is deteriorated. In 2018, the Huyong peptide topic group discovered Ti-doped P2-Na0.86Co0.475Mn0.475Ti0.05O2The capacity of the material is not high. It was found that since Cr has multiple oxidation states, there are multiple redox statesFor, monometallic O3-NaCrO2The discharge capacity is 113-120mAh/g, but the structure is unstable. The Lifujun subject group prepares the P2 type sodium ion battery anode material by K doping, tests show that the electrochemical performance is greatly improved, and doping shows that the structure can be more stable, so that the capacity attenuation of the material in the circulation process is more effectively inhibited, and the electrochemical performance is greatly improved. Qian et al synthesized Ti-doped Na0.54Mn0.5Ti0.5O2The discharge capacity of the nano-rod after carbon coating is 122mAh/g, no complex phase transformation occurs, and the structural stability is ensured. To solve the problem of Mn in the charging and discharging process3+The Taylor effect of ginger causes the problem of structural instability, and the brave et al substitutes Fe and Ti for part of Mn to synthesize Na0.61[Mn0.61-xFexTi0.39]O2The material has the reversible specific capacity of 90mAh/g, the working voltage of 3.56V and can stably exist in the air. The researchers have synthesized Li doped Na0.95Li0.15(Ni0.15Mn0.55Co0.1)O2、Na0.78Li0.18Ni0.25Mn0.583O2And quaternary material Na (Mn)0.25Fe0.25Co0.25Ni0.25) O2, and the Li doped material has no complex phase change process and good cycling stability.
With respect to the above doping mainly focused on single doping at the transition metal site or co-doping of various cations, there are few reports on doping at the Na site and the transition metal site.
Disclosure of Invention
The invention aims to solve the technical problem of providing a P2 type layered sodium-ion battery anode material and a preparation method thereof, wherein the anode material is codoped at a Na position and a transition metal position, so that the electrochemical performance of the material is improved.
In order to solve the technical problems, according to one aspect of the invention, a P2 type layered positive electrode material for a sodium-ion battery is provided, wherein the positive electrode material is modified by co-doping a Na site and a transition metal site, and the chemical formula of the positive electrode material for the sodium-ion battery isIs Na0.67-xMxMn1-yNyO2Wherein M = Zn, Al, Mg, K, Ca, Li; n = Fe, Cr, V, Ni, Ti, Cu, Nb, Co; 0<x≤0.1,0<y is less than or equal to 0.3. By adopting the co-doping method at the transition metal site and the Na site, partial trivalent manganese ions are replaced by N ions to inhibit the Jahn-Taller effect so as to improve the circulation stability of the material, and meanwhile, M ions are doped to enlarge the interlayer spacing of a sodium ion layer, so that a certain supporting effect is achieved during circulation, the structure of the material is further stable, the circulation stability of the material is further improved, and the electrochemical performance of the material is greatly improved.
According to another aspect of the present invention, there is provided a method for preparing the above-mentioned P2-type layered sodium-ion battery positive electrode material, comprising:
step one, respectively weighing sodium salt, manganese salt and M salt and N salt corresponding to M, N elements according to the molar ratio of the elements in the chemical formula, dissolving the manganese salt, the M salt and the N salt in deionized water, adding the sodium salt, stirring and dissolving to prepare a mixed metal salt solution, wherein the total molar concentration of metal ions is preferably 1-3 mol/L;
step two, preparing a citric acid solution with the mass concentration of 2-20% as a complexing agent;
placing a complexing agent on a heatable magnetic stirrer, adding a mixed metal salt solution into the complexing agent, and adding ammonia water to adjust the pH value of the solution to 8-11; then controlling the rotating speed and the temperature of a magnetic stirrer, stirring and evaporating to dryness to obtain gel;
and step four, drying and crushing the gel obtained in the step three, pre-burning in an air atmosphere, then sintering, and cooling to room temperature to obtain the cathode material.
The method has good repeatability, can sinter a single phase and has low cost for preparing the Na-site and transition metal-site co-doped P2 type layered sodium ion anode material. Compared with the prior solid phase method, the method adopts the sol-gel method to uniformly and quantitatively dope some trace elements, thereby realizing intermolecular doping.
Further, in the first step, the manganese salt is one or more of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride.
Further, in the first step, the M salt and the N salt are one or more of corresponding sulfate, nitrate or carbonate.
Further, in the third step, the rotating speed of the magnetic stirrer is 200-600 rpm, and the heating temperature is 60-90 ℃.
Further, in the fourth step, the pre-sintering is carried out by raising the temperature to 900-1050 ℃ at a slow temperature raising rate in the atmosphere, preserving the temperature for 1-4h, and then quenching and tabletting.
Further, in the fourth step, the temperature of the sintering is raised to 600-700 ℃ at the heating rate of 1-10 ℃/min, the temperature is kept for 2-4 h, then the temperature is slowly lowered to 300-500 ℃, and then quenching is carried out.
According to another aspect of the present invention, there is provided a sodium-ion battery whose positive electrode includes the above-described P2-type layered sodium-ion battery positive electrode material.
The transition metal site is mainly selected from Fe, Cr, V, Ni, Ti, Cu, Nb, Co and other elements, the ions contained in the cation layer comprise Zn, Al, Mg, K, Ca, Li and other elements, and the invention selects a mode of Co-doping several elements in the transition metal site to modify the P2 type laminar sodium-ion battery anode material, thereby not only improving the specific capacity of the material, but also improving the cycling stability of the material.
Compared with the prior art, the invention has the following advantages and technical effects:
the invention provides a Na-site and transition metal site ion co-doped P2 type sodium ion battery positive electrode material Na0.67- xMxMn1-yNyO2Through the synergistic effect of M ions and N ions, on one hand, the replacement of part of trivalent manganese ions in the material inhibits the Jahn-Taller effect and enlarges the interlayer spacing of a sodium ion layer, and the material plays a supporting role in the circulating process.
The method for preparing the M, N ion co-doped P2 type sodium ion battery anode material provided by the invention adopts a method of combining a liquid phase synthesis precursor with high-temperature calcination, has the characteristics of simplicity, reliability and low cost, and the prepared sodium ion battery anode material has the advantages of smooth whole surface, uniform particles, compact structure, good electrochemical performance and good industrial application prospect.
The invention provides a Na-site and transition metal site ion co-doped P2 type sodium ion battery positive electrode material Na0.67- xMxMn1-yNyO2The composite material is used for sodium ion batteries, and shows excellent electrochemical properties such as high specific capacity, rate capability and cycling stability.
Drawings
A and b in fig. 1 are layered sodium ion positive electrode material Na of P2 type prepared in example 3 and example 6 of the present invention, respectively0.67MnO2And Na0.62K0.05Mn0.8Ti0.2O2XRD pattern of (a).
In FIG. 2, a and b are Na in example 1 and example 6 of the present invention, respectively0.67MnO2And Na0.62K0.05Mn0.8Ti0.2O2SEM image of (d).
A, b and c in fig. 3 are layered sodium ion cathode materials Na0 of P2 type prepared in example 1, example 3 and example 6 of the present invention, respectively.67MnO2 、Na0.67Mn0.8Ti0.2O2And Na0.62K0.05Mn0.8Ti0.2O2A cycle life curve chart when the voltage interval is 2-4.2V and the current density is 100 mA/g.
A and b in fig. 4 are layered sodium ion positive electrode materials Na of the P2 type prepared in examples 3 and 6 of the present invention, respectively0.67Ti0.2Mn0.8O2And Na0.62K0.05Ti0.2Mn0.8O2A first charge-discharge curve chart under the current density of 100mA/g and the voltage of 2-4.2V.
FIG. 5 shows a layered Na ion positive electrode material for P2 type prepared in example 60.62Li0.05Ti0.2Mn0.8O2Cyclic voltammogram of (a).
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
According to the synthesis of 10g of Na0.67MnO2Weighing sodium acetate (with 5% excess) and manganese acetate according to the molar ratio of the Na element to the Mn element, dissolving the sodium acetate and the manganese acetate in 200ml of citric acid solution with the deionized water mass concentration of 2% -20%, and continuously stirring until the metal salt solution is dissolved. 2g of citric acid is weighed and dissolved in deionized water to prepare a citric acid solution with the mass concentration of 15%, and the citric acid solution is stirred and dissolved. And slowly adding the metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 8 by using alkali, stirring and evaporating at 80 ℃ by using a magnetic stirrer at the rotating speed of 500rpm to obtain a xerogel substance.
Drying the obtained gel at 120 ℃, crushing, heating to 900 ℃ at a slow heating rate in an air atmosphere, preserving heat for 1h, and then quenching and tabletting. Then raising the temperature to 600 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, slowly lowering the temperature to 300 ℃, and quenching to obtain the P2 type layered sodium ion anode material Na0.67MnO2。
Example 2
According to the synthesis of 10g of Na0.67Mn0.9Al0.1O2Sodium acetate (excessive 5 percent), aluminum chloride and manganese acetate are weighed according to the molar ratio of Na, Al and Mn elements and dissolved in 250ml of deionized water, and the stirring is continuously carried out until the metal salt solution is dissolved. 2g of citric acid is weighed and dissolved in deionized water to prepare a citric acid solution with the mass concentration of 15%, and the citric acid solution is stirred and dissolved. Slowly adding the metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 9 by using alkali, and stirring and evaporating at 85 ℃ by using a magnetic stirrer at the rotating speed of 500rpm to obtain a gel substance.
Drying the obtained gel at 120 ℃, crushing, heating to 900 ℃ at the heating rate of 1 ℃/min in the air atmosphere, preserving heat for 2h, and then quenching and tabletting. Then raising the temperature to 600 ℃ at the rate of 5 ℃/min, and preserving the heatSlowly cooling to 400 ℃ for 2h, and then quenching to obtain the P2 type layered sodium ion anode material Na0.67Mn0.9 Al0.1O2。
Example 3
According to the synthesis of 10g of Na0.67Mn0.9Co0.2O2Sodium nitrate (5 percent of excessive), cobalt nitrate and manganese nitrate are weighed according to the molar ratio of Na, Co and Mn elements and dissolved in 250ml of deionized water, and the stirring is continuously carried out until the metal salt solution is dissolved. 1g of citric acid is weighed and dissolved in deionized water to prepare a citric acid solution with the mass concentration of 2%, and the citric acid solution is stirred and dissolved. Slowly adding the metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 10 by using alkali, stirring and evaporating at 90 ℃ by using a magnetic stirrer at the rotating speed of 500rpm to obtain a gel substance.
Drying the obtained gel at 120 ℃, crushing, heating to 900 ℃ at the heating rate of 1 ℃/min in the air atmosphere, preserving heat for 3h, and then quenching and tabletting. Then raising the temperature to 650 ℃ at the heating rate of 5 ℃/min, preserving the heat for 3h, slowly lowering the temperature to 300 ℃, and then quenching to obtain the P2 type layered sodium ion anode material Na0.67Mn0.8Co0.2O2。
Example 4
According to the synthesis of 10g of Na0.67Ti0.3Mn0.7O2Sodium sulfate (excessive 5 percent), nano titanium oxide and manganese sulfate are weighed according to the molar ratio of Na, Ti and Mn elements and dissolved in 500ml of deionized water, and the stirring is continuously carried out until the metal salt solution is dissolved. 5g of citric acid is weighed and dissolved in deionized water to prepare a citric acid solution with the mass concentration of 20%, and the citric acid solution is stirred and dissolved. Slowly adding the metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 9 by using alkali, and stirring and evaporating at 90 ℃ by using a magnetic stirrer at the rotating speed of 500rpm to obtain a gel substance.
Drying the obtained gel at 120 ℃, crushing, heating to 1000 ℃ at the heating rate of 1 ℃/min in the air atmosphere, preserving heat for 3h, and then quenching and tabletting. Then raising the temperature to 600 ℃ at the heating rate of 5 ℃/min, preserving the heat for 3h, slowly lowering the temperature to 500 ℃, and quenching to obtain the P2 type layered sodium ion anode materialMaterial Na0.67Ti0.3Mn0.7O2。
Example 5
According to the synthesis of 10g of Na0.66K0.01Mn0.8Ti0.2O2Sodium acetate (excessive 5 percent), cobalt nitrate, manganese acetate and potassium carbonate are weighed according to the molar ratio of Na, Ti, Mn and K elements and dissolved in 250ml of deionized water, and the stirring is continuously carried out until the metal salt solution is dissolved. 2g of citric acid is weighed and dissolved in deionized water to prepare a citric acid solution with the mass concentration of 20%, and the citric acid solution is stirred and dissolved. Slowly adding the metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 8 by using alkali, stirring and evaporating at 85 ℃ by using a magnetic stirrer at the rotating speed of 200rpm to obtain a gel substance.
Drying the obtained gel at 120 ℃, crushing, heating to 900 ℃ at the heating rate of 1 ℃/min in the air atmosphere, preserving heat for 2h, and then quenching and tabletting. Then raising the temperature to 700 ℃ at the rate of raising the temperature by 5 ℃/min, preserving the heat for 4h, slowly lowering the temperature to 400 ℃, and quenching to obtain the P2 type layered sodium ion anode material Na0.66K0.01Mn0.8Ti0.2O2。
Example 6
According to the synthesis of 10g of Na0.62Li0.05Mn0.8Ti0.2O2Sodium nitrate (excessive 5 percent), nano titanium oxide, manganese acetate and lithium carbonate are weighed according to the molar ratio of Na, Ti, Mn and Li elements in 250ml of deionized water, and the mixture is continuously stirred until the metal salt solution is dissolved. 1g of citric acid is weighed and dissolved in deionized water to prepare a citric acid solution with the mass concentration of 15%, and the citric acid solution is stirred and dissolved. Slowly adding the metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 10 by using alkali, stirring and evaporating at 90 ℃ by using a magnetic stirrer at the rotating speed of 500rpm to obtain a gel substance.
Drying the obtained gel at 120 ℃, crushing, heating to 1050 ℃ at the heating rate of 1 ℃/min in the air atmosphere, preserving heat for 1h, and then quenching and tabletting. Then raising the temperature to 600 ℃ at the heating rate of 1 ℃/min, preserving the heat for 4h, slowly lowering the temperature to 300 ℃, and quenching to obtain the P2 type layered sodium ion anode materialMaterial Na0.62Li0.05Mn0.8Ti0.2O2。
Example 7
According to the synthesis of 10g of Na0.57K0.1Mn0.7Ni0.3O2Sodium sulfate (5 percent excess), nickel acetate, manganese sulfate and potassium carbonate are weighed in a molar ratio of Na, Ni, Mn and K elements in 250ml of deionized water, and stirring is continuously carried out until a metal salt solution is dissolved. 1g of citric acid is weighed and dissolved in deionized water to prepare a citric acid solution with the mass concentration of 2%, and the citric acid solution is stirred and dissolved. Slowly adding the metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 11 by using alkali, and stirring and evaporating at 60 ℃ by using a magnetic stirrer at the rotating speed of 600rpm to obtain a gel substance.
Drying the obtained gel at 120 ℃, crushing, heating to 950 ℃ at the heating rate of 1 ℃/min in the air atmosphere, preserving heat for 4h, and then quenching and tabletting. Then raising the temperature to 700 ℃ at the heating rate of 10 ℃/min, preserving the heat for 2h, slowly lowering the temperature to 500 ℃, and quenching to obtain the P2 type layered sodium ion anode material Na0.57K0.1Mn0.8Ni0.2 O2。
Application examples
Respectively grinding the Na-site and transition metal-site co-doped P2 type layered sodium ion positive electrode material obtained in each embodiment with a conductive agent and a binder PVDF uniformly according to the mass ratio of 8:1:1, adding a proper amount of NMP to prepare slurry, uniformly coating the slurry on a pretreated aluminum foil, drying the pretreated aluminum foil for 1h at 80 ℃ in a forced air drying oven, and drying the pretreated aluminum foil for 12h at 120 ℃ in a vacuum drying oven; then, the anode plate was cut into a 12mm circular anode plate by a cutter. A sodium metal sheet with the diameter of 12mm and the thickness of 0.2mm is taken as a negative electrode, 0.1mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution is taken as electrolyte, a polypropylene film with the diameter of 19mm is taken as a diaphragm, and the CR2016 button cell is assembled in a glove box filled with high-purity argon. And testing the electrochemical performance of the material within a voltage range of 2V-4.2V.
The XRD pattern shown in figure 1 can be seen to have a layered structure, and the diffraction peak is sharp, the splitting is obvious, and no other obvious impurity peak exists; as can be seen from the graph (b), the peak shape of the XRD pattern of the cathode material co-doped with Na site and transition metal site is consistent with that of PDF #27-0751, except that the positions of the diffraction peaks are somewhat shifted, indicating that M ions and N ions have been doped into the material.
The SEM image shown in FIG. 2 shows that the primary particles of the two materials both have a nano-sheet structure, smooth secondary surfaces and compact structures; as can be seen from fig. (b), the primary particles after co-doping of the two ions become significantly larger.
FIG. 3 shows three materials Na when the voltage range is 2-4.2V and the current density is 100mA/g0.67MnO2(curve a), Na0.67Co0.2Mn0.8O2(curves b) and Na0.62Li0.05Mn0.8Ti0.2O2(curve c) cycle life plot. It can be seen from the figure that after 50 cycles, the capacity retention rate of the sodium-ion battery prepared from the P2 type layered metal oxide cathode material modified by co-doping of Li and Ti ions is 93.46%, which is better than 81.95% of doping of single ions, and which is better than 70.17% of unmodified ions.
FIG. 4 shows that when the voltage range is 2-4.2V and the current density is 100mA/g, the co-doped Na ion anode material Na0.62Li0.05Ti0.2Mn0.8O2The charge-discharge curves of the 1 st, 25 th and 50 th circles. As can be seen from the figure, the initial discharge capacity of the P2 type layered metal oxide cathode material after co-doping modification is 115mAh/g, and the discharge capacity of the 50 th circle is 105.7 mAh/g.
FIG. 5 shows a P2-type layered Na ion positive electrode material0.62Li0.05Mn0.8Ti0.2O2Cyclic voltammogram of (a). As can be seen from the figure: the lithium ion and Ti ion co-doping has good cycle reversibility.
The foregoing embodiments illustrate the principles, main features and advantages of the present invention, and the present invention is not limited to the above embodiments, which are only illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the scope of the principles of the present invention, and these changes and modifications should be construed as being included in the protection scope of the present invention.
Claims (8)
1. A P2 type laminated sodium-ion battery anode material is characterized in that: is modified by codoping Na site and transition metal site, and the chemical formula of the positive electrode material of the sodium ion battery is Na0.67-xMxMn1-yNyO2Wherein M = Zn, Al, Mg, K, Ca, Li; n = Fe, Cr, V, Ni, Ti, Cu, Nb, Co; 0<x≤0.1,0<y≤0.3。
2. The preparation method of the P2 type layered sodium-ion battery positive electrode material as claimed in claim 1, which comprises:
step one, respectively weighing sodium salt, manganese salt and M salt and N salt corresponding to M, N elements according to the molar ratio of each element in the chemical formula of claim 1, dissolving the manganese salt, the M salt and the N salt in deionized water, adding the sodium salt, stirring and dissolving to prepare a mixed metal salt solution;
step two, preparing a citric acid solution with the mass concentration of 2-20% as a complexing agent;
placing a complexing agent on a heatable magnetic stirrer, adding a mixed metal salt solution into the complexing agent, and adding ammonia water to adjust the pH value of the solution to 8-11; then controlling the rotating speed and the temperature of a magnetic stirrer, stirring and evaporating to dryness to obtain gel;
and step four, drying and crushing the gel obtained in the step three, pre-burning in an air atmosphere, then sintering, and cooling to room temperature to obtain the cathode material.
3. The method of claim 2, wherein: in the first step, the manganese salt is one or more of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride.
4. The method of claim 3, wherein: in the first step, the M salt and the N salt are one or more of corresponding sulfate, nitrate or carbonate.
5. The method according to claim 2 or 4, characterized in that: in the third step, the rotating speed of the magnetic stirrer is 200-600 rpm, and the heating temperature is 60-90 ℃.
6. The method of claim 5, wherein: in the fourth step, the pre-sintering is carried out by raising the temperature to 900-1050 ℃ at a slow heating rate in the atmosphere, preserving the temperature for 1-4h, and then quenching and tabletting.
7. The method of claim 6, wherein: in the fourth step, the temperature of the sintering is raised to 600-700 ℃ at the heating rate of 1-10 ℃/min, the temperature is kept for 2-4 h, then the temperature is slowly lowered to 300-500 ℃, and then quenching is carried out.
8. A sodium ion battery, characterized by: the positive electrode of the sodium-ion battery comprises the P2 type layered sodium-ion battery positive electrode material of claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105428641A (en) * | 2015-12-10 | 2016-03-23 | 桂林理工大学 | Method for preparing lithium manganese oxide cathode material by synergistically doping aluminum and sodium with high rate performance |
| CN106898758A (en) * | 2017-04-26 | 2017-06-27 | 东莞市迈科新能源有限公司 | A kind of yttrium, sodium-ion battery positive material of molybdenum doping and preparation method thereof |
| CN107275636A (en) * | 2017-07-10 | 2017-10-20 | 东北大学 | A kind of sodium-ion battery positive material Na0.7Li0.3Mn0.75O2Preparation method |
| CN108023082A (en) * | 2017-12-04 | 2018-05-11 | 中南大学 | A kind of preparation method of the sodium-ion battery positive material with poly-phase composite layer shape structure |
| CN111129483A (en) * | 2019-12-26 | 2020-05-08 | 上海大学 | Rare earth metal element doped P2 phase sodium ion battery positive electrode material and preparation method thereof |
-
2021
- 2021-09-25 CN CN202111124855.1A patent/CN113921809A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105428641A (en) * | 2015-12-10 | 2016-03-23 | 桂林理工大学 | Method for preparing lithium manganese oxide cathode material by synergistically doping aluminum and sodium with high rate performance |
| CN106898758A (en) * | 2017-04-26 | 2017-06-27 | 东莞市迈科新能源有限公司 | A kind of yttrium, sodium-ion battery positive material of molybdenum doping and preparation method thereof |
| CN107275636A (en) * | 2017-07-10 | 2017-10-20 | 东北大学 | A kind of sodium-ion battery positive material Na0.7Li0.3Mn0.75O2Preparation method |
| CN108023082A (en) * | 2017-12-04 | 2018-05-11 | 中南大学 | A kind of preparation method of the sodium-ion battery positive material with poly-phase composite layer shape structure |
| CN111129483A (en) * | 2019-12-26 | 2020-05-08 | 上海大学 | Rare earth metal element doped P2 phase sodium ion battery positive electrode material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 周苗苗 等: "P2型锰基钠离子正极材料的制备与改性", 有色金属科学与工程, vol. 10, no. 5, pages 61 - 66 * |
| 邱进旭: "P2型Na0.6Li0.07Mn0.66Co0.17Ni0.17O2正极材料的制备、掺杂改性及储钠性能研究", 中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑, pages 23 - 36 * |
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| CN116544417A (en) * | 2023-07-06 | 2023-08-04 | 宁波容百新能源科技股份有限公司 | Positive electrode active material, preparation method thereof, positive electrode plate and sodium ion battery |
| CN116544417B (en) * | 2023-07-06 | 2024-03-19 | 宁波容百新能源科技股份有限公司 | Positive electrode active material, preparation method thereof, positive electrode plate and sodium ion battery |
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