CN114655991A - Modified sodium manganate material and preparation method and application thereof - Google Patents
Modified sodium manganate material and preparation method and application thereof Download PDFInfo
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- CN114655991A CN114655991A CN202210297024.2A CN202210297024A CN114655991A CN 114655991 A CN114655991 A CN 114655991A CN 202210297024 A CN202210297024 A CN 202210297024A CN 114655991 A CN114655991 A CN 114655991A
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- sodium manganate
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- BNBLBRISEAQIHU-UHFFFAOYSA-N disodium dioxido(dioxo)manganese Chemical class [Na+].[Na+].[O-][Mn]([O-])(=O)=O BNBLBRISEAQIHU-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000000463 material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 25
- 238000011282 treatment Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 claims abstract description 11
- 238000010304 firing Methods 0.000 claims description 40
- 239000002243 precursor Substances 0.000 claims description 37
- 239000010936 titanium Substances 0.000 claims description 31
- -1 transition metal salt Chemical class 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 13
- 150000002696 manganese Chemical class 0.000 claims description 13
- 159000000000 sodium salts Chemical class 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 150000003608 titanium Chemical class 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229940099596 manganese sulfate Drugs 0.000 claims description 7
- 239000011702 manganese sulphate Substances 0.000 claims description 7
- 235000007079 manganese sulphate Nutrition 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 6
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 3
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229940087562 sodium acetate trihydrate Drugs 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 239000011572 manganese Substances 0.000 abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000004090 dissolution Methods 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 6
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 13
- 239000010949 copper Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 6
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 235000011837 pasties Nutrition 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- 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 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910014485 Na0.44MnO2 Inorganic materials 0.000 description 1
- 229910020510 Na4Mn9O18 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
Images
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a modified sodium manganate material as well as a preparation method and application thereof, belongs to the technical field of preparation of water-based ion batteries, and solves the technical problem of poor cycle stability of a water-based battery caused by the dissolution phenomenon of the existing manganese oxide as a positive electrode material. The preparation method of the modified sodium manganate material disclosed by the invention is characterized in that pure-phase sodium manganate is prepared by a coupling agent-assisted sol-gel method, and doping treatment is carried out on Mn sites through different transition metals on the basis of preparing the pure-phase sodium manganate, so that the crystal stability and the electrochemical performance are improved. The modified sodium manganate prepared by the method is used as a positive electrode material of a water-based ion battery and has good cycling stability.
Description
Technical Field
The invention belongs to the technical field of preparation of water-based ion batteries, and particularly relates to a modified sodium manganate material as well as a preparation method and application thereof.
Background
Among all the secondary battery systems at present, lithium ion batteries have no doubt taken a leading role, and have been widely applied to electric automobiles and portable electric appliancesSub-products and other various fields of people's daily life. However, due to the inherent problems of scarce lithium resources and toxic and flammable organic electrolytes, the lithium ion battery system cannot meet the increasing demands of the large-scale energy storage application field. Aqueous zinc ion batteries have unique appeal due to the following advantages: (1) suitable operating potentials: the standard oxidation-reduction potential of zinc (Zn) metal is-0.76V, which is higher than the hydrogen evolution potential of the water-system electrolyte, and the zinc (Zn) metal can be suitable for a water-system electrolyte system; (2) the theoretical capacity is high: the theoretical volume capacity of the Zn negative electrode is 5851mAh/cm3The mass specific capacity is 819 mAh/g; (3) the aqueous electrolyte is non-toxic and has good safety. Although aqueous zinc ion batteries have many advantages, there are problems such as zinc dendrites, corrosion, electrolyte decomposition, and dissolution of the positive electrode material. The most important problem is that the positive electrode material is easily dissolved in the aqueous electrolyte, and the cycle stability of the battery is poor. In order to solve this problem, researchers have tried to modify electrode materials and electrolytes, but none of them is satisfactory.
The manganese-based oxide is one of the most ideal anode materials of the water system zinc ion battery due to the advantages of high specific capacity, environmental friendliness and the like. However, the traditional manganese oxide has the problem of dissolution, and the cycle performance of the battery is poor, so that the battery cannot meet the practical application.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a modified sodium manganate material, and a preparation method and application thereof, which are used for solving the technical problem that the existing manganese oxide as a positive electrode material has a dissolution phenomenon, so that the cycling stability of an aqueous battery is poor.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a modified sodium manganate material, which comprises the following steps:
step 1: mixing and dissolving transition metal salt, sodium salt and coupling agent in ultrapure water, heating and stirring, and evaporating to obtain gel;
step 2: drying the gel to obtain a powdery precursor;
and step 3: carrying out first firing treatment on the powdery precursor, grinding the powdery precursor, and carrying out second firing treatment to obtain a modified sodium manganate material;
the transition metal salt includes a manganese salt, a titanium salt, or a copper salt.
Further, the manganese salt comprises one or more of manganese acetate tetrahydrate, manganese (II) nitrate tetrahydrate, and manganese sulfate; the sodium salt comprises one or more of anhydrous sodium carbonate, sodium acetate trihydrate and sodium chloride.
Further, the coupling agent comprises one or more of citric acid, oxalic acid, polyvinylpyrrolidone and ethylene glycol; the titanium salt comprises one or more of titanium (IV) tetra-n-butoxide, titanium tetrachloride and titanium acyl sulfate; the copper salt includes one or more of copper nitrate trihydrate, anhydrous copper sulfate, and copper chloride.
Further, the molar ratio of the coupling agent to metal ions in the transition metal salt is 0.75-1; the molar ratio of the sodium salt to the transition metal salt is 0.49-0.53; the molar ratio of the titanium salt or the copper salt to the manganese salt is 0.11-0.33.
Further, in the step 1, the heating time is 4-6 h, and the heating temperature is 80-90 ℃; in the step 2, the drying time is 9-12 h, and the drying temperature is 50-80 ℃.
Further, in step 3, the process parameters of the first firing treatment are as follows: firing at 300-500 deg.c for 8-10 hr.
Further, in step 3, the process parameters of the second firing treatment are as follows: firing at 850-950 ℃ for 9-12 h.
The invention also discloses the modified sodium manganate material prepared by the preparation method of the modified sodium manganate material.
Further, the modified sodium manganate material has an orthogonal tunnel type ion conduction structure.
The invention also discloses an application of the modified sodium manganate material, and the modified sodium manganate material is used as a positive electrode material of a water-based ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a modified sodium manganate material, which is characterized in that pure-phase sodium manganate is prepared by a coupling agent-assisted sol-gel method, doping treatment is carried out on Mn positions through different transition metals (Ti and Cu) on the basis of preparing the pure-phase sodium manganate, and the material structure of the pure-phase sodium manganate is regulated and controlled through transition metal ions with different valence states and ionic radii; because different transition metals (Ti and Cu) are introduced to partially substitute Mn sites in pure-phase sodium manganate, lattice Mn is inhibited in the charge-discharge process3+The generated disproportionation reaction inhibits the dissolution of manganese, and the electrochemical performance (high cycle stability and specific capacity) of the modified sodium manganate material is improved; the preparation process has the advantages of low cost, simple process, good repeatability, environmental friendliness, easiness for large-scale production and wide application prospect.
The invention also discloses the modified sodium manganate material prepared by the preparation method, and relevant experimental results show that the modified sodium manganate material prepared by the invention has a consistent crystal form compared with pure-phase sodium manganate, but the crystal stability of the modified sodium manganate material is better; meanwhile, the modified sodium manganate material has a 2 x 2 orthogonal tunnel type ion conduction structure and MnO shared by sides6Octahedral formed tunnels and three different types of sodium sites and MnO5The S-shaped orthogonal tunnel has a stable structure, the ion channel is favorable for the insertion and the separation of ions in the charge and discharge process, and tetravalent transition metal ions Ti4+The introduction of (A) does not cause the change of the crystal structure of the pure phase material, no obvious new phase appears, and meanwhile, Ti4+Will occupy Mn in pure phase material4+The sites can effectively improve the lattice stability of the anode material, thereby reducing the dissolution of the anode material in aqueous electrolyte and improving the electrochemical performance (high cycle stability and specific capacity).
The modified sodium manganate material has good lattice stability, so that the occurrence of a dissolution phenomenon is reduced when the modified sodium manganate material is used as a cathode material of a water-based ion battery, and a battery system constructed by the material only needs conventional electrolyte concentration (1m/2m) because the modified sodium manganate material has good electrochemical performance (high cycle stability and specific capacity), does not need high-concentration electrolyte, and is a water-based ion battery cathode material with excellent performance.
Drawings
FIG. 1 is a graph of the performance of the pure phase sodium manganate of comparative example 1;
wherein: a-X-ray diffraction pattern; b-scanning electron microscope picture; c-1A/g current density;
FIG. 2 is a scanning electron micrograph of a modified sodium manganate material;
wherein: the doping amount of a-Ti is 0.11; the doping amount of b-Ti is 0.22; the doping amount of c-Ti is 0.33;
FIG. 3 is an X-ray diffraction pattern of a modified sodium manganate material;
FIG. 4 is a graph comparing the cycle performance at 1A/g current density of the pure-phase sodium manganate obtained in comparative example 1 and the modified sodium manganate material obtained in the invention (Ti doping amount of 0.11, 0.22, 0.33);
FIG. 5 is a graph comparing the cycle performance of the pure-phase sodium manganate obtained in comparative example 1 and the modified sodium manganate material obtained in the invention (Cu doping amount is 0.22) at a current density of 1A/g;
FIG. 6 is a schematic diagram of a modified sodium manganate material.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Unless otherwise specified herein, "comprising," including, "" containing, "" having, "or the like, means" consisting of … … "and" consisting essentially of … …, "e.g.," a comprises a "means" a comprises a and the other, "and" a comprises a only.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The following examples use instrumentation conventional in the art. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Example 1
A preparation method of a modified sodium manganate material comprises the following steps:
step 1: will fourTitanium (IV) n-butoxide (C)16H36O4Ti, Ti ═ 0.11), anhydrous sodium carbonate (Na)2CO3) Manganese acetate tetrahydrate ((CH)3COO)2Mn·4H2O) and citric acid are mixed and dissolved in ultrapure water, heated for 4 hours at 80 ℃, stirred uniformly and then evaporated with deionized water to obtain gel; the molar ratio of the coupling agent to the metal ions in the transition metal salt is 1;
wherein the molar ratio of the sodium salt to the transition metal salt is 0.51; the molar ratio of the titanium salt to the manganese salt is 0.11;
and 2, step: putting the gel into a pre-heated oven at 80 ℃ to dry for 12h, and drying to obtain a powdery precursor;
and step 3: grinding the powdery precursor, putting the ground powdery precursor into a tube furnace, firing for 8h at 300 ℃ in the air atmosphere, carrying out primary firing treatment, then firing for 9h at 900 ℃ after grinding, and carrying out secondary firing treatment to obtain the modified sodium manganate material, wherein the modified sodium manganate material is sodium manganate (Na) with 0.11Ti doping amount0.44Mn0.89Ti0.11O2)。
Example 2
A preparation method of a modified sodium manganate material comprises the following steps:
step 1: titanium (IV) tetra-n-butoxide (C)16H36O4Ti, Ti ═ 0.22), anhydrous sodium carbonate (Na)2CO3) Manganese acetate tetrahydrate ((CH)3COO)2Mn·4H2O) and citric acid are mixed and dissolved in ultrapure water, heated for 5 hours at 80 ℃, stirred uniformly and then evaporated with deionized water to obtain gel; the molar ratio of the coupling agent to the metal ions in the transition metal salt is 1;
wherein the molar ratio of the sodium salt to the transition metal salt is 0.51; the molar ratio of the titanium salt to the manganese salt is 0.22;
step 2: putting the gel into a pre-heated oven at 80 ℃ to dry for 12h, and drying to obtain a powdery precursor;
and step 3: grinding the powdery precursor, putting the ground powdery precursor into a tube furnace, firing for 8h at 300 ℃ in the air atmosphere, carrying out primary firing treatment, grinding, firing for 9h at 900 ℃,carrying out second firing treatment to obtain a modified sodium manganate material, wherein the modified sodium manganate material is sodium manganate (Na) with 0.22Ti doping amount0.44Mn0.78Ti0.22O2)。
Example 3
A preparation method of a modified sodium manganate material comprises the following steps:
step 1: titanium (IV) tetra-n-butoxide (C)16H36O4Ti, Ti ═ 0.33), anhydrous sodium carbonate (Na)2CO3) Manganese acetate tetrahydrate ((CH)3COO)2Mn·4H2O) and citric acid are mixed and dissolved in ultrapure water, heated for 12 hours at 80 ℃, stirred uniformly and then evaporated with deionized water to obtain gel;
wherein the molar ratio of the coupling agent to the metal ions in the transition metal salt is 1; the molar ratio of the sodium salt to the transition metal salt is 0.51; the molar ratio of the titanium salt to the manganese salt is 0.33;
step 2: putting the gel into a pre-heated oven at 80 ℃ to dry for 12h to obtain a powdery precursor;
and step 3: grinding the powdery precursor, putting the ground powdery precursor into a tube furnace, firing the ground powdery precursor for 8 hours at 300 ℃ in an air atmosphere, carrying out primary firing treatment, firing the ground powdery precursor for 9 hours at 900 ℃, and carrying out secondary firing treatment to obtain a modified sodium manganate material, wherein the modified sodium manganate material is 0.33 Ti-doped sodium manganate (Na)0.44Mn0.67Ti0.33O2)。
Example 4
A preparation method of a modified sodium manganate material comprises the following steps:
step 1: mixing copper nitrate trihydrate (Cu (NO)3)2·3H2O, Cu ═ 0.22)), anhydrous sodium carbonate (Na)2CO3) Manganese acetate tetrahydrate ((CH)3COO)2Mn·4H2O) and citric acid are mixed and dissolved in ultrapure water, heated for 6 hours at 80 ℃, stirred uniformly and then evaporated with deionized water to obtain gel;
wherein the molar ratio of the coupling agent to the metal ions in the transition metal salt is 1; the molar ratio of sodium salt to transition metal salt is 0.51; the molar ratio of the copper salt to the manganese salt is 0.22;
step 2: putting the gel into a pre-heated oven at 80 ℃ to dry for 12h to obtain a powdery precursor;
and step 3: grinding the powdery precursor, putting the ground powdery precursor into a tube furnace, firing the ground powdery precursor for 8 hours at 300 ℃ in an air atmosphere, carrying out primary firing treatment, firing the ground powdery precursor for 9 hours at 900 ℃, and carrying out secondary firing treatment to obtain a modified sodium manganate material, wherein the modified sodium manganate material is 0.22 Cu-doped sodium manganate (Na)0.44Mn0.78Cu0.22O2)。
Example 5
A preparation method of a modified sodium manganate material comprises the following steps:
step 1: titanium tetrachloride (TiCl)4Ti ═ 0.22), sodium acetate trihydrate (CH)3COONa·3H2O), manganese (II) nitrate tetrahydrate (Mn (NO)3)2·4H2O) and oxalic acid are mixed and dissolved in ultrapure water, heated for 5 hours at 85 ℃, stirred evenly and evaporated with deionized water to obtain gel; the molar ratio of the coupling agent to the metal ions in the transition metal salt is 0.75;
wherein the molar ratio of the sodium salt to the transition metal salt is 0.49; the molar ratio of the titanium salt to the manganese salt is 0.22;
step 2: putting the gel into a preheated oven at 50 ℃ for drying for 9h to obtain a powdery precursor after drying;
and step 3: grinding the powdery precursor, putting the ground powdery precursor into a tube furnace, firing the ground powdery precursor for 9 hours at 400 ℃ in an air atmosphere, carrying out primary firing treatment, firing the ground powdery precursor for 10 hours at 950 ℃, and carrying out secondary firing treatment to obtain a modified sodium manganate material, wherein the modified sodium manganate material is sodium manganate (Na) with 0.22Ti doping amount0.44Mn0.78Ti0.22O2)。
Example 6
A preparation method of a modified sodium manganate material comprises the following steps:
step 1: titanium sulfate acyl (TiOSO)4) Ti ═ 0.11), sodium chloride (NaCl), manganese sulfate (Mn)SO4) Mixing with polyvinylpyrrolidone (PVP), dissolving in ultrapure water, heating at 90 deg.C for 6 hr, stirring, and evaporating deionized water to obtain gel; the molar ratio of the coupling agent to the metal ions in the transition metal salt is 0.83;
wherein the molar ratio of the sodium salt to the transition metal salt is 0.53; the molar ratio of the titanium salt to the manganese salt is 0.11;
step 2: putting the gel into a pre-heated oven at 70 ℃ to dry for 10h, and drying to obtain a powdery precursor;
and step 3: grinding the powdery precursor, putting the ground powdery precursor into a tube furnace, firing the powdery precursor for 10h at 400 ℃ in the air atmosphere, carrying out primary firing treatment, then firing the powdery precursor for 10h at 850 ℃ after grinding, and carrying out secondary firing treatment to obtain a modified sodium manganate material, wherein the modified sodium manganate material is sodium manganate (Na) with 0.11Ti doping amount0.44Mn0.78Ti0.11O2)。
Example 7
A preparation method of a modified sodium manganate material comprises the following steps:
step 1: adding anhydrous copper sulfate (CuSO)4) Cu ═ 0.11), sodium chloride (NaCl), manganese sulfate (MnSO)4) Mixing with ethylene glycol, dissolving in ultrapure water, heating at 90 deg.C for 6 hr, stirring, and evaporating deionized water to obtain gel; the molar ratio of the coupling agent to the metal ions in the transition metal salt is 0.83;
wherein the molar ratio of the sodium salt to the transition metal salt is 0.53; the molar ratio of the copper salt to the manganese salt is 0.11;
step 2: putting the gel into a pre-heated oven at 70 ℃ to dry for 10h, and drying to obtain a powdery precursor;
and step 3: grinding the powdery precursor, putting the ground powdery precursor into a tube furnace, firing the powdery precursor for 10h at 500 ℃ in the air atmosphere, carrying out primary firing treatment, then firing the powdery precursor for 12h at 900 ℃ after grinding, and carrying out secondary firing treatment to obtain a modified sodium manganate material, wherein the modified sodium manganate material is sodium manganate (Na) with 0.11Cu doping amount0.44Mn0.78Cu0.11O2)。
Application example 1
A preparation method of a button cell adopting the modified sodium manganate material obtained in example 1 as a positive electrode material comprises the following steps:
the modified sodium manganate material obtained in example 1, conductive carbon black and a binder polyvinylidene fluoride are mixed according to a mass ratio of 8: 1: 1, adding N-methylpyrrolidone (NMP), mixing to form uniform pasty slurry, coating the slurry on a current collector, and processing to prepare a positive plate;
the battery case, the zinc sheet, 2m (wherein m is mass concentration, unit is mol/Kg) of zinc trifluoromethanesulfonate (ZnOTF) +1m of sodium trifluoromethanesulfonate (NaOTF) +0.1m of manganese sulfate (MnSO)4) And (4) stacking the electrolyte and the positive plate in sequence and then assembling to obtain the button cell.
Application example 2
A preparation method of a button cell adopting the modified sodium manganate material obtained in example 2 as a positive electrode material comprises the following steps:
the modified sodium manganate material obtained in example 2, the conductive carbon black and the binder polyvinylidene fluoride are mixed according to the mass ratio of 8: 1: 1, adding N-methyl pyrrolidone (NMP), mixing to form uniform pasty slurry, coating the slurry on a current collector, and processing to prepare a positive plate;
the battery case, the zinc sheet, 2m zinc trifluoromethanesulfonate (ZnOTF) +1m sodium trifluoromethanesulfonate (NaOTF) +0.1m manganese sulfate (MnSO)4) And stacking the electrolyte and the positive plate in sequence and then assembling to obtain the button cell.
Application example 3
A preparation method of a button cell adopting the modified sodium manganate material obtained in example 3 as a positive electrode material comprises the following steps:
the modified sodium manganate material obtained in example 3, the conductive carbon black and the binding agent polyvinylidene fluoride are mixed according to the mass ratio of 8: 1: 1, adding N-methyl pyrrolidone (NMP), mixing to form uniform pasty slurry, coating the slurry on a current collector, and processing to prepare a positive plate;
mixing battery case, zinc sheet, 2m zinc trifluoromethanesulfonate (ZnOTF), 1m sodium trifluoromethanesulfonate (NaOTF), 0.1m manganese sulfate (MnSO)4) An electrolyte,And sequentially stacking the positive plates in sequence and then assembling the positive plates to obtain the button battery.
Comparative example 1
In contrast to example 1, a pure-phase sodium manganate (Na) was obtained without adding titanium salt and with the same procedure and parameters as in example 10.44MnO2)。
The obtained pure-phase sodium manganate (Na)0.44MnO2) In the same manner as in application example 1, a coin cell using pure-phase sodium manganate as a positive electrode material was prepared.
FIG. 1 is a graph showing the performance test of pure-phase sodium manganate in comparative example 1, and FIG. 1a is an X-ray diffraction image of pure-phase sodium manganate material, and standard Na4Mn9O18The phases (PDF #27-0750) remained consistent. As shown in FIG. 1b, which is a scanning electron microscope image, it can be seen that the morphology of the material is a tunnel-type structure. The cycle performance of the battery is measured by a Xinwei battery test system, the charge-discharge range is 0.8-1.8V, and the charge-discharge current density is as follows: 1A/g. As shown in fig. 1c, the cycle performance of the pure-phase sodium manganate positive electrode is poor, and the cycle can only be about 700 cycles.
Fig. 2 is a scanning electron microscope image of the modified sodium manganate material, and it can be seen that the sodium manganate material after Ti doping maintains a tunnel structure, and the structure of pure-phase sodium manganate is not changed by Ti doping.
FIG. 3 is an X-ray diffraction pattern of a modified sodium manganate material; it can be seen that after Ti doping, the material remains in pure phase with Na0.44MnO2Similar crystal structure, but a slight shift in diffraction peaks due to the change in interplanar spacing.
Fig. 4 is a comparison graph of the cycle performance of the pure-phase sodium manganate obtained in comparative example 1 and the modified sodium manganate material obtained in the invention (with Ti doping amounts of 0.11, 0.22 and 0.33) at a current density of 1A/g, and it can be seen that the cycle stability of the sodium manganate material can be effectively improved by Ti doping, the material with 22% Ti doping amount performs best, a specific capacity of 113mAh/g can be provided at a current density of 1A/g, and a capacity retention rate of 71% can be achieved after 2400 cycles. The 11% doping capacity material can only provide the specific capacity of about 50 mAh/g. But the performance is obviously improved compared with that of pure-phase sodium manganate which can be cycled for only 700 times.
Fig. 5 is a graph comparing the cycle performance of the pure-phase sodium manganate obtained in comparative example 1 and the modified sodium manganate material obtained in the invention (Cu doping amount is 0.22) at a current density of 1A/g, and it can be seen that although the cycle performance of the material is improved by the addition of Cu ions: 700 turns maintain a specific capacity of 50mAh/g, but result in an increase in the number of activation turns of the battery: the maximum capacity is reached at 200 revolutions.
FIG. 6 is a schematic structural diagram of a modified sodium manganate material, and it can be seen from the diagram that the modified sodium manganate material prepared by the present application has a 2 × 2 orthogonal tunnel type ion conduction structure, and MnO shared by sides6Octahedral formed tunnels and three different types of sodium sites and MnO5Polyhedral, S-shaped, orthogonal tunnels, tetravalent transition metal ions Ti4+The introduction of (A) does not cause the change of the crystal structure of the pure phase material, no obvious new phase appears, and meanwhile, Ti4+Will occupy Mn in pure phase material4+The sites can effectively improve the lattice stability of the anode material, thereby reducing the dissolution of the anode material in aqueous electrolyte and improving the electrochemical performance.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The preparation method of the modified sodium manganate material is characterized by comprising the following steps:
step 1: mixing and dissolving transition metal salt, sodium salt and coupling agent in ultrapure water, heating and stirring, and evaporating to obtain gel;
step 2: drying the gel to obtain a powdery precursor;
and step 3: carrying out first firing treatment on the powdery precursor, grinding the powdery precursor, and carrying out second firing treatment to obtain a modified sodium manganate material;
the transition metal salt includes a manganese salt, a titanium salt, or a copper salt.
2. The method of claim 1, wherein the manganese salt comprises one or more of manganese acetate tetrahydrate, manganese (II) nitrate tetrahydrate, and manganese sulfate; the sodium salt comprises one or more of anhydrous sodium carbonate, sodium acetate trihydrate and sodium chloride.
3. The method for preparing the modified sodium manganate material as claimed in claim 1, wherein said coupling agent comprises one or more of citric acid, oxalic acid, polyvinylpyrrolidone and ethylene glycol; the titanium salt comprises one or more of titanium (IV) tetra-n-butoxide, titanium tetrachloride and titanium acyl sulfate; the copper salt includes one or more of copper nitrate trihydrate, anhydrous copper sulfate, and copper chloride.
4. The method for preparing the modified sodium manganate material of claim 1, wherein the molar ratio of the coupling agent to the metal ions in the transition metal salt is 0.75-1; the molar ratio of the sodium salt to the transition metal salt is 0.49-0.53; the molar ratio of the titanium salt or the copper salt to the manganese salt is 0.11-0.33.
5. The method for preparing the modified sodium manganate material as claimed in claim 1, wherein in step 1, the heating time is 4-6 h, and the heating temperature is 80-90 ℃; in the step 2, the drying time is 9-12 h, and the drying temperature is 50-80 ℃.
6. The method for preparing the modified sodium manganate material as claimed in claim 1, wherein in step 3, the process parameters of the first firing treatment are as follows: firing at 300-500 deg.c for 8-10 hr.
7. The method for preparing the modified sodium manganate material as claimed in claim 1, wherein in step 3, the process parameters of the second firing treatment are as follows: firing at 850-950 ℃ for 9-12 h.
8. The modified sodium manganate material prepared by the method for preparing the modified sodium manganate material according to any one of claims 1 to 7.
9. The modified sodium manganate material of claim 8, wherein said modified sodium manganate material is characterized by having an orthogonal tunnel type ion conducting structure.
10. The use of the modified sodium manganate material of claim 8, wherein said modified sodium manganate material is used as a positive electrode material of an aqueous ion battery.
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