CN114655991B - Modified sodium manganate material and preparation method and application thereof - Google Patents
Modified sodium manganate material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114655991B CN114655991B CN202210297024.2A CN202210297024A CN114655991B CN 114655991 B CN114655991 B CN 114655991B CN 202210297024 A CN202210297024 A CN 202210297024A CN 114655991 B CN114655991 B CN 114655991B
- Authority
- CN
- China
- Prior art keywords
- salt
- sodium manganate
- modified sodium
- manganate material
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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 101
- 239000000463 material Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 25
- 239000007774 positive electrode material Substances 0.000 claims abstract description 16
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000010304 firing Methods 0.000 claims description 40
- 239000002243 precursor Substances 0.000 claims description 31
- -1 transition metal salt Chemical class 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 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
- 238000002156 mixing Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 13
- 238000010438 heat treatment 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
- 239000007822 coupling agent Substances 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
- 238000001704 evaporation Methods 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 238000003756 stirring 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
- 150000001879 copper Chemical class 0.000 claims description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- 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
- 239000011780 sodium chloride Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 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 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 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 3
- 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
- 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
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 239000011572 manganese Substances 0.000 abstract description 20
- 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
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 23
- 239000011734 sodium Substances 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 13
- 239000010949 copper Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 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
- 235000011837 pasties Nutrition 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Chemical compound [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
- 230000008569 process Effects 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 5
- 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 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 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
- 230000008859 change Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012360 testing method Methods 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
- 230000004913 activation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 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
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007323 disproportionation reaction Methods 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
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a modified sodium manganate material, a preparation method and application thereof, belongs to the technical field of preparation of water-based ion batteries, and solves the technical problem that the circulation stability of the water-based battery is poor due to the dissolution phenomenon of the existing manganese oxide serving as a positive electrode material. According to the preparation method of the modified sodium manganate material, disclosed by the invention, the pure-phase sodium manganate is prepared by using a couplant-assisted sol-gel method, and doping treatment is carried out on Mn positions 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 the water-based ion battery, and has good circulation 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, a preparation method and application thereof.
Background
In all secondary battery systems at present, lithium ion batteries have certainly taken the dominant role, and have been widely applied to various fields of people's daily lives, such as electric automobiles, portable electronic products and the like. However, due to the inherent problems of lithium resource scarcity, toxicity, flammability, etc., lithium ion battery systems are unable to meet the demands of increasingly large-scale energy storage applications. Aqueous zinc ion batteries are uniquely attractive due to the following advantages: (1) suitable operating potential: the standard oxidation-reduction potential of zinc (Zn) metal is-0.76V, which is higher than the hydrogen evolution potential of the water-based electrolyte, and can be applied to a water-based electrolyte system; (2) high theoretical capacity: theory of Zn negative electrodeVolumetric capacity of 5851mAh/cm 3 The mass specific capacity is 819mAh/g; and (3) the water-based electrolyte is nontoxic 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 cathode material is easily dissolved in an aqueous electrolyte, resulting in poor cycle stability of the battery. In order to solve this problem, researchers have attempted to modify the electrode material and the electrolyte, but the effect is not ideal.
The manganese-based oxide is one of the most ideal water-based zinc ion battery anode materials because of the advantages of high specific capacity, environmental friendliness and the like. However, the conventional manganese oxide has the problem of dissolution, and the cycle performance of the battery is poor, so that the practical application cannot be satisfied.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a modified sodium manganate material, a preparation method and application thereof, which are used for solving the technical problem that the circulation stability of a water-based battery is poor due to the dissolution phenomenon of the existing manganese oxide serving as a positive electrode material.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of a modified sodium manganate material, which comprises the following steps:
step 1: mixing transition metal salt, sodium salt and coupling agent, dissolving in ultrapure water, heating and stirring, and evaporating to obtain gel;
step 2: drying the gel to obtain a powdery precursor;
step 3: carrying out first firing treatment on the powdery precursor, grinding and then carrying out second firing treatment to obtain a modified sodium manganate material;
the transition metal salt includes manganese salt, titanium salt or copper salt.
Further, the manganese salt includes one or more of manganese acetate tetrahydrate, manganese (II) nitrate tetrahydrate, and manganese sulfate; the sodium salt includes 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 titanyl 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 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 copper salt to the manganese salt is 0.11-0.33.
Further, in the step 1, the heating time is 4-6 hours, 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 deg.c for 9-12 hr.
The invention also discloses a 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 application of the modified sodium manganate material, and the modified sodium manganate material is used as a positive electrode material of the 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 comprises the steps of preparing pure-phase sodium manganate by using a couplant-assisted sol-gel method, doping treatment on Mn positions through different transition metals (Ti and Cu) on the basis of preparing the pure-phase sodium manganate, and regulating and controlling the material structure of the pure-phase sodium manganate through transition metal ions with different valence states and ion radiuses; due to the introduction of different transition metals (Ti,Cu) partially substitutes Mn sites in pure-phase sodium manganate to inhibit lattice Mn in the charge-discharge process 3+ The disproportionation reaction is generated to inhibit the dissolution of manganese, so that 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, easy mass production and wide application prospect.
The invention also discloses a modified sodium manganate material prepared by the preparation method, and related experimental results show that compared with pure-phase sodium manganate, the modified sodium manganate material prepared by the preparation method has a consistent crystal form, but the crystal stability of the modified sodium manganate material is better; meanwhile, the modified sodium manganate material has a 2X 2 orthogonal tunnel type ion conduction structure and is shared by MnO (metal oxide semiconductor) by edges 6 Octahedral tunnel and three different types of sodium sites and MnO 5 The polyhedral structure, the S-shaped orthogonal tunnel has stable structure, the ion channel is favorable for the intercalation and deintercalation of ions in the charge and discharge process, and the tetravalent transition metal ion Ti 4+ The introduction of the titanium alloy does not cause the change of the crystal structure of the pure phase material, no obvious new phase appears, and simultaneously, ti 4+ Will occupy Mn in the pure phase material 4+ The sites can effectively improve the lattice stability of the positive electrode material, thereby reducing the dissolution of the positive electrode material in the water-based electrolyte and improving the electrochemical performance (high cycle stability and specific capacity).
The invention also discloses application of the modified sodium manganate material, which reduces dissolution phenomenon when the modified sodium manganate material is used as a positive electrode material of a water-based ion battery because the modified sodium manganate material has good lattice stability, and the battery system constructed by the modified sodium manganate material only needs conventional electrolyte concentration (1 m/2 m) and does not need high-concentration electrolyte, so that the modified sodium manganate material is a positive electrode material of the water-based ion battery with excellent performance.
Drawings
FIG. 1 is a graph of performance testing of pure phase sodium manganate of comparative example 1;
wherein: a-X-ray diffraction pattern; b-scanning electron microscope images; c-1A/g cycle performance plot at current density;
FIG. 2 is a scanning electron microscope image 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 showing a comparison of the cycle performance of the pure phase sodium manganate obtained in comparative example 1 and the modified sodium manganate material obtained in the present invention (Ti doping amounts of 0.11, 0.22, 0.33) at a current density of 1A/g;
FIG. 5 is a graph showing a comparison of the cycle performance of the pure phase sodium manganate obtained in comparative example 1 and the modified sodium manganate material obtained in the present invention (Cu doping amount of 0.22) at a current density of 1A/g;
fig. 6 is a schematic structural diagram of a modified sodium manganate material.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, 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, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features such as values, amounts, and concentrations that are defined herein in the numerical or percent ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise indicated, "comprising," "including," "having," or similar terms encompass the meanings of "consisting of … …" and "consisting essentially of … …," e.g., "a includes a" encompasses the meanings of "a includes a and the other and" a includes a only.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The following examples use instrumentation conventional in the art. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The following examples used various starting materials, unless otherwise indicated, were conventional commercial products, the specifications of which are conventional in the art. In the description of the present invention and the following examples, "%" means weight percent, and "parts" means parts by weight, and ratios means weight ratio, unless otherwise specified.
Example 1
The preparation method of the modified sodium manganate material comprises the following steps:
step 1: titanium (IV) tetra-n-butoxide (C 16 H 36 O 4 Ti, ti=0.11), anhydrous sodium carbonate (Na 2 CO 3 ) Manganese acetate tetrahydrate ((CH) 3 COO) 2 Mn·4H 2 Mixing O) and citric acid, dissolving in ultrapure water, heating at 80 ℃ for 4 hours, uniformly 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 1;
wherein the molar ratio of sodium salt to transition metal salt is 0.51; the molar ratio of the titanium salt to the manganese salt is 0.11;
step 2: placing the gel into a preheated oven at 80 ℃ for drying for 12 hours, and obtaining a powdery precursor after drying;
step 3: grinding the powdery precursor, putting the ground powdery precursor into a tube furnace, firing for 8 hours at 300 ℃ in an air atmosphere, performing first firing treatment, firing for 9 hours at 900 ℃ after grinding, and performing second firing treatment to obtain a modified sodium manganate material, wherein the modified sodium manganate material is sodium manganate (Na 0.44 Mn 0.89 Ti 0.11 O 2 )。
Example 2
The preparation method of the modified sodium manganate material comprises the following steps:
step 1: titanium (IV) tetra-n-butoxide (C 16 H 36 O 4 Ti, ti=0.22), anhydrous sodium carbonate (Na 2 CO 3 ) Manganese acetate tetrahydrate ((CH) 3 COO) 2 Mn·4H 2 Mixing O) and citric acid, dissolving in ultrapure water, heating at 80 ℃ for 5 hours, uniformly 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 1;
wherein the molar ratio of sodium salt to transition metal salt is 0.51; the molar ratio of the titanium salt to the manganese salt is 0.22;
step 2: placing the gel into a preheated oven at 80 ℃ for drying for 12 hours, and obtaining a powdery precursor after drying;
step 3: grinding the powdery precursor, putting the ground powdery precursor into a tube furnace, firing for 8 hours at 300 ℃ in an air atmosphere, performing first firing treatment, firing for 9 hours at 900 ℃ after grinding, and performing second firing treatment to obtain a modified sodium manganate material, wherein the modified sodium manganate material is sodium manganate (Na 0.44 Mn 0.78 Ti 0.22 O 2 )。
Example 3
The preparation method of the modified sodium manganate material comprises the following steps:
step 1: titanium (IV) tetra-n-butoxide (C 16 H 36 O 4 Ti, ti=0.33), anhydrous sodium carbonateNa 2 CO 3 ) Manganese acetate tetrahydrate ((CH) 3 COO) 2 Mn·4H 2 Mixing O) and citric acid, dissolving in ultrapure water, heating at 80 ℃ for 12 hours, uniformly stirring, and evaporating deionized water to obtain gel;
wherein, the mol 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: placing the gel into a preheated oven at 80 ℃ for drying for 12 hours, and obtaining a powdery precursor after drying;
step 3: grinding the powdery precursor, putting the ground powdery precursor into a tube furnace, firing for 8 hours at 300 ℃ in an air atmosphere, performing first firing treatment, firing for 9 hours at 900 ℃ after grinding, and performing second firing treatment to obtain a modified sodium manganate material, wherein the modified sodium manganate material is sodium manganate (Na 0.44 Mn 0.67 Ti 0.33 O 2 )。
Example 4
The preparation method of the modified sodium manganate material comprises the following steps:
step 1: copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 O, cu=0.22)), anhydrous sodium carbonate (Na) 2 CO 3 ) Manganese acetate tetrahydrate ((CH) 3 COO) 2 Mn·4H 2 Mixing O) and citric acid, dissolving in ultrapure water, heating at 80 ℃ for 6 hours, uniformly stirring, and evaporating deionized water to obtain gel;
wherein, the mol 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 copper salt to the manganese salt is 0.22;
step 2: placing the gel into a preheated oven at 80 ℃ for drying for 12 hours, and obtaining a powdery precursor after drying;
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, performing first firing treatment, firing the ground powdery precursor for 9 hours at 900 ℃ and performing second firing treatment to obtain a modified sodium manganate material, wherein the modified sodium manganate material is prepared byThe material is sodium manganate (Na) 0.44 Mn 0.78 Cu 0.22 O 2 )。
Example 5
The preparation method of the modified sodium manganate material comprises the following steps:
step 1: titanium tetrachloride (TiCl) 4 Ti=0.22), sodium acetate trihydrate (CH 3 COONa·3H 2 O), manganese (II) nitrate tetrahydrate (Mn (NO) 3 ) 2 ·4H 2 Mixing O) and oxalic acid, dissolving in ultrapure water, heating at 85 ℃ for 5 hours, uniformly 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 0.75;
wherein the molar ratio of sodium salt to transition metal salt is 0.49; the molar ratio of the titanium salt to the manganese salt is 0.22;
step 2: placing the gel into a preheated oven at 50 ℃ for drying for 9 hours, and obtaining a powdery precursor after drying;
step 3: grinding the powdery precursor, putting the ground powdery precursor into a tube furnace, firing for 9 hours at 400 ℃ in an air atmosphere, performing first firing treatment, firing for 10 hours at 950 ℃ after grinding, and performing second firing treatment to obtain a modified sodium manganate material, wherein the modified sodium manganate material is sodium manganate (Na 0.44 Mn 0.78 Ti 0.22 O 2 )。
Example 6
The preparation method of the modified sodium manganate material comprises the following steps:
step 1: titanium sulfate (TiOSO) 4 ) Ti=0.11), sodium chloride (NaCl), manganese sulfate (MnSO 4 ) Mixing with polyvinylpyrrolidone (PVP) and dissolving in ultrapure water, heating at 90 ℃ for 6 hours, stirring uniformly, 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 sodium salt to transition metal salt is 0.53; the molar ratio of the titanium salt to the manganese salt is 0.11;
step 2: placing the gel into a preheated oven at 70 ℃ for drying for 10 hours, and obtaining a powdery precursor after drying;
step 3: grinding the powdery precursor, putting the ground powdery precursor into a tube furnace, firing the ground powdery precursor for 10 hours at 400 ℃ in an air atmosphere, performing first firing treatment, firing the ground powdery precursor for 10 hours at 850 ℃ and performing second firing treatment to obtain a modified sodium manganate material, wherein the modified sodium manganate material is sodium manganate (Na 0.44 Mn 0.78 Ti 0.11 O 2 )。
Example 7
The preparation method of the modified sodium manganate material comprises the following steps:
step 1: 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 ℃ for 6 hours, stirring uniformly, 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 sodium salt to transition metal salt is 0.53; the molar ratio of the copper salt to the manganese salt is 0.11;
step 2: placing the gel into a preheated oven at 70 ℃ for drying for 10 hours, and obtaining a powdery precursor after drying;
step 3: grinding the powdery precursor, putting the ground powdery precursor into a tube furnace, firing the ground powdery precursor for 10 hours at 500 ℃ in an air atmosphere, performing first firing treatment, firing the ground powdery precursor for 12 hours at 900 ℃ and performing second firing treatment to obtain a modified sodium manganate material, wherein the modified sodium manganate material is 0.11Cu doped sodium manganate (Na 0.44 Mn 0.78 Cu 0.11 O 2 )。
Application example 1
The preparation method of the button cell adopting the modified sodium manganate material obtained in the embodiment 1 as the positive electrode material comprises the following steps:
the modified sodium manganate material obtained in the example 1, conductive carbon black and polyvinylidene fluoride as binders are mixed according to the mass ratio of 8:1:1, mixing, adding N-methyl pyrrolidone (NMP), mixing to form uniform pasty slurry, coating the pasty slurry on a current collector, and processing to prepare a positive plate;
the battery case, the zinc sheet and 2m (wherein m is massThe concentration of the amount is as follows: mol/Kg) zinc triflate (ZnOTF) +1m sodium triflate (NaOTF) +0.1m manganese sulfate (MnSO) 4 ) And sequentially stacking and assembling the electrolyte and the positive plate to obtain the button cell.
Application example 2
The preparation method of the button cell adopting the modified sodium manganate material obtained in the embodiment 2 as the positive electrode material comprises the following steps:
the modified sodium manganate material obtained in the example 2, conductive carbon black and polyvinylidene fluoride binder are mixed according to the mass ratio of 8:1:1, mixing, adding N-methyl pyrrolidone (NMP), mixing to form uniform pasty slurry, coating the pasty slurry on a current collector, and processing to prepare a positive plate;
a battery case, a zinc sheet, 2m of zinc trifluoromethane sulfonate (ZnOTF) +1m of sodium trifluoromethane sulfonate (NaOTF) +0.1m of manganese sulfate (MnSO) 4 ) And sequentially stacking and assembling the electrolyte and the positive plate to obtain the button cell.
Application example 3
The preparation method of the button cell adopting the modified sodium manganate material obtained in the embodiment 3 as the positive electrode material comprises the following steps:
the modified sodium manganate material obtained in the example 3, conductive carbon black and polyvinylidene fluoride binder are mixed according to the mass ratio of 8:1:1, mixing, adding N-methyl pyrrolidone (NMP), mixing to form uniform pasty slurry, coating the pasty slurry on a current collector, and processing to prepare a positive plate;
a battery case, a zinc sheet, 2m of zinc trifluoromethane sulfonate (ZnOTF) +1m of sodium trifluoromethane sulfonate (NaOTF) +0.1m of manganese sulfate (MnSO) 4 ) And sequentially stacking and assembling the electrolyte and the positive plate to obtain the button cell.
Comparative example 1
Unlike example 1, no titanium salt was added, and the other steps and parameters were the same as in example 1 to obtain pure phase sodium manganate (Na 0.44 MnO 2 )。
The obtained pure phase sodium manganate (Na 0.44 MnO 2 ) In the same manner as in application example 1, a pure-phase manganate was preparedButton cell with sodium as positive electrode material.
FIG. 1 is a graph showing the performance test of pure phase sodium manganate in comparative example 1, FIG. 1a is an X-ray diffraction image of pure phase sodium manganate material, and standard Na 4 Mn 9 O 18 The phases (PDF # 27-0750) remain identical. As shown in fig. 1b, which is a scanning electron microscope image, the morphology of the material can be seen as a tunnel structure. The cycle performance of the battery is measured by a Xinwei battery test system, the charging and discharging range is 0.8-1.8V, and the charging and discharging current density is: 1A/g. As shown in fig. 1c, the pure-phase sodium manganate positive electrode has poor cycle performance and can only be cycled for about 700 circles.
Fig. 2 shows a scanning electron microscope image of a modified sodium manganate material, and it can be seen that the sodium manganate material doped with Ti maintains a tunnel structure, and the doping of Ti does not change the structure of pure-phase sodium manganate.
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 as pure phase Na 0.44 MnO 2 Similar crystal structure, but with slight shifts in diffraction peaks due to changes in interplanar spacing.
Fig. 4 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 (Ti doping amount is 0.11, 0.22, 0.33) at a current density of 1A/g, and it can be seen that the Ti doping can effectively improve the cycle stability of the sodium manganate material, the material with 22% Ti doping amount performs best, can provide a specific capacity of 113mAh/g at a current density of 1A/g, and can also have a capacity retention rate of 71% after 2400 cycles. The 11% doping amount material can only provide the specific capacity of about 50 mAh/g. But the performance of the pure phase sodium manganate can only be circulated 700 times is obviously improved.
FIG. 5 is a graph showing comparison of the cycle performance of the pure phase sodium manganate obtained in comparative example 1 and the modified sodium manganate material obtained in the present invention (Cu doping amount of 0.22) at a current density of 1A/g, and it can be seen that the addition of Cu ions although improves the cycle performance of the material: the specific capacity of 50mAh/g is maintained at 700 turns, but the activation turns of the battery are increased: maximum capacity is reached at 200 turns.
FIG. 6 is a junction of a modified sodium manganate materialFrom the schematic diagram, it can be seen that the modified sodium manganate material prepared by the method has a 2×2 orthogonal tunnel type ion conduction structure, and MnO shared by edges 6 Octahedral tunnel and three different types of sodium sites and MnO 5 Polyhedral structure, S-shaped orthogonal tunnel, tetravalent transition metal ion Ti 4+ The introduction of the titanium alloy does not cause the change of the crystal structure of the pure phase material, no obvious new phase appears, and simultaneously, ti 4+ Will occupy Mn in the pure phase material 4+ The sites can effectively improve the lattice stability of the positive electrode material, thereby reducing the dissolution of the positive electrode material in the water-based electrolyte and improving the electrochemical performance.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (7)
1. The preparation method of the modified sodium manganate material is characterized by comprising the following steps of:
step 1: mixing transition metal salt, sodium salt and coupling agent, dissolving in ultrapure water, heating and stirring, and evaporating to obtain gel;
the couplant 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 titanyl sulfate; the copper salt comprises one or more of copper nitrate trihydrate, anhydrous copper sulfate, and copper chloride;
step 2: drying the gel to obtain a powdery precursor;
step 3: carrying out first firing treatment on the powdery precursor, grinding and then carrying out second firing treatment to obtain a modified sodium manganate material;
the technological parameters of the first firing treatment are as follows: firing at 300-500 ℃ for 8-10 hours;
the technological parameters of the second firing treatment are as follows: firing at 850-950 ℃ for 9-12 h;
the transition metal salt includes manganese salt, titanium salt or copper salt.
2. The method of preparing a modified sodium manganate material according to claim 1, wherein the manganese salt comprises one or more of manganese acetate tetrahydrate, manganese (II) nitrate tetrahydrate and manganese sulfate; the sodium salt includes one or more of anhydrous sodium carbonate, sodium acetate trihydrate and sodium chloride.
3. The preparation method of the modified sodium manganate material according to claim 1, wherein 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 copper salt to the manganese salt is 0.11-0.33.
4. The preparation method of the modified sodium manganate material according to claim 1, wherein in the step 1, the heating time is 4-6 hours, 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 ℃.
5. A modified sodium manganate material prepared by the preparation method of any one of claims 1 to 4.
6. The modified sodium manganate material of claim 5, wherein the modified sodium manganate material has an ion conducting structure of orthogonal tunnel type.
7. The use of the modified sodium manganate material of claim 5, wherein the modified sodium manganate material is used as a positive electrode material of an aqueous ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210297024.2A CN114655991B (en) | 2022-03-24 | 2022-03-24 | Modified sodium manganate material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210297024.2A CN114655991B (en) | 2022-03-24 | 2022-03-24 | Modified sodium manganate material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114655991A CN114655991A (en) | 2022-06-24 |
| CN114655991B true CN114655991B (en) | 2024-01-09 |
Family
ID=82032378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210297024.2A Active CN114655991B (en) | 2022-03-24 | 2022-03-24 | Modified sodium manganate material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114655991B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006216509A (en) * | 2005-02-07 | 2006-08-17 | Sanyo Electric Co Ltd | Positive electrode and nonaqueous electrolyte secondary battery using the same |
| CN104716317A (en) * | 2015-03-09 | 2015-06-17 | 郑州大学 | Method for synthesizing NaxMnO2 cathode material of sodium-ion battery |
| CN109119610A (en) * | 2018-08-20 | 2019-01-01 | 武汉大学 | A kind of alkaline aqueous solution sodium-ion battery |
| CN110921713A (en) * | 2019-12-10 | 2020-03-27 | 广东工业大学 | Sodium manganate smoothing material and preparation method and application thereof |
| CN111180706A (en) * | 2020-01-08 | 2020-05-19 | 太原理工大学 | Preparation method of sodium titanium manganese acid sodium as positive electrode material of sodium ion battery |
| CN113921809A (en) * | 2021-09-25 | 2022-01-11 | 天津理工大学 | P2 type layered sodium-ion battery positive electrode material and preparation method thereof |
| CN113921781A (en) * | 2021-09-25 | 2022-01-11 | 天津理工大学 | Titanium-doped modified P2 type layered sodium-ion battery positive electrode material and preparation method thereof |
| WO2022041989A1 (en) * | 2020-08-28 | 2022-03-03 | 瑞海泊(青岛)能源科技有限公司 | Cathode material, preparation method therefor, and application thereof |
| CN114180633A (en) * | 2020-09-15 | 2022-03-15 | 中国科学院大连化学物理研究所 | Preparation method and application of sodium manganate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109980211B (en) * | 2019-04-23 | 2021-03-19 | 深圳大学 | Sodium ion battery positive electrode material and preparation method and application thereof |
-
2022
- 2022-03-24 CN CN202210297024.2A patent/CN114655991B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006216509A (en) * | 2005-02-07 | 2006-08-17 | Sanyo Electric Co Ltd | Positive electrode and nonaqueous electrolyte secondary battery using the same |
| CN104716317A (en) * | 2015-03-09 | 2015-06-17 | 郑州大学 | Method for synthesizing NaxMnO2 cathode material of sodium-ion battery |
| CN109119610A (en) * | 2018-08-20 | 2019-01-01 | 武汉大学 | A kind of alkaline aqueous solution sodium-ion battery |
| CN110921713A (en) * | 2019-12-10 | 2020-03-27 | 广东工业大学 | Sodium manganate smoothing material and preparation method and application thereof |
| CN111180706A (en) * | 2020-01-08 | 2020-05-19 | 太原理工大学 | Preparation method of sodium titanium manganese acid sodium as positive electrode material of sodium ion battery |
| WO2022041989A1 (en) * | 2020-08-28 | 2022-03-03 | 瑞海泊(青岛)能源科技有限公司 | Cathode material, preparation method therefor, and application thereof |
| CN114180633A (en) * | 2020-09-15 | 2022-03-15 | 中国科学院大连化学物理研究所 | Preparation method and application of sodium manganate |
| CN113921809A (en) * | 2021-09-25 | 2022-01-11 | 天津理工大学 | P2 type layered sodium-ion battery positive electrode material and preparation method thereof |
| CN113921781A (en) * | 2021-09-25 | 2022-01-11 | 天津理工大学 | Titanium-doped modified P2 type layered sodium-ion battery positive electrode material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 草酸前驱体法制备高性能钠离子电池正极材料NaNi_(0.5)Mn_(0.5)O_2;***;徐守冬;史文静;王忠德;刘世斌;张鼎;;人工晶体学报(第08期);全文 * |
| 钠锰比对Na_xMnO_2的性能和钠离子脱嵌过程的影响;谢永纯;王成;蒋芳;杨洋;苏静;龙云飞;文衍宣;;电化学(第04期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114655991A (en) | 2022-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102738458B (en) | Surface modification method of lithium-rich cathode material | |
| CN102177605A (en) | Positive electrode materials for lithium ion batteries having a high specific discharge capacity and processes for the synthesis of these materials | |
| CN102870256A (en) | Metal oxide coated positive electrode materials for lithium-based batteries | |
| CN102171868A (en) | Fluorine doped lithium rich metal oxide positive electrode battery materials with high specific capacity and corresponding batteries | |
| CN115224254B (en) | Cu, zn and Mg co-doped layered oxide sodium ion battery positive electrode material, and preparation method and application thereof | |
| WO2024055519A1 (en) | Preparation method and use of lithium manganese iron phosphate | |
| CN110380043A (en) | The positive electrode and preparation method thereof of fluoro- phosphorus doping tin oxide coating modification | |
| CN114744186B (en) | Layered lithium-rich manganese-based composite positive electrode material, preparation method and battery | |
| Han et al. | The effects of copper and titanium co-substitution on LiNi 0.6 Co 0.15 Mn 0.25 O 2 for lithium ion batteries | |
| CN116504940A (en) | Polyanion type sodium ion battery positive electrode material, preparation method and application thereof | |
| CN110112385B (en) | Method for improving stability and rate performance of ternary cathode material | |
| CN111682174A (en) | Antimony-coated lithium battery positive electrode material and preparation method and application thereof | |
| CN115064670A (en) | Preparation method of doped coated modified sodium nickel manganese oxide cathode material | |
| CN113066980B (en) | Method for preparing phosphomolybdic acid modified high-nickel single crystal positive electrode material | |
| Franger et al. | Chemistry and Electrochemistry of Low‐Temperature Manganese Oxides as Lithium Intercalation Compounds | |
| CN113644274A (en) | O2 type lithium ion battery anode material and preparation method and application thereof | |
| CN109037669A (en) | Modified nickel-cobalt lithium aluminate anode material and preparation method and application thereof | |
| CN111653782A (en) | Positive electrode material and preparation method and application thereof | |
| CN112103482A (en) | Rare earth metal or transition metal doped lithium titanium phosphate/carbon composite material and preparation method and application thereof | |
| CN116845230A (en) | Mn and Al-containing vanadium-based phosphate positive electrode material, preparation method thereof, battery and energy storage equipment | |
| CN116454267A (en) | Sodium-electricity layered oxide and preparation method thereof | |
| CN114655991B (en) | Modified sodium manganate material and preparation method and application thereof | |
| CN115224259A (en) | Titanium-doped lithium nickel manganese oxide positive electrode material, preparation method and application thereof, and lithium ion battery | |
| CN116101994A (en) | Heteropolyacid modified layered oxide sodium battery positive electrode material and preparation method thereof | |
| Shen et al. | Effects of Gd 3+ doping on the microstructure and electrochemical properties of Li 1.20 [Mn 0.54 Ni 0.13 Co 0.13] O 2 as cathode for lithium-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |