CN110589892A - Monoclinic structure positive electrode material for sodium-ion battery and preparation method thereof - Google Patents
Monoclinic structure positive electrode material for sodium-ion battery and preparation method thereof Download PDFInfo
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- CN110589892A CN110589892A CN201810606087.5A CN201810606087A CN110589892A CN 110589892 A CN110589892 A CN 110589892A CN 201810606087 A CN201810606087 A CN 201810606087A CN 110589892 A CN110589892 A CN 110589892A
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 32
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 27
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007772 electrode material Substances 0.000 claims description 18
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000010406 cathode material Substances 0.000 claims description 9
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 239000010408 film Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 20
- 239000004744 fabric Substances 0.000 description 20
- 239000013078 crystal Substances 0.000 description 15
- 239000011572 manganese Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 229910019898 NaxMnO2 Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 150000002696 manganese Chemical class 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910019338 NaMnO2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 229910004591 Na2FePO4F Inorganic materials 0.000 description 1
- 229910020657 Na3V2(PO4)3 Inorganic materials 0.000 description 1
- 229910021225 NaCoO2 Inorganic materials 0.000 description 1
- 229910021271 NaCrO2 Inorganic materials 0.000 description 1
- 229910021312 NaFePO4 Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a sodium ion battery anode material and a preparation method thereof, and Mn is used3O4The material is a precursor material, and is placed in a sodium source aqueous solution for two-step hydrothermal reaction to obtain a product, and the product is subjected to heat treatment to obtain NaMnO with a monoclinic structure2‑y(OH)2yOr NaMnO2‑y‑δ(OH)2yA material. The sodium ion battery anode material disclosed by the invention is simple in preparation process and low in energy consumption, and the prepared sodium ion anode material has excellent electrochemical properties such as specific capacity, rate capability, cycling stability and first coulombic efficiency.
Description
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a sodium-ion battery positive electrode material and a preparation method thereof.
Background
Compared with the positive electrode material of a sodium ion battery, such as NaFePO4、NaCoO2、Na2FePO4F、Na3V2(PO4)3And NaCrO2Etc. NaxMnO2The material has higher theoretical specific capacity, and simultaneously, the manganese element is taken as NaxMnO2One of the main raw materials has the advantages of low price, wide source and the like, so NaxMnO2The research on the positive electrode material has received a lot of attention, and most researchers will use NaxMnO2The research focus of the cathode material is mainly focused on O3-, tunnel (tunnel), and P2-type structures. However, O3-, tunnel-, and P2-Na have been reported so farxMnO2The positive electrode material has disadvantages in electrochemical performance. Such as O3-NaxMnO2The positive electrode material can provide higher discharge capacity (up to 197mAh/g, Ma XH, et al.J.electrochem.Soc.2011,158, A1307-A1312), but the crystal lattice structure is easy to distort and is converted into a spinel structure in the charge and discharge process due to the crystal structure of the positive electrode material, so that the capacity attenuation is easy to occur (Caballero A, et al.J.solid State chem.,2003,174, 365-); P2-NaxMnO2The positive electrode material has a stable structure and good cycling stability, but is difficult to show good rate performance; and tunnel-NaxMnO2The positive electrode material can show better cycling stability and rate performance (Cao YL, et al. adv. Mater.2011,23,3155-xMnO2The restriction of the content of the medium sodium element cannot exert a high discharge capacity. Therefore, a new synthesis method can be developed to prepare Na with high capacity, better rate capability and cycling stabilityxMnO2A positive electrode material is needed to be solved.
On the other hand, related studies show that: birnessite structured NaxMnO2The cathode material has good electrochemical performance, can be used as a cathode material of an aqueous sodium-ion battery (US2009025305A1) and can also be used as a cathode material of a non-aqueous sodium-ion battery (Guo SH, et al. ChemSusChem chem,2014,7,2115-2121), and can show good cycle stability and rate capability. Na of birnessite structure prepared at presentxMnO2Presence of positive electrode materialThe prepared Birnesselite-Na has obvious defectsxMnO2The content of sodium element in the material is low (x)<0.65)), which limits Birnessite-Na to a large extentxMnO2The capacity of the material is exerted. In addition, consider Birnessite-NaMnO2The conductivity of the material is poor due to the crystal water between the middle layers, and the crystal water is removed in the charging and discharging process and then undergoes side reaction with the electrolyte, so that the Birnessite-NaMnO needs to be removed2Crystal water in (1). Based on the related reports, if Birnessite-Na can be further improvedxMnO2The content of Na in the product is equal to 1 to obtain Birnessite-NaMnO2The Na storage performance of the composite material can be greatly improved, and the influence of crystal water is eliminated. Theoretically, the positive electrode material of the sodium-ion battery has higher capacity, better rate performance and cycling stability, and no relevant research report exists at present.
Disclosure of Invention
The invention aims to provide a monoclinic structure cathode material with high sodium content and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows: the cathode material with the monoclinic structure is NaMnO2-y(OH)2y(I) Or NaMnO2-y-δ(OH)2y(II) having the following structural formulae:
the preparation method of the monoclinic structure cathode material comprises the step of adding Mn3O4The material is subjected to a two-step hydrothermal method and heat treatment in air to obtain NaMnO2-y(OH)2yThe material is subjected to heat treatment under argon to obtain NaMnO containing oxygen vacancies2-y-δ(OH)2yA material. The method comprises the following specific steps:
adding Mn3O4The material is subjected to low-temperature reaction in a high-concentration sodium source water solution for 6-10 h, then subjected to high-temperature reaction in a low-concentration sodium source water solution for 8-12 h, cooled to room temperature, washed and dried in vacuum to obtain NaMnO2-y(OH)2y·nH2O, finally in airObtaining NaMnO with monoclinic structure after conditioning for 2-12 h2-y(OH)2yOr treating in argon for 2-12 h to obtain NaMnO with an oxygen vacancy monoclinic structure2-y-δ(OH)2yAn electrode material.
Preferably, the Mn is3O4The material adopts Mn3O4Powder material or Mn3O4A film material.
More preferably, the Mn is3O4The thin film material is Mn grown on a conductive substrate3O4The film or the nano array, and the conductive substrate material is stainless steel, Ti, Ni, Au and carbon material.
Preferably, the sodium source is selected from NaOH and NaHCO3、NaCl、NaNO3、Na2SO4、Na2CO3And CH3COONa.
Preferably, the molar concentration of sodium in the high-concentration sodium source aqueous solution is 2.0-4.0 mol/L, and the molar concentration of sodium in the low-concentration sodium source aqueous solution is 0.5-1.5 mol/L.
Preferably, the reaction temperature of the low-temperature reaction is 65-90 ℃, and the reaction temperature of the high-temperature reaction is 160-200 ℃.
Preferably, the heat treatment temperature is 200-300 ℃ under the air or argon atmosphere, and the purpose of the treatment under the air or argon atmosphere is to remove NaMnO2-y(OH)2y·nH2Crystal water in the O material improves the conductivity of the material.
NaMnO prepared by the invention2-y-δ(OH)2yThe electrode material has excellent charge and discharge performance and can be used as a positive electrode material of a sodium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method synthesizes Birnessite-NaMnO with high sodium content by a two-step hydrothermal method2-y(OH)2y·nH2O electrode material, have reaction energy consumption advantage such as being lower; (2) adding Birnessite-NaMnO2-y(OH)2y·nH2O material in air or argonAfter heat treatment in the atmosphere, Monoclinic-NaMnO was obtained2-y(OH)2yOr Monoclinic-NaMnO2-y-δ(OH)2yThe multiplying power performance is obviously improved; (3) the method is used for preparing Monoclinic-NaMnO2-y-δ(OH)2yThe capacity, the first coulombic efficiency, the rate capability, the cycling stability and other electrochemical properties of the electrode material show excellent performances.
Drawings
FIG. 1 shows Mn prepared in example 1 of the present invention3O4A/carbon cloth composite material (marked as S1), Birnessite-NaMnO2-y(OH)2y·nH2O/carbon cloth composite (labeled S2) and argon heat treated Monoclinic-NaMnO2-y-δ(OH)2yRaman spectra of the/carbon cloth composite (labeled S3).
FIG. 2 shows Mn prepared in example 1 of the present invention3O4A/carbon cloth composite material (marked as S1), Birnessite-NaMnO2-y(OH)2y·nH2O/carbon cloth composite material (S2) and Monoclinic-NaMnO treated by argon heat treatment2-y-δ(OH)2yX-ray diffraction pattern of the/carbon cloth composite (S3).
FIG. 3 is a Birnessite-NaMnO prepared in example 1 of the present invention2-y(OH)2y·nH2And (3) a field emission scanning electron microscope image of the O/carbon cloth composite material.
FIG. 4 shows Mn prepared in example 1 of the present invention3O4/carbon cloth composite material (S1) and Birnessite-NaMnO2-y(OH)2y·nH2O/carbon cloth composite material (S2) and Monoclinic-NaMnO treated by argon heat treatment2-y-δ(OH)2yAn X-ray photoelectron spectrum of the/carbon cloth composite material (S3).
FIG. 5 is a Birnessite-NaMnO prepared in example 1 of the present invention2-y(OH)2y·nH2O/carbon cloth composite (S2, panel (A)) and Monoclinic-NaMnO treated with argon2-y-δ(OH)2yCharge and discharge curves of the/carbon cloth composite (S3, panel (B)) at 0.2C.
FIG. 6 (A) is Birnessite-NaMnO prepared in example 1 of the present invention2-y(OH)2y·nH2O/carbon cloth composite material (S2) and Monoclinic-NaMnO treated by argon heat treatment2-y-δ(OH)2yA discharge capacity test result graph of the/carbon cloth composite material (S3) under different multiplying factors; FIG. B shows Birnessite-NaMnO prepared in example 1 of the present invention2-y(OH)2y·nH2O/carbon cloth composite material (S2) and Monoclinic-NaMnO treated by argon heat treatment2-y-δ(OH)2yCycling performance profile of the/carbon cloth composite (S3) at 10C.
FIG. 7 is a Monoclinic-NaMnO solution after argon heat treatment in example 1 of the present invention2-y-δ(OH)2yX-ray photoelectron spectroscopy analysis curve of the/carbon cloth composite material (S3).
Detailed Description
The invention is further elucidated with reference to the figures and embodiments. But the content of the invention is not limited thereto.
【Mn3O4Preparation of thin film Material
Placing the conductive substrate in a mixed aqueous solution of manganese salt and inorganic sodium salt, and depositing Mn (OH) on the surface of the conductive substrate in a constant potential mode in situ2Naturally drying the mixture in the air at normal temperature for 12-18 h, washing and then drying the mixture in vacuum to obtain Mn growing on a current collector3O4The constant potential deposition potential of the nanosheet array is-1.30 to-1.85V, the electrodeposition time is 5 to 15min, the ratio of the molar weight of manganese in the manganese salt to the molar weight of sodium in the inorganic sodium salt is 1:1-3, the manganese salt is selected from manganese acetate, manganese nitrate or manganese sulfate, and the inorganic sodium salt is selected from sodium sulfate or sodium nitrate. A current collector is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and a mixed aqueous solution of manganese salt and sodium salt is used as an electrolyte (Xia H, Nanosci. Nanotechnol. Lett.2012,4, 559-.
【Monoclinic-NaMnO2-y(OH)2yElectrochemical Performance testing of electrode materials
Firstly, the Monoclinic-NaMnO prepared by the invention2-y(OH)2yThe powder, superconducting carbon black (Super P) and polyacrylic acid (PAA) are mixed according to the mass ratio of 8: 1:1, dissolving in N-methylpyrrolidone (NMP) after uniform mixing, andcoating on the surface of an aluminum foil, and drying in a vacuum oven at 120 ℃ for 12h to obtain Monoclinic-NaMnO2-y(OH)2yA positive plate; ② the Monoclinic-NaMnO prepared by the invention2-y(OH)2yThe film material can be directly used as a positive electrode. Metallic sodium sheet as negative electrode, 1.0mol/L NaClO4Propylene carbonate as an electrolyte, constituting a half cell in a glove box under an argon atmosphere, and examining Monoclinic-NaMnO of the present invention2-y(OH)2yThe capacity, rate capability, cycling stability and first coulombic efficiency of the electrode material are shown, and the test voltage range is 2.0-4.0V.
Example 1:
0.015mol of manganese acetate and 0.015mol of sodium sulfate are dissolved in 50mL of deionized water, the mixture is rapidly and uniformly stirred, and the water solution is mixed for standby. Carbon cloth is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, a mixed aqueous solution is used as an electrolyte, constant potential deposition is carried out for 10min at-1.8V, natural drying is carried out for 12h in the air at normal temperature, and vacuum drying is carried out after washing to obtain Mn3O4The material is put into a carbon cloth (S1) and then reacts for 8 hours in 3.0mol/L sodium carbonate aqueous solution, and the hydrothermal temperature is 80 ℃; then reacting for 8 hours in 1.0mol/L sodium carbonate aqueous solution, wherein the hydrothermal temperature is 180 ℃; cooling to room temperature, washing and vacuum drying to obtain S2, and treating at 250 deg.C under argon for 2 hr to obtain Monoclinic-NaxMnO2-y-δ(OH)2yThe/carbon cloth composite electrode material (S3). 290, 322 and 374cm marked in FIG. 1-1The peak is corresponding to Mn-O absorption vibration peak of mangano-manganic oxide in S1, 280, 399, 500, 581 and 638cm-1The peak corresponds to MnO in S2 and S36Absorption vibration peak of octahedron; the diffraction peaks of the crystal planes of (101), (112), (103) and (211) marked in FIG. 2 correspond to the diffraction peaks of the crystal of manganomanganic oxide in the S1 sample, and the diffraction peaks of the crystal planes of (001) and (002) are the monoclinic structure Na in the S3 samplexMnO2-y-δ(OH)2yThe crystal diffraction peak of (a) is slightly reduced compared with the spacing of the S2 crystal planes; FIG. 3 is a scanning electron micrograph of the S2 sample, and it can be seen that the S2 sample has a porous structure; FIG. 4 shows the X-ray photoelectron spectra of the S1-S3 samples, from which it can be easily seen that the S1 sample does not contain sodium element, S2 andthe S3 sample is clearly seen to contain sodium element, fig. 5(a) and (B) show the charging and discharging curves of the S2 and S3 samples, respectively, and it can be seen from the graph that the coulombic efficiency of the S3 sample is higher than that of the S2 sample, and the existence of crystal water in the S2 sample causes a large capacity attenuation at the second turn; FIG. 6 shows that the magnification of the S3 sample is significantly higher than that of the S2 sample, which indicates that the S3 sample has better conductivity, and the poor cycling performance of the S2 sample further indicates the adverse effect caused by the crystal water; FIG. 7 shows an X-ray photoelectron spectrum of O1S of the S3 sample, and it can be seen that the S3 sample still has-OH after the crystal water is removed by heat treatment, so that the S3 sample has the structure of the above formula II, whose molecular formula is NaxMnO2-y-δ(OH)2y。
Example 2:
dissolving 0.01mol of manganese nitrate and 0.03mol of sodium nitrate in 50mL of deionized water, quickly and uniformly stirring, and mixing the water solution for later use. Gold foil is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, a mixed aqueous solution is used as an electrolyte, constant potential deposition is carried out for 15min under the condition of-1.35V, natural drying is carried out for 18h in the air at normal temperature, and vacuum drying is carried out after washing to obtain Mn3O4Au, then the material is reacted in 2.5mol/L aqueous solution of sodium hydroxide for 6h, and the hydrothermal temperature is 60 ℃; then reacting in 1.0mol/L sodium hydroxide aqueous solution for 10h, wherein the hydrothermal temperature is 200 ℃; cooling to room temperature, washing, vacuum drying, and treating at 300 deg.C under argon for 3 hr to obtain Monoclinic-NaxMnO2-y-δ(OH)2ythe/Au composite electrode material.
Example 3:
0.02mol of manganese sulfate and 0.01mol of sodium sulfate are dissolved in 50mL of deionized water, quickly and uniformly stirred, and mixed with an aqueous solution for later use. Taking a steel foil as a working electrode, an Ag/AgCl electrode as a reference electrode, a Pt electrode as a counter electrode, taking a mixed aqueous solution as an electrolyte, depositing for 5min at constant potential under-1.85V, naturally drying for 16h in the air at normal temperature, washing, and drying in vacuum to obtain Mn3O4Steel foil, and then reacting the material in 2.5mol/L sodium acetate water solution for 8 hours at the hydrothermal temperature of 80 ℃; then reacting in 0.5mol/L sodium acetate water solutionThe hydrothermal temperature is 160 ℃ for 12 h; cooling to room temperature, washing and vacuum drying, and finally treating in air at 200 ℃ for 4h to obtain Monoclinic-NaxMnO2-y(OH)2ySteel foil composite electrode material.
Example 4:
adding Mn3O4Reacting the powder in 1.0mol/L sodium hydroxide aqueous solution for 8 hours at the hydrothermal temperature of 80 ℃; then reacting in 1.0mol/L sodium acetate water solution for 10h, wherein the hydrothermal temperature is 160 ℃; cooling to room temperature, washing, vacuum drying, and treating at 250 deg.C under argon for 4 hr to obtain Monoclinic-NaxMnO2-y-δ(OH)2yAn electrode material.
Example 5:
adding Mn3O4Reacting the powder in 3.0mol/L sodium hydroxide aqueous solution for 6 hours at the hydrothermal temperature of 80 ℃; then reacting in 1.5mol/L sodium bicarbonate water solution for 12h, wherein the hydrothermal temperature is 180 ℃; cooling to room temperature, washing, vacuum drying, and treating in air at 300 deg.C for 4 hr to obtain Monoclinic-NaxMnO2-y(OH)2yAn electrode material.
【Monoclinic-NaxMnO2-y(OH)2yElectrochemical Performance testing of electrode materials
Monocolic-NaMnO prepared in examples 1-52-y(OH)2yElectrode material as positive electrode, metal sodium sheet as negative electrode, 1.0mol/L NaClO4Propylene carbonate as electrolyte, half cells were constructed in an argon glove box and tested with Monoclinic-NaMnO according to the invention2-y(OH)2yThe capacity, rate capability, cycling stability and first coulombic efficiency of the electrode material are shown, and the test voltage range is 2.0-4.0V.
Table 1 shows Monoclinic-Na prepared in examples 1 to 5 of the present inventionxMnO2-y(OH)2yElectrical property data of the electrode material.
TABLE 1
Table 2 shows the present inventionMonocolic-Na prepared in EXAMPLES 1 to 5xMnO2-y(OH)2yThe molar ratio of the sodium element to the manganese element in the electrode material.
TABLE 2
The preferred embodiments described above are only technical embodiments of the present invention and do not limit the present invention, but it should be apparent to those skilled in the art that the present invention may be variously modified and changed in form and detail without departing from the scope of the present invention claimed in the claims.
Claims (10)
1. The monoclinic structure anode material is characterized in that the anode material is NaMnO2-y(OH)2y(I) The structural formula is as follows:
2. the monoclinic structure anode material is characterized in that the anode material is NaMnO2-y-δ(OH)2y(II) having the formula:
3. the method for preparing a monoclinic structure cathode material according to claim 1, characterized in that the method comprises the following steps:
adding Mn3O4The material is subjected to low-temperature reaction in a high-concentration sodium source water solution for 6-10 h, then subjected to high-temperature reaction in a low-concentration sodium source water solution for 8-12 h, cooled to room temperature, washed and dried in vacuum to obtain NaMnO2-y(OH)2y·nH2O, and finally treating in the air for 2-12 h to obtain NaMnO with a monocline structure2-y(OH)2yAn electrode material.
4. The method for preparing a monoclinic structure cathode material according to claim 2, characterized in that the method comprises the following steps:
adding Mn3O4The material is subjected to low-temperature reaction in a high-concentration sodium source water solution for 6-10 h, then subjected to high-temperature reaction in a low-concentration sodium source water solution for 8-12 h, cooled to room temperature, washed and dried in vacuum to obtain NaMnO2-y(OH)2y·nH2O, and finally treating in argon for 2-12 h to obtain NaMnO with an oxygen vacancy monoclinic structure2-y-δ(OH)2yAn electrode material.
5. The method according to claim 3 or 4, wherein Mn is present3O4The material adopts Mn3O4Powder material or Mn3O4A film material; wherein Mn is3O4The thin film material is Mn grown on a conductive substrate3O4The film or the nano array, and the conductive substrate material is stainless steel, Ti, Ni, Au and carbon material.
6. The process of claim 3 or 4, wherein the sodium source is selected from NaOH and NaHCO3、NaCl、NaNO3、Na2SO4、Na2CO3And CH3COONa.
7. The method according to claim 3 or 4, wherein the molar concentration of sodium in the high-concentration sodium source aqueous solution is 2.0 to 4.0mol/L, and the molar concentration of sodium in the low-concentration sodium source aqueous solution is 0.5 to 1.5 mol/L.
8. The method according to claim 3 or 4, wherein the reaction temperature of the low-temperature reaction is 65 to 90 ℃ and the reaction temperature of the high-temperature reaction is 160 to 200 ℃.
9. The method according to claim 3 or 4, wherein the temperature of the heat treatment in the air atmosphere is 200-300 ℃; the heat treatment temperature under the argon atmosphere is 200-300 ℃.
10. Use of the monoclinic structure positive electrode material as defined in claim 1 or 2 as a positive electrode material for a sodium-ion battery.
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