CN1905251A - Mg secondary cell - Google Patents

Mg secondary cell Download PDF

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CN1905251A
CN1905251A CNA2006100132330A CN200610013233A CN1905251A CN 1905251 A CN1905251 A CN 1905251A CN A2006100132330 A CNA2006100132330 A CN A2006100132330A CN 200610013233 A CN200610013233 A CN 200610013233A CN 1905251 A CN1905251 A CN 1905251A
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barium oxide
secondary cell
oxide nanotube
ethyl alcohol
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焦丽芳
袁华堂
王一菁
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Nankai University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • 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
    • 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
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Abstract

The invention relates to an Mg secondary cell, comprising vanadium oxide nanotube or molybdenum oxide active material as anode, Mg as cathode, Mg(AlBu2Cl2)2 as electrolyte and diaphragm celgard 2300, where the nanotube comprises metallic cation-doped vanadium oxide nanotube, the doping metallic cations account for 10 mol%-30 mol% of the vanadium oxide, and the doping metallic cations are copper or silver ions. And it has higher initial discharge specific capacity and powerful discharge property. And it has advantages of low price and good safety and as a power battery, has great application and development prospects.

Description

Mg secondary cell
Technical field
The invention belongs to Mg secondary cell, it is the Mg secondary cell of positive electrode active materials with the oxide of barium oxide nanotube, doped vanadium oxide nanotube and molybdenum.
Background technology
Novel energy-storing system such as secondary cell are widely used on electric vehicle and other equipment.Electrochemical research mainly concentrates on the lithium secondary battery at present.But consider that magnesium metal has: ABUNDANT NATUREAL RESOURSES; Lower capacity equivalent (as: Mg:12g/F, Li:7g/F, Na:23g/F); Low relatively price and security performance advantages of higher make magnesium metal promise to be novel secondary battery cathode material [T.D.Gregory, R.J.Hoffman, and R.C.Winterton, J.Electrochem.Soc., 1990,137:775-780; L.P.Lossius, and F.Emmenegger, Electrochim Acta, 1996,41:445.].
The operation principle that with the magnesium metal is the Mg secondary cell of negative pole is: 1. during battery charge, and Mg 2+Take off embedding from embedding positive electrode, on negative pole with Mg 0Form is deposited on negative terminal surface; 2. during battery discharge, Mg 2+Move to positive pole by electrolyte and be embedded into the positive electrode from negative pole dissolving.Therefore positive electrode plays important effect in the entire cell system, and to the requirement of positive electrode mainly be: 1. at first positive electrode has the invertibity of embedding magnesium; 2. can reach relative higher voltage; 3. has higher specific capacity.Much point out because Mg about the report of the positive electrode that can embed magnesium ion 2+Have strong solvation character and make Mg 2+It is slower to be embedded into the speed that can embed positive electrode, thereby improves Mg 2+Migration velocity in positive electrode is necessary [P.Nov á k, W.Scheifele, and O.Haas, J.Power Sources1995,54:479; M.E.Spahr:Ph.D.Thesis No.12281, ETH Zurich, Switzerland, 1997.].
The research of positive electrode is carried out more extensive, mainly concentrates on transient metal sulfide, oxide, boride and vanadate etc., and wherein oxide is a kind of just widely used anode electrode material.Strong oxygen metallic bond in oxide makes to have high ionic feature in the transition metal oxide, make compound have high energy of oxidation and make battery have high current potential [C.Delmas, (Ed.), Lithium Batteries.New Materials, Developments and Perspectives, Elsevier, Amsterdam, 1994, p.457.].In addition, oxide has higher chemical stability than sulfide.For hope the battery in long life-span is arranged, the electrode material that stability is good is desirable.People such as Spahr only think that the oxide material based on vanadium and molybdenum is that the positive pole of Mg secondary cell just can show specific capacity and cyclic reversibility [M.E.Spahr, P.Nov á k, O.Haas, R.Nesper, J.Power Sources, 1995,54:346.] preferably.The Pereira-Ramos report is pointed out V 2O 5During as rechargeable magnesium cell anodal, in the dimethyl sulfone or sulfolane of 150 ℃ of thawings, with Mg (ClO 4) 2Be electrolyte Mg 2+Be embedded into V 2O 5Example, (0.1mA/cm under low current density 2) discharge, best result generates Mg 0.5V 2O 5, its charging and discharging currents density is less, thereby has limited its application [J.P.Pereira-Ramos, R.Messina, J.Perichon, J.Electroanal.Chem., 1987,218:241.] in the high current charge-discharge electrokinetic cell.
Along with the development of nanometer technology, increasing novel nano-material emerges in recent years.Nano material intrinsic big specific area, it has small scale structures, magnesium ion embeds that the degree of depth is little, stroke short, produces effective electric transmission, is a kind of embedding of magnesium ion and the ideal basis material of deviating from.And nano tube structure has bigger interlamellar spacing owing to it, and bigger bore and external diameter etc. help the structure that magnesium ion embeds.This structure is highly beneficial to the telescopiny of magnesium ion: 1. the diffusion distance in electrode interior shortens; 2. the kinetic property that is diffused into the main body phase from electrode surface improves, and makes the diffusion velocity of ion accelerate; 3. in tube chamber, can store electrolyte, thereby accelerate the speed that ion is moved to electrode surface.It is different that the method and CN03125385.7 openly prepare the method for doped vanadium oxide nanotube, and doped vanadium oxide nanotube and the bar-shaped MoO of micron order 3Do not appear in the newspapers as magnesium cell anode material.
Summary of the invention
The purpose of this invention is to provide a kind of Mg secondary cell, battery of the present invention has higher initial discharge specific capacity and high-rate discharge ability.Advantages such as the present invention has low price, and fail safe is good as electrokinetic cell, have great application and DEVELOPMENT PROSPECT.
Mg secondary cell provided by the invention is that the oxide active material with barium oxide nanotube or molybdenum is a positive pole, and magnesium is negative pole, Mg (AlBu 2Cl 2) 2Constitute as electrolyte solution and barrier film.
Described barium oxide nanotube comprises metal cation doped vanadium oxide nanotube, and the cationic amount of doping metals is the 10mol%～30mol% of barium oxide.Wherein preferably be doped to copper, silver.
Barium oxide nanotube of the present invention has typical layer structure, nanometer pipe range 1-3 μ m, and internal diameter 15-40nm, external diameter 60-100nm, and be opening, interlamellar spacing is about 3.5nm.
The preparation method of barium oxide nanotube of the present invention is as follows:
1) with mol ratio 1: 1V 2O 5Stir 2h with octadecylamine in absolute ethyl alcohol, add 3 times of water to absolute ethyl alcohol again and continue to stir 48h, mixture is transferred in the stainless steel cauldron of polytetrafluoroethylsubstrate substrate, at 180 ℃ of isothermal reaction 7d;
2) through absolute ethyl alcohol, the n-hexane cyclic washing is removed unreacted amine, and 70 ℃ of dry 6h in vacuum drying chamber get the black product and (can be expressed as: VO x-NTs).
The barium oxide nanotube of doping metals of the present invention has typical layer structure, and its preparation method is as follows:
1) under the water cooling (room temperature), polycrystalline V 2O 5With 10% H 2O 2(V 2O 5With 10% H 2O 2By weight/volume be 1: 100) stirring reaction 2h, in an about week of solution left standstill, produce thick reddish black V 2O 5Hydrogel.
2) with V 2O 5Hydrogel and doping metals Cu powder or Ag powder mixed, doping is the 10mol%～30mol% of barium oxide, it is oxidized fully constantly to be stirred to metal powder, the precursor that preparation is mixed (can be expressed as: M yV 2O 5NH 2O, M=Cu or Ag).
3) precursor (M of Can Zaing yV 2O 5NH 2O) with octadecane amine, according to V/ amine=(mol ratio) was dissolved in the acetone soln in 2: 1, stir 16h, mixture is transferred in the stainless steel cauldron of polytetrafluoroethylsubstrate substrate, reaction 7d obtains the black product under 180 ℃, and product successively passes through H 2O, absolute ethyl alcohol, the unreacted amine of cyclohexane cyclic washing, product in vacuum drying chamber in 70 ℃ of dry 1d.Get the barium oxide nanotube of doping metals.
The barium oxide nanotube that can obtain copper doped of the present invention, silver metal as stated above (can be expressed as: Cu y-dopedVO x-NTs, Ag y-doped VO x-NTs, M yVO x-NTs, M=Cu, Ag; Y=0.1,0.2,0.3).
The bar-shaped MoO of micron order of the present invention 3With lamelliform MoO 3The novel preparation method step respectively as follows:
The bar-shaped MoO of micron order 3:
With para-molybdic acid ammonia (NH 4) 6Mo 7O 244H 2The O solid is dissolved in the water, adds 28% ammoniacal liquor simultaneously, and the w/v of para-molybdic acid ammonia and ammoniacal liquor 5: 1 gets colourless transparent solution; The pH value of the spirit of vinegar regulator solution with 36% is 3.5, leave standstill 24h after, with absolute ethyl alcohol cyclic washing white precipitate product, remove and anhydrate; In 60 ℃ of dry 12h, the products therefrom note is done: MC in vacuum drying chamber.With drying is good precipitation respectively under 300 ℃ and 600 ℃ in tube furnace sintering, the bar-shaped MoO of the micron order that obtains 3, note is done respectively: M30 and M60.
Lamelliform MoO 3:
1) uses 3M HCl acidifying 1M Na down at 100 ℃ 2MoO 4Solution produces yellow MoO 32H 2O;
2) by 2: 1 molar ratio ingredient with MoO 32H 2O and octadecylamine are dissolved in the absolute ethyl alcohol, stir 2h under the room temperature;
3) in mixed solution, add H 2O, at room temperature stir 48h after, become white precipitate;
4) mixture is transferred in the stainless steel cauldron of polytetrafluoroethylsubstrate substrate 120 ℃ of following hydro-thermal reactions 5 days.After filtration, obtain the lamelliform MoO that white product promptly comprises template behind absolute ethyl alcohol and the ether cyclic washing 3Note is done: MoO 3-Temp.
Since magnesium divalent ion electric charge height, and radius is little, and so polarization is very strong, common and solvent embeds in the positive electrode altogether, so Mg 2+Migration velocity in positive electrode is than Li +Slowly, the selection of feasible can the embedding-Tuo embedding host material is restricted.The transition metal oxide of the present invention preparation shows superior chemical property with respect to the corresponding oxide of polycrystalline attitude as the positive electrode of Mg secondary cell.Electrochemistry experiment proves that this nano metal oxide materials helps quick embedding magnesium, improved the limitation that positive electrode in the past is subjected to the magnesium ion diffusion control.Therefore, nano metal oxide materials is used for Mg secondary cell can significantly improve its chemical property, and vast potential for future development and range of application are arranged.
The present invention be with the preparation nano material be positive electrode, magnesium metal is a negative pole, alkyl magnesium aluminium complex Mg (AlBu 2Cl 2) 2Be electrolyte.Adopt computer-controlled battery test system to carry out electrochemical property test.
The present invention has effectively improved specific discharge capacity, the high-rate discharge ability of battery, and the application of nano-metal-oxide positive electrode active materials has promoted the application of Mg secondary cell greatly.This battery system has can discharge and recharge balance, opening voltage about 1.2V, low price, fail safe is good, as electrokinetic cell, has great development and application prospect.
Description of drawings
The scanning electron microscope analysis of Fig. 1 barium oxide nanotube.
The TEM (transmission electron microscope) analysis of Fig. 2 barium oxide nanotube.
The cyclic voltammetry curve of Fig. 3 barium oxide nanotube the last fortnight.
The initial discharge capacity curve of Fig. 4 barium oxide nanotube under different discharge current densities.
Fig. 5 Cu 0.1-doped VO xThe initial discharge capacity curve of-NTs under different discharge current densities.
Fig. 6 Ag y-doped VO xThe initial discharge capacity curve of-NTs (y=0.1,0.2,0.3) under the 5mA/g discharge current density.
The bar-shaped MoO of Fig. 7 micron order 3TEM (transmission electron microscope) analysis.
Fig. 8 lamelliform MoO 3TEM (transmission electron microscope) analysis.
Fig. 9 lamelliform MoO 3The interlamellar spacing chart.
Figure 10 different shape MoO 3The initial discharge capacity curve.
Embodiment
Embodiment 1: the preparation of barium oxide nanotube and electrochemical property test thereof
The preparation of barium oxide nanotube
V with 10mmol 2O 5(the A.R. level Fluka) adds 5ml absolute ethyl alcohol and stirring 2h to the octadecylamine of (A.R. level) and 10mmol; And then adding 15ml deionized water continues to stir 48h; Mixture is transferred in the stainless steel cauldron of polytetrafluoroethylsubstrate substrate, at 180 ℃ of isothermal reaction 7d; Pass through absolute ethyl alcohol at last, the n-hexane cyclic washing, 70 ℃ of dry 6h in vacuum drying chamber get black product (VO x-NTs), productive rate＞90%.
(note is done: Cu for copper, silver-colored doped vanadium oxide nanotube y-doped VO x-NTs, Ag y-doped VO x-NTs) preparation:
Under constantly stirring with polycrystalline V 2O 5(1g) join the H of 100ml 10% 2O 2In, the vessel water cooling, behind the solution stir about 2h, O 2Slowly stop to emit, color becomes orange-yellow; With orange-yellow one week of solution left standstill, the cohesion of the gel of rufous has produced thick reddish black hydrogel and (can be expressed as: V 2O 5NH 2O).
With the V for preparing previously 2O 5Hydrogel add respectively the Cu powder of 1mmol, 2mmol and 3mmol or Ag powder mixed after, it is oxidized fully constantly to be stirred to Cu or Ag, the precursor (M that preparation is mixed yV 2O 5NH 2O, M=Cu or Ag).
The acetone soln that adds octadecane amine then respectively according to V/ amine=2: 1 (mol ratio), the green mixture continuous stirring 16h that obtains.At last mixture is transferred in the autoclave, reaction 7d obtains the black product under 180 ℃.This black product successively passes through H 2O, absolute ethyl alcohol, the unreacted amine of cyclohexane cyclic washing, end product in vacuum drying chamber in 70 ℃ of dry 1d.Obtain the barium oxide nanotube of doped with Cu, Ag, analyze the metal element content of doping through inductively coupled plasma atomic emission spectrum.[its structure can be expressed as: M yVO x-NTs (M=Cu or Ag; Y=0.1,0.2,0.3)].
Pattern to the barium oxide nanotube of above-mentioned preparation has carried out scanning electron microscope analysis.Accompanying drawing 1 is the SEM electromicroscopic photograph of barium oxide nanotube of preparation, and the result shows that the black product that obtains mainly is made up of the barium oxide nanotube, illustrates that to prepare the productive rate of barium oxide nanotube with the method higher.Accompanying drawing 2 is TEM electromicroscopic photographs of barium oxide nanotube, and TEM result shows that the black product mainly is made up of the barium oxide nanotube, has typical layer assembling structure.Nanometer pipe range 1-3 μ m, internal diameter 15-40nm, external diameter 60-100nm, and be opening, interlamellar spacing is about about 3.5nm.Product has special anisotropic structure, can provide better embedding magnesium position on more embedded space and the thermodynamics for magnesium ion, as nanometer tube chamber, tube wall VO xInterlayer etc.In addition, nanotube VO xInterlamellar spacing is with respect to V 2O 5Obviously increase, the result forms orderly " accurate layer structure ", and the active force of interlayer is very weak, therefore, and Mg 2+Easier embedding and deviating from.
The barium oxide nanotube of the present invention's preparation is used for positive electrode material of secondary Mg battery, adopts to be assembled into simulated battery, and the cyclic voltammetric of material adopts three-electrode system, and anode pole piece is by active material VO x-NTs, acetylene black and binding agent (PTFE) by mass ratio are: 50: 37.5: 12.5 mixed pressuring plates, and negative pole is the magnesium sheet of polishing light, and reference electrode is the Mg band, and electrolyte is the Mg (AlBu of homemade 0.25M 2Cl 2) 2/ THF.Barrier film is: celgard 2300.In being full of the glove box of high-purity argon gas, the content of water assembles three-electrode battery less than 5ppm.
Mg (AlBu 2Cl 2) 2The preparation method of/THF: getting the cyclohexane solution of dibutyl magnesium, is 2: 1 required anhydrous Aluminum chlorides of adding in molar ratio, stirring at normal temperature 48 hours.The upper strata is a yellow-green soln, separates out the milky crystal, and decant goes out supernatant liquor.Under nitrogen protection, be spin-dried for remaining solvent, and with the sample drying of gained.The anhydrous tetrahydro furan dissolving that dropping is handled well, and the electrolyte solution of preparation desired concn [D.Aurbach, Z.Lu, A.Schecher, Y.Gofer, H.Gizbar, R.Turgeman, Y.Cohen, M.Moshkovich, E.Levi, Nature 2000,407:724; D.Aurbach, A.Schecher, M.shkovich, Y.Cohen, J.Electrochem.Soc.2001,178:A1004.].
From accompanying drawing 3 as can be seen, a pair of redox peak there is first week.The electrochemistry insertion reaction of magnesium ion in nanotube in the reduction peak correspondence that the about 0.9V of current potential (vsMg) occurs; The oxidation peak that occurs about the about 1.2V of current potential is reacted from the embedding of taking off in the nanotube corresponding to magnesium ion.This process can be represented with following reaction equation:
We are to the simulated battery Mg|0.25M Mg (AlBu of assembling 2Cl 2) 2/ THF|VO x-NTs battery carries out discharge test under different current densities, test result is seen accompanying drawing 4.Discharge capacity first and cycle performance that the battery low current density discharges down are all bad, and battery table reveals higher first discharge specific capacity and better cycle performance under bigger current density.Simulated battery carries out reversible discharging and recharging, and cycle life can reach more than 50 times.The barium oxide nanotube positive electrode active materials of the present invention's preparation shows superior chemical property.
Embodiment 2:Cu 0.1-doped VO xThe chemical property of-NTs
We press the Cu of the assembled battery condition of embodiment 1 with embodiment 1 preparation 0.1Doped vanadium oxide nanotube active material is assembled into simulated battery and tests under different discharge current densities.As can be seen, curved line relation shows that initial discharge capacity is the highest when battery discharges under with the 10mA/g current density in the accompanying drawing 5, and cycle efficieny is also better.And the cycle performance of unadulterated barium oxide nanotube when current density 5mA/g is best, and initial discharge capacity also has only 81mAh/g, the nanotube Cu after the doping 0.1-doped VO xThe capacity of-NTs when big discharge current density 10mA/g can reach 120.2mAh/g.The barium oxide nanotube is described after mixing, cycle performance and heavy-current discharge performance all make moderate progress and improve.Simulated battery carries out reversible discharging and recharging, and cycle life can reach more than 50 times.
Embodiment 3:Ag y-doped VO xThe chemical property of-NTs (y=0.1,0.2,0.3)
We press the Ag of the assembled battery condition of embodiment 1 with embodiment 1 preparation y-doped VO x-NTs (y=0.1,0.2,0.3) active material is assembled into simulated battery and tests under the 5mA/g discharge current density.Accompanying drawing 6 is barium oxide nanotube initial discharge capacity curve (A1:Ag under the 5mA/g discharge current density of different doping Ag tenors 0.1-dopedVO x-NTs, A2:Ag 0.2-doped VO x-NTs, A3:Ag 0.3-doped VO x-NTs), as can be seen when Ag doping percentage composition is the 20mol% of barium oxide, simulated battery initial discharge specific capacity is the highest, reaches 108.4mAh/g from curve.
Embodiment 4: different shape MoO 3Preparation and electrochemical property test
The bar-shaped MoO of micron order 3Preparation:
With 5g para-molybdic acid ammonia (NH 4) 6Mo 7O 244H 2The O solid is dissolved in the 250m1 deionized water, adds less ammonia (about 1ml) simultaneously and gets colourless transparent solution; The pH value of the spirit of vinegar regulator solution with 36% is 3.5, leave standstill 24h after, in order to prevent reunion,, remove and anhydrate with absolute ethyl alcohol cyclic washing white precipitate product in follow-up thermal dehydration step; Make ethanol molecule replace hydrone as far as possible.Because the surface tension of ethanol molecule is much smaller than H 2The O molecule is sloughed at low temperature in dry run easily.In 60 ℃ of dry 12h, the products therefrom note is done: MC in vacuum drying chamber.With drying is good precipitation respectively under 300 ℃ and 600 ℃ in tube furnace sintering, the bar-shaped MoO of the micron order that obtains 3Note is done respectively: M30 and M60.
Lamelliform MoO 3Preparation:
1) MoO 3.2H 2The preparation of O: use 3M HCl acidifying 1M Na down at 100 ℃ 2MoO 4Solution produces yellow MoO 32H 2O;
2) with 10mmol MoO 32H 2O and 5mmol octadecylamine are dissolved in the 5ml absolute ethyl alcohol, stir 2h under the room temperature;
3) in mixed solution, add 15ml distilled water H 2O becomes white precipitate after yellow suspension-turbid liquid at room temperature stirs 48h;
4) at last mixture is transferred in the reactor 120 ℃ of following hydro-thermal reactions 5 days.After filtration, obtain the lamelliform MoO that white product promptly comprises template behind absolute ethyl alcohol and the ether cyclic washing 3Note is done: MoO 3-Temp.
The present invention relates to a kind of easy, quick, prepare α-MoO in enormous quantities 3Method.α-the MoO of preparation in the accompanying drawing 7 3For bar-shaped, length 2-5 μ m does not wait.Accompanying drawing 8 is lamelliform MoO 3The TEM photo of-Temp, this compound has layer structure.Chart by the interlamellar spacing of Fig. 9, from Fig. 9, can calculate interlamellar spacing and be about 3.5nm, and the radius of monovalence magnesium ion is 0.082nm that the radius of divalence magnesium ion is 0.062nm, this material has bigger interlamellar spacing, thereby this structure helps the embedding of magnesium and deviates from.
Press the micron order bar-shaped MoO of the assembled battery condition of embodiment 1 with embodiment 4 preparations 3, lamelliform MoO 3And commercially available polycrystalline MoO 3Be assembled into simulated battery initial discharge performance (accompanying drawing 10) under with the 20mA/g discharge current density as positive electrode active materials, discharge capacity is closed and is first as can be seen: lamelliform MoO 3-Temp (81mAhg -1The bar-shaped MoO of)＞micron order 3(70.4mAhg -1)＞polycrystalline MoO 3(56.5mAhg -1).Simulated battery carries out reversible discharging and recharging, and cycle life can reach more than 50 times.The present invention has tentatively inquired into the structure of material and the relation between the chemical property, thinks that the material of porous, stratiform, tubular structure helps the embedding of magnesium and deviates from.

Claims (7)

1, a kind of Mg secondary cell is characterized in that it is that oxide active material with barium oxide nanotube or molybdenum is a positive pole, and magnesium is negative pole, Mg (AlBu 2Cl 2) 2Constitute as electrolyte solution and barrier film; Described barium oxide nanotube has typical layer structure, nanometer pipe range 1-3 μ m, and internal diameter 15-40nm, external diameter 60-100nm, and be opening, interlamellar spacing is about 3.5nm; The oxide of described molybdenum is the bar-shaped MoO of micron order 3Or lamelliform MoO 3
2, according to the described Mg secondary cell of claim 1, it is characterized in that described barium oxide nanotube comprises metal cation doped vanadium oxide nanotube, the cationic amount of doping metals is 10～30% of a barium oxide mole.
3,, it is characterized in that the preparation method of described barium oxide nanotube comprises the steps: according to the described Mg secondary cell of claim 1
1) with mol ratio 1: 1V 2O 5Stir 2h with octadecylamine in absolute ethyl alcohol, add 3 times of water to absolute ethyl alcohol again and continue to stir 48h, mixture is transferred in the stainless steel cauldron of polytetrafluoroethylsubstrate substrate, at 180 ℃ of isothermal reaction 7d;
2) through absolute ethyl alcohol, the n-hexane cyclic washing is removed unreacted amine, and 70 ℃ of dry 6h in vacuum drying chamber get the black product.
4,, it is characterized in that the preparation method of barium oxide nanotube of described doping metals is as follows according to the described Mg secondary cell of claim 2:
1) under the room temperature water cooling, polycrystalline V 2O 5With 10% H 2O 2Stirring reaction 2h in an about week of solution left standstill, produces thick reddish black hydrogel;
2) with V 2O 5Hydrogel and doping metals Cu powder or Ag powder are mixed, and it is oxidized fully constantly to be stirred to metal powder, the precursor of preparation doped with Cu or Ag; Doping is 10～30mol% of barium oxide;
3) precursor of Can Zaing and octadecane amine according to mol ratio V/ amine=2: 1, are dissolved in the acetone soln, stir 16h, mixture are transferred in the stainless steel cauldron of polytetrafluoroethylsubstrate substrate, in 180 ℃ of reaction 7d down, obtain the black product, and product successively passes through H 2O, absolute ethyl alcohol, the unreacted amine of cyclohexane cyclic washing, product in vacuum drying chamber in 70 ℃ of dry 1d.Get the barium oxide nanotube of doping metals.
5,, it is characterized in that V in preparation method's step 1) of barium oxide nanotube of described doping metals according to the described Mg secondary cell of claim 5 2O 5With 10% H 2O 2By weight/volume be 1: 100.
6,, it is characterized in that the bar-shaped MoO of described micron order according to the described Mg secondary cell of claim 1 3Preparation method's step as follows: with para-molybdic acid ammonia (NH 4) 6Mo 7O 244H 2The O solid is dissolved in the water, adds 28% ammoniacal liquor simultaneously, and the w/v of para-molybdic acid ammonia and ammoniacal liquor 5: 1 gets colourless transparent solution; The pH value of the spirit of vinegar regulator solution with 36% is 3.5, leave standstill 24h after, with absolute ethyl alcohol cyclic washing white precipitate product, remove and anhydrate; In vacuum drying chamber in 60 ℃ of dry 12h, with drying is good precipitation respectively under 300 ℃ and 600 ℃ in tube furnace sintering, the bar-shaped MoO of the micron order that obtains 3
7,, it is characterized in that described lamelliform MoO according to the described Mg secondary cell of claim 1 3Preparation method's step as follows:
1) uses 3M HCl acidifying 1M Na down at 100 ℃ 2MoO 4Solution produces yellow MoO 32H 2O;
2) by 2: 1 molar ratio ingredient with MoO 32H 2O and octadecylamine are dissolved in the absolute ethyl alcohol, stir 2h under the room temperature;
3) in mixed solution, add H 2O, at room temperature stir 48h after, become white precipitate;
4) mixture is transferred in the stainless steel cauldron of polytetrafluoroethylsubstrate substrate 120 ℃ of following hydro-thermal reactions 5 days, after filtration, the product that obtains white behind absolute ethyl alcohol and the ether cyclic washing promptly comprises the lamelliform MoO of template 3
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CN101217194B (en) * 2007-12-27 2010-06-23 上海交通大学 A magnesium secondary battery anode material and the corresponding preparation method
CN102064323A (en) * 2010-12-09 2011-05-18 中国人民武装警察部队医学院 Mesoporous vanadium dioxide nano strip material as well as preparation method and application thereof
CN102478200A (en) * 2010-11-25 2012-05-30 西安中科麦特电子技术设备有限公司 Solar energy storage streetlamp
CN101689680B (en) * 2007-07-11 2012-08-22 索尼公司 Magnesium ion-containing nonaqueous electrolyte, process for producing the nonaqueous electrolyte, and electrochemical device
CN101997107B (en) * 2009-08-11 2012-12-26 中国电子科技集团公司第十八研究所 Magnesium electrode for magnesium battery and preparation method thereof
CN103400974A (en) * 2013-08-09 2013-11-20 重庆大学 Application of vanadium oxide in serving as magnesium secondary battery cathode material and sol-gel preparation method thereof
CN109638257A (en) * 2018-12-18 2019-04-16 中科廊坊过程工程研究院 A kind of compound vanadic anhydride based material and its preparation method and application
CN110078121A (en) * 2019-05-21 2019-08-02 上海交通大学 A kind of preparation method and application of Magnesium ion battery vanadic anhydride positive electrode

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101689680B (en) * 2007-07-11 2012-08-22 索尼公司 Magnesium ion-containing nonaqueous electrolyte, process for producing the nonaqueous electrolyte, and electrochemical device
CN101217194B (en) * 2007-12-27 2010-06-23 上海交通大学 A magnesium secondary battery anode material and the corresponding preparation method
CN101997107B (en) * 2009-08-11 2012-12-26 中国电子科技集团公司第十八研究所 Magnesium electrode for magnesium battery and preparation method thereof
CN102478200A (en) * 2010-11-25 2012-05-30 西安中科麦特电子技术设备有限公司 Solar energy storage streetlamp
CN102064323A (en) * 2010-12-09 2011-05-18 中国人民武装警察部队医学院 Mesoporous vanadium dioxide nano strip material as well as preparation method and application thereof
CN102064323B (en) * 2010-12-09 2012-09-19 中国人民武装警察部队后勤学院 Mesoporous vanadium dioxide nano strip material as well as preparation method and application thereof
CN103400974A (en) * 2013-08-09 2013-11-20 重庆大学 Application of vanadium oxide in serving as magnesium secondary battery cathode material and sol-gel preparation method thereof
CN103400974B (en) * 2013-08-09 2016-01-06 重庆大学 Vanadium system oxide makes application and the sol-gel process for preparing thereof of magnesium secondary battery cathode material
CN109638257A (en) * 2018-12-18 2019-04-16 中科廊坊过程工程研究院 A kind of compound vanadic anhydride based material and its preparation method and application
CN110078121A (en) * 2019-05-21 2019-08-02 上海交通大学 A kind of preparation method and application of Magnesium ion battery vanadic anhydride positive electrode

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