CN101320806A - Preparation method for anode material manganese magnesium silicate of rechargeable magnesium cell - Google Patents

Preparation method for anode material manganese magnesium silicate of rechargeable magnesium cell Download PDF

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CN101320806A
CN101320806A CNA2008100404620A CN200810040462A CN101320806A CN 101320806 A CN101320806 A CN 101320806A CN A2008100404620 A CNA2008100404620 A CN A2008100404620A CN 200810040462 A CN200810040462 A CN 200810040462A CN 101320806 A CN101320806 A CN 101320806A
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magnesium
manganese
preparation
rechargeable
anode material
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CN100583511C (en
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努丽燕娜
杨军
冯真真
李云
王久林
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Shanghai Jiaotong 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
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a production method for manganous/magnesium silicate of chargeable magnesium battery positive pole material, which is the manganous/magnesium silicate of chargeable magnesium battery positive pole material using molten salts as reaction medium and having the characteristics of quickening up reaction speed, shortening reaction cycle, simplifying synthesis course, reducing synthesis cost, small synthesis particle size and symmetrical distribution of the particles. The material exhibits remarkable electrochemical charge and discharge effects, the steady discharge platform works up to 1.6V and 1.1V(vs.Mg/Mg<2+>); on the charge and discharge conditions of C/20 current density, the discharge capacitance can reach 289.3mAh*g<-1>(theoretical capacitance is 92%). In contrast to the relatively ideal positive pole material Mo3S4 of the current chargeable magnesium battery, the manganous/magnesium silicate positive pole material produced by the molten salt process has the advantages of simple production, large capacitance, high discharge voltage platform and the like.

Description

A kind of preparation method of anode material manganese magnesium silicate of rechargeable magnesium cell
Technical field
The present invention relates to a kind of preparation method's of battery electrode material, particularly a kind of anode material manganese magnesium silicate of rechargeable magnesium cell preparation method.
Background technology
Along with the continuous attention of people, press for research and development high-performance, Green Chemistry power supply cheaply to the energy, resource and environmental area.Magnesium is a kind of ripple of living, is in the II group family metal of diagonal positions with lithium that in the periodic table of elements theoretical specific capacity is (2205mAhg greatly -1).Compare with lithium, cheap (be about lithium 1/24) of magnesium, environmental friendliness, fusing point height (649 ℃), easy processed, safe, therefore the rechargeable magnesium cell of making negative pole with magnesium is a kind of chemical power source that good prospect is arranged, though it can not be competed with the lithium battery that is applied to small scale (as portable electronic instrument), but aspect the big load purposes potential advantages are being arranged, be considered to be expected to be applicable to very much a kind of green storage battery (the Prototype systems for rechargeablemagnesium batteries of electric automobile, Nature, 2000,407:724).
With respect to Li +, Mg 2+Ionic radius little, charge density is big, solvation is even more serious, therefore people are in the embedding that numerous secondary cells are used/take off in the embedding investigation of materials, finding can be less as the positive electrode of rechargeable magnesium cell, mainly contain (Magnesium insertion electrodes for rechargeable nonaqueousbatteries-a competitive alternative to lithium, Electrochimica Acta, 1999,45:351): MoO 3, Co 3O 4, V 2O 5And MV 3O 8(H 2O) y(M=Li, Na, K, Ca 0.5Or Mg 0.5) vanadate, the oxide of spinel-type, the Mg of Todorokite type xMnO 2YH 2The Mg of O, Nasicon structure 0.5Ti 2(PO 4) 3And Mg 0.5+y(Fe yTi 1-y) 2(PO 4) 3, the Cheverel phase Mo 3S 4, monocline MgV 2O 6(renewable magnesium ion cell positive material MgV 2O 6Preparation and Electrochemical Properties thereof, electrochemistry, 2004,10:460), MgTi 2O 5(rechargeable magnesium cell anode material MgTi 2O 5Research, Nankai University's journal (natural science edition), 2006,39:39).Wherein, Mo 3S 4Be desirable material (Prototype systems for rechargeable magnesium batteries comparatively at present, Nature, 2000,407:724), in a series of non-aqueous electrolytic solutions, magnesium ion can insert/take off the embedding electrochemical reaction quickly, and theoretical discharge capacity can reach 122mAhg -1, the actual discharge capacity is 100mAhg -1About, discharge voltage plateau has two, respectively at 1.2V and 1.0V (vs.Mg/Mg 2+) about.But it is relatively poor that the major defect of sulfide is a non-oxidizability, and Mo 3S 4Preparation condition relatively harsh, need under vacuum or argon gas atmosphere, synthesize (A short review on the comparison between Li battery systems andrechargeable magnesium battery technology by high temperature, J.Power Sources, 2001,97～98:28).The manganous silicate magnesium that this seminar obtains the modification sol-gel method is as rechargeable magnesium cell anode material (a kind of Mg secondary cell positive electrode and preparation method thereof, Chinese patent, application number: 200710173280.6), obtained certain effect, the stable discharging platform reaches 1.6V (vs.Mg/Mg 2+), little electric current discharges and recharges that discharge capacity can reach 243.9mAhg under the condition (C/100) -1(theoretical capacity 78%).
Summary of the invention
The objective of the invention is to propose a kind of preparation method of anode material manganese magnesium silicate of rechargeable magnesium cell, this method is as reaction medium with fused salt, but fast reaction speed, shorten reaction time, simplify building-up process, reduce synthetic cost, synthetic particle diameter is little, the anode material manganese magnesium silicate of rechargeable magnesium cell of even particle distribution, thereby improves the performance of rechargeable magnesium cell.
The preparation method of a kind of anode material manganese magnesium silicate of rechargeable magnesium cell of the present invention is as follows:
The nano silicon of the magnesium source of 1～10 mole fused salt and 1 mole, 1 mole manganese salt and 1 mole ground 30 minutes in agate mortar after; put into the corundum boat; 80～120 ℃ of following vacuumizes 12～48 hours; first 300～600 ℃ of heat treatments 1～3 hour under the protective atmosphere condition then; further 700～1000 ℃ of heat treatments 5～8 hours; naturally cool to room temperature at last, obtain a kind of rechargeable magnesium cell manganese silicate of cathode material magnesium.
The fused salt that the present invention uses is 0.464: 0.336 as the mixture of KCl or KCl and NaCl, the mol ratio of KCl and NaCl.
Nano silicon (the SiO that the present invention uses 2) purity more than or equal to 99%, particle size range is 10～100 nanometers.
The magnesium source that the present invention uses is magnesium oxide (MgO), magnesium acetate (Mg (CH 3COO) 24H 2O) or magnesium oxalate (MgC 2O 42H 2O).
The manganese salt that the present invention uses is manganese carbonate (MnCO 3), manganese acetate (Mn (CH 3COO) 24H 2O) or manganese oxalate (MnC 2O 42H 2O).
Protective gas of the present invention is the mist of argon gas, nitrogen, argon gas and hydrogen or the mist of nitrogen and hydrogen, and hydrogen volume content is 2～10% in the mist.
Among the preparation method of a kind of anode material manganese magnesium silicate of rechargeable magnesium cell of the present invention, adopted fused salt to make reaction medium, but fast reaction speed, shorten reaction time, simplify building-up process, reduce synthetic cost, improve the crystal structure of product, but also can effectively control the granularity and the shape of powder, synthetic particle diameter is little, the nano level magnesium silicate manganese of even particle distribution, as rechargeable magnesium cell anode material, Mg 2+The evolving path is short, and it is little to polarize, and helps improving the electro-chemical activity of product, and the stable discharging platform reaches 1.6V and 1.1V (vs.Mg/Mg 2+), discharge and recharge in the C/20 current density that discharge capacity can reach 289.3mAhg under the condition -1(theoretical capacity 92%).And the manganous silicate magnesium that the modification sol-gel method obtains is as rechargeable magnesium cell anode material, and the stable discharging platform reaches 1.6V (vs.Mg/Mg 2+), little electric current discharges and recharges that discharge capacity is 243.9mAhg under the condition (C/100) -1(theoretical capacity 78%).Usually use Mo 3S 4The actual discharge capacity be 100mAhg -1About, discharge voltage plateau is respectively at 1.2V and 1.0V (vs.Mg/Mg 2+).
Description of drawings
The XRD spectra of the rechargeable magnesium cell anode material magnesium silicate manganese that Fig. 1 (a) obtains for embodiment 1; The XRD spectra of the rechargeable magnesium cell anode material magnesium silicate manganese that (b) obtains for embodiment 2.
The rechargeable magnesium cell anode material magnesium silicate manganese that Fig. 2 obtains for embodiment 1 is assembled into the charging and discharging curve of battery under the C/20 condition.
The rechargeable magnesium cell anode material magnesium silicate manganese that Fig. 3 obtains for embodiment 2 is assembled into the discharge capacity of battery under the C/20 condition and the curve of cycle-index.
The XRD spectra of the rechargeable magnesium cell anode material magnesium silicate manganese that Fig. 4 obtains for embodiment 3.
Embodiment
Following embodiment is that the present invention is further described, but does not limit the scope of the invention.
The silicate as positive pole material magnesium manganese of the rechargeable magnesium cell that following examples obtain is applied in the rechargeable magnesium cell, and method of testing is as follows:
The acetylene black that adds 6～18wt% in the rechargeable magnesium cell anode material magnesium silicate manganese that following examples obtain is as conductive agent, and (PVDF is the 0.02gmL for preparing to the PVDF of 4～16wt% (Kynoar) -1PVDF/NMP solution, NMP is the N-methyl pyrrolidone) as binding agent, after stirring, be coated on the Copper Foil, after putting into 60～80 ℃ baking oven oven dry, drift with 10～16 millimeters of diameters is washed into pole piece, be the pressure lower sheeting of 1～2 MPa at pressure after, put into 100～130 ℃ dry 3～10 hours of vacuum drying oven, transfer to then in the argon gas glove box, with the metal magnesium rod is negative pole, and Cellgard 2400 is a barrier film, 0.2～0.5molL -1Mg (AlCl 2BuEt) 2/ THF is an electrolyte, is assembled into the CR2016 button cell, carries out the constant current charge-discharge performance test on LAND battery test system (the blue electric Electronics Co., Ltd. in Wuhan provides), discharges and recharges cut-ff voltage with respect to Mg/Mg 2+Be 0.5～2.1V.
Embodiment 1
Mg (CH with 4 moles KCl and 1 mole 3COO) 24H 2O, 1 mole Mn (CH 3COO) 24H 2The SiO of O and 1 mole 2In agate mortar, grind after 30 minutes; put into the corundum boat; 100 ℃ of following vacuumizes 12 hours; first 500 ℃ of heat treatments 2 hours under the protective atmosphere condition of argon gas and hydrogen gas mixture then; further 1000 ℃ of heat treatments 6 hours; naturally cool to room temperature at last, obtain a kind of rechargeable magnesium cell manganese silicate of cathode material magnesium.
With the rechargeable magnesium cell of above-mentioned preparation manganese silicate of cathode material magnesium, on the Rigaku D/MAX2200PC type X-ray diffractometer of day island proper Tianjin company production, carry out the powder x-ray diffraction experiment.Experiment condition is as follows: copper target, X ray wavelength 0.15406 nanometer, Ni filter; Used light pipe voltage 40kV, electric current is 20mA, sweep limits is 15～75 °, 4 ° of min of sweep speed -1
Fig. 1 (a) is the XRD spectra of the anode material manganese magnesium silicate of rechargeable magnesium cell that obtains of embodiment 1, and the result shows that product has good crystal structure, does not exist the impurity peaks such as oxide of magnesium or manganese.
With the rechargeable magnesium cell anode material magnesium silicate manganese assemble of embodiment 1 preparation, wherein manganous silicate magnesium: acetylene black: Kynoar (PVDF)=78: 12: 10 (mass ratio).The bonding agent Kynoar is dissolved in the N-methyl pyrrolidone in advance.After stirring, be coated on the Copper Foil, after putting into 80 ℃ baking oven oven dry, drift with 12.5 millimeters of diameters is washed into pole piece, be the pressure lower sheeting of 1 MPa at pressure after, put into 120 ℃ dry 8 hours of vacuum drying oven, transfer to then in the argon gas glove box, with the metal magnesium rod is negative pole, and Cellgard 2400 is a barrier film, 0.25molL -1Mg (AlCl 2BuEt) 2/ THF is an electrolyte, is assembled into the CR2016 button cell, carries out the constant current charge-discharge performance test on LAND battery test system (the blue electric Electronics Co., Ltd. in Wuhan provides), discharges and recharges cut-ff voltage with respect to Mg/Mg 2+Be 0.5～2.1V.Fig. 2 is the charging and discharging curve of battery under the C/20 multiplying power.Charging capacity can reach 102.8mAhg -1, discharge capacity is 82.8mAhg -1
Embodiment 2
With 4 moles KCl and 1 mole MgO, 1 mole MnCO 3SiO with 1 mole 2In agate mortar, grind after 30 minutes; put into the corundum boat; 100 ℃ of following vacuumizes 12 hours; first 350 ℃ of heat treatments 2 hours under the protective atmosphere condition of argon gas and hydrogen gas mixture then; further 1000 ℃ of heat treatments 6 hours; naturally cool to room temperature at last, obtain a kind of rechargeable magnesium cell manganese silicate of cathode material magnesium.
With the rechargeable magnesium cell of above-mentioned preparation manganese silicate of cathode material magnesium, on the Rigaku D/MAX2200PC type X-ray diffractometer of day island proper Tianjin company production, carry out the powder x-ray diffraction experiment.Experiment condition is as follows: copper target, X ray wavelength 0.15406 nanometer, Ni filter; Used light pipe voltage 40kV, electric current is 20mA, sweep limits is 15～75 °, 4 ° of min of sweep speed -1
Fig. 1 (b) is the XRD spectra of the rechargeable magnesium cell anode material magnesium silicate manganese that obtains of embodiment 2, and the result shows that product has good crystal structure, does not exist the impurity peaks such as oxide of magnesium or manganese.
With rechargeable magnesium cell anode material magnesium silicate manganese assemble prepared among the embodiment 2, wherein manganous silicate magnesium: acetylene black: Kynoar (PVDF)=78: 12: 10 (mass ratio).The bonding agent Kynoar is dissolved in the N-methyl pyrrolidone in advance.After stirring, be coated on the Copper Foil, after putting into 80 ℃ baking oven oven dry, drift with 12.5 millimeters of diameters is washed into pole piece, be the pressure lower sheeting of 1 MPa at pressure after, put into 120 ℃ dry 8 hours of vacuum drying oven, transfer to then in the argon gas glove box, with the metal magnesium rod is negative pole, and Cellgard 2400 is a barrier film, 0.25molL -1Mg (AlCl 2BuEt) 2/ THF is an electrolyte, is assembled into the CR2016 button cell, carries out the constant current charge-discharge performance test on LAND battery test system (the blue electric Electronics Co., Ltd. in Wuhan provides), discharges and recharges cut-ff voltage with respect to Mg/Mg 2+Be 0.5～2.1V.Fig. 3 is the discharge capacity of battery under the C/20 multiplying power and the curve of cycle-index.As seen from the figure, first, the 5th and the tenth discharge capacity reaches 272.7,293.5 and 224.0mAhg respectively -1
Embodiment 3
With 0.464 mole KCl, 0.336 mole NaCl and 1 mole MgO, 1 mole MnCO 3SiO with 1 mole 2In agate mortar, grind after 30 minutes; put into the corundum boat; 100 ℃ of following vacuumizes 12 hours; first 350 ℃ of heat treatments 2 hours under the protective atmosphere condition of argon gas and hydrogen gas mixture then; further 800 ℃, 900 ℃ or 1000 ℃ of heat treatment 6 hours; naturally cool to room temperature at last, obtain a kind of rechargeable magnesium cell manganese silicate of cathode material magnesium.
With the rechargeable magnesium cell of above-mentioned preparation manganese silicate of cathode material magnesium, on the Rigaku D/MAX2200PC type X-ray diffractometer of day island proper Tianjin company production, carry out the powder x-ray diffraction experiment.Experiment condition is as follows: copper target, X ray wavelength 0.15406 nanometer, Ni filter; Used light pipe voltage 40kV, electric current is 20mA, sweep limits is 15～75 °, 4 ° of min of sweep speed -1
Fig. 4 is the XRD spectra of the rechargeable magnesium cell anode material that obtains of embodiment 3, and the result shows that product has good crystal structure, does not exist the impurity peaks such as oxide of magnesium or manganese.

Claims (6)

1, a kind of preparation method of anode material manganese magnesium silicate of rechargeable magnesium cell is characterized in that the preparation method is as follows:
The nano silicon of the magnesium source of 1～10 mole fused salt and 1 mole, 1 mole manganese salt and 1 mole ground 30 minutes in agate mortar after; put into the corundum boat; 80～120 ℃ of following vacuumizes 12～48 hours; first 300～600 ℃ of heat treatments 1～3 hour under the protective atmosphere condition then; further 700～1000 ℃ of heat treatments 5～8 hours; naturally cool to room temperature at last, obtain a kind of rechargeable magnesium cell manganese silicate of cathode material magnesium.
2, the preparation method of a kind of anode material manganese magnesium silicate of rechargeable magnesium cell according to claim 1 is characterized in that fused salt is the mixture of KCl or KCl and NaCl, and the mol ratio of KCl and NaCl is 0.464: 0.336.
3, the preparation method of a kind of anode material manganese magnesium silicate of rechargeable magnesium cell according to claim 1, the purity that it is characterized in that nano silicon are more than or equal to 99%, and particle size range is 10～100 nanometers.
4, the preparation method of a kind of anode material manganese magnesium silicate of rechargeable magnesium cell according to claim 1 is characterized in that the magnesium source is magnesium oxide, magnesium acetate or magnesium oxalate.
5, the preparation method of a kind of anode material manganese magnesium silicate of rechargeable magnesium cell according to claim 1 is characterized in that the manganese salt that uses is manganese carbonate, manganese acetate or manganese oxalate.
6, the preparation method of a kind of anode material manganese magnesium silicate of rechargeable magnesium cell according to claim 1; it is characterized in that protective atmosphere is the mist of argon gas, nitrogen, argon gas and hydrogen or the mist of nitrogen and hydrogen, hydrogen volume content is 2～10% in the mist.
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Cited By (11)

* Cited by examiner, † Cited by third party
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CN101924213A (en) * 2010-09-07 2010-12-22 上海交通大学 Application of cobaltous magnesium silicate in rechargeable magnesium battery anode material
WO2011150093A1 (en) 2010-05-25 2011-12-01 Pellion Technologies Inc. Electrode materials for magnesium batteries
CN102280620A (en) * 2011-07-05 2011-12-14 内蒙古科技大学 Method for preparing magnesium secondary battery anode material of rare-earth-doped manganese magnesium silicate
CN101439861B (en) * 2008-12-25 2012-03-21 上海交通大学 Manufacture method of ferrosilite magnesium, and application in rechargeable magnesium cell anode material
CN103449459A (en) * 2012-06-05 2013-12-18 中央民族大学 Preparation method of one-dimensional calcium silicate nano material
US9325004B2 (en) 2013-09-23 2016-04-26 Samsung Electronics Co., Ltd. Cathode active material, and cathode and magnesium secondary battery including the cathode active material
US9425483B2 (en) 2013-11-21 2016-08-23 Samsung Electronics Co., Ltd. Electrolyte solution, method of preparing the same, and magnesium battery including the electrolyte solution
CN106981655A (en) * 2017-03-30 2017-07-25 宁波职业技术学院 A kind of novel magnesium ion cell positive material and preparation method thereof
US9728781B2 (en) 2013-09-30 2017-08-08 Samsung Electronics Co., Ltd. Sodium manganese composite oxide and electrode and sodium secondary battery using the same
US9887419B2 (en) 2013-08-26 2018-02-06 Samsung Electronics Co., Ltd. Active material, method of preparing the active material electrode including the active material, and secondary battery including the electrode
US10658662B2 (en) 2013-10-29 2020-05-19 Samsung Electronics Co., Ltd. Electrode active material for magnesium battery

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101439861B (en) * 2008-12-25 2012-03-21 上海交通大学 Manufacture method of ferrosilite magnesium, and application in rechargeable magnesium cell anode material
EP2577780A4 (en) * 2010-05-25 2016-01-20 Pellion Technologies Inc Electrode materials for magnesium batteries
WO2011150093A1 (en) 2010-05-25 2011-12-01 Pellion Technologies Inc. Electrode materials for magnesium batteries
EP2577780A1 (en) * 2010-05-25 2013-04-10 Pellion Technologies Inc. Electrode materials for magnesium batteries
CN103155235A (en) * 2010-05-25 2013-06-12 佩里昂技术公司 Electrode materials for magnesium batteries
CN101924213B (en) * 2010-09-07 2012-09-05 上海交通大学 Application of cobaltous magnesium silicate in rechargeable magnesium battery anode material
CN101924213A (en) * 2010-09-07 2010-12-22 上海交通大学 Application of cobaltous magnesium silicate in rechargeable magnesium battery anode material
CN102280620A (en) * 2011-07-05 2011-12-14 内蒙古科技大学 Method for preparing magnesium secondary battery anode material of rare-earth-doped manganese magnesium silicate
CN102280620B (en) * 2011-07-05 2013-10-02 内蒙古科技大学 Method for preparing magnesium secondary battery anode material of rare-earth-doped manganese magnesium silicate
CN103449459A (en) * 2012-06-05 2013-12-18 中央民族大学 Preparation method of one-dimensional calcium silicate nano material
CN103449459B (en) * 2012-06-05 2016-02-10 中央民族大学 A kind of preparation method of one-dimensional calcium silicate nano material
US9887419B2 (en) 2013-08-26 2018-02-06 Samsung Electronics Co., Ltd. Active material, method of preparing the active material electrode including the active material, and secondary battery including the electrode
US9325004B2 (en) 2013-09-23 2016-04-26 Samsung Electronics Co., Ltd. Cathode active material, and cathode and magnesium secondary battery including the cathode active material
US9728781B2 (en) 2013-09-30 2017-08-08 Samsung Electronics Co., Ltd. Sodium manganese composite oxide and electrode and sodium secondary battery using the same
US10658662B2 (en) 2013-10-29 2020-05-19 Samsung Electronics Co., Ltd. Electrode active material for magnesium battery
US9425483B2 (en) 2013-11-21 2016-08-23 Samsung Electronics Co., Ltd. Electrolyte solution, method of preparing the same, and magnesium battery including the electrolyte solution
CN106981655A (en) * 2017-03-30 2017-07-25 宁波职业技术学院 A kind of novel magnesium ion cell positive material and preparation method thereof
CN106981655B (en) * 2017-03-30 2020-08-18 宁波职业技术学院 Novel magnesium ion battery positive electrode material and preparation method thereof

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