CN1170328C - Chargeable magnesium battery - Google Patents

Chargeable magnesium battery Download PDF

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Publication number
CN1170328C
CN1170328C CNB021461430A CN02146143A CN1170328C CN 1170328 C CN1170328 C CN 1170328C CN B021461430 A CNB021461430 A CN B021461430A CN 02146143 A CN02146143 A CN 02146143A CN 1170328 C CN1170328 C CN 1170328C
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hour
mos
mgco
magnesium
solution
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CN1411083A (en
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袁华堂
曹建胜
王永梅
焦丽芳
武绪丽
刘秀生
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Nankai University
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Nankai University
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    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to the manufacture of a secondary battery, particularly to a chargeable magnesium battery which comprises electrode materials of the chargeable magnesium battery, electrolyte materials and the preparation method of the chargeable magnesium battery and the electrolyte materials. The negative electrode of the present invention is composed of magnesium alloy, and the component of the negative electrode is MgM#-<x>M#-<y>(0<x, y<0.5), namely alloy above the duality (M is Ni, Cu, Ti, Co, Si, B, etc.). The positive electrode is composed of a nano level M#-<z>Co#-<t>O#-<4>(0<z<2, 0<t<3) or MoS#-<2>, and the electrolytic solution is a metal organic compound Mg (ZnBuCl#-<2>) #-<2>. The battery system has the advantages of balanced charge and discharge, low price and high safety; the opening voltage is about 2.0V; the present invention is used as a power battery, and the present invention has great development and application prospects.

Description

Rechargeable magnesium cell
Affiliated technical field
The present invention relates to the manufacturing of secondary cell, particularly rechargeable magnesium cell, comprise the rechargeable magnesium cell electrode material, electrolyte and their preparation method.
Background technology
Rechargeable magnesium cell is a kind of novel chargeable battery of development by the lithium battery amplification.Magnesium and lithium are in cornerwise position in periodic table, thereby have similar physics and chemical property, such as negative electronegativity, similar atomic radius and ionic radius are arranged.These character are that rechargeable magnesium cell has been constructed basic condition, and magnesium low price (be about lithium 1/24) is poor with respect to the lithium activity in addition, stable in the air, be difficult for catching fire, fail safe is preferably arranged, these characteristics have been opened up wide space for the practicability of rechargeable magnesium cell again.
The operation principle of rechargeable magnesium cell is identical with the operation principle of lithium battery, though magnesium and lithium similar performance have difference after all.One, the surface formation oxide of lithium is more open, and the electrochemical dissolution-deposition of lithium is unrestricted in the charge discharge process, and magnesium surface formation oxide is dense, can not form electrochemical dissolution-sedimentation equilibrium in the charge discharge process; Its two, the magnesium ion polarization is strong, difficult the insertion in the general matrix, thereby hindered the development of rechargeable magnesium cell.
Carry out more work recent years, comprised the research of (1) positive electrode, the research of (2) negative material, the research of (3) electrolyte solution and the research of (4) rechargeable magnesium cell system.
The research of positive electrode is carried out more extensive, comprises oxide, oxysalt, sulfide etc., and wherein the research of spinelle and intercalation material is quite deep, and has obtained goodish effect.People such as Gregory [T.D.Gregory, R.J.Hoffman, R.C.Winterton.J.Electrochem.Soc., 137 (1990) 775] in the hexane solvent of dibutylmagnesium, are inserted into MoS to magnesium ion with chemical method 2In, the highest specific capacity reaches 140mAh/g, but does not take off the embedding phenomenon.
The research of negative material is fewer, and the one, to the research of magnesium, the 2nd, the research of graphite magnesium, but making little progress of obtaining mainly can not form electrochemical dissolution-sedimentation equilibrium.
Electrolytical research is also more deep, and basic principle is the conductance height, potential window is wide and organic molecule is little.Lossius[L.P.Lossius, F.Emmenegger, Ekectrochim.Acta, 41 (1996) 445] investigated 9 kinds of magnesium salts in the conductivity of their mixture of more than 20 kinds of aprotic solvents and 70 kinds, stability etc.
The research of rechargeable magnesium cell system, almost each researcher in research material, will study the rechargeable magnesium cell system, but great majority are unsuccessful.In general, the system of being studied or electrochemical dissolution is arranged can not deposit; Has only deposition, not dissolving.Gregory etc. use the tetrahydrofuran solution of grignard reagent as electrolyte solution, have observed electrochemical dissolution-sedimentation equilibrium, but very unstable.D.Aurbach[D.Aurbach, Z.Lu, A.Schechter, Y.Gofer, R.Turgeman, Y.Cohen, M.Moshkovich, E.Levi, Nature, 407 (2000) 724-727] use Mg xMo 2S 3As positive pole, and with the ethereal solution of ring aluminate as electrolyte, obtained effect preferably, make rechargeable magnesium cell be achieved, but the low 1.1-1.3V that is about of open circuit voltage.
Summary of the invention
The purpose of this invention is to provide a kind of magnesium cell that fills, battery of the present invention has been carried out discharging and recharging experiment, have and can discharge and recharge balance and open circuit voltage preferably, open circuit voltage is about 2.0V.The present invention has low price, and the characteristics that fail safe is good as electrokinetic cell, have great development and application prospect.
Rechargeable magnesium cell of the present invention is that the MgM1xM2y with doping vario-property is a negative pole, with nanometer Mg zCo tO 4Or MoS 2As positive pole, Mg (ZnBuCl 2) 2Constitute as electrolyte solution and barrier film, wherein M1 is Ni among the MgM1xM2y, and M2 is Cu, Ti, Co, Si, B etc., 0＜x, y＜0.5, Mg zCo tO 4In 0＜z＜2,0＜t＜3, nanometer Mg zCo tO 4Or MoS 2Particle size range is at 50-800nm.
The present invention is the MgM1 with doping vario-property xM2 yAs negative pole, with nanometer MgCo 2O 4Or MoS 2As positive pole, Mg (ZnBuCl 2) 2Constitute as electrolyte solution and barrier film, wherein, MgM1 xM2 yMiddle M1 is Ni, and M2 is Cu or Ti, 0＜x, y＜0.5.
The preparation method of doping vario-property negative material MgM1xM2y of the present invention is:
Under argon atmosphere, press the MgM1xM2y stoichiometric proportion, take by weighing MgH in proportion 2With form metal dust high speed ball milling 5-7 hour, 560 ℃ of insulations 3-4 hour, cooling, continued ball milling 5-100 hour, and the magnesium alloy powder that obtains carried out fluorination treatment (the magnesium alloy powder is put into 0.01M magnesium fluoride or ammonium fluoride and soaked 1-15 minute), this magnesium alloy powder has the good oxidization resistance energy.
Nanometer Mg zCo tO 4The preparation method of positive electrode is:
Take by weighing CoCl 26H 2O and MgCl 26H 2O, the molar ratio of the two is t: z, is mixed with mixed solution, be transferred to pH=6～7 with ammoniacal liquor, join then in the oxalic acid solution, can produce a large amount of precipitations immediately, continue to stir after 30 minutes, filter washing, dry 3 hours, make precursor, it is heated in tube furnace, and kept 1 hour down, obtain Mg at 320 ℃ zCo tO 4The spinelle sample.With sample high speed ball milling 10-100 hour, promptly get nanoscale Mg zCo tO 4, particle size in scope in the 50-800nm scope.
MoS 2The preparation method of positive electrode is:
Under nitrogen atmosphere, with (NH 4) 2MoS 4800-900 ℃ of down heating 4-6 hour, cooling in high speed ball mill ball milling 10-80 hour, promptly gets nanoscale MoS 2, particle size is in the 50-800nm scope.
Electrolyte Mg (ZnBuCl 2) 2The preparation method be:
Get the ether-cyclohexane solution 100ml of dibutyl magnesium, added anhydrous zinc chloride in 1: 1 in molar ratio, reflux steamed solvent in 3.5 hours, added the anhydrous tetrahydro furan of handling well (THF), filtering solution.Measure constituent content in the solution than being Mg: Zn: Cl=1: 2: 4, thus obtain containing the Mg (ZnBuCl of oxolane 2) 2Electrolyte solution.
The present invention is a kind of novel battery system-rechargeable magnesium cell system.This battery system has can discharge and recharge balance, open circuit voltage about 2.0V, low price, fail safe is good, as electrokinetic cell, has great development and application prospect.
Description of drawings
(positive electrode is MgCo to the charging and discharging curve of Fig. 1 simulated battery 2O 4).
(positive electrode is MoS to the charging and discharging curve of Fig. 2 simulated battery 2).
(positive electrode is MoS to Fig. 3 simulated battery charge and discharge cycles figure 2).
Embodiment
Embodiment 1
Cathode pole piece is made
With MgH 2With 1: 0.01: 0.01 in molar ratio mixed of metallic element Ni, Ti, ball milling is 6 hours under argon atmospher, and insulation is 4 hours under 560 ℃, argon atmospher, cooling, ball milling 80 hours in high speed ball mill then, powder size is 50-600nm, and the magnesium alloy powder is put into the 0.01M magnesium fluoride and soaked 1 minute, with magnesium alloy powder and carbonyl nickel powder and PTFE furnishing pasty state, be coated on the copper mesh, be pressed into diameter 13mm under 30MPa pressure, thick is the cathode pole piece of 1mm, puts into vacuum desiccator and preserves.
Anode pole piece is made
Take by weighing proper C oCl 26H 2O and MgCl 26H 2O, the molar ratio of the two is 2: 1, is mixed with certain density mixed solution, be transferred to pH=6～7 with ammoniacal liquor, join then in an amount of oxalic acid solution, can produce a large amount of precipitations immediately, continue to stir after 30 minutes, filter washing, dry 3 hours, make precursor, it is heated in tube furnace, and kept 1 hour down, obtain MgCo at 320 ℃ 2O 4The spinelle sample.With sample ball milling 60 hours in high speed ball mill, powder particle is in the 50-800nm scope, with MgCo 2O 4Powder, acetylene black and PTFE (85: 10: 5) furnishing pasty state, it is online to be coated in aluminium, under 30MPa pressure, is pressed into diameter 13mm, and thickness is the anodal sample of 1mm, puts into vacuum desiccator and preserves.
The simulated battery assembling.
In the glove box of argon atmospher, (long is 43mm at the simulated battery overcoat, internal diameter is 14mm) polyethylene pipe, an end is inserted in the teflon tube, stops to the centre, put into cathode pole piece, the currect collecting net of pole piece contacts with rod iron, puts into porous polypropylene barrier film (Celgard), puts into anode pole piece then, the anode pole piece active material is in the face of barrier film, in addition with dropper Dropwise 5-6 electrolyte (Mg (ZnBuCl 2) 2THF solution), insert rod iron at the other end of polyethylene pipe again, compress rod iron, placed 24 hours, electrolyte is fully soaked into.
Simulation rechargeable magnesium cell open circuit voltage is 2.0 volts, discharges and recharges with 0.1C, and charging platform is steady, is 2.85 volts, and discharge voltage is 1.75 volts, and can carry out reversible discharging and recharging, and cycle life is more than 50 times.Experimental result is seen Fig. 1.(positive electrode is MgCo to Fig. 1 for the charging and discharging curve of simulated battery 2O 4).
Embodiment 2
Cathode pole piece is made identical with embodiment 1
The making of anode pole piece
Under nitrogen atmosphere, with (NH 4) 2MoS 4850 ℃ of heating 6 hours, cooling, ball milling is 80 hours in the high speed ball milling, and powder particle is in the 50-800nm scope, with MoS 2Powder, acetylene black powder and PTFE (85: 10: 5) furnishing pasty state, it is online to be coated in aluminium, under 30MPa pressure, is pressed into diameter 13mm, and thick is the anodal sample of 1mm, puts into vacuum desiccator and preserves.
The assembling of simulated battery
Except using MoS 2Anode pole piece replaces MgCo 2O 4Outside the anode pole piece, other is identical with embodiment 1.
The opening voltage of simulated battery is 1.4V, and 0.1C discharges and recharges, and charging voltage is steady, is 2.8V, and simulated battery can carry out reversible discharging and recharging, and the discharge cycles life-span is more than 50 times.Experimental result is seen Fig. 2, Fig. 3.Fig. 2 is that (positive electrode is MoS for the charging and discharging curve of simulated battery 2); (positive electrode is MoS to Fig. 3 for simulated battery charge and discharge cycles figure 2).
Embodiment 3
With 1: 0.01: 0.005 in molar ratio mixed of Mg powder, copper powder and nickel powder, ball milling is 6 hours under argon atmospher, heating is 4 hours under 560 ℃, argon atmospher, cooling, ball is 80 hours in high speed ball mill, powder size is in the 80-800nm scope, the magnesium powder is put into the 0.01M magnesium fluoride and was soaked 3 minutes, with magnesium alloy powder and carbonyl nickel powder and PTFE (85: 10: 5) furnishing pasty state, be coated on the copper mesh, under 30MPa pressure, be pressed into diameter 13mm, the electrode plates of thickness 1m is put into vacuum desiccator and is preserved.
Anode pole piece is made identical with embodiment 1.
Simulated battery is made identical with embodiment 1.
Simulated battery opening voltage is 2.0 volts, discharges and recharges with 0.1C, and charging voltage on average is about 2.85 volts, and discharge voltage is 1.75V, and simulated battery can carry out reversible discharging and recharging, and charge and discharge circulation life is more than 50 times.

Claims (7)

1, a kind of rechargeable magnesium cell is characterized in that this battery is the MgM1 with doping vario-property xM2 yAs negative pole, with nanometer MgCo 2O 4Or MoS 2As positive pole, Mg (ZnBuCl 2) 2Constitute as electrolyte solution and barrier film, wherein, MgM1 xM2 yMiddle M1 is Ni, and M2 is Cu or Ti, 0＜x, y＜0.5.
2, according to the described rechargeable magnesium cell of claim 1, it is characterized in that described nanometer MgCo 2O 4Or MoS 2Particle size range is at 50-800nm.
3,, it is characterized in that described doping vario-property negative material MgM1 according to the described rechargeable magnesium cell of claim 1 xM2 yThe preparation method be:
Under inert atmosphere, press MgM1 xM2 yStoichiometric proportion takes by weighing MgH in proportion 2With form metal dust high speed ball milling 5-7 hour, 560 ℃ of insulations 3-4 hour, cooling continued ball milling 5-100 hour, and the magnesium alloy powder that obtains is carried out fluorination treatment.
4, according to the described rechargeable magnesium cell of claim 1, it is characterized in that described nanometer MgCo 2O 4The preparation method of positive electrode is:
Take by weighing CoCl 26H 2O and MgCl 26H 2O, the molar ratio of the two is 1: 2, is mixed with mixed solution, is transferred to pH=6～7 with ammoniacal liquor, joins then in the oxalic acid solution, continue to stir after 30 minutes, filter, washing, dry 3 hours, make precursor, it is heated in tube furnace, and kept 1 hour down, obtain MgCo at 320 ℃ 2O 4The spinelle sample with sample high speed ball milling 10-100 hour, promptly gets nanoscale MgCo 2O 4
5, according to the described rechargeable magnesium cell of claim 1, it is characterized in that described nanometer MoS 2The preparation method of positive electrode is:
Under nitrogen atmosphere, with (NH 4) 2MoS 4800-900 ℃ of down heating 4-6 hour, cooling in high speed ball mill ball milling 10-80 hour, promptly gets nanoscale MoS 2
6,, it is characterized in that described electrolyte Mg (ZnBuCl according to the described rechargeable magnesium cell of claim 1 2) 2The preparation method be:
Get the ether-cyclohexane solution 100ml of dibutyl magnesium, added anhydrous zinc chloride in 1: 1 in molar ratio, reflux steamed solvent in 3.5 hours, add anhydrous tetrahydro furan, filter, the constituent content in the solution is than being Mg: Zn: Cl=1: 2: 4, thus obtain containing the Mg (ZnBuCl of oxolane 2) 2Electrolyte solution.
7,, it is characterized in that described fluorination treatment is the magnesium alloy powder to be put into fluoride aqueous solution soaked 1-15 minute according to the described rechargeable magnesium cell of claim 3.
CNB021461430A 2002-11-01 2002-11-01 Chargeable magnesium battery Expired - Fee Related CN1170328C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN101420031B (en) * 2008-12-11 2010-06-02 浙江大学 Electrochemical magnesium ionic insertion/deinsertion electrode and production method thereof

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CN100411230C (en) * 2006-06-08 2008-08-13 上海交通大学 Application of organic sulfide in positive electrode material of secondary Mg battery
JP5245108B2 (en) * 2007-07-11 2013-07-24 ソニー株式会社 Magnesium ion-containing non-aqueous electrolyte, method for producing the same, 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
JP5206758B2 (en) * 2010-07-15 2013-06-12 トヨタ自動車株式会社 Negative electrode material, metal secondary battery, and negative electrode material manufacturing method
EP2605325B1 (en) * 2010-08-09 2015-11-18 LG Chem, Ltd. Cathode current collector coated with a primer and magnesium secondary battery including same
CN102024996B (en) * 2010-11-26 2012-12-19 南开大学 High-performance rechargeable magnesium battery and manufacturing method thereof
CN102651485B (en) * 2011-02-28 2016-03-30 丰田自动车株式会社 The application in rechargeable magnesium cell of rechargeable magnesium cell, electrolyte and the electrolyte for rechargeable magnesium cell
CN109565074A (en) * 2016-05-31 2019-04-02 深圳中科瑞能实业有限公司 A kind of secondary cell and preparation method thereof
CN107369564B (en) * 2017-07-17 2019-11-15 深圳中科瑞能实业有限公司 Conductive metal material is used as magnesium ion hybrid super capacitor cathode and magnesium ion hybrid super capacitor and preparation method thereof
CN109888267A (en) * 2019-04-08 2019-06-14 陕西科技大学 A kind of nickel catalytic nanometer magnesium anode material and preparation method for the double salt batteries of magnesium-lithium
CN115188955B (en) * 2022-06-28 2024-05-14 中国科学院青岛生物能源与过程研究所 Composite magnesium metal anode active material with multiphase material and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101420031B (en) * 2008-12-11 2010-06-02 浙江大学 Electrochemical magnesium ionic insertion/deinsertion electrode and production method thereof

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