CN106935796A - A kind of sulphur/sulfide/copper tri compound positive pole and its preparation and the application in magnesium sulphur battery - Google Patents
A kind of sulphur/sulfide/copper tri compound positive pole and its preparation and the application in magnesium sulphur battery Download PDFInfo
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- CN106935796A CN106935796A CN201710341319.4A CN201710341319A CN106935796A CN 106935796 A CN106935796 A CN 106935796A CN 201710341319 A CN201710341319 A CN 201710341319A CN 106935796 A CN106935796 A CN 106935796A
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/00—Electrodes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
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- 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
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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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to magnesium cell technical field, the preparation and its utilization in magnesium sulphur battery of a kind of sulphur/sulfide/copper tri compound positive pole are disclosed.Sulphur/sulfide/copper tri compound positive pole includes sublimed sulfur, metal sulfide and metal copper foil.Simultaneously magnesium sulphur battery is assembled into using the sulphur/sulfide/copper tri compound positive pole and magnesium ion electrolyte and magnesium metal negative pole.Many sulphions can not only be effectively strapped in positive pole zone by the anode composite, so as to suppress " shuttle effect ", and can be relied on the dissolving of metal copper foil and be generated non-stoichiometric copper sulfide（Cu x S, 0<x≤2）Interphase, and then promote the electrochemical conversion reaction of discharging product MgS, significantly improve the charging and discharging capacity of battery and improve the cyclical stability of magnesium sulphur battery.
Description
Technical field
The invention belongs to novel battery technical field, and in particular to a kind of sulphur/sulfide/copper ternary composite cathode material
Prepare and its utilization in magnesium-sulphur battery.
Background technology
The fields such as the miniaturization of electronic product, electric automobile and space technology develop rapidly, and greatly having promoted has
The development of the battery technology of new generation of high-energy-density, long circulation life, low cost and operation safety.Lithium rechargeable battery is received
It is limited to the theoretical capacity of positive electrode（Conventional anode material for lithium-ion batteries LiFePO4、LiMn2O4、LiCoO2Theoretical capacity
Respectively 170 mAh/g, 148 mAh/g, 274 mAh/g.）, density is far from the requirement for meeting era development.Secondly, lithium
In improper use, negative pole produces dendrite puncture barrier film to cause the internal short-circuit of battery to cause potential safety hazard to ion battery.Separately
Outward, magnesium resource content in the earth's crust again（2%）It is abundant, it is lithium content（0.0065%）104Times, the price of magnesium metal is also only lithium
The sixtieth of metal.Under such historical background, magnesium sulphur battery will turn into the focus of secondary cell research and development of future generation.
Magnesium sulphur battery be using sulphur as positive pole, magnesium as negative pole secondary cell, its theoretical energy density is 3200 Wh/
L.Used as a kind of emerging secondary energy storage battery technology, magnesium sulphur battery has the security higher compared to conventional lithium ion battery
Energy, less expensive price and volume energy density higher etc..Sedimentation products pattern subglobular, is difficult when magnesium is as negative pole
Dendrite is produced, with high security；Magnesium is insensitive to air and water, and applicability is good.
However, the main reason of limitation magnesium-sulphur battery development is following 2 points at present：1）Positive electrode active materials sulphur with
And discharging product MgS or MgS2It is insulator, its reactivity is poor, the reversible charge/discharge capacity of magnesium-sulphur battery plays limited（Surely
Constant volume only 200 mAh g-1）;2）Positive electrode active materials sulphur generates polysulfide in charge and discharge process, and polysulfide is worn
Shuttle effect causes the passivation of magnesium negative pole, and then causes magnesium sulphur cell decay serious.Being commonly designed S/C composites can effectively solve
Certainly sulphur and MgS or MgS2Poorly conductive problem, but the addition of C-material reduces the overall energy density of battery, and, it is many
Sulfide discharge deposits to form bulky grain, the MgS or MgS of the effect of strong ionic bond2There is still a need for higher during subsequent charge
Overpotential（>1.5 V vs. Mg）Its reactivity could be improved.Additionally, the design of S/C composites can not suppress many sulphur
The shuttle effect of compound, this causes magnesium sulphur cycle performance of battery to be difficult to be lifted.
Based on above problem, this patent proposes to be used as magnesium-sulphur by design sulfur/sulfide/copper ternary composite electrode structure
Cell positive material.The patent innovation is as follows：1）Sulfide（MS）With excellent conductive capability, sulphur/sulfide can be improved
The electronic conductivity of composite；2）The addition of metal sulfide can effectively suppress polysulfide shuttle effect；3）Metal
Copper Foil is dissolved in electrolyte in charge and discharge process and generates non-stoichiometric copper sulfide with polysulfide reaction（Cu x S, 0<x
≤2）Interphase, the interphase being capable of effective activation MgS or MgS2Further charging process to improve conversion reaction speed,
The charging polarization potential of battery can be substantially reduced during subsequent charge（<0.4 V vs. Mg）；3）Sulphur/sulfide/copper three
First composite yet there are no open report as magnesium-sulphur cell positive electrode material.
The content of the invention
The present invention is to suppress in magnesium-sulphur battery charge and discharge process polysulfide " shuttle effect " and improving MgS
Phase conversion reaction process during recharging, using sulphur/sulfide/copper trielement composite material as positive electrode active materials,
To improve the specific discharge capacity and cyclical stability of magnesium-sulphur battery.
To achieve the above object, the present invention use technical scheme for：
A kind of sulphur/sulfide/copper tri compound positive pole, anode composite component includes sublimed sulfur, transient metal sulfide and gold
Category Copper Foil.
The transient metal sulfide is FeS2、Ni2S3、NiS2、Co9S8、Co3S4、CoS2、SnS2、WS2、MoS2、TiS2、
Bi2S3In the mixing of one or more.
A kind of preparation method of sulphur/sulfide/copper tri compound positive pole, comprises the following steps：
（1）Transient metal sulfide described in claim 2 is mixed with sublimed sulfur arbitrary proportion, appropriate solvent, ball milling is added
2-24 hrs obtain the mixture of uniform sulphur/sulfide；Wherein solvent is the one kind in ethanol, acetone；
（2）Mixture, conductive agent and the binding agent grinding for weighing sulphur/sulfide successively obtain slurry；The conductive agent is
One or more mixing in Super-P carbon blacks, Ketjen black, acetylene black, CNT, Graphene；The binding agent is hydroxyl first
Base cellulose（CMC）, butadiene-styrene rubber（SBR）, Kynoar（PVDF）, polytetrafluoroethylene (PTFE)（PTFE）, polyacrylic acid（PAA）In
One or more mixing；The mass ratio 1 of the mixture, conductive agent and binding agent of the sulphur/sulfide:0.2-5.0:0.2-
3.0；
（3）Slurry coating is obtained into sulphur/sulfide/copper tri compound positive pole after drying on metal copper foil collector.
A kind of magnesium sulfur rechargeable battery, magnesium-sulfur rechargeable battery includes above-mentioned sulphur/sulfide/copper ternary composite cathode material, magnesium
Ion electrolyte and magnesium metal negative pole.
The magnesium ion electrolyte is nonaqueous electrolytic solution, electrolyte composition：0.05 mol/L magnesium fluorides and 0.2 mol/L boron
Sour three (hexafluoro isopropyl) esters are dissolved in the electrolyte constituted in glycol dimethyl ether.
The magnesium metal negative pole is magnesium metal paper tinsel.
Metal sulfide such as FeS is used in the invention described above technical scheme2、Ni2S3、NiS2、Co9S8、Co3S4、CoS2、
SnS2、WS2、MoS2、TiS2、Bi2S3Deng as polysulfide sorbing material, using sublimed sulfur as active material.Conductive agent
Addition can improve the electric conductivity of electrode material.And the metal copper foil in the present invention determines prepared combination electrode material tool
There is excellent electrochemical performance.The present invention is from binary sulfide without using ternary（Quaternary）Sulfide, it is therefore an objective to which binary vulcanizes
Thing is not easily decomposed in the intraoral stabilization of electrochemical window of magnesium-sulphur battery.Selected material is commercial product, is easily prepared with simple
Advantage.
Advantage for present invention：
Sulphur/sulfide/copper ternary composite cathode material of the present invention includes sublimed sulfur, metal sulfide and metal copper foil composition；
Constituted including negative pole, electrolyte and above-mentioned combination electrode material etc. using the magnesium-sulphur battery of combination electrode material assembling simultaneously
Part, the composite positive pole has than existing magnesium-sulphur battery more preferable capability retention of sulphur carbon electrode material（>90%）, more
Coulombic efficiency high（>99%）, the high rate performance of battery can be greatly improved.
Brief description of the drawings
Fig. 1 is the cyclic voltammetry curve of magnesium-sulphur battery that sulphur/stannic disulfide/copper provided in an embodiment of the present invention is positive pole
Figure.
Fig. 2 is the constant current charge-discharge diagram of magnesium-sulphur battery that sulphur/stannic disulfide/copper provided in an embodiment of the present invention is positive pole.
Fig. 3 is the cyclic voltammetry curve figure of magnesium-sulphur battery that sulphur/carbon/copper provided in an embodiment of the present invention is positive pole.
Fig. 4 is the constant current charge-discharge diagram of magnesium-sulphur battery that sulphur/carbon/copper provided in an embodiment of the present invention is positive pole.
Specific embodiment
One aspect of the present invention aims to provide a kind of magnesium-sulphur cell positive electrode, and it is according to principle：Metal sulfide energy
It is complexed with polysulfide, so as to effectively suppress shuttle effect；Metal copper foil be dissolved in charge and discharge process electrolyte and with it is many
Sulfide reaction generation non-stoichiometric copper sulfide（Cu x S, 0<x≤2）Interphase, the interphase can effective activation MgS or
MgS2Further charging process is improving conversion reaction speed.Specifically, the core of the positive pole is configured to binary metal sulphur
Compound, sublimed sulfur and metal copper foil.
Following examples are further illustrated to of the invention, but the present invention is not limited solely to following examples.
Embodiment 1
1.0 g stannic disulfides are weighed by electronic balance, then is weighed 2.0 g-8.0 g distillations sulphur powder and is placed in and fill 10 mL ethanol
Agate jar in the h of ball milling 8（It is preferred that sublimed sulfur is 4.0 g）.Volatilize to remove and obtain sulphur/stannic disulfide composite.Will be through
Sulphur/the stannic disulfide for crossing dried process is placed in 150-160 °C for the treatment of 12-36 h in closed stainless steel inner lining reactor（It is preferred that
155 °C, 24 h）.
With 80:10:10 mass ratio weighs sulphur/stannic disulfide composite, super P carbon blacks, polyacrylic acid respectively
（PAA）Dispersed slurry is prepared by grinding, and applies drying on Copper Foil and obtain anode pole piece.
In the glove box full of argon gas, using the pole piece as assembled battery positive plate, magnesium sheet is negative pole, 0.05
The mixture that mol/L magnesium fluorides and 0.2 mol/L boric acid three (hexafluoro isopropyl) ester are dissolved in glycol dimethyl ether is electrolyte
Assembled battery, and volt-ampere test is circulated to the battery, scanning voltage scope is 0.4-2.0 V vs. Mg（Fig. 1）.The figure
Show that the composite positive pole has excellent embedding magnesium ability.Constant-current discharge is carried out to the battery, electric current is set to 0.5 mA
cm-2, discharge time is 10 h.Fig. 2 is constant current charge-discharge diagram.
Embodiment 2
1.0g stannic disulfides are weighed by electronic balance and is placed in ultrasound in the beaker for filling 50mL deionized waters and 10mL ethanol
Obtain A.2.0g-8.0g distillations sulphur powder is weighed to be placed in ultrasound in the beaker for filling 50mL ethylenediamines and obtain B.A is slowly added into B
In and add acid regulation PH to neutral or faintly acid.Filtration drying obtains sulphur/stannic disulfide composite.It is preferred that sublimed sulfur is
4.0g。
With 80:10:10 mass ratio weighs sulphur/stannic disulfide composite, super P carbon blacks, polyacrylic acid respectively
（PAA）Dispersed slurry is prepared by grinding, and applies drying on Copper Foil and obtain anode pole piece.
In the glove box full of argon gas, using the pole piece as assembled battery positive plate, magnesium sheet is negative pole, 0.05
Mol/L magnesium fluorides and 0.2 mol/L boric acid three (hexafluoro isopropyl) ester are dissolved in glycol dimethyl ether for electrolyte assembled battery, and
Volt-ampere test is circulated to the battery, scanning voltage scope is 0.4-2.0 V vs. Mg.The bright anode composite material of the chart
Material has excellent embedding magnesium ability.Constant-current discharge is carried out to the battery, electric current is set to 0.5 mA cm-2, discharge time is 10
h。
Comparative example 1
1.0g carbon blacks are weighed by electronic balance, then weighs 2.0g-8.0g distillations sulphur powder and be placed in the agate ball for filling 10mL ethanol
Ball milling 8h in grinding jar（It is preferred that sublimed sulfur is 4.0g）.Volatilize to remove and obtain sulphur/carbon composite.By by the sulphur of dried process/
Carbon is placed in 150-160 DEG C for the treatment of 12-36h in closed stainless steel inner lining reactor（It is preferred that 155 DEG C, 24h）.
With 80:10:10 mass ratio weighs sulphur/carbon composite, Super P carbon blacks, polyacrylic acid respectively（PAA）It is logical
Cross grinding and prepare dispersed slurry, and apply drying on Copper Foil and obtain anode pole piece.
In the glove box full of argon gas, using the pole piece as assembled battery positive plate, magnesium sheet is negative pole, 0.05
Mol/L magnesium fluorides and 0.2 mol/L boric acid three (hexafluoro isopropyl) ester are dissolved in glycol dimethyl ether for electrolyte assembled battery, and
Volt-ampere test is circulated to the battery（Referring to Fig. 3）, scanning voltage scope is 0.4-2.0 V vs. Mg.The chart it is bright this just
Pole material has excellent embedding magnesium ability.Constant-current discharge is carried out to the battery by Fig. 3, electric current is set to 0.5 mA cm-2, electric discharge
Time is 10 h.Fig. 4 is constant current charge-discharge diagram.
Embodiment 3
1.0 g ferrous disulfides are weighed by electronic balance, then is weighed 2.0 g-8.0 g distillations sulphur powder and is placed in and fill 10 mL ethanol
Agate jar in the h of ball milling 8（It is preferred that sublimed sulfur is 4.0 g）.Volatilize to remove and obtain sulphur/ferrous disulfide composite.Will be through
Sulphur/the ferrous disulfide for crossing dried process is placed in 150-160 °C for the treatment of 12-36 h in closed stainless steel inner lining reactor（It is preferred that
155 °C, 24 h）.
With 80:10:10 mass ratio weighs sulphur/ferrous disulfide composite, Super P carbon blacks, polyacrylic acid respectively
（PAA）Dispersed slurry is prepared by grinding, and applies drying on Copper Foil and obtain anode pole piece.
In the glove box full of argon gas, using the pole piece as assembled battery positive plate, magnesium sheet is negative pole, 0.05
The mixture that mol/L magnesium fluorides and 0.2 mol/L boric acid three (hexafluoro isopropyl) ester are dissolved in glycol dimethyl ether is electrolyte
Assembled battery, and volt-ampere test is circulated to the battery, scanning voltage scope is 0.4-2.0 V vs. Mg.
Embodiment 4
1.0 g ferrous disulfides are weighed by electronic balance, then is weighed 2.0 g-8.0 g distillations sulphur powder and is placed in and fill 10 mL ethanol
Agate jar in the h of ball milling 8（It is preferred that sublimed sulfur is 4.0 g）.Volatilize to remove and obtain sulphur/ferrous disulfide composite.Will be through
Sulphur/the ferrous disulfide for crossing dried process is placed in 150-160 °C for the treatment of 12-36 h in closed stainless steel inner lining reactor（It is preferred that
155 °C, 24 h）.
With 80:10:10 mass ratio weighs sulphur/ferrous disulfide composite, Super P carbon blacks, polyvinylidene fluoride respectively
Alkene（PVDF）Dispersed slurry is prepared by grinding, and applies drying on Copper Foil and obtain anode pole piece.
In the glove box full of argon gas, using the pole piece as assembled battery positive plate, magnesium sheet is negative pole, 0.05
The mixture that mol/L magnesium fluorides and 0.2 mol/L boric acid three (hexafluoro isopropyl) ester are dissolved in glycol dimethyl ether is electrolyte
Assembled battery, and volt-ampere test is circulated to the battery, scanning voltage scope is 0.4-2.0 V vs. Mg.
Embodiment 5
1.0 g ferrous disulfides are weighed by electronic balance, then is weighed 2.0 g-8.0 g distillations sulphur powder and is placed in and fill 10 mL ethanol
Agate jar in the h of ball milling 8（It is preferred that sublimed sulfur is 4.0 g）.Volatilize to remove and obtain sulphur/ferrous disulfide composite.Will be through
Sulphur/the ferrous disulfide for crossing dried process is placed in 150-160 °C for the treatment of 12-36 h in closed stainless steel inner lining reactor（It is preferred that
155 °C, 24 h）.
With 80:10:It is fine that 10 mass ratio weighs sulphur/ferrous disulfide composite, Super P carbon blacks, carboxymethyl respectively
Dimension element（CMC）:Butadiene-styrene rubber（SBR）(1:1 wt%) dispersed slurry is prepared by grinding, and apply drying on Copper Foil
Obtain anode pole piece.
In the glove box full of argon gas, using the pole piece as assembled battery positive plate, magnesium sheet is negative pole, 0.05
The mixture that mol/L magnesium fluorides and 0.2 mol/L boric acid three (hexafluoro isopropyl) ester are dissolved in glycol dimethyl ether is electrolyte
Assembled battery, and volt-ampere test is circulated to the battery, scanning voltage scope is 0.4-2.0 V vs. Mg.
Embodiment 6
1.0 g titanium disulfides are weighed by electronic balance, then is weighed 2.0 g-8.0 g distillations sulphur powder and is placed in and fill 10 mL ethanol
Agate jar in the h of ball milling 8（It is preferred that sublimed sulfur is 4.0 g）.Volatilize to remove and obtain sulphur/titanium disulfide composite.Will be through
Sulphur/the titanium disulfide for crossing dried process is placed in 150-160 °C for the treatment of 12-36 h in closed stainless steel inner lining reactor（It is preferred that
155 °C, 24 h）.
With 80:10:10 mass ratio weighs sulphur/titanium disulfide composite, CNT, carboxymethylcellulose calcium respectively
（CMC）:Butadiene-styrene rubber（SBR）(1:1, wt%) dispersed slurry is prepared by grinding, and applies and dried on Copper Foil
To anode pole piece.
In the glove box full of argon gas, using the pole piece as assembled battery positive plate, magnesium sheet is negative pole, 0.05
The mixture that mol/L magnesium fluorides and 0.2 mol/L boric acid three (hexafluoro isopropyl) ester are dissolved in glycol dimethyl ether is electrolyte
Assembled battery, and volt-ampere test is circulated to the battery, scanning voltage scope is 0.4-2.0 V vs. Mg.
Embodiment 7
1.0 g boron sulfides are weighed by electronic balance, then is weighed 2.0 g-8.0 g distillations sulphur powder and is placed in and fill 10 mL second
The h of ball milling 8 in the agate jar of alcohol（It is preferred that sublimed sulfur is 4.0 g）.Volatilize to remove and obtain sulphur/boron sulfide composite.
150-160 °C for the treatment of 12-36 in closed stainless steel inner lining reactor will be placed in by the sulphur/boron sulfide of dried process
h（It is preferred that 155 °C, 24 h）.
With 80:10:10 mass ratio weighs sulphur/boron sulfide composite, CNT, Kynoar respectively
（PVDF）Dispersed slurry is prepared by grinding, and applies drying on Copper Foil and obtain anode pole piece.
In the glove box full of argon gas, using the pole piece as assembled battery positive plate, magnesium sheet is negative pole, 0.05
The mixture that mol/L magnesium fluorides and 0.2 mol/L boric acid three (hexafluoro isopropyl) ester are dissolved in glycol dimethyl ether is electrolyte
Assembled battery, and volt-ampere test is circulated to the battery, scanning voltage scope is 0.4-2.0 V vs. Mg.
Embodiment 8
1.0 g tungsten disulfides are weighed by electronic balance, then is weighed 2.0 g-8.0 g distillations sulphur powder and is placed in and fill 10 mL ethanol
Agate jar in the h of ball milling 8（It is preferred that sublimed sulfur is 4.0 g）.Volatilize to remove and obtain sulphur/tungsten disulfide composite.Will be through
Sulphur/the tungsten disulfide for crossing dried process is placed in 150-160 °C for the treatment of 12-36 h in closed stainless steel inner lining reactor（It is preferred that
155 °C, 24 h）.
With 80:10:10 mass ratio weighs sulphur/tungsten disulfide composite, acetylene black, polytetrafluoroethylene (PTFE) respectively
（PTFE）Dispersed slurry is prepared by grinding, and applies drying on Copper Foil and obtain anode pole piece.
In the glove box full of argon gas, using the pole piece as assembled battery positive plate, magnesium sheet is negative pole, 0.05
The mixture that mol/L magnesium fluorides and 0.2 mol/L boric acid three (hexafluoro isopropyl) ester are dissolved in glycol dimethyl ether is electrolyte
Assembled battery, and volt-ampere test is circulated to the battery, scanning voltage scope is 0.4-2.0 V vs. Mg.
Embodiment 9
1.0 g molybdenum bisuphide are weighed by electronic balance, then is weighed 2.0 g-8.0 g distillations sulphur powder and is placed in and fill 10 mL ethanol
Agate jar in the h of ball milling 8（It is preferred that sublimed sulfur is 4.0 g）.Volatilize to remove and obtain sulphur/molybdenum bisuphide composite.Will be through
Sulphur/the molybdenum bisuphide for crossing dried process is placed in 150-160 °C for the treatment of 12-36 h in closed stainless steel inner lining reactor（It is preferred that
155 °C, 24 h）.
With 80:10:10 mass ratio weighs sulphur/molybdenum bisuphide composite, acetylene black, the poly- methyl of polyacrylonitrile respectively
Methyl acrylate（PANPMMA）Dispersed slurry is prepared by grinding, and applies drying on Copper Foil and obtain anode pole piece.
In the glove box full of argon gas, using the pole piece as assembled battery positive plate, magnesium sheet is negative pole, 0.05
The mixture that mol/L magnesium fluorides and 0.2 mol/L boric acid three (hexafluoro isopropyl) ester are dissolved in glycol dimethyl ether is electrolyte
Assembled battery, and volt-ampere test is circulated to the battery, scanning voltage scope is 0.4-2.0 V vs. Mg.
Claims (6)
1. a kind of sulphur/sulfide/copper tri compound positive pole, it is characterised in that：Anode composite component includes sublimed sulfur, transition metal
Sulfide and metal copper foil.
2. a kind of sulphur/sulfide/copper tri compound positive pole as described in claim 1, it is characterised in that：The Transition Metal Sulfur
Compound is FeS2、Ni2S3、NiS2、Co9S8、Co3S4、CoS2、SnS2、WS2、MoS2、TiS2、Bi2S3In one or more mixed
Close.
3. the preparation method of a kind of sulphur/sulfide/copper tri compound positive pole as described in claim 1 or 2, it is characterised in that
Comprise the following steps：
（1）Transient metal sulfide described in claim 2 is mixed with sublimed sulfur arbitrary proportion, appropriate solvent, ball milling is added
2-24 hrs obtain the mixture of uniform sulphur/sulfide；Wherein solvent is the one kind in ethanol, acetone；
（2）Mixture, conductive agent and the binding agent grinding for weighing sulphur/sulfide successively obtain slurry；The conductive agent is
One or more mixing in Super-P carbon blacks, Ketjen black, acetylene black, CNT, Graphene；The binding agent is hydroxyl first
Base cellulose（CMC）, butadiene-styrene rubber（SBR）, Kynoar（PVDF）, polytetrafluoroethylene (PTFE)（PTFE）, polyacrylic acid（PAA）In
One or more mixing；The mass ratio 1 of the mixture, conductive agent and binding agent of the sulphur/sulfide:0.2-5.0:0.2-
3.0；
（3）Slurry coating is obtained into sulphur/sulfide/copper tri compound positive pole after drying on metal copper foil collector.
4. a kind of magnesium sulfur rechargeable battery, it is characterised in that：Magnesium-sulfur rechargeable battery includes sulphur/sulfide/copper described in claim 1
Ternary composite cathode material, magnesium ion electrolyte and magnesium metal negative pole.
5. a kind of magnesium sulfur rechargeable battery as described in claim 4, it is characterised in that：Magnesium ion electrolyte is nonaqueous electrolytic solution,
Electrolyte is constituted：0.05 mol/L magnesium fluorides and 0.2 mol/L boric acid three (hexafluoro isopropyl) ester are dissolved in glycol dimethyl ether
The electrolyte of composition.
6. a kind of magnesium sulfur rechargeable battery as described in claim 4, it is characterised in that：The magnesium metal negative pole is magnesium metal paper tinsel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710341319.4A CN106935796B (en) | 2017-05-16 | 2017-05-16 | Sulfur/sulfide/copper ternary composite positive electrode, preparation thereof and application thereof in magnesium-sulfur battery |
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| CN110828892B (en) * | 2019-11-18 | 2023-02-03 | 中国科学院青岛生物能源与过程研究所 | Solid magnesium-sulfur battery, preparation method and application in deep sea |
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