CN109037623A - A kind of positive electrode of Mg secondary cell and preparation method thereof - Google Patents
A kind of positive electrode of Mg secondary cell and preparation method thereof Download PDFInfo
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- CN109037623A CN109037623A CN201810776325.7A CN201810776325A CN109037623A CN 109037623 A CN109037623 A CN 109037623A CN 201810776325 A CN201810776325 A CN 201810776325A CN 109037623 A CN109037623 A CN 109037623A
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- secondary cell
- positive electrode
- carbon
- ferrous disulfide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011777 magnesium Substances 0.000 claims abstract description 52
- 229940095991 ferrous disulfide Drugs 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 12
- 239000002086 nanomaterial Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000005864 Sulphur Substances 0.000 claims description 14
- 239000002048 multi walled nanotube Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 244000137852 Petrea volubilis Species 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Natural products SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 3
- 239000004201 L-cysteine Substances 0.000 claims description 3
- 235000013878 L-cysteine Nutrition 0.000 claims description 3
- 125000000415 L-cysteinyl group Chemical group O=C([*])[C@@](N([H])[H])([H])C([H])([H])S[H] 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 abstract description 12
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 10
- 239000010406 cathode material Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910003092 TiS2 Inorganic materials 0.000 description 8
- 229910052976 metal sulfide Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910052960 marcasite Inorganic materials 0.000 description 6
- 229910052683 pyrite Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 230000001052 transient effect Effects 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052603 melanterite Inorganic materials 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 sulphur Compound Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of positive electrode of Mg secondary cell, the positive electrode is that carbon nanomaterial in-stiu coating ferrous disulfide is formed by ferrous disulfide/nano carbon composite material, and it is applied in Mg secondary cell, the weight percent of carbon material and ferrous disulfide in the ferrous disulfide/nano carbon composite material are as follows: carbon material 2%~5%, ferrous disulfide 98%~95%.The present invention, as basic material, is carried out carbon coating in situ using dopen Nano grade carbon material, obtains final composite material by " one step hydro thermal method " using ferrous disulfide.When so that the material being used for magnesium secondary battery cathode material, can for magnesium ion can counter diffusion more channels are provided so that battery is with higher charging and discharging capacity and excellent cycle performance.The synthesis of base material of the invention only needs two kinds of elements, and step method is easy, is not necessarily to high-temperature calcination, can directly apply after preparation, prepares abundant raw material, at low cost, is easy to be mass produced.
Description
Technical field
The present invention relates to secondary cell fields more particularly to a kind of positive electrode of Mg secondary cell and preparation method thereof.
Background technique
As worldwide energy consumption is increasing, environmental pollution is increasingly aggravated, and people generally recognize to develop and utilize
The importance of green regenerative energy sources.Therefore, some novel environment friendlies, large capacity secondary cell receive the extensive of researcher
Concern, including lithium ion battery, lead-acid battery, nickel-cadmium cell etc..However lithium ion battery there are higher cost and safety compared with
The problem of difference, lead-acid battery and nickel-cadmium cell contain harmful element, can pollute to environment.
Magnesium metal and lithium metal are diagonal entry, so the features such as its chemical property and ionic radius and lithium have very much
Similarity.In addition, magnesium rich content in the earth's crust, about the 10 of lithium4Times, and the stability of magnesium metal is higher, fusing point
Higher than lithium, keep it safer relative to lithium, is considered to be the metal negative electrode material of the height ratio capacity density with applications well prospect
Material.Although theoretical specific capacity is not as good as lithium (3862mAh g-1), but also more considerable (2205mAh g-1).Mg secondary cell conduct
New Green Battery is researched and developed extensively by people, the lithium ion battery mature compared to research, although now on portable devices
Develop not as good as lithium ion battery, but Mg secondary cell is expected to obtain in terms of price, usage safety performance and big load
It is broken through to further.However, magnesium ion has biggish charge density, and solvation phenomenon is tighter compared with lithium ion
Weight, thus cause magnesium ion to be more difficult to be embedded into basis material than lithium ion, therefore find and carry out reversible abjection for magnesium ion
Basis material with insertion is the emphasis of Mg secondary cell research.
Currently, the research of magnesium secondary battery cathode material focus primarily upon transition metal oxide, transient metal sulfide,
The compounds such as polyanionic compound.Wherein transient metal sulfide has considerable as the positive electrode of Mg secondary cell
Research Prospects, and transient metal sulfide is considered as a kind of typical reversible intercalation/deintercalation host material.With transition metal
Oxide is compared, and the crystal structure of transient metal sulfide is not easy to capture magnesium ion, and the reversible deintercalation of magnesium ion can be improved
Degree.Mg secondary cell sulfide positive electrode mainly includes thanking to freire (Chevrel) phase compound (Mo6S8) and binary
Metal sulfide (MoS2、TiS2Deng).Chevrel phase compound (Mo6S8) it is counted as a kind of base of good magnesium ion insertion
Body material has good cycle performance and kinetics of diffusion as magnesium secondary battery cathode material Chevrel phase compound
Matter, however the preparation condition of this material is harsher, need include three kinds of elements (copper, molybdenum, sulphur) compound specific
Atmosphere, at a temperature of reaction is for a long time to prepare, and reaction process is cumbersome.Binary metal sulfide (MoS2、TiS2Deng) it is used as magnesium two
Primary cell positive electrode is also widely studied and achieves certain achievement.There is researcher to provide by chemical reaction preparation between liquid
There is the MoS of different structure feature2It is applied in Mg secondary cell as positive electrode, however, the specific discharge capacity of battery is only 2
~25mAh g-1, cycle efficieny is 10%~40%.TiS with layer structure2, ion can be made to be embedded into the gap of lamella
In, researcher compares two-dimensional layer (1-TiS2)TiS2With three-dimensional cubic (c-TiS2)TiS2In 0.2mol L-1Dibutyl
The embedding magnesium performance of chemistry in magnesium eletrolysis liquid, has respectively obtained Mg0.25TiS2And Mg0.22TiS2, can be realized to the reversible of magnesium ion
Deintercalation, but the capacity attenuation of battery is than more serious.
Ferrous disulfide (FeS2) it is a kind of important transient metal sulfide, since its own is with high theoretical energy
And the features such as environmental protection, it has caused researcher and has widely paid close attention to, FeS2Application range also than wide, but the secondary electricity of magnesium
Application is but had no in the sulfide positive electrode of pond.
Summary of the invention
The object of the present invention is to provide positive electrodes of a kind of Mg secondary cell and preparation method thereof, select binary metal sulphur
Compound FeS2As base material, a certain amount of nano-carbon material is mixed by situ, synthetic composite material is as the secondary electricity of magnesium
The positive electrode in pond to expand disulphide in the application of Mg secondary cell, and improves the performance of Mg secondary cell.
To achieve the above object, the present invention is implemented with the following technical solutions:
A kind of positive electrode of Mg secondary cell, the positive electrode are carbon nanomaterial in-stiu coating ferrous disulfide
It is formed by ferrous disulfide/nano carbon composite material, and is applied in Mg secondary cell, the ferrous disulfide/
The weight percent of carbon material and ferrous disulfide in nano carbon composite material are as follows: carbon material 2%~5%, ferrous disulfide
98%~95%.
A kind of preparation method of the positive electrode of Mg secondary cell, the specific method is as follows:
A. composite material ferrous disulfide/nano-sized carbon is prepared:
Source of iron and sulphur source are mixed in molar ratio, and are added in the deionized water of 150~170mL, is vigorously stirred
It is completely dissolved to mixture, then acid treated carbon material is added into mixed solution, and 0.5~1h is sufficiently stirred, will mixed
Liquid is transferred in the reaction kettle with polytetrafluoroethyllining lining and is heated, and is always maintained in hydrothermal reaction process and quickly stirs
Mix, cooled to room temperature after hydro-thermal reaction is centrifuged with the revolving speed of 8000~10000r/min, with dehydrated alcohol and
Deionized water washs product repeatedly, is finally freeze-dried, and the ferrous disulfide of carbon nanomaterial in-stiu coating is obtained
Composite material；
B. electrode slice is prepared:
Composite material obtained in step a is fully ground with conductive agent, and is added to the organic of dissolution binder
It is stirred in solvent, is after mixing evenly uniformly coated on slurry on copper current collector with coating machine, carry out tabletting after dry,
Obtain positive plate；Selection is negative electrode tab with the bright magnesium metal of sand paper polishing.
The source of iron is ferrous sulfate.
The sulphur source is L-cysteine.
The molar ratio of the source of iron and sulphur source is 1~1.2 ︰ 4~4.2.
The hydrothermal temperature is 160~170 DEG C, the water reaction time are as follows: 10~12h.
The carbon material is multi-walled carbon nanotube or single-walled carbon nanotube or graphene.
The mass ratio of composite material, conductive agent, binder in step b is 6~8 ︰, 1~2 ︰ 1~2.
Drying condition in step b is 70~80 DEG C of 8~10h of vacuum drying.
Compared with prior art, the beneficial effects of the present invention are:
A kind of positive electrode of Mg secondary cell of the present invention and preparation method thereof, using ferrous disulfide as basic material
Material carries out carbon coating in situ using dopen Nano grade carbon material, obtains final composite material by " one step hydro thermal method ".So that
The material be used for magnesium secondary battery cathode material when, can for magnesium ion can counter diffusion more channels are provided so that battery
With higher charging and discharging capacity and excellent cycle performance.
The synthesis of base material of the invention only needs two kinds of elements, and step method is easy, is not necessarily to high-temperature calcination, can after preparation
It directly applies, prepares abundant raw material, it is at low cost, it is easy to be mass produced.
Detailed description of the invention
Fig. 1 is a kind of reaction unit schematic diagram for magnesium secondary battery cathode material.
Fig. 2 is ferrous disulfide/MWCNTs positive electrode in 20mA g-1Constant current charge-discharge curve graph under current density
(embodiment 1).
Fig. 3 is ferrous disulfide/Graphene positive electrode in 20mA g-1Constant current charge-discharge curve graph under current density
(embodiment 2).
In figure: 1- reaction kettle, 2- sample stirrer, 3- silicone oil, 4- heating tube, 5- oil bath pan, 6- reaction solution, 7- temperature-sensitive
Resistance.
Specific embodiment
It elaborates below with reference to embodiment to the present invention, but practical range of the invention is not limited only to following realities
Apply example.
A kind of positive electrode of Mg secondary cell, the positive electrode are carbon nanomaterial in-stiu coating ferrous disulfide
It is formed by ferrous disulfide/nano carbon composite material (FeS2/ C), and be applied in Mg secondary cell, two sulphur
Change the weight percent of carbon material and ferrous disulfide in ferrous iron/nano carbon composite material are as follows: carbon material 2%~5%, curing
Ferrous iron 98%~95%.Show higher charging and discharging capacity, excellent cycle performance and high rate performance.
A kind of preparation method of the positive electrode of Mg secondary cell, the specific method is as follows:
A. composite material ferrous disulfide/nano-sized carbon is prepared:
Source of iron and sulphur source are mixed in molar ratio, and are added in the deionized water of 150~170mL, is vigorously stirred
It is completely dissolved to mixture, then acid treated carbon material is added into mixed solution, and 0.5~1h is sufficiently stirred, will mixed
Liquid is transferred in the reaction kettle with polytetrafluoroethyllining lining and is heated, and is always maintained in hydrothermal reaction process and quickly stirs
Mix, cooled to room temperature after hydro-thermal reaction is centrifuged with the revolving speed of 8000~10000r/min, with dehydrated alcohol and
Deionized water washs product repeatedly, is finally freeze-dried, and completes cold in subzero 70 DEG C freezings in advance finally to room temperature
Freeze drying process, obtains the composite material of the ferrous disulfide of carbon nanomaterial in-stiu coating.
As shown in Figure 1, synthetic method is " one step hydro thermal method " in reaction kettle 1, by oil bath pan 5 to equipped with mixture
Closed reactor 1 heats while stirring, and speed of agitator is 600~800rpm, one-step synthesis composite material.This method can be real
Existing product FeS2The nanosizing of/C, and make two kinds of component FeS2It is mixed with C more evenly abundant.
B. electrode slice is prepared:
Composite material obtained in step a is fully ground with conductive agent, and is added to the organic of dissolution binder
It is stirred in solvent, is after mixing evenly uniformly coated on slurry on copper current collector with coating machine, carry out tabletting after dry,
Obtain positive plate；Selection is negative electrode tab with the bright magnesium metal of sand paper polishing.
The source of iron is ferrous sulfate (FeSO4·7H2O)。
The sulphur source is L-cysteine (C3H7NO2S)。
The molar ratio of the source of iron and sulphur source is 1~1.2 ︰ 4~4.2.
The hydrothermal temperature is 160~170 DEG C, the water reaction time are as follows: 10~12h.
The carbon material is multi-walled carbon nanotube (MWCNTs) or single-walled carbon nanotube (SWCNTs) or graphene
(Graphene)。
The mass ratio of composite material, conductive agent, binder in step b is 6~8 ︰, 1~2 ︰ 1~2.
Drying condition in step b is 70~80 DEG C of 8~10h of vacuum drying.
The present invention uses source of iron and sulphur source, develops a kind of " one step hydro thermal method " and prepares FeS2/ C nano composite material.It should
Method can be such that hydro-thermal reaction carries out under conditions of high temperature, high pressure, quick stirring exist simultaneously, and make two kinds of component FeS2And C
Mix more evenly abundant, realization product FeS2The nanosizing of/C.
Embodiment 1: the weight of carbon material and ferrous disulfide in the ferrous disulfide/nano carbon composite material of the present embodiment
Percentage are as follows: carbon material 2%, ferrous disulfide 98%
Multi-walled carbon nanotube (MWCNTs) needs to carry out pickling, and a certain amount of MWCNTs is placed in the salt that volume ratio is 3 ︰ 1
In the mixed solution of sour (concentration 98%) and nitric acid (concentration 98%), ultrasonic disperse is carried out, is carried out repeatedly after being uniformly dispersed
Washing is finally filtered, and the MWCNTs after pickling is dried in vacuo at 60 DEG C until solution is neutral.It takes
MWCNTs after 40mg pickling, which is placed in the deionized water of 40mL, carries out ultrasonic disperse, after being uniformly dispersed, is transferred to 2.22g's
FeSO4·7H2O and 3.87g C3H7NO2In S mixed solution (molar ratio 1:4), deionized water total amount is 160mL in solution, and
Adequately stirred.Above-mentioned mixed solution is being transferred in the reaction kettle with clean, smooth polytetrafluoroethyllining lining
(volume 200mL).Under the conditions of 160 DEG C, the closed reactor equipped with mixture stir in heating by oil bath pan
It mixes (as shown in Figure 1), the revolving speed of stirring is 600~800rpm, and the hydro-thermal reaction time 12h is cooled to room temperature, the production that will be obtained
Object is first separated with centrifuge, then is washed repeatedly with deionized water and dehydrated alcohol, is finally freeze-dried, subzero 70
DEG C freezing in advance completes freezing dry process, obtains ferrous disulfide/MWCNTs composite material finally to room temperature.
Ferrous disulfide/the MWCNTs prepared is adequately ground, and with conductive carbon black (Super P), poly- inclined
Vinyl fluoride (PVDF) is 8 ︰, 1 ︰ 1 weighing according to mass ratio, and the 0.2mol L of 1.2mL will first be added dropwise in load weighted PVDF-1N- first
Base pyrrolidones (NMP) carries out magnetic agitation and is completely dissolved to PVDF, then ferrous disulfide/MWCNTs is mixed with Super P
And be added after being fully ground in above-mentioned solution, continue to stir into paste, it is clean that slurry is uniformly coated on surface with coating machine
Copper foil on, dry 10h under the conditions of coated copper flow collection sheet is placed in a vacuum drying oven 80 DEG C, being cut into diameter is
The disk of 1.0cm is controlled as positive plate, the quality of active material in 1.5~2.0mg.
This exemplary application is in the button cell with good development prospect.
The assembling of battery and the test of performance: the magnesium metal for selecting sand paper polishing bright is as negative electrode tab, by above-mentioned preparation
Good positive plate and negative electrode tab is transferred in the glove box with argon atmosphere (control oxygen content, water content≤0.1ppm), with
0.25M Mg(AlCl2EtBu)2/ THF carries out assembling Mg secondary cell as electrolyte, and the model CR2032 of battery chooses
The Mg secondary cell of this kind of model is the material prepared through the method for the present invention since it is with the advantages such as small in size, easy to operate
Applied to this kind of model Mg secondary cell discharge capacity with higher, there is good answer as a kind of environmental type energy
Use prospect.
As shown in Fig. 2, being the present embodiment in 20mA g-1Constant current charge-discharge curve graph under current density.The head of the battery
Secondary specific discharge capacity is up to 167mAh g-1, and after the circle of circulation 50, specific discharge capacity remains to be maintained at 148mAh g-1,
Show that the composite material of the in-stiu coating preparation of nano-carbon material improves electrode material as magnesium secondary battery cathode material
Electric conductivity provides more channels for the transmission of magnesium ion, to make electrode material initial specific capacities with higher, well
Cyclical stability and structural stability.
Embodiment 2: the weight of carbon material and ferrous disulfide in the ferrous disulfide/nano carbon composite material of the present embodiment
Percentage are as follows: carbon material 2%, ferrous disulfide 98%.
It takes the graphene of 40mg to be placed in the deionized water of 40mL and carries out ultrasonic disperse, after being uniformly dispersed, be transferred to 2.22g
FeSO4·7H2O and 3.87g C3H7NO2In S mixed solution, deionized water total amount is 160mL in solution, and is carried out sufficient
Stirring.(volume is being transferred to above-mentioned mixed solution in the reaction kettle with clean, smooth polytetrafluoroethyllining lining
200mL).Under the conditions of 160 DEG C, heated while stirring (such as Fig. 1 by oil bath pan to the closed reactor equipped with mixture
It is shown), the revolving speed of stirring is 600~800rpm, and hydro-thermal reaction 12h is cooled to room temperature, by obtained product first use centrifuge into
Row separation, then washed repeatedly with deionized water and dehydrated alcohol, it is finally freeze-dried, in subzero 70 DEG C freezings in advance, most
Afterwards to room temperature, freezing dry process is completed, ferrous disulfide/Graphene composite material is obtained.
Ferrous disulfide/the Graphene prepared is adequately ground, and with conductive carbon black (Super P), poly-
Vinylidene (PVDF) is 8 ︰, 1 ︰ 1 weighing according to mass ratio, and the 0.2mol L of 1.2mL will first be added dropwise in load weighted PVDF-1N-
Methyl pyrrolidone (NMP) carries out magnetic agitation and is completely dissolved to PVDF, then ferrous disulfide/MWCNTs and Super P is mixed
Merging is added in above-mentioned solution after being fully ground, and continues to stir into paste, slurry is uniformly coated on surface with coating machine and is done
On net copper foil, by coated copper flow collection sheet to dry 10h under the conditions of 80 DEG C in a vacuum drying oven, being cut into diameter is
The disk of 1.0cm is controlled as positive plate, the quality of active material (ferrous disulfide/Graphene) in 1.5~2.0mg.
The assembling of battery and the test of performance: the magnesium metal for selecting sand paper polishing bright is as negative electrode tab, by above-mentioned preparation
Good positive plate and negative electrode tab is transferred in the glove box with argon atmosphere (control oxygen content, water content≤0.1ppm), with
0.25M Mg(AlCl2EtBu)2/ THF carries out assembling Mg secondary cell as electrolyte, and the model CR2032 of battery chooses
The Mg secondary cell of this kind of model is the material prepared through the method for the present invention since it is with the advantages such as small in size, easy to operate
Applied to this kind of model Mg secondary cell discharge capacity with higher, there is good answer as a kind of environmental type energy
Use prospect.
As shown in figure 3, being the present embodiment in 20mA g-1Constant current charge-discharge curve graph under current density.The head of the battery
Secondary specific discharge capacity reaches 50mAh g-1。
Claims (9)
1. a kind of positive electrode of Mg secondary cell, which is characterized in that the positive electrode is carbon nanomaterial in-stiu coating
Ferrous disulfide is formed by ferrous disulfide/nano carbon composite material, and is applied in Mg secondary cell, and described two
The weight percent of carbon material and ferrous disulfide in ferrous sulfide/nano carbon composite material are as follows: carbon material 2%~5%, two sulphur
Change ferrous iron 98%~95%.
2. a kind of preparation method of the positive electrode of Mg secondary cell as described in claim 1, which is characterized in that specific method
It is as follows:
A. composite material ferrous disulfide/nano-sized carbon is prepared:
Source of iron and sulphur source are mixed in molar ratio, and are added in the deionized water of 150~170mL, is vigorously stirred to mixed
It closes object to be completely dissolved, then acid treated carbon material is added into mixed solution, and 0.5~1h is sufficiently stirred, by mixing liquid
It is transferred in the reaction kettle with polytetrafluoroethyllining lining and is heated, quick stirring, water are always maintained in hydrothermal reaction process
Cooled to room temperature after thermal response is centrifuged with the revolving speed of 8000~10000r/min, with dehydrated alcohol and go from
Sub- water washs product repeatedly, is finally freeze-dried, and the compound of the ferrous disulfide of carbon nanomaterial in-stiu coating is obtained
Material；
B. electrode slice is prepared:
Composite material obtained in step a is fully ground with conductive agent, and is added to the organic solvent of dissolution binder
In be stirred, slurry is uniformly coated on copper current collector with coating machine after mixing evenly, tabletting is carried out after dry, obtains
Positive plate；Selection is negative electrode tab with the bright magnesium metal of sand paper polishing.
3. a kind of preparation method of the positive electrode of Mg secondary cell according to claim 2, which is characterized in that described
Source of iron is ferrous sulfate.
4. a kind of preparation method of the positive electrode of Mg secondary cell according to claim 2, which is characterized in that described
Sulphur source is L-cysteine.
5. a kind of preparation method of the positive electrode of Mg secondary cell according to claim 2, which is characterized in that described
The molar ratio of source of iron and sulphur source is 1~1.2 ︰ 4~4.2.
6. a kind of preparation method of the positive electrode of Mg secondary cell according to claim 2, which is characterized in that described
Hydrothermal temperature is 160~170 DEG C, the water reaction time are as follows: 10~12h.
7. a kind of preparation method of the positive electrode of Mg secondary cell according to claim 2, which is characterized in that described
Carbon material is multi-walled carbon nanotube or single-walled carbon nanotube or graphene.
8. a kind of preparation method of the positive electrode of Mg secondary cell according to claim 2, which is characterized in that step b
In composite material, conductive agent, binder mass ratio be 6~8 ︰, 1~2 ︰ 1~2.
9. a kind of preparation method of the positive electrode of Mg secondary cell according to claim 2, which is characterized in that step b
In drying condition be 70~80 DEG C of 8~10h of vacuum drying.
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| CN109817950A (en) * | 2019-03-15 | 2019-05-28 | 贵州梅岭电源有限公司 | A kind of C cladding MoxCo1-xS2The preparation method of composite positive pole |
| CN111960477A (en) * | 2020-08-20 | 2020-11-20 | 辽宁科技大学 | Preparation method of all-solid-state supercapacitor electrode material |
| WO2021166280A1 (en) * | 2020-02-21 | 2021-08-26 | パナソニックＩｐマネジメント株式会社 | Positive electrode active material and magnesium secondary battery |
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| CN102460796A (en) * | 2009-06-09 | 2012-05-16 | 吉列公司 | Magnesium cell with improved electrolyte |
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| CN102460796A (en) * | 2009-06-09 | 2012-05-16 | 吉列公司 | Magnesium cell with improved electrolyte |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109817950A (en) * | 2019-03-15 | 2019-05-28 | 贵州梅岭电源有限公司 | A kind of C cladding MoxCo1-xS2The preparation method of composite positive pole |
| WO2021166280A1 (en) * | 2020-02-21 | 2021-08-26 | パナソニックＩｐマネジメント株式会社 | Positive electrode active material and magnesium secondary battery |
| JP7546222B2 (en) | 2020-02-21 | 2024-09-06 | パナソニックＩｐマネジメント株式会社 | Positive electrode active material and magnesium secondary battery |
| CN111960477A (en) * | 2020-08-20 | 2020-11-20 | 辽宁科技大学 | Preparation method of all-solid-state supercapacitor electrode material |
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