CN106876702B - A kind of preparation method and application of sodium-ion battery cathode - Google Patents
A kind of preparation method and application of sodium-ion battery cathode Download PDFInfo
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- CN106876702B CN106876702B CN201710069960.7A CN201710069960A CN106876702B CN 106876702 B CN106876702 B CN 106876702B CN 201710069960 A CN201710069960 A CN 201710069960A CN 106876702 B CN106876702 B CN 106876702B
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- sodium chloride
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- tar pitch
- sodium
- ion battery
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 100
- 239000011780 sodium chloride Substances 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011294 coal tar pitch Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 32
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 26
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 21
- 239000013077 target material Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 14
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 14
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 11
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 10
- -1 thio ammonium molybdate Chemical compound 0.000 claims abstract description 10
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 235000021463 dry cake Nutrition 0.000 claims abstract description 4
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 235000012970 cakes Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 240000000972 Agathis dammara Species 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 230000002441 reversible effect Effects 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 239000010405 anode material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 235000002639 sodium chloride Nutrition 0.000 description 44
- 239000007789 gas Substances 0.000 description 9
- 239000007773 negative electrode material Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 8
- 239000006230 acetylene black Substances 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/36—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
-
- 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)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to nano material production technical field, a kind of sodium-ion battery cathode coal tar pitch resin base amorphous carbon coats the preparation method and application of few layer molybdenum disulfide nano box.Preparation method includes following procedure: saturated aqueous sodium chloride is added dropwise in dehydrated alcohol, sodium chloride template is made in dry cake after suction filtration, coal tar pitch resin, four thio ammonium molybdate, pore creating material polymethyl methacrylate and sodium chloride template are added to by a certain percentage in N-methyl pyrrolidones, agitating and heating solvent evaporated carries out carbonization treatment, it is cooled to room temperature taking-up, it adopts and sodium chloride template is washed with deionized, obtain target material after dry and be applied particularly in sodium-ion battery.The invention has the advantages that: the carbon source and pore creating material used is from a wealth of sources, cheap;Sodium chloride template and N-methyl pyrrolidinone solvent can be recycled, at low cost;Target material shows higher reversible storage sodium capacity and preferable high rate performance as anode material of lithium-ion battery.
Description
Technical field
Wataru of the present invention and a kind of sodium-ion battery cathode coat few layer molybdenum disulfide with coal tar pitch resin base amorphous carbon and receive
The preparation method and application of rice box, belongs to nano material production technical field.
Background technique
Electric energy is the critical energy for maintaining human society operation and development, and needs largely to store up during the utilization of electric energy
It can device.Lithium ion battery has the excellent properties such as high voltage, high-energy density and long circulation life, obtains in daily life
It is widely applied.But lithium resource content in the earth's crust is limited and is unevenly distributed, and in the case where not considering recycling, has verified lithium
Resource reserve is only able to satisfy the demand of human future decades.Thus make using lithium ion battery as extensive energy storage device
With, however it remains it is some to be difficult to overcome the problems, such as.In view of sodium and lithium have similar physicochemical properties and similar storage
Mechanism, and rich reserves, the cost of raw material are cheap in nature, sodium-ion battery has huge for large-scale energy storage system
Potentiality.
Electrode material is the critical issue in sodium-ion battery technology, for negative electrode material, novel sodium-ion battery master
It will be using amorphous carbon, metal sulfide, tin, antimony etc..Wherein the conductive good, structure of amorphous carbon is easy to regulation, cost
The advantages that low, good cycling stability, but its to store up sodium specific capacity limited.Laminated metal sulfide specific capacity with higher, still
Poorly conductive, and volume change is obvious in cyclic process, capacity attenuation is rapid.Xie X [Xie X, Makaryan T, Zhao
M, et al. MoS2 Nanosheets Vertically Aligned on Carbon Paper: A Freestanding
Electrode for Highly Reversible Sodium‐Ion Batteries [J]. Advanced Energy
Materials, 2015, DOI:10.1002/aenm.201502161] by molybdenum disulfide nano sheet vertical-growth on carbon paper
It is prepared for carbon/molybdenum disulfide composite material, but since molybdenum disulfide nano sheet is not coated by carbon base body, and nanometer sheet is multilayer
The reasons such as structure, the specific capacity and high rate performance of material are still not ideal enough.Carbon coating is lacked layer molybdenum disulfide structure and can obviously be pressed down
Volume change in charge and discharge process processed, while carbon substrate ensure that the good electric conductivity of composite material, be expected to obtain specific capacity
High, good cycling stability anode material of lithium-ion battery.
The microscopic appearance and structure of C-base composte material will affect material and electrolyte contacts area, sodium ion diffusion path
Deng finally influencing material electrochemical performance.Nanometer box is the nanostructure assembled by two-dimensional nano piece, is had and electrolysis
The advantages that liquid contact area is big, and sodium ion transmission path is short is expected to prepare high performance electrode material.Traditional carbon-based nano box with
Di-iron trioxide nano particle etc. is template, needs pickling to remove removing template, preparation process complexity and environment easy to pollute after carbonization, no
Conducive to large-scale production.
Summary of the invention
In order to overcome the deficiencies in the prior art, it is an object of the present invention to provide a kind of sodium-ion battery cathode to be dripped with coal
Green resin base amorphous carbon coats the preparation method and application of few layer molybdenum disulfide nano box.The preparation method preparation process letter
Single, raw material sources are abundant, and prepared composite material, which is used as sodium-ion battery cathode, has that specific capacity is high, good rate capability and follow
The advantages that ring is had excellent performance.
In order to achieve the above-mentioned object of the invention, in the presence of solving the problems, such as prior art, technical solution that the present invention takes
Be: a kind of sodium-ion battery cathode coal tar pitch resin base amorphous carbon coats the preparation side of few layer molybdenum disulfide nano box
Method, comprising the following steps:
Step 1, at room temperature, saturated aqueous sodium chloride is added dropwise in dehydrated alcohol, and dry cake is made after suction filtration
Sodium chloride template, the saturated aqueous sodium chloride and dehydrated alcohol mass ratio are 1:5-30, and filtration cakes torrefaction temperature is controlled in 80-
120 oC, drying time control in 2-10 h;
Coal tar pitch resin is dissolved in N-methyl pyrrolidones by step 2, and four thio ammonium molybdate and the poly- first of pore creating material is added
The sodium chloride template as made from step 1 is added in base methyl acrylate thereto after being completely dissolved, stir lower solvent evaporated, described
Solvent vapo(u)rizing temperature is controlled in 150-210oThe mass ratio of C, coal tar pitch resin and N-methyl pyrrolidones is 1:5-50, coal drip
The mass ratio of green resin and pore creating material polymethyl methacrylate is 1:0.1-2, the matter of coal tar pitch resin and four thio ammonium molybdate
Ratio is measured as 1:0.5-5, the mass ratio of coal tar pitch resin and sodium chloride template is 1:1-20;
Step 3, the mixture for obtaining step 2 carry out carbonization treatment under inert gas protection, and temperature is with 2 ~ 10oC/
Min heating rate rises to 600-900oC, constant temperature 1-3 h, the inert gas are selected from one of nitrogen or argon gas;
Sample after step 3 carbonization treatment is cooled to room temperature by step 4, adopts and sodium chloride template is washed with deionized simultaneously
It is dried, temperature is controlled in 90-120oC, time control in 3-10 h, and it is amorphous to obtain target material coal tar pitch resin base
Carbon coating lacks layer molybdenum disulfide nano box.
The preparation method prepares coal tar pitch resin base amorphous carbon and coats few layer molybdenum disulfide nano box in sodium ion
Application in battery.
The medicine have the advantages that a kind of sodium-ion battery cathode coal tar pitch resin base amorphous carbon coats few two sulphur of layer
Change the preparation method and application of molybdenum nanometer box, wherein preparation method is the following steps are included: (1) at room temperature, sodium chloride is saturated
Aqueous solution is added dropwise in dehydrated alcohol, and sodium chloride template is made in dry cake after suction filtration, and coal tar pitch resin is dissolved in nitrogen by (2)
In methyl pyrrolidone, four thio ammonium molybdate and pore creating material polymethyl methacrylate is added, is added thereto after being completely dissolved
The sodium chloride template as made from step 1 stirs lower solvent evaporated, and the mixture that (3) obtain step 2 is under inert gas protection
Carbonization treatment is carried out, the sample after step 3 carbonization treatment is cooled to room temperature, adopts and sodium chloride template is washed with deionized by (4)
And be dried, it obtains target material coal tar pitch resin base amorphous carbon and coats few layer molybdenum disulfide nano box.With existing skill
Art is compared, the invention has the following advantages that first is that, carbon source used in the present invention and pore creating material are from a wealth of sources, cheap;Two
It is that preparation method is simple, it is environmentally protective using water-soluble sodium chloride template;Third is that sodium chloride template and N-methyl pyrroles
Alkanone solvent can be recycled, lower production costs, it is easy to accomplish large-scale production;Fourth is that molybdenum disulfide is dispersed with few layer
In carbon substrate, be conducive to sufficiently inhibit volume change in charge and discharge process;Fifth is that coal tar pitch resin base prepared by the present invention without
Setting carbon coating lacks layer molybdenum disulfide nano box as anode material of lithium-ion battery and shows higher reversible storage sodium capacity,
Preferable high rate performance and excellent cycle performance.
Detailed description of the invention
Fig. 1 is that coal tar pitch resin base amorphous carbon prepared by the embodiment of the present invention 1 coats few layer molybdenum disulfide nano box
Stereoscan photograph figure.
Fig. 2 is that coal tar pitch resin base amorphous carbon prepared by the embodiment of the present invention 1 coats few layer molybdenum disulfide nano box
Transmission electron microscope photo figure.
Fig. 3 is that coal tar pitch resin base amorphous carbon prepared by the embodiment of the present invention 1 coats few layer molybdenum disulfide nano box
X ray diffracting spectrum.
Fig. 4 is that coal tar pitch resin base amorphous carbon prepared by the embodiment of the present invention 1 coats few layer molybdenum disulfide nano box
Charge-discharge performance curve graph in sodium ion half-cell under different current densities.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Embodiment 1
At room temperature, 100 g saturated aqueous sodium chlorides are added dropwise in 500 g dehydrated alcohols, filter and filter cake exists
100 oC is dry, and sodium chloride template is made in 2 h;2 g coal tar pitch resins are dissolved in 60 g N-methyl pyrrolidones, thereto
3 g four thio ammonium molybdates, 1 g pore creating material polymethyl methacrylate are added, 20 g sodium chloride templates are added after being completely dissolved,
205 oAgitating and heating is evaporated N-methyl pyrrolidones in C oil bath;Obtained mixture is carbonized, in tube furnace under argon gas protection
With 5oC/min is warming up to 700oC, 2 h of constant temperature, takes out after being cooled to room temperature, then sodium chloride template is washed with deionized,
90 oC dries 8 h, and target material coal tar pitch resin base amorphous carbon is made and coats few layer molybdenum disulfide nano box.It is scanned
Electromicroscopic photograph figure as shown in Figure 1, transmission electron microscope photo figure as shown in Fig. 2, X ray diffracting spectrum is as shown in Figure 3.By target material
With acetylene black, PVDF(polyvinylidene fluoride) according to 7:2:1 mass ratio preparation negative electrode material, collector is copper foil, in glove box
Middle assembling sodium-ion battery.Battery performance, charging/discharging voltage are tested on Land CT2001A type battery test system
Range is 0.01-3 V, measures the material in 0.1 A g of charge-discharge velocity-1Under conditions of reversible capacity up to 552.9 mAh g-1,
Its charge-discharge performance curve graph is as shown in Figure 4.
Embodiment 2
At room temperature, 150 g saturated aqueous sodium chlorides are added dropwise in 1000 g dehydrated alcohols, filter and filter cake exists
100 oC is dry, and sodium chloride template is made in 2 h;2 g coal tar pitch resins are dissolved in 40 g N-methyl pyrrolidones, thereto
3 g four thio ammonium molybdates, 2 g pore creating material polymethyl methacrylates are added, 20 g sodium chloride templates are added after being completely dissolved,
200 oAgitating and heating is evaporated N-methyl pyrrolidones in C oil bath;Obtained mixture is carbonized, in tube furnace under argon gas protection
With 5oC/min is warming up to 800oC, 1 h of constant temperature, takes out after being cooled to room temperature, then sodium chloride template is washed with deionized,
90 oC dries 10h, and target material coal tar pitch resin base amorphous carbon is made and coats few layer molybdenum disulfide nano box.By target
Material and acetylene black, PVDF(polyvinylidene fluoride) according to 7:2:1 mass ratio preparation negative electrode material, collector is copper foil, in hand
Sodium-ion battery is assembled in casing.Battery performance, charge and discharge are tested on Land CT2001A type battery test system
Voltage range is 0.01-3 V, measures the material in 0.1 A g of charge-discharge velocity-1Under conditions of reversible capacity up to 514.3 mAh
g-1。
Embodiment 3
At room temperature, 130 g saturated aqueous sodium chlorides are added dropwise in 700 g dehydrated alcohols, filter and filter cake exists
80 oC is dry, and sodium chloride template is made in 10 h;2 g coal tar pitch resins are dissolved in 80 g N-methyl pyrrolidones, thereto
2 g four thio ammonium molybdates, 1g pore creating material polymethyl methacrylate are added, are added 20 g sodium chloride templates after being completely dissolved, 200oAgitating and heating is evaporated N-methyl pyrrolidones in C oil bath;Obtained mixture is carbonized, with 5 under argon gas protection in tube furnaceoC/min is warming up to 700oC, 2 h of constant temperature, takes out after being cooled to room temperature, then sodium chloride template is washed with deionized, 90oC
Dry 8h is made target material coal tar pitch resin base amorphous carbon and coats few layer molybdenum disulfide nano box.By target material with
Acetylene black, PVDF(polyvinylidene fluoride) according to 7:2:1 mass ratio preparation negative electrode material, collector is copper foil, in glove box
Assemble sodium-ion battery.Battery performance, charging/discharging voltage model are tested on Land CT2001A type battery test system
It encloses for 0.01-3 V, measures the material in 0.1 A g of charge-discharge velocity-1Under conditions of reversible capacity up to 473.1 mAh g-1。
Embodiment 4
At room temperature, 90 g saturated aqueous sodium chlorides are added dropwise in 500 g dehydrated alcohols, are filtered and by filter cake 90oC is dry, and sodium chloride template is made in 2h;2 g coal tar pitch resins are dissolved in 60 g N-methyl pyrrolidones, are added thereto
4g four thio ammonium molybdate, 1g pore creating material polymethyl methacrylate, are added 20 g sodium chloride templates after being completely dissolved, and 200oC oil
Agitating and heating is evaporated N-methyl pyrrolidones in bath;Obtained mixture is carbonized, with 5 under argon gas protection in tube furnaceoC/
Min is warming up to 700oC, constant temperature 3h take out after being cooled to room temperature, then sodium chloride template is washed with deionized, 100oC is dry
4h is made target material coal tar pitch resin base amorphous carbon and coats few layer molybdenum disulfide nano box.By target material and acetylene
Black, PVDF(polyvinylidene fluoride) according to 7:2:1 mass ratio preparation negative electrode material, collector is copper foil, is assembled in glove box
Sodium-ion battery.Battery performance is tested on Land CT2001A type battery test system, charging/discharging voltage range is
0.01-3 V measures the material in 0.1 A g of charge-discharge velocity-1Under conditions of reversible capacity up to 546.8 mAh g-1。
Embodiment 5
At room temperature, 100 g saturated aqueous sodium chlorides are added dropwise in 500 g dehydrated alcohols, filter and filter cake exists
100 oC is dry, and sodium chloride template is made in 5h;2 g coal tar pitch resins are dissolved in 60 g N-methyl pyrrolidones, thereto
3g four thio ammonium molybdate, 2g pore creating material polymethyl methacrylate is added, 20 g sodium chloride templates are added after being completely dissolved,
205oAgitating and heating is evaporated N-methyl pyrrolidones in C oil bath;Obtained mixture is carbonized, in tube furnace under argon gas protection with
5 oC/min is warming up to 900oC, constant temperature 1h take out after being cooled to room temperature, then sodium chloride template is washed with deionized, 100oC dries 5h, and target material coal tar pitch resin base amorphous carbon is made and coats few layer molybdenum disulfide nano box.By target material
With acetylene black, PVDF(polyvinylidene fluoride) according to 7:2:1 mass ratio preparation negative electrode material, collector is copper foil, in glove box
Middle assembling sodium-ion battery.Battery performance, charging/discharging voltage are tested on Land CT2001A type battery test system
Range is 0.01-3 V, measures the material in 0.1 A g of charge-discharge velocity-1Under conditions of reversible capacity up to 533.7 mAh g-1。
Embodiment 6
At room temperature, 130 g saturated aqueous sodium chlorides are added dropwise in 700 g dehydrated alcohols, filter and filter cake exists
90 oC is dry, and sodium chloride template is made in 5h;2 g coal tar pitch resins are dissolved in 50 g N-methyl pyrrolidones, thereto plus
Enter 3g four thio ammonium molybdate, 1g pore creating material polymethyl methacrylate, is added 10 g sodium chloride templates after being completely dissolved, 200oC
Agitating and heating is evaporated N-methyl pyrrolidones in oil bath;Obtained mixture is carbonized, with 5 under argon gas protection in tube furnaceoC/
Min is warming up to 800oC, constant temperature 2h take out after being cooled to room temperature, then sodium chloride template is washed with deionized, 90oC is dry
10h is made target material coal tar pitch resin base amorphous carbon and coats few layer molybdenum disulfide nano box.By target material and acetylene
Black, PVDF(polyvinylidene fluoride) according to 7:2:1 mass ratio preparation negative electrode material, collector is copper foil, is assembled in glove box
Sodium-ion battery.Battery performance is tested on Land CT2001A type battery test system, charging/discharging voltage range is
0.01-3 V measures the material in 0.1 A g of charge-discharge velocity-1Under conditions of reversible capacity up to 548.2 mAh g-1。
Comparative example 1
At room temperature, 100 g saturated aqueous sodium chlorides are added dropwise in 500 g dehydrated alcohols, filter and filter cake exists
100 oC is dry, and sodium chloride template is made in 2h;2 g coal tar pitch resins are dissolved in 60 g N-methyl pyrrolidones, thereto
1g pore creating material polymethyl methacrylate is added, addition 20g sodium chloride template after being completely dissolved, 200oAgitating and heating in C oil bath
It is evaporated N-methyl pyrrolidones;Obtained mixture is carbonized, with 5 under argon gas protection in tube furnaceoC/min is warming up to 700oC,
Constant temperature 2h takes out after being cooled to room temperature, then sodium chloride template is washed with deionized, 100oC dries 5h, and composite wood is made
Material.By composite material and acetylene black, PVDF(polyvinylidene fluoride) according to 7:2:1 mass ratio preparation negative electrode material, collector is
Copper foil assembles sodium-ion battery in glove box.Battery electrochemical is tested on Land CT2001A type battery test system
Can, charging/discharging voltage range is 0.01-3 V, measures the material in 0.1 A g of charge-discharge velocity-1Under conditions of reversible capacity reach
276.4 mAh g-1。
Comparative example 2
At room temperature, 90 g saturated aqueous sodium chlorides are added dropwise in 500 g dehydrated alcohols, filter and filter cake exists
100 oC is dry, and sodium chloride template is made in 2h;2 g coal tar pitch resins are dissolved in 60 g N-methyl pyrrolidones, thereto
3 g four thio ammonium molybdates are added, addition 20g sodium chloride template after being completely dissolved, 200oAgitating and heating is evaporated N-methyl in C oil bath
Pyrrolidones;Obtained mixture is carbonized, with 5 under argon gas protection in tube furnaceoC/min is warming up to 700oC, constant temperature 2h are cold
But to taking out after room temperature, then sodium chloride template is washed with deionized, 100oC dries 5h, and composite material is made.It will be compound
Material and acetylene black, PVDF(polyvinylidene fluoride) according to 7:2:1 mass ratio preparation negative electrode material, collector is copper foil, in hand
Sodium-ion battery is assembled in casing.Battery performance, charge and discharge are tested on Land CT2001A type battery test system
Voltage range is 0.01-3 V, measures the material in 0.1 A g of charge-discharge velocity-1Under conditions of reversible capacity up to 432.7 mAh
g-1。
Four thio ammonium molybdate is added without from comparative example 1(), comparative example 2(is added without pore creating material polymethyl methacrylate) system
The composite material obtained is found out compared with embodiment 1 to 6, and battery electrification is tested on Land CT2001A type battery test system
Performance is learned, charging/discharging voltage range is 0.01-3 V, measures the material in 0.1 A g of charge-discharge velocity-1Under conditions of reversible appearance
Amount significantly reduces.
Claims (2)
1. a kind of sodium-ion battery cathode coats the preparation method of molybdenum disulfide nano box with coal tar pitch resin base amorphous carbon,
Characterized by the following steps:
Step 1, at room temperature, saturated aqueous sodium chloride is added dropwise in dehydrated alcohol, and chlorination is made in dry cake after suction filtration
Sodium template, the saturated aqueous sodium chloride and dehydrated alcohol mass ratio are 1:5-30, and filtration cakes torrefaction temperature is controlled in 80-120oC, drying time control in 2-10 h;
Coal tar pitch resin is dissolved in N-methyl pyrrolidones by step 2, and four thio ammonium molybdate and the poly- methyl-prop of pore creating material is added
The sodium chloride template as made from step 1 is added in e pioic acid methyl ester thereto after being completely dissolved, stir lower solvent evaporated, the solvent
Vapo(u)rizing temperature is controlled in 150-210oThe mass ratio of C, coal tar pitch resin and N-methyl pyrrolidones is 1:5-50, coal tar pitch tree
The mass ratio of rouge and pore creating material polymethyl methacrylate is 1:0.1-2, the mass ratio of coal tar pitch resin and four thio ammonium molybdate
For 1:0.5-5, the mass ratio of coal tar pitch resin and sodium chloride template is 1:1-20;
Step 3, the mixture for obtaining step 2 carry out carbonization treatment under nitrogen or argon, and temperature is with 2 ~ 10oC/min
Heating rate rises to 600-900oC, constant temperature 1-3 h;
Sample after step 3 carbonization treatment is cooled to room temperature by step 4, adopts and sodium chloride template is washed with deionized and carries out
Dry, temperature is controlled in 90-120oC, time control in 3-10 h, obtain target material coal tar pitch resin Ji Wudingxingtanbao
Cover molybdenum disulfide nano box.
2. the coal tar pitch resin base amorphous carbon of preparation method preparation coats molybdenum disulfide nano box according to claim 1
Application in sodium-ion battery.
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