CN105788886B - A kind of preparation method of manganous oxide@composite carbon electrode materials - Google Patents
A kind of preparation method of manganous oxide@composite carbon electrode materials Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 title claims abstract description 35
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 27
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 19
- 229930006000 Sucrose Natural products 0.000 claims abstract description 19
- 239000005720 sucrose Substances 0.000 claims abstract description 19
- 230000001681 protective effect Effects 0.000 claims abstract description 14
- 150000002696 manganese Chemical class 0.000 claims abstract description 10
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 14
- 229910052748 manganese Inorganic materials 0.000 abstract description 13
- 239000011572 manganese Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- 239000003990 capacitor Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000010405 anode material Substances 0.000 description 12
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 11
- 239000007832 Na2SO4 Substances 0.000 description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 235000002867 manganese chloride Nutrition 0.000 description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 description 11
- 235000011152 sodium sulphate Nutrition 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical class N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 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 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- CGYXXOAWBMZIEZ-UHFFFAOYSA-L [Mn](=O)(Br)Br Chemical class [Mn](=O)(Br)Br CGYXXOAWBMZIEZ-UHFFFAOYSA-L 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- QWYFOIJABGVEFP-UHFFFAOYSA-L manganese(ii) iodide Chemical class [Mn+2].[I-].[I-] QWYFOIJABGVEFP-UHFFFAOYSA-L 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention belongs to combination electrode material preparation fields, and in particular to a kind of preparation method of manganous oxide@composite carbon electrode materials.The specific steps are：Sucrose, ammonium salt and manganese salt are uniformly mixed and is put into crucible and is placed in tube furnace, using inert gas as protective atmosphere, high-temperature calcination is carried out to mixture, after being cooled to room temperature, acquisition manganous oxide@composite carbon electrode materials.Raw material is cheap and easy to get, is not necessarily to any solvent, and technological operation is easy, has saved production cost, and prepared novel oxidized sub- manganese@composite carbon electrode materials have shown excellent chemical property.
Description
Technical field
The invention belongs to combination electrode material preparation fields, and in particular to a kind of manganous oxide@composite carbon electrode materials
Preparation method.
Background technology
With the development of society, demand of the mankind to the energy also increasingly increases.Since traditional fossil energy is increasingly in short supply,
While advocating energy saving and raising energy use efficiency, the energy substitution also repeated in active development passes for national governments
The system energy.The mankind will become more dependent on environmental-friendly, recyclable, efficient new energy, this has more energy storage device
High requirement.Ultracapacitor has both the advantages of ordinary capacitor and rechargeable battery, as energy density is high, power density is high, can
Fast charging and discharging has extended cycle life, has instantaneous high-current discharge and the characteristics such as environmentally safe, is to develop nearly ten years
The novel energy-storing equipment come.And electrode material plays an important role in ultracapacitor, therefore study with high energy storage
The electrode material of performance is the important directions of ultracapacitor research.
Manganous oxide is a kind of important transition metal oxide material, and with rich reserves, cheap, environment is compatible
The advantages that property is good, in recent years, very big progress is achieved in battery, electrode material for super capacitor etc..But it aoxidizes
The low electric conductivity of sub- manganese itself and in charge and discharge process huge volume change cause it is poor caused by the dusting of electrode material
Cyclicity limits the extensive use of manganous oxide ultracapacitor.Therefore, research is with high electrochemical performance, high stability
Novel oxidized sub- manganese base electrode material have a good application prospect.
Secondly, the method for preparing metal salt MnO sills in the prior art is complex and difficult, the specific capacitance value of acquisition
It is relatively low, it is unfavorable for its further popularization and application.
Invention content
For above technical problem, the present invention proposes a kind of one-step calcination of simplicity, and to prepare novel oxidized sub- manganese multiple
Close the application of the method and this material of carbon electrode material in ultracapacitor.
The present invention preparation method the specific steps are：
(1) sucrose, ammonium salt and manganese salt are uniformly mixed,
Wherein, manganese salt is the anaerobics manganese salts, preferably manganese chloride such as the chloride of manganese, bromide, iodide or charing manganese,
The mass ratio of manganese salt and sucrose is 1:1,0.9：1,1.45:1,1.9:1.
Ammonium salt is the water soluble salts, preferably ammonium chloride such as chloride, sulfate, carbonate, nitrate of ammonium,
Ammonium salt plays the role of pore-creating and dispersed metal salt,
The mass ratio of ammonium salt and sucrose is 1:1,2.9：1,2.45:1,1.4:1,1.45:1；
(2) mixture obtained in step (1) crucible is put into be placed in tube furnace；
(3) in the tube furnace in step (2), using inert gas as protective atmosphere, high-temperature calcination is carried out to mixture,
Inert gas is nitrogen, argon gas or the helium that purity is more than 99.99%,
High-temperature calcination operation is, with the heating rate of 1~10 DEG C/min, to be warming up to 500~1050 DEG C, and maintain 1~5h,
As preferred：With the heating rate of 4~8 DEG C/min, 700~1000 DEG C are warming up to, and maintain 2.5~4.5h；
(4) after the product after calcining step (3) high temperature is cooled to room temperature (25 DEG C), manganous oxide@composite carbons are obtained
Electrode material.
The beneficial effects of the present invention are：Manganous oxide@composite carbon electrode materials have been prepared in situ by one-step calcination method
Material.Raw material manganese salt, sucrose and ammonium salt are cheap and easy to get, are not necessarily to any solvent, technological operation is easy, has saved production cost.
Description of the drawings
Fig. 1 is the XRD diagram of the novel oxidized sub- manganese@composite carbon electrode materials obtained by embodiment 1.
Fig. 2 is the novel oxidized sub- manganese@composite carbon electrodes material obtained by embodiment 1 in 1MNa2SO4 solution, 1A/g
Current density under performance cycle figure.
Fig. 3 is the preparation method flow chart of the novel oxidized sub- manganese@composite carbon electrode materials of the present invention.
Specific implementation mode
Embodiment 1
(1) 2g sucrose, 2gNH4Cl and 2g manganese chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) crucible is put into be placed in tube furnace；
(3) in the tube furnace in step (2), the nitrogen using purity more than 99.99% as protective atmosphere, with 6 DEG C/
The heating rate of min rises to 900 DEG C, and maintains this temperature 2.5h, realizes and calcines to mixture；
(4) product after calcining in step (3) is cooled to room temperature, obtains manganous oxide@composite carbon electrode materials.
Fig. 1 is the XRD diagram of above-mentioned product, is characterized through X-ray powder diffraction (XRD), and obtained product is that oxidation is sub-
Manganese@complex carbon materials, wherein manganous oxide corresponds to (JCPDS:07-0230).
Fig. 2 is performance cycle figure of the above-mentioned obtained manganous oxide@complex carbon materials under 1A/g current densities, from
After its cycle charge-discharge 3500 times, it can be seen that obviously decaying does not occur in its specific capacitance.
Supercapacitor positive electrode material is used for using the novel oxidized sub- manganese@composite carbon electrode materials that embodiment 1 is prepared
Material, obtains higher specific capacitance, the experimental results showed that：In 1M Na2SO4 solution, under the current density of 1A/g, than electricity
Appearance has reached 635F/g, shows excellent chemical property.
Embodiment 2
(1) 2g sucrose, 5.8g (NH4) 2CO3 and 1.8g manganess carbides be sufficiently mixed uniformly；
(2) mixture in step (1) crucible is put into be placed in tube furnace；
(3) in the tube furnace in step (2), the nitrogen using purity more than 99.99% as protective atmosphere, with 10 DEG C/
The heating rate of min rises to 1050 DEG C, and maintains this temperature 0.5h, realizes and calcines to mixture；
(4) product after calcining in step (3) is cooled to room temperature, obtains manganous oxide@composite carbon electrode materials.
The manganous oxide@composite carbon electrode materials that this method is prepared are used for super capacitor anode material, obtain
Higher specific capacitance, the experimental results showed that：In 1M Na2SO4 solution, under the current density of 1A/g, specific capacitance reaches
610F/g shows excellent chemical property.
Embodiment 3
(1) 2g sucrose, 4.9g (NH4) 2SO4 and 2.9g manganous bromides be sufficiently mixed uniformly；
(2) mixture in step (1) crucible is put into be placed in tube furnace；
(3) in the tube furnace in step (2), the nitrogen using purity more than 99.99% as protective atmosphere, with 9 DEG C/
The heating rate of min rises to 1000 DEG C, and maintains this temperature 1h, realizes and calcines to mixture；
(4) after being cooled to room temperature the product after calcining in step (3), metal oxide@composite carbon electrode materials are obtained
Material.
The manganous oxide@carbon composites that this method is prepared are used for super capacitor anode material, obtain higher
Specific capacitance, the experimental results showed that：In 1M Na2SO4 solution, under the current density of 1A/g, specific capacitance has reached 628F/
G shows excellent chemical property.
Embodiment 4
(1) 2g sucrose, 2.8g ammonium acetates and 3.8g manganese iodides be sufficiently mixed uniformly；
(2) mixture in step (1) crucible is put into be placed in tube furnace；
(3) in the tube furnace in step (2), the nitrogen using purity more than 99.99% as protective atmosphere, with 8 DEG C/
The heating rate of min rises to 950 DEG C, and maintains this temperature 1.5h, realizes and calcines to mixture；
(4) after being cooled to room temperature the product after calcining in step (3), manganous oxide@composite carbon electrode materials are obtained.
The metal oxide@composite carbon electrode materials that this method is prepared are used for super capacitor anode material, obtain
Higher specific capacitance, the experimental results showed that：In 1M Na2SO4 solution, under the current density of 1A/g, specific capacitance reaches
621F/g shows excellent chemical property.
Embodiment 5
(1) 2g sucrose, 2.2g urea and 2g manganese chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) crucible is put into be placed in tube furnace；
(3) in the tube furnace in step (2), the high pure nitrogen using purity more than 99.99% is as protective atmosphere, with 7
DEG C/heating rate of min rises to 950 DEG C, and maintains this temperature 2h, mixture is realized and is calcined；
(4) after being cooled to room temperature the product after calcining in step (3), manganous oxide@composite carbon electrode materials are obtained.
The manganous oxide@composite carbon electrode materials that this method is prepared are used for super capacitor anode material, obtain
Higher specific capacitance, the experimental results showed that：In 1M Na2SO4 solution, under the current density of 1A/g, specific capacitance reaches
621F/g shows excellent chemical property.
Embodiment 6
(1) 2g sucrose, 2.9gNH4HCO3 and 2g manganese chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) crucible is put into be placed in tube furnace；
(3) in the tube furnace in step (2), the high pure nitrogen using purity more than 99.99% is as protective atmosphere, with 5
DEG C/heating rate of min rises to 850 DEG C, and maintains this temperature 3h, mixture is realized and is calcined；
(4) after being cooled to room temperature the product after calcining in step (3), manganous oxide@composite carbon electrode materials are obtained.
The manganous oxide@composite carbon electrode materials that this method is prepared are used for super capacitor anode material, obtain
Higher specific capacitance, the experimental results showed that：In 1M Na2SO4 solution, under the current density of 1A/g, specific capacitance reaches
615F/g shows excellent chemical property.
Embodiment 7
(1) 2g sucrose, 2gNH4Cl and 2g manganese chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) crucible is put into be placed in tube furnace；
(3) in the tube furnace in step (2), the nitrogen using purity more than 99.99% as protective atmosphere, with 4 DEG C/
The heating rate of min rises to 800 DEG C, and maintains this temperature 3.5h, realizes and calcines to mixture；
(4) after being cooled to room temperature the product after calcining in step (3), metal oxide@composite carbon electrode materials are obtained
Material.
The metal oxide@composite carbon electrode materials that this method is prepared are used for super capacitor anode material, obtain
Higher specific capacitance, the experimental results showed that：In 1M Na2SO4 solution, under the current density of 1A/g, specific capacitance reaches
609F/g shows excellent chemical property.
Embodiment 8
(1) 2g sucrose, 2gNH4Cl and 2g manganese chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) crucible is put into be placed in tube furnace；
(3) in the tube furnace in step (2), the high pure nitrogen using purity more than 99.99% is as protective atmosphere, with 3
DEG C/heating rate of min rises to 700 DEG C, and maintains this temperature 4h, mixture is realized and is calcined；
(4) after being cooled to room temperature the product after calcining in step (3), manganous oxide@composite carbon electrode materials are obtained.
The novel oxidized sub- manganese@composite carbon electrode materials that this method is prepared are used for super capacitor anode material, obtain
Higher specific capacitance was obtained, the experimental results showed that：In 1M Na2SO4 solution, under the current density of 1A/g, specific capacitance reaches
587F/g, shows preferable chemical property.
Embodiment 9
(1) 2g sucrose, 2gNH4Cl and 2g manganese chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) crucible is put into be placed in tube furnace；
(3) in the tube furnace in step (2), the nitrogen using purity more than 99.99% as protective atmosphere, with 2 DEG C/
The heating rate of min rises to 600 DEG C, and maintains this temperature 4.5h, realizes and calcines to mixture；
(4) after being cooled to room temperature the product after calcining in step (3), manganous oxide@composite carbon electrode materials are obtained.
The novel oxidized sub- manganese@composite carbon electrode materials that this method is prepared are used for super capacitor anode material, obtain
Higher specific capacitance was obtained, the experimental results showed that：In 1M Na2SO4 solution, under the current density of 1A/g, specific capacitance reaches
469F/g, shows preferable chemical property.
Embodiment 10
(1) 2g sucrose, 2gNH4Cl and 2g manganese chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) crucible is put into be placed in tube furnace；
(3) in the tube furnace in step (2), the high pure nitrogen using purity more than 99.99% is as protective atmosphere, with 1
DEG C/heating rate of min rises to 500 DEG C, and maintains this temperature 5h, mixture is realized and is calcined；
(4) after being cooled to room temperature the product after calcining in step (3), manganous oxide@composite carbon electrode materials are obtained.
The manganous oxide@composite carbon electrode materials that this method is prepared are used for super capacitor anode material, obtain
Very high specific capacitance, the experimental results showed that：In 1M Na2SO4 solution, under the current density of 1A/g, specific capacitance reaches
402F/g shows preferable chemical property.
Reference examples 1
The preparation method of nano oxidized Asia manganese particle, includes the following steps：
(1) by 2g manganese chloride ultrasonic dissolutions in water, sodium hydroxide solution is added dropwise and adjusts pH to 12, stirs evenly；
(2) product of step (1) is filtered, isolates solid product；
(3) solid product obtained in step (2) is put into crucible to be placed in tube furnace, with nitrogen, (purity is more than
99.99%)/hydrogen rises to 500 DEG C as atmosphere, with the heating rate of 3 DEG C/min, and maintains this temperature 5h, after reaction,
Obtain nanometer MnO particles.
Super capacitor anode material is used for using the nanometer MnO granular materials that reference examples 1 are prepared, in 1MNa2SO4
In solution, under the current density of 1A/g, specific capacitance only has 35F/g, shows that its chemical property is very poor.
Reference examples 2
The preparation method of nano-metal-oxide-carbon composite, includes the following steps：
(1) 2g sucrose and 2g manganese chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) crucible is put into be placed in tube furnace；
(3) in the tube furnace in step (2), the high pure nitrogen using purity more than 99.99% is as protective atmosphere, with 6
DEG C/heating rate of min rises to 900 DEG C, and maintains this temperature 2.5h, mixture is realized and is calcined；
(4) after being cooled to room temperature the product after calcining in step (3), metal oxide-carbon composite materials are obtained.
It is used for super capacitor anode material using the metal oxide-carbon composite materials that reference examples 2 are prepared, in 1M
In Na2SO4 solution, under the current density of 1A/g, specific capacitance has reached 127F/g, shows its chemical property relative to this hair
Bright novel oxidized sub- manganese complex carbon material wants poor.
Reference examples 3
The preparation method of nano-metal-oxide-graphene (RGO) composite material, includes the following steps：
(1) 2g graphite oxides are placed in ultrasonic disperse 30min in 60mL ethyl alcohol；
(2) 2g manganese chloride ultrasonic dissolutions are added dropwise in the mixed liquor of (1) and are stirred evenly, then hydroxide is added dropwise in water
Sodium solution adjusts pH to 11, stirs evenly, is placed in water heating kettle, 120 DEG C of reaction 4h；
(3) product of step (2) is filtered, isolates solid product；
(4) as atmosphere, 900 DEG C are risen to the heating rate of 6 DEG C/min for nitrogen (purity is more than 99.99%)/hydrogen,
And this temperature 2.5h is maintained, MnO-RGO composite materials are obtained after reaction.
Super capacitor anode material is used for using the MnO-RGO composite materials that reference examples 3 are prepared, in 1MNa2SO4
In solution, under the current density of 1A/g, specific capacitance only has 340F/g, shows its chemical property relative to the novel of the present invention
Wanting for manganous oxide complex carbon material is poor.
Claims (7)
1. a kind of preparation method of manganous oxide composite carbon electrode material, it is characterised in that：The specific steps of the preparation method
For,
(1) sucrose, ammonium salt and manganese salt are uniformly mixed；The manganese salt is anaerobic manganese salt；
(2) mixture obtained in step (1) crucible is put into be placed in tube furnace；
(3) in the tube furnace in step (2), using inert gas as protective atmosphere, high-temperature calcination is carried out to the mixture；
(4) after the product after calcining step (3) high temperature is cooled to room temperature, manganous oxide composite carbon electrode material is obtained.
2. the preparation method of manganous oxide composite carbon electrode material as described in claim 1, it is characterised in that：In step (1),
The mass ratio of manganese salt and sucrose is 1:1,0.9：1,1.45:1,1.9:1.
3. the preparation method of manganous oxide composite carbon electrode material as described in claim 1, it is characterised in that：In step (1)
The ammonium salt is ammonium chloride.
4. the preparation method of manganous oxide composite carbon electrode material as described in claim 1, it is characterised in that：In step (1),
The mass ratio of ammonium salt and sucrose is 1:1,2.9：1,2.45:1,1.4:1,1.45:1.
5. the preparation method of manganous oxide composite carbon electrode material as described in claim 1, it is characterised in that：In step (3)
The inert gas is nitrogen, argon gas or the helium that purity is more than 99.99%.
6. the preparation method of manganous oxide composite carbon electrode material as described in claim 1, it is characterised in that：In step (3)
The high-temperature calcination operation is to be warming up to 500~1050 DEG C with the heating rate of 1~10 DEG C/min, and maintain 1~5h.
7. the manganous oxide composite carbon electrode material that the preparation method as shown in any one of claim 1 to 6 obtains is in super electricity
Application in container.
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Application publication date: 20160720 Assignee: JIANGSU RONGSHENG ELECTRONIC CO.,LTD. Assignor: CHANGZHOU University|NANTONG JIANGHAI CAPACITOR Co.,Ltd. Contract record no.: X2024980000484 Denomination of invention: Preparation method of manganese oxide @ composite carbon electrode material Granted publication date: 20181019 License type: Common License Record date: 20240110 |