CN109378473A - The modified carbon-supported copper catalyst of nitrogen and its application in terms of cell positive material - Google Patents
The modified carbon-supported copper catalyst of nitrogen and its application in terms of cell positive material Download PDFInfo
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- CN109378473A CN109378473A CN201810949789.3A CN201810949789A CN109378473A CN 109378473 A CN109378473 A CN 109378473A CN 201810949789 A CN201810949789 A CN 201810949789A CN 109378473 A CN109378473 A CN 109378473A
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- nitrogen
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- modified carbon
- copper catalyst
- supported copper
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000010949 copper Substances 0.000 title claims abstract description 63
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 61
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019441 ethanol Nutrition 0.000 claims abstract description 9
- 239000002608 ionic liquid Substances 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- FQTUOJOWQBMFTM-UHFFFAOYSA-N 1-butyl-3-ethenyl-2h-imidazole Chemical compound CCCCN1CN(C=C)C=C1 FQTUOJOWQBMFTM-UHFFFAOYSA-N 0.000 claims abstract description 4
- WLWHLUQQCLCFNE-UHFFFAOYSA-N 1-ethenyl-3-methyl-2h-imidazole Chemical compound CN1CN(C=C)C=C1 WLWHLUQQCLCFNE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000003273 ketjen black Substances 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 8
- 229960004756 ethanol Drugs 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 150000001721 carbon Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000001354 calcination Methods 0.000 abstract description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 17
- 239000007788 liquid Substances 0.000 description 14
- 229910006124 SOCl2 Inorganic materials 0.000 description 12
- 229920000831 ionic polymer Polymers 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 229910006762 Li—SOCl2 Inorganic materials 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- DGIDDDIFEQSDJB-UHFFFAOYSA-J [Cl-].[Cl-].[Cl-].[Cl-].[Li+].[Li+].[Li+].[Li+] Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Li+].[Li+].[Li+].[Li+] DGIDDDIFEQSDJB-UHFFFAOYSA-J 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000011152 fibreglass Substances 0.000 description 3
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- 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
- 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
-
- 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
- H01M4/626—Metals
-
- 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
Abstract
The invention discloses the modified carbon-supported copper catalyst of nitrogen, which is prepared by the following method to obtain: ionic liquid and nano cupric oxide being dispersed in after ethyl alcohol, azodiisobutyronitrile is added, in N270 ~ 90 DEG C back flow reaction 20 ~ 25 hours under the atmosphere of protection, centrifuge washing obtains paste precursor, under nitrogen atmosphere 500 ~ 600 DEG C of calcining 6 ~ 8 hours carbon-supported copper catalysts modified up to nitrogen；Ionic liquid is 1- vinyl -3- methylimidazole cdicynanmide, 1- vinyl -3- ethyl imidazol(e) cdicynanmide or 1- vinyl -3- butyl imidazole cdicynanmide.The invention also discloses application of the catalyst in terms of cell positive material.The modified carbon-supported copper catalyst of nitrogen of the present invention has high catalytic activity and electric conductivity.
Description
Technical field
The present invention relates to the modified carbon-supported copper catalyst of nitrogen and its applications in terms of cell positive material, belong to electrification
Learn technical field.
Background technique
Lithium thionyl chloride cell (Li-SOCl2) be known because of the advantage of its high working voltage and high-energy density.
As one kind of lithium battery, for the battery system using lithium as cathode, carbon is anode, aluminum tetrachloride lithium and thionyl chloride (SOCl2) be
Electrolyte.Since with excellent chemical property, such as stable load voltage, longer battery life and wide temperature are answered
With range, many concerns are caused in the practical applications such as military and civilian product.However, actually Li-SOCl2Battery
Energy density is far below theoretical value (590 Wh kg-1), hinder its extensive use.Existing research shows SOCl2It is adsorbed onto
Reduction reaction occurs when on porous carbon anode: 2SOCl2+4e-→S+SO2+4Cl-.Porous carbon positive electrode serves not only as SOCl2's
Carrier and catalysis SOCl2Reduction, but SOCl2Reduction in solid electrolyte interface is slow and cannot support high electricity
Galvanic electricity tank discharge.Therefore, to raising Li-SOCl2Battery performance, a kind of possible way are addition catalyst.
According to previous studies, transition metal macrocyclic compound is considered as SOCl2The effective catalyst of reduction, such as mistake
The complex for crossing metal (Co, Ni, V, Cu, Mn) phthalocyanine and porphyrin composition can effectively be catalyzed SOCl2Reduction.
Meanwhile researcher has found binuclear metal phthalocyanine coordination compound in Li-SOCl2Higher catalytic performance ratio is shown in battery in list
In core phthalocyanine.Researcher's preparation has synthesized a variety of binuclear transition metal macrocyclic compound elctro-catalysts and has applied in Li-SOCl2Electricity
Pond.However, above-mentioned transition metal macrocyclic catalyst is soluble in Li-SOCl2In the electrolyte of battery, the big ring of soluble transition metal
Catalyst in anodic deposition and usually will increase the corrosion rate of cathode of lithium and anodic protection film thickness caused to be spent by migration
Greatly, it is restricted so as to cause its practical application.
In a fuel cell as a kind of efficient elctro-catalyst application, wherein N doped carbon is to pass through carbon material to N doped carbon
The thermal decomposition mixed with nitrogen-containing precursor is obtained.Zheng et al. (Electrochem. Commun., 28 (2013) 24- 26) describe pyrolytic N doping carbon material, it was confirmed that N doping after there is carbon structure defect while generating new activity
Site.Liu et al. (Appl. Catal., A, 523 (2016) 241-246) mixed by high temperature thermal decomposition urea and graphene
Object is closed, N doped graphene elctro-catalyst is prepared for and is applied to Li-SOCl2Battery, so that the operating voltage of battery and capacity have one
Fixed raising.However, synthesis is more stable and does not dissolve in SOCl2Electrolyte simultaneously can efficient catalytic SOCl2The catalyst of reduction is very
It is necessary to.Therefore, many researchs concentrate on exploitation for restoring SOCl2Effective catalyst significantly to reduce overpotential.
As the allotrope of covalent carbonitride solid, the modified carbon of nitrogen has big specific surface area, effective electricity
The transport and separation in sub- hole pair, and the carbon that nitrogen is modified is due to its special electronic band structure, it is novel as one kind
Non-metal catalyst be successfully introduced.In addition, nitrogen species play to pass weight the excellent catalytic performance of metal nitrogen C catalyst
The effect wanted, wherein nitrogen species can be used as potential promotor to construct active site and adjust the electronic property of catalyst.Meanwhile
Metallic copper has the second high conductivity, and (only 6%) smaller than Ag, the performance of active site can be improved in this.Therefore, it is catalyzed containing Cu
Material is widely used in catalytic industries.Cu polymerization of olefin using catalyst compound such as Cu(II) phthalocyanine be in homogeneous or heterogeneous catalytic reaction write
The oxidation reduction catalyst of name.
Summary of the invention
The purpose of the present invention is to provide the modified carbon-supported copper catalyst of nitrogen and its answering in terms of cell positive material
With.
The modified carbon-supported copper catalyst of nitrogen of the present invention has high catalytic activity and electric conductivity.The present invention is with ion
It after the fully wrapped around nano cupric oxide of liquid, is roasted in a nitrogen atmosphere in this, as carrier, what wherein poly ion liquid wrapped up receives
Rice copper oxide is reduced into Ni metal, and the modified carbon-supported copper catalyst of the nitrogen being prepared is as non-water system Li-SOCl2Battery
Anode catalyst when, to SOCl2Reduction catalytic activity with higher.The high activity of catalyst of the present invention has benefited from
The strong catalytic capability of the modified carbon-supported copper of nitrogen itself and the high conductivity of Ni metal, meanwhile, the modified carbon-supported copper of nitrogen with
SOCl2Between it is possible interaction and catalyst more contact site make its overpotential potential reduction, to improve electricity
The overall performance in pond.And the synthetic method of catalyst of the present invention is relatively easy, and synthesis material is abundant.
The modified carbon-supported copper catalyst of nitrogen, it is characterised in that the catalyst is prepared by the following method to obtain: by ion
Azodiisobutyronitrile is added after being dispersed in ethyl alcohol in liquid and nano cupric oxide, in N270 ~ 90 DEG C of reflux are anti-under the atmosphere of protection
It answers 20 ~ 25 hours, centrifuge washing obtains paste precursor, is modified under nitrogen atmosphere up to nitrogen within calcining 6 ~ 8 hours for 500 ~ 600 DEG C
Carbon-supported copper catalyst；The ionic liquid is 1- vinyl -3- methylimidazole cdicynanmide ([VMIm] [DCA]), 1- ethylene
Base -3- ethyl imidazol(e) cdicynanmide ([VEIm] [DCA]) or 1- vinyl -3- butyl imidazole cdicynanmide ([VBIm] [DCA]).
The mass ratio of the ionic liquid, nano cupric oxide and azodiisobutyronitrile is 1 ~ 5:0.2 ~ 1.0:0.02 ~ 0.1,
Preferred scope is 1 ~ 2:0.2 ~ 0.4:0.02 ~ 0.05.
The nano cupric oxide is the particle that diameter is 20 ~ 50nm.
In the modified carbon-supported copper catalyst of the nitrogen atom mass rate of carbon, nitrogen and copper be 1:0.1 ~ 0.19:0.13 ~
0.25；The specific surface area of the modified carbon-supported copper catalyst of the nitrogen is 70 ~ 100 m2 g-1, aperture is 8 ~ 13nm, Kong Rongwei
0.2~0.6 cm3 g-1, wherein the diameter of the copper supported is 150 ~ 200nm.
Application of the modified carbon-supported copper catalyst of above-mentioned nitrogen in terms of cell positive material.
Application of the modified carbon-supported copper catalyst of above-mentioned nitrogen in terms of positive electrode of lithium thionyl chloride battery material, by section's qin
The carbon-supported copper catalyst that black, polytetrafluoroethylene (PTFE) emulsion and nitrogen are modified mixes, and dehydrated alcohol is added and is sufficiently stirred to form paste
Object, is shaped to disc-shaped, 45 ~ 80 DEG C drying 12 hours, 240 ~ 280 DEG C are handled 10 ~ 15 minutes, obtain positive electrode.
The mass ratio of the modified carbon-supported copper catalyst of the Ketjen black, polytetrafluoroethylene (PTFE) emulsion and nitrogen is 5:1 ~ 3:
0.1 ~ 1.2, preferred scope is 5:1 ~ 1.5:0.2 ~ 0.8.
The total amount of the modified carbon-supported copper catalyst of the Ketjen black, polytetrafluoroethylene (PTFE) emulsion, nitrogen and dehydrated alcohol
Mass volume ratio is 100g/3-5 liter.
Beneficial effects of the present invention: it after nano cupric oxide is wrapped up with poly ion liquid, is sintered in a nitrogen atmosphere, nanometer
Copper oxide is reduced into the modified carbon of the meeting shape nitrogen of the dicyanamide anion (dca) in elemental copper and poly ion liquid, can be catalyzed thionyl
The features such as high conductivity of the ability of chlorine reduction reaction and elemental copper, combines, and makes the carbon-supported copper catalysis that the nitrogen to be formed is modified
The effect of agent performance cooperative compensating.The present invention in Ketjen black by adding the modified carbon-supported copper catalyst of nitrogen, so that electrode
Surface has more active sites；Big porosity makes electrolyte have bigger migration space, increases electrode reaction
Contact area；Since nano cupric oxide is reduced into elemental copper, so that the internal resistance of entire battery significantly decreases, electricity is improved
The discharge voltage and discharge platform in pond.Present invention process is simple, easy to operate, has practical value.
Detailed description of the invention
Fig. 1 is that the modified carbon-supported copper catalyst battery of 10 wt% nitrogen in embodiment 8 and blank battery discharge are bent
Line.
Fig. 2 is 10 wt% nitrogen in embodiment 11 modified carbon-supported copper catalyst battery and blank battery in low temperature-
30 DEG C of battery discharge curve.
Specific embodiment
For a better understanding of the present invention, it is illustrated below with reference to embodiment further progress, but these embodiments should not manage
Solution is any limitation of the invention.
Embodiment 1
The nano oxidized of 0.2g is added after the 1- vinyl -3- methylimidazole cdicynanmide of 1 g is dissolved in the ethyl alcohol of 30 mL
Copper, will the dispersion liquid be ultrasonically treated 30 minutes after be added 0.035 g azodiisobutyronitrile, nitrogen protection atmosphere next time
Stream reaction 24 hours.The nano cupric oxide wrapped up with poly ion liquid is obtained after water and ethyl alcohol centrifuge washing.The production that will be obtained
Object is calcined 6 hours for 550 DEG C in a nitrogen atmosphere, and subsequent poly ion liquid forms the nitrogen that copper content is 13% with nano cupric oxide and changes
The carbon-supported copper catalyst of property.
Embodiment 2
The nano oxidized of 0.3 g is added after the 1- vinyl -3- ethyl imidazol(e) cdicynanmide of 2 g is dissolved in the ethyl alcohol of 40 mL
Copper, will the dispersion liquid be ultrasonically treated 30 minutes after be added 0.045 g azodiisobutyronitrile, nitrogen protection atmosphere next time
Stream reaction 24 hours.The nano cupric oxide wrapped up with poly ion liquid is obtained after water and ethyl alcohol centrifuge washing.The production that will be obtained
Object is calcined 6 hours for 550 DEG C in a nitrogen atmosphere, and subsequent poly ion liquid forms the nitrogen that copper content is 17% with nano cupric oxide and changes
The carbon-supported copper catalyst of property.
Embodiment 3
The nano oxidized of 0.6g is added after the 1- vinyl -3- butyl imidazole cdicynanmide of 4 g is dissolved in the ethyl alcohol of 60 mL
Copper, will the dispersion liquid be ultrasonically treated 30 minutes after be added 0.078 g azodiisobutyronitrile, nitrogen protection atmosphere next time
Stream reaction 24 hours.The nano cupric oxide wrapped up with poly ion liquid is obtained after water and ethyl alcohol centrifuge washing.The production that will be obtained
Object is calcined 6 hours for 550 DEG C in a nitrogen atmosphere, and subsequent poly ion liquid forms the nitrogen that copper content is 25% with nano cupric oxide and changes
The carbon-supported copper catalyst of property.
Embodiment 4
By the Ketjen black of 0.5 g, dispersion mixing is uniformly ultrasonically treated 30 minutes afterwards in dehydrated alcohol, measures polytetrafluoroethylene (PTFE) cream
Turbid 0.05g after mixture then is added in binder, is made into for magnetic agitation 24 hours as binder to get positive paste
Film, then it is cut into the disk that diameter is 1 ± 0.2 cm, carbon anode is dried 15~18 hours at 45 ± 5 DEG C of vacuum oven, it
The carbon anode of drying is put into 240~280 DEG C of Muffle furnace afterwards, is sintered 10~15 minutes.Carbon anode quality, which is prepared, is
0.06 ± 0.02g, lithium metal (0.1g) are cathode, between positive electrode and negative electrode using the fibreglass diaphragm that diameter is 25 mm every
Open, electrolyte by 1.5M aluminum tetrachloride lithium (LiAlCl4) thionyl chloride (SOCl2) solution composition and water content be lower than
15 ppm are assembled into lithium-thionyl chloride blank battery and carry out 10 mA cm in room temperature-2The discharge capacity of discharge test, battery is
2482 mAh g-1, discharge voltage 3.41V, discharge capacity curve is as shown in Figure 1.
Embodiment 5
The carbon-supported copper catalyst that the nitrogen that the copper content that embodiment 1 is prepared is 13% is modified is applied to lithium-thionyl chloride electricity
Chi Shang, the modified carbon-supported copper catalyst of the nitrogen of the Ketjen black and 0.0051g (1 wt%) that weigh 0.5 g, in dehydrated alcohol
Dispersion mixing is uniformly ultrasonically treated 30 minutes afterwards, measures polytetrafluoroethylene (PTFE) emulsion 0.05g as binder, then by binder
After mixture is added, film is made into get positive paste within magnetic agitation 24 hours, then be cut into the circle that diameter is 1 ± 0.2 cm
Carbon anode is dried 15~18 hours at 45 ± 5 DEG C of vacuum oven, the carbon anode of drying is put into 240~280 DEG C later by piece
Muffle furnace in, be sintered 10~15 minutes.It is 0.06 ± 0.02g that carbon anode quality, which is prepared, and lithium metal (0.1g) is cathode,
Between positive electrode and negative electrode using diameter be 25 mm fibreglass diaphragm separate, electrolyte by 1.5M aluminum tetrachloride lithium
(LiAlCl4) thionyl chloride (SOCl2) solution composition and water content be lower than 15 ppm, be assembled into lithium-thionyl chloride entity
Battery simultaneously carries out 10 mA cm in room temperature-2The discharge capacity of discharge test, battery increases about 193 mAh g than blank battery-1, discharge voltage about improves 70mV.
Embodiment 6
The content of the modified carbon-supported copper catalyst of nitrogen in 5 preparation process of embodiment is increased as 0.015g (3 wt%), assembling
10 mA cm are carried out at lithium-thionyl chloride entity battery and in room temperature-2The discharge capacity of discharge test, battery increases than blank battery
About 443 mAh g are added-1, discharge voltage about improves 75mV.
Embodiment 7
The content of the modified carbon-supported copper catalyst of nitrogen in 5 preparation process of embodiment is increased as 0.026g (5 wt%), assembling
10 mA cm are carried out at lithium-thionyl chloride entity battery and in room temperature-2The discharge capacity of discharge test, battery increases than blank battery
About 695 mAh g are added-1, discharge voltage about improves 77mV.
Embodiment 8
The content of the modified carbon-supported copper catalyst of nitrogen in 5 preparation process of embodiment is increased as 0.056g (10 wt%), group
It dresses up lithium-thionyl chloride entity battery and carries out 10 mA cm in room temperature-2Discharge test, the discharge capacity of battery is than blank battery
Increase about 935 mAh g-1Discharge voltage about improves 100mV, and discharge capacity curve is as shown in Figure 1.
Embodiment 9
The content of the modified carbon-supported copper catalyst of nitrogen in 5 preparation process of embodiment is increased as 0.088g (15 wt%), group
It dresses up lithium-thionyl chloride entity battery and carries out 10 mA cm in room temperature-2Discharge test, the discharge capacity of battery is than blank battery
Reduce about 207 mAh g-1, but discharge voltage about improves 72mV.
Embodiment 10
The content of the modified carbon-supported copper catalyst of nitrogen in 5 preparation process of embodiment is increased as 0.125g (20 wt%), group
It dresses up lithium-thionyl chloride entity battery and carries out 10 mA cm in room temperature-2Discharge test, the discharge capacity of battery is than blank battery
Reduce about 393 mAh g-1, but discharge voltage about improves 80mV.
Embodiment 11
The content of the modified carbon-supported copper catalyst of nitrogen in 5 preparation process of embodiment is increased as 0.056g (10 wt%), system
The standby carbon anode quality that obtains is 0.35 ± 0.04g, and lithium metal (0.35g) is cathode, and it is 25 that diameter is used between positive electrode and negative electrode
The fibreglass diaphragm of mm separates, and electrolyte is by 1.5M LiAlCl4(SOCl2) solution composition and water content be lower than 15
ppm.It is assembled into lithium-thionyl chloride entity battery and carries out 3 mA cm of low temperature-2Discharge test, the discharge capacity of battery is than blank electricity
Pond increases about 376 mAh, and discharge voltage about improves 120mV.Discharge capacity curve is as shown in Figure 2.
Claims (10)
1. the modified carbon-supported copper catalyst of nitrogen, it is characterised in that the catalyst is prepared by the following method to obtain: by ionic liquid
Azodiisobutyronitrile is added after being dispersed in ethyl alcohol in body and nano cupric oxide, in N270 ~ 90 DEG C of back flow reactions under the atmosphere of protection
20 ~ 25 hours, centrifuge washing obtained paste precursor, calcined 6 ~ 8 hours under nitrogen atmosphere up to nitrogen modification for 500 ~ 600 DEG C
Carbon-supported copper catalyst；The ionic liquid is 1- vinyl -3- methylimidazole cdicynanmide, 1- vinyl -3- ethyl imidazol(e) two
Cyanamide or 1- vinyl -3- butyl imidazole cdicynanmide.
2. catalyst as described in claim 1, it is characterised in that the ionic liquid, nano cupric oxide and azodiisobutyronitrile
Mass ratio be 1 ~ 5:0.2 ~ 1.0:0.02 ~ 0.1.
3. catalyst as claimed in claim 2, it is characterised in that the ionic liquid, nano cupric oxide and azodiisobutyronitrile
Mass ratio be 1 ~ 2:0.2 ~ 0.4:0.02 ~ 0.05.
4. catalyst as described in claim 1, it is characterised in that the nano cupric oxide is the particle that diameter is 20 ~ 50nm.
5. catalyst as described in claim 1, it is characterised in that carbon, nitrogen and copper in the modified carbon-supported copper catalyst of the nitrogen
Atom mass rate be 1:0.1 ~ 0.19:0.13 ~ 0.25；The specific surface area of the modified carbon-supported copper catalyst of the nitrogen is 70 ~
100 m2 g-1, aperture is 8 ~ 13nm, 0.2 ~ 0.6 cm of Kong Rongwei3 g-1, wherein the diameter of the copper supported is 150 ~ 200nm.
6. modified carbon-supported copper catalyst the answering in terms of cell positive material of nitrogen as described in any one of claims 1 to 5
With.
7. application as claimed in claim 6, it is characterised in that the modified carbon-supported copper catalyst of the nitrogen is in lithium-thionyl chloride
Application in terms of cell positive material mixes the modified carbon-supported copper catalyst of Ketjen black, polytetrafluoroethylene (PTFE) emulsion and nitrogen,
Dehydrated alcohol is added to be sufficiently stirred to form paste, is shaped to disc-shaped, 45 ~ 80 DEG C drying 12 hours, 240 ~ 280 DEG C
Processing 10 ~ 15 minutes, obtains positive electrode.
8. the use as claimed in claim 7, it is characterised in that the modified carbon of the Ketjen black, polytetrafluoroethylene (PTFE) emulsion and nitrogen
The mass ratio for supporting copper catalyst is 5:1 ~ 3:0.1 ~ 1.2.
9. application as claimed in claim 8, it is characterised in that the modified carbon of the Ketjen black, polytetrafluoroethylene (PTFE) emulsion and nitrogen
The mass ratio for supporting copper catalyst is 5:1 ~ 1.5:0.2 ~ 0.8.
10. the use as claimed in claim 7, it is characterised in that the modified carbon of the Ketjen black, polytetrafluoroethylene (PTFE) emulsion, nitrogen
The mass volume ratio of the total amount and dehydrated alcohol that support copper catalyst is 100g/3-5 liter.
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