CN105742746A - Method for preparing Ni/NiO/C nanometer composite powder material by using waste nickel-hydrogen battery - Google Patents
Method for preparing Ni/NiO/C nanometer composite powder material by using waste nickel-hydrogen battery Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 23
- 239000001257 hydrogen Substances 0.000 title claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 title claims abstract description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 57
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 176
- 229910052759 nickel Inorganic materials 0.000 claims description 63
- 239000011858 nanopowder Substances 0.000 claims description 50
- 239000000706 filtrate Substances 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- JGUQDUKBUKFFRO-GGWOSOGESA-N (NE)-N-[(3E)-3-hydroxyiminobutan-2-ylidene]hydroxylamine Chemical compound O\N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-GGWOSOGESA-N 0.000 claims description 18
- 230000001476 alcoholic effect Effects 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 238000004064 recycling Methods 0.000 claims description 18
- 239000007772 electrode material Substances 0.000 claims description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 12
- 229910018095 Ni-MH Inorganic materials 0.000 claims description 10
- 229910018477 Ni—MH Inorganic materials 0.000 claims description 10
- 238000002386 leaching Methods 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 6
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 6
- 229910052598 goethite Inorganic materials 0.000 claims description 6
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- -1 rare earth ion Chemical class 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 abstract description 14
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract 2
- FPYYNALBDHWLNB-UHFFFAOYSA-N C(C)O.CC(C(=NO)C)=NO Chemical compound C(C)O.CC(C(=NO)C)=NO FPYYNALBDHWLNB-UHFFFAOYSA-N 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 239000010959 steel Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 15
- 229910000480 nickel oxide Inorganic materials 0.000 description 13
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 13
- 239000008187 granular material Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XNSXBDISIVKKCL-UHFFFAOYSA-N [Ni].[C].[Ni] Chemical compound [Ni].[C].[Ni] XNSXBDISIVKKCL-UHFFFAOYSA-N 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000126 substance 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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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
- H01M4/36—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention provides a method for preparing a Ni/NiO/C nanometer composite powder material by using a waste nickel-hydrogen battery. The method comprises the following steps of disassembling the waste nickel-hydrogen battery, removing a steel shell and a diaphragm, immersing a negative electrode after being roasted and a positive electrode with nitric acid, adding a citric acid into a filter liquid, adding an associated precipitant to recycle a part of metal, adding a dimethylglyoxime ethanol solution into the filter liquid after filtering, filtering and washing the product, and roasting filter residue with microwave under an inertia atmosphere to obtain an Ni/C nanometer composite powder material, and obtaining the Ni/NiO/C nanometer composite material after annealing. The method adopts microwave roasting, the temperature is rapidly risen, the material is uniformly heated, the particle uniformity is ensured, the particle completeness and high crystallinity are ensured, the proportion of each constituent in the Ni/NiO/C nanometer composite powder material is controlled by controlling an annealing condition, and the composite powder material with different content proportions can be obtained.
Description
Technical field
The present invention relates to a kind of method utilizing waste nickel hydrogen battery to prepare Ni/NiO/C composite nano-powder material, belong to the recovery technology field of Ni-MH battery.
Background technology
Use in a large number along with Ni-MH battery and discard, its management and final disposal become a problem in the urgent need to address, in numerous disposal methods, Regeneration Treatment is current research focus, also it is the scheme of most development prospect: it is possible not only to solve to scrap the series of environmental problems that Ni-MH battery brings simultaneously, and by the regeneration of valuable metal in battery is reclaimed, recycled, effectively alleviate the anxiety of resource, accomplish sustainable development, therefore become the optimal path that electron wastes processes and controls.
Carbon covered metal granule is a kind of novel nanometer nanocarbon/metal composite material, Carbon-encapsulated Metal Nanoparticles is with one of the morphosis and the character study hotspot having become world wide internal medicine worker of its uniqueness, as a kind of novel functional material, have a wide range of applications in a lot of fields, such as fields such as electron and electrician, medicine, environmental protection, chemical industry；Owing to carbon shell can confine metallics in only small space, the environment impact on nano metal material can be avoided, solving nano-metal particle can not the problem of stable existence, difference furthermore according to metallic and carbon back, this material can have different purposes, nickel nickel carbon nano-composite material to be used as electromagnetic shielding material, oxygen reduction catalyst, hydrocarbon reformation catalyst, fuel electrode material etc..
Traditional mode of heating is according to conduction of heat, thermal convection current and radiation theory, heat always from outward appearance to inner essence transmits heated material, material is inevitably present thermograde, so heated material is uneven, cause material that hot-spot occurs, microwave heating technique is different from traditional heating mode, it is moved by heated object internal dipole square molecule high-frequency reciprocating, produce internal friction heat and make heated material temperature raise, do not need any heat transfer process, internal batch just can be made to heat simultaneously, heat up simultaneously, firing rate is fast and uniform, only need the part of traditional heating mode energy consumption or tens/reaching heating purpose.
Summary of the invention
It is an object of the invention to provide a kind of method utilizing waste nickel hydrogen battery to prepare Ni/NiO/C composite nano-powder material, specifically include following steps:
(1) being disassembled by waste nickel hydrogen battery, remove box hat, barrier film, obtain the positive and negative electrode of Ni-MH battery, by negative pole 700 DEG C of roastings 2 hours, obtain the oxide of negative material, oxide negative pole roasting obtained mixes with positive powder；
(2) the powdered electrode material that step (1) obtains adds nitric acid, and leaching, wherein the mass percent concentration of nitric acid is 2mol/L ~ 4mol/L, and extraction temperature is 50-80 DEG C, and extraction time is 120-240min；
(3) rare earth ion in mode recycling step (2) leachate of anhydrous sodium sulfate precipitating rare earth is adopted；Adopt the ferrous ion in goethite process recycling step (2) leachate；The manganese in mode recycling step (2) leachate of manganese is precipitated with Ammonium persulfate.；
(4) volume ratio adding citric acid solution, nickeliferous salpeter solution and citric acid solution in the filtrate of step (3) is 20:1-50:1, and the concentration of citric acid solution is 15-30g/L；
(5) solution that step (4) obtains being heated to 50-70 DEG C, add diacetyldioxime alcoholic solution while stirring, the concentration of diacetyldioxime alcoholic solution is 20-40g/L, and the addition of diacetyldioxime alcoholic solution is 200-300mL/g electrode material；
(6) being filtered by the solution of step (5), wash filtering residue, obtain nickel dimethylglyoximate and detect the content of nickel in filtrate, if the content of nickel is higher than 2% in filtrate, repeat the above steps (4) and step (5) process, until the content of nickel in filtrate lower than 2%；
(7) nickel dimethylglyoximate that step (6) obtains is carried out roasting under an inert atmosphere, obtain Ni/C composite nano-powder material；Ni/C composite nano-powder material is annealed, obtains Ni/NiO/C composite nano-powder material.
The mixing speed 300-1500r/min of described step (2) leaching.
In described step (5), mixing speed is 900-1500r/min, and mixing time is 1-5min.
Roasting in described step (7) is to carry out under microwave condition, and roasting condition is: 3-15min is warmed up to 550-650 DEG C, is incubated 10-40min；Annealing conditions is: 180-260 DEG C of insulation 90-150min, by controlling annealing conditions, it is possible to obtain the Ni/NiO/C composite nano-powder material of different proportion content.
Beneficial effects of the present invention:
(1) adopting nitric acid leaching, in roasting process, nitrate anion is easily removed, and the purity of gained composite powder material is higher.
(2) in preparation process, the valuable metal in Ni-MH battery obtains recovery.
(3) method that the present invention adopts microwave-assisted By Means of Pyrolyzed Precursor, prepare Ni/C composite nano-powder material under an inert atmosphere, the composite powder material obtained is heated evenly good dispersion, good crystallinity, energy consumption is lower, and the mode heating rate of Microwave-assisted firing is than very fast, crystal grain has little time to grow up, making the granule of Ni/C composite nano-powder material prepared less and uniform, the temperature retention time in roasting process is shorter, it is ensured that granule complete.
(4) ratio of each material in Ni/NiO/C composite nano-powder material is controlled by control annealing conditions, it is possible to obtain the composite of different proportion content.
Accompanying drawing explanation
Fig. 1 is that the present invention utilizes waste nickel hydrogen battery to produce the preparation flow figure of Ni/NiO/C composite nano-powder material；
Fig. 2 is the transmission electron microscope picture of the Ni/C composite nano-powder material that the embodiment of the present invention 1 prepares；
Fig. 3 is the XRD figure sheet of the Ni/C composite nano-powder material that the embodiment of the present invention 1 prepares；
Fig. 4 is the XRD figure sheet of the Ni/NiO/C composite nano-powder material that the embodiment of the present invention 1 prepares.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.
Embodiment 1
A kind of method utilizing waste nickel hydrogen battery to prepare Ni/NiO/C composite nano-powder material described in the present embodiment, specifically includes following steps:
(1) being disassembled by waste nickel hydrogen battery, remove box hat, barrier film, obtain the positive and negative electrode of Ni-MH battery, by negative pole 700 DEG C of roastings 2 hours, obtain the oxide of negative material, oxide negative pole roasting obtained mixes with positive powder；
(2) the powdered electrode material that step (1) obtains adds nitric acid, and leaching, wherein the mass percent concentration of nitric acid is 2mol/L, and extraction temperature is 50 DEG C, and extraction time is 120min, and mixing speed is 300r/min；
(3) rare earth ion in mode recycling step (2) leachate of anhydrous sodium sulfate precipitating rare earth is adopted；Adopt the ferrous ion in goethite process recycling step (2) leachate；The manganese in mode recycling step (2) leachate of manganese is precipitated with Ammonium persulfate.；
(4) volume ratio adding citric acid solution, nickeliferous salpeter solution and citric acid solution in the filtrate of step (3) is 20:1, and the concentration of citric acid solution is 15g/L；
(5) solution that step (4) obtains is heated to 50 DEG C, adding diacetyldioxime alcoholic solution while stirring, the concentration of diacetyldioxime alcoholic solution is 20g/L, and the addition of diacetyldioxime alcoholic solution is 200mL/g electrode material, wherein mixing speed is 1500r/min, and mixing time is 1 minute；
(6) being filtered by the solution of step (5), wash filtering residue, obtain nickel dimethylglyoximate and detect the content of nickel in filtrate, if the content of nickel is higher than 2% in filtrate, repeat the above steps (4) and step (5) process, until the content of nickel in filtrate lower than 2%；
(7) nickel dimethylglyoximate step (6) obtained is under microwave condition, with the logical Ar calcination of atmosphere furnace, and roasting condition is: 3min is warmed up to 580 DEG C, is incubated 10min, obtains Ni/C composite nano-powder material；Being annealed by Ni/C composite nano-powder material, annealing conditions is: 180 DEG C of insulation 100min, obtains Ni/NiO/C composite nano-powder material.
Except nickel and carbon in the Ni/C composite nano-powder material that the present embodiment obtains, impurity content is lower than 3%, and nickel particle size is less than 15nm, and carbon is wrapped in around nickel granule uniformly as shown in Figure 2；Obtaining nickel oxide particle in Ni/NiO/C composite nano-powder material and be smaller in size than 20nm, carbon wraps up around nickel oxide particle uniformly；The product obtained through step (7) roasting as shown in Figure 3 contains nickel；The product obtained through step (7) annealing as shown in Figure 4 contains nickel and nickel oxide, accounts for the 20% of Ni/NiO/C composite nano-powder material through calculating wherein nickel oxide.
Embodiment 2
A kind of method utilizing waste nickel hydrogen battery to prepare Ni/NiO/C composite nano-powder material described in the present embodiment, specifically includes following steps:
(1) being disassembled by waste nickel hydrogen battery, remove box hat, barrier film, obtain the positive and negative electrode of Ni-MH battery, by negative pole 700 DEG C of roastings 2 hours, obtain the oxide of negative material, oxide negative pole roasting obtained mixes with positive powder；
(2) the powdered electrode material that step (1) obtains adds nitric acid, and leaching, wherein the mass percent concentration of nitric acid is 3mol/L, and extraction temperature is 60 DEG C, and extraction time is 180min, and mixing speed is 1000r/min；
(3) rare earth ion in mode recycling step (2) leachate of anhydrous sodium sulfate precipitating rare earth is adopted；Adopt the ferrous ion in goethite process recycling step (2) leachate；The manganese in mode recycling step (2) leachate of manganese is precipitated with Ammonium persulfate.；
(4) volume ratio adding citric acid solution, nickeliferous salpeter solution and citric acid solution in the filtrate of step (3) is 30:1, and the concentration of citric acid solution is 20g/L；
(5) solution that step (4) obtains is heated to 60 DEG C, adding diacetyldioxime alcoholic solution while stirring, the concentration of diacetyldioxime alcoholic solution is 30g/L, and the addition of diacetyldioxime alcoholic solution is 250mL/g electrode material, wherein mixing speed is 1000r/min, and mixing time is 5 minutes；
(6) being filtered by the solution of step (5), wash filtering residue, obtain nickel dimethylglyoximate and detect the content of nickel in filtrate, if the content of nickel is higher than 2% in filtrate, repeat the above steps (4) and step (5) process, until the content of nickel in filtrate lower than 2%；
(7) nickel dimethylglyoximate step (6) obtained is under microwave condition, with the logical nitrogen roasting of atmosphere furnace, and roasting condition is: 10min is warmed up to 550 DEG C, is incubated 25min, obtains Ni/C composite nano-powder material；Being annealed by Ni/C composite nano-powder material, annealing conditions is: 200 DEG C of insulation 150min, obtains Ni/NiO/C composite nano-powder material.
Except nickel and carbon in the Ni/C composite nano-powder material that the present embodiment obtains, impurity content is lower than 3%, and nickel particle size is less than 18nm, and carbon is wrapped in around nickel granule uniformly；The present embodiment obtains Ni/NiO/C composite nano-powder material, and nickel oxide particle is smaller in size than 30nm, and carbon is wrapped in around nickel oxide particle uniformly, and wherein nickel oxide accounts for the 47% of Ni/NiO/C composite nano-powder material.
Embodiment 3
A kind of method utilizing waste nickel hydrogen battery to prepare Ni/NiO/C composite nano-powder material described in the present embodiment, specifically includes following steps:
(1) being disassembled by waste nickel hydrogen battery, remove box hat, barrier film, obtain the positive and negative electrode of Ni-MH battery, by negative pole 700 DEG C of roastings 2 hours, obtain the oxide of negative material, oxide negative pole roasting obtained mixes with positive powder；
(2) the powdered electrode material that step (1) obtains adds nitric acid, and leaching, wherein the mass percent concentration of nitric acid is 4mol/L, and extraction temperature is 70 DEG C, and extraction time is 200min, and mixing speed is 1200r/min；
(3) rare earth ion in mode recycling step (2) leachate of anhydrous sodium sulfate precipitating rare earth is adopted；Adopt the ferrous ion in goethite process recycling step (2) leachate；The manganese in mode recycling step (2) leachate of manganese is precipitated with Ammonium persulfate.；
(4) volume ratio adding citric acid solution, nickeliferous salpeter solution and citric acid solution in the filtrate of step (3) is 40:1, and the solubility of citric acid solution is 25g/L；
(5) solution that step (4) obtains is heated to 60 DEG C, adding diacetyldioxime alcoholic solution while stirring, the concentration of diacetyldioxime alcoholic solution is 35g/L, and the addition of diacetyldioxime alcoholic solution is 250mL/g electrode material, wherein mixing speed is 1200r/min, and mixing time is 3 minutes；
(6) being filtered by the solution of step (5), wash filtering residue, obtain nickel dimethylglyoximate and detect the content of nickel in filtrate, if the content of nickel is higher than 2% in filtrate, repeat the above steps (4) and step (5) process, until the content of nickel in filtrate lower than 2%；
(7) nickel dimethylglyoximate step (6) obtained is under microwave condition, with the logical Ar calcination of atmosphere furnace, and roasting condition is: 12min is warmed up to 650 DEG C, is incubated 30min, obtains Ni/C composite nano-powder material；Being annealed by Ni/C composite nano-powder material, annealing conditions is: 260 DEG C of insulation 120min, obtains Ni/NiO/C composite nano-powder material.
Except nickel and carbon in the Ni/C composite nano-powder material that the present embodiment obtains, impurity content is lower than 3%, and nickel particle size is less than 20nm, and carbon is wrapped in around nickel granule uniformly；The present embodiment obtains Ni/NiO/C composite nano-powder material, and nickel oxide particle is smaller in size than 28nm, and carbon is wrapped in around nickel oxide particle uniformly, and wherein nickel oxide accounts for the 35% of Ni/NiO/C composite nano-powder material.
Embodiment 4
A kind of method utilizing waste nickel hydrogen battery to prepare Ni/NiO/C composite nano-powder material described in the present embodiment, specifically includes following steps:
(1) being disassembled by waste nickel hydrogen battery, remove box hat, barrier film, obtain the positive and negative electrode of Ni-MH battery, by negative pole 700 DEG C of roastings 2 hours, obtain the oxide of negative material, oxide negative pole roasting obtained mixes with positive powder；
(2) the powdered electrode material that step (1) obtains adds nitric acid, and leaching, wherein the mass percent concentration of nitric acid is 4mol/L, and extraction temperature is 80 DEG C, and extraction time is 240min, and mixing speed is 1500r/min；
(3) rare earth ion in mode recycling step (2) leachate of anhydrous sodium sulfate precipitating rare earth is adopted；Adopt the ferrous ion in goethite process recycling step (2) leachate；The manganese in mode recycling step (2) leachate of manganese is precipitated with Ammonium persulfate.；
(4) volume ratio adding citric acid solution, nickeliferous salpeter solution and citric acid solution in the filtrate of step (3) is 50:1, and the concentration of citric acid solution is 30g/L；
(5) solution that step (4) obtains is heated to 70 DEG C, adding diacetyldioxime alcoholic solution while stirring, the concentration of diacetyldioxime alcoholic solution is 40g/L, and the addition of diacetyldioxime alcoholic solution is 300mL/g electrode material, wherein mixing speed is 900r/min, and mixing time is 4 minutes；
(6) being filtered by the solution of step (5), wash filtering residue, obtain nickel dimethylglyoximate and detect the content of nickel in filtrate, if the content of nickel is higher than 2% in filtrate, repeat the above steps (4) and step (5) process, until the content of nickel in filtrate lower than 2%；
(7) nickel dimethylglyoximate step (6) obtained is under microwave condition, with the logical Ar calcination of atmosphere furnace, and roasting condition is: 15min is warmed up to 600 DEG C, is incubated 40min, obtains Ni/C composite nano-powder material；Being annealed by Ni/C composite nano-powder material, annealing conditions is: 240 DEG C of insulation 90min, obtains Ni/NiO/C composite nano-powder material.
Except nickel and carbon in the Ni/C composite nano-powder material that the present embodiment obtains, impurity content is lower than 3%, and nickel particle size is less than 25nm, and carbon is wrapped in around nickel granule uniformly；The present embodiment obtains Ni/NiO/C composite nano-powder material, and nickel oxide particle is smaller in size than 35nm, and carbon is wrapped in around nickel oxide particle uniformly, and wherein nickel oxide accounts for the 29% of Ni/NiO/C composite nano-powder material.
Claims (5)
1. one kind utilizes the method that waste nickel hydrogen battery prepares Ni/NiO/C composite nano-powder material, it is characterised in that specifically include following steps:
(1) being disassembled by waste nickel hydrogen battery, remove box hat, barrier film, obtain the positive and negative electrode of Ni-MH battery, by negative pole 700 DEG C of roastings 2 hours, obtain the oxide of negative material, oxide negative pole roasting obtained mixes with positive powder；
(2) the powdered electrode material that step (1) obtains adds nitric acid, and leaching, wherein the mass percent concentration of nitric acid is 2mol/L ~ 4mol/L, and extraction temperature is 50-80 DEG C, and extraction time is 120-240min；
(3) rare earth ion in mode recycling step (2) leachate of anhydrous sodium sulfate precipitating rare earth is adopted；Adopt the ferrous ion in goethite process recycling step (2) leachate；The manganese in mode recycling step (2) leachate of manganese is precipitated with Ammonium persulfate.；
(4) volume ratio adding citric acid solution, nickeliferous salpeter solution and citric acid solution in the filtrate of step (3) is 20:1-50:1, and the concentration of citric acid solution is 15-30g/L；
(5) solution that step (4) obtains being heated to 50-70 DEG C, add diacetyldioxime alcoholic solution while stirring, the concentration of diacetyldioxime alcoholic solution is 20-40g/L, and the addition of diacetyldioxime alcoholic solution is 200-300mL/g electrode material；
(6) being filtered by the solution of step (5), wash filtering residue, obtain nickel dimethylglyoximate and detect the content of nickel in filtrate, if the content of nickel is higher than 2% in filtrate, repeat the above steps (4) and step (5) process, until the content of nickel in filtrate lower than 2%；
(7) nickel dimethylglyoximate that step (6) obtains is carried out roasting under an inert atmosphere, obtain Ni/C composite nano-powder material；Ni/C composite nano-powder material is annealed, obtains Ni/NiO/C composite nano-powder material.
2. the method utilizing waste nickel hydrogen battery to prepare Ni/NiO/C composite nano-powder material according to claim 1, it is characterised in that: the mixing speed of step (2) described leaching is 300-1500r/min.
3. the method utilizing waste nickel hydrogen battery to prepare Ni/NiO/C composite nano-powder material according to claim 1, it is characterised in that: in step (5), mixing speed is 900-1500r/min, and mixing time is 1-5min.
4. the method utilizing waste nickel hydrogen battery to prepare Ni/NiO/C composite nano-powder material according to claim 1, it is characterized in that, roasting condition in step (7) is: 3-15min is warmed up to 550-650 DEG C, is incubated 10-40min, and annealing conditions is: 180-260 DEG C of insulation 90-150min.
5. the method utilizing waste nickel hydrogen battery to prepare Ni/NiO/C composite nano-powder material according to claim 1, it is characterised in that: the roasting in step (7) is to carry out under microwave condition.
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