CN105742746B - A kind of method that Ni/NiO/C composite nano-powder materials are prepared using waste nickel hydrogen battery - Google Patents

A kind of method that Ni/NiO/C composite nano-powder materials are prepared using waste nickel hydrogen battery Download PDF

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CN105742746B
CN105742746B CN201610247364.9A CN201610247364A CN105742746B CN 105742746 B CN105742746 B CN 105742746B CN 201610247364 A CN201610247364 A CN 201610247364A CN 105742746 B CN105742746 B CN 105742746B
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CN105742746A (en
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张正富
王立丽
冷崇燕
易健宏
刘警峰
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Kunming University of Science and Technology
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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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The present invention provides a kind of method that Ni/NiO/C composite nano-powder materials are prepared using waste nickel hydrogen battery, comprising the concrete steps that for this method first disassembles waste nickel hydrogen battery, remove box hat, membrane, anode is reinstated nitric acid with cathode one after being roasted and is leached, citric acid solution is added in filtrate, dependent precipitation agent is added to be recycled part metals, dimethylglyoxime ethanol solution is added after filtering in filtrate, filtering, washing, microwave calcining filter residue is utilized under inert atmosphere, obtain Ni/C composite nano-powder materials, Ni/NiO/C composite nano-powder materials are obtained after annealing；The method of the invention uses microwave calcining, it is rapidly heated, material is heated evenly, it ensure that the uniformity of particle, and shorter soaking time, it ensure that the complete and crystallinity of particle is high, control the ratio of each component in Ni/NiO/C composite nano-powder materials by controlling annealing conditions, the composite powder material of different proportion content can be obtained.

Description

It is a kind of to prepare Ni/NiO/C composite nano-powder materials using waste nickel hydrogen battery Method
Technical field
The present invention relates to a kind of method that Ni/NiO/C composite nano-powder materials are prepared using waste nickel hydrogen battery, belong to The recovery technology field of Ni-MH battery.
Background technology
As Ni-MH battery is largely used and discarded, it is managed and final disposal becomes one and in the urgent need to address asks Topic, in numerous disposal methods, regeneration treatment is current research focus, while is also the scheme of most development prospect：It is not It can only solve to scrap a series of environmental problems caused by Ni-MH battery, and be returned by the regeneration to valuable metal in battery Receive, recycle, effectively alleviate the anxiety of resource, accomplished sustainable development, thus as electron wastes processing with The optimal path of control.
Carbon covered metal particle is a kind of new nanometer nanocarbon/metal composite material, and Carbon-encapsulated Metal Nanoparticles are only with its Special morphosis and property are as one of research hotspot of world wide clinical practice worker, as a kind of new function Material, has a wide range of applications in many fields, such as electron and electrician, medicine, environmental protection, chemical industry field；Since carbon shell can To confine metallics in the space of very little, influence of the environment to nano metal material can be avoided, solves nano-metal particle The problem of cannot being stabilized, furthermore according to metallic and carbon-based difference, which can have different purposes, nickel/oxygen Change nickel carbon nanocomposite and be used as electromagnetic shielding material, oxygen reduction catalyst, hydrocarbon reformation catalysis Agent, fuel electrode material etc..
Traditional mode of heating is always from outward appearance to inner essence to transmit heating according to heat transfer, thermal convection current and radiation theory, heat Material, is inevitably present temperature gradient in material, so heated material is uneven, causes material hot-spot occur, micro- Wave heating technology is different from traditional heating mode, is to be moved by heated object internal dipole square molecule high-frequency reciprocating, in generation Frictional heat and raise heated material temperature, it is not necessary to any heat transfer process, with regard to that can make inside material while heat while rise Temperature, firing rate are fast and uniformly, it is only necessary to which the part of traditional heating mode energy consumption 1/tens can reach heating Purpose.
The content of the invention
It is an object of the invention to provide one kind Ni/NiO/C composite nano-powder materials are prepared using waste nickel hydrogen battery Method, specifically include following steps：
（1）Waste nickel hydrogen battery is disassembled, box hat, membrane is removed, obtains the positive and negative electrode of Ni-MH battery, anode is existed When 700 DEG C of roastings 2 are small, the oxide of negative material is obtained, the oxide that anode is roasted is mixed with positive powder；
（2）Step（1）Obtained powdered electrode material adds nitric acid, the mass percent of leaching, wherein nitric acid Concentration is 2mol/L ~ 4mol/L, and extraction temperature is 50-80 DEG C, extraction time 120-240min；
（3）The recycling step by the way of anhydrous sodium sulfate precipitating rare earth（2）Rare earth ion in leachate；Using pin iron Ore deposit method recycling step（2）Ferrous ion in leachate；The mode recycling step of used ammonium sulfate precipitation manganese（2）In leachate Manganese；
（4）In step（3）Filtrate in add the volume ratio of citric acid solution, nickeliferous salpeter solution and citric acid solution For 20:1-50:1, the concentration of citric acid solution is 15-30g/L；
（5）By step（4）Obtained solution is heated to 50-70 DEG C, adds dimethylglyoxime ethanol solution, fourth two while stirring The concentration of ketoxime ethanol solution is 20-40g/L, and the addition of dimethylglyoxime ethanol solution is 200-300mL/g electrode materials；
（6）By step（5）Solution filtering, wash filter residue, obtain nickel dimethylglyoximate and detect the content of nickel in filtrate, if The content of nickel is higher than 2% in filtrate, repeats the above steps（4）And step（5）Process, until the content of nickel in filtrate is less than 2%；
（7）By step（6）Obtained nickel dimethylglyoximate is roasted under an inert atmosphere, obtains Ni/C composite nano-powders Material；Ni/C composite nano-powder materials are annealed, obtain Ni/NiO/C composite nano-powder materials.
The step（2）The mixing speed 300-1500r/min of leaching.
The step（5）Middle mixing speed is 900-1500r/min, mixing time 1-5min.
The step（7）In roasting be to carry out under microwave condition, roasting condition is：3-15min is warming up to 550-650 DEG C, keep the temperature 10-40min；Annealing conditions are：180-260 DEG C of insulation 90-150min, by controlling annealing conditions, can obtain not The Ni/NiO/C composite nano-powder materials of content in proportion.
Beneficial effects of the present invention：
（1）Using nitric acid leaching, nitrate anion is easily removed in roasting process, the purity of gained composite powder material Higher.
（2）Valuable metal in preparation process in Ni-MH battery is recycled.
（3）The method that the present invention uses microwave radiation technology Means of Pyrolyzed Precursor, prepares Ni/C nano composite powders under an inert atmosphere Body material, obtained composite powder material are heated evenly good dispersion, and good crystallinity, energy consumption is lower, and Microwave-assisted firing Mode heating rate than very fast, crystal grain has little time to grow up so that the particle for the Ni/C composite nano-powder materials being prepared Smaller and uniform, the soaking time in roasting process is shorter, ensure that the complete of particle.
（4）The ratio of each material in Ni/NiO/C composite nano-powder materials is controlled by controlling annealing conditions, can be with Obtain the composite material of different proportion content.
Brief description of the drawings
Fig. 1 is the preparation flow figure that the present invention produces Ni/NiO/C composite nano-powder materials using waste nickel hydrogen battery；
Fig. 2 is the transmission electron microscope picture for the Ni/C composite nano-powder materials that the embodiment of the present invention 1 is prepared；
Fig. 3 is the XRD diagram piece for the Ni/C composite nano-powder materials that the embodiment of the present invention 1 is prepared；
Fig. 4 is the XRD diagram piece for the Ni/NiO/C composite nano-powder materials that the embodiment of the present invention 1 is prepared.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, but protection scope of the present invention is simultaneously It is not limited to the content.
Embodiment 1
A kind of method that Ni/NiO/C composite nano-powder materials are prepared using waste nickel hydrogen battery described in the present embodiment, tool Body comprises the following steps：
（1）Waste nickel hydrogen battery is disassembled, box hat, membrane is removed, obtains the positive and negative electrode of Ni-MH battery, anode is existed When 700 DEG C of roastings 2 are small, the oxide of negative material is obtained, the oxide that anode is roasted is mixed with positive powder；
（2）Step（1）Obtained powdered electrode material adds nitric acid, the mass percent of leaching, wherein nitric acid Concentration is 2mol/L, and extraction temperature is 50 DEG C, extraction time 120min, mixing speed 300r/min；
（3）The recycling step by the way of anhydrous sodium sulfate precipitating rare earth（2）Rare earth ion in leachate；Using pin iron Ore deposit method recycling step（2）Ferrous ion in leachate；The mode recycling step of used ammonium sulfate precipitation manganese（2）In leachate Manganese；
（4）In step（3）Filtrate in add the volume ratio of citric acid solution, nickeliferous salpeter solution and citric acid solution For 20:1, the concentration of citric acid solution is 15g/L；
（5）By step（4）Obtained solution is heated to 50 DEG C, adds dimethylglyoxime ethanol solution, diacetyl while stirring The concentration of oxime ethanol solution is 20g/L, and the addition of dimethylglyoxime ethanol solution is 200mL/g electrode materials, wherein stirring speed It is 1 minute to spend for 1500r/min, mixing time；
（6）By step（5）Solution filtering, wash filter residue, obtain nickel dimethylglyoximate and detect the content of nickel in filtrate, if The content of nickel is higher than 2% in filtrate, repeats the above steps（4）And step（5）Process, until the content of nickel in filtrate is less than 2%；
（7）By step（6）Obtained nickel dimethylglyoximate leads to Ar calcination, roasting condition under microwave condition, with atmosphere furnace It is：3min is warming up to 580 DEG C, keeps the temperature 10min, obtains Ni/C composite nano-powder materials；By Ni/C composite nano-powder materials Anneal, annealing conditions are：180 DEG C of insulation 100min, obtain Ni/NiO/C composite nano-powder materials.
Except nickel and carbon, impurity content are less than 3% in the Ni/C composite nano-powder materials that the present embodiment obtains, nickel particle Size is less than 15nm, and carbon is uniformly wrapped in around nickel particle as shown in Figure 2；Obtain Ni/NiO/C composite nano-powder materials Middle nickel oxide particle size is less than 20nm, and carbon is uniformly wrapped up around nickel oxide particle；Pass through step as shown in Figure 3（7）Roasting Obtained product contains nickel；Pass through step as shown in Figure 4（7）Obtained product of annealing contains nickel and nickel oxide, by calculating Go out wherein nickel oxide accounts for Ni/NiO/C composite nano-powder materials 20%.
Embodiment 2
A kind of method that Ni/NiO/C composite nano-powder materials are prepared using waste nickel hydrogen battery described in the present embodiment, tool Body comprises the following steps：
（1）Waste nickel hydrogen battery is disassembled, box hat, membrane is removed, obtains the positive and negative electrode of Ni-MH battery, anode is existed When 700 DEG C of roastings 2 are small, the oxide of negative material is obtained, the oxide that anode is roasted is mixed with positive powder；
（2）Step（1）Obtained powdered electrode material adds nitric acid, the mass percent of leaching, wherein nitric acid Concentration is 3mol/L, and extraction temperature is 60 DEG C, and extraction time 180min, mixing speed is 1000r/min；
（3）The recycling step by the way of anhydrous sodium sulfate precipitating rare earth（2）Rare earth ion in leachate；Using pin iron Ore deposit method recycling step（2）Ferrous ion in leachate；The mode recycling step of used ammonium sulfate precipitation manganese（2）In leachate Manganese；
（4）In step（3）Filtrate in add the volume ratio of citric acid solution, nickeliferous salpeter solution and citric acid solution For 30:1, the concentration of citric acid solution is 20g/L；
（5）By step（4）Obtained solution is heated to 60 DEG C, adds dimethylglyoxime ethanol solution, diacetyl while stirring The concentration of oxime ethanol solution is 30g/L, and the addition of dimethylglyoxime ethanol solution is 250mL/g electrode materials, wherein stirring speed It is 5 minutes to spend for 1000r/min, mixing time；
（6）By step（5）Solution filtering, wash filter residue, obtain nickel dimethylglyoximate and detect the content of nickel in filtrate, if The content of nickel is higher than 2% in filtrate, repeats the above steps（4）And step（5）Process, until the content of nickel in filtrate is less than 2%；
（7）By step（6）Obtained nickel dimethylglyoximate leads to nitrogen roasting, roasting condition under microwave condition, with atmosphere furnace It is：10min is warming up to 550 DEG C, keeps the temperature 25min, obtains Ni/C composite nano-powder materials；By Ni/C composite nano-powder materials Anneal, annealing conditions are：200 DEG C of insulation 150min, obtain Ni/NiO/C composite nano-powder materials.
Except nickel and carbon, impurity content are less than 3% in the Ni/C composite nano-powder materials that the present embodiment obtains, nickel particle Size is less than 18nm, and carbon is uniformly wrapped in around nickel particle；The present embodiment obtains Ni/NiO/C composite nano-powder materials, oxygen Change nickel particle size and be less than 30nm, carbon is uniformly wrapped in around nickel oxide particle, and wherein nickel oxide accounts for Ni/NiO/C nanometers The 47% of composite powder material.
Embodiment 3
A kind of method that Ni/NiO/C composite nano-powder materials are prepared using waste nickel hydrogen battery described in the present embodiment, tool Body comprises the following steps：
（1）Waste nickel hydrogen battery is disassembled, box hat, membrane is removed, obtains the positive and negative electrode of Ni-MH battery, anode is existed When 700 DEG C of roastings 2 are small, the oxide of negative material is obtained, the oxide that anode is roasted is mixed with positive powder；
（2）Step（1）Obtained powdered electrode material adds nitric acid, the mass percent of leaching, wherein nitric acid Concentration is 4mol/L, and extraction temperature is 70 DEG C, extraction time 200min, mixing speed 1200r/min；
（3）The recycling step by the way of anhydrous sodium sulfate precipitating rare earth（2）Rare earth ion in leachate；Using pin iron Ore deposit method recycling step（2）Ferrous ion in leachate；The mode recycling step of used ammonium sulfate precipitation manganese（2）In leachate Manganese；
（4）In step（3）Filtrate in add the volume ratio of citric acid solution, nickeliferous salpeter solution and citric acid solution For 40:1, the solubility of citric acid solution is 25g/L；
（5）By step（4）Obtained solution is heated to 60 DEG C, adds dimethylglyoxime ethanol solution, diacetyl while stirring The concentration of oxime ethanol solution is 35g/L, and the addition of dimethylglyoxime ethanol solution is 250mL/g electrode materials, wherein stirring speed It is 3 minutes to spend for 1200r/min, mixing time；
（6）By step（5）Solution filtering, wash filter residue, obtain nickel dimethylglyoximate and detect the content of nickel in filtrate, if The content of nickel is higher than 2% in filtrate, repeats the above steps（4）And step（5）Process, until the content of nickel in filtrate is less than 2%；
（7）By step（6）Obtained nickel dimethylglyoximate leads to Ar calcination, roasting condition under microwave condition, with atmosphere furnace It is：12min is warming up to 650 DEG C, keeps the temperature 30min, obtains Ni/C composite nano-powder materials；By Ni/C composite nano-powder materials Anneal, annealing conditions are：260 DEG C of insulation 120min, obtain Ni/NiO/C composite nano-powder materials.
Except nickel and carbon, impurity content are less than 3% in the Ni/C composite nano-powder materials that the present embodiment obtains, nickel particle Size is less than 20nm, and carbon is uniformly wrapped in around nickel particle；The present embodiment obtains Ni/NiO/C composite nano-powder materials, Nickel oxide particle size is less than 28nm, and carbon is uniformly wrapped in around nickel oxide particle, and wherein nickel oxide accounts for Ni/NiO/C and receives The 35% of rice composite powder material.
Embodiment 4
A kind of method that Ni/NiO/C composite nano-powder materials are prepared using waste nickel hydrogen battery described in the present embodiment, tool Body comprises the following steps：
（1）Waste nickel hydrogen battery is disassembled, box hat, membrane is removed, obtains the positive and negative electrode of Ni-MH battery, anode is existed When 700 DEG C of roastings 2 are small, the oxide of negative material is obtained, the oxide that anode is roasted is mixed with positive powder；
（2）Step（1）Obtained powdered electrode material adds nitric acid, the mass percent of leaching, wherein nitric acid Concentration is 4mol/L, and extraction temperature is 80 DEG C, extraction time 240min, mixing speed 1500r/min；
（3）The recycling step by the way of anhydrous sodium sulfate precipitating rare earth（2）Rare earth ion in leachate；Using pin iron Ore deposit method recycling step（2）Ferrous ion in leachate；The mode recycling step of used ammonium sulfate precipitation manganese（2）In leachate Manganese；
（4）In step（3）Filtrate in add the volume ratio of citric acid solution, nickeliferous salpeter solution and citric acid solution For 50:1, the concentration of citric acid solution is 30g/L；
（5）By step（4）Obtained solution is heated to 70 DEG C, adds dimethylglyoxime ethanol solution, diacetyl while stirring The concentration of oxime ethanol solution is 40g/L, and the addition of dimethylglyoxime ethanol solution is 300mL/g electrode materials, wherein stirring speed It is 4 minutes to spend for 900r/min, mixing time；
（6）By step（5）Solution filtering, wash filter residue, obtain nickel dimethylglyoximate and detect the content of nickel in filtrate, if The content of nickel is higher than 2% in filtrate, repeats the above steps（4）And step（5）Process, until the content of nickel in filtrate is less than 2%；
（7）By step（6）Obtained nickel dimethylglyoximate leads to Ar calcination, roasting condition under microwave condition, with atmosphere furnace It is：15min is warming up to 600 DEG C, keeps the temperature 40min, obtains Ni/C composite nano-powder materials；By Ni/C composite nano-powder materials Anneal, annealing conditions are：240 DEG C of insulation 90min, obtain Ni/NiO/C composite nano-powder materials.
Except nickel and carbon, impurity content are less than 3% in the Ni/C composite nano-powder materials that the present embodiment obtains, nickel particle Size is less than 25nm, and carbon is uniformly wrapped in around nickel particle；The present embodiment obtains Ni/NiO/C composite nano-powder materials, Nickel oxide particle size is less than 35nm, and carbon is uniformly wrapped in around nickel oxide particle, and wherein nickel oxide accounts for Ni/NiO/C and receives The 29% of rice composite powder material.

Claims (4)

  1. A kind of 1. method that Ni/NiO/C composite nano-powder materials are prepared using waste nickel hydrogen battery, it is characterised in that specific Comprise the following steps：
    （1）Waste nickel hydrogen battery is disassembled, box hat, membrane is removed, the positive and negative electrode of Ni-MH battery is obtained, by anode at 700 DEG C Roast 2 it is small when, obtain the oxide of negative material, the oxide that anode is roasted and positive powder mix；
    （2）Step（1）Obtained powdered electrode material adds nitric acid, the mass percent concentration of leaching, wherein nitric acid For 2mol/L-4mol/L, extraction temperature is 50-80 DEG C, extraction time 120-240min；
    （3）The recycling step by the way of anhydrous sodium sulfate precipitating rare earth（2）Rare earth ion in leachate；Using goethite process Recycling step（2）Ferrous ion in leachate；The mode recycling step of used ammonium sulfate precipitation manganese（2）Manganese in leachate；
    （4）In step（3）Filtrate in add citric acid solution, the volume ratio of nickeliferous salpeter solution and citric acid solution is 20:1-50:1, the concentration of citric acid solution is 15-30g/L；
    （5）By step（4）Obtained solution is heated to 50-70 DEG C, adds dimethylglyoxime ethanol solution, dimethylglyoxime while stirring The concentration of ethanol solution is 20-40g/L, and the addition of dimethylglyoxime ethanol solution is 200-300mL/g electrode materials；
    （6）By step（5）Solution filtering, wash filter residue, obtain nickel dimethylglyoximate and detect the content of nickel in filtrate, if filtrate The content of middle nickel is higher than 2%, repeats the above steps（4）And step（5）Process, until the content of nickel in filtrate is less than 2%；
    （7）By step（6）Obtained nickel dimethylglyoximate is roasted under an inert atmosphere, and roasting condition is：3-15min is warming up to 550-650 DEG C, 10-40min is kept the temperature, obtains Ni/C composite nano-powder materials；Ni/C composite nano-powder materials are moved back Fire, annealing conditions are：180-260 DEG C of insulation 90-150min, obtains Ni/NiO/C composite nano-powder materials.
  2. 2. the method according to claim 1 that Ni/NiO/C composite nano-powder materials are prepared using waste nickel hydrogen battery, It is characterized in that：Step（2）The mixing speed of the leaching is 300-1500r/min.
  3. 3. the method according to claim 1 that Ni/NiO/C composite nano-powder materials are prepared using waste nickel hydrogen battery, It is characterized in that：Step（5）Middle mixing speed is 900-1500r/min, mixing time 1-5min.
  4. 4. the method according to claim 1 that Ni/NiO/C composite nano-powder materials are prepared using waste nickel hydrogen battery, It is characterized in that：Step（7）In roasting be to carry out under microwave condition.
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