CN103146957A - Method for making hydrogen storage alloy through utilizing non-serviceable nickel-metal hydride battery - Google Patents
Method for making hydrogen storage alloy through utilizing non-serviceable nickel-metal hydride battery Download PDFInfo
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- CN103146957A CN103146957A CN2013100525185A CN201310052518A CN103146957A CN 103146957 A CN103146957 A CN 103146957A CN 2013100525185 A CN2013100525185 A CN 2013100525185A CN 201310052518 A CN201310052518 A CN 201310052518A CN 103146957 A CN103146957 A CN 103146957A
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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
Abstract
The invention provides a preparation method of a hydrogen storage alloy raw material. The preparation method comprises the following steps: dissolving the electrical core of a disassembled non-serviceable nickel-metal hydride battery in a mixed solution composed of an acid and an oxidant, adding sulfate of an alkali metal to the obtained solution, carrying out high temperature treatment of a solid separated after a reaction, supplementing a deletion metal, smelting at a high temperature, and quickly chilling to obtain the hydrogen storage alloy material. In the invention, rare earth ore is not needed to provide the production raw material, so the natural resource is substantially saved; the non-serviceable nickel-metal hydride battery is effectively recovered, and the rare earth resource in the non-serviceable nickel-metal hydride battery is reasonably utilized; and the material obtained in the invention accords with requirements on the rare earth raw material by the hydrogen storage alloy powder material for the nickel-metal hydride battery.
Description
Technical field
The present invention relates to a kind of nickel metal hydride battery material preparation method, particularly the preparation method of negative active core-shell material hydrogen storing alloy powder.
Background technology
At present the preparation hydrogen storing alloy powder has a lot of techniques and method, but is substantially all selecting the at high temperature melting of the metals such as required rare earth and nickel, cobalt by stoicheiometry and making of adopting, and the rare earth source is for refining the raw material rare earth that makes from ore.And need to choose according to the alloy powder ratio corresponding rare earth element raw material rare earth from different rare earth elements in the middle of preparation, to satisfy the requirement of hydrogen storing alloy powder.The preparation method of this routine need to use a large amount of non-renewable rare-earth ore resources.
Summary of the invention
The present invention aims to provide a kind of preparation method that can effectively save the alloy material storing hydrogen of rare-earth ore resource.The present invention realizes by following scheme:
A kind of preparation method of alloy material storing hydrogen comprises the following steps:
I, take the inefficacy nickel metal hydride battery as raw material, after the dump energy of battery is discharged, disassemble battery and sub-elect battery core and other parts of battery, and battery core is broken into powder, wherein battery core comprises positive pole, negative pole and barrier film etc., other parts mainly refer to the shell of battery;
II, the battery core solid powder that I step is obtained add in the mixed aqueous solution system that is comprised of acid and oxygenant and react, and keep reacting and carry out in dynamic system, until the pH value to 0.1 of system～5 stop, more reacted system are carried out solid-liquid separation; The general mode that stirs that adopts makes during reaction system is in dynamically, and the stir shaft speed of rotation is general≤1000r/min.
III, get the solution after II step solid-liquid separation, add wherein alkali metal sulfates, keep the pH value 0.1～4 of reaction system, every liter of solution adds the alkali metal sulfates solid of 30～100g, and after reaction, solid-liquid separation is got the solids after separation; Temperature of reaction system should be selected 50～100 ℃;
IV, get solids high-temperature roasting under 300～1200 ℃ of conditions of III step gained, then the solid fused salt electrolysis after roasting has been obtained specific blend rare earth metal solid; Fused salt electrolysis process can adopt existing processing method to realize.This specific blend rare earth metal solid is to have comprised the metal that various rare earth elements form, and the mass ratio of the kind of its rare earth elements and each element is substantially suitable to the requirement of rare earths material with prepared hydrogen storage alloy.
V, the specific blend rare earth solid that makes after fused salt electrolysis is placed in high-temperature resistant container, press the nickel-hydrogen battery negative pole active material---the chemical component of hydrogen storage alloy, fill into wherein again the metal of corresponding disappearance, the metal of metallic nickel for filling into, remaining metal, the rare earth of certain particular types, cobalt metal etc., according to filling into, carry out high melt again in protective atmosphere (being generally argon gas) environment, the condition that is smelt in the step of hydrogen storage alloy by the hybrid metal high temperature melting in its melting condition and at present conventional hydrogen storage alloy preparation technology is identical, obtain hydrogen storage alloy after cooling rapidly.
Taking environmental conservation into consideration needs, reduce the exhaust gas emission of sulfurous gas, after the solid-liquid separation in described III step, solids after separating is preferably first done following processing: with adding carbonate or oxalate again in solution after the acid dissolving, solid-liquid separation again after reaction is completed, the solids that makes after above processing change the described IV step over to.
For raising the efficiency, described II is in the step, and every kilogram of battery core solid powder adds the mixed aqueous solution of 5～30L, and [H in mixed aqueous solution
+]: 1～5mol/L, oxygenant is according to the ratio of every kilogram of battery core powder correspondence 4～20mol oxidation electronics, the hydrogen peroxide that oxygenant preferential oxidation performance is stronger, alkaline metal hypochlorite or alkaline metal chlorate.
Compared with prior art, the present invention utilizes the inefficacy nickel metal hydride battery, has obtained preparation nickel-hydrogen battery negative pole active material after processing through battery recycling---the rare earths material source of hydrogen storage alloy.Substantially do not need on the one hand rare-earth mineral to provide to produce and use raw material, greatly saved natural resources; Its two, the inefficacy nickel metal hydride battery has obtained effective recycling, not only recyclable nickel metal wherein, and rare earth resources has wherein also obtained reasonable utilization, has also found the suitable approach that utilizes for the rare earth resources of this form; They are three years old, adopt rare earths material that the present invention obtains through four steps owing to deriving from nickel metal hydride battery, so the raw material that the crystalline form feature that had of its composition, material self etc. derives from rare-earth mineral more meet the requirement of hydrogen storage alloy powder material to rare earths material that use for nickel-hydrogen battery.
Embodiment
Embodiment 1
A kind of preparation method of alloy material storing hydrogen, carry out according to the following steps:
I, the inefficacy nickel metal hydride battery of getting some amount were soaked in clear water more than 1 hour, in battery dump energy discharge after, take out dry; Utilize afterwards cutting machine that battery is disassembled, sub-elect battery core and shell; Again battery core is broken into powder.
II, the battery core solid powder that the processing of I step is obtained add in the mixed aqueous solution system that is comprised of sulfuric acid and oxygenant clorox, and the stirring body system keeps the general 500r/min of stir shaft speed of rotation, and temperature of reaction is 50 ℃; Every kilogram of battery core solid powder adds the mixed aqueous solution of 25L, and [H in mixed aqueous solution
+] be 3mol/L, clorox is according to the ratio-dependent add-on of the corresponding 5mol oxidation of every kilogram of battery core powder electronics.Stopped reaction during to the pH value 2 of system; Again reacted system is carried out solid-liquid separation afterwards.
III, get the solution after II step solid-liquid separation, add wherein sodium sulfate, every liter of solution adds sodium sulfate solid 35g, keeps the pH value of reaction system between 0.1～4, and temperature of reaction is at 50 ℃, and solid-liquid separation again after reaction is got the solids after separation.
IV, solids high-temperature roasting under 1100 ℃ of conditions of getting III step gained, then the solid after roasting is adopted conventional fused salt electrolysis process, make specific blend rare earth metal solid; This specific blend rare earth metal solid is to have comprised the metal that various rare earth elements form, and the mass ratio of the kind of its rare earth elements and each element and prepared hydrogen storage alloy are to the requirement of rare earths material suitable (cerium: 30%, lanthanum 60%, praseodymium 4%, neodymium 6%) substantially.
V, the specific blend rare earth solid that makes after fused salt electrolysis is placed in crucible, press the nickel-hydrogen battery negative pole active material---the chemical component of hydrogen storage alloy, fill into wherein metallic nickel, then carry out high melt in the argon gas atmosphere environment, obtain hydrogen storage alloy after cooling rapidly.
Embodiment 2
I, the inefficacy nickel metal hydride battery of getting some amount were soaked in clear water more than 3 hours, after the dump energy in battery discharges, took out dry; Utilize afterwards cutting machine that battery is disassembled, sub-elect battery core and shell; Again battery core is broken into powder.
II, the battery core solid powder that the processing of I step is obtained add in the mixed aqueous solution system that is comprised of sulfuric acid and oxidants hydrogen peroxide, and the stirring body system keeps the general 8000r/min of stir shaft speed of rotation, and temperature of reaction is 80 ℃; Every kilogram of battery core solid powder adds the mixed aqueous solution of 5L, and [H in mixed aqueous solution
+] be 1mol/L, clorox is according to the ratio-dependent add-on of the corresponding 20mol oxidation of every kilogram of battery core powder electronics.PH value 2 stopped reaction to system; Again reacted system is carried out solid-liquid separation afterwards.
III, get the solution after II step solid-liquid separation, add wherein vitriolate of tartar, every liter of solution adds the 98g vitriolate of tartar, keeps the pH value of reaction system between 0.1～4, and temperature of reaction is at 80 ℃, and solid-liquid separation again after reaction is got the solids after separation.Solids after separating is added sodium carbonate after with dissolving with hydrochloric acid again in solution, solid-liquid separation again after reaction is completed.
IV, solids high-temperature roasting under 400 ℃ of conditions of getting III step gained, then the solid after roasting is adopted conventional fused salt electrolysis process, make specific blend rare earth metal solid; This specific blend rare earth metal solid is to have comprised the metal that various rare earth elements form, and the mass ratio of the kind of its rare earth elements and each element and prepared hydrogen storage alloy are to the requirement of rare earths material suitable (cerium: 30%, lanthanum 60%, praseodymium 4%, neodymium 6%) substantially.
V, the specific blend rare earth solid that makes after fused salt electrolysis is placed in crucible, press the nickel-hydrogen battery negative pole active material---the chemical component of hydrogen storage alloy, fill into wherein metallic nickel, then carry out high melt in the argon gas atmosphere environment, obtain hydrogen storage alloy after cooling rapidly.
Claims (4)
1. the preparation method of a hydrogen storage alloy raw material is characterized in that: comprises the following steps,
I, take the inefficacy nickel metal hydride battery as raw material, after battery dump energy is discharged, disassemble battery and sub-elect battery core and other parts of battery, and battery core is broken into powder;
II, the battery core solid powder that I step is obtained add in the mixed aqueous solution system that is comprised of acid and oxygenant and react, and keep reacting and carry out in dynamic system, until the pH value to 0.1 of system～5 stop, more reacted system are carried out solid-liquid separation;
III, get the solution after II step solid-liquid separation, add wherein alkali metal sulfates, keep the pH value 0.1～4 of reaction system, after reaction, solid-liquid separation is got the solids after separation;
IV, get solids high-temperature roasting under 300～1200 ℃ of conditions of III step gained, then the solid fused salt electrolysis after roasting is obtained specific blend rare earth metal solid;
V, the specific blend rare earth solid that makes after fused salt electrolysis is placed in high-temperature resistant container, presses the hydrogen storage alloy chemical component, then fill into wherein the metal of corresponding disappearance, carry out melting in the protective atmosphere environment, obtain hydrogen storage alloy after cooling rapidly.
2. the preparation method of a kind of hydrogen storage alloy raw material as claimed in claim 1, it is characterized in that: after the solid-liquid separation in described III step, solids after separating is done following processing: with adding carbonate or oxalate again in solution after the acid dissolving, solid-liquid separation again after reaction is completed changes the solids that makes over to the described IV step.
3. the preparation method of a kind of hydrogen storage alloy raw material as claimed in claim 1 or 2 is characterized in that: described II is in the step, and every kilogram of battery core solid powder adds the mixed aqueous solution of 5～30L, and [H in mixed aqueous solution
+]: 1～5mol/L, oxygenant is according to the ratio of every kilogram of battery core powder correspondence 4～20mol oxidation electronics.
4. the preparation method of a kind of hydrogen storage alloy raw material as claimed in claim 3, is characterized in that: the preferred hydrogen peroxide of oxygenant, alkaline metal hypochlorite or alkaline metal chlorate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789573A (en) * | 2014-01-22 | 2014-05-14 | 西北工业大学 | Zr-based Laves phase hydrogen storage alloy and preparation method thereof |
| CN107217149A (en) * | 2017-07-10 | 2017-09-29 | 山东理工大学 | The system of recovering rare earth from capacitor type nickel-hydrogen battery negative pole material |
| CN107267783A (en) * | 2017-07-10 | 2017-10-20 | 山东理工大学 | The method of recovering rare earth from asymmetric capacitor type Ni-MH battery |
| CN107312944A (en) * | 2017-07-10 | 2017-11-03 | 山东理工大学 | Utilize the method for asymmetric capacitor type Ni-MH battery recovering rare earth |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295355A (en) * | 2000-12-19 | 2001-05-16 | 南开大学 | Regeneration method of deactivated negative alloy powder of secondary nickel-hydrogen battery |
| CN101886178A (en) * | 2010-07-28 | 2010-11-17 | 江门市长优实业有限公司 | Comprehensive recovery method for nickel-hydrogen waste battery |
| CN102304620A (en) * | 2011-09-23 | 2012-01-04 | 先进储能材料国家工程研究中心有限责任公司 | Comprehensive recovery and treatment method of waste nickel-hydrogen battery |
| CN102576919A (en) * | 2009-10-23 | 2012-07-11 | 三井金属矿业株式会社 | Process for production of hydrogen-storing alloy composition |
| JP2012153929A (en) * | 2011-01-25 | 2012-08-16 | Mitsui Mining & Smelting Co Ltd | Method for producing hydrogen storage alloy composite |
-
2013
- 2013-02-18 CN CN201310052518.5A patent/CN103146957B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295355A (en) * | 2000-12-19 | 2001-05-16 | 南开大学 | Regeneration method of deactivated negative alloy powder of secondary nickel-hydrogen battery |
| CN102576919A (en) * | 2009-10-23 | 2012-07-11 | 三井金属矿业株式会社 | Process for production of hydrogen-storing alloy composition |
| CN101886178A (en) * | 2010-07-28 | 2010-11-17 | 江门市长优实业有限公司 | Comprehensive recovery method for nickel-hydrogen waste battery |
| JP2012153929A (en) * | 2011-01-25 | 2012-08-16 | Mitsui Mining & Smelting Co Ltd | Method for producing hydrogen storage alloy composite |
| CN102304620A (en) * | 2011-09-23 | 2012-01-04 | 先进储能材料国家工程研究中心有限责任公司 | Comprehensive recovery and treatment method of waste nickel-hydrogen battery |
Non-Patent Citations (1)
| Title |
|---|
| 李丽等: "镍氢动力电池回收与再生研究进展", 《功能材料》, vol. 38, no. 12, 31 December 2007 (2007-12-31), pages 1928 - 1932 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789573A (en) * | 2014-01-22 | 2014-05-14 | 西北工业大学 | Zr-based Laves phase hydrogen storage alloy and preparation method thereof |
| CN103789573B (en) * | 2014-01-22 | 2015-11-18 | 西北工业大学 | A kind of Zr base Laves phase hydrogen storage alloy and preparation method thereof |
| CN107217149A (en) * | 2017-07-10 | 2017-09-29 | 山东理工大学 | The system of recovering rare earth from capacitor type nickel-hydrogen battery negative pole material |
| CN107267783A (en) * | 2017-07-10 | 2017-10-20 | 山东理工大学 | The method of recovering rare earth from asymmetric capacitor type Ni-MH battery |
| CN107312944A (en) * | 2017-07-10 | 2017-11-03 | 山东理工大学 | Utilize the method for asymmetric capacitor type Ni-MH battery recovering rare earth |
| CN107217149B (en) * | 2017-07-10 | 2018-10-16 | 山东理工大学 | The system of recovering rare earth from capacitive nickel-hydrogen battery negative pole material |
| CN107267783B (en) * | 2017-07-10 | 2019-06-18 | 山东理工大学 | The method of recovering rare earth from asymmetric capacitive nickel-metal hydride battery |
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