CN107331913A - The method that double rear-earth-doped Conjugate ferrite magnetostriction materials are prepared using waste and old lithium ion battery - Google Patents
The method that double rear-earth-doped Conjugate ferrite magnetostriction materials are prepared using waste and old lithium ion battery Download PDFInfo
- Publication number
- CN107331913A CN107331913A CN201710579257.0A CN201710579257A CN107331913A CN 107331913 A CN107331913 A CN 107331913A CN 201710579257 A CN201710579257 A CN 201710579257A CN 107331913 A CN107331913 A CN 107331913A
- Authority
- CN
- China
- Prior art keywords
- earth
- waste
- lithium ion
- ion battery
- doped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N35/00—Magnetostrictive devices
- H10N35/01—Manufacture or treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N35/00—Magnetostrictive devices
- H10N35/80—Constructional details
- H10N35/85—Magnetostrictive active materials
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Abstract
The invention discloses a kind of method that utilization waste and old lithium ion battery prepares double rear-earth-doped Conjugate ferrite magnetostriction materials, waste and old lithium ion battery is split, acidleach, the fully Co in precipitation positive electrode2+、Fe3+；Sediment nitric acid is dissolved, supplement adds cobalt nitrate, ferric nitrate and the rare earth nitrades of stoichiometric proportion, add citric acid, the pH of regulation solution carries out sol-gel process；Will after gel drying add ethanol light progress self-propagating combustion obtain CoCexNd0.1‑xFe1.9O4Powder；Poly-vinyl alcohol solution is added in powder and is pressed into cylinder, rear-earth-doped Conjugate ferrite magnetostrictive device is made in 650 DEG C of calcining 6h coolings, 1450 DEG C of sintering 6h.The secondary utilization waste and old lithium ion battery of the present invention, avoids the waste of metals resources while reduction environmental pollution, reduce the cost of material preparation, and synthetic method is simple, and the cycle is short, saves energy consumption, obtained CoCexNd0.1‑xFe1.9O4Function admirable.
Description
Technical field
The invention belongs to solid waste renewable resources and the preparing technical field of magnetostriction materials, and in particular to a kind of
The method that double rear-earth-doped Conjugate ferrite magnetostriction materials are prepared using waste and old lithium ion battery.
Background technology
Magnetostriction materials are because in terms of noncontacting proximity sensor and brake there is extensive potential using value to attract
The extensive concerns of scientists.Relative to wide variety of rare earth alloy magnetostriction materials TbxDy1-xFe2Deng many of, sintering
Brilliant Conjugate ferrite is cheap because of its, with larger coercive field and saturation magnetization, higher magnetocrystalline anisotropy,
Mechanical strength is good, and good chemical stability, corrosion-resistant and wear-resistant etc. performance are widely studied.Ground at present to ferritic
Study carefully preparation mainly to synthesize by chemical raw material, preparation method is various, have the preparation technology of maturation but cost is higher.And waste and old lithium from
Contain Large Amount of Co, iron metal ion in sub- battery, waste and old lithium ion battery is mixed by dismantling, dissolving, isolate metal ion
Compound is directly used in the preparation of Conjugate ferrite, not only reduces the separation requirement to waste and old lithium ion battery, and reduce cobalt
Ferritic cost of manufacture.
By the cobalt ions or iron ion in different metal ion replacing cobalt ferrites, the point for entering Conjugate ferrite is brilliant
In stone lattice different degrees of change can be caused to the properity of Conjugate ferrite.Rare earth ion（RE3+）Because having big ion
Radius and stable chemical valence, when it replaces Fe3+Enter in cubic lattice, RE-Fe reciprocation and 3d-4f tracks occur
Spin coupling, because the spin of the interaction between ion and atomic orbital can change the magnetostriction of Conjugate ferrite,
At present still not on the relevant report using the double rear-earth-doped Conjugate ferrite magnetostriction materials of waste and old lithium ion battery preparation.
The content of the invention
Present invention solves the technical problem that there is provided one kind prepares double rear-earth-doped ferro-cobalts using waste and old lithium ion battery
The method of oxysome magnetostriction materials, this method by it is rare earth doped make Conjugate ferrite obtained under conditions of downfield compared with
Big magnetostriction, and preparation process is simple, with low cost, economical and efficient and obtained properties of product are excellent.
The present invention is adopted the following technical scheme that to solve above-mentioned technical problem, and double rare earths are prepared using waste and old lithium ion battery
The method of cation doping ferrite magnetostriction materials, it is characterised in that concretely comprise the following steps：
（1）Waste lithium ion cell anode material after fractionation is dissolved in containing H2O2Molar concentration be 3.5mol/L sulfuric acid
In solution, regulation pH value makes Co2+、Fe3+Fully precipitate, the filter residue after filtering is dissolved with nitric acid；
（2）By step（1）Middle dissolving filter residue resulting solution measures the Co in solution with atomic absorption spectrophotometer2+、Fe3+'s
Content, supplement adds Co (NO3)2·6H2O、Fe(NO3)3·9H2O、Ce(NO3)3·6H2O and Nd (NO3)3·6H2O makes each ion
Mol ratio Co2+:Ce3+:Nd3+:Fe3+ =1:x:0.1-x:1.9, wherein x are 0.02-0.08, and adding citric acid makes itself and gold
It is 1 to belong to ion mole total amount ratio:1, stirring makes it fully dissolve；
（3）By step（2）In the solution that is completely dissolved adjust pH=6.5 with ammoniacal liquor in 60 DEG C, and be warming up to 80 DEG C of gels, until
Gel-forming is dried to obtain xerogel after 110 DEG C；
（4）By step（3）In add 2mL ethanol in obtained xerogel and ignite, start self-propagating combustion and obtain double rare earths to mix
Miscellaneous CoFe2O4Powder；
（5）By step（4）In obtained double rear-earth-doped CoFe2O4The polyvinyl alcohol that mass concentration is 8%-10% is added in powder
Solution, grinding is uniform, the compression leg under 12MPa pressure；
（6）By step（5）Prior to the 650 DEG C calcining 6h coolings of the sample column of middle compacting, are to obtain mangneto then at 1450 DEG C of sintering 6h
Flexible double rear-earth-doped CoFe2O4Device.
The present invention has the advantages that compared with prior art：
1st, using waste and old lithium ion battery as raw material, the waste of metals resources is avoided while reduction environmental pollution, material is reduced
Expect the cost prepared；
2nd, it is simple to operate using the double rear-earth-doped cobalt ferrite powders of method preparation of sol-tgel self-propagating, it is easy to control to react
Process；
3rd, the collective effect of two kinds of rare earth elements, not only effectively improves the performance parameter of Conjugate ferrite, and solve dilute
The problem of native alloy magnetostriction material high cost.
Brief description of the drawings
Fig. 1 is CoCe made from the embodiment of the present invention 10.02Nd0.08Fe1.9O4The XRD of magnetostriction materials；
Fig. 2 is CoCe made from the embodiment of the present invention 10.02Nd0.08Fe1.9O4The magnetostriction coefficient figure of magnetostriction materials；
Fig. 3 is CoCe made from the embodiment of the present invention 10.02Nd0.08Fe1.9O4The magnetostrictive strain curve of magnetostriction materials
Figure.
Embodiment
The above to the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
（1）Waste lithium ion cell anode material after fractionation is dissolved in containing H2O2Molar concentration be 3.5mol/L sulfuric acid
In solution, regulation pH value makes Co2+、Fe3+Fully precipitate, the filter residue after filtering is dissolved with nitric acid；
（2）By step（1）Middle dissolving filter residue resulting solution measures the Co in solution with atomic absorption spectrophotometer2+、Fe3+'s
Content, supplement adds Co (NO3)2·6H2O、Fe(NO3)3·9H2O、Ce(NO3)3·6H2O and Nd (NO3)3·6H2O makes each ion
Mol ratio Co2+:Ce3+:Nd3+:Fe3+ =1:0.02:0.08:1.9, adding citric acid makes itself and metal ion mole total amount
Than for 1:1, stirring makes it fully dissolve；
（3）By step（2）In the solution that is completely dissolved adjust pH=6.5 with ammoniacal liquor in 60 DEG C, and be warming up to 80 DEG C of gels, until
Gel-forming is dried to obtain xerogel after 110 DEG C；
（4）By step（3）In add 2mL ethanol in obtained xerogel and ignite, start self-propagating combustion and obtain double rare earths to mix
Miscellaneous CoFe2O4Powder；
（5）By step（4）In obtained double rear-earth-doped CoFe2O4Mass concentration is added in powder molten for 8% polyvinyl alcohol
Liquid, grinding is uniform, the compression leg under 12MPa pressure；
（6）By step（5）Prior to the 650 DEG C calcining 6h coolings of the sample column of middle compacting, are to obtain mangneto then at 1450 DEG C of sintering 6h
Flexible double rear-earth-doped CoFe2O4Device.
Embodiment 2
（1）Waste lithium ion cell anode material after fractionation is dissolved in containing H2O2Molar concentration be 3.5mol/L sulfuric acid
In solution, regulation pH value makes Co2+、Fe3+Fully precipitate, the filter residue after filtering is dissolved with nitric acid；
（2）By step（1）Middle dissolving filter residue resulting solution measures the Co in solution with atomic absorption spectrophotometer2+、Fe3+'s
Content, supplement adds Co (NO3)2·6H2O、Fe(NO3)3·9H2O、Ce(NO3)3·6H2O and Nd (NO3)3·6H2O makes each ion
Mol ratio Co2+:Ce3+:Nd3+:Fe3+ =1:0.04:0.06:1.9, adding citric acid makes itself and metal ion mole total amount
Than for 1:1, stirring makes it fully dissolve；
（3）By step（2）In the solution that is completely dissolved adjust pH=6.5 with ammoniacal liquor in 60 DEG C, and be warming up to 80 DEG C of gels, until
Gel-forming is dried to obtain xerogel after 110 DEG C；
（4）By step（3）In add 2mL ethanol in obtained xerogel and ignite, start self-propagating combustion and obtain double rare earths to mix
Miscellaneous CoFe2O4Powder；
（5）By step（4）In obtained double rear-earth-doped CoFe2O4Mass concentration is added in powder molten for 9% polyvinyl alcohol
Liquid, grinding is uniform, the compression leg under 12MPa pressure；
（6）By step（5）Prior to the 650 DEG C calcining 6h coolings of the sample column of middle compacting, are to obtain mangneto then at 1450 DEG C of sintering 6h
Flexible double rear-earth-doped CoFe2O4Device.
Embodiment 3
（1）Waste lithium ion cell anode material after fractionation is dissolved in containing H2O2Molar concentration be 3.5mol/L sulfuric acid
In solution, regulation pH value makes Co2+、Fe3+Fully precipitate, the filter residue after filtering is dissolved with nitric acid；
（2）By step（1）Middle dissolving filter residue resulting solution measures the Co in solution with atomic absorption spectrophotometer2+、Fe3+'s
Content, supplement adds Co (NO3)2·6H2O、Fe(NO3)3·9H2O、Ce(NO3)3·6H2O and Nd (NO3)3·6H2O makes each ion
Mol ratio Co2+:Ce3+:Nd3+:Fe3+ =1:0.08:0.02:1.9, adding citric acid makes itself and metal ion mole total amount
Than for 1:1, stirring makes it fully dissolve；
（3）By step（2）In the solution that is completely dissolved adjust pH=6.5 with ammoniacal liquor in 60 DEG C, and be warming up to 80 DEG C of gels, until
Gel-forming is dried to obtain xerogel after 110 DEG C；
（4）By step（3）In add 2mL ethanol in obtained xerogel and ignite, start self-propagating combustion and obtain double rare earths to mix
Miscellaneous CoFe2O4Powder；
（5）By step（4）In obtained double rear-earth-doped CoFe2O4Mass concentration is added in powder molten for 10% polyvinyl alcohol
Liquid, grinding is uniform, the compression leg under 12MPa pressure；
（6）By step（5）Prior to the 650 DEG C calcining 6h coolings of the sample column of middle compacting, are to obtain mangneto then at 1450 DEG C of sintering 6h
Flexible double rear-earth-doped CoFe2O4Device.
Embodiment above describes general principle, principal character and the advantage of the present invention, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (1)
1. the method for double rear-earth-doped Conjugate ferrite magnetostriction materials is prepared using waste and old lithium ion battery, it is characterised in that tool
Body step is：
（1）Waste lithium ion cell anode material after fractionation is dissolved in containing H2O2Molar concentration be 3.5mol/L sulfuric acid
In solution, regulation pH value makes Co2+、Fe3+Fully precipitate, the filter residue after filtering is dissolved with nitric acid；
（2）By step（1）Middle dissolving filter residue resulting solution measures the Co in solution with atomic absorption spectrophotometer2+、Fe3+Contain
Amount, supplement adds Co (NO3)2·6H2O、Fe(NO3)3·9H2O、Ce(NO3)3·6H2O and Nd (NO3)3·6H2O makes each ion
Mol ratio Co2+:Ce3+:Nd3+:Fe3+ =1:x:0.1-x:1.9, wherein x are 0.02-0.08, and adding citric acid makes itself and metal
Ion mole total amount ratio is 1:1, stirring makes it fully dissolve；
（3）By step（2）In the solution that is completely dissolved adjust pH=6.5 with ammoniacal liquor in 60 DEG C, and be warming up to 80 DEG C of gels, until
Gel-forming is dried to obtain xerogel after 110 DEG C；
（4）By step（3）In add 2mL ethanol in obtained xerogel and ignite, start self-propagating combustion and obtain double rare earths to mix
Miscellaneous CoFe2O4Powder；
（5）By step（4）In obtained double rear-earth-doped CoFe2O4The polyvinyl alcohol that mass concentration is 8%-10% is added in powder
Solution, grinding is uniform, the compression leg under 12MPa pressure；
（6）By step（5）Prior to the 650 DEG C calcining coolings of the sample column of middle compacting, are to obtain mangneto to stretch then at 1450 DEG C of sintering 6h
The double rear-earth-doped CoFe of contracting2O4Device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710579257.0A CN107331913A (en) | 2017-07-17 | 2017-07-17 | The method that double rear-earth-doped Conjugate ferrite magnetostriction materials are prepared using waste and old lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710579257.0A CN107331913A (en) | 2017-07-17 | 2017-07-17 | The method that double rear-earth-doped Conjugate ferrite magnetostriction materials are prepared using waste and old lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107331913A true CN107331913A (en) | 2017-11-07 |
Family
ID=60227387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710579257.0A Pending CN107331913A (en) | 2017-07-17 | 2017-07-17 | The method that double rear-earth-doped Conjugate ferrite magnetostriction materials are prepared using waste and old lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107331913A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108118194A (en) * | 2017-11-22 | 2018-06-05 | 包头稀土研究院 | The preparation method of Fe-Co base magnetic strictions alloy and its B alloy wire |
| CN112745115A (en) * | 2021-01-11 | 2021-05-04 | 电子科技大学 | Magnetostrictive material with high strain sensitivity in low magnetic field and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103182514A (en) * | 2013-04-11 | 2013-07-03 | 中国石油大学(华东) | Method for preparing neodymium iron boron magnetic powder by self-propagating combustion |
| CN104557006A (en) * | 2015-01-19 | 2015-04-29 | 河南师范大学 | Method for preparing cobalt ferrite magnetostrictive material from waste lithium ion batteries in low magnetic field |
| CN104600390A (en) * | 2015-01-19 | 2015-05-06 | 河南师范大学 | Method for preparing magnetostriction material by utilizing spent lithium ion batteries |
| CN104600391A (en) * | 2015-01-19 | 2015-05-06 | 河南师范大学 | Method for preparing manganese-doped cobalt ferrite magnetostriction material by utilizing spent lithium ion batteries |
-
2017
- 2017-07-17 CN CN201710579257.0A patent/CN107331913A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103182514A (en) * | 2013-04-11 | 2013-07-03 | 中国石油大学(华东) | Method for preparing neodymium iron boron magnetic powder by self-propagating combustion |
| CN104557006A (en) * | 2015-01-19 | 2015-04-29 | 河南师范大学 | Method for preparing cobalt ferrite magnetostrictive material from waste lithium ion batteries in low magnetic field |
| CN104600390A (en) * | 2015-01-19 | 2015-05-06 | 河南师范大学 | Method for preparing magnetostriction material by utilizing spent lithium ion batteries |
| CN104600391A (en) * | 2015-01-19 | 2015-05-06 | 河南师范大学 | Method for preparing manganese-doped cobalt ferrite magnetostriction material by utilizing spent lithium ion batteries |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108118194A (en) * | 2017-11-22 | 2018-06-05 | 包头稀土研究院 | The preparation method of Fe-Co base magnetic strictions alloy and its B alloy wire |
| CN112745115A (en) * | 2021-01-11 | 2021-05-04 | 电子科技大学 | Magnetostrictive material with high strain sensitivity in low magnetic field and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3090821B1 (en) | Method for preparing neodymium-iron-boron magnet by utilizing waste material | |
| CN103964828B (en) | A kind of high-performance permanent magnetic ferrite material and preparation method thereof | |
| CN104557006B (en) | Utilize the method that waste and old lithium ion battery downfield prepares Conjugate ferrite magnetostriction materials | |
| CN102191388B (en) | Process for extracting vanadium from stone coal through two-section curing with concentrated acid | |
| CN104529424B (en) | A kind of have two-phase exchange coupling and keep the composite permanet magnet ferrite of high-coercive force | |
| CN104600390B (en) | Method for preparing magnetostriction material by utilizing spent lithium ion batteries | |
| CN103449808B (en) | Preparation method of biphase composite hard magnetic ferrite nano-powder with exchange coupling | |
| CN102674824A (en) | Method for manufacturing MnZn ferrite by using MnZn ferrite core grinding waste | |
| CN107331913A (en) | The method that double rear-earth-doped Conjugate ferrite magnetostriction materials are prepared using waste and old lithium ion battery | |
| CN104600391A (en) | Method for preparing manganese-doped cobalt ferrite magnetostriction material by utilizing spent lithium ion batteries | |
| CN102408102B (en) | Preparation method of nanometer iron phosphate | |
| CN101698496B (en) | Preparation method of electronic grade high-purity copper oxide superfine powder | |
| CN106745318B (en) | A kind of method using iron vitriol slag one-step synthesis magnetic ferroferric oxide | |
| CN103951416B (en) | A kind of composite Nano ZnO voltage-sensitive ceramic raw powder's production technology | |
| CN103191698B (en) | Method for preparing graphene/ferroferric oxide composite microspheres | |
| CN107369510A (en) | A kind of preparation method of low-cost and high-performance compound soft magnetic material | |
| CN102219493B (en) | Method for preparing MnZn ferrite material powder from acid washing waste liquid and galvanized zinc slag | |
| CN102442702A (en) | Holmium-doped bismuth ferric multiferroic material and preparation method thereof | |
| CN106145917A (en) | A kind of coercitive secondary of permanently magnetic strontium ferrite that improves is combined adding method | |
| CN107331914A (en) | The method that the rare earth doped Conjugate ferrite magnetostriction materials of transiting state metal are prepared using waste and old lithium ion battery | |
| CN104310479A (en) | Silver-doped lithium niobate nano polycrystalline powder and preparation method thereof | |
| CN1645657A (en) | Method for preparing manganese-zinc ferrite by using waste zinc-manganese battery | |
| CN106938927A (en) | The method for preparing Ni-Co ferrite magnetostriction materials using waste and old lithium ion battery doping nickel | |
| CN103601483B (en) | The synthetic method of lanthanum additive Mn iron strontium oxide magnetic powder | |
| CN101921103A (en) | Manganese zinc ferrite with high magnetic conductivity and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171107 |