CN110511015A - The preparation method of manganese-zinc ferrite - Google Patents
The preparation method of manganese-zinc ferrite Download PDFInfo
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- CN110511015A CN110511015A CN201910939097.5A CN201910939097A CN110511015A CN 110511015 A CN110511015 A CN 110511015A CN 201910939097 A CN201910939097 A CN 201910939097A CN 110511015 A CN110511015 A CN 110511015A
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Abstract
In the preparation method of manganese-zinc ferrite provided by the present application, by extracting cobalt oxide substance from battery anode slice, ferrite presoma is recycled using oxalate coprecipitation method from industrial waste simultaneously, finally prepares manganese-zinc ferrite, in which: by extracting Co from battery2O3Substance, section can make temperature-power consumption profile relatively flat of material；Three kinds of manganese, zinc and iron elements can be made to mix in atom level using oxalate coprecipitation method in the application, the reactivity of material is higher, the sintering temperature in sintering process can be reduced, 1200-1300 DEG C can be reduced to by existing 1350 DEG C, and then improve grain structure, it obtains that crystal structure is fine, the sintered body of crystallite dimension more evenly, guarantees the uniformity of crystal grain, the magnetic hystersis loss and eddy-current loss of material are reduced, to improve the magnetic conductivity of material and reduce the loss of material.
Description
Technical field
This application involves Ferrite Material technical field more particularly to a kind of preparation methods of manganese-zinc ferrite.
Background technique
Manganese-zinc ferrite is a kind of soft magnetic material with spinel structure, because it is with high magnetic conductivity, low-loss
It waits physicochemical properties and is widely used in the industries such as communication, sensing, television set；With people energy-saving and emission-reduction are proposed it is higher
It is required that it is more urgent to the performance requirement of consumption manganese-zinc ferrite, such as high magnetic permeability, low-loss, wherein loss mainly includes magnetic hysteresis
Loss and eddy-current loss.
The preparation flow of manganese-zinc ferrite includes ball milling, pre-burning, doping, sintering etc., wherein doping is directed to reaction system
Middle addition Co2O3、TiO2Equal additives improve the microcosmic result of material and then improve ferritic electromagnetic performance；Wherein agglomerant
Skill refers under the melting temperature state lower than material, makes the different material of moulded blank at distribution by the method for heating and calcining
Raw solid phase reaction and shrinking densification makes crystal grow up the ferritic process of polycrystalline ultimately generated with certain physical property,
This key parameter of middle sintering temperature can influence the uniformity of crystal, and then the performances such as magnetic conductivity, loss for influencing product.
However since cobalt element is a kind of rare heavy metal, and then increase preparation cost；Current ferritic system simultaneously
Sintering temperature is higher during standby, and when sintering temperature is higher, the crystal grain stomata of crystal increases and becomes uneven, occurs abnormal
Big crystal grain, crystal grain is larger and uniformity is poor and then influences the performances such as magnetic conductivity, the loss of product.
Summary of the invention
This application provides a kind of preparation methods of manganese-zinc ferrite, to solve because sintering temperature is excessively high to product magnetic conductance
The technical issues of being adversely affected caused by the performances such as rate, loss.
In order to solve the above-mentioned technical problem, the embodiment of the present application discloses following technical solution:
A kind of preparation method of manganese-zinc ferrite provided by the present application, it is described to include:
A kind of preparation method of manganese-zinc ferrite provided by the present application, which comprises
Battery anode slice is dipped in sulfuric acid-hydrogen peroxide mixed solution and filtrate a is obtained by filtration；
Dilute acid soln is added into the filtrate a makes system pH 4~5.5, and filtrate b is obtained by filtration after dissolution；
Oxalic acid solution is added into the filtrate b, cobalt oxalate or cobalt oxalate-nickel oxalate-manganese oxalate copolymer is obtained by filtration；
Cobalt oxide or cobalt oxide-will be obtained after the cobalt oxalate or cobalt oxalate-nickel oxalate-manganese oxalate Copolymer sintering
Nickel oxide-manganese oxide mixed powder；
Sulfuric acid solution is added into ferrite waste residue makes system pH control be 1~5, and filtrate c is obtained after filtering；
The pH to 3~6 that ammonium hydroxide adjusts solution is added into the filtrate c, oxalic acid solution is added and obtains sediment, it will be described
Sediment high-temperature roasting obtains ferrite presoma；
According to the measurement result of iron, manganese and Zn content in the ferrite presoma, mended in the ferrite presoma
Mixture d is obtained after adding iron oxide, manganese oxide and zinc oxide with measurement result corresponding amount；
The cobalt oxide or cobalt oxide-nickel oxide-manganese oxide mixed powder and additive are added to the mixture d,
Obtain Mischung；
Manganese-zinc ferrite will be obtained after the Mischung high temperature sintering.
Preferably, it is described battery anode slice is dipped in sulfuric acid-hydrogen peroxide mixed solution and filtrate a is obtained by filtration before,
The method also includes:
Waste lithium cell Mechanical Crushing is decomposed, battery anode slice and negative electrode tab are obtained；
Diafiltration obtains copper foil and graphite slurry after the negative electrode tab is impregnated in water；
Dilute acid soln is added into the graphite slurry makes system pH control between 1~3, obtains mixed liquor f；
Filter residue g is obtained after ageing, diafiltration after the removing of ascorbic acid ultrasound is added into the mixed liquor f；
Grapheme material will be obtained after the filter residue g high-temperature roasting.
Preferably, described that oxalic acid solution is added into the filtrate b, cobalt oxalate or cobalt oxalate-nickel oxalate-grass is obtained by filtration
After sour manganese copolymer, the method also includes:
Ammonium carbonate is added into filtrate b and obtains lithium carbonate, it is 99% that purity will be obtained after the lithium carbonate high-temperature calcination
Lithium carbonate.
Optionally, described ferrite waste residue is dipped in sulfuric acid solution makes system pH control for after 1~5, the method
Further include:
It is filtered after polyacrylamide absorption suspended impurity is added into system.
It is optionally, described that the sediment high-temperature roasting is obtained into ferrite presoma, comprising:
The sediment is obtained into ferrite presoma in 700~900 DEG C of roasting temperatures.
Optionally, the temperature of second of high temperature sintering is 1200-1300 DEG C.
Optionally, in the test ferrite presoma after iron, manganese and Zn content, add iron oxide, manganese oxide and
Mixture d is obtained after zinc oxide, comprising:
It is measured in ferrite presoma after iron, manganese and Zn content using fluorescence analyser, adds iron oxide, manganese oxide and oxygen
Changing zinc makes iron oxide 52~53mol% of molar ratio, and zinc oxide molar ratio is 10~11%, manganese oxide molar ratio for 36~
38%.
It is optionally, described to add additive into the mixture d, comprising:
The Nb of addition 0.01~0.04% into the mixture d2O5, 0.01~0.06% V2O5, 0.01~0.06%
Calcium carbonate, 0.1~0.5% nickel oxide.
It is optionally, described to be sanded, be spray-dried after addition additive into the mixture d, comprising:
The Nb of addition 0.01~0.04% into the mixture d2O5, 0.01~0.06% V2O5, 0.01~0.06%
Calcium carbonate, be sanded after 0.1~0.5% nickel oxide, a certain amount of polyvinyl alcohol, spray drying be added.
Optionally, it is described the filtrate is deposited in enamel pot after, the method also includes:
Ferrum sulfuricum oxydatum solutum and the pH to 5-7 with ammonia water conditioning system are added into the enamel pot, obtains oxalic acid after filtering
Iron and filtrate e, the filtrate e crystallizing and drying.
Compared with prior art, the application has the beneficial effect that
As shown from the above technical solution, in the preparation method of manganese-zinc ferrite provided by the present application, by being mentioned from battery
Cobalt oxide substance is taken, while ferrite presoma is recycled using oxalate coprecipitation method from industrial waste, finally prepares MnZn
Ferrite, in which:
(1) by extracting Co from old and useless battery2O3Substance has saved production cost, and a certain amount of Co2O3In high temperature
It can make temperature-power consumption profile relatively flat of material down；The incorporation of Co may also suppress part Fe simultaneously2+Appearance, Jin Erke
Improve the resistivity of material.
(2) three kinds of manganese, zinc and iron elements can be made to mix in atom level using oxalate coprecipitation method in the application,
The reactivity of material is higher, can reduce the sintering temperature in sintering process, can be reduced to 1200- by existing 1350 DEG C
It 1300 DEG C, and then improve grain structure, obtains that crystal structure is fine, the sintered body of crystallite dimension more evenly, guarantees the equal of crystal grain
Even property, reduces the magnetic hystersis loss and eddy-current loss of material, to improve the magnetic conductivity of material and reduce the loss of material.
(3) lithium battery main component is nickel, cobalt, manganese in the application, and these three elements are exactly needed for manganese-zinc ferrite
Element, therefore the introducing of this method can make full use of waste lithium cell material, and the performance of the manganese-zinc ferrite to preparation
It does not have an impact.
It should be understood that above general description and following detailed description be only it is exemplary and explanatory, not
The application can be limited.
Detailed description of the invention
In order to illustrate more clearly of the technical solution of the application, letter will be made to attached drawing needed in the embodiment below
Singly introduce, it should be apparent that, for those of ordinary skills, without creative efforts, also
Other drawings may be obtained according to these drawings without any creative labor.
Fig. 1 is the preparation method flow diagram of manganese-zinc ferrite provided in an embodiment of the present invention；
Fig. 2 is temperature-power consumption relation schematic diagram of manganese-zinc ferrite provided in an embodiment of the present invention.
Specific embodiment
In order to make those skilled in the art better understand the technical solutions in the application, below in conjunction with the application reality
The attached drawing in example is applied, the technical scheme in the embodiment of the application is clearly and completely described, it is clear that described implementation
Example is only some embodiments of the present application, rather than whole embodiments.Based on the embodiment in the application, the common skill in this field
The application protection all should belong in art personnel every other embodiment obtained without making creative work
Range.
Please refer to attached drawing 1, wherein Fig. 1 is that the process of the preparation method of manganese-zinc ferrite provided in an embodiment of the present invention is shown
It is intended to.The description of following specific embodiments is based on attached drawing 1.
As shown in Figure 1, a kind of preparation method of manganese-zinc ferrite provided by the present application, described to include:
S110: battery anode slice is dipped in sulfuric acid-hydrogen peroxide mixed solution and filtrate a is obtained by filtration；
Dilute acid soln is added in S120: Xiang Suoshu filtrate a makes system pH 4~5.5, and filtrate b is obtained by filtration after dissolution；
In this application, wherein battery anode slice is chosen as the positive plate of waste lithium cell, method particularly includes: by waste and old lithium
Battery machine is broken to be decomposed, and obtains battery anode slice and negative electrode tab, positive plate be it is used herein, positive plate is put in 1~
In 3mol/L sulfuric acid and hydrogen peroxide mixed solution in 60~80 DEG C impregnate 2 hours more than after filter, be added in filtrate a certain amount of
Ammonium carbonate, and with dilute sulfuric acid strict control pH value of solution between 4~5.5, filtrate b is obtained by filtration after 1 hour in ageing.
Oxalic acid solution is added in S130: Xiang Suoshu filtrate b, cobalt oxalate is obtained by filtration or cobalt oxalate-nickel oxalate-manganese oxalate is total
Polymers；
S140: cobalt oxide or oxygen will be obtained after the cobalt oxalate or cobalt oxalate-nickel oxalate-manganese oxalate Copolymer sintering
Change cobalt-nickel oxide-manganese oxide mixed powder；
A certain amount of oxalic acid solution is added in filtrate, be obtained by filtration cobalt oxalate or cobalt oxalate, nickel oxalate, manganese oxalate two
Member or terpolymer, and filtrate is added a certain amount of ammonium carbonate and controls pH and lithium carbonate is obtained by filtration 7 or more, by oxalates
Copolymer and lithium carbonate are calcined respectively at 600 DEG C and 450 DEG C, and it is lower and be suitable for production wide temperature low-power consumption iron to obtain primary particle size
The mixed powder of the cobalt oxide or manganese oxide of ferrite, nickel oxide.
By extracting Co from old and useless battery2O3Substance has saved production cost, and a certain amount of Co2O3At high temperature may be used
So that power consumption-temperature curve of material also can relatively flat；The incorporation of Co may also suppress part Fe simultaneously2+Appearance, Jin Erke
Improve the resistivity of material.
S150: sulfuric acid solution is added into ferrite waste residue makes system pH control be 1~5, and filtrate c is obtained after filtering；
The pH to 3~6 that ammonium hydroxide adjusts solution is added in S160: Xiang Suoshu filtrate c, oxalic acid solution is added and obtains sediment,
The sediment high-temperature roasting is obtained into ferrite presoma；
A large amount of dust can be generated by caning hardly be avoided in the production process of ferrite powder, producer generally pass through gravitational dust collection or
Filters pressing after washout tower etc. is recycled dust, the filter residue after filters pressing due to formulation stability difference and contain a large amount of foreign ion
Such as Cl, Na, Si, therefore at a low price or can only pay out of one's own pocket and be given to ceramic tile manufacturer and used as construction material, therefore the application fills
Divide and utilizes ferrite waste residue.
The waste residue that ferrite producer is recycled, main component Fe2O3, Mn3O4, ZnO etc., which are poured into sulfuric acid solution, to be controlled
PH is 1~5, and after sufficiently reacting at 60 DEG C, the polyacrylamide of addition solution weight 2 ‰ filters after adsorbing suspended impurity,
Filtrate is added to the pH of a certain amount of ammonium hydroxide adjusting solution at 80 DEG C between 3~6, the oxalic acid solution of 1~5mol/L is added
Sediment is obtained, 700~900 DEG C of thorough roastings will be deposited in and obtain the ferrite presoma that molecular level mixes, this kind of presoma
Reactivity more with higher than manganese-zinc ferrite made from traditional industry method.
S170: according to the measurement result of iron, manganese and Zn content in the ferrite presoma, in the ferrite presoma
In add iron oxide, manganese oxide and zinc oxide with measurement result corresponding amount after obtain mixture d；
S180: the cobalt oxide or cobalt oxide-nickel oxide-manganese oxide mixed powder and additive are added to the mixing
Object d, obtains Mischung；
S190: manganese-zinc ferrite will be obtained after the Mischung high temperature sintering.
The ingredient that ferrimanganic zinc in obtained ferrite presoma is tested using XRF fluorescence analyser, is added a certain amount of
Iron oxide, manganese oxide or zinc oxide make wherein 52~53mol% of iron oxide molar ratio, and 10~11%, remaining is zinc oxide
Cobalt oxide powder obtained in 3 or oxalic acid are added in said mixture by manganese oxide by cobalt oxide weight ratio 0.1~0.2%,
0.01~0.04% Nb is added simultaneously2O5, 0.01~0.06% V2O5, 0.01~0.06% calcium carbonate, 0.1~0.5%
Nickel oxide be subsequently placed in sand mill be sufficiently sanded after be added a certain amount of poly (vinyl alcohol) binder, spray drying obtains MnZn
Ferrite powder.
Old and useless battery and industrial waste are recycled by the application using the technique of dry and wet mixing, Ke Yiti
The rate of recovery of high material obtains molecular level blended product.
Three kinds of manganese, zinc and iron elements can be made to mix in atom level using oxalate coprecipitation method in the application, material
The reactivity of material is higher, can reduce the sintering temperature in sintering process, can be reduced to 1200- by existing 1350 DEG C
It 1300 DEG C, and then improve grain structure, obtains that crystal structure is fine, the sintered body of crystallite dimension more evenly, guarantees the equal of crystal grain
Even property, reduces the magnetic hystersis loss and eddy-current loss of material, to improve the magnetic conductivity of material and reduce the loss of material.
And lithium battery main component is nickel, cobalt, manganese in the application, and these three elements are exactly needed for manganese-zinc ferrite
Element, therefore the introducing of this method can make full use of waste lithium cell material, and not to the performance of the manganese-zinc ferrite of preparation
It has an impact.
In order to improve the utilization rate of old and useless battery, recycling cathode is carried out in the application, graphite can be obtained by recycling cathode
Alkene, specific method include:
Diafiltration obtains copper foil and graphite slurry after the negative electrode tab is impregnated in water, is added in Xiang Suoshu graphite slurry dilute
Acid solution makes system pH control between 1~3, obtains filtrate and filter after ageing, diafiltration after the removing of ascorbic acid ultrasound is added
Slag will obtain grapheme material after the filter residue high-temperature roasting, the filtrate deposited in enamel pot.
Since recycling battery is generally through 3000 times or more charge and discharge cycles, graphite layers by lithium ion insertion abjection away from being drawn
Greatly, after a certain amount of ascorbic acid and sulfuric acid ultrasound is added, it may occur that it is partially stripped, forms a certain amount of grapheme material,
The electric conductivity of graphite itself can be greatly improved in this kind of material, have very extensive application prospect and economic value.
It is described that oxalic acid solution is added into the filtrate b in the embodiment of the present invention, cobalt oxalate or cobalt oxalate-is obtained by filtration
After nickel oxalate-manganese oxalate copolymer, the method also includes:
Ammonium carbonate is added into filtrate b and obtains lithium carbonate, technical grade high-purity carbon will be obtained after the lithium carbonate high-temperature calcination
Sour lithium.
The specific method for obtaining lithium carbonate is optional are as follows: ammonium carbonate is added into filtrate b and controls pH and is obtained by filtration 7 or more
450 DEG C of lithium carbonate are calcined, obtain technical grade pure Lithium Carbonate by lithium carbonate.
In the present embodiment also carry out waste liquid recycling, it is described the filtrate is deposited in enamel pot after, the method
Further include:
Ferrum sulfuricum oxydatum solutum and the pH to 5-7 with ammonia water conditioning system are added into the enamel pot, obtains oxalic acid after filtering
Iron and filtrate e, the filtrate e crystallizing and drying.
Embodiment 1:
The positive plate of old and useless battery is put in 1mol/L sulfuric acid and hydrogen peroxide mixed solution to mistake after impregnating 2 hours in 60 DEG C
Filter obtains filtrate a；
A certain amount of ammonium carbonate is added in filtrate a, and with dilute sulfuric acid strict control pH value of solution between 4, is aged 1 hour
After filtrate b is obtained by filtration；
A certain amount of oxalic acid solution is added in filtrate b, cobalt oxalate or cobalt oxalate, nickel oxalate, manganese oxalate is obtained by filtration
Two-spot or terpolymer, and it is 7 lithium carbonate to be obtained by filtration that a certain amount of ammonium carbonate, which is added, in filtrate and controls pH, and oxalates is total to
Polymers and lithium carbonate are calcined respectively at 600 DEG C and 450 DEG C, and it is lower and be suitable for production wide temperature low-power consumption iron oxygen to obtain primary particle size
The mixed powder of the cobalt oxide or manganese oxide of body material, nickel oxide；
The waste residue that ferrite producer is recycled, main component Fe2O3, Mn3O4, ZnO etc., which are poured into sulfuric acid solution, to be controlled
PH is 2, and after sufficiently reacting at 60 DEG C, the polyacrylamide of addition solution weight 2 ‰ filters after adsorbing suspended impurity, filters
After obtain filtrate c；
Filtrate c is added to the pH of a certain amount of ammonium hydroxide adjusting solution at 80 DEG C 3, the oxalic acid solution that 1mol/L is added obtains
To sediment, 700 DEG C of thorough roastings will be deposited in and obtain the ferrite presoma that molecular level mixes, this kind of presoma is than traditional work
The reactivity with higher of manganese-zinc ferrite made from industry method；
Using XRF fluorescence analyser measure it is obtained as above to ferrite presoma in ferrimanganic zinc ingredient, add certain
Iron oxide, manganese oxide or the zinc oxide of amount make wherein iron oxide molar ratio 52mol%, and for zinc oxide 10%, remaining is oxidation
Manganese；
Resulting cobalt oxide powder or oxalic acid are added in said mixture by cobalt oxide weight ratio 0.1%, added simultaneously
Enter 0.01% Nb2O5, 0.01% V2O5, 0.01% calcium carbonate, 0.1% nickel oxide is subsequently placed in sand mill sufficiently
Mischung is obtained after sand milling；
A certain amount of poly (vinyl alcohol) binder is added into the Mischung, obtains MnZn after spray drying, high-temperature calcination
Ferrite powder.
Embodiment 2:
The positive plate of old and useless battery is put in 3mol/L sulfuric acid and hydrogen peroxide mixed solution to mistake after impregnating 4 hours in 80 DEG C
Filter, is obtained by filtration filtrate a；
A certain amount of ammonium carbonate is added in filtrate a, and is 5.5 with dilute sulfuric acid strict control pH value of solution, after ageing 1 hour
Filtrate b is obtained by filtration；
A certain amount of oxalic acid solution is added in filtrate b, cobalt oxalate or cobalt oxalate, nickel oxalate, manganese oxalate is obtained by filtration
Two-spot or terpolymer, and it is 8 lithium carbonate to be obtained by filtration that a certain amount of ammonium carbonate, which is added, in filtrate and controls pH, and oxalates is total to
Polymers and lithium carbonate are calcined respectively at 600 DEG C and 450 DEG C, and it is lower and be suitable for production wide temperature low-power consumption iron oxygen to obtain primary particle size
The mixed powder of the cobalt oxide or manganese oxide of body material, nickel oxide；
The waste residue that ferrite producer is recycled, main component Fe2O3, Mn3O4, ZnO etc., which are poured into sulfuric acid solution, to be controlled
PH is 5, and after sufficiently reacting at 60 DEG C, the polyacrylamide of addition solution weight 2 ‰ filters after adsorbing suspended impurity, is filtered
After obtain filtrate c；
It is 6 that filtrate c is added to a certain amount of ammonium hydroxide at 80 DEG C and adjusts the pH of solution, and the oxalic acid solution that 5mol/L is added obtains
To sediment, 900 DEG C of thorough roastings will be deposited in and obtain the ferrite presoma that molecular level mixes, this kind of presoma is than traditional work
The reactivity with higher of manganese-zinc ferrite made from industry method；
The ingredient that ferrimanganic zinc in obtained ferrite presoma in 4 is measured using XRF fluorescence analyser, is added a certain amount of
Iron oxide, manganese oxide or zinc oxide make wherein iron oxide molar ratio 53mol%, for zinc oxide 11%, remaining is manganese oxide；
Resulting cobalt oxide powder or oxalic acid are added in said mixture by cobalt oxide weight ratio 0.2%, added simultaneously
Enter 0.04% Nb2O5, 0.06% V2O5, 0.06% calcium carbonate, 0.5% nickel oxide is subsequently placed in sand mill sufficiently
Mischung is obtained after sand milling；
A certain amount of poly (vinyl alcohol) binder is added to the Mischung, obtains MnZn iron after spray drying, high-temperature calcination
Ferromagnetic powder.
As shown in Fig. 2, Fig. 2 is the temperature and power consumption relation schematic diagram of manganese-zinc ferrite provided by the present application；It can from Fig. 2
To find out, the product temperature section as made from the preparation method of the application is within the scope of 25 DEG C -140 DEG C, and volume power consumption is small
In 400kw/m3, meet the requirement of wide temperature low-power consumption manganese-zinc ferrite.
As shown from the above technical solution, in the preparation method of manganese-zinc ferrite provided by the present application, by being mentioned from battery
Cobalt oxide substance is taken, while ferrite presoma is recycled using oxalate coprecipitation method from industrial waste, finally prepares MnZn
Ferrite, in which:
By extracting Co from old and useless battery2O3Substance has saved production cost, and a certain amount of Co2O3At high temperature may be used
So that power consumption-temperature curve of material also can relatively flat；The incorporation of Co may also suppress part Fe simultaneously2+Appearance, Jin Erke
Improve the resistivity of material.
Three kinds of manganese, zinc and iron elements can be made to mix in atom level using oxalate coprecipitation method in the application, material
The reactivity of material is higher, can reduce the sintering temperature in sintering process, can be reduced to 1200- by existing 1350 DEG C
It 1300 DEG C, and then improve grain structure, obtains that crystal structure is fine, the sintered body of crystallite dimension more evenly, guarantees the equal of crystal grain
Even property, reduces the magnetic hystersis loss and eddy-current loss of material, to improve the magnetic conductivity of material and reduce the loss of material.
Since embodiment of above is that reference combination is illustrated on other modes, have between different embodiments
There is identical part, identical, similar part may refer to each other between each embodiment in this specification.Herein no longer in detail
It illustrates.
Those skilled in the art will readily occur to its of the application after considering specification and practicing the disclosure invented here
His embodiment.This application is intended to cover any variations, uses, or adaptations of the invention, these modifications, purposes or
Person's adaptive change follows the general principle of the application and including the undocumented common knowledge in the art of the application
Or conventional techniques.The description and examples are only to be considered as illustrative, and the true scope and spirit of the application are wanted by right
The content asked is pointed out.
Above-described the application embodiment does not constitute the restriction to the application protection scope.
Claims (10)
1. a kind of preparation method of manganese-zinc ferrite, which is characterized in that the described method includes:
Battery anode slice is dipped in sulfuric acid-hydrogen peroxide mixed solution and filtrate a is obtained by filtration；
Dilute acid soln is added into the filtrate a makes system pH 4~5.5, and filtrate b is obtained by filtration after dissolution；
Oxalic acid solution is added into the filtrate b, cobalt oxalate or cobalt oxalate-nickel oxalate-manganese oxalate copolymer is obtained by filtration；
Cobalt oxide or cobalt oxide-oxidation will be obtained after the cobalt oxalate or cobalt oxalate-nickel oxalate-manganese oxalate Copolymer sintering
Nickel-manganese oxide mixed powder；
Sulfuric acid solution is added into ferrite waste residue makes system pH control be 1~5, and filtrate c is obtained after filtering；
The pH to 3~6 that ammonium hydroxide adjusts solution is added into the filtrate c, oxalic acid solution is added and obtains sediment, by the precipitating
Object high-temperature roasting obtains ferrite presoma；
According to the measurement result of iron, manganese and Zn content in the ferrite presoma, added in the ferrite presoma with
Mixture d is obtained after the iron oxide of measurement result corresponding amount, manganese oxide and zinc oxide；
The cobalt oxide or cobalt oxide-nickel oxide-manganese oxide mixed powder and additive are added to the mixture d, obtained
Mischung；
Manganese-zinc ferrite will be obtained after the Mischung high temperature sintering.
2. the preparation method of manganese-zinc ferrite according to claim 1, which is characterized in that described to be dipped in battery anode slice
In sulfuric acid-hydrogen peroxide mixed solution and it is obtained by filtration before filtrate a, the method also includes:
Waste lithium cell Mechanical Crushing is decomposed, battery anode slice and negative electrode tab are obtained；
Diafiltration obtains copper foil and graphite slurry after the negative electrode tab is impregnated in water；
Dilute acid soln is added into the graphite slurry makes system pH control between 1~3, obtains mixed liquor f；
Filter residue g is obtained after ageing, diafiltration after the removing of ascorbic acid ultrasound is added into the mixed liquor f；
Grapheme material will be obtained after the filter residue g high-temperature roasting.
3. the preparation method of manganese-zinc ferrite according to claim 1, which is characterized in that described to add into the filtrate b
Enter oxalic acid solution, is obtained by filtration after cobalt oxalate or cobalt oxalate-nickel oxalate-manganese oxalate copolymer, the method also includes:
Ammonium carbonate is added into filtrate b and obtains lithium carbonate, carbonic acid of the purity for 99% will be obtained after the lithium carbonate high-temperature calcination
Lithium.
4. the preparation method of manganese-zinc ferrite according to claim 1, which is characterized in that described to be dipped in ferrite waste residue
After making system pH control be 1~5 in sulfuric acid solution, the method also includes:
It is filtered after polyacrylamide absorption suspended impurity is added into system.
5. the preparation method of manganese-zinc ferrite according to claim 1, which is characterized in that described by the sediment high temperature
Roasting obtains ferrite presoma, comprising:
The sediment is obtained into ferrite presoma in 700~900 DEG C of roasting temperatures.
6. the preparation method of manganese-zinc ferrite according to claim 1, which is characterized in that described into the mixture d
Manganese-zinc ferrite is obtained after sand milling, spray drying, high temperature sintering after addition additive, wherein
The temperature of the high temperature sintering is 1200-1300 DEG C.
7. the preparation method of manganese-zinc ferrite according to claim 1, which is characterized in that it is described according to the ferrite before
The measurement result for driving iron, manganese and Zn content in body, adds the oxidation with measurement result corresponding amount in the ferrite presoma
Mixture d is obtained after iron, manganese oxide and zinc oxide, comprising:
It is measured in ferrite presoma after iron, manganese and Zn content using fluorescence analyser, adds iron oxide, manganese oxide and zinc oxide
Make iron oxide 52~53mol% of molar ratio, zinc oxide molar ratio is 10~11%, and manganese oxide molar ratio is 36~38%.
8. the preparation method of manganese-zinc ferrite according to claim 1, which is characterized in that described into the mixture d
Add additive, comprising:
The Nb of addition 0.01~0.04% into the mixture d2O5, 0.01~0.06% V2O5, 0.01~0.06% carbon
Sour calcium, 0.1~0.5% nickel oxide.
9. the preparation method of manganese-zinc ferrite according to claim 1, which is characterized in that described into the mixture d
It is sanded, is spray-dried after addition additive, comprising:
The Nb of addition 0.01~0.04% into the mixture d2O5, 0.01~0.06% V2O5, 0.01~0.06% carbon
Sour calcium is sanded after 0.1~0.5% nickel oxide, a certain amount of polyvinyl alcohol, spray drying is added.
10. the preparation method of manganese-zinc ferrite according to claim 2, which is characterized in that described to store the filtrate
After in enamel pot, the method also includes:
Ferrum sulfuricum oxydatum solutum and the pH to 5-7 with ammonia water conditioning system are added into the enamel pot, obtained after filtering ferric oxalate with
Filtrate e, the filtrate e crystallizing and drying.
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