CN108336343A - A kind of preparation method and application of zinc ferrite/manganese dioxide composite material - Google Patents
A kind of preparation method and application of zinc ferrite/manganese dioxide composite material Download PDFInfo
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- CN108336343A CN108336343A CN201810207863.4A CN201810207863A CN108336343A CN 108336343 A CN108336343 A CN 108336343A CN 201810207863 A CN201810207863 A CN 201810207863A CN 108336343 A CN108336343 A CN 108336343A
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- 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
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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Abstract
The invention discloses a kind of preparation method and applications of zinc ferrite/manganese dioxide composite material, are related to technical field of lithium ion.The preparation method of the composite material includes the following steps：A certain amount of zinc nitrate hexahydrate, nine water ferric nitrates and urea are added in the mixed solution being made of isopropanol and glycerine, after being sufficiently stirred, reaction solution is transferred to stainless steel autoclave and carries out solvent thermal reaction.Presoma obtained by the reaction obtains zinc ferrite after centrifugation, washing, drying and annealing.It is transferred to stainless steel autoclave after again mixing the zinc ferrite of preparation, potassium permanganate and aqueous hydrochloric acid solution according to a certain percentage and carries out hydro-thermal reaction, obtained reacting final product zinc ferrite/manganese dioxide can be used as lithium ion battery negative material.Preparation method of the present invention is simple, of low cost, efficient, and low energy consumption, and controllability is good.In addition, the composite material has the features such as higher initial discharge capacity, the cycle life and stability of overlength.
Description
Technical field
The present invention relates to lithium ion battery negative material more particularly to a kind of systems of zinc ferrite/manganese dioxide composite material
Preparation Method and application belong to advanced nanocomposite fabricating technology field.
Background technology
The development of high performance electrode material is next-generation lithium ion battery with high energy density development and widely applied key.
Commercialized graphite has been widely used in lithium ion battery negative material.However, due to forming plug-in type compound L iC6,
So its highest theoretical capacity is 372 every gram of milliampere hour, and intercalation potential is low, and graphite surface may draw in charge and discharge process
The deposition of lithium metal is played, there are some potential safety problemss.Therefore, in order to meet the energy need of various different commercialization electronic equipments
It asks, considerable effort, which has been concentrated on, finds alternative electrode material.
Recently, the zinc oxide of nanostructure and ternary zinc metal oxide (such as：Zinc ferrite, zinc manganate and cobalt acid zinc
Deng) promising lithium storage material is used as greatly to be paid close attention to, since they have height ratio capacity, low cost and environment
Friendly feature.However, the conductivity of their differences and the stereomutation in cyclic process, significantly limit their multiplying power
Performance simultaneously causes electrode dusting.The zinc-base metal oxide electrode material for rationally designing and being readily synthesized is for high magnification and reversible
Lithium storage still have sizable challenge.In a variety of different strategies, structure hollow-core construction has attracted widely
Concern.Transition metal oxide provides many infusive selections to realize big reversible appearance by a variety of different strategies
Amount, including alloying/removal alloying process and conversion reaction etc..
There is zinc ferrite the spinel structure of standard, zinc ion to occupy tetrahedral site, and iron ion occupies octahedral
Site.Zinc ferrite provides the combination of conversion reaction and alloying/removal alloying reaction mechanism.The zinc ferrite of each unit can be with
Nine lithiums are accommodated, therefore there is higher theoretical capacity (1072 every gram of milliampere hour), thus receive the concern of people.But due to
The shortcomings that zinc ferrite self-conductive difference and volume expansion, capacity attenuation is fast in charge and discharge process and high-rate charge-discharge capability
Difference, thus limit its Commercialization application.In order to improve the chemical property of zinc ferrite, researcher has carried out a large amount of research work
Make, the nanostructure and structure hollow-core construction for being concentrated mainly on synthesis different-shape then form composite material etc., such as existing
Technology " " Polypyrrole-coated zinc ferrite hollow spheres with improved cycling
stability for lithium-ion batteries”,Xiaoran Sun et al.,Small 12(2016)3732-
Mention that " specific discharge capacity of hollow zinc ferrite after polypyrrole cladding is significantly improved, in 400 milliamperes of every gram of electricity in 3737 "
Be capable of providing the specific discharge capacities of 698 every gram of milliampere hour after 100 circle of cycle under current density ", however cycle life need into
One step improves.Such as in the prior art " " One-pot synthesis of ZnFe2O4/C hollow spheres as
superior anode materials for lithium ion batteries”,Yuanfu Deng et al.,
Chem.Commun.47(2011)6828-6830”、““A facile bubble-assisted synthesis of porous
Zn ferrite hollow microsphere and their excellent performance as an anode in
It is mentioned in lithium ion battery ", J Solid State Electrochem 17 (2013) 2055-2060 " " hollow
The zinc ferrite of structure increases itself specific surface area, promote contact of the electrode with electrolyte and effective to alleviate volume swollen
It is swollen ", however specific discharge capacity needs to further increase.Currently, solving the cyclical stability of zinc ferrite and improving zinc ferrite
Specific discharge capacity be to need the technical barrier that solves, the present invention is directed to this problem, proposes using zinc ferrite as modification phase, two
Manganese oxide forms the flower-shaped zinc ferrite/manganese dioxide nucleocapsid of silk ball, enhances zinc ferrite/bis- with this as surface coating layer
The cyclical stability of manganese oxide composite material and improve its specific discharge capacity.
Invention content
The object of the present invention is to provide a kind of preparation method and application of zinc ferrite/manganese dioxide composite material, preparation sides
Method is simple, of low cost, low energy consumption, controllability is good, zinc ferrite/manganese dioxide composite material excellent electrochemical performance of preparation.
Can reach discharge capacity after 2026 cycles under the current density of 800 milliamperes/gram still can keep 1120.7 milliampere hour every
Gram, the capacity attenuation rate of single cycle is 0.02%, and operating temperature range is subzero 25 degrees Celsius~40 degrees Celsius above freezing, no note
Recall effect, self-discharge rate is low.
The technical scheme is that：
(1) by 10-15 milliliters of isopropanol, 1-5 milliliters of glycerine, 0.2-1 mMs of zinc nitrate hexahydrate, 0.5-2 millis
Mole nine water ferric nitrates and 0.5-2 mMs of urea are separately added into beaker, and stirring forms uniform mixed solution, then shifts
It is solvent thermal reaction 10-30 hours lower at 150-300 degrees Celsius into stainless steel autoclave；
(2) presoma prepared by step (1) is cooled to room temperature, centrifugation, is washed respectively with deionized water and absolute ethyl alcohol
It washs three times；
(3) the ferrous acid zinc precursor prepared by step (2) is put into 80 degrees Celsius of baking ovens to be dried, then sets sample
In porcelain boat, it is put into tube furnace, air themperature is 300-600 degrees Celsius, anneals 1-5 hours, obtains final product zinc ferrite；
(4) zinc ferrite for preparing 0.5-3 mMs of step (3), 1-3 mMs of potassium permanganate and 5-10 mMs
Concentrated hydrochloric acid is separately added into clean beaker, and stirring forms uniform mixed solution, is then transferred into 50 milliliters of stainless steel high pressures
It is hydro-thermal reaction 10-20 hours lower at 100-300 degrees Celsius in reaction kettle；
(5) the cooling, centrifugation by the turbid solution prepared by step (4), is washed with deionized three times, it is dry to be then placed in baking oven
Dry 12 hours, obtain final product zinc ferrite/manganese dioxide composite material.
A kind of preparation method and application of the zinc ferrite/manganese dioxide composite material：Zinc ferrite/manganese dioxide is compound
Material can be used for lithium ion battery negative material, have overlength cycle life, ultra-high capacity, superelevation cyclical stability, nontoxic, ring
The features such as border is friendly.
The method of use is hydrothermal synthesis method, solvent-thermal process method and annealing.Compared with prior art, the present invention has
It has the advantage that:
(1) zinc ferrite prepared by the present invention/manganese dioxide binary metal composite oxide use raw material is environmental-friendly, nothing
Poison, synthetic method is simple, of low cost；
(2) since prepared zinc ferrite/manganese dioxide composite material has special silk ball floriform appearance and stabilization
Nucleocapsid, therefore zinc ferrite/manganese dioxide composite material prepared by the present invention, as lithium ion battery negative material,
The cyclical stability of cycle life, superelevation with overlength.
Description of the drawings
Fig. 1 is zinc ferrite/manganese dioxide composite material for preparing at different temperatures of the present invention, (1) 100 DEG C, (2) 140
DEG C, the transmission electron microscope picture of (3) 180 DEG C of scanning electron microscope (SEM) photograph and (4) zinc ferrite.
The X-ray diffractogram of zinc ferrite, manganese dioxide, zinc ferrite/manganese dioxide that Fig. 2 is prepared for the present invention, can by figure
See that apparent manganese dioxide exists in zinc ferrite/manganese dioxide composite material.
Fig. 3 is cycle of the zinc ferrite/manganese dioxide composite material of the invention prepared under 200 milliamperes of every gram of current densities
Curve graph, it can be seen from the figure that its with outstanding cycle performance, specific discharge capacity is that 1420 milliampere hour are every after 400 cycles
Gram, it is recycled 400 times.
Fig. 4 is cycle of the zinc ferrite/manganese dioxide composite material of the invention prepared under 800 milliamperes of every gram of current densities
Curve graph, 2026 times cycle after specific discharge capacity remain at 1120.7 every gram of milliampere hour, be recycled 2026 times.
Specific implementation mode
Embodiment one
(1) by 15 milliliters of isopropanol, 4 milliliters of glycerine, 0.5 mM of zinc nitrate hexahydrate, 1 mM of nine water nitric acid
Iron and 1 mM of urea are separately added into beaker, and stirring forms uniform mixed solution, is then transferred into stainless steel reaction under high pressure
In kettle, in 180 degrees Celsius of lower solvent thermal reactions 21 hours；
(2) presoma prepared by step (1) is cooled to room temperature, centrifugation, is washed respectively with deionized water and absolute ethyl alcohol
It washs three times；
(3) the ferrous acid zinc precursor prepared by step (2) is put into 80 degrees Celsius of baking ovens to be dried, then sets sample
In porcelain boat, it is put into tube furnace, air themperature is 450 degrees Celsius, anneals 2 hours, obtains final product zinc ferrite；
(4) zinc ferrite for preparing 0.5 mM of step (3), 1.4 mMs of potassium permanganate and 6 mMs of dense salt
Acid is separately added into clean beaker, forms uniform mixed solution, is then transferred into 50 milliliters of stainless steel autoclaves,
In 100 degrees Celsius of lower hydro-thermal reactions 12 hours；
(5) the cooling, centrifugation by the turbid solution prepared by step (4), is washed with deionized three times, it is dry to be then placed in baking oven
Dry 12 hours, obtain final product zinc ferrite/manganese dioxide composite material.
The performance tested in subsequent figures is that the present embodiment one is measured.
Embodiment two
(1) by 12.5 milliliters of isopropanol, 2.5 milliliters of glycerine, 0.25 mM of zinc nitrate hexahydrate, 0.6 mM
Nine water ferric nitrates and 0.6 mM of urea are separately added into beaker, and stirring forms uniform mixed solution, is then transferred into stainless
In steel autoclave, solvent thermal reaction 13 hours at one hundred and twenty degrees centigrade；
(2) presoma prepared by step (1) is cooled to room temperature, centrifugation, is washed respectively with deionized water and absolute ethyl alcohol
It washs three times；
(3) the ferrous acid zinc precursor prepared by step (2) is put into 80 degrees Celsius of baking ovens to be dried, then sets sample
In porcelain boat, it is put into tube furnace, air themperature is 400 degrees Celsius, anneals 1.5 hours, obtains final product zinc ferrite；
(4) zinc ferrite for preparing 1 mM of step (3), 1.2 mMs of potassium permanganate and 5 mMs of concentrated hydrochloric acid
It is separately added into clean beaker, forms uniform mixed solution, be then transferred into 50 milliliters of stainless steel autoclaves,
140 degrees Celsius of lower hydro-thermal reactions 10 hours；
(5) the cooling, centrifugation by the turbid solution prepared by step (4), is washed with deionized three times, it is dry to be then placed in baking oven
Dry 12 hours, obtain final product zinc ferrite/manganese dioxide composite material.
Embodiment three
(1) by 13 milliliters of isopropanol, 3 milliliters of glycerine, 0.35 mM of zinc nitrate hexahydrate, 0.8 mM of nine water
Ferric nitrate and 0.8 mM of urea are separately added into beaker, and stirring forms uniform mixed solution, is then transferred into stainless steel height
It presses in reaction kettle, in 140 degrees Celsius of lower solvent thermal reactions 15 hours；
(2) presoma prepared by step (1) is cooled to room temperature, centrifugation, is washed respectively with deionized water and absolute ethyl alcohol
It washs three times；
(3) the ferrous acid zinc precursor prepared by step (2) is put into 80 degrees Celsius of baking ovens to be dried, then sets sample
In porcelain boat, it is put into tube furnace, air themperature is 450 degrees Celsius, anneals 2.5 hours, obtains final product zinc ferrite；
(4) zinc ferrite for preparing 1.5 mMs of steps (3), 1.6 mMs of potassium permanganate and 7 mMs of dense salt
Acid is separately added into clean beaker, forms uniform mixed solution, is then transferred into 50 milliliters of stainless steel autoclaves,
In 160 degrees Celsius of lower hydro-thermal reactions 14 hours；
(5) the cooling, centrifugation by the turbid solution prepared by step (4), is washed with deionized three times, it is dry to be then placed in baking oven
Dry 12 hours, obtain final product zinc ferrite/manganese dioxide composite material.
Example IV
(1) by 13.5 milliliters of isopropanol, 3.5 milliliters of glycerine, 0.45 mM of zinc nitrate hexahydrate, 1.2 mMs
Nine water ferric nitrates and 1.2 mMs of urea are separately added into beaker, and stirring forms uniform mixed solution, is then transferred into stainless
In steel autoclave, in 160 degrees Celsius of lower solvent thermal reactions 17 hours；
(2) presoma prepared by step (1) is cooled to room temperature, centrifugation, is washed respectively with deionized water and absolute ethyl alcohol
It washs three times；
(3) the ferrous acid zinc precursor prepared by step (2) is put into 80 degrees Celsius of baking ovens to be dried, then sets sample
In porcelain boat, it is put into tube furnace, air themperature is 500 degrees Celsius, anneals 3 hours, obtains final product zinc ferrite；
(4) zinc ferrite for preparing 2 mMs of steps (3), 1.8 mMs of potassium permanganate and 8 mMs of concentrated hydrochloric acid
It is separately added into clean beaker, forms uniform mixed solution, be then transferred into 50 milliliters of stainless steel autoclaves,
180 degrees Celsius of lower hydro-thermal reactions 16 hours；
(5) the cooling, centrifugation by the turbid solution prepared by step (4), is washed with deionized three times, it is dry to be then placed in baking oven
Dry 12 hours, obtain final product zinc ferrite/manganese dioxide composite material.
Embodiment five
(1) by 14 milliliters of isopropanol, 4 milliliters of glycerine, 0.55 mM of zinc nitrate hexahydrate, 1.4 mM of nine water
Ferric nitrate and 1.4 mMs of urea are separately added into beaker, and stirring forms uniform mixed solution, is then transferred into stainless steel height
It presses in reaction kettle, at 200 degrees celsius solvent thermal reaction 19 hours；
(2) presoma prepared by step (1) is cooled to room temperature, centrifugation, is washed respectively with deionized water and absolute ethyl alcohol
It washs three times；
(3) the ferrous acid zinc precursor prepared by step (2) is put into 80 degrees Celsius of baking ovens to be dried, then sets sample
In porcelain boat, it is put into tube furnace, air themperature is 550 degrees Celsius, anneals 3.5 hours, obtains final product zinc ferrite；
(4) zinc ferrite for preparing 2.5 mMs of steps (3), 2 mMs of potassium permanganate and 9 mMs of concentrated hydrochloric acid
It is separately added into clean beaker, forms uniform mixed solution, be then transferred into 50 milliliters of stainless steel autoclaves,
200 degrees Celsius of lower hydro-thermal reactions 18 hours；
(5) the cooling, centrifugation by the turbid solution prepared by step (4), is washed with deionized three times, it is dry to be then placed in baking oven
Dry 12 hours, obtain final product zinc ferrite/manganese dioxide composite material.
Embodiment six
(1) by 14.5 milliliters of isopropanol, 4.5 milliliters of glycerine, 0.65 mM of zinc nitrate hexahydrate, 1.6 mMs
Nine water ferric nitrates and 1.6 mMs of urea are separately added into beaker, and stirring forms uniform mixed solution, is then transferred into stainless
In steel autoclave, in 220 degrees Celsius of lower solvent thermal reactions 23 hours；
(2) presoma prepared by step (1) is cooled to room temperature, centrifugation, is washed respectively with deionized water and absolute ethyl alcohol
It washs three times；
(3) the ferrous acid zinc precursor prepared by step (2) is put into 80 degrees Celsius of baking ovens to be dried, then sets sample
In porcelain boat, it is put into tube furnace, air themperature is 600 degrees Celsius, anneals 4 hours, obtains final product zinc ferrite；
(4) zinc ferrite for preparing 3 mMs of steps (3), 2.2 mMs of potassium permanganate and 10 mMs of concentrated hydrochloric acid
It is separately added into clean beaker, forms uniform mixed solution, be then transferred into 50 milliliters of stainless steel autoclaves,
220 degrees Celsius of lower hydro-thermal reactions 20 hours；
(5) the cooling, centrifugation by the turbid solution prepared by step (4), is washed with deionized three times, it is dry to be then placed in baking oven
Dry 12 hours, obtain final product zinc ferrite/manganese dioxide composite material.
Claims (8)
1. a kind of preparation method of zinc ferrite/manganese dioxide composite material, it is characterised in that：
Outer layer of the zinc ferrite/manganese dioxide binary composite obtained by hydro-thermal reaction using manganese dioxide as nucleocapsid
Protective layer inhibits the volume expansion of zinc ferrite with this, and the cyclical stability of the composite electrode is greatly improved；The preparation side
Method selects zinc ferrite, potassium permanganate, concentrated hydrochloric acid as the substance that sets out, and using hydrothermal synthesis method, reaction product is centrifuged, washes
Zinc ferrite/manganese dioxide composite electrode material is washed, is dried in vacuo and is thermally treated resulting in, specific preparation process is as follows：
(1) by 10-15 milliliters of isopropanol, 1-5 milliliters of glycerine, 0.2-1 mMs of zinc nitrate hexahydrate, 0.5-2 mMs
Nine water ferric nitrates and 0.5-2 mMs of urea are separately added into beaker, and stirring forms uniform mixed solution, is then transferred into not
It is solvent thermal reaction 10-30 hours lower at 150-300 degrees Celsius in rust steel autoclave；
(2) presoma prepared by step (1) is cooled to room temperature, centrifugation, three is washed respectively with deionized water and absolute ethyl alcohol
It is secondary；
(3) the ferrous acid zinc precursor prepared by step (2) is put into 80 degrees Celsius of baking ovens to be dried, sample is then placed in porcelain
In boat, it is put into tube furnace, air themperature is 300-600 degrees Celsius, anneals 1-5 hours, obtains final product zinc ferrite；
(4) zinc ferrite for preparing 0.5-3 mMs of step (3), 1-3 mMs of potassium permanganate and 5-10 mMs of dense salt
Acid is separately added into clean beaker, and stirring forms uniform mixed solution, is then transferred into 50 milliliters of stainless steel reaction under high pressures
It is hydro-thermal reaction 10-20 hours lower at 100-300 degrees Celsius in kettle；
(5) the cooling, centrifugation by the turbid solution prepared by step (4), is washed with deionized three times, is then placed in oven drying 12
Hour, obtain final product zinc ferrite/manganese dioxide composite material.
2. a kind of preparation method of zinc ferrite/manganese dioxide composite material according to claim 1, it is characterised in that：
(1) by 15 milliliters of isopropanol, 4 milliliters of glycerine, 0.5 mM of zinc nitrate hexahydrate, 1 mM of nine water ferric nitrate and
1 mM of urea is separately added into beaker, and stirring forms uniform mixed solution, is then transferred into stainless steel autoclave
In, in 180 degrees Celsius of lower solvent thermal reactions 21 hours；
(2) presoma prepared by step (1) is cooled to room temperature, centrifugation, three is washed respectively with deionized water and absolute ethyl alcohol
It is secondary；
(3) the ferrous acid zinc precursor prepared by step (2) is put into 80 degrees Celsius of baking ovens to be dried, sample is then placed in porcelain
In boat, it is put into tube furnace, air themperature is 450 degrees Celsius, anneals 2 hours, obtains final product zinc ferrite；
(4) zinc ferrite for preparing 0.5 mM of step (3), 1.4 mMs of potassium permanganate and 6 mMs of concentrated hydrochloric acid point
It not being added in clean beaker, stirring forms uniform mixed solution, is then transferred into 50 milliliters of stainless steel autoclaves,
In 100 degrees Celsius of lower hydro-thermal reactions 12 hours；
(5) the cooling, centrifugation by the turbid solution prepared by step (4), is washed with deionized three times, is then placed in oven drying 12
Hour, obtain final product zinc ferrite/manganese dioxide composite material.
3. a kind of preparation method of zinc ferrite/manganese dioxide composite material according to claim 1, it is characterised in that：
(1) by 12.5 milliliters of isopropanol, 2.5 milliliters of glycerine, 0.25 mM of zinc nitrate hexahydrate, 0.6 mM of nine water
Ferric nitrate and 0.6 mM of urea are separately added into beaker, and stirring forms uniform mixed solution, is then transferred into stainless steel height
It presses in reaction kettle, at one hundred and twenty degrees centigrade solvent thermal reaction 13 hours；
(2) presoma prepared by step (1) is cooled to room temperature, centrifugation, three is washed respectively with deionized water and absolute ethyl alcohol
It is secondary；
(3) the ferrous acid zinc precursor prepared by step (2) is put into 80 degrees Celsius of baking ovens to be dried, sample is then placed in porcelain
In boat, it is put into tube furnace, air themperature is 350 degrees Celsius, anneals 1.5 hours, obtains final product zinc ferrite；
(4) zinc ferrite for preparing 1 mM of step (3), 1.2 mMs of potassium permanganate and 5 mMs of concentrated hydrochloric acid difference
It being added in clean beaker, stirring forms uniform mixed solution, is then transferred into 50 milliliters of stainless steel autoclaves,
140 degrees Celsius of lower hydro-thermal reactions 10 hours；
(5) the cooling, centrifugation by the turbid solution prepared by step (4), is washed with deionized three times, is then placed in oven drying 12
Hour, obtain final product zinc ferrite/manganese dioxide composite material.
4. a kind of preparation method of zinc ferrite/manganese dioxide composite material according to claim 1, it is characterised in that：
(1) by 13 milliliters of isopropanol, 3 milliliters of glycerine, 0.35 mM of zinc nitrate hexahydrate, 0.8 mM of nine water nitric acid
Iron and 0.8 mM of urea are separately added into beaker, and stirring forms uniform mixed solution, and it is anti-to be then transferred into stainless steel high pressure
It answers in kettle, in 140 degrees Celsius of lower solvent thermal reactions 15 hours；
(2) presoma prepared by step (1) is cooled to room temperature, centrifugation, three is washed respectively with deionized water and absolute ethyl alcohol
It is secondary；
(3) the ferrous acid zinc precursor prepared by step (2) is put into 80 degrees Celsius of baking ovens to be dried, sample is then placed in porcelain
In boat, it is put into tube furnace, air themperature is 400 degrees Celsius, anneals 2.5 hours, obtains final product zinc ferrite；
(4) zinc ferrite for preparing 1.5 mMs of steps (3), 1.6 mMs of potassium permanganate and 7 mMs of concentrated hydrochloric acid point
It not being added in clean beaker, stirring forms uniform mixed solution, is then transferred into 50 milliliters of stainless steel autoclaves,
In 160 degrees Celsius of lower hydro-thermal reactions 14 hours；
(5) the cooling, centrifugation by the turbid solution prepared by step (4), is washed with deionized three times, is then placed in oven drying 12
Hour, obtain final product zinc ferrite/manganese dioxide composite material.
5. a kind of preparation method of zinc ferrite/manganese dioxide composite material according to claim 1, it is characterised in that：
(1) by 13.5 milliliters of isopropanol, 3.5 milliliters of glycerine, 0.45 mM of zinc nitrate hexahydrate, 1.2 mM of nine water
Ferric nitrate and 1.2 mMs of urea are separately added into beaker, and stirring forms uniform mixed solution, is then transferred into stainless steel height
It presses in reaction kettle, in 160 degrees Celsius of lower solvent thermal reactions 17 hours；
(2) presoma prepared by step (1) is cooled to room temperature, centrifugation, three is washed respectively with deionized water and absolute ethyl alcohol
It is secondary；
(3) the ferrous acid zinc precursor prepared by step (2) is put into 80 degrees Celsius of baking ovens to be dried, sample is then placed in porcelain
In boat, it is put into tube furnace, air themperature is 500 degrees Celsius, anneals 3.5 hours, obtains final product zinc ferrite；
(4) zinc ferrite for preparing 2 mMs of steps (3), 1.8 mMs of potassium permanganate and 8 mMs of concentrated hydrochloric acid difference
It being added in clean beaker, stirring forms uniform mixed solution, is then transferred into 50 milliliters of stainless steel autoclaves,
180 degrees Celsius of lower hydro-thermal reactions 16 hours；
(5) the cooling, centrifugation by the turbid solution prepared by step (4), is washed with deionized three times, is then placed in oven drying 12
Hour, obtain final product zinc ferrite/manganese dioxide composite material.
6. a kind of preparation method of zinc ferrite/manganese dioxide composite material according to claim 1, it is characterised in that：
(1) by 14 milliliters of isopropanol, 4 milliliters of glycerine, 0.55 mM of zinc nitrate hexahydrate, 1.4 mM of nine water nitric acid
Iron and 1.4 mMs of urea are separately added into beaker, and stirring forms uniform mixed solution, and it is anti-to be then transferred into stainless steel high pressure
It answers in kettle, at 200 degrees celsius solvent thermal reaction 19 hours；
(2) presoma prepared by step (1) is cooled to room temperature, centrifugation, three is washed respectively with deionized water and absolute ethyl alcohol
It is secondary；
(3) the ferrous acid zinc precursor prepared by step (2) is put into 80 degrees Celsius of baking ovens to be dried, sample is then placed in porcelain
In boat, it is put into tube furnace, air themperature is 550 degrees Celsius, anneals 4.5 hours, obtains final product zinc ferrite；
(4) zinc ferrite for preparing 2.5 mMs of steps (3), 2 mMs of potassium permanganate and 9 mMs of concentrated hydrochloric acid difference
It is added in clean beaker, forms uniform mixed solution, be then transferred into 50 milliliters of stainless steel autoclaves, 200
Degree Celsius lower hydro-thermal reaction 18 hours；
(5) the cooling, centrifugation by the turbid solution prepared by step (4), is washed with deionized three times, is then placed in oven drying 12
Hour, obtain final product zinc ferrite/manganese dioxide composite material.
7. a kind of preparation method of zinc ferrite/manganese dioxide composite material according to claim 1, it is characterised in that：
(1) by 14.5 milliliters of isopropanol, 4.5 milliliters of glycerine, 0.65 mM of zinc nitrate hexahydrate, 1.6 mM of nine water
Ferric nitrate and 1.6 mMs of urea are separately added into beaker, and stirring forms uniform mixed solution, is then transferred into stainless steel height
It presses in reaction kettle, in 220 degrees Celsius of lower solvent thermal reactions 23 hours；
(2) presoma prepared by step (1) is cooled to room temperature, centrifugation, three is washed respectively with deionized water and absolute ethyl alcohol
It is secondary；
(3) the ferrous acid zinc precursor prepared by step (2) is put into 80 degrees Celsius of baking ovens to be dried, sample is then placed in porcelain
In boat, it is put into tube furnace, air themperature is 600 degrees Celsius, anneals 5.5 hours, obtains final product zinc ferrite；
(4) zinc ferrite for preparing 3 mMs of steps (3), 2.2 mMs of potassium permanganate and 10 mMs of concentrated hydrochloric acid difference
It being added in clean beaker, stirring forms uniform mixed solution, is then transferred into 50 milliliters of stainless steel autoclaves,
220 degrees Celsius of lower hydro-thermal reactions 20 hours；
(5) the cooling, centrifugation by the turbid solution prepared by step (4), is washed with deionized three times, is then placed in oven drying 12
Hour, obtain final product zinc ferrite/manganese dioxide composite material.
8. a kind of application of zinc ferrite/manganese dioxide composite material according to any one of claims 1 to 7, feature exist
In：
Zinc ferrite/the manganese dioxide composite material can be used for negative electrode of lithium ion battery material with the nucleocapsid that silk ball is flower-shaped
Material, the cyclical stability with higher specific discharge capacity, the cycle life of overlength and superelevation.
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Application publication date: 20180727 |