CN105958032B - A kind of method and application improving zinc ferrite chemical property by doping nickel element - Google Patents
A kind of method and application improving zinc ferrite chemical property by doping nickel element Download PDFInfo
- Publication number
- CN105958032B CN105958032B CN201610517654.0A CN201610517654A CN105958032B CN 105958032 B CN105958032 B CN 105958032B CN 201610517654 A CN201610517654 A CN 201610517654A CN 105958032 B CN105958032 B CN 105958032B
- Authority
- CN
- China
- Prior art keywords
- hours
- mms
- metal oxide
- degrees celsius
- zinc ferrite
- 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.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of methods and application that zinc ferrite charge and discharge cycles ability is improved by doping nickel element, are related to composite cathode material of lithium ion battery preparation field.A kind of ternary metal oxide is formed by adulterating nickel element in zinc ferrite, six water nickel nitrates, zinc nitrate hexahydrate, ferrous sulfate heptahydrate, urea and ammonium fluoride is selected to be mixed to form uniform mixed solution with certain molal weight, after hydrothermal synthesis, calcining, Ni is obtainedxZn1‑xFe2O4(0 < x < 1) metal oxide.The Ni of excellent electrochemical performance can be not only made in this methodxZn1‑xFe2O4(0 < x < 1) metal oxide, and synthetic method is fairly simple, low energy consumption, and controllability is good, and yield is high, and it is low in cost, it is suitable for being mass produced.The invention also discloses the NixZn1‑xFe2O4The application of (0 < x < 1) metal oxide is used for lithium ion battery negative material, has the characteristics that charging and discharging capacity height, good cycling stability.
Description
Technical field
The present invention relates to composite cathode material of lithium ion battery preparation fields, more particularly to one kind to be mentioned by adulterating nickel element
The method and application of ferric acid zinc chemical property belong to advanced composite material fabricating technology field.
Background technique
In recent years, with the continuous deterioration of the increasingly in short supply and ecological environment of traditional fossil energy, new green energy
Develop the attention increasingly by countries in the world.The one kind of electrochmical power source as new energy has mobility and higher
The advantages that energy density, has attracted more concern.Lithium ion secondary battery is a kind of novel electrochmical power source, because its is superior
Chemical property and environmentally protective advantage, become the first choice of current secondary cell, are set in large quantities applied to portable electronic
In standby, such as laptop, mobile phone and digital camera.Currently, new-energy automobile has become the important research of countries in the world
Project, and traditional lithium ion battery is unable to satisfy the demand for development of new-energy automobile, therefore it is secondary to research and develop high performance lithium
Battery has great importance.
Obtain the ideal lithium ion battery of performance, it is desirable to positive and negative pole material structure be reversibly embedded in lithium ion and
In the case where abjection, it is able to maintain the stabilization of self structure.Negative electrode material plays important work for the performance of lithium ion battery
With in contrast, the progress of negative electrode material is slower, it is difficult to meet the requirement of high-performance power battery, develop performance
Excellent negative electrode material is extremely urgent.
In the development of early stage, lithium metal is because its high theoretical capacity is used as negative electrode material, but due to its chemical property
Compare active, easy burning, and in charge and discharge process, lithium is easy to react uneven and form Li dendrite, and Li dendrite then can
Puncture diaphragm and cause short circuit, battery is caused to damage, or even cause fire, explosion etc..Therefore, using lithium anode, there is tight
The security risk of weight.Gradually, by carbon material instead of lithium as cathode, theoretical capacity is every gram of 200-400 milliampere hour.Carbon
Although the theoretical capacity of material is far below lithium metal, its composed structure is more stable, and safety is secure, therefore has quite high
Use value, being commercialized more negative electrode material at present is still carbon-based material.Rather than the commercialization of carbons cathode still faces
Many challenges, it may be said that be the continuous research and development and the progressive development for having driven lithium ion battery of negative electrode material.In addition to meet
Can store lithium ion, theoretical capacity it is higher except, negative electrode material should also have excellent electric conductivity, stable chemistry knot
The features such as structure, lower reaction potential, cheap and safety and environmental protection.To solve the above problems, researcher is to negative electrode material
It is furtherd investigate, negative electrode material is improved by different approach and method, continues to optimize its chemical property.Many height
Capacity lithium ion battery negative electrode material cannot put into practical application main difficult technical be in charge and discharge process volume change compared with
Greatly, cause cycle performance very poor.
Currently, researcher both domestic and external mainly solves this problem by following measure: (1) preparing nanoscale
Material buffer volumes can expand to a certain extent, and have shorter ion transmission path；(2) it prepares compound
Material, for example adulterate or coat by carbon material, carbon material has excellent electric conductivity, and itself steady chemical structure,
Volume change in charge and discharge process is smaller, and active material is distributed in carbon-based material, has certain delay to volume expansion
Solution effect；(3) it introduces an other phase and forms alloy, the electro-chemical activity for introducing phase is usually poor, and main function is exactly to buffer
The active volume expansion mutually generated.
Since graphite is cheap, resourceful, it is often used as the negative electrode material of commercial Li-ion batteries, however stone
The theoretical capacity of ink is only 372 every gram of milliampere hour, to limit its extensive use.Therefore, researcher, which pays, much exerts
The negative electrode material that power looks for substitute graphite improves its specific capacity and safety.Transition metal oxide picture in recent years
ZnMn2O4, ZnCo2O4And ZnFe2O4It is considered as coming negative electrode material.Transition metal oxide can overcome graphite
Some disadvantages, they have high theoretical capacity.In these transition metal oxides, due to ZnFe2O4Cheap, nontoxic,
Environmental-friendly, especially having high specific capacity is 1000.5 every gram of milliampere hour, however ZnFe2O4Cycle life it is short, stable circulation
Property is low, and volume change is big in charge and discharge process, these disadvantages limit its practical application.In order to improve these disadvantages, study
Personnel have done many effort, such as to ZnFe2O4Middle doped metallic elements, the pattern for optimizing it and carbon coating ZnFe2O4.As now
There is technology " Corncob-shaped ZnFe2O4/C nanostructures for improved anode rate and
cycle performance in lithium-ion batteries.RSC Advances,2015,5:31807-31814.”
In, researchers utilize the ZnFe of easy Co deposited synthesis corn spike2O4The composite material of/C nano structure, composite wood
Material carries out electro-chemical test under the current density of 100 every gram of milliampere hour, and initial capacity is 1591.6 every gram of milliampere hour, passes through
Discharge capacity remains to the high discharge capacity for being maintained at 1119.1 every gram of milliampere hour after 100 circulations.The method is to pass through carbon coating
To improve ZnFe2O4Chemical property."Mixed Oxides,(Ni1–xZnx)Fe2O4(x=0,0.25,0.5,0.75,1):
Molten salt synthesis,characterization and its lithium-storage performance
for lithium ion batteries.The Journal of Physical Chemistry C 2015,119,4709-
In 4718. ", researchers synthesize five kinds of compounds using molten-salt growth method, wherein Ni0.75Zn0.25Fe2O4Chemical property is most excellent,
Under the current density of 60 every gram of milliampere hour, discharge capacity is 819 every gram of milliampere hour after 50 circle of circulation.And the present invention is directed to pass through
Nickel element is adulterated, and improves ZnFe using traditional hydrothermal synthesis method2O4Chemical property.
Ni0.25Zn0.75Fe2O4Nano particle is tiny, and tiny particle can effectively shorten the diffusion length of lithium ion,
Conductivity is improved, alleviates the volume expansion in reaction process, the utilization rate of active material is improved, to improve chemical property.
And traditional hydrothermal synthesis method is utilized, synthetic method is simple, easy to operate, and process is convenient, practical.
Improving the specific capacity of lithium ion battery negative material, improving cyclical stability is that current performance of lithium ion battery is promoted
Key, the present invention by adulterating nickel element in zinc ferrite, with hydrothermal synthesis method and heat treatment realize lithium-ion negative pole material
Expect the stabilization and promotion of performance, NixZn1-xFe2O4(0 < x < 1) composite material can be used for the negative electrode material of lithium ion battery, have
The characteristics of yield is big, environmental-friendly, charging and discharging capacity is high, good cycling stability.
Summary of the invention
The method and application that the object of the present invention is to provide a kind of by adulterating nickel element raising zinc ferrite chemical property,
Synthetic method is simple, and low energy consumption, and controllability is good, and yield is big, cheap, the Ni of preparation0.25Zn0.75Fe2O4Sample electrochemistry
Can be excellent, specific discharge capacity can reach 855.9 every gram of milliampere hour after 100 circulations, and the capacity attenuation rate of single cycle is
0.02%, operating temperature range be subzero 25 degrees Celsius-it is 60 degrees Celsius above freezing, self-discharge rate is low.
The technical scheme is that
(1) by 0-1 mMs of six water nickel nitrates, 0-1 mMs of zinc nitrate hexahydrate, 1-3.5 mMs of ferrous sulfate heptahydrate,
2-6 mMs of urea and 1.5-5.5 mMs of ammonium fluoride are dissolved in 20-80 ml deionized water, and formation uniformly mixes molten
Liquid is then transferred into stainless steel cauldron, under 150-300 degrees Celsius, hydro-thermal reaction 18-42 hours；
(2) by step, (1) prepared turbid solution is cooling, centrifugation, is respectively cleaned three times with deionized water and alcohol；
(3) after (2) prepared sample is dried 24 hours in an oven, powder sample is sufficiently ground in mortar for step
Mill, after mixing, is placed in porcelain boat, in tube furnace, in air under 400-750 degrees Celsius, calcines 3-8 hours, obtain
NixZn1-xFe2O4(0 < x < 1) metal oxide.
A kind of application by adulterating the zinc ferrite of nickel element: NixZn1-xFe2O4(0 < x < 1) metal oxide can
For the negative electrode material of lithium ion battery, with specific discharge capacity is high, self-discharge rate is low, stable cycle performance, yield are big, environment
Friendly, nontoxic and cheap feature.
The method of use is hydrothermal synthesis method and heat treatment.Compared with prior art, the invention has the following advantages that
(1) Ni prepared by the present inventionxZn1-xFe2O4(0 < x < 1) metal oxide, the raw material sources of use are extensive, synthesis
Method is simple, and low energy consumption, environmental-friendly, and cheap and yield is big.
(2) due to the Ni of preparation0.25Zn0.75Fe2O4Nano particle is tiny, therefore prepared by the present invention
Ni0.25Zn0.75Fe2O4Metal oxide has charging and discharging capacity height, self-discharge rate as lithium ion battery negative material
The characteristics of low, good cycling stability.
Detailed description of the invention
Fig. 1 is the ZnFe using the method for the present invention preparation2O4And Ni0.25Zn0.75Fe2O4X ray diffracting spectrum.
Fig. 2-1 is the ZnFe using the method for the present invention preparation2O4The electron scanning micrograph of metal oxide；
Fig. 2-2 is the Ni using the method for the present invention preparation0.25Zn0.75Fe2O4The scanning electron microscope of metal oxide is shone
Piece.
Ni as seen from the figure0.25Zn0.75Fe2O4Nano particle is tiny.
Fig. 3 is the ZnFe using the method for the present invention preparation2O4And Ni0.25Zn0.75Fe2O4Metal oxide is as lithium-ion electric
The cycle performance figure of pond negative electrode material.
As seen from the figure, Ni prepared by the present invention0.25Zn0.75Fe2O4Metal oxide as lithium ion battery negative material,
Charge-discharge performance is excellent, and under 100 milliamperes of every gram of current densities, after charge and discharge cycles 100 are enclosed, specific discharge capacity reaches 855.9
Every gram of milliampere hour.And ZnFe2O4After 100 circle of circulation, discharge capacity is only 494.9 every gram of milliampere hour.
Specific embodiment
The present invention is made further instructions below by embodiment, but the invention is not limited to following examples.
Embodiment one
A method of zinc ferrite chemical property being improved by doping nickel element, the nickel of certain molal weight replaces certain
The zinc of molal weight forms a kind of ternary metal oxide, is prepared as follows step:
(1) by 0.15 mM of six water nickel nitrate, 0.85 mM of zinc nitrate hexahydrate, 1.5 mMs of ferrous sulfate heptahydrates,
2.5 mMs of urea and 1.7 mMs of ammonium fluorides are dissolved in 25 ml deionized waters, form uniform mixed solution, then
It is transferred in stainless steel cauldron, under 180 degrees Celsius, hydro-thermal reaction 20 hours；
(2) by step, (1) prepared turbid solution is cooling, centrifugation, is respectively cleaned three times with deionized water and alcohol；
(3) after (2) prepared sample is dried 24 hours in an oven, powder sample is sufficiently ground in mortar for step
Mill, after mixing, is placed in porcelain boat, in tube furnace, in air under 430 degrees Celsius, calcines 3.5 hours, obtain
Ni0.15Zn0.85Fe2O4Metal oxide.
Embodiment two
A method of zinc ferrite chemical property being improved by doping nickel element, the nickel of certain molal weight replaces certain
The zinc of molal weight forms a kind of ternary metal oxide, is prepared as follows step:
(1) by 0.25 mM of six water nickel nitrate, 0.75 mM of zinc nitrate hexahydrate, 2 mMs of ferrous sulfate heptahydrates, 5
MM urea and 2 mMs of ammonium fluorides are dissolved in 35 ml deionized waters, are formed uniform mixed solution, are then transferred into
In stainless steel cauldron, under 200 degrees Celsius, hydro-thermal reaction 24 hours；
(2) by step, (1) prepared turbid solution is cooling, centrifugation, is respectively cleaned three times with deionized water and alcohol；
(3) after (2) prepared sample is dried 24 hours in an oven, powder sample is sufficiently ground in mortar for step
Mill, after mixing, is placed in porcelain boat, in tube furnace, in air under 600 degrees Celsius, calcines 4 hours, obtain
Ni0.25Zn0.75Fe2O4Metal oxide.
Embodiment three
A method of zinc ferrite chemical property being improved by doping nickel element, the nickel of certain molal weight replaces certain
The zinc of molal weight forms a kind of ternary metal oxide, is prepared as follows step:
(1) by 0.35 mM of six water nickel nitrate, 0.65 mM of zinc nitrate hexahydrate, 1.8 mMs of ferrous sulfate heptahydrates,
3 mMs of urea and 2.5 mMs of ammonium fluorides are dissolved in 45 ml deionized waters, are formed uniform mixed solution, are then turned
It moves on in stainless steel cauldron, under 220 degrees Celsius, hydro-thermal reaction 28 hours；
(2) by step, (1) prepared turbid solution is cooling, centrifugation, is respectively cleaned three times with deionized water and alcohol；
(3) after (2) prepared sample is dried 24 hours in an oven, powder sample is sufficiently ground in mortar for step
Mill, after mixing, is placed in porcelain boat, in tube furnace, in air under 470 degrees Celsius, calcines 4.5 hours, obtain
Ni0.35Zn0.65Fe2O4Metal oxide.
Example IV
A method of zinc ferrite chemical property being improved by doping nickel element, the nickel of certain molal weight replaces certain
The zinc of molal weight forms a kind of ternary metal oxide, is prepared as follows step:
(1) by 0.45 mM of six water nickel nitrate, 0.55 mM of zinc nitrate hexahydrate, 2.3 mMs of ferrous sulfate heptahydrates,
3.5 mMs of urea and 3 mMs of ammonium fluorides are dissolved in 55 ml deionized waters, are formed uniform mixed solution, are then turned
It moves on in stainless steel cauldron, under 240 degrees Celsius, hydro-thermal reaction 32 hours；
(2) by step, (1) prepared turbid solution is cooling, centrifugation, is respectively cleaned three times with deionized water and alcohol；
(3) after (2) prepared sample is dried 24 hours in an oven, powder sample is sufficiently ground in mortar for step
Mill, after mixing, is placed in porcelain boat, in tube furnace, in air under 500 degrees Celsius, calcines 5 hours, obtain
Ni0.45Zn0.55Fe2O4Metal oxide.
Embodiment five
A method of zinc ferrite chemical property being improved by doping nickel element, the nickel of certain molal weight replaces certain
The zinc of molal weight forms a kind of ternary metal oxide, is prepared as follows step:
(1) by 0.55 mM of six water nickel nitrate, 0.45 mM of zinc nitrate hexahydrate, 2.5 mMs of ferrous sulfate heptahydrates,
4 mMs of urea and 3.5 mMs of ammonium fluorides are dissolved in 65 ml deionized waters, are formed uniform mixed solution, are then turned
It moves on in stainless steel cauldron, under 260 degrees Celsius, hydro-thermal reaction 36 hours；
(2) by step, (1) prepared turbid solution is cooling, centrifugation, is respectively cleaned three times with deionized water and alcohol；
(3) after (2) prepared sample is dried 24 hours in an oven, powder sample is sufficiently ground in mortar for step
Mill, after mixing, is placed in porcelain boat, in tube furnace, in air under 550 degrees Celsius, calcines 5.5 hours, obtain
Ni0.55Zn0.45Fe2O4Metal oxide.
Embodiment six
A method of zinc ferrite chemical property being improved by doping nickel element, the nickel of certain molal weight replaces certain
The zinc of molal weight forms a kind of ternary metal oxide, is prepared as follows step:
(1) by 0.65 mM of six water nickel nitrate, 0.35 mM of zinc nitrate hexahydrate, 3 mMs of ferrous sulfate heptahydrates,
4.5 mMs of urea and 4 mMs of ammonium fluorides are dissolved in 75 ml deionized waters, are formed uniform mixed solution, are then turned
It moves on in stainless steel cauldron, under 280 degrees Celsius, hydro-thermal reaction 40 hours；
(2) by step, (1) prepared turbid solution is cooling, centrifugation, is respectively cleaned three times with deionized water and alcohol；
(3) after (2) prepared sample is dried 24 hours in an oven, powder sample is sufficiently ground in mortar for step
Mill, after mixing, is placed in porcelain boat, in tube furnace, in air under 650 degrees Celsius, calcines 6 hours, obtain
Ni0.65Zn0.35Fe2O4Metal oxide.
Claims (8)
1. a kind of method for improving zinc ferrite chemical property by doping nickel element, it is characterised in that:
Nickel element is adulterated in the zinc ferrite and forms a kind of ternary metal oxide, selects six water nickel nitrates, zinc nitrate hexahydrate, seven
Aqueous ferrous sulfate, urea and ammonium fluoride are mixed to form uniform mixed solution with certain molal weight, through hydrothermal synthesis, forge
After burning, Ni is obtainedxZn1-xFe2O4Metal oxide, 0.15≤x < 1, specific preparation process is as follows:
(1) 0.15-1 mMs of six water nickel nitrates, 0.35-1 mMs of zinc nitrate hexahydrate, 1-3.5 mMs of seven water sulfuric acid are sub-
Iron, 2-6 mMs of urea and 1.5-5.5 mMs of ammonium fluoride are dissolved in 20-80 ml deionized water, form uniform mixing
Solution is then transferred into stainless steel cauldron, under 150-300 degrees Celsius, hydro-thermal reaction 18-42 hours；
(2) turbid solution prepared by step (1) is cooling, centrifugation, is respectively cleaned three times with deionized water and alcohol；
After (3) drying sample prepared by step (2) 24 hours in an oven, powder sample is fully ground in mortar,
After mixing, it is placed in porcelain boat, in tube furnace, air themperature is 400-750 degrees Celsius, calcines 3-8 hours, obtains
NixZn1-xFe2O4Metal oxide, 0.15≤x < 1.
2. a kind of method for improving zinc ferrite chemical property by doping nickel element according to claim 1, feature
It is:
(1) by 0.15 mM of six water nickel nitrate, 0.85 mM of zinc nitrate hexahydrate, 1.5 mMs of ferrous sulfate heptahydrates, 2.5
MM urea and 1.7 mMs of ammonium fluorides are dissolved in 25 ml deionized waters, are formed uniform mixed solution, are then shifted
Into stainless steel cauldron, under 180 degrees Celsius, hydro-thermal reaction 20 hours；
(2) turbid solution prepared by step (1) is cooling, centrifugation, is respectively cleaned three times with deionized water and alcohol；
After (3) drying sample prepared by step (2) 24 hours in an oven, powder sample is fully ground in mortar,
After mixing, it is placed in porcelain boat, in tube furnace, air themperature is 430 degrees Celsius, calcines 3.5 hours, obtains
Ni0.15Zn0.85Fe2O4Metal oxide.
3. a kind of method for improving zinc ferrite chemical property by doping nickel element according to claim 1, feature
It is:
(1) by 0.25 mM of six water nickel nitrate, 0.75 mM of zinc nitrate hexahydrate, 2 mMs of ferrous sulfate heptahydrates, 5 mmoles
That urea and 2 mMs of ammonium fluorides are dissolved in 35 ml deionized waters, are formed uniform mixed solution, are then transferred into stainless
In steel reaction kettle, under 200 degrees Celsius, hydro-thermal reaction 24 hours；
(2) turbid solution prepared by step (1) is cooling, centrifugation, is respectively cleaned three times with deionized water and alcohol；
After (3) drying sample prepared by step (2) 24 hours in an oven, powder sample is fully ground in mortar,
After mixing, it is placed in porcelain boat, in tube furnace, air themperature is 600 degrees Celsius, calcines 4 hours, obtains
Ni0.25Zn0.75Fe2O4Metal oxide.
4. a kind of method for improving zinc ferrite chemical property by doping nickel element according to claim 1, feature
It is:
(1) by 0.35 mM of six water nickel nitrate, 0.65 mM of zinc nitrate hexahydrate, 1.8 mMs of ferrous sulfate heptahydrates, 3 millis
Mole of urea and 2.5 mMs of ammonium fluorides are dissolved in 45 ml deionized waters and see, form uniform mixed solution, then shift
Into stainless steel cauldron, under 220 degrees Celsius, hydro-thermal reaction 28 hours；
(2) turbid solution prepared by step (1) is cooling, centrifugation, is respectively cleaned three times with deionized water and alcohol；
After (3) drying sample prepared by step (2) 24 hours in an oven, powder sample is fully ground in mortar,
After mixing, it is placed in porcelain boat, in tube furnace, air themperature is 470 degrees Celsius, calcines 4.5 hours, obtains
Ni0.35Zn0.65Fe2O4Metal oxide.
5. a kind of method for improving zinc ferrite chemical property by doping nickel element according to claim 1, feature
It is:
(1) by 0.45 mM of six water nickel nitrate, 0.55 mM of zinc nitrate hexahydrate, 2.3 mMs of ferrous sulfate heptahydrates, 3.5
MM urea and 3 mMs of ammonium fluorides are dissolved in 55 ml deionized waters, are formed uniform mixed solution, are then transferred into
In stainless steel cauldron, under 240 degrees Celsius, hydro-thermal reaction 32 hours；
(2) turbid solution prepared by step (1) is cooling, centrifugation, is respectively cleaned three times with deionized water and alcohol；
After (3) drying sample prepared by step (2) 24 hours in an oven, powder sample is fully ground in mortar,
After mixing, it is placed in porcelain boat, in tube furnace, air themperature is 500 degrees Celsius, calcines 5 hours, obtains
Ni0.45Zn0.55Fe2O4Metal oxide.
6. a kind of method for improving zinc ferrite chemical property by doping nickel element according to claim 1, feature
It is:
(1) by 0.55 mM of six water nickel nitrate, 0.45 mM of zinc nitrate hexahydrate, 2.5 mMs of ferrous sulfate heptahydrates, 4 millis
Mole of urea and 3.5 mMs of ammonium fluorides are dissolved in 65 ml deionized waters, are formed uniform mixed solution, are then transferred into
In stainless steel cauldron, under 260 degrees Celsius, hydro-thermal reaction 36 hours；
(2) turbid solution prepared by step (1) is cooling, centrifugation, is respectively cleaned three times with deionized water and alcohol；
After (3) drying sample prepared by step (2) 24 hours in an oven, powder sample is fully ground in mortar,
After mixing, it is placed in porcelain boat, in tube furnace, air themperature is 550 degrees Celsius, calcines 5.5 hours, obtains
Ni0.55Zn0.45Fe2O4Metal oxide.
7. a kind of method for improving zinc ferrite chemical property by doping nickel element according to claim 1, feature
It is:
(1) by 0.65 mM of six water nickel nitrate, 0.35 mM of zinc nitrate hexahydrate, 3 mMs of ferrous sulfate heptahydrates, 4.5 millis
Mole of urea and 4 mMs of ammonium fluorides are dissolved in 75 ml deionized waters, are formed uniform mixed solution, are then transferred into not
In rust steel reaction kettle, under 280 degrees Celsius, hydro-thermal reaction 40 hours；
(2) turbid solution prepared by step (1) is cooling, centrifugation, is respectively cleaned three times with deionized water and alcohol；
After (3) drying sample prepared by step (2) 24 hours in an oven, powder sample is fully ground in mortar,
After mixing, it is placed in porcelain boat, in tube furnace, air themperature is calcined 6 hours, obtained at 650 degrees Celsius
Ni0.65Zn0.35Fe2O4Metal oxide.
8. according to claim 1 to a kind of application by adulterating the zinc ferrite of nickel element made from any one of 7 the methods,
It is characterized in that:
NixZn1-xFe2O4Metal oxide can be used for the negative electrode material of lithium ion battery, 0.15≤x < 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610517654.0A CN105958032B (en) | 2016-07-04 | 2016-07-04 | A kind of method and application improving zinc ferrite chemical property by doping nickel element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610517654.0A CN105958032B (en) | 2016-07-04 | 2016-07-04 | A kind of method and application improving zinc ferrite chemical property by doping nickel element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105958032A CN105958032A (en) | 2016-09-21 |
| CN105958032B true CN105958032B (en) | 2018-12-11 |
Family
ID=56902223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610517654.0A Active CN105958032B (en) | 2016-07-04 | 2016-07-04 | A kind of method and application improving zinc ferrite chemical property by doping nickel element |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105958032B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450182A (en) * | 2016-09-29 | 2017-02-22 | 吉林大学 | Method for improving electrochemical properties of zinc ferrite by doping multiwalled carbon nanotube and application |
| CN106971855B (en) * | 2017-04-10 | 2019-01-08 | 江苏大学 | A kind of nickel ferrite based magnetic loaded nanoparticle electrode material and preparation method and purposes |
| CN107591535B (en) * | 2017-09-03 | 2019-11-19 | 河南师范大学 | Alkaline secondary cell negative electrode material [ZnxCuyFe2O4] and using the negative electrode material battery |
| CN107706367B (en) * | 2017-09-03 | 2019-11-19 | 河南师范大学 | Alkaline secondary cell negative electrode material [CuxZnyNizFe2O4] and using the negative electrode material battery |
| CN108336343A (en) * | 2018-03-14 | 2018-07-27 | 吉林大学 | A kind of preparation method and application of zinc ferrite/manganese dioxide composite material |
| CN108711621B (en) * | 2018-05-25 | 2021-05-11 | 上海应用技术大学 | Carbon-doped bimetallic oxide material and preparation method thereof |
| CN109950496B (en) * | 2019-03-29 | 2022-01-04 | 荆门市格林美新材料有限公司 | Double-coated lithium nickel cobalt aluminate ternary positive electrode material and preparation method thereof |
| CN111834616B (en) * | 2019-04-23 | 2021-11-16 | 四川佰思格新能源有限公司 | Composite negative electrode material, preparation method and lithium ion battery |
| CN111453773A (en) * | 2020-04-10 | 2020-07-28 | 陶健君 | Lithium battery negative electrode material and preparation method thereof |
| CN111883372B (en) * | 2020-08-10 | 2021-10-29 | 嘉兴嘉卫检测科技有限公司 | Zn-doped MnFe2O4@ C composite material for super capacitor and preparation method thereof |
| CN114921806A (en) * | 2022-05-16 | 2022-08-19 | 中国科学技术大学 | Zinc ferrite photoanode with ultralow water oxidation photocurrent initial potential, preparation method and application |
| CN114768831B (en) * | 2022-05-30 | 2023-08-29 | 中国海洋大学 | Photoelectrocatalysis anode material of zinc ferrite and nickel doped zinc indium sulfide heterojunction and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475368A (en) * | 2009-01-09 | 2009-07-08 | 东华大学 | Process for preparing nickel-zine ferrite (NixZn1-xFe2O4) magnetic nano powder by alcohol-heating method |
| CN102875140A (en) * | 2012-10-12 | 2013-01-16 | 中国航空工业集团公司北京航空材料研究院 | Nickel zinc ferrite powder and preparation method thereof |
| CN103449807A (en) * | 2013-09-12 | 2013-12-18 | 安徽工业大学 | Preparation method of biphase composite hard magnetic ferrite with exchange coupling |
-
2016
- 2016-07-04 CN CN201610517654.0A patent/CN105958032B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475368A (en) * | 2009-01-09 | 2009-07-08 | 东华大学 | Process for preparing nickel-zine ferrite (NixZn1-xFe2O4) magnetic nano powder by alcohol-heating method |
| CN102875140A (en) * | 2012-10-12 | 2013-01-16 | 中国航空工业集团公司北京航空材料研究院 | Nickel zinc ferrite powder and preparation method thereof |
| CN103449807A (en) * | 2013-09-12 | 2013-12-18 | 安徽工业大学 | Preparation method of biphase composite hard magnetic ferrite with exchange coupling |
Non-Patent Citations (1)
| Title |
|---|
| M. V. Reddy等.Mixed Oxides, (Ni1−xZnx)Fe2O4 (x = 0, 0.25, 0.5, 0.75, 1): Molten Salt Synthesis, Characterization and Its Lithium-Storage Performance for Lithium Ion Batteries.《The Journal of Physical Chemistry C》.2015,第119卷第4709-4718页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105958032A (en) | 2016-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105958032B (en) | A kind of method and application improving zinc ferrite chemical property by doping nickel element | |
| CN103682316B (en) | The preparation method of long-life, high-capacity lithium ion cell tertiary cathode material | |
| CN106340638B (en) | A kind of high-rate lithium-rich manganese-based anode material of double layer hollow structure and preparation method thereof | |
| CN102569781B (en) | High-voltage lithium ion battery cathode material and preparation method thereof | |
| CN102074682B (en) | Method for preparing high-temperature lithium manganate material for lithium ion power battery | |
| CN108598466A (en) | A kind of preparation method for the nickel-cobalt-manganese ternary material for making constituent content distribution gradient | |
| CN103117380A (en) | Preparation method of manganese Li-NiCoMn ternary material for lithium ion battery | |
| CN102208614B (en) | Method for preparing lithium ion battery cathode material coated iron sesquioxide | |
| CN105692721B (en) | A kind of sodium-ion battery positive material and preparation method thereof and application method | |
| CN102244236A (en) | Method for preparing lithium-enriched cathodic material of lithium ion battery | |
| CN102208637A (en) | ZnFe2O4/C composite cathode material with hollow sphere structure and one-step preparation method thereof | |
| CN103346317B (en) | Composite mixed and cladded type anode material for lithium-ion batteries LiFePO 4and preparation method thereof | |
| CN106558689B (en) | A kind of electrochemical in-situ method prepares the method and its application of two-arch tunnel mixed metal selenides | |
| CN103985854A (en) | Preparation method of nanoscale nickel lithium manganate positive pole material | |
| CN106299295B (en) | A kind of porous micro-nano structure lithium-enriched cathodic material of lithium ion battery and preparation method thereof with shuttle shape pattern | |
| CN102368547A (en) | Lithium ion battery and anode active material thereof | |
| CN101582500B (en) | Method for preparing anode material of metal oxide nano-sheet lithium ion battery | |
| CN105047905A (en) | Surface modification method of nickel-rich cathode material | |
| CN104319392A (en) | Modified spinel type lithium battery cathode material and preparation method thereof | |
| CN106082360A (en) | A kind of lithium ion battery negative material of flower-shaped high power capacity and preparation method and application | |
| CN105428628A (en) | Preparation method of porous spherical high-voltage lithium ion battery positive electrode material | |
| CN103606700A (en) | Lithium ion battery with good charge and discharge performance | |
| CN115020676A (en) | Sodium ion battery positive electrode material capable of stabilizing oxygen valence change and preparation method thereof | |
| CN104868110A (en) | Graphene-oriented mesoporous Co2V2O7 nanosheet material and production method and application thereof | |
| CN102832381A (en) | Preparation method of high-voltage cathode material Lil+xMn3/2-yNil/2-zMy+zO4 of lithium ion battery with long service life |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |