CN107069028A - A kind of magnetostriction LiMn2O4 anode material of lithium battery and preparation method - Google Patents
A kind of magnetostriction LiMn2O4 anode material of lithium battery and preparation method Download PDFInfo
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- CN107069028A CN107069028A CN201710164792.XA CN201710164792A CN107069028A CN 107069028 A CN107069028 A CN 107069028A CN 201710164792 A CN201710164792 A CN 201710164792A CN 107069028 A CN107069028 A CN 107069028A
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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention proposes a kind of magnetostriction LiMn2O4 anode material of lithium battery and preparation method.It is characterized in be under the conditions of 1,800 2000 DEG C by the prefabricated iron gallium magnetocrystalline nanometer powder of electrostatic spray, then LiMn2O4 predecessor is added, by solid state grinding reaction, sintering process, the ferromagnetic crystalline substance of galliumization is homogeneously scattered in LiMn2O4 structure, form the manganate cathode material for lithium with magnetostriction.Its significant advantage be the Nanoscale Iron gallium magnetocrystalline of equal distributed mutually during lithium ion mobility occurs for LiMn2O4, because the electromagnetic field of generation causes Nanoscale Iron gallium magnetocrystalline micro stretching to contract, so as to suppress and buffer the change of LiMn2O4 structure, imparting LiMn2O4 preferably stability.Manganate cathode material for lithium discharge voltage plateau prepared by this method reaches 4.8V, and maintains higher capacity, and the capacity of 1C discharge and recharges is more than 168mAh/g.
Description
Technical field
The invention belongs to field of lithium ion battery and field of energy source materials, and in particular to a kind of magnetostriction LiMn2O4 lithium electricity
Pond positive electrode.
Background technology
Policy inclination with countries in the world to new energy battery industry, lithium-ion-power cell develops as 21 century
The preferable energy, is increasingly paid close attention to by everybody.With the strict control of carbon emission, automobile industry replaces tradition with electrical source of power
The energy so that the application of lithium ion battery has very important status.
Production lithium-ion-power cell must be selected positive electrode.Theoretically, selection can be provided
Positive electrode is various in style, but at present really can be seldom using the lithium ion anode material of commodity production purposes, and conclusion is got off
Only LiFePO4, LiMn2O4 and ternary material.If it is considered that the safety and cycle life of battery, then only LiFePO4 and
LiMn2O4 can be competent at.
Because the tap density and conductance of LiFePO 4 material are poor, low operating temperatures poor performance, while by international monopoly
The complex process prepared in itself with material, up to the present the high restriction of cost, manganate cathode material for lithium is prepared by the electric industry of lithium
The primary selection of lithium-ion-power cell.LiMn2O4 is mainly the LiMn2O4 of spinel structure, and it is that a kind of typical ion is brilliant
Body, with Fd3m symmetry.Spinel structure LiMn2O4 prices are low, current potential is high, environment-friendly, security performance is high, be it is following very
Promising environment-friendly battery positive electrode.The electric industry of the lithium of China can realize preliminary commercial quantities to lithium-ion-power cell at present
The enterprise of productionization is about：The ATL of Japanese TDK investments, the BYD in Shenzhen, power god, the Jiangsu manganese gram in Changzhou and the Soviet Union of Tianjin
The star in state is identical.Wherein in addition to the BYD in Shenzhen is claimed and possesses " iron cell ", the lithium ion power electricity of other companies production
Chi Jun is using the positive electrode that LiMn2O4 is main body.
However, there is the hair that the shortcomings of capacity is relatively low, loop attenuation is fast, high-temperature behavior is not good constrains the material in LiMn2O4
Exhibition, also increases the industrial applications for limiting LiMn2O4.The main cause for these defects occur includes Mn3+ dissolving, Jahn-
Teller effects, electrolyte decomposition, the purity of X phase structures is not high or pattern is irregular.Improve following for lithium manganate material at present
The main method of ring performance and high-temperature behavior is to be modified to improve the cycle performance and height of lithium manganate material by doping or surface
Warm nature energy, and suppress the Jahn-Teller effects in charge and discharge process.For doping, major control factors have doping to change
Property, various ions dosages and with original structure binding ability, main dopant is including Cr, Ni, Mg, Co, Fe, Ca, Al etc..For
For surface modified, main research work be find be resistant to electrolytic corrosion, with Material cladding it is good, with single lithium from
The material of sub- selectivity, current coating layer material mainly includes ZnO, MgO, lithium boron composite oxides, lithium and cobalt oxides, lithium vanadium
Oxide etc..Such method is confirmed to be increased to the chemical property of LiMn2O4, and correlative study work is also carried out lasting.
In view of the advantages for development and its shortcoming of presence of LiMn2O4, a kind of it is necessory to be prepared using new approaches and new technology
In the manganate cathode material for lithium of high power capacity high stability, seeking economically viable method production can be with the LiMn2O4 of commercial application
Positive electrode, scale, pure electric vehicle popularization and application to electrokinetic cell have vital meaning.
The content of the invention
It is an object of the invention to propose a kind of magnetostriction LiMn2O4 anode material of lithium battery, it is characterised in that contain
Magnetostriction additive, by the mechanically deform of magnetostriction additive, so as to suppress and buffer the change of LiMn2O4 structure；Its
Described in magnetostriction additive be FeGa magnetocrystalline nanometer powders.From the FeGa magnetocrystalline nanometer powders with magnetostrictive effect
As additive, homogeneously it is scattered in LiMn2O4 structure, in charge and discharge process, because electric field changes, produces magnetic field, magnetic
Cause flexible additive mechanically deform occur, so as to suppress and buffer the change of LiMn2O4 structure, assign LiMn2O4 and preferably stablize
Property, while improving discharge capacity.
In order to achieve the above object, the process program that the present invention is used is as follows：
By the prefabricated FeGa magnetocrystallines nanometer powder of electrostatic spray under the conditions of 1800-2000 DEG C, the oxidation of manganese and lithium is then added
Thing or salt, by mechanical alloying, solid phase reaction, are crushed, double sintering and second-time breakage make FeGa magnetocrystallines homogeneously be scattered in
In LiMn2O4 structure, the manganate cathode material for lithium with magnetostriction is formed.
Specific preparation process includes：
(1) prepared by FeGa magnetocrystallines nanometer powder
By Fe sources and Ga sources according to FexGa100-x(8<x<40) carry out after dispensing, mixing, it is molten with middle frequency furnace under protective atmosphere
Melt, electrostatic atomizer is entered after melting, FeGa magnetocrystalline nanometer powders needed for obtaining.
The Fe sources are preferably one kind in carbonyl iron dust, nanometer iron powder；The Ga sources are gallium；The protective atmosphere
For nitrogen, argon gas or vacuum；The melting, temperature is 1800~2000 DEG C；The electrostatic atomizer fluid aperture is 0.5
~2 millimeters, voltage of electric field is 5~50kv；The FeGa magnetocrystallines nanometer powder is shot-range ordered structure, closes cluster preferred orientation, shape
Shape anisotropy, its magnetostriction value is 180~1780 × 10-6；Powder size is 50~500nm.
(2) manganate cathode material for lithium presoma dispensing is mixed
Manganese source and lithium source are weighed according to design proportion, after high-energy ball milling mixing, FeGa magnetocrystallines nanometer prepared by step (1) is added
After powder, mixed on low speed, dry and obtain manganate cathode material for lithium presoma.
The manganese source be preferably chemical manganese bioxide, manganous hydroxide, the manganese of titanium dioxide three, one kind in mangano-manganic oxide or
A variety of mixtures；The lithium source is one or more mixtures in lithium carbonate, lithium hydroxide, lithium oxalate and lithium nitrate；It is described
Design proportion is that lithium manganese atom compares 1:1.8~2；The high-energy ball milling is conventional machinery alloying ball mill, and ball material volume ratio is
5:1-20:1, a diameter of 3-10mm of zirconium ball, Ball-milling Time are 2~48 hours, and granularity is 0.1~1 μm after ball milling；The FeGa
The ratio that magnetocrystalline nanometer powder accounts for gross mass is 1~16wt%；The mixed on low speed speed is fast for 100~200r/min ball milling
Degree；The drying mode is vacuum drying and is spray-dried.
(3) solid phase reaction and broken
Manganate cathode material for lithium presoma made from step (2) is loaded into saggar, into kiln, sintering, after sintering, cooling, powder
Broken acquisition primary sintered material.
The sintering temperature is 480-660 DEG C, sintering time 2-12h；Described crush is preferably air-flow crushing, grain after crushing
D50=1-5um is spent, air-flow is preferably nitrogen.
(4) double sintering and second-time breakage
Primary sintered material prepared by step (3), pre-burning 4-10h, 800-1000 DEG C of sintering 10-25h, burns at 500-700 DEG C
Air is passed through during knot, magnetostriction LiMn2O4 anode material of lithium battery is obtained after having sintered cooling, air-flow crushing sieving.
Compared with prior art, heretofore described additive has the beneficial effect that：
1st, present invention firstly provides mixing magnetostriction materials in anode material of lithium battery, using its in charge and discharge process it is electric
Changes of magnetic field, causes the ferromagnetic brilliant micro stretching contracting of Nano-Gaization, so as to suppress and buffer the change of LiMn2O4 structure, imparting LiMn2O4 compared with
Good stability, is that the lifting of lithium battery anode LiMn2O4 stability opens new thinking and process.
2nd, by preparation method of the present invention, the ferromagnetic crystalline substance of galliumization makes LiMn2O4 Li+ ionic discharge voltage platforms reach 4.8V, and
Maintain higher capacity.The capacity of 1C discharge and recharges is more than 168mAh/g, compacted density 3.6g/cm3。
3rd, the reaction activity of material is advantageously reduced using high-energy ball milling, the temperature and time of solid phase reaction, control is reduced
Abnormal grain growth processed, elemental lithium is evenly distributed.
4th, this process needs additionally to add except FeGa magnetocrystalline nanometer powders device therefor, and other equipment is all normal
See that double sintering method produces the equipment and technique of manganate cathode material for lithium, without adjustment.With simple, quick, easy, high efficiency
And environmental protection, the advantage suitable for large-scale production.
Brief description of the drawings
Fig. 1 prepares the charge-discharge test curve map that product makes button cell for the present invention.
Claims (5)
1. a kind of magnetostriction LiMn2O4 anode material of lithium battery, it is characterised in that containing magnetostriction additive, pass through mangneto
The mechanically deform of flexible additive, so as to suppress and buffer the change of LiMn2O4 structure；Wherein described magnetostriction additive is
FeGa magnetocrystalline nanometer powders.
2. a kind of preparation method of magnetostriction LiMn2O4 anode material of lithium battery as claimed in claim 1, specific preparation process
Including：
（1）It is prepared by FeGa magnetocrystallines nanometer powder
By Fe sources and Ga sources according to Fe x Ga 100-x (8<x<40) carry out after dispensing, mixing, it is molten with middle frequency furnace under protective atmosphere
Melt, electrostatic atomizer is entered after melting, FeGa magnetocrystalline nanometer powders needed for obtaining；
（2）Manganate cathode material for lithium presoma dispensing is mixed
Manganese source and lithium source are weighed according to design proportion, after high-energy ball milling mixing, step is added（1）The FeGa magnetocrystallines nanometer of preparation
After powder, mixed on low speed, dry and obtain manganate cathode material for lithium presoma；
（3）Solid phase reaction and broken
By step（2）Obtained manganate cathode material for lithium presoma loads saggar, into kiln, sintering, after sintering, cooling, powder
Broken acquisition primary sintered material；
（4）Double sintering and second-time breakage
By step（3）The primary sintered material of preparation, pre-burning 4-10h, 800-1000 DEG C of sintering 10-25h, burns at 500-700 DEG C
Air is passed through during knot, magnetostriction LiMn2O4 anode material of lithium battery is obtained after having sintered cooling, air-flow crushing sieving.
3. the preparation method of magnetostriction LiMn2O4 anode material of lithium battery according to claim 2, it is characterised in that：Step
（1）Fe sources belonging to described are preferably one kind in carbonyl iron dust, nanometer iron powder；The Ga sources are gallium；The protective atmosphere
For nitrogen, argon gas or vacuum；The melting, temperature is 1800 ~ 2000 DEG C；The electrostatic atomizer fluid aperture be 0.5 ~
2 millimeters, voltage of electric field is 5 ~ 50kv；The FeGa magnetocrystallines nanometer powder is shot-range ordered structure, closes cluster preferred orientation, shape is each
Anisotropy, its magnetostriction value is 180 ~ 1780 × 10-6；Powder size is 50 ~ 500nm.
4. the preparation method of magnetostriction LiMn2O4 anode material of lithium battery according to claim 2, it is characterised in that：Step
（2）The manganese source is preferably the one or more in chemical manganese bioxide, manganous hydroxide, the manganese of titanium dioxide three, mangano-manganic oxide
Mixture；The lithium source is one or more mixtures in lithium carbonate, lithium hydroxide, lithium oxalate and lithium nitrate；The design
Ratio is that lithium manganese atom compares 1:1.8~2；The high-energy ball milling is conventional machinery alloying ball mill, and ball material volume ratio is 5:1-
20:1, a diameter of 3-10mm of zirconium ball, Ball-milling Time are 2 ~ 48 hours, and granularity is 0.1 ~ 1 μm after ball milling；The FeGa magnetocrystallines are received
The ratio that ground rice end accounts for gross mass is 1 ~ 16wt%；The mixed on low speed speed is 100 ~ 200r/min ball milling speed；It is described dry
Dry mode is vacuum drying and is spray-dried.
5. the preparation method of magnetostriction LiMn2O4 anode material of lithium battery according to claim 2, it is characterised in that：Step
（3）The sintering temperature is 480-660 DEG C, sintering time 2-12h；Described crush is preferably air-flow crushing, granularity D50 after crushing
=1-5um, air-flow is preferably nitrogen.
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| CN201710164792.XA CN107069028A (en) | 2017-03-20 | 2017-03-20 | A kind of magnetostriction LiMn2O4 anode material of lithium battery and preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108807946A (en) * | 2018-08-07 | 2018-11-13 | 许焕生 | The preparation method of anode material of lithium battery with multi-layer core-shell structure |
| CN109167050A (en) * | 2018-09-28 | 2019-01-08 | 河南福森新能源科技有限公司 | The production method of inexpensive 551530 type tertiary cathode material of high capacity |
-
2017
- 2017-03-20 CN CN201710164792.XA patent/CN107069028A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 孙敏等: "《智能材料技术》", 31 January 2014, 国防工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108807946A (en) * | 2018-08-07 | 2018-11-13 | 许焕生 | The preparation method of anode material of lithium battery with multi-layer core-shell structure |
| CN109167050A (en) * | 2018-09-28 | 2019-01-08 | 河南福森新能源科技有限公司 | The production method of inexpensive 551530 type tertiary cathode material of high capacity |
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Application publication date: 20170818 |