CN109309215A - A kind of modified lithium-rich manganese-based anode material and preparation method thereof - Google Patents
A kind of modified lithium-rich manganese-based anode material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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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
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- H—ELECTRICITY
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- 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
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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
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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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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
A kind of modified lithium-rich manganese-based anode material and preparation method thereof, the chemical formula of the positive electrode are as follows: Li2MnxM1‑xO2F, wherein 0.5≤x < 1, M are one or more of doped chemical, including Zr, Si, Ge, Sn, V, As, Sb, Cr, Mo, Se or Te.The preparation method is that: (1) according to metering ratio, manganese source, doped chemical source, Fluorine source and excessive lithium source are uniformly mixed；(2) under protective atmosphere, ball milling,.Anode material discharging gram volume of the present invention is high, and coulombic efficiency is high, and material structure is stablized, good cycle；For the battery of assembling at 22mA/g, 2.0~4.6V, electric discharge gram volume is up to 278.0mAh/g；At 110mA/g, 2.5~4.4V, after 200 circle of circulation, capacity retention ratio is up to 93.6%；The method of the present invention is simple, at low cost, is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of positive electrodes and preparation method thereof, and in particular to a kind of modified lithium-rich manganese-based anode material and
Preparation method.
Background technique
Lithium ion battery has the advantages that memory-less effect, high security, high-energy-density, self-discharge rate are low etc., is widely applied
In fields such as mobile device, power battery and energy-storage systems.Currently, power battery face short course continuation mileage, poor circulation and
The problems such as safety is insufficient seriously constrains its fast-developing and application.In recent years, lithium-rich manganese-based anode material specific discharge capacity
Up to 300mAh/g, energy density can break through 300Wh/kg, be considered as the ideal chose of next-generation dynamic lithium battery.However,
Lithium-rich manganese-based anode material is low in the presence of coulombic efficiency for the first time, and there are oxonium ion oxidation, structural instability, voltage platforms for charging process
The disadvantages of decaying and cyclical stability are poor, seriously hinders its commercialization process.
For lithium-rich manganese-based anode material disadvantages mentioned above, people have done a large amount of study on the modification, and main includes doping, surface
Modification, surface construction Lacking oxygen, particle nanosizing and the method for modifying such as rich lithium and other positive electrodes are compound.Currently, domestic
It is outer that there are many document and patent report metal oxide-type (Al2O3、TiO2、ZnO、ZrO2、SiO2、CeO2Deng), phosphoric acid salt
(AlPO4、LiNiPO4) and fluorides to carry out surface to rich lithium material modified, effectively reduce the appearance irreversible for the first time of material
Amount and cyclical stability.Doping vario-property is also commonly used to improve material structure stability, and commonly mixing doped chemical has Mg2+、Al3+、
Cr3+、Mo6+、Ti4+And F-Deng.Doping vario-property improves the structural stability and cyclical stability of material.Due to Li2MnO3Middle Mn
For+4 valences, no electro-chemical activity, therefore rich lithium manganese is needed in initial charge by the high voltage activation of 4.5V or more or acid
Reason competence exertion goes out high capacity, and the activation of 4.5V high voltage can cause oxonium ion in material to be oxidized to oxygen, cause material structure
Change, acid processing can also damage material structure.Therefore, two kinds of activation methods can all damage the steady of rich lithium manganese material structure
Qualitative, material structure is easy to happen transformation capacity attenuation and voltage platform is caused to reduce in following cycle, and acceleration leads to energy
The decline of density.
Traditional view thinks rich lithium manganese material Li2MnO3It can not be used separately as positive electrode, only in lithium-rich manganese-based solid solution
Play the role of rock-steady structure in body material.The technology of existing lithium-rich manganese base material doping vario-property is all concentrated on heteroion to richness
Lithium manganese based solid solution (xLi2MnO3·(1-x)LiMO2) material is doped, purpose is all stabilizing lithium rich manganese based solid solution material
The structure of material does not play and improves Li in rich lithium manganese base solid solution material2MnO3The effect of portion capacity.Such as
CN106532018A discloses a kind of lithium-rich manganese-based anode material and preparation method thereof, is carried out to rich lithium manganese base solid solution material
Vanadium doping, CN107146874A disclose the microwave heating method of lithium-rich manganese-based anode material, are to rich lithium manganese base solid solution material
Material carries out zirconium doping, and 107768664 A of CN discloses a kind of lithium-rich manganese-based anode material and preparation method thereof of molybdenum doping, is
Molybdenum doping is carried out to rich lithium manganese base solid solution material.Above-mentioned doping method all has stabilizing lithium rich manganese based solid solution material structure
Certain effect.Due to Li2MnO3Theoretical gram volume is high, and raw material is cheap and abundance, if suitable Li can be developed2MnO3
Method of modifying makes it play high capacity advantage, and power battery cost will be greatly reduced and improve power battery energy density.
Therefore, in order to break through Li2MnO3Commercialization bottleneck, improve the stability of its structure, oxonium ion in activation process be reduced or avoided
Oxidation, develop a kind of effective modified material and method be most important.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of change of manganese
Conjunction valence is low, and charge and discharge gram volume is high, and coulombic efficiency is high, and material structure is stablized, the modification lithium-rich manganese-based anode material of good cycle
Material.
The further technical problems to be solved of the present invention are to overcome drawbacks described above of the existing technology, provide a kind of work
Skill is simple, at low cost, is suitable for the preparation method of the modification lithium-rich manganese-based anode material of industrialized production.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of modified lithium-rich manganese-based anode material, institute
State the chemical formula of modified lithium-rich manganese-based anode material are as follows: Li2MnxM1-xO2F, wherein 0.5≤x < 1, M are doped chemical, including
One or more of Zr, Si, Ge, Sn, V, As, Sb, Cr, Mo, Se or Te.
Preferably, the chemical valence of the M element is+4 ,+5 or+6 valences, and the chemical valence range of Mn element is+2~+trivalent.More
Preferably, as x=0.5, the chemical valence of Mn is positive divalent, and the positive electrode has highest theoretical capacity.The present invention passes through
A fluorine ion is introduced instead of an oxonium ion, to stabilize material structure, it is suppressed that oxygen in lithium-rich manganese-based anode material
Ion is oxidized to oxygen；Meanwhile the present invention introduces the positive doped chemical of high price in lithium-rich manganese-based anode material structure, with
Make all or part of manganese+divalent simultaneously under fluorine ion collective effect, transferable two electronics of manganese, maximum journey in charge and discharge
Degree improves the gram volume of lithium-rich manganese-based anode material.
The present invention further solves technical solution used by its technical problem: a kind of modified lithium-rich manganese-based anode material
Preparation method, comprising the following steps:
(1) according to the metering ratio of each element in lithium-rich manganese-based anode material, by manganese source, doped chemical source, Fluorine source and excessive lithium
Source after evenly mixing, obtains mixture A；Wherein, the elemental lithium of addition is compared to theoretical amount excessive 2~5%；
(2) by mixture A obtained by step (1) under protective atmosphere, ball milling is carried out, modified lithium-rich manganese-based anode material is obtained.
Preferably, in step (1), the manganese source is manganese oxide.
Preferably, in step (1), the doped chemical source is the change of Zr, Si, Ge, Sn, V, As, Sb, Cr, Mo, Se or Te
Conjunction valence is the oxide of+4 ,+5 or+6 valences.
Preferably, in step (1), the Fluorine source is lithium fluoride.The lithium fluoride is used as lithium source simultaneously.
Preferably, in step (1), the lithium source is lithia and lithium fluoride.
Preferably, in step (1), when the manganese source is manganese oxide, manganese sulfate, formic acid manganese, manganese acetate, manganese oxalate, chlorination
One or more of manganese or manganese nitrate etc., the lithium source are lithia, lithium fluoride, lithium hydroxide, lithium carbonate, lithium acetate, nitre
One or more of sour lithium, lithium ethoxide, lithium acetate or lithium chloride etc., and manganese source and lithium source are not manganese oxide and oxidation simultaneously
When lithium and lithium fluoride, before carrying out ball milling, need to carry out precalcining first under protective atmosphere.
Preferably, the precalcining refers to more preferable 4~6 DEG C/min of 1~10 DEG C/min(of rate) it is warming up to 200~
800 DEG C (more preferable 300~600 DEG C), the more preferable 4~6h of 1~12h(of precalcining).The manganese source and lithium source of the non-oxidized substance exist
Manganese oxide or lithia are decomposed into after precalcining.
Preferably, the protective atmosphere is nitrogen and/or argon gas.More preferably argon gas.
Preferably, in step (1), the manganese source, doped chemical source, Fluorine source and lithium source are mixed by the way of liquid phase or solid phase
It closes.
Preferably, when being mixed by the way of liquid phase, the mass ratio of total solid and organic solution is 0.8~1.25:1.
Preferably, the organic solution is one or more of ethyl alcohol, acetone or N-Methyl pyrrolidone etc..
Preferably, in step (2), the revolution revolving speed of the ball milling is the more preferable 300~450r/ of 50~500r/min(
Min), rotation revolving speed is the more preferable 600~900r/min of 100~1000r/min(), the time of ball milling is that 5~60h(is more preferable
20~50h).It is further preferred that carrying out ball milling using planetary ball mill.
Preferably, in step (2), the protective atmosphere is nitrogen and/or argon gas.More preferably argon gas.
Protective atmosphere used in the present invention is high-purity gas, purity >=99.9%.
Beneficial effects of the present invention are as follows:
(1) chemical valence of Mn element is+2~+trivalent in the modified lithium-rich manganese-based anode material of the present invention, and the modification is lithium-rich manganese-based
The main diffraction maximum and Li of positive electrode2MnO3Standard card main peak is overlapped, it was demonstrated that its structure and Li2MnO3It is similar, and the modification
ICP-AES constituent content experimental result in lithium-rich manganese-based anode material is consistent with design object value；The modification is lithium-rich manganese-based
Positive electrode is spherical particle, and particle diameter is in 200~500nm；
(2) present invention adulterated by high price doped chemical and with fluorine ion substitution oxonium ion method, reduce it is lithium-rich manganese-based just
The chemical valence of manganese in the material of pole makes lithium-rich manganese-based anode material that can play high gram volume advantage without activation, in current density
Under 22mA/g, 2.0~4.6V, the gram volume that discharges for the first time is 278.0mAh/g, is higher than existing Li2MnO3The electric discharge gram of positive electrode
Capacity, coulombic efficiency is up to 84.6% for the first time；And the introducing of doped chemical and fluorine ion stabilizes material structure, reduces charging
When material analyse oxygen, the stable laminated structure of formation greatly improved lithium-rich manganese-based anode material charging oxonium ion be oxidized to oxygen
The problems such as being reduced with voltage platform after circulation, under 110mA/g current density, 2.5~4.4V voltage, after 200 circle of circulation, capacity
Conservation rate is up to 93.6%, and charge and discharge coulombic efficiency is 99% or so in cyclic process；
(2) the method for the present invention is simple and easy to control, at low cost, is suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the XRD of 1 lithium-rich manganese-based anode material of the embodiment of the present invention；
Fig. 2 is the TEM of 1 lithium-rich manganese-based anode material of the embodiment of the present invention；
Fig. 3 is the first charge-discharge curve graph of 1-1 of embodiment of the present invention lithium-rich manganese-based anode material institute assembled battery；
Fig. 4 is the circulation volume and charge and discharge coulombic efficiency of 1-1 of embodiment of the present invention lithium-rich manganese-based anode material institute assembled battery
Figure.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Purity >=99.9% of high pure nitrogen and high-purity argon gas used in the embodiment of the present invention；The embodiment of the present invention is made
Chemical reagent is obtained by routine business approach unless otherwise specified.
A kind of modified lithium-rich manganese-based anode material embodiment 1
The chemical formula of the modified lithium-rich manganese-based anode material are as follows: Li2Mn0.5V0.5O2F, the chemical valence of the V element are+4 valences,
The chemical valence of Mn element is+divalent.
As shown in Figure 1, the Li2Mn0.5V0.5O2The main diffraction maximum and Li of F2MnO3Standard card 73-0152 main peak is overlapped,
Prove synthesized material structure and Li2MnO3It is similar, and the Li2Mn0.5V0.5O2The ICP-AES constituent content experimental result of F
It is consistent with design object value, as shown in table 1.
As shown in Figure 2, the Li2Mn0.5V0.5O2F is spherical particle, and particle diameter is in 200~300nm.
A kind of preparation method embodiment 1-1 of modified lithium-rich manganese-based anode material
(1) by 1.42g(0.02mol) manganese oxide, 1.66g(0.02mol) vanadium dioxide, 1.04g(0.04mol) lithium fluoride and
0.62g(0.0208mol) lithia (lithium compared to theoretical amount excessive 2%) in a manner of solid phase after evenly mixing, obtain mixture A；
(2) mixture A obtained by step (1) is placed in planetary ball mill under high-purity argon gas protective atmosphere, in revolution revolving speed
For 300r/min, rotation revolving speed is to carry out ball milling under 600r/min for 24 hours, obtain modified lithium-rich manganese-based anode material
Li2Mn0.5V0.5O2F。
Battery assembly: by 2g Li obtained by the embodiment of the present invention2Mn0.5V0.5O2F is as anode, with 0.25g conductive agent
Super-P and 0.25g binder polyvinyladine floride is placed in N-Methyl pyrrolidone solvent dispersing agent, will using high-speed homogenization machine
It is mixed into homogeneous slurry, and using micrometer-adjustable film applicator scraper, even spread is carried out in Al foil collector, vacuum drying
Afterwards, diameter is made using slicer is 1.4cm electrode slice, and electrode slice is moved into (oxygen in the glove box full of high-purity argon gas atmosphere
Pressure, hydraulic pressure are below 0.1ppm), with lithium an- ode, Gelgard-2400 diaphragm, high-voltage electrolyte 1mol/L hexafluorophosphoric acid
Lithium/DMC:EC(volume ratio 1:1) and 1% dioxalic acid lithium borate mixture, CR2025 type button cell is assembled into, by assembling
Half-cell carries out charge-discharge test in the case where 25 DEG C, voltage range are 2.0~4.6V.
From the figure 3, it may be seen that lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.5V0.5O2The battery of F assembling, in electricity
Under current density 22mA/g, initial charge gram volume is 313.6mAh/g, and the gram volume that discharges for the first time is 249.3mAh/g, obtains library for the first time
Human relations efficiency is 79.5%.
As shown in Figure 4, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.5V0.5O2The battery of F assembling, in electricity
Under current density 110mA/g, 2.5~4.4V of voltage range, first Zhou Fang electricity gram volume is 225.4mAh/g, and circulation is after 200 weeks, electric discharge
Gram volume remains at 185.6mAh/g, and capacity retention ratio is up to 82.3%, and charge and discharge coulombic efficiency is on 99% left side in cyclic process
It is right.
A kind of preparation method embodiment 1-2 of modified lithium-rich manganese-based anode material
(1) by 2.86g(0.02mol) manganese oxalate, 1.66g(0.02mol) vanadium dioxide, 1.04g(0.04mol) lithium fluoride and
2.80g(0.0424mol) lithium acetate (lithium is compared to theoretical amount excessive 3%), is the liquid of 1:1 with the mass ratio of total solid and ethyl alcohol
Phase mode is uniformly mixed, and obtains mixture A；
(2) mixture A obtained by step (1) is first under high pure nitrogen protective atmosphere, it is placed in Muffle furnace, with 6 DEG C/min's
Rate is warming up to 600 DEG C, carries out precalcining 4h, then under high pure nitrogen protective atmosphere, be placed in planetary ball mill, is revolving
Revolving speed is 300r/min, and rotation revolving speed is to carry out ball milling under 600r/min for 24 hours, obtain lithium-rich manganese-based anode material
Li2Mn0.5V0.5O2F。
Battery assembly: with embodiment 1-1.
Through detecting, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.5V0.5O2The battery of F assembling, in electric current
Under density 22mA/g, initial charge gram volume is 307.8mAh/g, and the gram volume that discharges for the first time is 239.4mAh/g, obtains coulomb for the first time
Efficiency is 77.8%.
Through detecting, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.5V0.5O2The battery of F assembling, in electric current
Under density 110mA/g, 2.5~4.4V of voltage range, first Zhou Fang electricity gram volume is 221.3mAh/g, and circulation is after 200 weeks, and discharge ratio
Capacity remains at 187.9mAh/g, and capacity retention ratio is up to 84.9%, and charge and discharge coulombic efficiency is 99% or so in cyclic process.
A kind of modified lithium-rich manganese-based anode material embodiment 2
The chemical formula of the modified lithium-rich manganese-based anode material are as follows: Li2Mn0.5Si0.5O2F, the chemical valence of the Si element are+4
Valence, the chemical valence of Mn element are+divalent.
Through detecting, the Li2Mn0.5Si0.5O2The main diffraction maximum and Li of F2MnO3Standard card 73-0152 main peak is overlapped, card
Bright synthesized material structure and Li2MnO3It is similar, and the Li2Mn0.5Si0.5O2The ICP-AES constituent content experimental result of F
It is consistent with design object value, as shown in table 1.
Through detecting, the Li2Mn0.5Si0.5O2F is spherical particle, and particle diameter is in 300~400nm.
A kind of preparation method embodiment 2 of modified lithium-rich manganese-based anode material
(1) by 1.42g(0.02mol) manganese oxide, 1.20g(0.02mol) silica, 1.04g(0.04mol) lithium fluoride and
0.63g(0.0211mol) lithia (lithium is compared to theoretical amount excessive 2.75%) after homogeneous solid mixing, is obtained mixed in a manner of solid phase
Close object A；
(2) mixture A obtained by step (1) is placed in planetary ball mill under high-purity argon gas protective atmosphere, in revolution revolving speed
For 450r/min, rotation revolving speed is to carry out ball milling 40h under 900r/min, obtain lithium-rich manganese-based anode material Li2Mn0.5Si0.5O2F。
Battery assembly: with embodiment 1-1.
Through detecting, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.5Si0.5O2The battery of F assembling, in electric current
Under density 22mA/g, initial charge gram volume is 328.4mAh/g, and the gram volume that discharges for the first time is 274.2mAh/g, obtains coulomb for the first time
Efficiency is 83.5%.
Through detecting, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.5Si0.5O2The battery of F assembling, in electric current
Under density 110mA/g, 2.5~4.4V of voltage range, first Zhou Fang electricity gram volume is 249.1mAh/g, and circulation is after 200 weeks, and discharge ratio
Capacity remains at 204.5mAh/g, and capacity retention ratio is up to 82.1%, and charge and discharge coulombic efficiency is 99% or so in cyclic process.
A kind of modified lithium-rich manganese-based anode material embodiment 3
The chemical formula of the modified lithium-rich manganese-based anode material are as follows: Li2Mn0.5Zr0.5O2F, the chemical valence of the Zr element are+4
Valence, the chemical valence of Mn element are+divalent.
Through detecting, the Li2Mn0.5Zr0.5O2The main diffraction maximum and Li of F2MnO3Standard card 73-0152 main peak is overlapped, card
Bright synthesized material structure and Li2MnO3It is similar, and the Li2Mn0.5Zr0.5O2The ICP-AES constituent content experimental result of F
It is consistent with design object value, as shown in table 1.
Through detecting, the Li2Mn0.5Zr0.5O2F is spherical particle, and particle diameter is in 200~400nm.
A kind of preparation method embodiment 3 of modified lithium-rich manganese-based anode material
(1) by 1.42g(0.02mol) manganese oxide, 2.46g(0.02mol) zirconium dioxide, 1.04g(0.04mol) lithium fluoride and
0.65g(0.0218mol) lithia (lithium compared to theoretical amount excessive 4.5%) in a manner of solid phase after evenly mixing, obtain mixture A；
(2) mixture A obtained by step (1) is placed in planetary ball mill under high-purity argon gas protective atmosphere, in revolution revolving speed
For 450r/min, rotation revolving speed is to carry out ball milling 48h under 900r/min, obtain lithium-rich manganese-based anode material Li2Mn0.5Zr0.5O2F。
Battery assembly: with embodiment 1-1.
Through detecting, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.5Zr0.5O2The battery of F assembling, in electric current
Under density 22mA/g, initial charge gram volume is 281.5mAh/g, and the gram volume that discharges for the first time is 233.9mAh/g.Coulomb is imitated for the first time
Rate is 83.1%.
Through detecting, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.5Zr0.5O2The battery of F assembling, in electric current
Under density 110mA/g, 2.5~4.4V of voltage range, first Zhou Fang electricity gram volume is 194.2mAh/g, and circulation is after 200 weeks, and discharge ratio
Capacity remains at 181.8mAh/g, and capacity retention ratio is up to 93.6%, and charge and discharge coulombic efficiency is 99% or so in cyclic process.
A kind of modified lithium-rich manganese-based anode material embodiment 4
The chemical formula of the modified lithium-rich manganese-based anode material are as follows: Li2Mn0.75Mo0.25O2F, the chemical valence of the Mo element are+6
Valence, the chemical valence of Mn element are+divalent.
Through detecting, the Li2Mn0.75Mo0.25O2The main diffraction maximum and Li of F2MnO3Standard card 73-0152 main peak is overlapped,
Prove synthesized material structure and Li2MnO3It is similar, and the Li2Mn0.75Mo0.25O2The ICP-AES constituent content of F tests knot
Fruit is consistent with design object value, as shown in table 1.
Through detecting, the Li2Mn0.75Mo0.25O2F is spherical particle, and particle diameter is in 300~500nm.
A kind of preparation method embodiment 4 of modified lithium-rich manganese-based anode material
(1) by 5.19 g(0.03mol) manganese acetate, 1.44g(0.01mol) molybdenum trioxide, 1.04g(0.04mol) lithium fluoride and
2.80g(0.0424mol) lithium acetate (lithium is compared to theoretical amount excessive 3%), the mass ratio with total solid and acetone is 0.8:1's
Liquid phase mode is uniformly mixed, and obtains mixture A；
(2) mixture A obtained by step (1) is first under high-purity argon gas protective atmosphere, it is placed in Muffle furnace, with 4 DEG C/min's
Rate is warming up to 400 DEG C, carries out precalcining 6h, then under high-purity argon gas protective atmosphere, be placed in planetary ball mill, is revolving
Revolving speed is 450r/min, and rotation revolving speed is to carry out ball milling 40h under 900r/min, obtain lithium-rich manganese-based anode material
Li2Mn0.75Mo0.25O2F。
Battery assembly: with embodiment 1-1.
Through detecting, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.75Mo0.25O2The battery of F assembling, in electricity
Under current density 22mA/g, initial charge gram volume is 353.7mAh/g, and the gram volume that discharges for the first time is 278.0mAh/g, obtains library for the first time
Human relations efficiency is 78.6%.
Through detecting, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.75Mo0.25O2The battery of F assembling, in electricity
Under current density 110mA/g, 2.5~4.4V of voltage range, first Zhou Fang electricity gram volume is 263.6mAh/g, and circulation is after 200 weeks, electric discharge
Specific capacity remains at 202.2mAh/g, and capacity retention ratio is up to 76.7%, and charge and discharge coulombic efficiency is on 99% left side in cyclic process
It is right.
A kind of modified lithium-rich manganese-based anode material embodiment 5
The chemical formula of the modified lithium-rich manganese-based anode material are as follows: Li2Mn0.75V0.25O2F, the chemical valence of the V element are+4
Valence, the chemical valence of Mn element are+2.67 valences.
Through detecting, the Li2Mn0.75V0.25O2The main diffraction maximum and Li of F2MnO3Standard card 73-0152 main peak is overlapped, card
Bright synthesized material structure and Li2MnO3It is similar, and the Li2Mn0.75V0.25O2The ICP-AES constituent content experimental result of F
It is consistent with design object value, as shown in table 1.
Through detecting, the Li2Mn0.75V0.25O2F is spherical particle, and particle diameter is in 200~400nm.
A kind of preparation method embodiment 5 of modified lithium-rich manganese-based anode material
(1) by 2.13g(0.03mol) manganese oxide, 0.83g(0.01mol) vanadium dioxide, 1.04g(0.04mol) lithium fluoride and
0.63g(0.0211mol) lithia (lithium is compared to theoretical amount excessive 2.75%) is with the quality of total solid and N-Methyl pyrrolidone
Than being uniformly mixed for the liquid phase mode of 1:1, mixture A is obtained；
(2) mixture A obtained by step (1) is placed in planetary ball mill under high-purity argon gas protective atmosphere, in revolution revolving speed
For 350r/min, rotation revolving speed is to carry out ball milling under 600r/min for 24 hours, obtain lithium-rich manganese-based anode material Li2Mn0.75V0.25O2F。
Battery assembly: with embodiment 1-1.
Through detecting, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.75V0.25O2The battery of F assembling, in electricity
Under current density 22mA/g, initial charge gram volume is 308.3mAh/g, and the gram volume that discharges for the first time is 255.0mAh/g, obtains library for the first time
Human relations efficiency is 82.7%.
Through detecting, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.75V0.25O2The battery of F assembling, in electricity
Under current density 110mA/g, 2.5~4.4V of voltage range, first Zhou Fang electricity gram volume is 215.3mAh/g, and circulation is after 200 weeks, electric discharge
Specific capacity remains at 187.7mAh/g, and capacity retention ratio is up to 87.2%, and charge and discharge coulombic efficiency is on 99% left side in cyclic process
It is right.
A kind of modified lithium-rich manganese-based anode material embodiment 6
The chemical formula of the modified lithium-rich manganese-based anode material are as follows: Li2Mn0.9V0.1O2F, the chemical valence of the V element are+4 valences,
The chemical valence of Mn element is+2.89 valences.
Through detecting, the Li2Mn0.9V0.1O2The main diffraction maximum and Li of F2MnO3Standard card 73-0152 main peak is overlapped, card
Bright synthesized material structure and Li2MnO3It is similar, and the Li2Mn0.9V0.1O2The ICP-AES constituent content experimental result of F with
Design object value is consistent, as shown in table 1.
Through detecting, the Li2Mn0.9V0.1O2F is spherical particle, and particle diameter is in 300~500nm.
A kind of preparation method embodiment 6 of modified lithium-rich manganese-based anode material
(1) by 2.56g(0.036mol) manganese oxide, 0.33g(0.004mol) vanadium dioxide, 1.04g(0.04mol) lithium fluoride and
0.63g(0.0211mol) lithia (lithium is compared to theoretical amount excessive 2.75%) after evenly mixing, obtains mixture A；
(2) mixture A obtained by step (1) is placed in planetary ball mill under high-purity argon gas protective atmosphere, in revolution revolving speed
For 400r/min, rotation revolving speed is to carry out ball milling 36h under 700r/min, obtain lithium-rich manganese-based anode material Li2Mn0.9V0.1O2F。
Battery assembly: with embodiment 1-1.
Through detecting, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.9V0.1O2The battery of F assembling, in electric current
Under density 22mA/g, initial charge gram volume is 298.3mAh/g, and the gram volume that discharges for the first time is 252.4mAh/g, obtains coulomb for the first time
Efficiency is 84.6%.
Through detecting, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.9V0.1O2The battery of F assembling, in electric current
Under density 110mA/g, 2.5~4.4V of voltage range, first Zhou Fang electricity gram volume is 213.7mAh/g, and circulation is after 200 weeks, and discharge ratio
Capacity remains at 192.9mAh/g, and capacity retention ratio is up to 90.3%, and charge and discharge coulombic efficiency is 99% or so in cyclic process.
A kind of modified lithium-rich manganese-based anode material embodiment 7
The chemical formula of the modified lithium-rich manganese-based anode material are as follows: Li2Mn0.67As0.33O2F, the chemical valence of the As element are+5
Valence, the chemical valence of Mn element are+divalent.
Through detecting, the Li2Mn0.67As0.33O2The main diffraction maximum and Li of F2MnO3Standard card 73-0152 main peak is overlapped,
Prove synthesized material structure and Li2MnO3It is similar, and the Li2Mn0.67As0.33O2The ICP-AES constituent content of F tests knot
Fruit is consistent with design object value, as shown in table 1.
Through detecting, the Li2Mn0.67As0.33O2F is spherical particle, and particle diameter is in 300~400nm.
A kind of preparation method embodiment 7 of modified lithium-rich manganese-based anode material
(1) by 1.89g(0.027mol) manganese oxide, 1.53g(0.0067mol) diarsenic pentoxide, 1.04g(0.04mol) fluorination
Lithium and 0.63g(0.0211mol) lithia (lithium compares theoretical amount excessive 2.75%) after evenly mixing, obtain mixture A；
(2) mixture A obtained by step (1) is placed in planetary ball mill under high-purity argon gas protective atmosphere, in revolution revolving speed
For 400r/min, rotation revolving speed is to carry out ball milling 30h under 800r/min, obtain lithium-rich manganese-based anode material
Li2Mn0.67As0.33O2F。
Battery assembly: with embodiment 1-1.
Through detecting, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.67As0.33O2The battery of F assembling, in electricity
Under current density 22mA/g, initial charge gram volume is 324.8mAh/g, and the gram volume that discharges for the first time is 264.2mAh/g, obtains library for the first time
Human relations efficiency is 81.3%.
Through detecting, lithium-rich manganese-based anode material Li obtained by the embodiment of the present invention2Mn0.67As0.33O2The battery of F assembling, in electricity
Under current density 110mA/g, 2.5~4.4V of voltage range, first Zhou Fang electricity gram volume is 233.9mAh/g, and circulation is after 200 weeks, electric discharge
Specific capacity remains at 184.9mAh/g, and capacity retention ratio is up to 79.1%, and charge and discharge coulombic efficiency is on 98% left side in cyclic process
It is right.
The modified lithium-rich manganese-based anode material ICP-AES constituent content experimental result of 1 Examples 1 to 7 of table and design object value
Contrast table
As shown in Table 1, by ICP-AES elemental analysis, Examples 1 to 7 is modified each element content in lithium-rich manganese-based anode material
Than close to each material each element atom design theory molar ratio.
Claims (9)
1. a kind of modified lithium-rich manganese-based anode material, which is characterized in that the chemical formula of the modified lithium-rich manganese-based anode material are as follows:
Li2MnxM1-xO2F, wherein 0.5≤x < 1, M are in doped chemical, including Zr, Si, Ge, Sn, V, As, Sb, Cr, Mo, Se or Te
One or more.
2. according to claim 1 be modified lithium-rich manganese-based anode material, it is characterised in that: the chemical valence of the M element be+4,
+ 5 or+6 valences, the chemical valence range of Mn element are+2~+trivalent.
3. a kind of preparation method of modified lithium-rich manganese-based anode material as claimed in claim 1 or 2, which is characterized in that including with
Lower step:
(1) according to the metering ratio of each element in lithium-rich manganese-based anode material, by manganese source, doped chemical source, Fluorine source and excessive lithium
Source after evenly mixing, obtains mixture A；Wherein, the elemental lithium of addition is compared to theoretical amount excessive 2~5%；
(2) by mixture A obtained by step (1) under protective atmosphere, ball milling is carried out, modified lithium-rich manganese-based anode material is obtained.
4. being modified the preparation method of lithium-rich manganese-based anode material according to claim 3, it is characterised in that: in step (1), institute
Stating manganese source is manganese oxide；The doped chemical source be Zr, Si, Ge, Sn, V, As, Sb, Cr, Mo, Se or Te chemical valence be+4 ,+
The oxide of 5 or+6 valences；The Fluorine source is lithium fluoride；The lithium source is lithia and lithium fluoride.
5. being modified the preparation method of lithium-rich manganese-based anode material according to claim 3, it is characterised in that: in step (1), when
The manganese source is one or more of manganese oxide, manganese sulfate, formic acid manganese, manganese acetate, manganese oxalate, manganese chloride or manganese nitrate, institute
Stating lithium source is in lithia, lithium fluoride, lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium ethoxide, lithium acetate or lithium chloride
One or more, and manganese source and lithium source simultaneously for manganese oxide and lithia and lithium fluoride when, before carrying out ball milling, need first exist
Under protective atmosphere, precalcining is carried out.
6. being modified the preparation method of lithium-rich manganese-based anode material according to claim 5, it is characterised in that: the precalcining is
Refer to and is warming up to 200~800 DEG C with 1~10 DEG C/min of rate, 1~12h of precalcining；The protective atmosphere is nitrogen and/or argon
Gas.
7. the preparation method of modified lithium-rich manganese-based anode material according to one of claim 3~6, it is characterised in that: step
(1) in, the manganese source, doped chemical source, Fluorine source and lithium source are mixed by the way of liquid phase or solid phase；When by the way of liquid phase
When mixing, the mass ratio of total solid and organic solution is 0.8~1.25:1；The organic solution is ethyl alcohol, acetone or N- methyl
One or more of pyrrolidones.
8. the preparation method of modified lithium-rich manganese-based anode material according to one of claim 3~7, it is characterised in that: step
(2) in, the revolution revolving speed of the ball milling is 50~500r/min, and rotation revolving speed is 100~1000r/min, and the time of ball milling is 5
~60h.
9. the preparation method of modified lithium-rich manganese-based anode material according to one of claim 3~8, it is characterised in that: step
(2) in, the protective atmosphere is nitrogen and/or argon gas.
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| CN110808372A (en) * | 2019-11-12 | 2020-02-18 | 中国科学院过程工程研究所 | Modified lithium-rich manganese-based positive electrode material and preparation method and application thereof |
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Application publication date: 20190205 |