CN106207157A - Doping layered lithium manganate and its preparation method and application - Google Patents
Doping layered lithium manganate and its preparation method and application Download PDFInfo
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- CN106207157A CN106207157A CN201610577264.2A CN201610577264A CN106207157A CN 106207157 A CN106207157 A CN 106207157A CN 201610577264 A CN201610577264 A CN 201610577264A CN 106207157 A CN106207157 A CN 106207157A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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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
- 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
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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Abstract
The present invention proposes doping layered lithium manganate and its preparation method and application, and the doped chemical of this doping layered lithium manganate includes sodium element and aluminium element.Doping layered lithium manganate proposed by the invention, at least has one of following advantage compared with the LiMn2O4 of undoped p sodium and aluminum: higher electro-chemical activity；Higher capacitance；Higher specific discharge capacity；And two-dimensional layered structure is more stable in charge and discharge process.The preparation method of this doping layered lithium manganate includes: calcine the mixture containing lithium compound, manganese compound, sodium compound and aluminium compound, in order to the doping layered lithium manganate described in acquisition.The method of preparation doping layered lithium manganate proposed by the invention, method is simple, and process conditions are easily controllable, are suitable to extensive mass manufacture.
Description
Technical field
The present invention relates to new energy materials field, concrete, the present invention adulterates layered lithium manganate and preparation method thereof and answers
With, more specifically, the present invention relates to adulterate layered lithium manganate and preparation method thereof, positive electrode active materials, anode sizing agent, positive pole
Plate, battery and vehicle.
Background technology
LiMn2O4, as one of lithium ion anode material, mainly includes lithium manganate having spinel structure and layer structure LiMn2O4.
Wherein, layer structure LiMn2O4 (in this article, sometimes referred to simply as " layered lithium manganate ") be the more promising lithium of one from
Sub-positive electrode, has nontoxic, safety, theoretical capacity are the highest advantages such as (about 285mAh/g).
But, existing layered lithium manganate still haves much room for improvement.
Summary of the invention
It is contemplated that one of technical problem solved the most to a certain extent in correlation technique.
The present invention is following discovery based on inventor and completes:
Inventor finds in research process, use layered lithium manganate battery in the cyclic process of repeatedly discharge and recharge,
Mn due to metastable layered lithium manganate3+Can migrate to lithium layer and produce Jahn-Teller distortion effect, irreversibly change
Become the spinel structure of stable state, and the theoretical capacity of spinel structure LiMn2O4 is the half of layer structure, thus cause lithium
The decay rapidly of battery reversible capacity, cycle performance are deteriorated.The present inventor finds through further investigation, by stratiform
Adulterate in LiMn2O4 specific element, it is possible to effectively improves the structural stability of LiMn2O4, charge-discharge performance and raising
Its reversible capacity.
In view of this, the present invention proposes a kind of doping stratiform with high power capacity, high stability or high specific discharge capacity
LiMn2O4.
In a first aspect of the present invention, the present invention proposes a kind of doping layered lithium manganate.According to embodiments of the invention,
The doped chemical of described doping layered lithium manganate includes sodium element and aluminium element.
Inventors be surprised to learn that, doping layered lithium manganate according to embodiments of the present invention, with undoped p sodium and the mangaic acid of aluminum
Lithium is compared at least has one of following advantage: higher electro-chemical activity；Higher capacitance；Higher specific discharge capacity；With
And two-dimensional layered structure is more stable in charge and discharge process.
It addition, doping layered lithium manganate according to embodiments of the present invention, it is also possible to have a following additional technical characteristic:
According to embodiments of the invention, described doping layered lithium manganate has following chemical formula: Li1-XNaXMn1-YAlYO2,
Wherein, X=0.018～0.022, Y=0.01～0.07.Thus, doping layered lithium manganate according to embodiments of the present invention passes through
Use specific sodium element and aluminium element doping scope, can have higher electro-chemical activity, higher electric capacity further
In amount, higher specific discharge capacity and/or charge and discharge process, two-dimensional layered structure is more stable.
According to embodiments of the invention, described doping layered lithium manganate is selected from Li0.98Na0.02Mn0.99Al0.01O2、
Li0.98Na0.02Mn0.97Al0.03O2、Li0.98Na0.02Mn0.95Al0.05O2And Li0.98Na0.02Mn0.93Al0.07O2At least one.By
This, doping layered lithium manganate according to embodiments of the present invention is by using specific sodium element and aluminium element doping, Ke Yijin
One step has in higher electro-chemical activity, higher capacitance, higher specific discharge capacity and/or charge and discharge process
Two-dimensional layered structure is more stable.
According to embodiments of the invention, described sodium element be by sodium carbonate and sodium bicarbonate at least one provide.By
This, the doping layered lithium manganate of the embodiment of the present invention, by the specific sodium element that adulterates, can improve layered lithium manganate further
The reversible capacitance of material, and the cost of sodium carbonate and sodium bicarbonate is relatively low, raw material sources wide, beneficially low-cost industrial produces
Realize.
According to embodiments of the invention, described aluminium element is provided by aluminium oxide.Thus, the doping of the embodiment of the present invention
Layered lithium manganate, by the specific aluminium element that adulterates, can be stablized the stratiform of LiMn2O4 during charge and discharge cycles further and tie
Structure, meanwhile, relative to expensive and that preparation method is complicated transistion metal compound, aluminium oxide is the most excellent honest and clean, the lowest one-tenth
The realization of this industrialized production.
In a second aspect of the present invention, the present invention proposes a kind of method preparing above-mentioned doping layered lithium manganate, described side
Method includes: calcine the mixture containing lithium compound, manganese compound, sodium compound and aluminium compound, in order to before acquisition
The doping layered lithium manganate that face is mentioned.
Inventor it was unexpectedly observed that according to embodiments of the present invention preparation doping layered lithium manganate method, it is possible to obtain
Doping stratiform lithium manganate material, and preparation method is simple, process conditions are easily controllable, are suitable to extensive mass manufacture.Ability
Field technique personnel it is understood that above for doping layered lithium manganate describe feature and advantage, be still applied to this doping
The preparation method of layered lithium manganate, does not repeats them here.
It addition, the preparation method of doping layered lithium manganate according to the above embodiment of the present invention, it is also possible to have the most attached
The technical characteristic added:
According to embodiments of the invention, described lithium compound is Lithium hydrate, and manganese compound is manganese sesquioxide managnic oxide, and sodium is closed
Thing is sodium carbonate or sodium bicarbonate, and aluminium compound is aluminium oxide.Thus, preparation stratiform mangaic acid according to embodiments of the present invention
The method of lithium, each cost of material is relatively low and source is wide, the realization that beneficially low-cost industrial produces.
According to embodiments of the invention, described mixture is little by carrying out ball milling 5～10 under conditions of there is ethanol
Time and obtain.Thus, the method preparing layered lithium manganate according to embodiments of the present invention, it is possible to obtain doped layer further
Shape lithium manganate material, and preparation method is simpler, process conditions are more easily controlled, and are more suitable for extensive mass manufacture.
According to embodiments of the invention, before described calcining, in advance to described mixture in air atmosphere, 300～500
Precalcining 4～8 hours are carried out under degree Celsius.Thus, the method preparing layered lithium manganate according to embodiments of the present invention, it is possible to enter
One step ground obtains doping stratiform lithium manganate material, and preparation method is simpler, and process conditions are more easily controlled, and is more suitable for extensive
Mass manufactures.
According to embodiments of the invention, the preparation method of described doping layered lithium manganate is in nitrogen atmosphere, 600～
Described calcining 6～30 hours are carried out under 850 degrees Celsius.Thus, the method preparing layered lithium manganate according to embodiments of the present invention,
Can obtain doping stratiform lithium manganate material further, and preparation method is simpler, process conditions are more easily controlled, and are more suitable for
Extensive mass manufacture.
In a third aspect of the present invention, the present invention proposes a kind of positive electrode active materials, containing above-mentioned doping stratiform mangaic acid
Lithium.
Inventor it was unexpectedly observed that according to embodiments of the present invention containing doping layered lithium manganate positive electrode active materials,
There is one of following advantage: improve the electro-chemical activity of material；Possesses the performance of cycle charge-discharge；And keep discharge and recharge
The stability of chemical constitution in journey.It will be appreciated to those of skill in the art that above for doping layered lithium manganate and system thereof
Feature and advantage described by Preparation Method, are still applied to this positive electrode active materials, do not repeat them here.
In a fourth aspect of the present invention, the present invention proposes a kind of anode sizing agent, containing aforesaid positive electrode active materials.
Inventor, it was unexpectedly observed that anode sizing agent according to an embodiment of the invention, fills containing high electrochemical activity, circulation
In discharge performance and charge and discharge process structural stability at least one positive electrode active materials, may be used for preparing further
The positive plate of high discharge capacity.It will be appreciated to those of skill in the art that above for doping layered lithium manganate and preparation thereof
Feature and advantage described by method and positive electrode active materials, are still applied to this anode sizing agent, do not repeat them here.
In a fifth aspect of the present invention, the present invention proposes a kind of positive plate, containing aforesaid positive electrode active materials.
Inventor it was unexpectedly observed that positive plate according to an embodiment of the invention, have preferable lithium ion conductivity and
Electron conductivity, can be further used for preparing high-capacitance or the battery of high discharge capacity.Those skilled in the art can manage
Solve, above for doping layered lithium manganate and preparation method thereof, positive electrode active materials and the feature described by anode sizing agent
And advantage, it is still applied to this positive plate, does not repeats them here.
In a sixth aspect of the present invention, the present invention proposes a kind of battery, including aforesaid positive plate.
Inventor it was unexpectedly observed that battery according to an embodiment of the invention, has one of following advantage: high-capacitance or
Person's height discharge capacity；Preferably cyclical stability；Clean and effective；And preferable battery safety.And described battery is permissible
For preparing new-energy automobile.It will be appreciated to those of skill in the art that above for doping layered lithium manganate and preparation thereof
Method, positive electrode active materials, anode sizing agent and the feature and advantage described by positive plate, be still applied to this battery, at this no longer
Repeat.
In a seventh aspect of the present invention, the present invention proposes a kind of vehicle, including aforesaid battery.
Inventor it was unexpectedly observed that vehicle according to an embodiment of the invention, has one of following advantage: higher continuation of the journey
Use ability；Horsepower is stable；And clean environment firendly.It will be appreciated to those of skill in the art that above for doping Layered Manganese
Acid lithium and preparation method thereof, positive electrode active materials, anode sizing agent, positive plate and the feature and advantage described by battery, be still suitable for
In this vehicle, do not repeat them here.
It addition, vehicle according to the above embodiment of the present invention, it is also possible to have a following additional technical characteristic:
According to embodiments of the invention, described vehicle is electric automobile or hybrid vehicle.Thus, the present invention implements
The vehicle of example, has that higher continuation of the journey use ability, horsepower is stable or the advantage of clean environment firendly further.People in the art
Member is it is understood that above for doping layered lithium manganate and preparation method thereof, positive electrode active materials, anode sizing agent, positive pole
Feature and advantage described by plate and battery, are still applied to this vehicle, do not repeat them here.
Accompanying drawing explanation
Above-mentioned and/or the additional aspect of the present invention and advantage are from combining the accompanying drawings below description to embodiment and will become
Substantially with easy to understand, wherein:
Fig. 1 is XRD figure according to an embodiment of the invention；
Fig. 2 is cycle performance figure in accordance with another embodiment of the present invention；
Fig. 3 is the cycle-index according to another embodiment of the present invention and specific capacity graph of a relation；
Fig. 4 is the AC impedance figure according to another embodiment of the present invention；
Fig. 5 is the cyclic voltammogram according to another embodiment of the present invention；And
Fig. 6 is the cyclic voltammogram according to another embodiment of the present invention.
Detailed description of the invention
Embodiments of the invention are described below in detail, and those skilled in the art is it will be appreciated that example below is intended to for solving
Release the present invention, and be not construed as limitation of the present invention.Unless stated otherwise, embodiment below is not expressly recited specifically
Technology or condition, those skilled in the art can be according to the conventional technology in this area or condition or according to product description
Carry out.Raw materials used, reagent or instrument unreceipted production firm person, be can by city available from conventional products.
In one aspect of the invention, the present invention proposes a kind of layered lithium manganate.
According to embodiments of the invention, the doped chemical of this doping layered lithium manganate includes sodium element and aluminium element.Ability
Field technique personnel are it is understood that there is a lot of research about layered lithium manganate doping vario-property at present, primarily to improve
Its structural stability, charge-discharge performance and improve its reversible capacity.
The present inventor is through deeply finding, doped chemical selects Na and Al, it is possible to improve stratiform mangaic acid significantly
The electro-chemical activity of lithium material and capacitance, stablize two-dimensional layered structure in charge and discharge process, and specific discharge capacity can reach
To more than 200mAh/g.And method simple solid phase method preparation doping stratiform lithium manganate material can be used, have and realize low cost
The potential of industrialized production.Inventor finds that the type of doped chemical has a significant impact, such as the performance of lithium manganate material
Suresh etc., by doping two kinds of elements of Fe and Zn, find that doping Fe and Zn can improve the cycle performance of material, but can cause electricity
The decline of capacity.Zhong etc. with coprecipitation method prepare Ni, Co adulterate layered lithium manganate, its first discharge capacity be 148mAh/
G, kwh loss minimum 8.2% after circulating 30 times.Ni, Co that C.Nithya, R. use sol-gal process to prepare at present mix
Miscellaneous layered lithium manganate, it is possible to the highest discharge capacity reached is about 175mAh/g.So, above doping method is the most steady
Determine the structure of layered lithium manganate material, but preparation method is complicated and discharge capacity is the highest.
It should be noted that due to Na+(ionic radius is 0.0950nm) compares Mn3+(ionic radius is 0.0660nm) and Li+(ionic radius is 0.0600nm) is all big, so the cell volume of layered lithium manganate material has a certain amount of increase after Can Za.
After Na, Al doping stratiform lithium manganate material, the increase of cell parameter, can expand the three-dimensional channel of lithium ion mobility, be more beneficial for
The deintercalation of lithium ion, thus improve the reversible capacity of layered lithium manganate material.Meanwhile, Al3+Can also reduce and suppress discharge and recharge
The Jahn-Teller distortion effect that in journey, manganese ion causes, thus play the effect of stable LiMn2O4 layer structure.
It addition, doping layered lithium manganate according to embodiments of the present invention, it is also possible to there is following chemical formula: Li1- XNaXMn1-YAlY O2, wherein, X=0.018～0.022, Y=0.01～0.07.The present inventor studies discovery, doping
A small amount of Na element and Al element, in charge and discharge process, can either stably support LiMn2O4 two-dimensional layered structure originally, also
The exchange capacity of reversible lithium ion can be increased, thus improve the reversible capacity of adulterated lithium manganate.
It addition, according to embodiments of the invention, described doping layered lithium manganate is selected from Li0.98Na0.02Mn0.99Al0.01O2、
Li0.98Na0.02Mn0.97Al0.03O2、Li0.98Na0.02Mn0.95Al0.05O2And Li0.98Na0.02Mn0.93Al0.07O2At least one.This
The inventor of invention studies discovery through in depth, and in the electrochemical property test after doping Na, Al element, adulterate stratiform mangaic acid
The first discharge specific capacity of lithium is above unadulterated layered lithium manganate, and activation number of times reduces, and illustrates that Na, Al doping is all right
Improve the electro-chemical activity of layered lithium manganate material.
It addition, according to embodiments of the invention, described sodium element be by sodium carbonate and sodium bicarbonate at least one provide
's.Inventor is it was unexpectedly observed that use sodium carbonate or sodium bicarbonate to provide the Na element of doping for layered lithium manganate, due to relatively
The introducing of the alkali metal ion of large volume, adds the exchange capacity of reversible lithium ion, thus improve layered lithium manganate material can
Reciprocal capacity；And the cost of sodium carbonate and sodium bicarbonate is relatively low and source is wide, the realization that beneficially low-cost industrial produces.
It addition, according to embodiments of the invention, described aluminium element is provided by aluminium oxide.Inventor it was unexpectedly observed that
Aluminium oxide is used to provide the Al element of doping for layered lithium manganate, due to Al3+Ionic radius less and replace Mn3+After, energy
Caving in of the layer structure that reduction Jahn-Teller effect causes, can stablize the layer of LiMn2O4 during charge and discharge cycles
Shape structure；Meanwhile, and transistion metal compound that preparation method complicated expensive relative to Co, Ni etc., aluminium oxide is more excellent
Honest and clean, that beneficially low-cost industrial produces realization.
In sum, according to embodiments of the invention, the present invention proposes a kind of layered lithium manganate, with undoped p sodium and aluminum
LiMn2O4 compare this layered lithium manganate at least there is one of following advantage: higher electro-chemical activity；Higher capacitance；More
High specific discharge capacity；And two-dimensional layered structure is more stable in charge and discharge process.
In another aspect of the present invention, the present invention proposes a kind of method preparing above-mentioned doping layered lithium manganate.
According to embodiments of the present invention, this preparation method includes: to containing lithium compound, manganese compound, sodium compound and aluminum
The mixture of compound is calcined, in order to obtain above-mentioned doping layered lithium manganate.
It will be appreciated to those of skill in the art that the preparation method of the embodiment of the present invention belongs to high temperature solid-state method, can obtain
Obtaining nano level layered lithium manganate, the distribution of prepared material particle size scope is narrow, and the technique of course of reaction is simple and is prone to control
System.The system of laboratory is suitable to relative to sol-gel synthesis method, ion exchange, hydrothermal synthesis method and coprecipitation method etc.
Preparation Method, the cost of solid phase method is relatively low and is suitable to produce in a large number, the realization that beneficially low-cost industrial produces.
It addition, according to embodiments of the invention, described lithium compound is Lithium hydrate, manganese compound is manganese sesquioxide managnic oxide,
Sodium compound is sodium carbonate or sodium bicarbonate, and aluminium compound is aluminium oxide.
It addition, according to embodiments of the invention, described mixture be by carry out under conditions of there is ethanol ball milling 5～
10 hours and obtain.It was found by the inventors of the present invention that using ethanol as dispersant, can be by various raw materials after carrying out ball-milling treatment
The most levigate and mix homogeneously, in order to subsequent calcination is obtained in that nano level doping layered lithium manganate product.
It addition, according to embodiments of the invention, before described calcining, in advance to described mixture in air atmosphere, 300
～under 500 degrees Celsius, carry out precalcining 4～8 hours.It was found by the inventors of the present invention that at by the precalcining of the embodiment of the present invention
After reason, it is possible to obtain the doping layered lithium manganate that performance is more excellent, it is also possible to shorten the time of subsequent calcination, improve preparation
Efficiency and the productivity of product.
It addition, according to embodiments of the invention, the preparation method of described doping layered lithium manganate is in nitrogen atmosphere,
Described calcining 6～30 hours are carried out under 600～850 degrees Celsius.It was found by the inventors of the present invention that under the protection of nitrogen atmosphere,
The side reaction in calcination process can be reduced, improve productivity and the purity of doping layered lithium manganate；And after above-mentioned calcining,
Precalcining intermediate can be completely converted into doping layered lithium manganate substantially, and the cycle of calcining is shorter, and the most industrialized half
Continuous batch produces.
In sum, according to embodiments of the invention, the present invention proposes a kind of method preparing doping layered lithium manganate,
Being obtained in that doping stratiform lithium manganate material, and preparation method is simple, process conditions are easily controllable, are suitable to extensive mass system
Make.It will be appreciated to those of skill in the art that the feature and advantage described above for doping layered lithium manganate, be still applied to
The preparation method of this doping layered lithium manganate, does not repeats them here.
In an additional aspect of the present invention, the present invention proposes a kind of positive electrode active materials.
According to embodiments of the invention, this positive electrode active materials contains above-mentioned doping layered lithium manganate.The art
Personnel are appreciated that and are not limited only to the layered lithium manganate that adulterates, and this positive electrode active materials can also comprise other kinds of activity material
Material.
In sum, according to embodiments of the invention, the present invention proposes a kind of positive electrode active materials, and utilizing should be containing mixing
The positive electrode active materials of miscellaneous layered lithium manganate, has one of following advantage: improve the electro-chemical activity of material；Possess circulation to fill
The performance of electric discharge；And the stability of chemical constitution in holding charge and discharge process.Before it will be appreciated to those of skill in the art that
Face, for doping layered lithium manganate and preparation method thereof described feature and advantage, is still applied to this positive electrode active materials,
This repeats no more.
In an additional aspect of the present invention, the present invention proposes a kind of anode sizing agent.
According to embodiments of the invention, this anode sizing agent contains aforesaid positive electrode active materials.Those skilled in the art can
To understand, anode sizing agent is beyond containing positive electrode active materials, it is also possible to include the component such as electrolyte, conductive additive.Positive pole
Slurry obtains after each component being sufficiently mixed in media as well, is directly coated with by including but not limited to anode sizing agent
Cover, the forming method such as heating and mould pressing can prepare positive plate.Wherein, those skilled in the art is it is understood that medium is permissible
It is conventional organic solvent, it is possible to the compositions such as positive electrode active materials are dissolved and mix homogeneously fully, did not did at this
Many restrictions.
In sum, according to embodiments of the invention, the present invention proposes a kind of anode sizing agent, utilizes this anode sizing agent,
Containing in high electrochemical activity, cycle charge discharge electrical property and charge and discharge process structural stability at least one positive-active
Material, may be used for preparing further the positive plate of high conductance.It will be appreciated to those of skill in the art that above for
Doping layered lithium manganate and preparation method thereof and the feature and advantage described by positive electrode active materials, be still applied to this positive pole slurry
Material, does not repeats them here.
In an additional aspect of the present invention, the present invention proposes a kind of positive plate.
According to embodiments of the invention, this positive plate contains aforesaid positive electrode active materials.Those skilled in the art are permissible
Understanding, this positive plate also includes the parts of other necessity, and such as electrolyte, conductive additive and dispersant etc., no longer enter at this
Row too much repeats.
In sum, according to embodiments of the invention, the present invention proposes a kind of positive plate, and this positive plate has preferably
Lithium ion conductivity and electron conductivity, can be further used for preparing high-capacitance or the battery of high discharge capacity.This area
Skilled artisan will appreciate that, above for described by doping layered lithium manganate and preparation method thereof and positive electrode active materials
Feature and advantage, are still applied to this positive plate, do not repeat them here.
In an additional aspect of the present invention, the present invention proposes a kind of battery.
According to embodiments of the invention, this battery includes aforesaid positive plate.It will be understood by those skilled in the art that this electricity
Pond also includes the parts of other necessity, such as electrolyte, negative plate etc., the most too much repeats at this.
In sum, according to embodiments of the invention, the present invention proposes a kind of battery, this battery have following advantage it
One: high-capacitance or high discharge capacity；Preferably cyclical stability；Clean and effective；And preferable battery safety.Ability
Field technique personnel are it is understood that above for doping layered lithium manganate and preparation method thereof, positive electrode active materials and positive pole
Feature and advantage described by plate, are still applied to this battery, do not repeat them here.
In an additional aspect of the present invention, the present invention proposes a kind of vehicle.
According to embodiments of the invention, this vehicle includes aforesaid battery.It will be understood by those skilled in the art that this vehicle
Also including the parts of other necessity, such as electromotor, chassis, vehicle body and electrical equipment etc., the most too much repeat at this.
It addition, according to embodiments of the invention, this vehicle is electric automobile or hybrid vehicle.People in the art
Member is it is understood that the battery power resources that to be new-energy automobile important, the security performance of battery, flying power, discharge and recharge
Cycle and recycling stability, all directly influence the serviceability of electric automobile or hybrid vehicle.
In sum, according to embodiments of the invention, the present invention proposes a kind of vehicle, this vehicle have following advantage it
One: higher continuation of the journey uses ability；Horsepower is stable；And clean environment firendly.It will be appreciated to those of skill in the art that above pin
To doping layered lithium manganate and preparation method thereof, positive electrode active materials, positive plate and the feature and advantage described by battery, still fit
For this vehicle, do not repeat them here.
Embodiment 1
Preparation method: use solid phase method, weigh LiOH H by a certain percentage2O、Mn2O3、Na2CO3And Al2O3Put into ball milling
Tank, adds ethanol, and ball milling 5 hours, after drying, in air atmosphere, 300 degrees Celsius carry out precalcining 8 hours, at nitrogen atmosphere
In 600 degrees Celsius carry out calcining 30 hours, synthesize Li0.98Na0.02Mn0.99Al0.01O2。
Embodiment 2
Prepare doping layered lithium manganate according to the method for embodiment 1, synthesize Li0.98Na0.02Mn0.97Al0.03O2.Distinguish
In, Ball-milling Time is 7 hours, and it is 6 hours with the time that the temperature of precalcining is 350 degrees Celsius, and the temperature of calcining is 650 degrees Celsius
It it is 15 hours with the time.
Embodiment 3
Prepare doping layered lithium manganate according to the method for embodiment 1, synthesize Li0.98Na0.02Mn0.95Al0.05O2.Distinguish
In, Ball-milling Time is 8 hours, and it is 5 hours with the time that the temperature of precalcining is 450 degrees Celsius, and the temperature of calcining is 750 degrees Celsius
It it is 20 hours with the time.
Embodiment 4
Prepare doping layered lithium manganate according to the method for embodiment 1, synthesize Li0.98Na0.02Mn0.93Al0.07O2.Distinguish
In, Ball-milling Time is 10 hours, and the temperature of precalcining is 500 degrees Celsius and the time is 4 hours, and the temperature of calcining is 800 Celsius
Degree and time are 6 hours.
Comparative example 1
Prepare unadulterated layered lithium manganate according to the method for embodiment 1, synthesize LiMnO2.Difference is, Ball-milling Time
Being 5 hours, it is 6 hours with the time that the temperature of precalcining is 350 degrees Celsius, and it is 12 with the time that the temperature of calcining is 750 degrees Celsius
Hour.
Embodiment 5
In this embodiment, the powder of the doping stratiform lithium manganate material of embodiment 1～4 is carried out XRD test.This implements
The XRD figure of example is as shown in Figure 1.
As seen from Figure 1, comparing with standard card PDF 35-0749, the peak position of all samples diffraction maximum is essentially identical,
Free from admixture peak occurs, shows that doped samples is stratiform orthohormbic structure, and foreign atom comes into stratiform LiMnO2Lattice
In, do not form impurity phase.And along with the increase of doping ratio, there is some difference for sample diffraction peak intensity.Wherein with Na:Al's
Mol ratio is the sample of 0.02:0.05, and in corresponding XRD figure, 2 θ are that 15 ° and 45 ° neighbouring peak types are the most sharp-pointed, and this ratio is described
Doping effect best.
Concrete, the cell parameter of embodiment 1～4 and comparative example 1 is as shown in the table, illustrate that the crystal of layered lithium manganate is tied
Structure is the most unchanged before and after doping, and only unit cell volume V slightly increases, and this expands the three-dimensional of lithium ion mobility to a certain extent
Passage, is more beneficial for the deintercalation of lithium ion, thus improves the reversible capacity of material:
Embodiment 6
In this embodiment, to embodiment 1～4 and the layered lithium manganate material of comparative example 1 first carry out smear, negative pole is lithium
Sheet, electrolyte are lithium hexafluoro phosphate, after being assembled into battery, then are circulated performance test.Loop test uses LAND battery to survey
Test system, INSTRUMENT MODEL is CT2001A.The condition of cycle performance test is: voltage range 2.0～4.3V, circulation is
0.1C.The cycle performance figure of this embodiment is as shown in Figure 2.
As seen from Figure 2, when 0.1C circulation, Na, Al doped samples first discharge specific capacity is above undoped p
LiMnO2Sample, and activation number of times minimizing, the most about circulation is activated for 15 times completely, illustrates that Na, Al doping can improve material
The electro-chemical activity of material.Wherein, the mol ratio of Na:Al is the sample Li of 0.02:0.050.98Na0.02Mn0.95Al0.05O2, at 0.1C
It is recycled to the 10th time the most fully activated, and specific discharge capacity is up to 201mAh/g, and there is less activation number of times；And
When 1C circulation, capability retention is 91.9%.Illustrating, the mol ratio of Na:Al is the sample of 0.02:0.05
Li0.98Na0.02Mn0.95Al0.05O2Doping vario-property best results.
Embodiment 7
In this embodiment, to Li in embodiment 60.98Na0.02Mn0.95Al0.05O2The assembled battery of material, individually follows
Ring performance test, loop test is carried out according to the condition that embodiment 6 is essentially identical.The 1st of this embodiment, 2,5,10,20 and
30 times circulation charge-discharge performance figure as it is shown on figure 3, and each charge/discharge capacity data are as shown in the table:
Wherein, 4V scope refers to 3.75～4.30V.
As seen from Figure 3, the variation tendency of this material charging platform and discharge platform and known undoped p LiMnO2Sample
Product are consistent.Having a longer charging platform at 3.5V during circulation first, from the beginning of second time circulation, 3.5V charging platform disappears
Lose.Then, charging platform rises, and discharge curve discharge platform occurs at about 4V.Understand, along with cycle-index in conjunction with upper table
Increasing, 4V scope specific discharge capacity proportion is gradually increased, and illustrates that 4V range of voltages platform is more and more obvious, the structure of material
Change more and more abundant.After circulating 30 times, compared with known undoped p sample (37.72%),
Li0.98Na0.02Mn0.95Al0.05O2Sample specific discharge capacity is to have reduced at 4V scope proportion (33.2%).
Li0.98Na0.02Mn0.95Al0.05O2The first discharge specific capacity of sample is 94.2mAh/g, after circulating 10 times,
Li0.98Na0.02Mn0.95Al0.05O2The specific discharge capacity of sample reaches 201mAh/g；And known unadulterated LiMnO2Sample
First discharge specific capacity is 48.4mAh/g, and after circulating 20 times, specific discharge capacity reaches 181.1mAh/g, so Na, Al doping can
To improve the electro-chemical activity of material, it is possible to reduce stratiform LiMnO2Activation number of times, improve stratiform LiMnO2Electric discharge specific volume
Amount.Li0.98Na0.02Mn0.95Al0.05O2Sample is followed successively by 63.2% at the coulombic efficiency of different cycle-indexes, 105.0%,
104.0%, 98.8%, 99.9% and 98.1%.
Embodiment 8
In this embodiment, to Li in embodiment 60.98Na0.02Mn0.95Al0.05O2The assembled battery of material, carries out exchange resistance
Anti-test.The electrochemical workstation that ac impedance measurement uses model to be CHI-660C is tested.The exchange resistance of this embodiment
As shown in Figure 4, and the kinetic parameter that the EIS before and after Equivalent Circuit Fitting discharge and recharge obtains is as shown in following table for anti-figure:
Can be found by Fig. 4 and upper table, after charge and discharge cycles, the Rct of this sample is reduced to 196.8 Ω, D by 269.6 Ω0By
1.387E-18cm2·s-1Increase to 8.665E-18cm2·s-1, this explains and circulate initial stage material discharging specific capacity meeting why
Increase.With known undoped p LiMnO2Sample is compared, before and after discharge and recharge, and Li0.98Na0.02Mn0.95Al0.05O2The lithium ion of sample
Diffusion coefficient is all higher than undoped p LiMnO2Sample, illustrates Na, Al doping LiMnO2Sample is more beneficial for the diffusion of lithium ion, should
This has higher capacity, consistent with charge-discharge test result.
Embodiment 9
In this embodiment, to Li in embodiment 60.98Na0.02Mn0.95Al0.05O2LiMnO with comparative example 12The group of material
The battery of dress, carries out contrasting cyclic voltammetry.The condition of cyclic voltammetry is: voltage range is 2.5～4.5V, scanning speed
Degree is 0.1mV/s.Cyclic voltammogram before the discharge and recharge of this embodiment is as it is shown in figure 5, cyclic voltammogram such as Fig. 6 after discharge and recharge
Shown in.
As seen from Figure 5, before discharge and recharge, doped samples Li0.98Na0.02Mn0.95Al0.05O2With LiMnO2Cyclic voltammogram
Identical, there are 2 asymmetric oxidoreduction peaks, and the peak area of adulterated lithium manganate is more than LiMnO2Sample, explanation
Li0.98Na0.02Mn0.95Al0.05O2Sample has higher capacity, and this is consistent with charge-discharge test result above.
As seen from Figure 6, after charge and discharge cycles, doped samples Li0.98Na0.02Mn0.95Al0.05O2Cyclic voltammogram at 4V
Near oxidoreduction peak occurs, illustrative material structure in charge and discharge process changes；And Li0.98Na0.02Mn0.95Al0.05O2
The peak area of sample oxidation peak and reduction peak is both greater than LiMnO2, this reaches 205.7mAh/g and height with this sample specific discharge capacity
In LiMnO2Consistent.
Sum up
Integrated embodiment 1～9 can draw, a kind of doping layered lithium manganate proposed by the invention and preparation method thereof, adopts
With the layered lithium manganate material of Solid phase synthesis Na, Al doping, o-LiMnO can be increased by Na, Al doping2Lattice body
Amass, expanded lithium ion mobility passage, improve the electro-chemical activity of layered lithium manganate.Charge-discharge test shows, Na, Al mix
Miscellaneous mol ratio is the sample Li of 0.02:0.050.98Na0.02Mn0.95Al0.05O2, there is more excellent chemical property.This sample exists
After 0.1C circulates 10 times, specific discharge capacity is up to 201mAh/g, and after circulating 20 times, specific discharge capacity is 205.7mAh/g, circulation
After 30 times, specific discharge capacity is maintained at 197.8mAh/g；Meanwhile, Na, Al doping reduces the charge transfer resistance of material, improves
Lithium ion diffusion coefficient, so the chemical property of layered lithium manganate material has been clearly not available raising after Can Za.
Thus, the layered lithium manganate of Na, Al doping, compared with the LiMn2O4 of undoped p sodium and aluminum, at least has following advantage
One of: higher electro-chemical activity；Higher capacitance；Higher specific discharge capacity；And two-dimensional layer in charge and discharge process
Structure is more stable.And this preparation method is simple, and process conditions are easily controllable, are suitable to extensive mass manufacture, the lowest one-tenth
The realization of this industrialized production.
In the description of this specification, reference term " embodiment ", " some embodiments ", " example ", " specifically show
Example " or the description of " some examples " etc. means to combine this embodiment or example describes specific features, structure, material or spy
Point is contained at least one embodiment or the example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be in office
One or more embodiments or example combine in an appropriate manner.Additionally, in the case of the most conflicting, the skill of this area
The feature of the different embodiments described in this specification or example and different embodiment or example can be tied by art personnel
Close and combination.
Although above it has been shown and described that embodiments of the invention, it is to be understood that above-described embodiment is example
Property, it is impossible to being interpreted as limitation of the present invention, those of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, revises, replaces and modification.
Claims (16)
1. one kind doping layered lithium manganate, it is characterised in that the doped chemical of described doping layered lithium manganate include sodium element and
Aluminium element.
Doping layered lithium manganate the most according to claim 1, it is characterised in that described doping layered lithium manganate has following
Chemical formula:
Li1-XNaXMn1-YAlYO2
Wherein, X=0.018～0.022, Y=0.01～0.07.
Doping layered lithium manganate the most according to claim 1, it is characterised in that described doping layered lithium manganate is for being selected from down
At least one of row:
Li0.98Na0.02Mn0.99Al0.01O2；
Li0.98Na0.02Mn0.97Al0.03O2；
Li0.98Na0.02Mn0.95Al0.05O2；And
Li0.98Na0.02Mn0.93Al0.07O2。
Doping layered lithium manganate the most according to claim 1, it is characterised in that described sodium element is by sodium carbonate and carbonic acid
Hydrogen sodium at least one provide.
Doping layered lithium manganate the most according to claim 1, it is characterised in that described aluminium element is to be provided by aluminium oxide
's.
6. a positive electrode active materials, it is characterised in that containing the doping layered lithium manganate described in any one of Claims 1 to 5.
7. the method for the doping layered lithium manganate that a kind is prepared described in any one of Claims 1 to 5, it is characterised in that including:
Mixture containing lithium compound, manganese compound, sodium compound and aluminium compound is calcined, in order to described in acquisition
Doping layered lithium manganate.
Method the most according to claim 7, it is characterised in that
Described lithium compound is Lithium hydrate；
Described manganese compound is manganese sesquioxide managnic oxide；
Described sodium compound is sodium carbonate or sodium bicarbonate；Or
Described aluminium compound is aluminium oxide.
Method the most according to claim 7, it is characterised in that described mixture is by entering under conditions of there is ethanol
Row ball milling 5～10 hours and obtain.
Method the most according to claim 7, it is characterised in that before described calcining, in advance to described mixture at sky
During atmosphere is enclosed, under 300～500 degrees Celsius, carry out precalcining 4～8 hours.
11. methods according to claim 7, it is characterised in that in nitrogen atmosphere, carry out institute under 600～850 degrees Celsius
State calcining 6～30 hours.
12. 1 kinds of anode sizing agents, it is characterised in that containing the positive electrode active materials described in claim 6.
13. 1 kinds of positive plates, it is characterised in that containing the positive electrode active materials described in claim 6.
14. 1 kinds of batteries, it is characterised in that include the positive plate described in claim 13.
15. 1 kinds of vehicles, it is characterised in that include the battery described in claim 14.
16. vehicles according to claim 15, it is characterised in that described vehicle is electric automobile or hybrid power vapour
Car.
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| CN113193188A (en) * | 2021-04-30 | 2021-07-30 | 云南脉冲科技有限公司 | Quaternary positive electrode material of sodium-ion battery and preparation method thereof |
| CN113812021A (en) * | 2021-08-11 | 2021-12-17 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
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