CN107394157A - A kind of method of modifying of the lithium-rich manganese-based anode material for lithium-ion batteries based on ascorbic acid - Google Patents
A kind of method of modifying of the lithium-rich manganese-based anode material for lithium-ion batteries based on ascorbic acid Download PDFInfo
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- CN107394157A CN107394157A CN201710591225.2A CN201710591225A CN107394157A CN 107394157 A CN107394157 A CN 107394157A CN 201710591225 A CN201710591225 A CN 201710591225A CN 107394157 A CN107394157 A CN 107394157A
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- 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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Abstract
The invention discloses a kind of method of modifying of the lithium-rich manganese-based anode material for lithium-ion batteries based on ascorbic acid, comprise the following steps：(1) ascorbic acid is dissolved in deionized water, forms ascorbic acid solution；(2) modified lithium-rich manganese-based anode material for lithium-ion batteries will be needed to be added in the ascorbic acid solution obtained after the step (1), carries out heating stirring processing, form suspension；(3) suspension obtained after step (2) is filtered, washed, dried, obtain the positive electrode powder handled through ascorbic acid；(4) the positive electrode powder that step (3) is handled by ascorbic acid is subjected to follow-up sintering processing in atmosphere, that is, obtains modified lithium-rich manganese-based anode material for lithium-ion batteries.The method of modifying can realize the regulation and control to lithium-rich manganese-based anode material for lithium-ion batteries body phase micro-structural in modifying process, can significantly improve stability and high rate performance of the positive electrode in cyclic process.
Description
Technical field
The invention belongs to modification of lithium ion battery anode material technical field, more particularly to a kind of richness based on ascorbic acid
The method of modifying of lithium manganese base lithium ion cell positive material.
Background technology
Lithium ion battery is succeeded in developing in nineteen ninety by Japanese Sony companies and is commercialized first first, and it is as a kind of high
Energy storage device, have the advantages that voltage is high, energy density is high, service life is long, good cycle and memoryless.Lithium ion battery
Positive electrode is the important component of secondary lithium battery, excessive family metal oxide or polyanion generally containing lithium
Compound, it serves not only as electrode material and participates in electrochemical reaction, lithium ion source is also used as, to the electrochemistry of lithium ion battery
Performance has a major impact.At present, the main development thinking of positive electrode is in LiCoO2、LiMn2O4、LiFePO4Deng the base of material
On plinth, develop all kinds of derived materials of correlation.The lithium-rich manganese-based anode material of high power capacity is currently research and small lot life
A kind of stratified material of production, can be expressed as xLi2MnO3·(1-x)LiMnyM1-yO2, the one kind of wherein M expressions in addition to Mn
Or two metal ion species.xLi2MnO3·(1-x)LiMnyM1-yO2It is a kind of α-NaFeO2Type solid-solution material, by stratiform
Li2MnO3And LiMO2(M=Mn, Ni, Co, Ni0.5Mn0.5, Cr, Ni1/3Co1/3Mn1/3, Fe ...) and composition.The material
There is higher specific discharge capacity, 250mAh/g specific capacity can be released under 0.2C multiplying powers, be current lithium ion cell positive material
The study hotspot of material.
Patent document CN102013481A (application numbers：201010522413.8) disclose a kind of spherical gradient lithium-rich anode
Material xLi2MnO3·(1-x)Li[Ni0.4Co0.2Mn0.4O2] (0.1≤x≤0.4) synthetic method, with existing commercialization ball
Shape presoma [Ni0.4Co0.2Mn0.4](OH)2Mn element claddings are carried out, heat treatment, 0.2C multiplying powers electricity are then mixed with lithium hydroxide
Discharge and recharge is flowed, first discharge specific capacity 242mAh/g, specific capacity is 221mAh/g after 50 circulations.But the material also exist with
Lower shortcoming：First charge-discharge irreversible capacity is big, high rate performance difference etc..
In order to solve the above problems, many researchers carry out Surface coating processing to lithium-rich manganese-based anode material, mainly
It is to utilize other metals or nonmetal oxide (such as MgO, SiO2, ZnO, Al2O3, ZrO2Deng) Surface coating is carried out, improve first
Secondary coulombic efficiency, charging and discharging capacity is improved, improve cycle performance and high rate performance.But clad and lithium-rich manganese-based anode material
Expect poor compatibility, interface impedance substantially increases, and after cladding, resistance increase is more, and high rate performance declines, and preparation technology answers
It is miscellaneous.Therefore the positive electrode that at present prepared by this kind of surface coating modification method can not be used widely.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention in background above technology and defect, by anti-
The modification of body phase in lithium-rich manganese-based anode material, and the original position of particle surface spinelle clad are realized in bad hematic acid solution processing
Prepare, be finally reached the purpose for being obviously improved material electrochemical performance.
In order to solve the above technical problems, technical scheme proposed by the present invention is a kind of rich lithium manganese based on ascorbic acid of offer
The method of modifying of base lithium ion cell positive material, comprises the following steps：
(1) ascorbic acid is dissolved in deionized water, forms ascorbic acid solution；
(2) modified lithium-rich manganese-based anode material for lithium-ion batteries will be needed to be added to obtain after the step (1) anti-
In bad hematic acid solution, heating stirring processing is carried out, forms suspension；
(3) suspension obtained after step (2) is filtered, washed, dried, obtain the positive pole handled through ascorbic acid
Material powder；
(4) the positive electrode powder that step (3) is handled by ascorbic acid is subjected to follow-up sintering processing in atmosphere, i.e.,
Obtain modified lithium-rich manganese-based anode material for lithium-ion batteries.
Above-mentioned method of modifying, it is preferred that in the step (1), the concentration of ascorbic acid solution is 1-20g/L.
Preferably, in the step (2), the formula of lithium-rich manganese-based anode material for lithium-ion batteries is：xLi2MnO3·(1-
x)LiMn1-y-zNiyCozO2, wherein 0<x<1,0≤y≤1,0≤z≤1,0<y+z≤1.
Preferably, in the step (2), lithium-rich manganese-based anode material for lithium-ion batteries resists with contained in ascorbic acid solution
The mass ratio of bad hematic acid is 1-10:1.
Preferably, in the step (2), the temperature of heating stirring is 60-95 DEG C, mixing time 10-1200min.
Preferably, in the step (3), dry temperature is 60 DEG C -150 DEG C.
Preferably, in the step (4), the temperature of follow-up sintering is 300-600 DEG C, time 30-240min.
During lithium-rich manganese-based anode material for lithium-ion batteries is mixed with ascorbic acid solution, ascorbic acid solution
In H+With the Li in positive electrode+Exchange, the H exchanged+Li in positive electrode can be occupied+Position, make positive electrode
Internal and surface forms a number of H+, can be by positive pole material at the same time because ascorbic acid has very strong reproducibility
Expect the high valence transition metal cation reduction on top layer and separate out, especially Mn4+To Mn3+And Mn2+, and Ni2+Due to inherently low
Valency, can not be reduced, so the process can cause the precipitation of material surface element-specific, cause material surface transition metal sun from
The change of son, forms the room of a number of transition-metal cation, along with the reduction of transition-metal cation, can exist
The precipitation of portion of material top layer Lattice Oxygen, forms a number of lattice defect.
Positive electrode after ascorbic acid is handled is in sintering process, the H inside positive electrode+Can be with the oxygen in air
With reference to generation water, make that a number of cation vacancy can be formed inside positive electrode, so, at high temperature metal sun from
A small amount of local migration can occur for son, such as part Ni2+Occupy Li+Position, form stable crystal structure, the structure can show
Write the stability for improving positive electrode in cyclic process.Added because positive electrode surface has a number of lattice defect
The presence in metal ion room in sintering process, positive electrode surface can be formed in situ the spinelle clad of densification, crystalline substance point
Stone clad can dramatically increase the electronics and lithium ion conductivity of material, to accelerate the redox on positive electrode surface
Journey, and then lift the high rate performance of positive electrode.
Compared with prior art, beneficial effects of the present invention are：
The method of modifying of the present invention, not only with technique is simple and easy to control, cost is cheap, environment-friendly (without using organic molten
Agent and poisonous and harmful reagent) the advantages that, and can be realized to lithium-rich manganese-based anode material for lithium-ion batteries in modifying process
The regulation and control of body phase micro-structural, it is embodied at following 2 points：(1) positive electrode after ascorbic acid is handled is in sintering process
In, the H inside positive electrode+Water can be generated with the oxygen reaction in air, positive electrode inside is formed a number of
Cation vacancy, so, a small amount of local migration, such as part can occur for metal cation in a certain temperature conditions
Ni2+Occupy Li+Position, form stable crystal structure, the structure can significantly improve positive electrode in cyclic process
Stability；(2), can be by the high valence transition metal cation on positive electrode top layer because ascorbic acid has very strong reproducibility
Reduction and precipitation, form a number of lattice defect, plus the presence in metal ion room in sintering process, positive electrode table
Face can be formed in situ the spinelle clad of densification, and the sharp stone clad of the crystalline substance can dramatically increase the electronics and lithium-ion electric of material
Conductance, to accelerate the oxidation-reduction process on positive electrode surface, and then lift the high rate performance of positive electrode.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
These accompanying drawings obtain other accompanying drawings.
Fig. 1 is the lithium-rich manganese-based anode material for lithium-ion batteries Li of the present invention1.2Mn0.54Ni0.13Co0.13O2Before modification (a),
The XRD of embodiment 1 (b) and embodiment 2 (c).
Fig. 2 is the lithium-rich manganese-based anode material for lithium-ion batteries Li of the present invention1.2Mn0.54Ni0.13Co0.13O2TEM before modified
Figure.
Fig. 3 is the lithium-rich manganese-based anode material for lithium-ion batteries Li of the present invention1.2Mn0.54Ni0.13Co0.13O2Embodiment 2 is modified
TEM figures afterwards.
Fig. 4 is the lithium-rich manganese-based anode material for lithium-ion batteries Li of the present invention1.2Mn0.54Ni0.13Co0.13O2Before modification (a),
The first charge-discharge curve of embodiment 1 (b) and embodiment 2 (c).
Fig. 5 is the lithium-rich manganese-based anode material for lithium-ion batteries Li of the present invention1.2Mn0.54Ni0.13Co0.13O2Before modification (a),
The cycle performance curve of embodiment 1 (b) and embodiment 2 (c).
Embodiment
For the ease of understanding the present invention, the present invention is done below in conjunction with Figure of description and preferred embodiment more complete
Face, meticulously describe, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical terms used hereinafter are generally understood that implication phase with those skilled in the art
Together.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention's
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
The present embodiment provides a kind of method of modifying of the lithium-rich manganese-based anode material for lithium-ion batteries based on ascorbic acid, institute
It is Li with initial lithium-rich manganese-based anode material for lithium-ion batteries1.2Mn0.54Ni0.13Co0.13O2, comprise the following steps：
(1) 0.5g ascorbic acids are dissolved in 100ml deionized waters, form the ascorbic acid solution of clarification；
(2) by 1g Li1.2Mn0.54Ni0.13Co0.13O2Positive electrode powder is added to ascorbic acid mixing obtained above
In liquid, heating stirring handles 10min under 95 DEG C of water bath conditions；
(3) above-mentioned suspension is filtered, washed, dried at 120 DEG C, to obtain the positive electrode handled through ascorbic acid
Powder；
(4) the positive electrode powder handled through ascorbic acid is put into Muffle furnace, subsequently burnt in air atmosphere
Knot processing, sintering temperature are 350 DEG C, sintering time 240min, that is, obtain modified lithium-rich manganese-based lithium ion cell positive material
Material.
Embodiment 2：
The present embodiment provides a kind of method of modifying of the lithium-rich manganese-based anode material for lithium-ion batteries based on ascorbic acid, institute
It is Li with initial lithium-rich manganese-based anode material for lithium-ion batteries1.2Mn0.54Ni0.13Co0.13O2, comprise the following steps：
(1) 0.5g ascorbic acids are dissolved in 100ml deionized waters, form the ascorbic acid solution of clarification；
(2) by 1g Li1.2Mn0.54Ni0.13Co0.13O2Positive electrode powder is added to ascorbic acid mixing obtained above
In liquid, heating stirring handles 30min under 95 DEG C of water bath conditions；
(3) above-mentioned suspension is filtered, washed, dried at 120 DEG C, to obtain the positive electrode handled through ascorbic acid
Powder；
(4) the positive electrode powder handled through ascorbic acid is put into Muffle furnace, subsequently burnt in air atmosphere
Knot processing, sintering temperature are 350 DEG C, sintering time 240min, that is, obtain modified lithium-rich manganese-based lithium ion cell positive material
Material.
From XRD spectrum as shown in Figure 1, XRD spectrum gives the partial enlarged drawing at part peak, modified positive pole
There is projection in the shoulder of material diffraction maximum, shows that modified positive electrode surface produces Spinel, illustrates ascorbic acid pair
The phase structure of material generates influence.The surface of positive electrode before modified is without Spinel it can be seen from Fig. 2 TEM figures,
And it can be seen from Fig. 3 TEM figures after ascorbic acid treats 30min, there is point in modified positive electrode surface
Spar phase.As shown in Figure 4, the first discharge specific capacity of positive electrode before modified is 269.7mAh/g, and efficiency is first
80.6%；The modified anode material first discharge specific capacity that embodiment 1 obtains is 288.6mAh/g, and efficiency is 88.7% first；
The modified anode material first discharge specific capacity that embodiment 2 obtains is 294.4mAh/g, and efficiency is 93.6% first.Can by Fig. 5
Know, positive electrode before modified circulates 100 circles, discharge capacitance 76.4% under 0.5C；The modification that embodiment 1 obtains
Positive electrode circulates 100 circles, discharge capacitance 76.7% under 0.5C；The modified anode material that embodiment 2 obtains exists
The circle of circulation 100, discharge capacitance 78.4% under 0.5C.As can be seen here, method of modifying of the invention can significantly improve
Stability and high rate performance of the positive electrode in cyclic process.
Embodiment 3：
The present embodiment provides a kind of method of modifying of the lithium-rich manganese-based anode material for lithium-ion batteries based on ascorbic acid, institute
It is Li with initial lithium-rich manganese-based anode material for lithium-ion batteries1.2Mn0.6Ni0.2O2, comprise the following steps：
(1) 0.2g ascorbic acids are dissolved in 100ml deionized waters, form the ascorbic acid solution of clarification；
(2) by 1g Li1.2Mn0.6Ni0.2O2Positive electrode powder is added in ascorbic acid mixed liquor obtained above,
Heating stirring handles 600min under 60 DEG C of water bath conditions；
(3) above-mentioned suspension is filtered, washed, dried at 80 DEG C, to obtain the positive electrode handled through ascorbic acid
Powder；
(4) the positive electrode powder handled through ascorbic acid is put into Muffle furnace, subsequently burnt in air atmosphere
Knot processing, sintering temperature are 500 DEG C, sintering time 30min, that is, obtain modified lithium-rich manganese-based lithium ion cell positive material
Material.
Embodiment 4：
The present embodiment provides a kind of method of modifying of the lithium-rich manganese-based anode material for lithium-ion batteries based on ascorbic acid, institute
It is Li with initial lithium-rich manganese-based anode material for lithium-ion batteries1.2Mn0.6Ni0.2O2, comprise the following steps：
(1) 0.6g ascorbic acids are dissolved in 100ml deionized waters, the concentration for forming clarification is 1-20g/L ascorbic acid
Solution；
(2) by 1g Li1.2Mn0.6Ni0.2O2Positive electrode powder is added in ascorbic acid mixed liquor obtained above,
Heating stirring handles 60min under 80 DEG C of water bath conditions；
(3) above-mentioned suspension is filtered, washed 1~5 time, dried at 100 DEG C, handled just through ascorbic acid with obtaining
Pole material powder；
(4) the positive electrode powder handled through ascorbic acid is put into Muffle furnace, subsequently burnt in air atmosphere
Knot processing, sintering temperature are 400 DEG C, sintering time 120min, that is, obtain modified lithium-rich manganese-based lithium ion cell positive material
Material.
Claims (7)
1. a kind of method of modifying of the lithium-rich manganese-based anode material for lithium-ion batteries based on ascorbic acid, comprises the following steps：
(1) ascorbic acid is dissolved in deionized water, forms ascorbic acid solution；
(2) modified lithium-rich manganese-based anode material for lithium-ion batteries will be needed to be added to the Vitamin C obtained after the step (1)
In acid solution, heating stirring processing is carried out, forms suspension；
(3) suspension obtained after step (2) is filtered, washed, dried, obtain the positive electrode handled through ascorbic acid
Powder；
(4) the positive electrode powder that step (3) is handled by ascorbic acid is subjected to follow-up sintering processing in atmosphere, that is, obtained
Modified lithium-rich manganese-based anode material for lithium-ion batteries.
2. method of modifying according to claim 1, it is characterised in that in the step (1), the concentration of ascorbic acid solution
For 1-20g/L.
3. method of modifying according to claim 1, it is characterised in that in the step (2), lithium-rich manganese-based lithium ion battery
The formula of positive electrode is：xLi2MnO3·(1-x)LiMn1-y-zNiyCozO2, wherein 0<x<1,0≤y≤1,0≤z≤1,0<y+
z≤1。
4. method of modifying according to claim 1, it is characterised in that in the step (2), lithium-rich manganese-based lithium ion battery
The mass ratio of positive electrode and contained ascorbic acid in ascorbic acid solution is 1-10:1.
5. method of modifying according to claim 1, it is characterised in that in the step (2), the temperature of heating stirring is
60-95 DEG C, mixing time 10-1200min.
6. method of modifying according to claim 1, it is characterised in that in the step (3), dry temperature be 60 DEG C-
150℃。
7. according to the method for modifying any one of claim 1-6, it is characterised in that in the step (4), follow-up sintering
Temperature be 300-600 DEG C, time 30-240min.
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| CN110676449B (en) * | 2019-10-14 | 2022-05-27 | 江苏正力新能电池技术有限公司 | Modified anode material and preparation method and application thereof |
| CN114678522A (en) * | 2022-04-25 | 2022-06-28 | 西安理工大学 | Modification method of lithium-rich manganese-based positive electrode material by regulating manganese vacancy and application of material |
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