CN107317024A - Lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis and preparation method thereof - Google Patents
Lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis and preparation method thereof Download PDFInfo
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- 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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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention particularly discloses a kind of lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, its chemical general formula xLi2MnO3·(1‑x)LiMO2, wherein, 0.1≤x≤0.9, M is Mn, Co and Ni；Including following raw material components：Manganese raw material, nickel raw material, cobalt raw material, lithium salts, complexing agent, vinasse and solvent；Also disclose its preparation method：Manganese raw material, nickel raw material, cobalt raw material and lithium salts are dissolved in solvent successively, complexing agent is then added, stirs, vinasse are added, then stirring carries out ultrasonic infiltration, negative pressure impregnation, drying, be finally heat-treated, produced successively to dissolving.The present invention is prepared the lithium-rich manganese-based layered lithium ion battery positive electrode of favorable dispersibility, is significantly improved specific discharge capacity, discharge platform stability and the high rate performance of anode material for lithium-ion batteries using the loose and porous structure of industrial waste vinasse.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of lithium-rich manganese-based Layered Lithium of vinasse auxiliary synthesis
Ion battery positive electrode and preparation method thereof.
Background technology
Environmental problem becomes increasingly conspicuous, and national many areas are shrouded among haze, cause environmental problem principal element it
One is the discharge of a large amount of vehicle exhausts, and electric automobile is to reduce one of approach of auto-pollution discharge.Lithium ion battery is technology
The Prospect of EVS Powered with Batteries of comparative maturity.The positive electrode of existing conventional lithium ion battery, it is impossible to meet high-energy-density
With the use requirement of high-specific-power.It would therefore be highly desirable to develop the more preferable electrode material of performance.
Manganese nickel cobalt ternary material (the LiNi of stratiform1-x-yMnxCoyO2), because with good cycle performance, height ratio capacity,
Preparation technology is simple, and high security etc. is paid close attention to.Through research, excessive Li is added in such material and just obtains lithium-rich manganese-based
Layered cathode material, such material can regard LiMO as2(M=Ni, Co, Fe, Ni1/2Mn1/2、Ni1/3Mn1/3Co1/3) and
Li2MnO3Solid solution, it has height ratio capacity, good heat endurance and a cycle performance, wide charging/discharging voltage scope and
Low cost, the advantages of pollution-free, such material is presently believed to be most potential electrode material.
For prior art, lithium-rich manganese-based stratified material is calcined within the temperature range of 850-900 DEG C and can tied
Brilliant good electro-chemical activity phase.But in up to 900 DEG C of temperature calcination, the particle size of material can constantly grow up, particle
Reunite abnormal serious, this can influence the chemical property of resulting materials.If a kind of reduction particle size can be found, suppress cluster of grains
Poly- technique, it is highly beneficial to the chemical property of raising material.The dispersiveness of powder body material is generally improved before material
Drive in body and add surfactant, but this additive is expensive, cost is too high.
The content of the invention
For problems of the prior art, it is an object of the invention to provide a kind of auxiliary synthesis of vinasse is lithium-rich manganese-based
Layered lithium ion battery positive electrode and preparation method thereof.The preparation method is with low cost, is remarkably improved lithium-rich manganese-based stratiform
The dispersiveness of anode material for lithium-ion batteries, and then the specific discharge capacity of anode material for lithium-ion batteries, discharge platform can be improved
Stability and high rate performance.
In order to achieve the above object, the present invention is achieved using following technical scheme.
(1) the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, it is characterised in that its chemistry is logical
Formula xLi2MnO3·(1-x)LiMO2, wherein, 0.1≤x≤0.9, M is Mn, Co and Ni.
(2) the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, it is characterised in that including following
Raw material components：Manganese raw material, nickel raw material, cobalt raw material, lithium salts, complexing agent, vinasse and solvent.
Preferably, the manganese raw material is manganese metal, Mn oxide, inorganic salts containing manganese, organic salt containing manganese or alkoxide containing manganese.
It is further preferred that the manganese raw material is manganese nitrate, manganese sulfate, formic acid manganese or manganese acetate.
Preferably, the nickel raw material is metallic nickel, nickel oxide, nickeliferous inorganic salts, nickeliferous organic salt or nickeliferous alkoxide.
It is further preferred that the nickel raw material is nickel acetate, nickel nitrate, nickel sulfate or nickel formate.
Preferably, the cobalt raw material is metallic cobalt, cobalt/cobalt oxide, inorganic salts containing cobalt, organic salt containing cobalt or alkoxide containing cobalt.
It is further preferred that the cobalt raw material is cobalt acetate, cobalt nitrate, cobaltous sulfate or cobaltous formate.
Preferably, the lithium salts is oxidate for lithium, inorganic salts containing lithium, organic salt containing lithium or containing lithium alkoxide.
It is further preferred that the lithium salts is lithium nitrate, lithium acetate, lithium formate, lithium hydroxide or lithium carbonate.
Preferably, the complexing agent includes alcamines complexing agent, hydroxycarboxylic acid complexing agent, organic phosphate complexing agent
Or polyacrylic complexing agent.
It is further preferred that the complexing agent is citric acid, acetylacetone,2,4-pentanedione, ethylenediamine tetra-acetic acid, sucrose or glucose.
Preferably, the vinasse are that brewery produces the industrial waste produced during wine.
Preferably, the solvent is deionized water, ethylene glycol ethyl ether or ethanol.
Preferably, in the lithium salts, manganese raw material, nickel raw material and cobalt raw material, when manganese raw material is that bivalent manganese raw material, nickel raw material are
When nickelous raw material, cobalt raw material are divalence cobalt raw material, wherein, Li+、Mn2+、Ni2+With Co2+Mol ratio be (1.1~1.9)：
(0.3997~0.9333)：(0.2997~0.0333)：(0.2997~0.0333).
Preferably, the chemical general formula of the lithium-rich manganese-based layered lithium ion battery positive electrode of the vinasse auxiliary synthesis is
xLi2MnO3·(1-x)LiMO2, M is Mn, Co and Ni；The mole of the complexing agent and the xLi2MnO3·(1-x)LiMO2
The ratio between middle M mole is 1:1~2:1.
(3) preparation method of the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, its feature exists
In following the steps below：Manganese raw material, nickel raw material, cobalt raw material and lithium salts are dissolved in solvent successively, complexing is then added
Agent, stirs, and adds vinasse, and then stirring carries out ultrasonic infiltration, negative pressure impregnation, drying, finally carry out successively to dissolving
Heat treatment, produces lithium-rich manganese-based layered lithium ion battery positive electrode.
Preferably, the temperature of the stirring is room temperature.
Preferably, during the ultrasound infiltration, the frequency of ultrasonic wave is 40KHz, and the time of ultrasound infiltration is 20-40min.
Preferably, the condition of the negative pressure impregnation is (- 0.08) MPa- (- 0.06) MPa.
Preferably, the time of the negative pressure impregnation is 8-16h.
Preferably, the heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere, first in 350-550
3-5h is calcined under the conditions of DEG C, then calcines under the conditions of 800-950 DEG C 12-24h.
Vinasse in the present invention, alias red wine dregs, fermented grain grain, the dregs of rice etc., it is remaining residue after the wine brewing such as rice, wheat, jowar.
Compared with prior art, beneficial effects of the present invention are：
The lithium-rich manganese-based layered lithium ion battery positive electrode of the vinasse auxiliary synthesis of the present invention, utilizes industrial waste vinasse
Loose and porous structure, prepare the lithium-rich manganese-based layered lithium ion battery positive electrode of favorable dispersibility, significantly improve
Specific discharge capacity, discharge platform stability and the high rate performance of anode material for lithium-ion batteries.This method effectively utilizes discarded money
Source, with low cost, easy marketing.
Brief description of the drawings
The present invention is described in further details with specific embodiment below in conjunction with the accompanying drawings.
The scanning electron for the lithium-rich manganese-based layered lithium ion battery positive electrode that Fig. 1 synthesizes for the vinasse auxiliary of embodiment 1
Microscope figure；
Fig. 2 is lithium-rich manganese-based layered cathode active material the filling under different current densities that synthesis is aided in without vinasse
Discharge curve；In figure, abscissa is the specific capacity of material, and unit is mAh/g；Ordinate is voltage, and unit is V；
Fig. 3 aids in the lithium-rich manganese-based layered lithium ion battery positive electrode of synthesis in different electric currents for the vinasse of embodiment 1
Charging and discharging curve figure under density；In figure, abscissa is the specific capacity of material, and unit is mAh/g；Ordinate is voltage, unit
For V；
Fig. 4 is to aid in the lithium-rich manganese-based layered cathode active material of synthesis to be aided in the vinasse of embodiment 1 without vinasse
Circulation figure of the lithium-rich manganese-based layered lithium ion battery positive electrode of synthesis under different current densities；In figure, abscissa
For the circulation number of turns, ordinate is the specific capacity of material, and unit is mAh/g.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
It will be appreciated that the following example is merely to illustrate the present invention, and it is not construed as limiting the scope of the present invention.
Embodiment 1
A kind of lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, its preparation method is as follows：
(1) by formic acid manganese 0.0667moL, cobaltous formate 0.0167moL, nickel formate 0.0167moL, lithium formate 0.015moL,
It is dissolved in successively in 20mL ethanol, adds 0.1mol acetylacetone,2,4-pentanediones, is stirred at room temperature to dissolving, forms homogeneous solution；
(2) 5g vinasse are weighed, the solution in (1) is poured into vinasse, are stirred, and under 40KHz ultrasonic frequency
Ultrasound infiltration 20min, then the negative pressure impregnation 8h under conditions of -0.06MPa, drying, are finally placed in Muffle furnace, 900
12h is calcined at DEG C, the powdered lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, its chemical formula is produced
For：0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2。
Embodiment 2
A kind of lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, its preparation method is as follows：
(1) by manganese acetate 0.016moL, cobalt acetate 0.012moL, nickel acetate 0.012moL and lithium acetate 0.044moL, according to
It is secondary to be dissolved in 25mL ethylene glycol ethyl ethers, 0.04moL ethylenediamine tetra-acetic acids are added, is stirred at room temperature to dissolving, is formed homogeneous
Solution；
(2) 8g vinasse are weighed, the solution in (1) is poured into vinasse, are stirred, and under 40KHz ultrasonic frequency
Ultrasound infiltration 40min, then the negative pressure impregnation 12h under conditions of -0.08MPa, drying, are finally placed in Muffle furnace, 800
24h is calcined at DEG C, the lithium-rich manganese-based layered cathode material of vinasse auxiliary synthesis is finally obtained, its chemical formula is：0.1Li2MnO3·
0.9LiMn1/3Ni1/3Co1/3O2。
Embodiment 3
A kind of lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, its preparation method is as follows：
(1) lithium nitrate 0.038moL, manganese nitrate 0.0187moL, nickel nitrate 0.00067moL and cobalt nitrate are weighed respectively
0.00067moL, is dissolved in 25mL deionized waters, adds 2moL glucose and makees complexing agent, is stirred at room temperature to dissolving, is formed
Homogeneous solution；
(2) 8g vinasse are weighed, the solution in (1) is poured into vinasse, are stirred, and under 40KHz ultrasonic frequency
Ultrasound infiltration 40min, then the negative pressure impregnation 16h under conditions of -0.08MPa, drying, are finally placed in Muffle furnace, 950 DEG C
Lower calcining 12h, obtains the powdered lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, and its chemical formula is：
0.9Li2MnO3·0.1LiMn1/3Ni1/3Co1/3O2。
Embodiment 4
A kind of lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, its preparation method is as follows：
(1) by manganese sulfate 0.0233moL, nickel sulfate 0.0133moL, cobaltous sulfate 0.0133moL and 0.06moL lithium hydroxide
Sour lithium is dissolved in 30ml deionized waters successively, and it is complexing agent to add 0.05mol sucrose, is stirred at room temperature to form homogeneous molten
Liquid；
(2) 12g vinasse are weighed, the solution in (1) is poured into vinasse, are stirred, and under 40KHz ultrasonic frequency
Ultrasound infiltration 30min, then the negative pressure impregnation 10h under conditions of -0.08MPa, drying, are finally placed in Muffle furnace, 900 DEG C
Lower calcining 12h, obtains the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, and it is powdered, its chemistry
Formula is：
0.2Li2MnO3·0.8LiMn1/3Ni1/3Co1/3O2。
Embodiment 5
A kind of lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, its preparation method is as follows：
(1) lithium nitrate 0.12moL, manganese nitrate 0.0533moL, nickel nitrate 0.0133moL and cobalt nitrate are weighed respectively
0.0133moL, is dissolved in 25mL deionized waters, adds 2moL citric acids and makees complexing agent, adjusts pH to 8 with ammoniacal liquor, stir at room temperature
Mix to being dissolved into homogeneous solution；
(2) 15g vinasse are weighed, the solution in (1) is poured into vinasse, are stirred, and under 40KHz ultrasonic frequency
Ultrasound infiltration 40min, then the negative pressure impregnation 12h under conditions of -0.08MPa, drying, are finally placed in Muffle furnace, 950 DEG C
Lower heating 12h, obtains the powdered lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, and its chemical formula is：
0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2。
To the electrochemistry of the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis of above-mentioned all embodiments
Performance is detected, as a result as follows：
Fig. 1 is the scanning electron for the lithium-rich manganese-based layered cathode active material of vinasse auxiliary synthesis that embodiment 1 is prepared
Microscope figure.As seen from the figure, the particle diameter of the lithium-rich manganese-based layered cathode active material of vinasse auxiliary synthesis is left in 120nm
The right side, the favorable dispersibility of particle it can be seen from scanning electron microscope (SEM) photograph, without obvious agglomeration.
Other embodiment ESEM result shows that its vinasse prepared auxiliary synthesizes the active material of lithium-rich manganese-based layered cathode
The particle diameter equal control of material is in 120nm or so, favorable dispersibility, without obvious agglomeration.
Fig. 2 is lithium-rich manganese-based layered cathode active material the filling under different current densities that synthesis is aided in without vinasse
Discharge curve.Fig. 3 aids in the lithium-rich manganese-based layered lithium ion battery positive electrode of synthesis in different electricity for the vinasse of embodiment 1
Charging and discharging curve figure under current density.In figure, curve represents charge data respectively into the curve of ascendant trend, and curve becomes into decline
The curve of gesture represents to circulate discharge data respectively.Knowable to Fig. 2 and Fig. 3 contrasts, the lithium ion cell positive for aiding in synthesizing by vinasse
The platform and specific discharge capacity of active material make moderate progress, and change gentle and more square, capacity attenuation is slow.With current density
Increase, aids in the platform of the lithium-rich manganese-based layered cathode active material of synthesis to decay quickly without vinasse, the continuous steepening of curve,
Under 400mA/g current density, capacity only has 78mAh/g；The not having property under 1000mA/g and 2000mA/g current density
Energy.By contrast, the platform decay of the lithium-rich manganese-based layered cathode active material after vinasse aid in synthesis is slack-off,
Electric discharge also maintains 103mAh/g specific capacity under 400mA/g current density, be put down under 1000mA/g current density
Platform, discharge capacity is 72mAh/g.It follows that by vinasse aid in synthesis positive electrode active materials discharge platform and
Specific discharge capacity is improved.
Fig. 4 is to aid in the lithium-rich manganese-based layered cathode active material of synthesis to be aided in the vinasse of embodiment 1 without vinasse
Circulation figure of the lithium-rich manganese-based layered lithium ion battery positive electrode of synthesis under different current densities.As seen from the figure, exist
Current density is passing through in 20mA/g cyclic process, to aid in the positive electrode active materials capacity attenuation of synthesis very fast without vinasse
Cross after vinasse auxiliary is synthesized and have clear improvement.It can be seen that material can be significantly improved after vinasse are scattered
Specific discharge capacity.Become apparent under high current density.Specific discharge capacity under contrast high current density is it can be found that when electricity
When current density is 1000mA/g, also to maintain 65mAh/g by scattered positive electrode capacity, and aid in synthesizing without vinasse
The specific capacity of positive electrode be almost 0；Under 2000mA/g current density, the lithium-rich manganese-based stratiform of vinasse auxiliary synthesis is just
Pole active material capacity also has 33.68mAh/g.Thus illustrate that using vinasse auxiliary synthesis lithium ion battery material can be obviously improved
The high rate performance of material.
Embodiment 2, the lithium-rich manganese-based layered lithium ion of vinasse auxiliary synthesis prepared by embodiment 3, embodiment 4 and embodiment 5
Cell positive material, its chemical property and embodiment 1 quite, equally show that height ratio capacity, platform are more square and decay slows down
With powerful advantage.
The dispersiveness that the present invention possesses using the loose and porous structure of vinasse is electric to improve lithium-rich manganese-based layered lithium ion
The dispersiveness of pond positive electrode, so improve lithium-rich manganese-based layered lithium ion battery positive electrode electrochemical stability and times
The electrode material of rate excellent performance；And vinasse are that brewery produces the trade waste produced during wine, and the present invention is also realized
The recycling of resource, reduces environmental pollution.
Although the present invention is described in detail with a general description of the specific embodiments in this specification,
But on the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.
Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed model
Enclose.
Claims (10)
1. the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, it is characterised in that its chemical general formula
xLi2MnO3·(1-x)LiMO2, wherein, 0.1≤x≤0.9, M is Mn, Co and Ni.
2. the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, it is characterised in that including following raw material group
Point：Manganese raw material, nickel raw material, cobalt raw material, lithium salts, complexing agent, vinasse and solvent.
3. the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis according to claim 2, its feature
It is, the manganese raw material is manganese metal, Mn oxide, inorganic salts containing manganese, organic salt containing manganese or alkoxide containing manganese；The nickel raw material is
Metallic nickel, nickel oxide, nickeliferous inorganic salts, nickeliferous organic salt or nickeliferous alkoxide；The cobalt raw material be metallic cobalt, cobalt/cobalt oxide,
Inorganic salts containing cobalt, organic salt containing cobalt or alkoxide containing cobalt；The lithium salts is oxidate for lithium, inorganic salts containing lithium, organic salt containing lithium or contained
Lithium alkoxide；The complexing agent includes alcamines complexing agent, hydroxycarboxylic acid complexing agent, organic phosphate complexing agent or polypropylene
Acids complexing agent；The solvent is deionized water, ethylene glycol ethyl ether or ethanol.
4. the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis according to claim 2, its feature
It is, the vinasse are that brewery produces the industrial waste produced during wine.
5. the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis according to claim 2, its feature
It is, in the lithium salts, manganese raw material, nickel raw material and cobalt raw material, when manganese raw material is that bivalent manganese raw material, nickel raw material are that nickelous is former
When material, cobalt raw material are divalence cobalt raw material, wherein, Li+、Mn2+、Ni2+With Co2+Mol ratio be (1.1~1.9)：(0.3997~
0.9333)：(0.2997~0.0333)：(0.2997~0.0333).
6. the preparation method of the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis, it is characterised in that according to
Following steps are carried out：Manganese raw material, nickel raw material, cobalt raw material and lithium salts are dissolved in solvent successively, complexing agent is then added, stirring is equal
It is even, vinasse are added, then stirring carries out ultrasonic infiltration, negative pressure impregnation, drying, be finally heat-treated, i.e., successively to dissolving
Obtain lithium-rich manganese-based layered lithium ion battery positive electrode.
7. the preparation side of the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis according to claim 6
Method, it is characterised in that during the ultrasound infiltration, the frequency of ultrasonic wave is 40KHz, and the time of ultrasound infiltration is 20-40min.
8. the preparation side of the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis according to claim 6
Method, it is characterised in that the condition of the negative pressure impregnation is (- 0.08) MPa- (- 0.06) MPa.
9. the preparation side of the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis according to claim 6
Method, it is characterised in that the time of the negative pressure impregnation is 8-16h.
10. the preparation of the lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis according to claim 6
Method, it is characterised in that the heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere, first in 350-
3-5h is calcined under the conditions of 550 DEG C, then calcines under the conditions of 800-950 DEG C 12-24h.
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