CN109437334A - A kind of preparation method of high magnification nickel cobalt codope lithium manganate having spinel structure material - Google Patents
A kind of preparation method of high magnification nickel cobalt codope lithium manganate having spinel structure material Download PDFInfo
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- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/54—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [Mn2O4]-, e.g. Li(NixMn2-x)O4, Li(MyNixMn2-x-y)O4
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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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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- 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
- H01M4/52—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 present invention relates to a kind of preparation methods of high magnification nickel cobalt codope lithium manganate having spinel structure material.Specific method is to prepare dopant dispersion, fuel agent dispersing liquid, mix and prepare product, reaction mixture slurry is obtained after mechanical stirring is uniform, it is subsequently placed in porcelain crucible, it places into the Muffle furnace that preset temperature is 500 DEG C, 1 h of combustion reaction in air atmosphere, taking-up cools down in air, and 650 DEG C of 6 h of Muffle kiln roasting are put into after grinding, obtains LiNi after taking out cooling in air, grindingxCo0.05Mn1.95‑xO4(x=0.01-0.10) positive electrode.The high rate performance for the nickel cobalt codope lithium manganate having spinel structure positive electrode that the present invention synthesizes is substantially better than LiCo made from other methods0.05Mn1.95O4, the present invention is using solid-liquid water mixed system, and mechanical stirring incorporation time is short, and reaction mixture slurry does not need drying, directly heats carry out combustion reaction, the preparation method is simple, quick, and electrochemical performance.
Description
Technical field
The present invention relates to a kind of high magnification nickel cobalt codope LiMn2O4 LiMn2O4Positive electrode and the nickel cobalt codope manganese
Sour lithium LiMn2O4The preparation method of material belongs to anode material for lithium-ion batteries technical field.
Background technique
Lithium ion battery has many advantages, such as height ratio capacity, high-energy-density as new green environment protection power supply, is portable set
The ideal source of standby and electronic and hybrid-electric car etc..And spinel-type LiMn2O4, high-energy-density environmental-friendly with its, manganese
The advantages that reserves are big becomes one of anode material for lithium-ion batteries research hotspot.But due to the defect of oxygen, manganese dissolution and
Jahn-Teller effect causes lithium manganate battery decaying very fast, and poor cycle performance and electrochemical stability greatly limit
Its industrialization.To improve the stable circulation performance of material to spinel-type LiMn2O4It is to improve it by bulk phase-doped be modified
One of effective way of performance, these substitutional ions can be Ni, Co, Fe, Al, Mg, Cu etc..Studies have shown that doping not only may be used
To improve the disordering degree of lattice, enhance the stability of spinel structure, and when the valence state of Doped ions≤3, can drop
Low Mn3+The content of ion improves the structural stability of material to inhibit Jahn-Teller effect.The present invention to spinelle into
The doping vario-property of row nickel and cobalt ions generates a kind of common substituting effect, effectively improves high rate performance, improves its cyclicity
Energy.For doping and composite doping modification measure, numerous researchs are reported.Such as Xiang M. W. et al., it is entitled
“Rapid synthesis of high-cycling performance LiMgxMn2–xO4 (x≤0.20) cathode
materials by a low-temperature solid-state combustion method”,《Electrochimica
Acta", 2014, 125:524-529;Ding X.N. et al., entitled " Electrochemical evaluation of
LiAl0.05Ni0.05Mn1.9O4 cathode material synthesized via electrospinning method”,
"Journal of Alloys and Compounds", 2015,632:147-151;Zhao H. et al., it is entitled
“Improved electrochemical performance of spinel-type LiMn1.90Mg0.05Si0.05O4
cathode materials synthesized by a citric acid-assisted sol-gel method”,
"Journal of Solid State Electrochemistry", 2015,19(4):1015-1026;Zhao H. et al.,
Entitled " Enhanced elevated-temperature performance of LiAlxSi0.05Mg0.05Mn1.90-xO4 (0
≤x≤0.08) cathode materials for high-performance lithium-ion batteries”,
"Electrochimica Acta", 2016, 199:18-26;Zhao H.Y. et al., entitled " Enhanced cycling
stability of LiCuxMn1.95-xSi0.05O4 cathode material obtained by solid-state
method","Materials", 2018, 11(8), 1302;Kadoma Y et al., entitled " Synthesis and
electrochemical properties of LiNi0.5-xMn1.5-xM2xO4 (M=Al, Cr) cathode materials
prepared by PVA method","Electrochemistry", 2010,78(8):658-661;Milewska A etc.
People, entitled " Structural, transport and electrochemical properties of LiNi0.5- yCuyMn1.5O4-δ spinel cathode materials” 《Solid State Ionics》, 2014, 267:27-31.
CN102903902A discloses a kind of spinel type lithium manganate electrode material, uses any two in Al, Mg, Cr, Co
Kind, LiMn is mixed as doped chemical2O4In, forming molecular formula is LiMn2-x-yMxNyO4Doped spinel type LiMn2O4 and obtain
More excellent chemical property is obtained, but uses the process of method production precursor cumbersome；
CN103474647A discloses a kind of Li(1+x)Mn(2-x-y)MyO4Preparation method (the wherein M of lithium manganate having spinel structure material
For doping vario-property agent, and 0≤x≤0.20,0≤y≤0.25), preparation process is surface-treated to reduce alkali content step, but
It is more difficult to accurately control alkali content；
CN104393276A discloses a kind of chromium-nickel co-doped LiMn2O4 synthetic method, improves crystal property, the electric discharge ratio of material
Capacity and energy density, but maturing temperature is too high, overlong time；
It is one of Al, Ni, Co, Cr, Fe, Cu, Zr and Y or two kinds that CN104319393A, which discloses a kind of doping metals,
Composite mixed spinel type lithium manganate electrode material, which has excellent chemical property, but it is not easily-controllable to adjust pH value
It makes and the reaction time is long；
CN105304894A discloses the preparation method that a kind of magnesium bromine is co-doped with lithium manganate having spinel structure, and positive electrode crystallization is good
Well, crystal grain is tiny and its chemical property is increased, but processing technology is complicated, reaction temperature is high；
A kind of method that CN105428641A discloses aluminium, sodium collaboration doping prepares manganate cathode material for lithium, obtained material tool
There are good high rate performance and a cyclical stability, but the reaction time is long, reaction temperature is high；
CN106450285A discloses a kind of preparation method of double-doped lithium manganate having spinel structure of sodium magnesium, but preparation process is complicated,
Time, time-consuming；
CN106784657A discloses a kind of LiNaxMn2yFeyO4Manganate cathode material for lithium synthetic method, but use the electrode
The high rate capability of the lithium ion battery of material is poor, is difficult to meet the requirement of high-power lithium ion battery；
CN108258202A discloses a kind of manganic acid lithium electrode material and its preparation process for adulterating terbium and dysprosium, but vacuum calcining
Temperature is high, and the reaction time is long.
Summary of the invention
The present invention uses solid-liquid water mixed system, and mechanical stirring incorporation time is short, and reaction mixture slurry does not need drying,
Carry out combustion reaction is directly heated, preparation method is simple, quick, and electrochemical performance.
It is an object of the present invention to provide one kind to inhibit Jahn-Teller effect, enhancing lithium manganate having spinel structure stable structure
On the basis of property, prepare a kind of stable structure, high rate capability nickel cobalt codope lithium manganate having spinel structure positive electrode.
The present invention relates to a kind of preparation methods of high magnification nickel cobalt codope lithium manganate having spinel structure material.
The synthetic method using lithium carbonate as lithium source, manganese carbonate is manganese source, nickel acetate is nickel dopant and cobalt carbonate is that cobalt is mixed
Miscellaneous dose, according to stoichiometric ratio Li:Mn:Ni:Co=1:(1.95-x): x:0.05 (x=0.01-0.10) proportion is former
Material, 5 wt.% citric acids of adding raw materials gross mass are fuel.It is characterized in that the step of this method, is as follows:
A, nickel dopant dispersion is prepared
According to stoichiometric ratio Li:Mn:Ni:Co=1:(1.95-x): x:0.05 (x=0.01-0.10) weighs solid
Nickel acetate, then the quality of nickel acetate, the volume of deionized water in terms of milliliter are 1:8- according to quality and volume ratio in gram
15, nickel acetate is added in deionized water, nickel acetate is completely dissolved, obtains the dispersion liquid of uniform nickel dopant；
B, fuel agent dispersing liquid is prepared
The ratio of deionized water is 1:2-10 according to citric acid in gram and in terms of milliliter, and lemon acid fuel is added to deionized water
In, sufficiently dissolution obtains a kind of uniform fuel agent dispersing liquid；
C, it mixes
According to stoichiometric ratio Li:Mn:Co=1:(1.95-x): 0.05 (x=0.01-0.10) weighing solid lithium carbonate,
Manganese carbonate and cobalt carbonate are placed in a beaker, then according to stoichiometric ratio Li:Mn:Ni:Co=1:(1.95-x): x:
0.05 (x=0.01-0.10), the accurate nickel dopant dispersion (obtained by step A) being added in terms of milliliter, then accurate addition is with milli
The lemon acid fuel agent dispersing liquid (obtained by step B) of meter is risen, last mechanical stirring certain time obtains a kind of homogeneous mixture slurry
Material；
D, product is prepared
Obtained homogeneous mixture slurry is moved into porcelain crucible, is then directly placed into the porcelain crucible equipped with mixture paste
Preset temperature is 500 DEG C of Muffle furnaces, until 1 h of combustion reaction occurs, taking-up natural cooling is obtained for the heating in air atmosphere
Black combustion product.Then, it is put into 650 DEG C of Muffle furnaces after product of roasting being ground, 6 h are roasted in air atmosphere, takes out
Product LiNi is obtained in air after natural cooling, grindingxCo0.05Mn1.95-xO4(x=0.01-0.10) positive electrode powder.
Using the D8 ADVANCE type X-ray diffractometer of X-ray diffraction analysis instrument, such as Bruker company, with Cu-K α target
It is 10-70 ° and the item of 4 °/min of sweep speed in 40 kV of operating voltage, 40 mA of operating current, 2 θ of scanning range for radiation source
Test analysis under part, the results are shown in attached drawings 1.Determined by the XRD analysis of testing of materials show the product be it is single-phase, without miscellaneous
Matter, has spinel structure, and space group isFd3m, referring specifically to attached drawing 1.
The product that synthetic method of the present invention synthesizes has carried out conventional electron microscope analysis.Using FEI Co., the U.S.
450 type field emission scanning electron microscope of NOVA NANOSEM and JEM-2100 transmission electron microscope, and in conventional item
It is tested under part.Attached drawing 2 (a) is LiNi0.01Co0.05Mn1.94O4SEM figure, which is 100-150 nm, thoroughly
Electron microscopic findings are penetrated to be listed in attached drawing 2 (b) and Fig. 2 (c).
It is tested charge and discharge 1000 times, is obtained at 1 C multiplying power with 25 DEG C of temperature using Land constant current charge-discharge test macro
Obtain nickel cobalt codope LiNixCo0.05Mn1.95-xO4The charge-discharge performance of (x=0.01-0.10) positive electrode, specifically
LiCo0.05Mn1.95O4And LiNi0.01Co0.05Mn1.94O4Positive electrode charge-discharge performance is referring to attached drawing 3 (a).
It is tested charge and discharge 1000 times, is obtained at 5 C multiplying powers with 25 DEG C of temperature using Land constant current charge-discharge test macro
Obtain nickel cobalt codope LiNixCo0.05Mn1.95-xO4The charge-discharge performance of (x=0.01-0.10) positive electrode, specifically
LiCo0.05Mn1.95O4And LiNi0.01Co0.05Mn1.94O4Positive electrode charge-discharge performance is referring to attached drawing 3 (b).
It is tested charge and discharge 1000 times at 10 C multiplying powers with 25 DEG C of temperature using Land constant current charge-discharge test macro,
Obtain nickel cobalt codope LiNixCo0.05Mn1.95-xO4The charge-discharge performance of (x=0.01-0.10) positive electrode, specifically
LiCo0.05Mn1.95O4And LiNi0.01Co0.05Mn1.94O4Positive electrode charge-discharge performance is referring to attached drawing 3 (c).
It is tested charge and discharge 1000 times at 15 C multiplying powers with 25 DEG C of temperature using Land constant current charge-discharge test macro,
Obtain nickel cobalt codope LiNixCo0.05Mn1.95-xO4The charge-discharge performance of (x=0.01-0.10) positive electrode, specifically
LiCo0.05Mn1.95O4And LiNi0.01Co0.05Mn1.94O4Positive electrode charge-discharge performance is referring to attached drawing 3 (d).
It is tested and is filled at 20 C, 30 C and 40 C multiplying powers and 25 DEG C of temperature using Land constant current charge-discharge test macro
Electric discharge 1000 times, specific LiNi0.01Co0.05Mn1.94O4The charge-discharge performance of positive electrode is referring to attached drawing 3 (e).
Using Land constant current charge-discharge test macro in 1,5,10,15,20,30,40,20,10 C multiplying powers and temperature 25
DEG C when distinguish each test charge and discharge 5 times, specific LiCo0.05Mn1.95O4And LiNi0.01Co0.05Mn1.94O4Positive electrode it is forthright again
It can be referring to attached drawing 3 (f).
Detailed description of the invention
Fig. 1 is the XRD for the ion co-doped front and back manganate cathode material for lithium of nickel cobalt that embodiment 1 and comparative example 1 obtain
Figure.
Fig. 2 is the LiNi that embodiment 1 obtains0.01Co0.05Mn1.94O4The scanning electron microscope (SEM) of positive electrode and thoroughly
Penetrate electron microscope (TEM) figure.In figure:
(a) LiNi0.01Co0.05Mn1.94O4The scanning electron microscope diagram of positive electrode；
(b) LiNi0.01Co0.05Mn1.94O4The transmission electron microscope figure of positive electrode；
(c) LiNi0.01Co0.05Mn1.94O4The high resolution transmission electron microscopy of positive electrode.
Fig. 3 is the electrical property for the ion co-doped front and back manganate cathode material for lithium of nickel cobalt that embodiment 1 and comparative example 1 obtain
It can figure.In figure:
(a) cycle performance figure at 1 C, 25 DEG C is tested using constant current charge-discharge；
(b) cycle performance figure at 5 C, 25 DEG C is tested using constant current charge-discharge；
(c) cycle performance figure at 10 C, 25 DEG C is tested using constant current charge-discharge；
(d) cycle performance figure at 15 C, 25 DEG C is tested using constant current charge-discharge；
(e) cycle performance figure at 20 C, 30 C, 40 C, 25 DEG C is tested using constant current charge-discharge；
(f) electrical in the multiplying power at 1,5,10,15,20,30,40,20,10 C and 25 DEG C using constant current charge-discharge test
It can figure.
The lithium manganate having spinel structure for the nickel and cobalt ions doping that embodiment 1 obtains in figure is denoted as LNCM；Comparative example 1
To single doping cobalt ions lithium manganate having spinel structure be denoted as LCM.
Specific embodiment
It will be better understood that the present invention by following embodiments.
Embodiment 1: nickel cobalt adulterated lithium manganate positive electrode synthesis of the present invention
The implementation steps of the embodiment are as follows:
The synthetic method using lithium carbonate as lithium source, manganese carbonate is manganese source, nickel acetate is nickel dopant and cobalt carbonate for cobalt dopant,
According to stoichiometric ratio Li:Mn:Ni:Co=1:1.94:0.01:0.05 match raw material, the 5 of adding raw materials gross mass
Wt.% citric acid is fuel.It is characterized in that the step of this method, is as follows:
A, nickel dopant dispersion is prepared
According to stoichiometric ratio Li:Mn:Ni:Co=1:1.94:0.01:0.05 weigh solid nickel acetate, then with gram
The quality of nickel acetate is counted, the volume of deionized water in terms of milliliter is 1:10 according to quality and volume ratio, nickel acetate is added to
In deionized water, it is completely dissolved nickel acetate, obtains the dispersion liquid of uniform nickel dopant；
B, fuel agent dispersing liquid is prepared
The ratio of deionized water is 1:10 according to citric acid in gram and in terms of milliliter, and lemon acid fuel is added in deionized water,
Sufficiently dissolution obtains a kind of uniform fuel agent dispersing liquid；
C, it mixes
0.8261 g lithium carbonate, 4.9856 g manganese carbonates are weighed according to stoichiometric ratio Li:Mn:Co=1:1.94:0.05
It is placed in a beaker with 0.1331 g cobalt carbonate, then according to stoichiometric ratio Li:Mn:Ni:Co=1:1.94:0.01:
0.05, the accurate nickel dopant dispersion (containing 0.0558 g nickel acetate) being added in terms of milliliter, then accurate addition is in terms of milliliter
Lemon acid fuel agent dispersing liquid (contains 0.30 g citric acid), obtains a kind of homogeneous mixture slurry after 2 h of mechanical stirring；
D, product is prepared
Obtained homogeneous mixture slurry is moved into porcelain crucible, is then directly placed into the porcelain crucible equipped with mixture paste
Preset temperature is 500 DEG C of Muffle furnaces, until 1 h of combustion reaction occurs, taking-up natural cooling is obtained for the heating in air atmosphere
Black combustion product.Then, it is put into 650 DEG C of Muffle furnaces after product of roasting being ground, 6 h are roasted in air atmosphere, takes out
Product LiNi is obtained in air after natural cooling, grinding0.01Co0.05Mn1.94O4Positive electrode powder.
1 C specific discharge capacity is 127 mAh/g, and capacity retention ratio is 90% after circulation 100 times；5 C, 10 C, 15 C times
Specific discharge capacity is respectively as follows: 122.6 mAh/g, 108.3 mAh/g, 105 mAh/g under the conditions of rate；20 C, 30 C, 40 C are put
Electric specific capacity is respectively as follows: 94.9 mAh/g, 76.1 mAh/g, 55.9 mAh/g.
Embodiment 2: nickel of the present invention, the synthesis of cobalt doped manganate cathode material for lithium
The implementation steps of the embodiment are as follows:
Be manganese source using lithium carbonate as lithium source, manganese carbonate, nickel acetate is nickel dopant and cobalt carbonate for cobalt dopant, according to chemistry count
Amount matches raw material, 5 wt.% citric acids of adding raw materials gross mass than Li:Mn:Ni:Co=1:1.92:0.03:0.05
For fuel.It is characterized in that the step of this method, is as follows:
A, nickel dopant dispersion is prepared
According to stoichiometric ratio Li:Mn:Ni:Co=1:1.92:0.03:0.05 weigh solid nickel acetate, then with gram
The quality of nickel acetate is counted, the volume of deionized water in terms of milliliter is 1:12 according to quality and volume ratio, nickel acetate is added to
In deionized water, it is completely dissolved nickel acetate, obtains the dispersion liquid of uniform nickel dopant；
B, fuel agent dispersing liquid is prepared
The ratio of deionized water is 1:6 according to citric acid in gram and in terms of milliliter, and lemon acid fuel is added in deionized water,
Sufficiently dissolution obtains a kind of uniform fuel agent dispersing liquid；
C, it mixes
0.8178 g lithium carbonate, 4.8664 g manganese carbonates are weighed according to stoichiometric ratio Li:Mn:Co=1:1.92:0.05
It is placed in a beaker with 0.1315 g cobalt carbonate, then according to stoichiometric ratio Li:Mn:Ni:Co=1:1.92:0.03:
0.05, the accurate nickel dopant dispersion (containing 0.1653 g nickel acetate) being added in terms of milliliter, then accurate addition is in terms of milliliter
Lemon acid fuel agent dispersing liquid (contains 0.30 g citric acid), obtains a kind of homogeneous mixture slurry after 2 h of mechanical stirring；
D, product is prepared
Obtained homogeneous mixture slurry is moved into porcelain crucible, is then directly placed into the porcelain crucible equipped with mixture paste
Preset temperature is 500 DEG C of Muffle furnaces, until 1 h of combustion reaction occurs, taking-up natural cooling is obtained for the heating in air atmosphere
Black combustion product.Then, it is put into 650 DEG C of Muffle furnaces after product of roasting being ground, 6 h are roasted in air atmosphere, takes out
Product LiNi is obtained in air after natural cooling, grinding0.03Co0.05Mn1.92O4Positive electrode powder.
1 C specific discharge capacity is 119 mAh/g, and capacity retention ratio is 88% after circulation 100 times；5 C and 10 C multiplying power items
Specific discharge capacity is respectively as follows: 111.2 mAh/g and 100.5 mAh/g under part.
Embodiment 3: nickel of the present invention, the synthesis of cobalt doped manganate cathode material for lithium
The implementation steps of the embodiment are as follows:
Be manganese source using lithium carbonate as lithium source, manganese carbonate, nickel acetate is nickel dopant and cobalt carbonate for cobalt dopant, according to chemistry count
Amount matches raw material, 5 wt.% citric acids of adding raw materials gross mass than Li:Mn:Ni:Co=1:1.90:0.05:0.05
For fuel.It is characterized in that the step of this method, is as follows:
A, nickel dopant dispersion is prepared
According to stoichiometric ratio Li:Mn:Ni:Co=1:1.90:0.05:0.05 weigh solid nickel acetate, then with gram
The quality of nickel acetate is counted, the volume of deionized water in terms of milliliter is 1:13 according to quality and volume ratio, nickel acetate is added to
In deionized water, it is completely dissolved nickel acetate, obtains the dispersion liquid of uniform nickel dopant；
B, fuel agent dispersing liquid is prepared
The ratio of deionized water is 1:3 according to citric acid in gram and in terms of milliliter, and lemon acid fuel is added in deionized water,
Sufficiently dissolution obtains a kind of uniform fuel agent dispersing liquid；
C, it mixes
0.8099 g lithium carbonate, 4.7878 g manganese carbonates are weighed according to stoichiometric ratio Li:Mn:Co=1:1.90:0.05
It is placed in a beaker with 0.1303 g cobalt carbonate, then according to stoichiometric ratio Li:Mn:Ni:Co=1:1.90:0.05:
0.05, the accurate nickel dopant dispersion (containing 0.2728 g nickel acetate) being added in terms of milliliter, then accurate addition is in terms of milliliter
Lemon acid fuel agent dispersing liquid (contains 0.30 g citric acid), obtains a kind of homogeneous mixture slurry after 2 h of mechanical stirring；
D, product is prepared
Obtained homogeneous mixture slurry is moved into porcelain crucible, is then directly placed into the porcelain crucible equipped with mixture paste
Preset temperature is 500 DEG C of Muffle furnaces, until 1 h of combustion reaction occurs, taking-up natural cooling is obtained for the heating in air atmosphere
Black combustion product.Then, it is put into 650 DEG C of Muffle furnaces after product of roasting being ground, 6 h are roasted in air atmosphere, takes out
Product LiNi is obtained in air after natural cooling, grinding0.05Co0.05Mn1.90O4Positive electrode powder.
1 C specific discharge capacity is 116 mAh/g, and capacity retention ratio is 87% after circulation 100 times；5 C and 10 C multiplying power items
Specific discharge capacity is respectively as follows: 109 mAh/g and 97.5 mAh/g under part.
Embodiment 4: nickel of the present invention, the synthesis of cobalt doped manganate cathode material for lithium
The implementation steps of the embodiment are as follows:
Be manganese source using lithium carbonate as lithium source, manganese carbonate, nickel acetate is nickel dopant and cobalt carbonate for cobalt dopant, according to chemistry count
Amount matches raw material, 5 wt.% citric acids of adding raw materials gross mass than Li:Mn:Ni:Co=1:1.85:0.10:0.05
For fuel.It is characterized in that the step of this method, is as follows:
A, nickel dopant dispersion is prepared
According to stoichiometric ratio Li:Mn:Ni:Co=1:1.85:0.10:0.05 weigh solid nickel acetate, then with gram
The quality of nickel acetate is counted, the volume of deionized water in terms of milliliter is 1:8 according to quality and volume ratio, nickel acetate is added to
In ionized water, it is completely dissolved nickel acetate, obtains the dispersion liquid of uniform nickel dopant；
B, fuel agent dispersing liquid is prepared
The ratio of deionized water is 1:2 according to citric acid in gram and in terms of milliliter, and lemon acid fuel is added in deionized water,
Sufficiently dissolution obtains a kind of uniform fuel agent dispersing liquid；
C, it mixes
0.7906 g lithium carbonate, 4.5501 g manganese carbonates are weighed according to stoichiometric ratio Li:Mn:Co=1:1.85:0.05
It is placed in a beaker with 0.1272 g cobalt carbonate, then according to stoichiometric ratio Li:Mn:Ni:Co=1:1.85:0.10:
0.05, the accurate nickel dopant dispersion (containing 0.5325 g nickel acetate) being added in terms of milliliter, then accurate addition is in terms of milliliter
Lemon acid fuel agent dispersing liquid (contains 0.30 g citric acid), obtains a kind of homogeneous mixture slurry after 2 h of mechanical stirring；
D, product is prepared
Obtained homogeneous mixture slurry is moved into porcelain crucible, is then directly placed into the porcelain crucible equipped with mixture paste
Preset temperature is 500 DEG C of Muffle furnaces, until 1 h of combustion reaction occurs, taking-up natural cooling is obtained for the heating in air atmosphere
Black combustion product.Then, it is put into 650 DEG C of Muffle furnaces after product of roasting being ground, 6 h are roasted in air atmosphere, takes out
Product LiNi is obtained in air after natural cooling, grinding0.10Co0.05Mn1.85O4Positive electrode powder.
1 C specific discharge capacity is 111 mAh/g, and capacity retention ratio is 84% after circulation 100 times；5 C and 10 C multiplying power items
Specific discharge capacity is respectively as follows: 106 mAh/g and 94.3 mAh/g under part.
Comparative example 1: list cation doping lithium manganate having spinel structure positive electrode synthesis of the present invention
The implementation steps of the embodiment are as follows:
Be manganese source and cobalt carbonate for cobalt dopant by lithium source, manganese carbonate of lithium carbonate, according to stoichiometric ratio Li:Mn:Co=
1:1.95:0.05 matches raw material, and 5 wt.% citric acids of adding raw materials gross mass are fuel.It is characterized in that the step of this method
It is rapid as follows:
A, fuel agent dispersing liquid is prepared
The ratio of deionized water is 1:10 according to citric acid in gram and in terms of milliliter, and lemon acid fuel is added in deionized water,
Sufficiently dissolution obtains a kind of uniform fuel agent dispersing liquid；
B, it mixes
0.8303 g lithium carbonate, 5.0362 g manganese carbonates are weighed according to stoichiometric ratio Li:Mn:Co=1:1.95:0.05
It is placed in a beaker with 0.1337 g cobalt carbonate, the accurate lemon acid fuel agent dispersing liquid being added in terms of milliliter (contains 0.30 g lemon
Acid), a kind of homogeneous mixture slurry is obtained after 2 h of mechanical stirring；
C, product is prepared
Obtained homogeneous mixture slurry is moved into porcelain crucible, is then directly placed into the porcelain crucible equipped with mixture paste
Preset temperature is 500 DEG C of Muffle furnaces, until 1 h of combustion reaction occurs, taking-up natural cooling is obtained for the heating in air atmosphere
Black combustion product.Then, it is put into 650 DEG C of Muffle furnaces after product of roasting being ground, 6 h are roasted in air atmosphere, takes out
Product LiCo is obtained in air after natural cooling, grinding0.05Mn1.95O4Positive electrode powder.
1 C specific discharge capacity is 129.4 mAh/g, and capacity retention ratio is 82% after circulation 100 times；5 C,10 C,15 C
Specific discharge capacity is respectively as follows: 105.4 mAh/g, 92.2 mAh/g, 91.7 mAh/g under the conditions of multiplying power；In 20 C, 30 C, 40
C specific discharge capacity is respectively as follows: 79.9 mAh/g, 27.1 mAh/g, 8.2 mAh/g.
By comparing the positive electrode that embodiment 1-4 and comparative example 1 synthesize, the nickel cobalt codope that the present invention synthesizes
LiNixCo0.05Mn1.95-xO4 The cycle performance and high rate performance of (x=0.01-0.10) positive electrode are substantially better than comparative example implementation
The LiCo that example 1 synthesizes0.05Mn1.95O4, show that the present invention has good chemical property.
Claims (7)
1. a kind of preparation method of high magnification nickel cobalt codope lithium manganate having spinel structure material, using lithium carbonate as lithium source, manganese carbonate
For manganese source, nickel acetate be nickel dopant and cobalt carbonate is cobalt dopant, according to stoichiometric ratio Li:Mn:Ni:Co=1:
(1.95-x): x: 0.05 (x=0.01-0.10) matches raw material, and 5 wt.% citric acids of adding raw materials gross mass are fuel.
It is characterized in that the step of this method, is as follows:
A, nickel dopant dispersion is prepared
According to stoichiometric ratio Li:Mn:Ni:Co=1:(1.95-x): x: 0.05 (x=0.01-0.10) weighs solid
Nickel acetate, then the quality of nickel acetate, the volume of deionized water in terms of milliliter are 1:8- according to quality and volume ratio in gram
15, nickel acetate is added in deionized water, nickel acetate is completely dissolved, obtains uniform nickel dopant dispersion.
B, fuel agent dispersing liquid is prepared
The ratio of deionized water is 1:2-10 according to citric acid in gram and in terms of milliliter, and lemon acid fuel is added to deionized water
In, sufficiently dissolution obtains a kind of uniform fuel agent dispersing liquid.
C, it mixes
According to stoichiometric ratio Li:Mn:Co=1:(1.95-x): 0.05 (x=0.01-0.10) weighing solid lithium carbonate,
Manganese carbonate and cobalt carbonate are placed in a beaker, then according to stoichiometric ratio Li:Mn:Ni:Co=1:(1.95-x): x:
0.05 (x=0.01-0.10), the accurate nickel dopant dispersion (obtained by step A) being added in terms of milliliter, then accurate addition is with milli
The lemon acid fuel agent dispersing liquid (obtained by step B) of meter is risen, last mechanical stirring certain time obtains a kind of homogeneous mixture slurry
Material.
D, product is prepared
Obtained homogeneous mixture slurry is moved into porcelain crucible, is then directly placed into the porcelain crucible equipped with mixture paste
Preset temperature is 500 DEG C of Muffle furnaces, until 1 h of combustion reaction occurs, taking-up natural cooling is obtained for the heating in air atmosphere
Black combustion product.Then, it is put into 650 DEG C of Muffle furnaces after product of roasting being ground, 6 h are roasted in air atmosphere, takes out
Product LiNi is obtained in air after natural cooling, grindingxCo0.05Mn1.95-xO4(x=0.01-0.10) positive electrode powder.
2. synthetic method according to claim 1, it is characterised in that lemon acid fuel agent point of the addition in terms of milliliter
It is needed in the volume of dispersion liquid containing 5 wt.% citric acid of total mass of raw material.
3. synthetic method according to claim 1, it is characterised in that the mechanical stirring time is 2 h.
4. synthetic method according to claim 1, it is characterised in that the homogeneous mixture slurry does not need drying, directly
The heating in porcelain crucible is until occur combustion reaction.
5. the material that preparation method described in any one of -4 claims synthesizes according to claim 1 is
LiNixCo0.05Mn1.95-xO4(x=0.01-0.10) positive electrode.
6. LiNi according to claim 5xCo0.05Mn1.95-xO4(x=0.01-0.10) positive electrode, it is characterised in that tool
There is spinel structure, space group isFd3m, particle size is about 100-250 nm.
7. LiNi according to claim 5xCo0.05Mn1.95-xO4(x=0.01-0.10) positive electrode, it is characterised in that times
It has following electrical properties when 1 C of rate:
Specific discharge capacity is 111 ~ 127 mAh/g, and the 100th specific discharge capacity is 93.2 ~ 114.9 mAh/g, conservation rate 84%
~90%；
Specific discharge capacity is 106 ~ 122.6 mAh/g under the conditions of 5 C multiplying power；
Specific discharge capacity is 94.3 ~ 108.3 mAh/g under the conditions of 10 C multiplying power.
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Application publication date: 20190308 |