CN102569807B - Coated-modified lithium manganese positive electrode material and preparation method thereof - Google Patents
Coated-modified lithium manganese positive electrode material and preparation method thereof Download PDFInfo
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- CN102569807B CN102569807B CN201110355755.XA CN201110355755A CN102569807B CN 102569807 B CN102569807 B CN 102569807B CN 201110355755 A CN201110355755 A CN 201110355755A CN 102569807 B CN102569807 B CN 102569807B
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Abstract
The invention discloses a coated-modified lithium manganese positive electrode material and the preparation method thereof. A manganese source compound, an M source compound and a lithium source compound are taken as raw material for preparing LiaMn2 -bMbO4 particles, and then are mixed with molten solvent and A-source compound, so as to obtain coated-modified lithium manganese positive electrode material. Compared with the prior art, the LiaMn2-bMbO4 particles are similar to spheres in shape and are in crystal face connection through curved surfaces which have no clear edges; on one hand, the LiaMn2 -bMbO4 particles have very small specific surface area, so that molten solvent and coating material are more evenly dispersed on the surfaces of the particles, and the control to average thickness of a coating is facilitated; on the other hand, the features have very small surface energy, the coating material is enabled to be more easily to be combined with the LiaMn2 -bMbO4 particles to form the coating. Therefore, the coated-modified lithium manganese positive electrode material has an excellent high temperature cycling performance.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly, relate to manganate cathode material for lithium of a kind of coated modification and preparation method thereof.
Background technology
Lithium ion battery has that discharge voltage is high, fail safe good, discharge and recharge long and advantages of environment protection of life-span, has been widely used in the fields such as mobile phone, notebook computer and digital product.The anode material for lithium-ion batteries that at present large-scale commercial has been produced comprises cobalt acid lithium, LiMn2O4, LiFePO4 and nickle cobalt lithium manganate ternary material etc., and wherein, but cobalt acid lithium specific discharge capacity is higher expensive and security performance is poor; LiFePO4 security performance is good but material consistency is poor; Nickle cobalt lithium manganate ternary material is moderate but security performance is poor.LiMn2O4 has that discharge voltage is high, cheap, reserves are abundant, security performance advantages of higher, and still, its high temperature cyclic performance is poor, thereby has limited the application of lithium manganate material in electrokinetic cell and energy storage field.In view of this, how to solve LiMn2O4 high temperature cyclic performance by modification and become the focus of scientific research personnel's research.
The main cause that affects lithium manganate material cycle performance is: (1) Jahn-Teller effect; (2) Mn in lithium manganate material
4+hyperoxia voltinism cause electrolyte to decompose; (3) Mn in lithium manganate material
2+the material structure that causes of dissolving change, reduced the electro-chemical activity of material etc.Researcher finds, is coated layer of metal compound by the surface at lithium manganate material, and specific area, the minimizing material surface that can reduce material directly contact with electrolytical, thereby reduces the dissolving of manganese, improves cycle performance.
The existing report widely of anode material for lithium-ion batteries and preparation method thereof, for example, the Chinese patent literature that application number is 201010175808.5 has been reported a kind of preparation method of anode material for lithium-ion batteries, the method is by Li (CH
3cOO) 2H
2o and Al (NO
3)
39H
2o joins in EGME, adds until completely dissolved PO (OC
4h
9)
3and Ti (OC
4h
9)
4and constantly stir, guarantee that solution does not precipitate; Then by Li
amn
2-bm
bo
4powder joins in the above-mentioned solution preparing, and in stirring, adds H
3bO
3, evaporate to dryness dry after stirring is calcined the dry powder obtaining in Muffle furnace, naturally cooling, and porphyrize obtains the coated yLi in surface
1+xal
xti
2-x(PO
4)
3(1-y) Li
3bO
3liMn2O4 or doping type lithium manganate powder, still, the method has been applied a large amount of organic solvents, the requirement that does not meet environmental protection is also unfavorable for large-scale industrial production.In addition, application number is the preparation method that 200610020510.0 Chinese patent literature has been reported a kind of manganate cathode material for lithium, at least one in surperficial Boron Coated lithium composite xoide, cobalt lithium composite xoide, vanadium lithium composite xoide and the carbon-coating of adulterated lithium manganate of the method, is improved normal temperature circulation and the high temperature circulation of LiMn2O4; In the Chinese patent literature that is 200910236078.2 at application number, on adulterated lithium manganate presoma, be coated, obtain LiMn2O4 material modified.
But, the LiMn2O4 raw material adopting due to the document of above-mentioned report is all for the second particle forming of being reunited by primary particle forms, there is the hole of a lot of primary particles in LiMn2O4 raw material surface, and specific area is larger, clad material is difficult to evenly be wrapped in LiMn2O4 raw material surface, thereby can not obtain desirable high temperature cyclic performance.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of manganate cathode material for lithium of coated modification, and this manganate cathode material for lithium has good high temperature cyclic performance; The technical problem to be solved in the present invention is also the preparation method of the manganate cathode material for lithium that a kind of coated modification is provided, and manganate cathode material for lithium prepared by the method has good high temperature cyclic performance.
In order to solve above technical problem, the invention provides a kind of manganate cathode material for lithium of coated modification, comprise Li
amn
2-bm
bo
4particle and be coated on described Li
amn
2-bm
bo
4the A of particle surface
cz
dlayer, described Li
amn
2-bm
bo
4particle has class spherical morphology and interplanar is connected by the curved surface without clear and definite rib, wherein, M is one or more in Li, B, Mg, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, Zr, Nb, Pd, Ce, Nd and Dy, A is one or more in Mg, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, Zr, Nb, Pd, Ce, Nd and Dy, Z is one or more in oxygen element, phosphate radical, silicate and selenate radical, 0.9≤a≤1.2,0≤b≤0.15,0≤c≤0.1,0≤d≤0.2.
Preferably, described Li
amn
2-bm
bo
4particle is single crystal grain.
Preferably, described Li
amn
2-bm
bo
4the particle diameter of particle is 0.1 μ m～20 μ m.
Accordingly, the present invention also provides a kind of preparation method of manganate cathode material for lithium of coated modification, comprises the following steps:
Step a) manganese source compound, M source compound and Li source compound are mixed after, sintering, fragmentation, classification, obtains Li
amn
2-bm
bo
4particle, described Li
amn
2-bm
bo
4particle has class spherical morphology and interplanar is connected by the curved surface without clear and definite rib, and M is one or more in Li, B, Mg, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, Zr, Nb, Pd, Ce, Nd and Dy;
Step is b) by described Li
amn
2-bm
bo
4particle, melting agent mix with A source compound, obtain mixture, A is one or more in Mg, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, Zr, Nb, Pd, Ce, Nd and Dy, A source compound is one or more in phosphate, the silicate of A and the selenate of A of oxide, A of A, 0.9≤a≤1.2,0≤b≤0.15;
Step, c) by described mixture roasting, cooling, broken, forms and is coated on described Li
amn
2-bm
bo
4the A of particle surface
cz
dlayer, obtains the manganate cathode material for lithium of coated modification, and Z is one or more in oxygen element, phosphate radical, silicate and selenate radical, 0≤c≤0.1,0≤d≤0.2.
Preferably, described manganese source compound is selected from one or more in manganese sulfate, manganese carbonate, manganese nitrate, manganese chloride, manganese oxalate, manganese dioxide, manganese sesquioxide managnic oxide and mangano-manganic oxide.
Preferably, described Li source compound is selected from one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium chloride and lithium fluoride.
Preferably, described melting agent is selected from one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium chloride, lithium fluoride, boric acid, boron nitride and boron hydroxide.
Preferably, described Li
amn
2-bm
bo
4particle is that particle diameter is the single crystal grain of 0.1 μ m～20 μ m.
Preferably, described step a) in, the temperature of described sintering is 800～1000 DEG C, the time of described sintering is 1～48 hour.
Preferably, described step c) in, the temperature of described roasting is 500 DEG C～900 DEG C, the time of described roasting is 1 hour～48 hours.
The manganate cathode material for lithium that the invention provides a kind of coated modification, comprises Li
amn
2-bm
bo
4particle and be coated on described Li
amn
2-bm
bo
4the A of particle surface
cz
dlayer, described Li
amn
2-bm
bo
4particle has class spherical morphology and interplanar is connected by the curved surface without clear and definite rib.Compared with prior art, due to this Li
amn
2-bm
bo
4particle has class spherical morphology and interplanar is connected by the curved surface without clear and definite rib, thus this Li
amn
2-bm
bo
4particle has less specific area, is conducive to A
cz
dlayer, at the uniform coating layer of coated formation on its surface, has reduced the dissolving of manganese effectively, has improved the high temperature cyclic performance of the manganate cathode material for lithium of coated modification.
The present invention also provides a kind of preparation method of manganate cathode material for lithium of coated modification, prepares Li taking manganese source compound, M source compound and Li source compound as raw material
amn
2-bm
bo
4particle, then mixes with A source compound with melting agent, obtains the manganate cathode material for lithium of coated modification after roasting, cooling, fragmentation.Compared with prior art, the Li that prepared by the present invention
amn
2-bm
bo
4particle has class spherical morphology and interplanar is connected by the curved surface without clear and definite rib, on the one hand, and this Li
amn
2-bm
bo
4particle has very little specific area, makes melting agent and clad material more easily be evenly dispersed in its surface, and is conducive to the control of the average thickness of coating layer; On the other hand, this pattern has very little surface energy, makes clad material more easily and Li
amn
2-bm
bo
4particle is in conjunction with forming coating layer.Therefore, with this Li
amn
2-bm
bo
4the manganate cathode material for lithium of coated modification prepared by particle has good high temperature cyclic performance.
In addition, the present invention has adopted melting agent in preparation process, because the fusing point of melting agent is lower than clad material and Li
amn
2-bm
bo
4the temperature of particle combination, therefore, after melting agent high temperature melting is molten state, can make clad material be dispersed in uniformly Li
amn
2-bm
bo
4the surface of particle, forms uniform coating layer, thereby effectively reduces the dissolving of manganese, has improved the high temperature cyclic performance of the manganate cathode material for lithium of this coated modification.Experiment shows, the manganate cathode material for lithium of coated modification prepared by the present invention and acetylene black, Kynoar prepare after positive plate, and its high temperature cyclic performance is better than the manganate cathode material for lithium without coated modification.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of the manganate cathode material for lithium of the coated modification prepared of the embodiment of the present invention 1;
Fig. 2 is the stereoscan photograph of the manganate cathode material for lithium of the coated modification prepared of the embodiment of the present invention 1;
Fig. 3 is the stereoscan photograph of the manganate cathode material for lithium before the coated modification a) prepared of the embodiment of the present invention 1 step;
Fig. 4 is the high temperature circulation curve of the lithium ion battery that provides of the manganate cathode material for lithium of the coated modification prepared of manganate cathode material for lithium before manganate cathode material for lithium, the coated modification that embodiment 1 step a) is prepared of the coated modification prepared of the embodiment of the present invention 1 and comparative example 1.
Embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
The manganate cathode material for lithium that the invention discloses a kind of coated modification, comprises Li
amn
2-bm
bo
4particle and be coated on described Li
amn
2-bm
bo
4the A of particle surface
cz
dlayer, described Li
amn
2-bm
bo
4particle has class spherical morphology and interplanar is connected by the curved surface without clear and definite rib, wherein, M is one or more in Li, B, Mg, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, Zr, Nb, Pd, Ce, Nd and Dy, A is one or more in Mg, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, Zr, Nb, Pd, Ce, Nd and Dy, Z is one or more in oxygen element, phosphate radical, silicate and selenate radical, 0.9≤a≤1.2,0≤b≤0.15,0≤c≤0.1,0≤d≤0.2.
The manganate cathode material for lithium of above-mentioned coated modification has the atomic ratio composition shown in formula (I):
Li
aMn
2-bM
bO
4·A
cZ
d
(I)。
In atomic ratio composition shown in described formula (I), the value of a is 0.9～1.2, is preferably 0.95～1.0; The value of b is 0～0.15, is preferably 0.02～0.1; The value of c is 0～0.1, is preferably 0.01～0.02; The value of d is 0～0.2, is preferably 0.02～0.04.
Compared with prior art, the Li adopting due to the present invention
amn
2-bm
bo
4particle has class spherical morphology, and interplanar is connected by the curved surface without clear and definite rib, thus this Li
amn
2-bm
bo
4particle has less specific area, is conducive to A
cz
dlayer, at the uniform coating layer of coated formation on its surface, reduces the dissolving of manganese effectively, improves the high temperature cyclic performance of the manganate cathode material for lithium of this coated modification.
Li
amn
2-bm
bo
4the particle diameter of particle is to affect clad material in its surface coated essential condition, excessive and too small coated on its surface of clad material, the described Li of being all unfavorable for of particle diameter
amn
2-bm
bo
4the particle diameter of particle is preferably 0.1 μ m～20 μ m, more preferably 1 μ m～10 μ m, and more preferably 3 μ m～5 μ m, under above-mentioned particle size range, can be at Li
amn
2-bm
bo
4evengranular coated A
cz
dlayer.Described Li
amn
2-bm
bo
4particle is preferably single crystal grain, has the crystal structure of cube spinelle (FD-3m), and the crystal structure of this cube spinelle (FD-3m) makes Li
amn
2-bm
bo
4particle has very little specific area and less surface energy, thereby is conducive to clad material being evenly coated on its surface.
Accordingly, the present invention also provides a kind of preparation method of manganate cathode material for lithium of coated modification, comprises the following steps:
Step a) manganese source compound, M source compound and Li source compound are mixed after, sintering, fragmentation, classification, obtains Li
amn
2-bm
bo
4particle, described Li
amn
2-bm
bo
4particle has class spherical morphology and interplanar is connected by the curved surface without clear and definite rib, and M is one or more in Li, B, Mg, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, Zr, Nb, Pd, Ce, Nd and Dy;
Step is b) by described Li
amn
2-bm
bo
4particle, melting agent mix with A source compound, obtain mixture, A is one or more in Mg, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, Zr, Nb, Pd, Ce, Nd and Dy, A source compound is one or more in phosphate, the silicate of A and the selenate of A of oxide, A of A, 0.9≤a≤1.2,0≤b≤0.15;
Step, c) by described mixture roasting, cooling, broken, forms and is coated on described Li
amn
2-bm
bo
4the A of particle surface
cz
dlayer, obtains the manganate cathode material for lithium of coated modification, and Z is one or more in oxygen element, phosphate radical, silicate and selenate radical, 0≤c≤0.1,0≤d≤0.2.
According to the present invention, described manganese source compound is selected from one or more in manganese sulfate, manganese carbonate, manganese nitrate, manganese chloride, manganese oxalate, manganese dioxide, manganese sesquioxide managnic oxide and mangano-manganic oxide; Described Li source compound is selected from one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium chloride and lithium fluoride.
Above-mentioned steps a) in, be not particularly limited for described mixed method, include but not limited to solid-phase ball milling method well known to those skilled in the art, wet ball grinding, mechanical mixing, spray drying process, liquid phase mixing post-drying polishing and freeze-drying etc.The temperature of described sintering is preferably 800 DEG C～1000 DEG C, more preferably 800 DEG C～950 DEG C, most preferably is 850 DEG C～900 DEG C; The time of described sintering is preferably 1 hour～and 48 hours, more preferably 5 hours～24 hours, most preferably be 8 hours～16 hours.Meanwhile, for the method for described fragmentation and classification, there is no particular restriction in the present invention, can adopt fragmentation well known to those skilled in the art and stage division to carry out.Through preparation a) of described step, obtain Li
amn
2-bm
bo
4particle, preferred, described Li
amn
2-bm
bo
4particle is single crystal grain, in addition, and described Li
amn
2-bm
bo
4the particle diameter of particle is preferably 0.1 μ m～20 μ m, more preferably 1 μ m～10 μ m, and more preferably 3 μ m～5 μ m, are conducive at Li in above-mentioned particle size range
amn
2-bm
bo
4evengranular coated A
cz
dlayer.
The Li that step a) is prepared
amn
2-bm
bo
4particle is preferably single crystal grain, has the crystal structure of cube spinelle (FD-3m), and the crystal structure of this cube spinelle (FD-3m) makes Li
amn
2-bm
bo
4particle has very little specific area and less surface energy, thereby is conducive to clad material being evenly coated on its surface.
Prepare Li
amn
2-bm
bo
4after particle, by described Li
amn
2-bm
bo
4particle, melting agent mix with A source compound, and wherein, described melting agent is preferably selected from one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium chloride, lithium fluoride, boric acid, boron nitride and boron hydroxide.Because the fusing point of melting agent is lower than clad material and Li
amn
2-bm
bo
4the temperature of particle combination, therefore, after melting agent high temperature melting is molten state, can make clad material be dispersed in uniformly Li
amn
2-bm
bo
4the surface of particle, forms uniform coating layer, thereby effectively reduces the dissolving of manganese, has improved the high temperature cyclic performance of the manganate cathode material for lithium of this coated modification.
Step c) in, sintering temperature is too high and be too lowly all unfavorable for that clad material is at Li
amn
2-bm
bo
4being coated of particle surface, described sintering temperature is preferably 400 DEG C～900 DEG C, more preferably 500 DEG C～800 DEG C, most preferably is 550 DEG C～750 DEG C; The time of described roasting is preferably 1 hour～and 48 hours, more preferably 2 hours～16 hours, most preferably be 3 hours～8 hours.For described cooling, broken method, there is no particular restriction in the present invention, can adopt cooling, breaking method well known to those skilled in the art to carry out.
Compared with prior art, the Li that prepared by the present invention
amn
2-bm
bo
4particle has class spherical morphology, and interplanar is connected by the curved surface without clear and definite rib, on the one hand, and this Li
amn
2-bm
bo
4particle has very little specific area, makes melting agent and clad material more easily be evenly dispersed in its surface, and is conducive to the control of the average thickness of coating layer; On the other hand, this pattern has very little surface energy, makes clad material more easily and Li
amn
2-bm
bo
4particle is in conjunction with forming coating layer.Therefore, with this Li
amn
2-bm
bo
4the manganate cathode material for lithium of coated modification prepared by particle has good high temperature cyclic performance.
In addition, the present invention has adopted melting agent in preparation process, because the fusing point of melting agent is lower than clad material and Li
amn
2-bm
bo
4the temperature of particle combination, therefore, after melting agent high temperature melting is molten state, can make clad material be dispersed in uniformly Li
amn
2-bm
bo
4the surface of particle, forms uniform coating layer, thereby effectively reduces the dissolving of manganese, has improved the high temperature cyclic performance of the manganate cathode material for lithium of this coated modification.
Obtain, after the manganate cathode material for lithium of coated modification, it being carried out to scanning electron microscopic observation, result shows, adopts the manganate cathode material for lithium of the coated modification that method provided by the invention prepares to have uniform coating layer.
The manganate cathode material for lithium of described coated modification, electrolyte and negative pole are assembled according to method well known in the art, can be obtained lithium ion battery.Obtain after lithium ion battery, adopt high temperature test instrument to carry out high temperature cyclic performance test to it, result shows, lithium ion battery provided by the invention has good high temperature cyclic performance at 55 DEG C of temperature.
In order to further illustrate technical scheme of the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
Embodiment 1～10
According to the raw material shown in table 1, consumption and condition, the manganate cathode material for lithium according to the coated modification of following steps preparation:
After manganese source compound, M source compound and Li source compound are mixed, roasting, fragmentation, classification, obtains the single crystal grain, class spherical morphology, interplanar of 0.1 μ m～20 μ m by the Li that does not have the curved surface of clear and definite rib to be connected
amn
2-bm
bo
4particle is manganate cathode material for lithium;
Described manganate cathode material for lithium, melting agent are mixed with the oxide of elements A, phosphate, the silicate of A or the selenate of A of A, obtain mixture;
By the mixture sintering obtaining, cooling, fragmentation, obtains the manganate cathode material for lithium of coated modification.
Formula and the condition of the manganate cathode material for lithium of the coated modification of table 1 embodiment of the present invention 1～10 preparation
Formula and the condition of the manganate cathode material for lithium of the coated modification of continued 1 embodiment of the present invention 1～10 preparation
Formula and the condition of the manganate cathode material for lithium of the coated modification of continued 2 embodiment of the present invention 1～10 preparation
Comparative example 1
The lithium manganate material of the coated modification of preparation, comprises the steps:
(1) be to take lithium carbonate, electrolytic manganese dioxide and magnesium oxide at 1.20: 1.95: 0.05 by Li, Mn and Mg mol ratio, be placed in ball grinder and mix, by the material mixing, in 850 DEG C of sintering, nature is to room temperature, fragmentation, sieves and obtains manganate precursor for lithium;
(2) manganate precursor for lithium and the Al that prepared by step (1)
2o
3in ball grinder, mix, wherein Al
2o
3with the mol ratio of Mn in step (1) be 1: 80, mix, obtain coated product;
(3) by the coated product in step (2) in 750 DEG C of sintering, naturally cool to room temperature, fragmentation, sieves and obtains the lithium manganate material of coated modification.
The polycrystalline diffractometer that the uses German Brooker company respectively manganate cathode material for lithium of the coated modification to embodiment 1～10 preparation carries out X-ray diffraction analysis, taking CuK α line as light source, the angle of diffraction 2 θ are from 10 ° to 90 °, result is referring to Fig. 1, Fig. 1 is the X ray diffracting spectrum of the manganate cathode material for lithium of the coated modification prepared of the embodiment of the present invention 1, as shown in Figure 1, the manganate cathode material for lithium of the coated modification that the embodiment of the present invention 1 prepares has positive spinel (FD-3M) cubic structure of standard, free from admixture phase.
The manganate cathode material for lithium of the coated modification to embodiment 1～10 preparation carries out electron-microscope scanning respectively, and result is referring to Fig. 2, and Fig. 2, for the manganate cathode material for lithium particle diameter of the coated modification that the embodiment of the present invention 1 provides is 2 μ m～10 μ m, has class spherical morphology.Fig. 3 is the stereoscan photograph of the manganate cathode material for lithium before the coated modification a) prepared of embodiment 1 preparation process, can find by contrast, and manganate cathode material for lithium surface exists significantly coating layer uniformly.
Manganate cathode material for lithium, 0.5g acetylene black, 0.5g Kynoar and the 30gN-methyl pyrrolidone of coated modification prepared by the manganate cathode material for lithium before the manganate cathode material for lithium of the coated modification of respectively being prepared by 9g embodiment 1～10, the coated modification that embodiment 1 preparation process a) obtains and comparative example 1 are mixed to form slurry at normal temperatures and pressures, are evenly coated in aluminium foil surface and make pole piece; After described pole piece is dried at 80 DEG C, compress, being cut into area is 1.32cm
2thin rounded flakes as positive pole, taking pour lithium slice as negative pole, with the LiPF of 1mol/L
6ethylene carbonate (EC) and dimethyl carbonate (DMC) solution be electrolyte, wherein, the volume ratio of EC and DMC is 1: 1, in the glove box that is full of argon gas, is assembled into lithium ion battery.
Use high temperature test instrument to carry out cycle performance test to the lithium ion battery of above-mentioned preparation, probe temperature is 55 DEG C, and charging and discharging currents is 0.4mA/cm
2charge cutoff voltage is 4.35V, discharge cut-off voltage is 3.0V, result is referring to Fig. 4, and Fig. 4 is the high temperature circulation curve of the lithium ion battery that provides of the manganate cathode material for lithium of the coated modification prepared of manganate cathode material for lithium before manganate cathode material for lithium, the coated modification that embodiment 1 step a) is prepared of the coated modification prepared of the embodiment of the present invention 1 and comparative example 1.Wherein, the high temperature circulation curve of the lithium ion battery that the manganate cathode material for lithium that curve 1 is the coated modification that adopts the embodiment of the present invention 1 and prepare obtains, the high temperature circulation curve of curve 2 manganate cathode material for lithium before for the coated modification that adopts the embodiment of the present invention 1 step and a) prepare, the high temperature circulation curve of the manganate cathode material for lithium that curve 3 is the coated modification that adopts comparative example 1 of the present invention and prepare.As shown in Figure 4, the high temperature cyclic performance of the manganate cathode material for lithium of coated modification is better than manganate cathode material for lithium before coated modification and the manganate cathode material for lithium of the coated modification of commonsense method.
From above-described embodiment and comparative example, method provided by the invention can prepare the manganate cathode material for lithium of described coated modification, can reduce material specific area, reduce material surface and directly contact with electrolytical, thereby the dissolving that effectively reduces manganese improves high temperature cyclic performance.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiment, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (5)
1. a preparation method for the manganate cathode material for lithium of coated modification, comprises the following steps:
Step a) manganese source compound, M source compound and Li source compound are mixed after, sintering, fragmentation, classification, obtains Li
amn
2-bm
bo
4particle, described Li
amn
2-bm
bo
4particle has class spherical morphology and interplanar is connected by the curved surface without clear and definite rib, and M is one or more in Li, B, Mg, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, Zr, Nb, Pd, Ce, Nd and Dy; Described Li
amn
2-bm
bo
4particle is that particle diameter is the single crystal grain of 3 μ m～5 μ m;
Step is b) by described Li
amn
2-bm
bo
4particle, melting agent mix with A source compound, obtain mixture, A is one or more in Mg, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, Zr, Nb, Pd, Ce, Nd and Dy, A source compound is one or more in phosphate, the silicate of A and the selenate of A of oxide, A of A, 0.9≤a≤1.2,0 < b≤0.15;
Step, c) by described mixture roasting, cooling, broken, forms and is coated on described Li
amn
2-bm
bo
4the A of particle surface
cz
dlayer, obtains the manganate cathode material for lithium of coated modification, and Z is one or more in oxygen element, phosphate radical, silicate and selenate radical, 0 < c≤0.1,0 < d≤0.2;
The temperature of described roasting is 500 DEG C～900 DEG C, and the time of described roasting is 1 hour～48 hours.
2. preparation method according to claim 1, is characterized in that, described manganese source compound is selected from one or more in manganese sulfate, manganese carbonate, manganese nitrate, manganese chloride, manganese oxalate, manganese dioxide, manganese sesquioxide managnic oxide and mangano-manganic oxide.
3. preparation method according to claim 1, is characterized in that, described Li source compound is selected from one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium chloride and lithium fluoride.
4. preparation method according to claim 1, is characterized in that, described melting agent is selected from one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium chloride, lithium fluoride, boric acid, boron nitride and boron hydroxide.
5. according to the preparation method described in claim 1～4 any one, it is characterized in that, described step a) in, the temperature of described sintering is 800～1000 DEG C, the time of described sintering is 1～48 hour.
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