The content of the invention
It is an object of the invention to provide a kind of spinelle/laminated hetero structural material, it is intended to solve existing anode
The not enough problem of material electrochemical performance.
The present invention is achieved in that a kind of spinelle/laminated hetero structural material, the spinelle/laminated hetero knot
Structure material system LiMn1.5Ni0.5O4Cladding Li1.2Mn0.54Ni0.13Co0.13O2The composite for being formed afterwards, wherein described
Li1.2Mn0.54Ni0.13Co0.13O2Particle diameter be 100-500nm, the LiMn1.5Ni0.5O4The thickness of clad is 2-40nm.This
Kind of material can bring unexpected chemical property, its cycle performance that significantly improve material, high rate performance and
Mean voltage.
Another object of the present invention is to provide a kind of preparation method of spinelle stratiform heterogeneous structure material.The method bag
Include following steps:
Step A:Prepare Li1.2Mn0.54Ni0.13Co0.13O2Particle, the Li1.2Mn0.54Ni0.13Co0.13O2Particle system
CH3COOLi·2H2O、Ni(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O and Co (CH3COO)2·4H2The mixture of O is adopted
With after solvent-thermal method by after high-temperature calcination twice obtain.Solvent-thermal method grows up on the basis of hydro-thermal method, refers to close
It is original under the self-generated pressure of certain temperature and solution with organic matter or non-aqueous solvent as solvent in closure system such as autoclave
A kind of synthetic method that mixture is reacted.Its difference with hydro-thermal method is used solvent for organic solvent
It is not water.In solvent thermal reaction, nonaqueous solvents is dissolved in by one or more presomas, in liquid phase or super critical condition
Under, the comparing that reactant disperses in the solution and becomes is active, and reaction occurs, and product is slowly generated.The process it is relatively easy and
And it is easily controllable, and the volatilization of noxious material can be effectively prevented in enclosed system and the forerunner to air-sensitive is prepared
Body.In addition, the formation of thing phase, the size of particle diameter, form can also be controlled, and, the dispersiveness of product is preferably.In solvent heat bar
Under part, the property (density, viscosity, peptizaiton) of solvent is influenced each other, and change is very big, and its property is differed with usual conditions
It is very big, accordingly, the dissolving of reactant (typically solid), disperseed and chemical reactivity is greatly improved or strengthened.This
Allowing for reaction can occur at a lower temperature.
Step B:Prepare integument mixed liquor;The integument mixed liquor system is by Ni (CH3COO)2·4H2O and Mn
(CH3COO)2·4H2O is obtained in being dissolved in deionized water.The volume of wherein deionized water is preferably 80 milliliters.
Step C:Spinelle/laminated hetero structural material is prepared, the spinelle/laminated hetero structural material system will be described
Li1.2Mn0.54Ni0.13Co0.13O2Particle is obtained after mixing with the integument mixed liquor using wet chemistry method.Wet chemical method
Claim NPP- methods, have that liquid phase participates in, material is prepared by chemically reacting method is referred to as wet chemistry method, and such as chemical liquid phase is sunk
Product (CBD), electrochemical deposition (plating), collosol and gel etc..Wet chemistry method in the present invention refers mainly to co-precipitation.Wet chemistry method
Principle of Process is the soluble metallic salt or oxide for selecting one or more to need, and is matched somebody with somebody by the composition metering of prepared material
Be made solution, make each element present lewis' acid state, the suitable precipitating reagent of reselection or by evaporation, distillation, hydrolysis etc.
Operation, by metal ion homogeneous precipitation or crystallizes out, treated to obtain powder.
Further technical scheme of the invention is:The step A include it is following step by step:
Step A1:Prepare ethanol solution step, the ethanol solution system is by CH3COOLi·2H2O、Ni(CH3COO)2·
4H2O,、Mn(CH3COO)2·4H2O、Co(CH3COO)2·4H2O is obtained in being dissolved in ethanol.Preferably, the volume of ethanol is
100 milliliters.
Step A2:Reaction solution step is prepared, the reaction solution system adds acclimatization agent in the ethanol solution, described
Precipitating reagent system oxalic acid solution;Wherein, the concentration of oxalic acid is 1-5mol/L, preferably 1M, and oxalic acid solution is by peristaltic pump with 2-
The speed of 10r/min adds preferably 5r/min in ethanol solution.
Step A3:Be transferred to the reaction solution in hydrothermal reaction kettle by solution thermal response step, the solution thermal response system
Dried after heating;Solution thermal response temperature is 150-200 DEG C in the step A3, wherein preferably 180 DEG C, the reaction time is
8-20h, wherein preferably 12h, drying temperature is 60-90 DEG C, wherein preferably 80 DEG C.
Step A4:First calcining step, the reaction that calcining step system will obtain after the solution thermal response step described just is produced
Thing is taken out and ground after calcining at constant temperature 5-8h at being warming up to 400-500 DEG C with 2-10 DEG C/min in Muffle furnace;It is wherein preferred
Heating rate is 5 DEG C/min, and calcining heat is 450 DEG C, and calcination time is 6h.
Step A5:Secondary clacining step:The product that the secondary clacining system will obtain after the just calcining step is with 2-10
DEG C/heating rate of min be warming up to 800-1000 DEG C at calcining at constant temperature 11-13h, obtain the Li1.2Mn0.54Ni0.13Co0.13O2
Grain.Wherein preferred heating rate is 5 DEG C/min, and calcining heat is 900 DEG C, and calcination time is 12h.
Further technical scheme of the invention is:CH described in the step A13COOLi·2H2O、Ni(CH3COO)2·
4H2O,、Mn(CH3COO)2·4H2O、Co(CH3COO)2·4H2The ratio of the amount of the material of O is 1.2:0.13:0.54:0.13.
Further technical scheme of the invention is:Ni (CH described in the step B3COO)2·4H2O and Mn
(CH3COO)2·4H2The ratio of the amount of the material of O is 1.8-3.6:1, wherein preferred value is 3:1.
Further technical scheme of the invention is:The step C include it is following step by step:
Step C1:Prepare particle mixed liquor, the particle mixed liquor system is by the Li1.2Mn0.54Ni0.13Co0.13O2Particle
Obtained after ultrasound 2-5h after mixing with the integument mixed liquor;Wherein Li1.2Mn0.54Ni0.13Co0.13O2The quality of particle is preferred
It is 0.2g, it is also possible to select other weight, as long as the liquid level of integument mixed liquor can cover particle.Ultrasonic time is preferred
1h。
Step C2:Heterojunction structure powder step is prepared, the particle mixed liquor stirs simultaneously in the heterojunction structure powder system
Obtained after being evaporated;The temperature for wherein stirring is 60-110 DEG C, preferably 80 DEG C.
Step C3:Prepare spinelle stratiform heterogeneous structure material step;The spinelle stratiform heterogeneous structure material system will
The heterojunction structure powder is heated and furnace cooling is obtained after being incubated.Heating-up temperature therein is 650-850 DEG C, and preferably 750 take the photograph
Family name's degree.The heating rate of heating is 2-10 DEG C/min, preferably 5 DEG C/min.Soaking time is 3-6h, preferably 5h.
The beneficial effects of the invention are as follows:The preparation method of the spinelle stratiform heterogeneous structure material that the present invention is provided simply may be used
OK, the material for preparing shows outstanding chemical property, significantly improves the cycle performance of material, high rate performance with
And mean voltage.
Specific embodiment
The explanation of following embodiment is, with reference to additional schema, to be used to illustrate the particular implementation that the present invention may be used to implement
Example.The direction term that the present invention is previously mentioned, for example " on ", D score, "front", "rear", "left", "right", " interior ", " outward ", " side "
Deng being only the direction with reference to annexed drawings.Therefore, the direction term for using is to illustrate and understand the present invention, and is not used to
The limitation present invention.
It is an object of the invention to provide a kind of spinelle/laminated hetero structural material, it is intended to solve existing anode
The not enough problem of material electrochemical performance.
The present invention is achieved in that a kind of spinelle/laminated hetero structural material, the spinelle/laminated hetero knot
Structure material system LiMn1.5Ni0.5O4Cladding Li1.2Mn0.54Ni0.13Co0.13O2The composite for being formed afterwards, wherein described
Li1.2Mn0.54Ni0.13Co0.13O2Particle diameter be 100-500nm, the LiMn1.5Ni0.5O4The thickness of clad is 2-40nm.This
Kind of material can bring unexpected chemical property, its cycle performance that significantly improve material, high rate performance and
Mean voltage.
Another object of the present invention is to provide a kind of preparation method of spinelle stratiform heterogeneous structure material.The method bag
Include following steps:
Step A:Prepare Li1.2Mn0.54Ni0.13Co0.13O2Particle, the Li1.2Mn0.54Ni0.13Co0.13O2Particle system
CH3COOLi·2H2O、Ni(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O and Co (CH3COO)2·4H2The mixture of O is adopted
With after solvent-thermal method by after high-temperature calcination twice obtain.Solvent-thermal method grows up on the basis of hydro-thermal method, refers to close
It is original under the self-generated pressure of certain temperature and solution with organic matter or non-aqueous solvent as solvent in closure system such as autoclave
A kind of synthetic method that mixture is reacted.Its difference with hydro-thermal method is used solvent for organic solvent
It is not water.In solvent thermal reaction, nonaqueous solvents is dissolved in by one or more presomas, in liquid phase or super critical condition
Under, the comparing that reactant disperses in the solution and becomes is active, and reaction occurs, and product is slowly generated.The process it is relatively easy and
And it is easily controllable, and the volatilization of noxious material can be effectively prevented in enclosed system and the forerunner to air-sensitive is prepared
Body.In addition, the formation of thing phase, the size of particle diameter, form can also be controlled, and, the dispersiveness of product is preferably.In solvent heat bar
Under part, the property (density, viscosity, peptizaiton) of solvent is influenced each other, and change is very big, and its property is differed with usual conditions
It is very big, accordingly, the dissolving of reactant (typically solid), disperseed and chemical reactivity is greatly improved or strengthened.This
Allowing for reaction can occur at a lower temperature.
Step B:Prepare integument mixed liquor;The integument mixed liquor system is by Ni (CH3COO)2·4H2O and Mn
(CH3COO)2·4H2O is obtained in being dissolved in deionized water.The volume of wherein deionized water is preferably 80 milliliters.
Step C:Spinelle/laminated hetero structural material is prepared, the spinelle/laminated hetero structural material system will be described
Li1.2Mn0.54Ni0.13Co0.13O2Particle is obtained after mixing with the integument mixed liquor using wet chemistry method.Wet chemical method
Claim NPP- methods, have that liquid phase participates in, material is prepared by chemically reacting method is referred to as wet chemistry method, and such as chemical liquid phase is sunk
Product (CBD), electrochemical deposition (plating), collosol and gel etc..Wet chemistry method in the present invention refers mainly to co-precipitation.Wet chemistry method
Principle of Process is the soluble metallic salt or oxide for selecting one or more to need, and is matched somebody with somebody by the composition metering of prepared material
Be made solution, make each element present lewis' acid state, the suitable precipitating reagent of reselection or by evaporation, distillation, hydrolysis etc.
Operation, by metal ion homogeneous precipitation or crystallizes out, treated to obtain powder.
Further technical scheme of the invention is:The step A include it is following step by step:
Step A1:Prepare ethanol solution step, the ethanol solution system is by CH3COOLi·2H2O、Ni(CH3COO)2·
4H2O,、Mn(CH3COO)2·4H2O、Co(CH3COO)2·4H2O is obtained in being dissolved in ethanol.Preferably, the volume of ethanol is
100 milliliters.
Step A2:Reaction solution step is prepared, the reaction solution system adds acclimatization agent in the ethanol solution, described
Precipitating reagent system oxalic acid solution;Wherein, the concentration of oxalic acid is 1-5mol/L, preferably 1M, and oxalic acid solution is by peristaltic pump with 2-
The speed of 10r/min adds preferably 5r/min in ethanol solution.
Step A3:Be transferred to the reaction solution in hydrothermal reaction kettle by solution thermal response step, the solution thermal response system
Dried after heating;Solution thermal response temperature is 150-200 DEG C in the step A3, wherein preferably 180 DEG C, the reaction time is
8-20h, wherein preferably 12h, drying temperature is 60-90 DEG C, wherein preferably 80 DEG C.
Step A4:First calcining step, the reaction that calcining step system will obtain after the solution thermal response step described just is produced
Thing is taken out and ground after calcining at constant temperature 5-8h at being warming up to 400-500 DEG C with 2-10 DEG C/min in Muffle furnace;It is wherein preferred
Heating rate is 5 DEG C/min, and calcining heat is 450 DEG C, and calcination time is 6h.
Step A5:Secondary clacining step:The product that the secondary clacining system will obtain after the just calcining step is with 2-10
DEG C/heating rate of min be warming up to 800-1000 DEG C at calcining at constant temperature 11-13h, obtain the Li1.2Mn0.54Ni0.13Co0.13O2
Grain.Wherein preferred heating rate is 5 DEG C/min, and calcining heat is 900 DEG C, and calcination time is 12h.
Further technical scheme of the invention is:CH described in the step A13COOLi·2H2O、Ni(CH3COO)2·
4H2O,、Mn(CH3COO)2·4H2O、Co(CH3COO)2·4H2The ratio of the amount of the material of O is 1.2:0.13:0.54:0.13.
Further technical scheme of the invention is:Ni (CH described in the step B3COO)2·4H2O and Mn
(CH3COO)2·4H2The ratio of the amount of the material of O is 1.8-3.6:1, wherein preferred value is 3:1.
Further technical scheme of the invention is:The step C include it is following step by step:
Step C1:Prepare particle mixed liquor, the particle mixed liquor system is by the Li1.2Mn0.54Ni0.13Co0.13O2Particle
Obtained after ultrasound 2-5h after mixing with the integument mixed liquor;Wherein Li1.2Mn0.54Ni0.13Co0.13O2The quality of particle is preferred
It is 0.2g, it is also possible to select other weight, as long as the liquid level of integument mixed liquor can cover particle.Ultrasonic time is preferred
1h。
Step C2:Heterojunction structure powder step is prepared, the particle mixed liquor stirs simultaneously in the heterojunction structure powder system
Obtained after being evaporated;The temperature for wherein stirring is 60-110 DEG C, preferably 80 DEG C.
Step C3:Prepare spinelle stratiform heterogeneous structure material step;The spinelle stratiform heterogeneous structure material system will
The heterojunction structure powder is heated and furnace cooling is obtained after being incubated.Heating-up temperature therein is 650-850 DEG C, and preferably 750 take the photograph
Family name's degree.The heating rate of heating is 2-10 DEG C/min, preferably 5 DEG C/min.Soaking time is 3-6h, preferably 5h.
A specific process for preparing the spinelle stratiform heterogeneous structure material that the present invention is provided is given below, to help
It is better understood from the present invention.
(1) solvent-thermal method prepares Li1.2Mn0.54Ni0.13Co0.13O2
A. by CH3COOLi·2H2O,Ni(CH3COO)2·4H2O,Mn(CH3COO)2·4H2O,Co(CH3COO)2·4H2O
It is dissolved in 100ml alcohol according to mol ratio;
B. the oxalic acid solution of appropriate 1mol/L is passed through into peristaltic pump with the speed above-mentioned solution of addition of 5r/min;
C. reaction solution is transferred in the hydrothermal reaction kettle of 100ml, 10h is heated at 180 DEG C;
D. above-mentioned reaction solution is dried at 80 DEG C;
E. calcining at constant temperature 12h at being warming up to 900 DEG C with 5 DEG C/min again, finally gives lithium-rich positive electrode
(Li1.2Mn0.54Ni0.13Co0.13O2)。
(2)LiMn1.5Ni0.5O4Cladding Li1.2Mn0.54Ni0.13Co0.13O2Spinelle/laminated hetero structural material preparation
Experiment prepares Li using solvent thermal process1.2Mn0.54Ni0.13Co0.13O2
A. by the Ni (CH of stoichiometric proportion3COO)2·4H2O and Mn (CH3COO)2·4H2O is dissolved in the deionization of 80ml
In water;
B. by 0.2gLi1.2Mn0.54Ni0.13Co0.13O2It is placed in above-mentioned solution, ultrasonic 1h;
C. above-mentioned reactant is stirred at 80 DEG C and is evaporated;
Powder will be obtained and be heated to 750 DEG C with 5 DEG C/min, be incubated 5h, then furnace cooling, finally give LiMn1.5Ni0.5O4
Cladding Li1.2Mn0.54Ni0.13Co0.13O2Spinelle/laminated hetero structural material.
In order to better illustrate the structure and its effect of present invention offer, the present invention is made of experimental data next
Go out to further explain.
Li is prepared first1.2Mn0.54Ni0.13Co0.13O2Particle, that is, not by integument LiMn1.5Ni0.5O4Bag
The particle wrapped up in, is designated as Pristine, the side for preparing spinelle stratiform heterogeneous structure material for then being provided according to the present invention
Method prepares the sample with the clad that mass fraction is 1%, 2% and 5% respectively, will be 1%, 2% and with mass fraction
The sample of 5% clad is denoted as HM1, HM2 and HM5 respectively.
Fig. 1 is the XRD powder diagrams of spinelle stratiform heterogeneous structure material provided in an embodiment of the present invention.Fig. 2 is Fig. 1
The partial enlarged drawing of center a parts.Fig. 3 is the partial enlarged drawing of Fig. 1 center b parts.
As can be seen that except spreading out between 2 θ=20-25 ° in the XRD powder diagrams of sample before and after cladding from Fig. 1-3
Peak, other all of diffraction maximums can correspond to α-NaFeO2Structure, RSpace group.Spreading out between 2 θ=20-25 °
Penetrating peak can correspond to monoclinic system, C2/m space groups.(006, the data mean out peak position, similarly hereinafter) peak and (012) peak with
And (108) peak is sharp with the peak shape at (110) peak and substantially cleaves, this good splitting shows that sample has good stratiform knot
Structure.The XRD powder diagrams of original material and covering material are not found by scheming us has an obvious difference, therefore can be with
Draw the LiMn of the clad of nano spinel structural material1.5Ni0.5O4The structure to bulk material is not damaged.But
It is that the XRD powder diagrams of heterogeneous structure material some weak peaks occur near (101) peak and (107) peak, the displaying of its enlarged drawing
In 2,3, as seen from the figure, with the increase of clad mass fraction, these weak peak intensity are being continuously increased.With JADE6.0
These and LiMn are found after matching1.5Ni0.5O4(PDF#32-0581, a bottom appearance) coincide substantially.LiMn1.5Ni0.5O4
Formation can give the credit in calcination process caused by lithium ion diffused out from LMNCO.
Fig. 4 is the Raman spectrum of the sample of spinelle stratiform heterogeneous structure material provided in an embodiment of the present invention.Due to
Raman spectrum are very sensitive for the difference of spinel structure and layer structure, therefore Raman spectrum are used to further confirm that
The structure of material.As shown in figure 4, the sample before and after cladding is all presented typical layer structure spectral signature;Positioned at 430cm-1's
Characteristic peak is due to Li2MnO3Caused by mutually vibrating;Positioned at 490cm-1EgPeak and positioned at 594cm-1A1gIt is R that peak is correspondingSpace group.The characteristic peak of spinel structure is located at 630-636cm-1, as seen from the figure, sample HM2 and HM5 are located at 630-
636cm-1Occur in that a shoulder breadth, thus can draw be coated with after occur in that Spinel in sample HM2 and HM5 again.
For the structure and pattern of further confirmatory sample, sample HM2 further uses high resolution TEM
(HRTEM) characterized, in the displaying of its result and Fig. 5,6.As shown in Figure 5, the thickness of clad is about 5.40nm, the crystalline substance of nexine
Compartment corresponds to hexagonal crystal system, R away from being 0.47nm(003) crystal face of space group;It will be appreciated from fig. 6 that the crystal face of bulk material
Spacing is 0.32nm, corresponds to monoclinic system, and (022) of C2/m space groups is further amplified and understood, the interplanar distance of clad
It is 0.14nm, this and LiMn1.5Ni0.5O4(022) interplanar distance match, therefore can further determine the material of clad
Expect to be LiMn1.5Ni0.5O4。
The 3s spectrograms of the Mn of each material are illustrated in Fig. 7-10.Wherein Fig. 7 is sample LMNCO;Fig. 8 is sample HM1;Fig. 9
It is sample HM2;Figure 10 is sample HM5.Wherein LMNCO refers to original uncoated material, and is prepared by solvent-thermal method
Li1.2Mn0.54Ni0.13Co0.13O2。
It can be seen that, in the 3s spectrograms of Mn, Δ E is usually used to the change of the valence state for weighing Mn, and the valence state of Mn is with the increasing of Δ E
Plus and decline.And known by Fig. 5,6, increase and LiMn with clad mass fraction1.5Ni0.5O4Content increase, Δ E's
Value constantly increases and the valence state of Mn is constantly declining.This is due to calcining the LiMn for obtaining at 750 DEG C1.5Ni0.5O4, its crystal
Structure is the disordered structure of non-stoichiometric, and wherein Mn is main to be existed in the form of+trivalent.Therefore with the quality of clad
The increase of fraction, Mn3+It is being continuously increased, is thus resulting in the decline of the overall valence state of sample top layer Mn.This also further checking
, in material LMNCO it is surface coated be non-stoichiometric disordered crystal structure LiMn1.5Ni0.5O4.This with it is above-mentioned
XRD, HRTEM result are consistent.
The structure of spinelle stratiform heterogeneous structure material of the invention can be determined in sum.
The chemical property of the spinelle stratiform heterogeneous structure material provided the present invention with reference to experimental result is made
Further illustrate.
Figure 11 is that spinelle stratiform heterogeneous structure material provided in an embodiment of the present invention is coating front and rear sample in 40mA g-1
First charge-discharge curve map under current density, test voltage scope is 2.0-4.8V.As seen from the figure, all samples first fill
Electric curve can be divided into two regions:In region of the charging voltage less than 4.5V, lithium ion is from LiMn1/3Ni1/3Co1/3O2Phase
Middle abjection, as charge compensation, Ni2+It is oxidized to Ni4+, Co3+It is oxidized to Co4+;Charging voltage more than 4.5V region, lithium from
Son is from Li2MnO3Deviate from phase, used as charge compensation, the O on sample top layer is with O2 -Form deviate from from sample, sample interior with
Mn connected O forms local electronic room.
Table 1 is the first discharge specific capacity and coulombic efficiency of sample.As seen from table, the specific discharge capacity of sample and coulomb are imitated
Rate increases with the increase of coating thickness, and when the mass fraction of clad is 2%, specific discharge capacity reaches maximum
263.9mAh g-1, it is 82.4% that coulombic efficiency reaches maximum.This can be attributed to due to three-dimensional lithium ion diffusion admittance
Clad presence so that the Lacking oxygen during initial charge is retained.But when the mass fraction of clad reaches
When 5%, its specific discharge capacity drops to 237.6mAh g-1, this is that have one because blocked up clad brings charge specific capacity
Caused by serious decline.
Table 1 coats the first charge-discharge specific capacity and coulombic efficiency of front and rear sample
Figure 12,13,14 show sample in 0.2C, 1C, 2C (1C=200mA g-1) cycle performance under multiplying power.
Under 0.2C multiplying powers, after the circle of circulation 50, sample original material LMNCO, the specific discharge capacity of sample HM1, HM2 and HM5 are remained
158.5、209.4、218.9、207.5mAh g-1.Additionally, under 1C multiplying powers, the first discharge specific capacity of sample HM2 is
203.8mA h g-1Even if after the circle of circulation 100, specific discharge capacity is still stablized in 191.8mAh g-1, and capability retention is high
Up to 94.1%.Conversely, the first discharge specific capacity of uncoated original material LMNCO is only 166.6mAh g-1, the circle of circulation 100
After, electric discharge specific volume only only has 134.0mAh g-1, capability retention only only 80.4%.In addition specific discharge capacity is first
There is a process for rising in the several circulations begun, this is to activate caused, subsequent appearance in initial procedure due to Li2MnO3 phases
The decay of amount can be attributed to the corrosiveness of electrolyte.Even if under multiplying power (2C) higher, after the circle of circulation 100, sample
The specific capacity of HM2 remains in that to be 152.4mAh g-1, conversely, the specific discharge capacity of uncoated original material LMNCO is only
There are 104.3mAh g-1.The outstanding cycle performance and high rate performance of sample HM2 can be attributed to have three-dimensional lithium ion diffusion admittance
LiMn1.5Ni0.5O4The presence of clad.
Figure 15 is the high rate performance of spinelle stratiform heterogeneous structure material sample provided in an embodiment of the present invention.In order to assess
The high rate performance of material, to the material before and after coating as the battery of positive pole carries out constant-current charge under 0.1C multiplying powers, then exists respectively
Electric discharge 5 is enclosed under 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 0.1C.Result as shown in figure 15, such as measure with again by the electric discharge of all samples
The increase of rate and reduce, this can be attributed to the polarization phenomena that high current density is brought.It is apparent from by figure, sample HM2 has most
Good high rate performance.Even if in big multiplying power 5C, the specific discharge capacity of sample HM2 remains able to reach 125.1mAh g-1, it is much high
95.1mAh g in original material LMNCO under the multiplying power-1.And sample HM2 is by after high rate cyclic, then at 0.1C times
When under rate, specific discharge capacity remains able to reach 242.8mA h g-1, this can be tieed up when showing that sample structure is circulated under big multiplying power
It is fixed to keep steady.The high rate performance of sample HM2 so contacts, can be attributed to have three-dimensional lithium ion diffusion admittance
LiMn1.5Ni0.5O4The presence of clad.This clad serves not only as a protective layer and lithium ion can be promoted to spread.
But when the mass percent of cladding reaches 5%, the too thick one side of clad causes capacitance loss excessive, and still further aspect can hinder
Hinder the diffusion of lithium ion, therefore cause the multiplying power of sample HM5 poor.
Figure 16 is the mean voltage of spinelle stratiform heterogeneous structure material sample provided in an embodiment of the present invention.Lithium-rich
Positive electrode Li1.2Ni0.13Co0.13Mn0.54O2Voltage attenuation in cyclic process is also a problem for needing to solve.It is all
As shown in figure 16, the mean voltage of all samples is with the increase of cycle-index for the mean voltage that sample is circulated under 0.2C multiplying powers
And decline, this can be attributed to stratiform causes to the transformation of spinel structure.Additionally, the mean voltage of sample is with cladding quality
The growth of percentage and increase, this can be attributed to high pressure spinel structure LiMn1.5Ni0.5O4Content increase.Sample HM5 exists
After the circle of circulation 50, mean voltage can also reach 3.36V.
In sum, the preparation method of the spinelle stratiform heterogeneous structure material that the present invention is provided is simple and feasible, is prepared into
To material show outstanding chemical property, significantly improve the cycle performance of material, high rate performance and intermediate value electricity
Pressure.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.