CN105161686A - Double-coated manganese-base layered lithium-rich material and preparation method thereof - Google Patents
Double-coated manganese-base layered lithium-rich material and preparation method thereof Download PDFInfo
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- CN105161686A CN105161686A CN201510586654.1A CN201510586654A CN105161686A CN 105161686 A CN105161686 A CN 105161686A CN 201510586654 A CN201510586654 A CN 201510586654A CN 105161686 A CN105161686 A CN 105161686A
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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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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- H—ELECTRICITY
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Abstract
The invention discloses a double-coated manganese-base layered lithium-rich material and a preparation method thereof. The preparation method comprises the following steps: dropwise adding an oxalic acid isopropyl alcohol solution to a mixed solution containing a manganese salt, a cobalt salt and a nickel salt under a stirring condition, so as to obtain an oxalate precursor; reacting the oxalate precursor with a proper amount of lithium source and potassium chloride, so as to obtain a manganese-base layered lithium-rich oxide; adding the prepared manganese-base layered lithium-rich oxide to an aluminum salt solution, and dripping a fluoride solution to obtain an aluminum fluoride-coated manganese-base layered lithium-rich oxide; and finally, carrying out mixing and ultrasound on the aluminum fluoride-coated manganese-base layered lithium-rich oxide and a certain amount of graphene, and stirring and evaporating the mixture, so as to obtain the final product, namely the double-coated manganese-base layered lithium-rich material. The double-coated manganese-base layered lithium-rich material with high cycling stability and rate capability prepared by the preparation method has the advantages of high specific capacity, high rate capability and good cycle performance.
Description
Technical field
The present invention relates to technical field of lithium ion, rich lithium material of manganese basic unit shape particularly relating to a kind of double-coated and preparation method thereof.
Background technology
In recent years, manganese base layered oxide (Li [Li
am
b] O
2, M=TransitionMetals, a+b=1) and due to (>3.5VvsLi/Li under higher operating potential
+) can 200mAhg be discharged
-1above specific discharge capacity and extensively concerned and research.Its high power capacity and high voltage are expected to the anode material for lithium-ion batteries becoming high-energy-density of future generation.
But the greatest problem that manganese base layered oxide faces is relatively low conductivity and cyclical stability.Low conductivity is mainly by the LiMn of its inner non-electroactive
6superlattice system affected, cyclical stability is then because inner layered crystal structure is transformed into the spinel structure not having electro-chemical activity in cyclic process, and under serious transition metal ions stripping and high workload current potential electrolyte caused by the catalytic oxidation of material surface.The former can improve its conductivity by nanometer process or Surface coating electron conduction object; and the latter is except this natural characteristic of irreversible conversion of internal structure cannot change, the decomposition of transition metal ions stripping and electrolyte then can be alleviated by Surface coating inertia protective layer.Current coating layer material mainly contains metal oxide, fluoride and phosphate etc.Wherein performance is it is preferred that aluminum fluoride, and it has extremely stable electrochemicaUy inert and low molecular weight, but low electronics and ionic conductivity make it totally improve the high rate performance of material and not obvious.
Summary of the invention
Based on this, the object of this invention is to provide a kind of preparation method of the rich lithium material of manganese basic unit shape of double-coated.
Concrete technical scheme is as follows:
A preparation method for the rich lithium material of manganese basic unit shape of double-coated, comprises the steps:
(1) low whipping speed is 300 ~ 1000rmin
-1condition under manganese salt, cobalt salt and nickel salt are dissolved in deionized water, stir 0.5 ~ 2h, obtain solution A, wherein the concentration of manganese salt is 0.5 ~ 2molL
-1, the concentration of cobalt salt and nickel salt is 0.005 ~ 2.56molL
-1;
(2) low whipping speed is 300 ~ 1000rmin
-1condition under by oxalic acid aqueous isopropanol with 0.5 ~ 2drops
-1the obtained solution A of speed instillation step (1) in, then continue stirring 0.5 ~ 2h, then with 10000 ~ 20000rmin
-1rotating speed centrifugation product, with absolute ethanol washing 3 ~ 5 times, finally in 40 ~ 80 DEG C of vacuumize 12 ~ 24h, obtain oxalate precursor; The mole of its mesoxalic acid is equal with the integral molar quantity of metallics all in solution A, and the volume ratio of solution A and oxalic acid aqueous isopropanol is 1:0.4 ~ 2.5;
(3) after the oxalate precursor that step (2) is obtained fully being mixed with lithium source and potassium chloride, with 2 ~ 5 DEG C of min in the atmosphere of air or oxygen
-1heating rate be heated to 700 ~ 900 DEG C of process 8 ~ 15h, spend deionized water 3 ~ 5 times after being down to room temperature again, finally in 80 ~ 120 DEG C of vacuumize 12 ~ 24h, obtain the rich lithium material of manganese basic unit shape; Lithium wherein in lithium source, be 1.02 ~ 1.07:1 with the mol ratio of the total amount of the manganese in manganese salt and the cobalt in cobalt salt and the nickel in nickel salt, the mol ratio of lithium source and potassium chloride is 1:5 ~ 10;
(4) the rich lithium material low whipping speed of manganese basic unit shape step (3) obtained is 300 ~ 1000rmin
-1condition under join in aluminum salt solution, to stir after 0.5 ~ 2h, then with 0.5 ~ 2drops
-1speed instillation fluoride aqueous solution, then continue stirring 0.5 ~ 2h, then with 10000 ~ 20000rmin
-1rotating speed centrifugation product, with absolute ethanol washing 3 ~ 5 times, finally in 80 ~ 120 DEG C of vacuumize 12 ~ 24h, then be heated to 350 ~ 450 in an inert atmosphere and continue 3 ~ 8h, obtaining the rich lithium material of the coated manganese basic unit shape of aluminum fluoride; Wherein the mol ratio of chloride ion and the rich lithium material of described manganese basic unit shape is 1:156.25 ~ 1000, and the mol ratio of chloride ion and fluorine ion is 1:2.5 ~ 3.5;
(5) rich for manganese basic unit shape coated for the aluminum fluoride that step (4) is obtained lithium material and Graphene are carried out abundant ground and mixed by the mass ratio of 10 ~ 100:1, adding acetone again and carry out ultrasonic process 0.5 ~ 2h, is 300 ~ 1000rmin at rotating speed subsequently again
-1, temperature is 40 ~ 60 DEG C and carries out adding thermal agitation evaporation process, and the solid after evaporate to dryness, again in 80 ~ 120 DEG C of vacuumize 12 ~ 24h, obtains the rich lithium material of manganese basic unit shape of aluminum fluoride and Graphene double-coated.
Wherein in an embodiment, described manganese salt is at least one in manganese acetate, manganese chloride, manganese nitrate and manganese sulfate; Described cobalt salt is at least one in cobalt acetate, cobalt chloride, cobalt nitrate and cobaltous sulfate; Described nickel salt is at least one in nickel acetate, nickel chloride, nickel nitrate and nickelous sulfate.
Wherein in an embodiment, the mol ratio of the manganese in the manganese salt described in step (1) and the cobalt in cobalt salt and the nickel in nickel salt is 1:0.01 ~ 1.28:0.01 ~ 1.28.
Wherein in an embodiment, the oxalate concentration in described oxalic acid aqueous isopropanol is 0.25 ~ 2molL
-1.
Wherein in an embodiment, the lithium source described in step (3) is at least one in lithium hydroxide, lithium nitrate, lithium carbonate and lithium acetate.
Wherein in an embodiment, the aluminium salt described in step (4) is at least one in aluminum nitrate, aluminium chloride, aluminum sulfate, lithium acetate; Described fluoride is at least one in ammonium fluoride, ammonium acid fluoride, sodium fluoride, potassium fluoride; Aluminum salt solution concentration is 5 ~ 10mmolL
-1; Fluorinion concentration is 20 ~ 50mmolL
-1.
Wherein in an embodiment, the Graphene described in step (5) is at least one in single-layer graphene, bilayer graphene, multi-layer graphene.
Another object of the present invention is to provide a kind of rich lithium material of manganese basic unit shape of double-coated.
Concrete technical scheme is as follows:
The rich lithium material of manganese basic unit shape of the double-coated that above-mentioned preparation method prepares.
Principle of the present invention is:
Utilize based on the pole low solubility of transition metal oxalates in water alcohol system, and utilize the stability of oxalates, and the high degree of dispersion of oxalates in water alcohol system prepares manganese basic unit shape rich oxidate for lithium.Use oxalic acid solution as precipitation reagent, it can be formed under normal temperature not easily the transition metal oxalate precipitation that is oxidized by the oxygen in air, that a larger improvement is (because hydroxide is easily oxidized than traditional hydroxide, thus material changes, the error of calculation may be introduced in follow-up lithiumation process).And oxalate in water-Isopropanol Solvent with the interaction of water and isopropyl alcohol molecule and make the dispersiveness of oxalate denominationby better than simple dispersiveness in water, thus the reuniting effect of presoma is diminished, therefore can obtain the nano particle of the rich lithium material of manganese basic unit shape of even particle size.The chemical stability utilizing aluminum fluoride extremely strong is to be used as the coating layer of the rich lithium material of manganese basic unit shape, and its coated process adopts co-precipitation coated, and coating layer can be made so even, and thickness is controlled.Therefore can cover all sidedly on the rich lithium material of manganese basic unit shape, rich lithium material can be protected completely, intercepted the erosion of electrolyte, improve the charge and discharge cycles stability of material.And Graphene can promote the overall electronic conductivity of material effectively as second layer coating layer, the polarity effect of the rich lithium material of the manganese basic unit shape thus making aluminum fluoride coated reduces greatly, and high rate performance improves greatly.In addition; the secondary of Graphene is coated to be made to fluoridize the stability of aluminium lamination on the rich lithium material of manganese basic unit shape and is also improved to some extent; its constraint effect makes material the coming off and collapse probability and be effectively reduced of aluminum fluoride in charge and discharge process, thus also again improves the charge and discharge cycles stability of material.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the rich lithium material of the manganese basic unit shape of the aluminum fluoride that obtains of preparation method of the present invention and Graphene double-coated has high specific capacity, high high rate performance, and good cycle performance.
(2) in simple, the reaction of preparation method of the present invention, free from admixture generates, and course of reaction is efficient and convenient, does not need to introduce complicated operating process.
(3) oxalic acid solution is prepared lithium anode material as precipitation reagent by the present invention, and manganese ion can be prevented like this to be oxidized in preparation process, thus error of calculation when having influence on follow-up lithiumation, transition metal ions also can be made in addition to be uniformly distributed.
(4) the present invention utilizes oxalate in water and Isopropanol Solvent, have good dispersiveness and make oxalate precursor have high dispersion, therefore makes material granule size have good homogeneity.
(5) the present invention utilizes coprecipitation to make aluminum fluoride be coated on the rich oxidate for lithium of manganese basic unit shape on the surface, and coating layer can be made to become very even by the control of concentration and mixing speed, thickness is alternative setting also.Material surface can be made so all to be completely wrapped, to have intercepted electrolyte and contacted with the direct of material surface, electrolyte can be reduced on the one hand and react and oxidized decomposition with the transition metal of the high catalytic action of material surface under high potential; Then play shell effect on the other hand, effectively can slow down the transition metal stripping that material causes in cyclic process.Thus improve the cyclical stability of material.Again by the coated layer graphene of ultrasonic evaporation on the rich oxidate for lithium of manganese basic unit shape after coated aluminum fluoride, the method has and is evenly distributed, the advantages such as thickness is controlled, material can be covered by Graphene completely, therefore, on the coated basis of original aluminum fluoride, again reduce the contact of material and electrolyte, improve cyclical stability.And the ultra-high conductivity of Graphene can make the conductivity of material monolithic greatly promote, decrease the polarity effect of material under high current density, thus improve the high rate performance of material.In addition, being coated with of Graphene helps alleviate and fluoridizes the deformation and breaking of causing that aluminium lamination produces at the effect of stress that material charge and discharge process causes, therefore also from the cyclical stability that to a certain degree improve material monolithic.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the coated rich oxidate for lithium of manganese basic unit shape of aluminum fluoride prepared by the rich oxidate for lithium of manganese basic unit shape prepared of the rich lithium material of manganese basic unit shape of double-coated prepared by embodiment 1 and comparative example 1 and comparative example 2;
Fig. 2 is the TEM figure of the coated rich oxidate for lithium of manganese basic unit shape of aluminum fluoride prepared by the rich oxidate for lithium of manganese basic unit shape prepared of the rich lithium material of manganese basic unit shape of double-coated prepared by embodiment 1 and comparative example 1 and comparative example 2;
Fig. 3 is the charge-discharge magnification performance comparison figure of the lithium ion battery that the coated rich oxidate for lithium of manganese basic unit shape of aluminum fluoride prepared by the rich oxidate for lithium of manganese basic unit shape prepared of the rich lithium material of manganese basic unit shape of double-coated prepared by embodiment 1 and comparative example 1 and comparative example 2 makes;
Fig. 4 is the charge-discharge performance comparison diagram of the lithium ion battery that the coated rich oxidate for lithium of manganese basic unit shape of aluminum fluoride prepared by the rich oxidate for lithium of manganese basic unit shape prepared of the rich lithium material of manganese basic unit shape of double-coated prepared by embodiment 1 and comparative example 1 and comparative example 2 makes.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
There is a preparation method for the rich lithium material of manganese basic unit shape of high cyclical stability and doubly forthright double-coated, comprise the following steps:
(1) in the hub beaker of 100mL, add 20mL deionized water, then low whipping speed is 300rmin
-1condition under add 5g manganese acetate, 1.3g nickel acetate and 1.3g cobalt acetate, and make it fully disperse, obtain solution A;
(2) at 1000rmin
-1mechanical agitation under, in the solution A that step (1) obtains, slowly add 20mL1.3molL with the speed of 1 per second
-1oxalic acid aqueous isopropanol, then in 20000rmin
-1under carry out centrifugal, with absolute ethanol washing 5 times, and at 60 DEG C of vacuumize 12h, obtain oxalate precursor;
(3) oxalate precursor step (2) obtained and Li
2cO
3with KCl in molar ratio for 1:1.05:5.8 fully mixes; Mixture is sent into Muffle furnace, with 3 DEG C of min
-1ramp to 800 DEG C, constant temperature 10h; Spend deionized water 5 times after being down to room temperature again, finally in 120 DEG C of vacuumize 12h, obtain the rich lithium material of manganese basic unit shape.
(4) the rich lithium material low whipping speed of manganese basic unit shape step (3) obtained is 1000rmin
-1condition under join 50mL7.2mmolL
-1in aluminum nitrate solution, after stirring 1h, then with 1drops
-1speed instillation 50mL20mmolL
-1ammonium fluoride aqueous solution, then continues to stir 2h, then with 15000rmin
-1rotating speed centrifugation product, with absolute ethanol washing 3 times, finally in 120 DEG C of vacuumize 12h, then be heated to 400 DEG C in an inert atmosphere and continue 5h, obtaining the rich lithium material of the coated manganese basic unit shape of aluminum fluoride.
(5) by rich for manganese basic unit shape coated for aluminum fluoride obtained for step (4) lithium material and Graphene in mass ratio for 19:1 carries out abundant ground and mixed, then adding 30mL acetone and carry out ultrasonic process 2h, is 1000rmin at rotating speed subsequently again
-1, temperature is 60 DEG C and carries out adding thermal agitation evaporation process, and the solid after evaporate to dryness, again in 120 DEG C of vacuumize 12h, obtains the rich lithium material of manganese basic unit shape of aluminum fluoride and Graphene double-coated.
Embodiment 2
There is a preparation method for the rich lithium material of manganese basic unit shape of high cyclical stability and doubly forthright double-coated, comprise the following steps:
(1) in the hub beaker of 100mL, add 30mL deionized water, then low whipping speed is 800rmin
-1condition under add 10g manganese acetate, 5.2g nickel acetate and 3.4g cobalt acetate, and make it fully disperse, obtain solution A;
(2) at 500rmin
-1mechanical agitation under, in the solution A that step (1) obtains, slowly add 50mL1.49molL with the speed of 0.5 per second
-1oxalic acid aqueous isopropanol, then in 18000rmin
-1under carry out centrifugal, with absolute ethanol washing 3 times, and at 80 DEG C of vacuumize 18h, obtain oxalate precursor;
(3) oxalate precursor step (2) obtained and Li
2cO
3with KCl in molar ratio for 1:1.07:8.56 fully mixes; Mixture is sent into Muffle furnace, with 5 DEG C of min
-1ramp to 850 DEG C, constant temperature 12h; Spend deionized water 3 times after being down to room temperature again, finally in 110 DEG C of vacuumize 18h, obtain the rich lithium material of manganese basic unit shape.
(4) the rich lithium material low whipping speed of manganese basic unit shape step (3) obtained is 500rmin
-1condition under join 80mL5mmolL
-1in aluminum nitrate solution, after stirring 0.5h, then with 1.5drops
-1speed instillation 40mL32mmolL
-1ammonium fluoride aqueous solution, then continues to stir 1.5h, then with 20000rmin
-1rotating speed centrifugation product, with absolute ethanol washing 4 times, finally in 100 DEG C of vacuumize 16h, then be heated to 450 DEG C in an inert atmosphere and continue 3h, obtaining the rich lithium material of the coated manganese basic unit shape of aluminum fluoride.
(5) by rich for manganese basic unit shape coated for aluminum fluoride obtained for step (4) lithium material and Graphene in mass ratio for 30:1 carries out abundant ground and mixed, then adding 50mL acetone and carry out ultrasonic process 0.5h, is 600rmin at rotating speed subsequently again
-1, temperature is 50 DEG C and carries out adding thermal agitation evaporation process, and the solid after evaporate to dryness, again in 100 DEG C of vacuumize 15h, obtains the rich lithium material of manganese basic unit shape of aluminum fluoride and Graphene double-coated.
Embodiment 3
There is a preparation method for the rich lithium material of manganese basic unit shape of high cyclical stability and doubly forthright double-coated, comprise the following steps:
(1) in the hub beaker of 100mL, add 50mL deionized water, then low whipping speed is 300rmin
-1condition under add 8g manganese acetate, 4.5g nickel acetate and 6.2g cobalt acetate, and make it fully disperse, obtain solution A;
(2) at 700rmin
-1mechanical agitation under, in the solution A that step (1) obtains, slowly add 30mL2.5molL with the speed of 2 per second
-1oxalic acid aqueous isopropanol, then in 19000rmin
-1under carry out centrifugal, with absolute ethanol washing 4 times, and at 70 DEG C of vacuumize 15h, obtain oxalate precursor;
(3) oxalate precursor step (2) obtained and Li
2cO
3with KCl in molar ratio for 1:1.03:8.8 fully mixes; Mixture is sent into Muffle furnace, with 4 DEG C of min
-1ramp to 750 DEG C, constant temperature 15h; Spend deionized water 4 times after being down to room temperature again, finally in 100 DEG C of vacuumize 18h, obtain the rich lithium material of manganese basic unit shape.
(4) the rich lithium material low whipping speed of manganese basic unit shape step (3) obtained is 1000rmin
-1condition under join 60mL10mmolL
-1in aluminum nitrate solution, after stirring 1.5h, then with 1.5drops
-1speed instillation 40mL50mmolL
-1ammonium fluoride aqueous solution, then continues to stir 1.5h, then with 18000rmin
-1rotating speed centrifugation product, with absolute ethanol washing 5 times, finally in 110 DEG C of vacuumize 13h, then be heated to 380 DEG C in an inert atmosphere and continue 4.5h, obtaining the rich lithium material of the coated manganese basic unit shape of aluminum fluoride.
(5) by rich for manganese basic unit shape coated for aluminum fluoride obtained for step (4) lithium material and Graphene in mass ratio for 99:1 carries out abundant ground and mixed, then adding 20mL acetone and carry out ultrasonic process 1h, is 800rmin at rotating speed subsequently again
-1, temperature is 55 DEG C and carries out adding thermal agitation evaporation process, and the solid after evaporate to dryness, again in 110 DEG C of vacuumize 18h, obtains the rich lithium material of manganese basic unit shape of aluminum fluoride and Graphene double-coated.
Comparative example 1
A preparation method for the rich oxidate for lithium of manganese basic unit shape, comprises the following steps:
(1) in the hub beaker of 100mL, add 20mL deionized water, then low whipping speed is 300rmin
-1condition under add 5g manganese acetate, 1.3g nickel acetate and 1.3g cobalt acetate, and make it fully disperse, obtain solution A;
(2) at 1000rmin
-1mechanical agitation under, in the solution A that step (1) obtains, slowly add 20mL1.3molL with the speed of 1 per second
-1oxalic acid aqueous isopropanol, then in 20000rmin
-1under carry out centrifugal, with absolute ethanol washing 5 times, and at 60 DEG C of vacuumize 12h, obtain oxalate precursor;
(3) oxalate precursor step (2) obtained and Li
2cO
3with KCl in molar ratio for 1:1.05:5.8 fully mixes; Mixture is sent into Muffle furnace, with 3 DEG C of min
-1ramp to 800 DEG C, constant temperature 10h; Spend deionized water 5 times after being down to room temperature again, finally in 120 DEG C of vacuumize 12h, obtain the rich lithium material of manganese basic unit shape.
Comparative example 2
A preparation method for the rich oxidate for lithium of manganese basic unit shape that aluminum fluoride is coated, comprises the following steps:
(1) in the hub beaker of 100mL, add 20mL deionized water, then low whipping speed is 300rmin
-1condition under add 5g manganese acetate, 1.3g nickel acetate and 1.3g cobalt acetate, and make it fully disperse, obtain solution A;
(2) at 1000rmin
-1mechanical agitation under, in the solution A that step (1) obtains, slowly add 20mL1.3molL with the speed of 1 per second
-1oxalic acid aqueous isopropanol, then in 20000rmin
-1under carry out centrifugal, with absolute ethanol washing 5 times, and at 60 DEG C of vacuumize 12h, obtain oxalate precursor;
(3) oxalate precursor step (2) obtained and Li
2cO
3with KCl in molar ratio for 1:1.05:5.8 fully mixes; Mixture is sent into Muffle furnace, with 3 DEG C of min
-1ramp to 800 DEG C, constant temperature 10h; Spend deionized water 5 times after being down to room temperature again, finally in 120 DEG C of vacuumize 12h, obtain the rich lithium material of manganese basic unit shape.
(4) the rich lithium material low whipping speed of manganese basic unit shape step (3) obtained is 1000rmin
-1condition under join 50mL7.2mmolL
-1in aluminum nitrate solution, after stirring 1h, then with 1drops
-1speed instillation 50mL20mmolL
-1ammonium fluoride aqueous solution, then continues to stir 2h, then with 15000rmin
-1rotating speed centrifugation product, with absolute ethanol washing 3 times, finally in 120 DEG C of vacuumize 12h, then be heated to 400 DEG C in an inert atmosphere and continue 5h, obtaining the rich lithium material of the coated manganese basic unit shape of aluminum fluoride.
Test case
(1) half-cell assembling: prepared by embodiment 1 have manganese basic unit shape richness oxidate for lithium prepared by high cyclical stability and the rich lithium material of doubly forthright manganese basic unit shape and comparative example 1 and the coated manganese basic unit shape richness oxidate for lithium of aluminum fluoride prepared by comparative example 2, respectively with acetylene black and PVDF in mass ratio 8:1:1 carry out slurrying and be coated with, then being cut into the pole piece of 1 × 1, is that negative pole is assembled into half-cell with metal lithium sheet.
(2) charge-discharge test: the lithium ion battery that having of embodiment 1 the being prepared rich oxidate for lithium of manganese basic unit shape prepared by high cyclical stability and the rich lithium material of doubly forthright manganese basic unit shape and comparative example 1 and the coated manganese basic unit shape richness oxidate for lithium of aluminum fluoride prepared by comparative example 2 make, carries out discharge and recharge under carrying out constant current under different multiplying.
Fig. 3 is the high rate performance comparison diagram of the lithium ion battery that the coated manganese basic unit shape richness oxidate for lithium of having of preparing of embodiment 1 manganese basic unit shape richness oxidate for lithium prepared by high cyclical stability and the rich lithium material of doubly forthright manganese basic unit shape and comparative example 1 and aluminum fluoride prepared by comparative example 2 makes.As seen from Figure 3, embodiment 1 gained has high cyclical stability and the rich lithium material of doubly forthright manganese basic unit shape at 1C, 2C and 5C (1C=200mAg
-1) multiplying power charge and discharge circulation in, the specific capacity of embodiment 1 is respectively 159.9.9mAhg
-1, 139.8mAhg
-1and 114.5mAhg
-1, and the specific capacity of comparative example 1 only has 143.5mAhg respectively
-1, 120.8mAhg
-1and 81.6mAhg
-1, and the specific capacity of comparative example 2 only has 154.5mAhg respectively
-1, 130.7mAhg
-1and 95mAhg
-1, after being circulated throughout by 60 rate charge-discharges, the specific capacity of embodiment 1 still maintains 143.3mAhg
-1, and comparative example 1 and comparative example 2 only have respectively, 123.6mAhg
-1and 129.9mAhg
-1, show that the rich oxidate for lithium of manganese basic unit shape that the rich lithium material of the manganese basic unit shape with high cyclical stability and doubly forthright double-coated prepared by the present invention is prepared than conventional method and the coated rich oxidate for lithium of manganese basic unit shape of aluminum fluoride have higher high rate performance and cycle performance.
Fig. 4 is the charge-discharge performance comparison diagram of the lithium ion battery that the coated manganese basic unit shape richness oxidate for lithium of having of preparing of embodiment 1 manganese basic unit shape richness oxidate for lithium prepared by high cyclical stability and the rich lithium material of doubly forthright manganese basic unit shape and comparative example 1 and aluminum fluoride prepared by comparative example 2 makes.As shown in Figure 4, embodiment 1 gained to have high cyclical stability and the rich lithium material of the doubly forthright manganese basic unit shape discharge capacity after 248 times that circulates under 2C multiplying power be 101.9mAhg
-1, capability retention is 70.2%, and the coated rich oxidate for lithium of manganese basic unit shape of the aluminum fluoride of the rich oxidate for lithium of the manganese basic unit shape of comparative example 1 gained and the comparative example 2 gained discharge capacity after 248 times that circulates equally is respectively 64.1mAhg
-1and 80.8mAhg
-1, capability retention is respectively 51.1% and 61.6%.Show prepared by the present invention there is the rich oxidate for lithium of manganese basic unit shape that high cyclical stability and the rich lithium material of doubly forthright manganese basic unit shape prepared than conventional method and the coated rich oxidate for lithium of manganese basic unit shape of aluminum fluoride has good cycle performance.
From the detection data of Fig. 3, Fig. 4, it is high that what preparation method of the present invention obtained have high cyclical stability and the rich lithium material of doubly forthright manganese basic unit shape have charge/discharge capacity, good rate capability, and stable cycle performance.
To be the SEM figure of the coated rich oxidate for lithium of manganese basic unit shape of having of preparing of the embodiment 1 rich oxidate for lithium of manganese basic unit shape prepared by high cyclical stability and the rich lithium material of doubly forthright manganese basic unit shape and comparative example 1 and aluminum fluoride prepared by comparative example 2, Fig. 2 be Fig. 1 that TEM that prepared by embodiment 1 has the rich oxidate for lithium of manganese basic unit shape prepared by high cyclical stability and the rich lithium material of doubly forthright manganese basic unit shape and comparative example 1 and a coated manganese basic unit shape richness oxidate for lithium of aluminum fluoride prepared by comparative example 2 schemes.As can be seen from Figure 1, the apparent structure pattern of three kinds of materials is basically identical, illustrates that Surface coating process can't cause large change to material surface.As can be seen from Figure 2, the material granule surface of comparative example 2 and embodiment 1 is all coated uniform coating layer of a layer thickness, illustrates that aluminum fluoride can cover the surface of material very equably in deposition process.Effectively can stop that electrolyte contacts with the direct of material like this, reduce electrolyte and decompose at the catalytic oxidation of material surface, meanwhile, the capacity attenuation that coating layer effectively can reduce the irreversible stripping of transition metal ions in charge and discharge cycles process and cause.See from Fig. 2, the material granule surface of embodiment 1, except having the uniform coating layer of one deck, is also covered with the Graphene of thin layer in intergranular outside again, illustrates that the distribution of Graphene is comparatively even, consistency of thickness.So not only effectively can improve the overall electron conduction of material, can also electrolyte be suppressed further to decompose at the catalytic oxidation of material surface, the mechanical structure of robust material, reduce material internal stress effect and division of caving in of causing in charge and discharge process, thus improve cyclical stability and the high rate performance of material.
Each technical characteristic of the above embodiment can combine arbitrarily, for making description succinct, the all possible combination of each technical characteristic in above-described embodiment is not all described, but, as long as the combination of these technical characteristics does not exist contradiction, be all considered to be the scope that this specification is recorded.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be construed as limiting the scope of the patent.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (8)
1. a preparation method for the rich lithium material of the manganese basic unit shape of double-coated, comprises the steps:
(1) low whipping speed is 300 ~ 1000rmin
-1condition under manganese salt, cobalt salt and nickel salt are dissolved in deionized water, stir 0.5 ~ 2h, obtain solution A, wherein the concentration of manganese salt is 0.5 ~ 2molL
-1, the concentration of cobalt salt and nickel salt is 0.005 ~ 2.56molL
-1;
(2) low whipping speed is 300 ~ 1000rmin
-1condition under by oxalic acid aqueous isopropanol with 0.5 ~ 2drops
-1the obtained solution A of speed instillation step (1) in, then continue stirring 0.5 ~ 2h, then with 10000 ~ 20000rmin
-1rotating speed centrifugation product, with absolute ethanol washing 3 ~ 5 times, finally in 40 ~ 80 DEG C of vacuumize 12 ~ 24h, obtain oxalate precursor; The mole of its mesoxalic acid is equal with the integral molar quantity of metallics all in solution A, and the volume ratio of solution A and oxalic acid aqueous isopropanol is 1:0.4 ~ 2.5;
(3) after the oxalate precursor that step (2) is obtained fully being mixed with lithium source and potassium chloride, with 2 ~ 5 DEG C of min in the atmosphere of air or oxygen
-1heating rate be heated to 700 ~ 900 DEG C of process 8 ~ 15h, spend deionized water 3 ~ 5 times after being down to room temperature again, finally in 80 ~ 120 DEG C of vacuumize 12 ~ 24h, obtain the rich lithium material of manganese basic unit shape; Lithium wherein in lithium source, be 1.02 ~ 1.07:1 with the mol ratio of the total amount of the manganese in manganese salt and the cobalt in cobalt salt and the nickel in nickel salt, the mol ratio of lithium source and potassium chloride is 1:5 ~ 10;
(4) the rich lithium material low whipping speed of manganese basic unit shape step (3) obtained is 300 ~ 1000rmin
-1condition under join in aluminum salt solution, to stir after 0.5 ~ 2h, then with 0.5 ~ 2drops
-1speed instillation fluoride aqueous solution, then continue stirring 0.5 ~ 2h, then with 10000 ~ 20000rmin
-1rotating speed centrifugation product, with absolute ethanol washing 3 ~ 5 times, finally in 80 ~ 120 DEG C of vacuumize 12 ~ 24h, then be heated to 350 ~ 450 in an inert atmosphere and continue 3 ~ 8h, obtaining the rich lithium material of the coated manganese basic unit shape of aluminum fluoride; Wherein the mol ratio of chloride ion and the rich lithium material of described manganese basic unit shape is 1:156.25 ~ 1000, and the mol ratio of chloride ion and fluorine ion is 1:2.5 ~ 3.5;
(5) rich for manganese basic unit shape coated for the aluminum fluoride that step (4) is obtained lithium material and Graphene are carried out abundant ground and mixed by the mass ratio of 10 ~ 100:1, adding acetone again and carry out ultrasonic process 0.5 ~ 2h, is 300 ~ 1000rmin at rotating speed subsequently again
-1, temperature is 40 ~ 60 DEG C and carries out adding thermal agitation evaporation process, and the solid after evaporate to dryness, again in 80 ~ 120 DEG C of vacuumize 12 ~ 24h, obtains the rich lithium material of manganese basic unit shape of aluminum fluoride and Graphene double-coated.
2. preparation method according to claim 1, is characterized in that, described manganese salt is at least one in manganese acetate, manganese chloride, manganese nitrate and manganese sulfate; Described cobalt salt is at least one in cobalt acetate, cobalt chloride, cobalt nitrate and cobaltous sulfate; Described nickel salt is at least one in nickel acetate, nickel chloride, nickel nitrate and nickelous sulfate.
3. preparation method according to claim 1, is characterized in that, the mol ratio of the manganese in the manganese salt described in step (1) and the cobalt in cobalt salt and the nickel in nickel salt is 1:0.01 ~ 1.28:0.01 ~ 1.28.
4. the preparation method according to any one of claim 1-3, is characterized in that, the oxalate concentration in described oxalic acid aqueous isopropanol is 0.25 ~ 2molL
-1.
5. the preparation method according to any one of claim 1-3, is characterized in that, the lithium source described in step (3) is at least one in lithium hydroxide, lithium nitrate, lithium carbonate and lithium acetate.
6. the preparation method according to any one of claim 1-3, is characterized in that, the aluminium salt described in step (4) is at least one in aluminum nitrate, aluminium chloride, aluminum sulfate, lithium acetate; Described fluoride is at least one in ammonium fluoride, ammonium acid fluoride, sodium fluoride, potassium fluoride; Aluminum salt solution concentration is 5 ~ 10mmolL
-1; Fluorinion concentration is 20 ~ 50mmolL
-1.
7. the preparation method according to any one of claim 1-3, is characterized in that, the Graphene described in step (5) is at least one in single-layer graphene, bilayer graphene, multi-layer graphene.
8. the rich lithium material of manganese basic unit shape of the double-coated that the preparation method described in any one of claim 1-7 prepares.
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| CN111933914A (en) * | 2020-09-03 | 2020-11-13 | 中南大学 | Vanadium pentoxide and rGO co-coated gradient ternary cathode material and preparation method thereof |
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