CN104362334A - Preparation method of lithium metasilicate coated lithium-enriched laminar positive electrode material of lithium ion battery - Google Patents
Preparation method of lithium metasilicate coated lithium-enriched laminar positive electrode material of lithium ion battery Download PDFInfo
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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Abstract
The invention relates to a preparation method of a lithium metasilicate coated lithium-enriched laminar positive electrode material of a lithium ion battery, belonging to the technical field of inorganic materials. According to the method, the lithium metasilicate coated lithium-enriched laminar positive electrode material is prepared by simple co-precipitation, and hydrothermal and high-temperature solid-phase sintering reaction. According to the method, the synthesis process is simple, the production efficiency is high and large-scale production is facilitated. According to the method, raw materials for reactants are easily available, have no toxin and are low in cost; a production process does not need special protection and reaction conditions are easy to control; and the obtained product has the advantages of large output, good result repeatability and the like. Compared with an uncoated material, the lithium metasilicate coated lithium-enriched laminar positive electrode material prepared by the method has the great improvement in the aspects of electrochemical performances including battery specific capacity, cycling stability, multiplying power and the like.
Description
Technical field
The present invention relates to the preparation method of the rich lithium layered cathode material of a kind of lithium metasilicate coated lithium ion battery, belong to technical field of inorganic material.
Background technology
The problems such as the sharply shortage of the non-renewable resources such as the day by day serious and fossil that world environments is polluted make the exploitation of new forms of energy seem particularly important.Lithium ion battery is as the energy storage system of a new generation, and the advantages such as efficient with it, clean, high-energy-density get most of the attention, and have been widely used in the miniature electronic product scopes such as mobile phone, notebook computer, digital camera.But, the specific capacity of lithium ion battery, energy density and fail safe etc. also cannot meet the needs of Development of Electric Vehicles, and the Main Bottleneck of limiting lithium ion cell energy density is positive electrode, therefore develop focus and difficult point that the positive electrode with high-energy-density is becoming Study on Li-ion batteries.Rich lithium layered cathode material because having theoretical capacity high (300mAh/g), low in raw material price, advantages of environment protection be considered to one of positive electrode of lithium ion battery most potentiality of future generation.But the problems such as rich lithium layered cathode material exists, and first charge-discharge efficiency is low, platform voltage continues to reduce, high rate performance and cyclical stability difference, these factors constrain its extensive use on electric automobile.The main method of current improvement rich lithium layered cathode material chemical property is coated (that is: at its Surface coating one deck oxide or fluoride materials etc.), element doping (as transition metals such as Cr, Ti).These methods can improve cyclical stability and high rate performance (fast charging and discharging performance) to a certain extent, but the improvement effect of high rate performance and electrochemistry capacitance long-time stability also not ideal, therefore need improving one's methods of development of new.Lithium metasilicate (being mainly lithium metasilicate and positive lithium metasilicate) is as a kind of Lithium Ionic Conducting Materials, there is higher lithium ion transport performance, if be coated on positive electrode surface, the transmission of lithium ion will be conducive to, thus greatly improve the cyclical stability, particularly high rate performance of lithium ion battery.But due to the restriction by synthetic method, also nobody reports so far.
Summary of the invention
The object of the invention is the preparation method proposing the rich lithium layered cathode material of a kind of lithium metasilicate (being mainly lithium metasilicate and positive lithium metasilicate) coated lithium ion battery, the preparation technology of existing anode material for lithium-ion batteries is improved, to improve cyclical stability and the high rate performance of the lithium ion battery of positive active material assembling.
The preparation method of the rich lithium layered cathode material of the lithium metasilicate coated lithium ion battery that the present invention proposes, comprises the following steps:
(1) preparation of oxalate precursor:
According to mol ratio by NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, obtain metallic ion mixed liquor, then configure the NaC that molar concentration is 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution joins in metallic ion mixed liquor, produce sediment, stir after 2 hours, centrifugation, use deionized water and washes of absolute alcohol sediment 2 times respectively, sediment is placed in 70 DEG C of baking ovens dry 12 hours, obtain oxalate precursor, the molecular formula of oxalate precursor is: Ni0.35Mn0.65C
2o
42H
2o;
(2) SiO
2the preparation of coated oxalate precursor:
Oxalate precursor 1.2mmol obtained above is dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse, according to Si:(Ni+Mn)=the molar ratio of α: 100, add the Si (OC that mass percent concentration is 10%wt
2h
5)
4ethanol solution, wherein 1≤α≤15, dispersed with stirring is even, obtain mixed liquor, then this mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, at 150 ~ 180 DEG C, process 5 ~ 12 hours, naturally after cooling, centrifuge washing, the sediment obtained by centrifuge washing at 80 DEG C dry 12 hours, obtains SiO
2coated oxalate precursor;
(3) the coated xLi of lithium metasilicate
2mnO
3(1-x) LiNi
0.
5mn
0.
5o
2preparation:
According to Li:(Ni+Mn)=(100+100x+2 α)/(100+ α): 1 or Li:(Ni+Mn)=(100+100x+4 α)/(100+ α): the molar ratio of 1, wherein 0 < x < 1,1≤α≤15, by the oxalate precursor of above-mentioned preparation and LiOHH
2o grinds and mixes, and is placed in Muffle furnace, with the heating rate of 3 ~ 5 DEG C/min, processes 12 ~ 24 hours, naturally cool to room temperature at 700 ~ 1000 DEG C, obtains the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery.
The preparation method of the rich lithium layered cathode material of a kind of lithium metasilicate coated lithium ion battery that the present invention proposes, its advantage is: the inventive method has prepared the evenly coated rich lithium layered cathode material of lithium metasilicate by simple co-precipitation, synchronous lithiumation and high temperature solid-phase sintering reaction.The inventive method synthesis technique is simple, and production efficiency is high, suitability for scale production.And the raw material required for the inventive method reactant is easy to get, nontoxic, with low cost, production process is without the need to special protection, and easy control of reaction conditions, the product obtained has the advantages such as output is large, result is reproducible.The rich lithium layered cathode material that the lithium metasilicate prepared of the inventive method is coated, compared with existing not coated material, is all greatly improved and improves in the battery performances such as battery specific capacity, cyclical stability and multiplying power.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the coated rich lithium layered cathode material of lithium metasilicate prepared by the inventive method.
Fig. 2 be lithium metasilicate coated with the specific discharge capacity circulation comparison diagram of not coated rich lithium layered cathode material under 100mA/g current density.
Fig. 3 be lithium metasilicate coated with the specific discharge capacity circulation comparison diagram of not coated rich lithium layered cathode material under different multiplying.
Embodiment
The preparation method of the rich lithium layered cathode material of the lithium metasilicate coated lithium ion battery that the present invention proposes, comprises the following steps:
(1) preparation of oxalate precursor:
According to mol ratio by NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, obtain metallic ion mixed liquor, then configure the NaC that molar concentration is 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution joins in metallic ion mixed liquor, produce sediment, stir after 2 hours, centrifugation, use deionized water and washes of absolute alcohol sediment 2 times respectively, sediment is placed in 70 DEG C of baking ovens dry 12 hours, obtain oxalate precursor, the molecular formula of oxalate precursor is: Ni0.35Mn0.65C
2o
42H
2o;
(2) SiO
2the preparation of coated oxalate precursor:
Oxalate precursor 1.2mmol obtained above is dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse, according to Si:(Ni+Mn)=the molar ratio of α: 100, add the Si (OC that mass percent concentration is 10%wt
2h
5)
4ethanol solution, wherein 1≤α≤15, dispersed with stirring is even, obtain mixed liquor, then this mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, at 150 ~ 180 DEG C, process 5 ~ 12 hours, naturally after cooling, centrifuge washing, the sediment obtained by centrifuge washing at 80 DEG C dry 12 hours, obtains SiO
2coated oxalate precursor;
(3) the coated xLi of lithium metasilicate
2mnO
3(1-x) LiNi
0.5mn
0.5o
2preparation:
According to Li:(Ni+Mn)=(100+100x+2 α)/(100+ α): 1 or Li:(Ni+Mn)=(100+100x+4 α)/(100+ α): the molar ratio of 1, wherein 0 < x < 1,1≤α≤15, by the oxalate precursor of above-mentioned preparation and LiOHH
2o grinds and mixes, and is placed in Muffle furnace, with the heating rate of 3 ~ 5 DEG C/min, processes 12 ~ 24 hours, naturally cool to room temperature at 700 ~ 1000 DEG C, obtains the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery.
Introduce the embodiment of the inventive method below:
Embodiment one:
(1) preparation of oxalate precursor: according to mol ratio by NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=3:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 180 degrees Celsius, process 5 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.3Li of lithium metasilicate
2mnO
30.7LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C, processes 12 hours, can obtain the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery after naturally cooling to room temperature.
The coated rich lithium layered cathode material of gained lithium metasilicate characterizes: the coated rich lithium layered cathode material of gained lithium metasilicate can be the solid solution of pure phase through X-ray diffractometer analysis, as shown in Figure 1.Rich lithium material coated to lithium metasilicate under the discharge current density of 100mA/g carries out battery performance test, and charge and discharge cycles 50 is enclosed, and contrast with not coated rich lithium material, battery discharge specific capacity and cyclical stability significantly improve as shown in Figure 2.At 40mA/g, 80mA/g, 120mAh/g, 160mA/g, 200mA/g, 300mA/g, under 400mA/g discharge current density, battery high rate performance is tested, result as shown in Figure 3 lithium metasilicate coated after rich lithium material high rate performance be obviously better than not coated rich lithium material.
Embodiment two:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=3:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 160 degrees Celsius, process 8 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.3Li of lithium metasilicate
2mnO
30.7LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C, processes 12 hours, can obtain the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery after naturally cooling to room temperature.
Embodiment three:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=1:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 150 degrees Celsius, process 12 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.3Li of lithium metasilicate
2mnO
30.7LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C, processes 12 hours, can obtain the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery after naturally cooling to room temperature.
Embodiment four:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of sediment immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol sediment 2 times respectively, sediment is placed in 70 degree of baking ovens dry 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=5:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 180 degrees Celsius, process 10 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.3Li of lithium metasilicate
2mnO
30.7LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C, processes 12 hours, can obtain the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery after naturally cooling to room temperature.
Embodiment five:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=7:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 180 degrees Celsius, process 5 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.3Li of lithium metasilicate
2mnO
30.7LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 900 DEG C, processes 12 hours, can obtain the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery after naturally cooling to room temperature.
Embodiment six:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=10:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 180 degrees Celsius, process 10 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.3Li of lithium metasilicate
2mnO
30.7LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 950 DEG C, processes 15 hours, can obtain the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery after naturally cooling to room temperature.
Embodiment seven:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=15:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 160 degrees Celsius, process 12 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.3Li of lithium metasilicate
2mnO
30.7LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C, processes 24 hours, can obtain the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery after naturally cooling to room temperature.
Embodiment eight:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=3:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 170 degrees Celsius, process 10 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.3Li of lithium metasilicate
2mnO
30.7LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 850 DEG C, processes 12 hours, can obtain the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery after naturally cooling to room temperature.
Embodiment nine:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=3:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 180 degrees Celsius, process 8 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.3Li of lithium metasilicate
2mnO
30.7LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 1000 DEG C, processes 12 hours, can obtain the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery after naturally cooling to room temperature.
Embodiment ten:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=10:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 150 degrees Celsius, process 12 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.3Li of lithium metasilicate
2mnO
30.7LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 1000 DEG C, processes 12 hours, can obtain the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery after naturally cooling to room temperature.
Embodiment 11:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=3:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 180 degrees Celsius, process 5 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.2Li of lithium metasilicate
2mnO
30.8LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C, processes 12 hours, can obtain the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery after naturally cooling to room temperature.
Embodiment 12:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=5:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 180 degrees Celsius, process 5 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.4Li of lithium metasilicate
2mnO
30.6LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C, processes 12 hours, can obtain the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery after naturally cooling to room temperature.
Embodiment 13:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=3:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 180 degrees Celsius, process 5 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.5Li of lithium metasilicate
2mnO
30.5LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C, processes 12 hours, can obtain the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery after naturally cooling to room temperature.
Embodiment 14:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=15:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 180 degrees Celsius, process 5 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.5Li of lithium metasilicate
2mnO
30.5LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 900 DEG C, processes 15 hours, can obtain the rich lithium layered cathode material of the coated lithium ion battery of lithium metasilicate after naturally cooling to room temperature.
Embodiment 15:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=3:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 180 degrees Celsius, process 5 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.2Li of lithium metasilicate
2mnO
30.8LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 1000 DEG C, processes 12 hours, can obtain the rich lithium layered cathode material of the coated lithium ion battery of lithium metasilicate after naturally cooling to room temperature.
Embodiment 16:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=5:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 180 degrees Celsius, process 5 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.2Li of lithium metasilicate
2mnO
30.8LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C, processes 12 hours, can obtain the rich lithium layered cathode material of the coated lithium ion battery of lithium metasilicate after naturally cooling to room temperature.
Embodiment 17:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, then configure the NaC of 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 70 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) SiO
2the synthesis of coated oxalate precursor: take oxalate precursor 1.2mmol obtained above and be dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse.According to Si:(Ni+Mn) molar ratio of=15:100, add the Si (OC that concentration is 10%wt
2h
5)
4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 180 degrees Celsius, process 5 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated 0.2Li of lithium metasilicate
2mnO
30.8LiNi
0.5mn
0.5o
2preparation: according to mol ratio by the oxalate precursor of above-mentioned preparation and LiOHH
2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 900 DEG C, processes 12 hours, can obtain the rich lithium layered cathode material of the coated lithium ion battery of lithium metasilicate after naturally cooling to room temperature.
Claims (1)
1. a preparation method for the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery, is characterized in that the method comprises the following steps:
(1) preparation of oxalate precursor:
According to mol ratio by NiSO
4, MnSO
4be dissolved in 50ml water, make the molar concentration of W metal ion and metal M n ion be 2mol/L, obtain metallic ion mixed liquor, then configure the NaC that molar concentration is 2mol/L
2o
4solution 50mL, by NaC under magnetic agitation
2o
4solution joins in metallic ion mixed liquor, produces sediment, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol sediment 2 times respectively, sediment is placed in 70 DEG C of baking ovens dry 12 hours, obtain oxalate precursor, the molecular formula of oxalate precursor is: Ni
0.35mn
0.65c
2o
42H
2o;
(2) SiO
2the preparation of coated oxalate precursor:
Oxalate precursor 1.2mmol obtained above is dispersed in 13ml absolute ethyl alcohol, stirs and ultrasonic disperse, according to Si:(Ni+Mn)=the molar ratio of α: 100, add the Si (OC that mass percent concentration is 10%wt
2h
5)
4ethanol solution, wherein 1≤α≤15, dispersed with stirring is even, obtain mixed liquor, then this mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, at 150 ~ 180 DEG C, process 5 ~ 12 hours, naturally after cooling, centrifuge washing, the sediment obtained by centrifuge washing at 80 DEG C dry 12 hours, obtains SiO
2coated oxalate precursor;
(3) the coated xLi of lithium metasilicate
2mnO
3(1-x) LiNi
0.5mn
0.5o
2preparation:
According to Li:(Ni+Mn)=(100+100x+2 α)/(100+ α): 1 or Li:(Ni+Mn)=(100+100x+4 α)/(100+ α): the molar ratio of 1, wherein 0 < x < 1,1≤α≤15, by the oxalate precursor of above-mentioned preparation and LiOHH
2o grinds and mixes, and is placed in Muffle furnace, with the heating rate of 3 ~ 5 DEG C/min, processes 12 ~ 24 hours, naturally cool to room temperature at 700 ~ 1000 DEG C, obtains the rich lithium layered cathode material of lithium metasilicate coated lithium ion battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901905A (en) * | 2009-05-27 | 2010-12-01 | 比亚迪股份有限公司 | Titanium composite, preparation method thereof and application thereof |
| CN102544478A (en) * | 2010-12-29 | 2012-07-04 | 比亚迪股份有限公司 | Cathode active material, preparation method thereof, cathode material and lithium ion battery |
| CN102730761A (en) * | 2012-06-18 | 2012-10-17 | 中国第一汽车股份有限公司 | Oxalate coprecipitation preparation method for high-capacity lithium-rich cathode material |
| CN102958836A (en) * | 2010-06-30 | 2013-03-06 | 霍加纳斯股份有限公司 | Lithium iron silicate cathode material and production thereof |
| CN103413930A (en) * | 2013-07-30 | 2013-11-27 | 南京航空航天大学 | Modified LiNi1/2Mn3/2O4 cathode material prepared by coating with lithium ion conductor Li2MO3 (M=Ti, Si or Zr) and preparation method thereof |
-
2014
- 2014-11-26 CN CN201410697075.XA patent/CN104362334B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901905A (en) * | 2009-05-27 | 2010-12-01 | 比亚迪股份有限公司 | Titanium composite, preparation method thereof and application thereof |
| CN102958836A (en) * | 2010-06-30 | 2013-03-06 | 霍加纳斯股份有限公司 | Lithium iron silicate cathode material and production thereof |
| CN102544478A (en) * | 2010-12-29 | 2012-07-04 | 比亚迪股份有限公司 | Cathode active material, preparation method thereof, cathode material and lithium ion battery |
| CN102730761A (en) * | 2012-06-18 | 2012-10-17 | 中国第一汽车股份有限公司 | Oxalate coprecipitation preparation method for high-capacity lithium-rich cathode material |
| CN103413930A (en) * | 2013-07-30 | 2013-11-27 | 南京航空航天大学 | Modified LiNi1/2Mn3/2O4 cathode material prepared by coating with lithium ion conductor Li2MO3 (M=Ti, Si or Zr) and preparation method thereof |
Cited By (13)
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|---|---|---|---|---|
| CN106450301B (en) * | 2015-04-30 | 2019-02-22 | 奇瑞汽车股份有限公司 | A kind of lithium ion battery boric acid ferrous iron lithium anode material and preparation method thereof |
| CN106450301A (en) * | 2015-04-30 | 2017-02-22 | 奇瑞汽车股份有限公司 | Lithium iron borate (LiFeBO3) anode material for lithium ion battery and preparation method thereof |
| CN104835959A (en) * | 2015-04-30 | 2015-08-12 | 奇瑞汽车股份有限公司 | Lithium ferrous borate anode material of lithium ion battery and preparation method thereof |
| CN104993113A (en) * | 2015-07-08 | 2015-10-21 | 中国科学院大学 | Preparation method of lithium manganate coated lithium ion battery ternary layered cathode material |
| CN104993113B (en) * | 2015-07-08 | 2017-12-08 | 中国科学院大学 | The preparation method of the ternary layered positive electrode of LiMn2O4 coated lithium ion battery |
| CN105789565A (en) * | 2016-04-11 | 2016-07-20 | 中国科学院大学 | Preparing method of zirconic acid lithium cladding lithium-ion battery lithium-rich manganese base layer oxide anode material |
| CN106876697A (en) * | 2017-03-31 | 2017-06-20 | 四川浩普瑞新能源材料股份有限公司 | Nickel-base material, its preparation method and lithium ion battery |
| CN107887587A (en) * | 2017-11-09 | 2018-04-06 | 中南大学 | Composite cathode material for lithium ion cell and preparation method thereof |
| CN109962217A (en) * | 2017-12-25 | 2019-07-02 | 格林美（无锡）能源材料有限公司 | Lithium manganese silicate coated nickel-cobalt-manganese ternary material and preparation method thereof |
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