CN104505505B - The preparation method of the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery - Google Patents
The preparation method of the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery Download PDFInfo
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- CN104505505B CN104505505B CN201410730319.XA CN201410730319A CN104505505B CN 104505505 B CN104505505 B CN 104505505B CN 201410730319 A CN201410730319 A CN 201410730319A CN 104505505 B CN104505505 B CN 104505505B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to the preparation method of a kind of ternary layered positive electrode of Lithium metasilicate coated lithium ion battery, belong to technical field of inorganic material.The inventive method has prepared the ternary layered positive electrode of Lithium metasilicate cladding by simple co-precipitation, hydro-thermal and high temperature solid-phase sintering reaction.The inventive method synthesis technique is simple, and production efficiency is high, suitable for scale production.And the raw material required for the inventive method reactant is easy to get, nontoxic, with low cost, production process has the advantages such as yield is big, result is reproducible without special protection, easy control of reaction conditions, obtained product.The ternary layered positive electrode of Lithium metasilicate cladding prepared by the inventive method, compared to uncoated material, is all greatly improved in terms of the chemical properties such as battery specific capacity, cyclical stability and multiplying power and improves.
Description
Technical field
The present invention relates to the preparation method of a kind of ternary layered positive electrode of Lithium metasilicate coated lithium ion battery, belong to inorganic material
Technical field.
Background technology
The exhaustion of conventional fossil resource and environmental pollution the most serious so that the exploitation of new forms of energy is extremely urgent.Lithium ion
Battery as the energy storage system of a new generation, with it efficiently, the advantage such as cleaning, high-energy-density get most of the attention, and the widest
General it is applied to the miniature electronic product scopes such as mobile phone, notebook computer, digital camera.But, the specific capacity of lithium ion battery,
Energy density and safety etc. also cannot meet the needs of Development of Electric Vehicles, and limiting lithium ion cell energy density is main
Bottleneck is positive electrode, therefore exploitation have the positive electrode of high-energy-density becoming Study on Li-ion batteries focus and
Difficult point.Ternary layered positive electrode is because having theoretical capacity height, good cycling stability, low in raw material price, environmental friendliness etc.
Advantage is considered as one of most potential positive electrode of lithium ion battery of future generation.But ternary layered positive electrode exists again
The problems such as rate poor-performing, these factors constrain its extensive application on electric automobile.Improve ternary layered positive pole at present
The main method of material electrochemical performance be cladding (that is: at one layer of oxide of its Surface coating or other inert electrode material),
Element doping (such as metallic elements such as Al, Ru).These methods can improve specific discharge capacity and the most forthright to a certain extent
Energy (fast charging and discharging performance), but the improvement effect of high rate performance and electrochemistry capacitance long-time stability are the most not ideal,
It is thus desirable to develop novel improved method.Lithium metasilicate (predominantly lithium metasilicate and positive Lithium metasilicate) is led as a kind of lithium ion
Body material, has higher lithium ion transport performance, if being coated on positive electrode surface, it will be conducive to lithium ion
Transmission, thus the cyclical stability of lithium ion battery, particularly high rate performance are greatly improved.But due to by synthetic method
Restriction, also nobody's report so far.
Summary of the invention
The purpose of the present invention is to propose to a kind of Lithium metasilicate (predominantly lithium metasilicate and positive Lithium metasilicate) coated lithium ion battery ternary
The preparation method of layered cathode material, improves the preparation technology of existing anode material for lithium-ion batteries, just to improve
The charging and discharging capacity of the lithium ion battery that pole active substance assembles and high rate performance.
The preparation method of the ternary layered positive electrode of 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 NiSO4、CoSO4、MnSO4Be dissolved in 50ml water, make W metal ion, metal Co from
The molar concentration of son and metal Mn ion is 2mol/L, obtains metallic ion mixed liquor, and being reconfigured at molar concentration is
The NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution joins in metallic ion mixed liquor, produces
Raw precipitate, after stir 2 hours, centrifugation, respectively with deionized water and washes of absolute alcohol precipitate 2 times, will sink
Shallow lake thing is placed in 70 DEG C of baking ovens and is dried 12 hours, obtains oxalate precursor, and the molecular formula of oxalate precursor is:
Ni0.333Co0.333Mn0.333C2O4·2H2O；
(2)SiO2The preparation of cladding oxalate precursor:
Oxalate precursor 1.2mmol obtained above is dispersed in 13ml dehydrated alcohol, stirring ultrasonic disperse, presses
According to Si:(Ni+Co+Mn)=the molar ratio of α: 100, add the Si (OC that mass percent concentration is 10%wt2H5)4Anhydrous
Ethanol solution, wherein 1≤α≤15, dispersed with stirring is uniform, obtains mixed liquor, then proceeds to this mixed liquor thoroughly be dried
Teflon-lined water heating kettle in, at 150～180 DEG C process 5～12 hours, after natural cooling, centrifuge washing,
The precipitate obtained by centrifuge washing is dried 12 hours at 80 DEG C, obtains SiO2Cladding oxalate precursor；
(3) Lithium metasilicate cladding LiNi0.333Co0.333Mn0.333O2Preparation:
According to Li:(Ni+Co+Mn)=(100+2 α)/(100+ α): 1 or Li:(Ni+Co+Mn)=(100+4 α)/(100+ α): 1
Molar ratio, wherein 1≤α≤15, by the oxalate precursor of above-mentioned preparation and LiOH H2O grinds and mixes, and is placed in Muffle
In stove, with the heating rate of 3～5 DEG C/min, process 12～24 hours at 700～1000 DEG C, naturally cool to room temperature,
Obtain the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery.
The preparation method of a kind of ternary layered positive electrode of Lithium metasilicate coated lithium ion battery that the present invention proposes, its advantage is:
The inventive method has prepared what Lithium metasilicate was uniformly coated with by simple co-precipitation, synchronization lithiumation and high temperature solid-phase sintering reaction
Ternary layered positive electrode.The inventive method synthesis technique is simple, and production efficiency is high, suitable for scale production.And this
Raw material required for bright method reactant is easy to get, nontoxic, with low cost, production process is held without special protection, reaction condition
Easy to control, obtained product has the advantages such as yield is big, result is reproducible.Lithium metasilicate cladding prepared by the inventive method
Ternary layered positive electrode, compared with existing uncoated material, in battery specific capacity, cyclical stability and multiplying power etc.
Battery performance aspect is all greatly improved and improves.The inventive method synthesis technique is simple, and production efficiency is high, suitably advises
Modelling produces.And the raw material required for the inventive method reactant is easy to get, nontoxic, with low cost, production process is without spy
Different protection, easy control of reaction conditions, obtained product has the advantages such as yield is big, result is reproducible.Side of the present invention
The ternary layered positive electrode of Lithium metasilicate cladding prepared by method is compared to uncoated material, at battery specific capacity, stable circulation
The chemical property aspect such as property and multiplying power is all greatly improved and improves.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram that Lithium metasilicate prepared by the inventive method is coated with ternary layered positive electrode.
Fig. 2 be cladding Lithium metasilicate with the ternary layered positive electrode of uncoated Lithium metasilicate under 1C (160mA/g) electric current density
Specific discharge capacity circulation comparison diagram.
Fig. 3 be cladding Lithium metasilicate with specific discharge capacity under different multiplying of the ternary layered positive electrode of uncoated Lithium metasilicate
Circulation comparison diagram.
Detailed description of the invention
The preparation method of the ternary layered positive electrode of 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 NiSO4、CoSO4、MnSO4Be dissolved in 50ml water, make W metal ion, metal Co from
The molar concentration of son and metal Mn ion is 2mol/L, obtains metallic ion mixed liquor, and being reconfigured at molar concentration is
The NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution joins in metallic ion mixed liquor, produces
Raw precipitate, after stir 2 hours, centrifugation, respectively with deionized water and washes of absolute alcohol precipitate 2 times, will sink
Shallow lake thing is placed in 70 DEG C of baking ovens and is dried 12 hours, obtains oxalate precursor, and the molecular formula of oxalate precursor is:
Ni0.333Co0.333Mn0.333C2O4·2H2O；
(2)SiO2The preparation of cladding oxalate precursor:
Oxalate precursor 1.2mmol obtained above is dispersed in 13ml dehydrated alcohol, stirring ultrasonic disperse, presses
According to Si:(Ni+Co+Mn)=the molar ratio of α: 100, add the Si (OC that mass percent concentration is 10%wt2H5)4Anhydrous
Ethanol solution, wherein 1≤α≤15, dispersed with stirring is uniform, obtains mixed liquor, then proceeds to this mixed liquor thoroughly be dried
Teflon-lined water heating kettle in, at 150～180 DEG C process 5～12 hours, after natural cooling, centrifuge washing,
The precipitate obtained by centrifuge washing is dried 12 hours at 80 DEG C, obtains SiO2Cladding oxalate precursor；
(3) Lithium metasilicate cladding LiNi0.333Co0.333Mn0.333O2Preparation:
According to Li:(Ni+Co+Mn)=(100+2 α)/(100+ α): 1 or Li:(Ni+Co+Mn)=(100+4 α)/(100+ α): 1
Molar ratio, wherein 1≤α≤15, by the oxalate precursor of above-mentioned preparation and LiOH H2O grinds and mixes, and is placed in Muffle
In stove, with the heating rate of 3～5 DEG C/min, process 12～24 hours at 700～1000 DEG C, naturally cool to room temperature,
Obtain the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery.
The embodiment of the inventive method be described below:
Embodiment one:
(1) according to mol ratio by NiSO4、CoSO4、MnSO4It is dissolved in 50ml water, makes W metal ion, metal
The molar concentration of Co ion and metal Mn ion is 2mol/L, obtains metallic ion mixed liquor.It is reconfigured at 2mol/L
NaC2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces big immediately
Amount precipitation, after stir 2 hours, centrifugation, use deionized water and washes of absolute alcohol 2 times respectively, be placed in 70 degree of bakings
Case is dried 12 hours, i.e. obtains oxalate precursor；
(2)SiO2The synthesis of cladding oxalate precursor: weigh oxalate precursor 1.2mmol obtained above and be dispersed in
In 13ml dehydrated alcohol, stirring ultrasonic disperse.According to Si:(Ni+Co+Mn) molar ratio of=3:100, adding concentration is
Si (the OC of 10%wt2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to poly-four be thoroughly dried
In the water heating kettle of fluorothene liner, processing 5 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding LiNi0.333Co0.333Mn0.333O2Preparation: according to mol ratio by the oxalates of above-mentioned preparation
Presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes at 800 DEG C
12 hours, after naturally cooling to room temperature, i.e. can get the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery.
Gained Lithium metasilicate is coated with ternary layered positive electrode and characterizes: gained Lithium metasilicate is coated with ternary layered positive electrode and penetrates through X
Line diffractometer analysis can be pure phase, as shown in Figure 1.Under the discharge current density of 1C (160mA/g), Lithium metasilicate is coated with
Ternary material carry out battery performance test, charge and discharge cycles 300 is enclosed, and uncoated ternary material contrast, such as Fig. 2 institute
Show that battery discharge specific capacity and cyclical stability significantly improve.At 0.2C, 0.5C, 1C, 2C, 5C, 10C, 20C discharge electricity
Under current density testing battery high rate performance, the ternary material high rate performance after result Lithium metasilicate as shown in Figure 3 cladding is bright
Show and be better than uncoated ternary material.
Embodiment two:
(1) preparation of oxalate precursor: according to mol ratio by NiSO4、CoSO4、MnSO4It is dissolved in 50ml water,
The molar concentration making W metal ion, metal Co ion and metal Mn ion is 2mol/L, obtains metal ion mixing
Solution.It is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds metal ion to be mixed
Close in solution, produce a large amount of precipitation, after stirring 2 hours, centrifugation immediately, clear with deionized water and dehydrated alcohol respectively
Wash 2 times, be placed in 70 degree of baking ovens and be dried 12 hours, i.e. obtain oxalate precursor；
(2)SiO2The synthesis of cladding oxalate precursor: weigh oxalate precursor 1.2mmol obtained above and be dispersed in
In 13ml dehydrated alcohol, stirring ultrasonic disperse.According to Si:(Ni+Co+Mn) molar ratio of=3:100, adding concentration is
Si (the OC of 10%wt2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to poly-four be thoroughly dried
In the water heating kettle of fluorothene liner, processing 8 hours under 160 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding LiNi0.333Co0.333Mn0.333O2Preparation: according to mol ratio by the oxalates of above-mentioned preparation
Presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes at 800 DEG C
12 hours, after naturally cooling to room temperature, i.e. can get the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery.
Embodiment three:
(1) preparation of oxalate precursor: according to mol ratio by NiSO4、CoSO4、MnSO4It is dissolved in 50ml water,
The molar concentration making W metal ion, metal Co ion and metal Mn ion is 2mol/L, obtains metal ion mixing
Solution.It is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds metal ion to be mixed
Close in solution, produce a large amount of precipitation, after stirring 2 hours, centrifugation immediately, clear with deionized water and dehydrated alcohol respectively
Wash 2 times, be placed in 70 degree of baking ovens and be dried 12 hours, i.e. obtain oxalate precursor；
(2)SiO2The synthesis of cladding oxalate precursor: weigh oxalate precursor 1.2mmol obtained above and be dispersed in
In 13ml dehydrated alcohol, stirring ultrasonic disperse.According to Si:(Ni+Co+Mn) molar ratio of=1:100, adding concentration is
Si (the OC of 10%wt2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to poly-four be thoroughly dried
In the water heating kettle of fluorothene liner, processing 12 hours under 150 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding LiNi0.333Co0.333Mn0.333O2Preparation: according to mol ratio by the oxalates of above-mentioned preparation
Presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes at 800 DEG C
12 hours, after naturally cooling to room temperature, i.e. can get the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery.
Embodiment four:
(1) according to mol ratio by NiSO4、CoSO4、MnSO4It is dissolved in 50ml water, makes W metal ion, metal
The molar concentration of Co ion and metal Mn ion is 2mol/L, obtains metallic ion mixed liquor.It is reconfigured at 2mol/L
NaC2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces big immediately
Amount precipitate, after stir 2 hours, centrifugation, respectively with deionized water and washes of absolute alcohol precipitate 2 times, will sink
Shallow lake thing is placed in 70 degree of baking ovens and is dried 12 hours, i.e. obtains oxalate precursor；
(2)SiO2The synthesis of cladding oxalate precursor: weigh oxalate precursor 1.2mmol obtained above and be dispersed in
In 13ml dehydrated alcohol, stirring ultrasonic disperse.According to Si:(Ni+Co+Mn) molar ratio of=5:100, adding concentration is
Si (the OC of 10%wt2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to poly-four be thoroughly dried
In the water heating kettle of fluorothene liner, processing 10 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding LiNi0.333Co0.333Mn0.333O2Preparation: according to mol ratio by the oxalates of above-mentioned preparation
Presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes at 800 DEG C
12 hours, after naturally cooling to room temperature, i.e. can get the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery.
Embodiment five:
(1) according to mol ratio by NiSO4、CoSO4、MnSO4It is dissolved in 50ml water, makes W metal ion, metal
The molar concentration of Co ion and metal Mn ion is 2mol/L, obtains metallic ion mixed liquor.It is reconfigured at 2mol/L
NaC2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces big immediately
Amount precipitation, after stir 2 hours, centrifugation, use deionized water and washes of absolute alcohol 2 times respectively, be placed in 70 degree of bakings
Case is dried 12 hours, i.e. obtains oxalate precursor；
(2)SiO2The synthesis of cladding oxalate precursor: weigh oxalate precursor 1.2mmol obtained above and be dispersed in
In 13ml dehydrated alcohol, stirring ultrasonic disperse.According to Si:(Ni+Co+Mn) molar ratio of=7:100, adding concentration is
Si (the OC of 10%wt2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to poly-four be thoroughly dried
In the water heating kettle of fluorothene liner, processing 5 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding LiNi0.333Co0.333Mn0.333O2Preparation: according to mol ratio by the oxalates of above-mentioned preparation
Presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes at 900 DEG C
12 hours, after naturally cooling to room temperature, i.e. can get the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery.
Embodiment six:
(1) preparation of oxalate precursor: according to mol ratio by NiSO4、CoSO4、MnSO4It is dissolved in 50ml water,
The molar concentration making W metal ion, metal Co ion and metal Mn ion is 2mol/L, obtains metal ion mixing
Solution.It is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds metal ion to be mixed
Close in solution, produce a large amount of precipitation, after stirring 2 hours, centrifugation immediately, clear with deionized water and dehydrated alcohol respectively
Wash 2 times, be placed in 70 degree of baking ovens and be dried 12 hours, i.e. obtain oxalate precursor；
(2)SiO2The synthesis of cladding oxalate precursor: weigh oxalate precursor 1.2mmol obtained above and be dispersed in
In 13ml dehydrated alcohol, stirring ultrasonic disperse.According to Si:(Ni+Co+Mn) molar ratio of=10:100, add concentration
Si (OC for 10%wt2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the driest gathering
In the water heating kettle of tetrafluoroethene liner, processing 10 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is done
Dry.
(3) Lithium metasilicate cladding LiNi0.333Co0.333Mn0.333O2Preparation: according to mol ratio by the oxalates of above-mentioned preparation
Presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes at 950 DEG C
15 hours, after naturally cooling to room temperature, i.e. can get the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery.
Embodiment seven:
(1) preparation of oxalate precursor: according to mol ratio by NiSO4、CoSO4、MnSO4It is dissolved in 50ml water,
The molar concentration making W metal ion, metal Co ion and metal Mn ion is 2mol/L, obtains metal ion mixing
Solution.It is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds metal ion to be mixed
Close in solution, produce a large amount of precipitation, after stirring 2 hours, centrifugation immediately, clear with deionized water and dehydrated alcohol respectively
Wash 2 times, be placed in 70 degree of baking ovens and be dried 12 hours, i.e. obtain oxalate precursor；
(2)SiO2The synthesis of cladding oxalate precursor: weigh oxalate precursor 1.2mmol obtained above and be dispersed in
In 13ml dehydrated alcohol, stirring ultrasonic disperse.According to Si:(Ni+Co+Mn) molar ratio of=15:100, add concentration
Si (OC for 10%wt2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the driest gathering
In the water heating kettle of tetrafluoroethene liner, processing 12 hours under 160 degrees Celsius, after natural cooling, centrifuge washing 80 degree is done
Dry.
(3) Lithium metasilicate cladding LiNi0.333Co0.333Mn0.333O2Preparation: according to mol ratio by the oxalates of above-mentioned preparation
Presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes at 800 DEG C
24 hours, after naturally cooling to room temperature, i.e. can get the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery.
Embodiment eight:
(1) preparation of oxalate precursor: according to mol ratio by NiSO4、CoSO4、MnSO4It is dissolved in 50ml water,
The molar concentration making W metal ion, metal Co ion and metal Mn ion is 2mol/L, obtains metal ion mixing
Solution.It is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds metal ion to be mixed
Close in solution, produce a large amount of precipitation, after stirring 2 hours, centrifugation immediately, clear with deionized water and dehydrated alcohol respectively
Wash 2 times, be placed in 70 degree of baking ovens and be dried 12 hours, i.e. obtain oxalate precursor；
(2)SiO2The synthesis of cladding oxalate precursor: weigh oxalate precursor 1.2mmol obtained above and be dispersed in
In 13ml dehydrated alcohol, stirring ultrasonic disperse.According to Si:(Ni+Co+Mn) molar ratio of=3:100, adding concentration is
Si (the OC of 10%wt2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to poly-four be thoroughly dried
In the water heating kettle of fluorothene liner, processing 10 hours under 170 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding LiNi0.333Co0.333Mn0.333O2Preparation: according to mol ratio by the oxalates of above-mentioned preparation
Presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes at 850 DEG C
12 hours, after naturally cooling to room temperature, i.e. can get the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery.
Embodiment nine:
(1) preparation of oxalate precursor: according to mol ratio by NiSO4、CoSO4、MnSO4It is dissolved in 50ml water,
The molar concentration making W metal ion, metal Co ion and metal Mn ion is 2mol/L, obtains metal ion mixing
Solution.It is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds metal ion to be mixed
Close in solution, produce a large amount of precipitation, after stirring 2 hours, centrifugation immediately, clear with deionized water and dehydrated alcohol respectively
Wash 2 times, be placed in 70 degree of baking ovens and be dried 12 hours, i.e. obtain oxalate precursor；
(2)SiO2The synthesis of cladding oxalate precursor: weigh oxalate precursor 1.2mmol obtained above and be dispersed in
In 13ml dehydrated alcohol, stirring ultrasonic disperse.According to Si:(Ni+Co+Mn) molar ratio of=3:100, adding concentration is
Si (the OC of 10%wt2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to poly-four be thoroughly dried
In the water heating kettle of fluorothene liner, processing 8 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding LiNi0.333Co0.333Mn0.333O2Preparation: according to mol ratio by the oxalates of above-mentioned preparation
Presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes at 1000 DEG C
12 hours, after naturally cooling to room temperature, i.e. can get the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery.
Embodiment ten:
(1) preparation of oxalate precursor: according to mol ratio by NiSO4、CoSO4、MnSO4It is dissolved in 50ml water,
The molar concentration making W metal ion, metal Co ion and metal Mn ion is 2mol/L, obtains metal ion mixing
Solution.It is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds metal ion to be mixed
Close in solution, produce a large amount of precipitation, after stirring 2 hours, centrifugation immediately, clear with deionized water and dehydrated alcohol respectively
Wash 2 times, be placed in 70 degree of baking ovens and be dried 12 hours, i.e. obtain oxalate precursor；
(2)SiO2The synthesis of cladding oxalate precursor: weigh oxalate precursor 1.2mmol obtained above and be dispersed in
In 13ml dehydrated alcohol, stirring ultrasonic disperse.According to Si:(Ni+Co+Mn) molar ratio of=10:100, add concentration
Si (OC for 10%wt2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the driest gathering
In the water heating kettle of tetrafluoroethene liner, processing 12 hours under 150 degrees Celsius, after natural cooling, centrifuge washing 80 degree is done
Dry.
(3) Lithium metasilicate cladding LiNi0.333Co0.333Mn0.333O2Preparation: according to mol ratio by the oxalates of above-mentioned preparation
Presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes at 1000 DEG C
12 hours, after naturally cooling to room temperature, i.e. can get the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery.
Claims (1)
1. the preparation method of the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery, it is characterised in that the method bag
Include following steps:
(1) preparation of oxalate precursor:
According to mol ratio by NiSO4、CoSO4、MnSO4Be dissolved in 50ml water, make W metal ion, metal Co from
The molar concentration of son and metal Mn ion is 2mol/L, obtains metallic ion mixed liquor, and configuration molar concentration is 2mol/L
NaC2O4Solution 50mL, by NaC under magnetic agitation2O4Solution joins in metallic ion mixed liquor, produces precipitation
Thing, after stirring 2 hours, centrifugation, respectively with deionized water and washes of absolute alcohol precipitate 2 times, precipitate is put
Being dried 12 hours in 70 DEG C of baking ovens, obtain oxalate precursor, the molecular formula of oxalate precursor is:
Ni0.333Co0.333Mn0.333C2O4·2H2O；
(2)SiO2The preparation of cladding oxalate precursor:
Oxalate precursor 1.2mmol obtained above is dispersed in 13ml dehydrated alcohol, stirring ultrasonic disperse, presses
According to Si:(Ni+Co+Mn)=the molar ratio of α: 100, add the Si (OC that mass percent concentration is 10%wt2H5)4Anhydrous
Ethanol solution, wherein 1≤α≤15, dispersed with stirring is uniform, obtains mixed liquor, and then this mixed liquor proceeds to the driest gathering
In the water heating kettle of tetrafluoroethene liner, process 5～12 hours at 150～180 DEG C, after natural cooling, centrifuge washing, will
The precipitate that centrifuge washing obtains is dried 12 hours at 80 DEG C, obtains SiO2Cladding oxalate precursor；
(3) Lithium metasilicate cladding LiNi0.333Co0.333Mn0.333O2Preparation:
According to Li:(Ni+Co+Mn)=(100+2 α)/(100+ α): 1 or Li:(Ni+Co+Mn)=(100+4 α)/(100+ α): 1
Molar ratio, wherein 1≤α≤15, by the oxalate precursor of above-mentioned preparation and LiOH H2O grinds and mixes, and is placed in Muffle
In stove, with the heating rate of 3～5 DEG C/min, process 12～24 hours at 700～1000 DEG C, naturally cool to room temperature,
Obtain the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery.
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| CN105047864A (en) * | 2015-06-09 | 2015-11-11 | 中国科学院大学 | Preparation method of lithium zirconate-coated ternary layered cathode material of lithium ion battery |
| CN105261754B (en) * | 2015-09-23 | 2018-07-10 | 中国科学院大学 | The preparation method of lithium ion conductor coated lithium ion battery lithium cobaltate cathode material |
| CN106450274A (en) * | 2016-09-29 | 2017-02-22 | 中国科学院大学 | Preparation method of spinel phase-ternary layered oxide nano composite positive electrode material |
| CN108666534B (en) * | 2017-03-27 | 2021-03-19 | 天津国安盟固利新材料科技股份有限公司 | Double-layer coated lithium ion battery anode material and preparation method thereof |
| 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 |
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| CN109616652B (en) * | 2018-12-11 | 2020-07-21 | 欣旺达电子股份有限公司 | Modified composite ternary material and preparation method thereof |
| CN110534736A (en) * | 2019-08-28 | 2019-12-03 | 电子科技大学 | A kind of high potential lithium ion battery NCM tertiary cathode material and preparation method thereof |
| CN112072082A (en) * | 2020-07-27 | 2020-12-11 | 西安交通大学 | Precursor of nickel-cobalt-manganese hydroxide of silicon dioxide coated lithium ion battery anode material and preparation method thereof |
| CN114203986A (en) * | 2021-11-23 | 2022-03-18 | 荆门市格林美新材料有限公司 | LiNi can be improved0.8Co0.15Al0.05O2Method for electrochemical performance of anode material |
| CN114156464A (en) * | 2021-12-07 | 2022-03-08 | 河北省科学院能源研究所 | Novel nickel-rich cathode material of lithium ion battery and preparation method thereof |
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| 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 |
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