CN104362334B - The preparation method of Lithium metasilicate coated lithium ion battery lithium-rich positive electrode - Google Patents

The preparation method of Lithium metasilicate coated lithium ion battery lithium-rich positive electrode Download PDF

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CN104362334B
CN104362334B CN201410697075.XA CN201410697075A CN104362334B CN 104362334 B CN104362334 B CN 104362334B CN 201410697075 A CN201410697075 A CN 201410697075A CN 104362334 B CN104362334 B CN 104362334B
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lithium
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cladding
oxalate precursor
positive electrode
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CN104362334A (en
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刘向峰
肖小玲
赵恩岳
胡中波
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University of Chinese Academy of Sciences
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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to the preparation method of a kind of Lithium metasilicate coated lithium ion battery lithium-rich positive electrode, belong to technical field of inorganic material.The inventive method has prepared the lithium-rich 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 lithium-rich 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

The preparation method of Lithium metasilicate coated lithium ion battery lithium-rich positive electrode
Technical field
The present invention relates to the preparation method of a kind of Lithium metasilicate coated lithium ion battery lithium-rich positive electrode, belong to inorganic material Technical field.
Background technology
The problems such as the drastically shortage of the non-renewable resources such as the day by day serious and fossil that world environments is polluted make new forms of energy Exploitation is particularly important.Lithium ion battery is as the energy storage system of a new generation, cleaning, high-energy-density etc. efficient with it Advantage gets most of the attention, and has been widely used for 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 limit The Main Bottleneck of preparing lithium ion battery energy density is positive electrode, and therefore exploitation has the positive electrode of high-energy-density Become focus and the difficult point of Study on Li-ion batteries.Lithium-rich positive electrode because of have theoretical capacity high (300mAh/g), Low in raw material price, advantages of environment protection are considered as one of most potential positive electrode of lithium ion battery of future generation.But Be lithium-rich positive electrode have that first charge-discharge efficiency is low, platform voltage persistently reduces, high rate performance and stable circulation Property the problem such as difference, these factors constrain its extensive application on electric automobile.Improve lithium-rich positive electrode electricity at present The main method of chemical property is cladding (that is: at its Surface coating one layer of oxide or fluoride materials etc.), element doping (such as transition metals such as Cr, Ti).These methods can improve cyclical stability to a certain extent and high rate performance is (fast Speed charge-discharge performance), but the improvement effect of high rate performance and electrochemistry capacitance long-time stability are the most not ideal, therefore need Develop novel improved method.A kind of Lithium Ionic Conducting Materials of Lithium metasilicate (predominantly lithium metasilicate and positive Lithium metasilicate) conduct, There is higher lithium ion transport performance, if being coated on positive electrode surface, it will be conducive to the transmission of lithium ion, Thus the cyclical stability of lithium ion battery, particularly high rate performance are greatly improved.But owing to being limited by synthetic method, So far also nobody reports.
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 richness lithium The preparation method of layered cathode material, improves the preparation technology of existing anode material for lithium-ion batteries, just to improve The cyclical stability of the lithium ion battery that pole active substance assembles and high rate performance.
The preparation method of the Lithium metasilicate coated lithium ion battery lithium-rich positive electrode that the present invention proposes, comprises the following steps:
(1) preparation of oxalate precursor:
According to mol ratio by NiSO4、MnSO4Be dissolved in 50ml water, make W metal ion and metal Mn ion mole Concentration is 2mol/L, obtains metallic ion mixed liquor, is reconfigured at the NaC that molar concentration is 2mol/L2O4Solution 50mL, By NaC under magnetic agitation2O4Solution joins in metallic ion mixed liquor, produces precipitate, after stirring 2 hours, centrifugal Separate, respectively with deionized water and washes of absolute alcohol precipitate 2 times, put the precipitate in that to be dried 12 in 70 DEG C of baking ovens little Time, obtaining oxalate precursor, the molecular formula of oxalate precursor is: Ni0.35Mn0.65C2O4·2H2O；
(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+Mn)=the molar ratio of α: 100, add the Si (OC that mass percent concentration is 10%wt2H5)4Anhydrous second Alcoholic solution, wherein 1≤α≤15, dispersed with stirring is uniform, obtains mixed liquor, then proceeds to this mixed liquor to be thoroughly dried In teflon-lined water heating kettle, process 5～12 hours at 150～180 DEG C, 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 xLi2MnO3·(1-x)LiNi0.5Mn0.5O2Preparation:
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 upper State oxalate precursor and the LiOH H of preparation2O grinds and mixes, and is placed in Muffle furnace, with the intensification speed of 3～5 DEG C/min Rate, processes 12～24 hours at 700～1000 DEG C, naturally cools to room temperature, obtains Lithium metasilicate coated lithium ion battery rich Lithium layered cathode material.
The preparation method of a kind of Lithium metasilicate coated lithium ion battery lithium-rich positive electrode 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 Lithium-rich 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 Lithium-rich 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.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of Lithium metasilicate cladding lithium-rich positive electrode prepared by the inventive method.
Fig. 2 be Lithium metasilicate cladding with uncoated lithium-rich positive electrode electric discharge specific volume under 100mA/g electric current density Amount circulation comparison diagram.
Fig. 3 is the right with the specific discharge capacity circulation under different multiplying of the uncoated lithium-rich positive electrode of Lithium metasilicate cladding Than figure.
Detailed description of the invention
The preparation method of the Lithium metasilicate coated lithium ion battery lithium-rich positive electrode that the present invention proposes, comprises the following steps:
(1) preparation of oxalate precursor:
According to mol ratio by NiSO4、MnSO4Be dissolved in 50ml water, make W metal ion and metal Mn ion mole Concentration is 2mol/L, obtains metallic ion mixed liquor, is reconfigured at the NaC that molar concentration is 2mol/L2O4Solution 50mL, By NaC under magnetic agitation2O4Solution joins in metallic ion mixed liquor, produces precipitate, after stirring 2 hours, centrifugal Separate, respectively with deionized water and washes of absolute alcohol precipitate 2 times, put the precipitate in that to be dried 12 in 70 DEG C of baking ovens little Time, obtaining oxalate precursor, the molecular formula of oxalate precursor is: Ni0.35Mn0.65C2O4·2H2O；
(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+Mn)=the molar ratio of α: 100, add the Si (OC that mass percent concentration is 10%wt2H5)4Anhydrous second Alcoholic solution, wherein 1≤α≤15, dispersed with stirring is uniform, obtains mixed liquor, then proceeds to this mixed liquor to be thoroughly dried In teflon-lined water heating kettle, process 5～12 hours at 150～180 DEG C, 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 xLi2MnO3·(1-x)LiNi0.5Mn0.5O2Preparation:
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 upper State oxalate precursor and the LiOH H of preparation2O grinds and mixes, and is placed in Muffle furnace, with the intensification speed of 3～5 DEG C/min Rate, processes 12～24 hours at 700～1000 DEG C, naturally cools to room temperature, obtains Lithium metasilicate coated lithium ion battery rich Lithium layered cathode material.
The embodiment of the inventive method be described below:
Embodiment one:
(1) preparation of oxalate precursor: according to mol ratio by NiSO4、MnSO4It is dissolved in 50ml water, makes metal The molar concentration of Ni ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, magnetic By NaC under power stirring2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, after stirring 2 hours, Centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=3:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 5 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.3Li2MnO3·0.7LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C Process 12 hours, after naturally cooling to room temperature, i.e. can get Lithium metasilicate coated lithium ion battery lithium-rich positive electrode.
Gained Lithium metasilicate cladding lithium-rich positive electrode characterizes: gained Lithium metasilicate cladding lithium-rich positive electrode is penetrated through X Line diffractometer analysis can be the solid solution of pure phase, as shown in Figure 1.To Lithium metasilicate under the discharge current density of 100mA/g The rich lithium material of cladding carries out battery performance test, and charge and discharge cycles 50 is enclosed, and contrasts with uncoated rich lithium material, such as Fig. 2 Shown battery discharge specific capacity and cyclical stability significantly improve.At 40mA/g, 80mA/g, 120mAh/g, 160mA/g, Under 200mA/g, 300mA/g, 400mA/g discharge current density, battery high rate performance is tested, result such as Fig. 3 institute Show that the rich lithium material high rate performance after Lithium metasilicate cladding is substantially better than uncoated rich lithium material.
Embodiment two:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=3:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 8 hours under 160 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.3Li2MnO3·0.7LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C Process 12 hours, after naturally cooling to room temperature, i.e. can get Lithium metasilicate coated lithium ion battery lithium-rich positive electrode.
Embodiment three:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=1:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 12 hours under 150 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.3Li2MnO3·0.7LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C Process 12 hours, after naturally cooling to room temperature, i.e. can get Lithium metasilicate coated lithium ion battery lithium-rich positive electrode.
Embodiment four:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitate immediately, stirring After 2 hours, centrifugation, respectively with deionized water and washes of absolute alcohol precipitate 2 times, put the precipitate 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+Mn) molar ratio of=5:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 10 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.3Li2MnO3·0.7LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C Process 12 hours, after naturally cooling to room temperature, i.e. can get Lithium metasilicate coated lithium ion battery lithium-rich positive electrode.
Embodiment five:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=7:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 5 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.3Li2MnO3·0.7LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 900 DEG C Process 12 hours, after naturally cooling to room temperature, i.e. can get Lithium metasilicate coated lithium ion battery lithium-rich positive electrode.
Embodiment six:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=10:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 10 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.3Li2MnO3·0.7LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 950 DEG C Process 15 hours, after naturally cooling to room temperature, i.e. can get Lithium metasilicate coated lithium ion battery lithium-rich positive electrode.
Embodiment seven:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=15:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 12 hours under 160 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.3Li2MnO3·0.7LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C Process 24 hours, after naturally cooling to room temperature, i.e. can get Lithium metasilicate coated lithium ion battery lithium-rich positive electrode.
Embodiment eight:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=3:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 10 hours under 170 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.3Li2MnO3·0.7LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 850 DEG C Process 12 hours, after naturally cooling to room temperature, i.e. can get Lithium metasilicate coated lithium ion battery lithium-rich positive electrode.
Embodiment nine:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=3:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 8 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.3Li2MnO3·0.7LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 1000 DEG C Process 12 hours, after naturally cooling to room temperature, i.e. can get Lithium metasilicate coated lithium ion battery lithium-rich positive electrode.
Embodiment ten:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=10:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 12 hours under 150 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.3Li2MnO3·0.7LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 1000 DEG C Process 12 hours, after naturally cooling to room temperature, i.e. can get Lithium metasilicate coated lithium ion battery lithium-rich positive electrode.
Embodiment 11:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=3:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 5 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.2Li2MnO3·0.8LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C Process 12 hours, after naturally cooling to room temperature, i.e. can get Lithium metasilicate coated lithium ion battery lithium-rich positive electrode.
Embodiment 12:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=5:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 5 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.4Li2MnO3·0.6LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C Process 12 hours, after naturally cooling to room temperature, i.e. can get Lithium metasilicate coated lithium ion battery lithium-rich positive electrode.
Embodiment 13:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=3:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 5 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C Process 12 hours, after naturally cooling to room temperature, i.e. can get Lithium metasilicate coated lithium ion battery lithium-rich positive electrode.
Embodiment 14:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=15:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 5 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 900 DEG C Process 15 hours, after naturally cooling to room temperature, i.e. can get the lithium ion battery lithium-rich positive electrode of Lithium metasilicate cladding.
Embodiment 15:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=3:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 5 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.2Li2MnO3·0.8LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 1000 DEG C Process 12 hours, after naturally cooling to room temperature, i.e. can get the lithium ion battery lithium-rich positive electrode of Lithium metasilicate cladding.
Embodiment 16:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=5:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 5 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.2Li2MnO3·0.8LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 800 DEG C Process 12 hours, after naturally cooling to room temperature, i.e. can get the lithium ion battery lithium-rich positive electrode of Lithium metasilicate cladding.
Embodiment 17:
(1) preparation of oxalate precursor: according to mol ratio by a certain amount of NiSO4、MnSO4It is dissolved in 50ml water, The molar concentration making W metal ion and metal Mn ion is 2mol/L, is reconfigured at the NaC of 2mol/L2O4Solution 50mL, by NaC under magnetic agitation2O4Solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs 2 After hour, centrifugation, respectively with deionized water and washes of absolute alcohol 2 times, it is placed in 70 degree of baking ovens and is 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+Mn) molar ratio of=15:100, addition concentration is 10%wt Si (OC2H5)4Ethanol solution, dispersed with stirring is uniform.Then mixed liquor is proceeded to the politef being thoroughly dried In the water heating kettle of liner, processing 5 hours under 180 degrees Celsius, after natural cooling, centrifuge washing 80 degree is dried.
(3) Lithium metasilicate cladding 0.2Li2MnO3·0.8LiNi0.5Mn0.5O2Preparation: according to mol ratio by the grass of above-mentioned preparation Hydrochlorate presoma and LiOH H2O is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, at 900 DEG C Process 12 hours, after naturally cooling to room temperature, i.e. can get the lithium ion battery lithium-rich positive electrode of Lithium metasilicate cladding.

Claims (1)

1. the preparation method of a Lithium metasilicate coated lithium ion battery lithium-rich positive electrode, it is characterised in that the method bag Include following steps:
(1) preparation of oxalate precursor:
According to mol ratio by NiSO4、MnSO4It is dissolved in 50ml water, makes the mole dense of W metal ion and metal Mn ion Degree adds up to 2mol/L, obtains metallic ion mixed liquor, is reconfigured at the NaC that molar concentration is 2mol/L2O4Solution 50mL, By NaC under magnetic agitation2O4Solution joins in metallic ion mixed liquor, produces precipitate, after stirring 2 hours, centrifugal Separate, respectively with deionized water and washes of absolute alcohol precipitate 2 times, put the precipitate in that to be dried 12 in 70 DEG C of baking ovens little Time, obtaining oxalate precursor, the molecular formula of oxalate precursor is: Ni0.35Mn0.65C2O4·2H2O；
(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+Mn)=the molar ratio of α: 100, add the Si (OC that mass percent concentration is 10%wt2H5)4Anhydrous second Alcoholic solution, wherein 1≤α≤15, dispersed with stirring is uniform, obtains mixed liquor, then proceeds to this mixed liquor to be thoroughly dried In teflon-lined water heating kettle, process 5～12 hours at 150～180 DEG C, 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 xLi2MnO3·(1-x)LiNi0.5Mn0.5O2Preparation:
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 upper State the SiO of preparation2Cladding oxalate precursor and LiOH H2O grinds and mixes, and is placed in Muffle furnace, with 3～5 DEG C/min Heating rate, at 700～1000 DEG C process 12～24 hours, naturally cool to room temperature, obtain Lithium metasilicate cladding lithium from Sub-battery lithium-rich positive electrode.
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