CN108346785A - A kind of preparation method of lithium ion conductor cladding phosphoric acid zirconium titanium sulphur lithium anode material - Google Patents

A kind of preparation method of lithium ion conductor cladding phosphoric acid zirconium titanium sulphur lithium anode material Download PDF

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CN108346785A
CN108346785A CN201810052757.3A CN201810052757A CN108346785A CN 108346785 A CN108346785 A CN 108346785A CN 201810052757 A CN201810052757 A CN 201810052757A CN 108346785 A CN108346785 A CN 108346785A
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lithium
lithium ion
ion conductor
sulphur
phosphoric acid
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王顺良
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

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Abstract

The invention discloses the preparation methods that a kind of lithium ion conductor coats phosphoric acid zirconium titanium sulphur lithium anode material, the present invention by inorganic fast lithium ion conductor precursor solution and anode material for lithium-ion batteries at a certain temperature after mixing, obtain the anode material for lithium-ion batteries that surface coats fast lithium ion conductor colloid, the surface is coated into the anode material for lithium-ion batteries of fast lithium ion conductor colloid after heat treatment, one layer of uniform clad is formed on positive electrode particle surface, the transmission activity of lithium ion inside electrode material can be promoted, improve the interface of electrolyte and positive interpolar, promote the performance of battery；The anode of the present invention is compatible in terms of charge and discharge potential, and all has and overcharge playing function, is anode with the composite positive pole, contributes to the raising of cycle performance.

Description

A kind of preparation method of lithium ion conductor cladding phosphoric acid zirconium titanium sulphur lithium anode material
Technical field
The present invention relates to battery material fields, and in particular to a kind of lithium ion conductor cladding phosphoric acid zirconium titanium sulphur lithium anode material The preparation method of material.
Background technology
Using lithium metal as sulphur lithium battery that cathode, elemental sulfur are anode it is theoretical than energy can reach 2600Wh/kg (lithium and The theoretical specific capacity of sulphur is respectively 3860mAh/g and 1675mAh/g), it is commercialized secondary cell much larger than used at this stage. In addition, cheap, the environmental-friendly characteristic of elemental sulfur makes the energy storage system great commercial value again.However in the prior art, sulphur Not high to the utilization rate of phosphoric acid zirconium titanium sulphur lithium active material sulphur in lithium battery, Capacity fading is serious, cycle performance compared with Difference, and chemical property is bad.In order to improve the performance of sulphur lithium battery, people are dedicated to the positive electrode to sulphur lithium battery at present Modified research, to improve its electric conductivity and cycle performance.Such as fill out sulphur in mesoporous carbon gap, the addition of mesoporous carbon improves Electric conductivity；In addition there are research workers to be modified sulphur using conducting polymer, and the addition of conducting polymer can have Effect improves the cycle performance of sulphur lithium battery.
It is to use a kind of material that physical and chemical performance is excellent that solwution method, which carries out coating modification, in positive electrode particle surface Form one layer of guard method uniformly coated.For the liquid lithium ionic cell for using liquid electrolyte, due in battery Charge and discharge cycles during, electrolyte to positive electrode have corrosiveness, lead to the Crystal Structure Distortion of positive electrode, follow The ring service life is lower.In solid lithium battery, the interface problem of electrolyte and positive interpolar is more notable, does not have between electrode material The infiltration of liquid electrolyte causes the lithium ion transport performance in anode portion poor, and battery entirety chemical property reduces.Cause This, coating modification is often applied to improve the chemical property of positive electrode.It is different that existing research is directed to above problem application Method coating modification has been carried out to anode material for lithium-ion batteries, some personnel using atomic layer deposition method, magnetron sputtering method Deng being coated to positive electrode, but its operating difficulties, cost are higher, cannot carry out large-scale industrialization production.
Invention content
The present invention provides a kind of preparation method of lithium ion conductor cladding phosphoric acid zirconium titanium sulphur lithium anode material, the method Using zircomium-tiatnium phosphate as carrier, cross appearance can effectively inhibit the self-discharge processes of battery, and sulfur granules are carried on institute It states in zircomium-tiatnium phosphate, since the unique layer structure of zircomium-tiatnium phosphate has tightly wrapped sulfur granules, can effectively inhibit its electric discharge The dissolving of intermediate product polysulfide improves the cycle performance of sulphur lithium battery；The present invention is by inorganic fast lithium ion conductor forerunner Liquid solution and anode material for lithium-ion batteries after mixing, obtain surface and coat fast lithium ion conductor colloid at a certain temperature Anode material for lithium-ion batteries, by the surface coat the anode material for lithium-ion batteries of fast lithium ion conductor colloid through heat at After reason, one layer of uniform clad is formed on positive electrode particle surface, the transmission activity of lithium ion inside electrode material can be promoted, The interface for improving electrolyte and positive interpolar, promotes the performance of battery；The anode of the present invention is compatible in terms of charge and discharge potential, And all have and overcharge playing function, it is anode with the composite positive pole, contributes to the raising of cycle performance.
To achieve the goals above, the present invention provides a kind of lithium ion conductor cladding phosphoric acid zirconium titanium sulphur lithium anode material Preparation method, this method comprises the following steps：
（1）Phosphoric acid zirconium titanium sulphur lithium active material is prepared
In molar ratio 0.4：1.8：4 weigh titanium salt, zirconates and phosphorus-containing compound, and titanium salt, zirconates are dissolved in 10-20 times and remove distilled water In, phosphorus-containing compound is added, after adjusting pH4-6 reactions 2-3h, stands 8-12h, is then filtered, washed, dries, obtain basic zirconium phosphate Titanium；
In mass ratio 10：（1-2）Will be dry after sulphur and above-mentioned zircomium-tiatnium phosphate addition solvent grinding 10-15h, regrind 50- 150min calcines 10-15h after then calcining 8-10h at 125-145 DEG C under an inert gas at 300-350 DEG C, is contained again Zircomium-tiatnium phosphate sulphur lithium active material；
（2）Prepare the precursor mixed solution of lithium ion conductor
According to chemical formula Li5La3.5Zr1.5O10Proportioning, lithium nitrate, lanthanum nitrate, zirconium nitrate are added in mixing vessel, are added suitable Amount ethylene glycol, oxalic acid are stirred at room temperature 4-6 hours, obtain the precursor mixed solution of lithium ion conductor；
（3）According to Li5La3.5Zr1.5O10Mass ratio with phosphoric acid zirconium titanium sulphur lithium active material is 1:150-180 contains above-mentioned Zircomium-tiatnium phosphate sulphur lithium active material is added to above-mentioned inorganic fast lithium ion conductor Li5La3.5Zr1.5O10Precursor solution In, the two is uniformly mixed at room temperature, and the ultrasound 2-3h in ultrasonic disperse machine, ultrasonic step is replaced to weight with whipping step Multiple to carry out, ultrasonic 12-15min stirs 15-20min, to ensure the two mixture homogeneity of material and the dispersibility of storeroom, Obtain mixed solution；
（4）Mixed solution is placed at 65-70 DEG C and stirs 6-8h, with the volatilization of solvent in mixed solution, is gradually become sticky Thick class colloidal materials, by such colloidal materials turn be dried, after solvent volatilization completely after, transfer them in crucible Heat treatment 6-8h is carried out at 680-720 DEG C, obtains lithium ion conductor cladding phosphoric acid zirconium titanium sulphur lithium anode material.
Preferably, in the step（1）In, titanium salt at least may include one kind in titanium sulfate, titanyl sulfate；Zirconates is at least It may include one kind in zirconium sulfate or zirconium nitrate；Phosphorus-containing compound at least may include one in ammonium dihydrogen phosphate or diammonium hydrogen phosphate Kind.
The invention has the advantages that and remarkable result：
（1）The present invention uses zircomium-tiatnium phosphate as carrier, and cross appearance can effectively inhibit the self-discharge processes of battery, and sulphur Particulate load is in the zircomium-tiatnium phosphate, since the unique layer structure of zircomium-tiatnium phosphate has tightly wrapped sulfur granules, Neng Gouyou Effect inhibits the dissolving of its intermediate product polysulfide that discharges, and improves the cycle performance of sulphur lithium battery.
（2）The present invention by inorganic fast lithium ion conductor precursor solution and anode material for lithium-ion batteries at a certain temperature After mixing, the anode material for lithium-ion batteries that surface coats fast lithium ion conductor colloid is obtained, the surface is coated fast The anode material for lithium-ion batteries of lithium ion conductor colloid after heat treatment, on positive electrode particle surface forms one layer of uniform cladding Layer can promote the transmission activity of lithium ion inside electrode material, improve the interface of electrolyte and positive interpolar, promote the property of battery Energy；The anode of the present invention is compatible in terms of charge and discharge potential, and all has and overcharge playing function, is with the composite positive pole Anode contributes to the raising of cycle performance.
Specific implementation mode
Embodiment one
In molar ratio 0.4：1.8：4 weigh titanium salt, zirconates and phosphorus-containing compound, and titanium salt, zirconates are dissolved in 10 times and gone in distilled water, Phosphorus-containing compound is added, after adjusting pH4 reactions 2h, stands 8h, is then filtered, washed, dries, obtain zircomium-tiatnium phosphate.Wherein, titanium Salt at least may include one kind in titanium sulfate, titanyl sulfate；Zirconates at least may include one kind in zirconium sulfate or zirconium nitrate；It is phosphorous Compound at least may include one kind in ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
In mass ratio 10：1 will be dry after sulphur and above-mentioned zircomium-tiatnium phosphate addition solvent grinding 10h, regrinds 50min, Then 10h is calcined at 300 DEG C again after calcining 8h at 125 DEG C under an inert gas, obtains phosphoric acid zirconium titanium sulphur lithium active material.
According to chemical formula Li5La3.5Zr1.5O10Proportioning, by lithium nitrate, lanthanum nitrate, zirconium nitrate be added mixing vessel in, add Enter proper amount of glycol, oxalic acid is stirred at room temperature 4 hours, obtain the precursor mixed solution of lithium ion conductor.
According to Li5La3.5Zr1.5O10Mass ratio with phosphoric acid zirconium titanium sulphur lithium active material is 1:150, by above-mentioned phosphoric acid Zirconium titanium sulphur lithium active material is added to above-mentioned inorganic fast lithium ion conductor Li5La3.5Zr1.5O10Precursor solution in, The two is uniformly mixed at room temperature, and the ultrasound 2h in ultrasonic disperse machine, ultrasonic step and whipping step is alternately repeated progress, Ultrasonic 12min stirs 15min, to ensure the two mixture homogeneity of material and the dispersibility of storeroom, obtains mixed solution.
Mixed solution is placed at 65 DEG C and stirs 6h, with the volatilization of solvent in mixed solution, is gradually become viscous Such colloidal materials are turned to be dried, after solvent volatilization completely, be transferred them in crucible at 680 DEG C by class colloidal materials Under carry out heat treatment 6h, obtain lithium ion conductor cladding phosphoric acid zirconium titanium sulphur lithium anode material.
Embodiment two
In molar ratio 0.4：1.8：4 weigh titanium salt, zirconates and phosphorus-containing compound, and titanium salt, zirconates are dissolved in 20 times and gone in distilled water, Phosphorus-containing compound is added, after adjusting pH6 reactions 3h, stands 12h, is then filtered, washed, dries, obtain zircomium-tiatnium phosphate.Wherein, Titanium salt at least may include one kind in titanium sulfate, titanyl sulfate；Zirconates at least may include one kind in zirconium sulfate or zirconium nitrate；Contain Phosphorus compound at least may include one kind in ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
In mass ratio 10：2 will be dry after sulphur and above-mentioned zircomium-tiatnium phosphate addition solvent grinding 15h, regrinds 150min, Then 15h is calcined at 350 DEG C again after calcining 10h at 145 DEG C under an inert gas, obtains phosphoric acid zirconium titanium sulphur lithium active matter Matter.
According to chemical formula Li5La3.5Zr1.5O10Proportioning, by lithium nitrate, lanthanum nitrate, zirconium nitrate be added mixing vessel in, add Enter proper amount of glycol, oxalic acid is stirred at room temperature 6 hours, obtain the precursor mixed solution of lithium ion conductor.
According to Li5La3.5Zr1.5O10Mass ratio with phosphoric acid zirconium titanium sulphur lithium active material is 1:180, by above-mentioned phosphoric acid Zirconium titanium sulphur lithium active material is added to above-mentioned inorganic fast lithium ion conductor Li5La3.5Zr1.5O10Precursor solution in, The two is uniformly mixed at room temperature, and the ultrasound 3h in ultrasonic disperse machine, ultrasonic step and whipping step is alternately repeated progress, Ultrasonic 15min stirs 20min, to ensure the two mixture homogeneity of material and the dispersibility of storeroom, obtains mixed solution.
Mixed solution is placed at 70 DEG C and stirs 8h, with the volatilization of solvent in mixed solution, is gradually become viscous Such colloidal materials are turned to be dried, after solvent volatilization completely, be transferred them in crucible at 720 DEG C by class colloidal materials Under carry out heat treatment 8h, obtain lithium ion conductor cladding phosphoric acid zirconium titanium sulphur lithium anode material.

Claims (2)

1. a kind of preparation method of lithium ion conductor cladding phosphoric acid zirconium titanium sulphur lithium anode material, this method comprises the following steps：
（1）Phosphoric acid zirconium titanium sulphur lithium active material is prepared
In molar ratio 0.4：1.8：4 weigh titanium salt, zirconates and phosphorus-containing compound, and titanium salt, zirconates are dissolved in 10-20 times and remove distilled water In, phosphorus-containing compound is added, after adjusting pH4-6 reactions 2-3h, stands 8-12h, is then filtered, washed, dries, obtain basic zirconium phosphate Titanium；
In mass ratio 10：（1-2）Will be dry after sulphur and above-mentioned zircomium-tiatnium phosphate addition solvent grinding 10-15h, regrind 50- 150min calcines 10-15h after then calcining 8-10h at 125-145 DEG C under an inert gas at 300-350 DEG C, is contained again Zircomium-tiatnium phosphate sulphur lithium active material；
（2）Prepare the precursor mixed solution of lithium ion conductor
According to chemical formula Li5La3.5Zr1.5O10Proportioning, lithium nitrate, lanthanum nitrate, zirconium nitrate are added in mixing vessel, are added suitable Amount ethylene glycol, oxalic acid are stirred at room temperature 4-6 hours, obtain the precursor mixed solution of lithium ion conductor；
（3）According to Li5La3.5Zr1.5O10Mass ratio with phosphoric acid zirconium titanium sulphur lithium active material is 1:150-180 contains above-mentioned Zircomium-tiatnium phosphate sulphur lithium active material is added to above-mentioned inorganic fast lithium ion conductor Li5La3.5Zr1.5O10Precursor solution In, the two is uniformly mixed at room temperature, and the ultrasound 2-3h in ultrasonic disperse machine, ultrasonic step is replaced to weight with whipping step Multiple to carry out, ultrasonic 12-15min stirs 15-20min, to ensure the two mixture homogeneity of material and the dispersibility of storeroom, Obtain mixed solution；
（4）Mixed solution is placed at 65-70 DEG C and stirs 6-8h, with the volatilization of solvent in mixed solution, is gradually become sticky Thick class colloidal materials, by such colloidal materials turn be dried, after solvent volatilization completely after, transfer them in crucible Heat treatment 6-8h is carried out at 680-720 DEG C, obtains lithium ion conductor cladding phosphoric acid zirconium titanium sulphur lithium anode material.
2. the method as described in claim 1, which is characterized in that in the step（1）In, titanium salt at least may include titanium sulfate, One kind in titanyl sulfate；Zirconates at least may include one kind in zirconium sulfate or zirconium nitrate；Phosphorus-containing compound at least may include phosphorus One kind in acid dihydride ammonium or diammonium hydrogen phosphate.
CN201810052757.3A 2018-01-19 2018-01-19 A kind of preparation method of lithium ion conductor cladding phosphoric acid zirconium titanium sulphur lithium anode material Pending CN108346785A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107039634A (en) * 2017-05-04 2017-08-11 北京科技大学 Composite lithium ion battery anode and flexible lithium battery, solid state lithium battery preparation method
CN107492646A (en) * 2017-08-11 2017-12-19 苏州思创源博电子科技有限公司 A kind of preparation method of the sulphur lithium anode material of carbon silicon cladding

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107039634A (en) * 2017-05-04 2017-08-11 北京科技大学 Composite lithium ion battery anode and flexible lithium battery, solid state lithium battery preparation method
CN107492646A (en) * 2017-08-11 2017-12-19 苏州思创源博电子科技有限公司 A kind of preparation method of the sulphur lithium anode material of carbon silicon cladding

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Application publication date: 20180731