CN107492646A - A kind of preparation method of the sulphur lithium anode material of carbon silicon cladding - Google Patents

A kind of preparation method of the sulphur lithium anode material of carbon silicon cladding Download PDF

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Publication number
CN107492646A
CN107492646A CN201710687163.5A CN201710687163A CN107492646A CN 107492646 A CN107492646 A CN 107492646A CN 201710687163 A CN201710687163 A CN 201710687163A CN 107492646 A CN107492646 A CN 107492646A
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silicon
sulphur
zircomium
titanium
phosphate
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不公告发明人
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Suzhou Sichuang Yuanbo Electronic Technology Co Ltd
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Suzhou Sichuang Yuanbo Electronic Technology Co Ltd
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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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, 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

Abstract

The invention discloses a kind of preparation method of the sulphur lithium anode material of carbon silicon cladding, methods described uses zircomium-tiatnium phosphate as carrier, its cross appearance can effectively suppress the self-discharge processes of battery, and sulfur granules are carried in the zircomium-tiatnium phosphate, because the unique layer structure of zircomium-tiatnium phosphate has tightly wrapped sulfur granules, the dissolving of its intermediate product polysulfide that discharges can effectively be suppressed, improve the cycle performance of lithium-sulfur cell；The porosity characteristic that carbon silicon covering material of the present invention has is advantageous to the absorption storage of electrolyte, and provide space to volumetric expansion in silicon materials charge and discharge process, porous silicon sized nanostructures level, also play and alleviate the effect of silicon grain bulk effect, therefore it is high with reversible capacity, good cycle, the advantages of high rate performance is excellent.

Description

A kind of preparation method of the sulphur lithium anode material of carbon silicon cladding
Technical field
The present invention relates to battery material field, and in particular to a kind of preparation method of the sulphur lithium anode material of carbon silicon cladding.
Background technology
Compared with the secondary cells such as traditional plumbic acid, NI-G, ni-mh, lithium rechargeable battery has operating voltage height, body The small, light weight of product, capacity density height, memory-less effect, it is pollution-free, self discharge is small and has extended cycle life the advantages that.From 1991 Since lithium ion battery is successfully realized commercialization by year certain Japanese company, lithium ion battery turned into mobile phone, notebook computer and The leading power supply of digital product, the application in the field such as electric automobile and energy storage are also more and more extensive.
Using lithium metal as negative pole, elemental sulfur for the lithium-sulfur cell of positive pole it is theoretical than energy can reach 2600Wh/kg (lithium and The theoretical specific capacity of sulphur is respectively 3860mAh/g and 1675mAh/g), much larger than used commercialization secondary cell at this stage. In addition, cheap, the environment-friendly characteristic of elemental sulfur makes the energy storage system great commercial value again.But in the prior art, lithium Not high to the utilization rate of positive active material sulphur in sulphur battery, its Capacity fading is serious, and cycle performance is poor, and electrochemistry Performance is bad.In order to improve the performance of lithium-sulfur cell, people are directed to the research of the positive electrode modification to lithium-sulfur cell at present, To improve its electric conductivity and cycle performance.Such as fill out sulphur in mesoporous carbon space, the addition of mesoporous carbon improves electric conductivity；This There is research worker to be modified using conducting polymer to sulphur outside, the addition of conducting polymer can be effectively improved lithium sulphur electricity The cycle performance in pond.However, although the above-mentioned method being modified to sulphur positive electrode can improve the electric conductivity of lithium-sulfur cell Or its cycle performance is improved, but the energy density of obtained lithium-sulfur cell reduces, that is to say, that it is this that sulphur positive electrode is entered The modified method of row can not improve the performance of lithium-sulfur cell on the whole.
Coated with carbon silicon materials are one of current effective ways for improving anode material for lithium-ion batteries deficiency, at present, Si-C composite material prepares main use：1）Nano silicon material and graphite material be compound and carbon coating；2）Thick silicon high-energy ball milling with Graphite is compound and carbon coating；3）One layer of silicon materials and carbon coating are coated in the vapour deposition of graphite particle surface chemistry.Using above-mentioned Method 1）Because using nano silicon material, its cost is higher, and because the agglomeration of nano material is difficult dispersed；Side Method 2 uses high-energy ball milling, and long preparation period, cost are high；Method 3）The chemical vapor deposition of use is difficult on graphite particle surface Uniform cladding silicon materials.In addition, above method is difficult to overcome to play with efficiency while taking into account first in capacity.
The content of the invention
The present invention provides a kind of preparation method of the sulphur lithium anode material of carbon silicon cladding, and methods described is made using zircomium-tiatnium phosphate For carrier, its cross appearance can effectively suppress the self-discharge processes of battery, and sulfur granules are carried in the zircomium-tiatnium phosphate, by Sulfur granules have tightly been wrapped in the unique layer structure of zircomium-tiatnium phosphate, can effectively suppress its intermediate product polysulfide that discharges Dissolving, improve the cycle performance of lithium-sulfur cell；The porosity characteristic that carbon silicon covering material of the present invention has is advantageous to electrolyte Absorption storage, and provide space to volumetric expansion in silicon materials charge and discharge process, porous silicon sized nanostructures level, also play alleviation The advantages of silicon grain bulk effect acts on, therefore high with reversible capacity, good cycle, and high rate performance is excellent.
To achieve these goals, the present invention provides a kind of preparation method of the sulphur lithium anode material of carbon silicon cladding, the party Method comprises the following steps：
（1）Phosphoric acid zirconium titanium sulphur lithium anode 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 into 10-20 times and remove distilled water In, phosphorus-containing compound is added, after regulation pH4-6 reacts 2-3h, stands 8-12h, then filters, wash, dry, obtain basic zirconium phosphate Titanium；
In mass ratio 10：（1-2）Dried after sulphur and above-mentioned zircomium-tiatnium phosphate are added into solvent grinding 10-15h, regrind 50- 150min, 10-15h is calcined at 300-350 DEG C again after then calcining 8-10h at 125-145 DEG C under an inert gas, is contained Zircomium-tiatnium phosphate sulphur lithium anode material；
（2）Prepare carbon silicon covering material
By micron silicon, paraffin, starch, ethylene glycol in mass ratio（15-35）：（30-10）：（15-25）：Ball after the mixing of 100 ratios Grind as ball-milled mixtures, ball-milled mixtures are dried with granulation and obtains the equally distributed presoma of micron silicon, paraffin, starch；
Gained presoma is heated, melts out paraffin, obtains the silicon and the equally distributed presoma material of carbon source of loose structure Material, it is 100-150 DEG C that the presoma heating, which controls heat treatment temperature, processing time 10-15h；
By gained persursor material, the high temperature sintering under inert atmosphere protection, carbon silicon covering material is obtained；The high temperature sintering is It is 900-1000 DEG C to control sintering temperature, and the heating rate of temperature is 5-15 DEG C/min when controlling sintering；Sintering time is 10- 20h；
（3）Compound coating
By the phosphoric acid zirconium titanium sulphur lithium anode material and the carbon silicon covering material according to mass ratio (85-60)：1 in batch mixer In be well mixed；
In atmospheric conditions, the material mixed is fired, is warming up to 860 DEG C -950 DEG C, be incubated 10-15h, cooling After obtain product.
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 its cross appearance can effectively suppress the self-discharge processes of battery, and sulphur Particulate load is in the zircomium-tiatnium phosphate, because the unique layer structure of zircomium-tiatnium phosphate has tightly wrapped sulfur granules, Neng Gouyou Effect suppresses the dissolving of its intermediate product polysulfide that discharges, and improves the cycle performance of lithium-sulfur cell.
（2）；The porosity characteristic that carbon silicon covering material of the present invention has is advantageous to the absorption storage of electrolyte, and gives silicon materials Volumetric expansion provides space in charge and discharge process, porous silicon sized nanostructures level, also plays and alleviates the effect of silicon grain bulk effect, because The advantages of this has that reversible capacity is high, good cycle, and high rate performance is excellent.
Embodiment
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 into 10 times and gone in distilled water, Phosphorus-containing compound is added, after regulation pH4 reacts 2h, stands 8h, then filters, wash, dry, 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 dry after sulphur and above-mentioned zircomium-tiatnium phosphate addition solvent grinding 10h, regrind 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 anode material.
By micron silicon, paraffin, starch, ethylene glycol in mass ratio 15：30：15：Ball milling is ball milling mixing after the mixing of 100 ratios Thing, ball-milled mixtures are dried with granulation and obtains the equally distributed presoma of micron silicon, paraffin, starch；By gained presoma Heat, melt out paraffin, obtain the silicon and the equally distributed persursor material of carbon source of loose structure, the presoma heating It is 100 DEG C that processing, which controls heat treatment temperature, processing time 10h.
By gained persursor material, the high temperature sintering under inert atmosphere protection, carbon silicon covering material is obtained；The high temperature burns Knot be control sintering temperature be 900 DEG C, control sinter when temperature heating rate be 5 DEG C/min；Sintering time is 10h.
By the phosphoric acid zirconium titanium sulphur lithium anode material and the carbon silicon covering material according to mass ratio 85：1 in batch mixer In be well mixed；In atmospheric conditions, the material mixed is fired, is warming up to 860 DEG C, 10h is incubated, after cooling Obtain product.
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 into 20 times and gone in distilled water, Phosphorus-containing compound is added, after regulation pH6 reacts 3h, stands 12h, then filters, wash, dry, 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 dry after sulphur and above-mentioned zircomium-tiatnium phosphate addition solvent grinding 15h, regrind 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 positive pole material Material.
By micron silicon, paraffin, starch, ethylene glycol in mass ratio 35：10：25：Ball milling is ball milling mixing after the mixing of 100 ratios Thing, ball-milled mixtures are dried with granulation and obtains the equally distributed presoma of micron silicon, paraffin, starch；By gained presoma Heat, melt out paraffin, obtain the silicon and the equally distributed persursor material of carbon source of loose structure, the presoma heating It is 150 DEG C that processing, which controls heat treatment temperature, processing time 15h.
By gained persursor material, the high temperature sintering under inert atmosphere protection, carbon silicon covering material is obtained；The high temperature burns Knot be control sintering temperature be 1000 DEG C, control sinter when temperature heating rate be 15 DEG C/min；Sintering time is 20h.
By the phosphoric acid zirconium titanium sulphur lithium anode material and the carbon silicon covering material according to mass ratio 60：1 in batch mixer In be well mixed；In atmospheric conditions, the material mixed is fired, is warming up to 950 DEG C, 15h is incubated, after cooling Obtain product.
Comparative example
Commercially available phosphorus sulphur lithium anode material.
Above-described embodiment one, two and comparative example products therefrom are used into NMP as solvent, by active material: SP: PVDF Be configured to slurry that solid content be 70% at=90: 5: 5 is evenly applied on Al paper tinsels, and positive pole is made.Negative pole is from diameter 14mm's Metal lithium sheet, electrolyte select 1mol LiFP6 (EC：DMC：EMC=1:1:1, v/v), with negative electrode casing-shell fragment-pad-lithium Battery is packaged by the order of piece-electrolyte-barrier film-positive plate-pad-anode cover, and whole process is all filled with argon Completed in the glove box of gas.Electric performance test is carried out at being 25 DEG C in test temperature, after tested the material of the embodiment one and two Compared with the product of comparative example, first charge-discharge reversible capacity improves 13-15%, and service life brings up to more than 10%.

Claims (2)

1. a kind of preparation method of the sulphur lithium anode material of carbon silicon cladding, this method comprise the following steps：
（1）Phosphoric acid zirconium titanium sulphur lithium anode 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 into 10-20 times and remove distilled water In, phosphorus-containing compound is added, after regulation pH4-6 reacts 2-3h, stands 8-12h, then filters, wash, dry, obtain basic zirconium phosphate Titanium；
In mass ratio 10：（1-2）Dried after sulphur and above-mentioned zircomium-tiatnium phosphate are added into solvent grinding 10-15h, regrind 50- 150min, 10-15h is calcined at 300-350 DEG C again after then calcining 8-10h at 125-145 DEG C under an inert gas, is contained Zircomium-tiatnium phosphate sulphur lithium anode material；
（2）Prepare carbon silicon covering material
By micron silicon, paraffin, starch, ethylene glycol in mass ratio（15-35）：（30-10）：（15-25）：Ball after the mixing of 100 ratios Grind as ball-milled mixtures, ball-milled mixtures are dried with granulation and obtains the equally distributed presoma of micron silicon, paraffin, starch；
Gained presoma is heated, melts out paraffin, obtains the silicon and the equally distributed presoma material of carbon source of loose structure Material, it is 100-150 DEG C that the presoma heating, which controls heat treatment temperature, processing time 10-15h；
By gained persursor material, the high temperature sintering under inert atmosphere protection, carbon silicon covering material is obtained；The high temperature sintering is It is 900-1000 DEG C to control sintering temperature, and the heating rate of temperature is 5-15 DEG C/min when controlling sintering；Sintering time is 10- 20h；
（3）Compound coating
By the phosphoric acid zirconium titanium sulphur lithium anode material and the carbon silicon covering material according to mass ratio (85-60)：1 in batch mixer In be well mixed；
In atmospheric conditions, the material mixed is fired, is warming up to 860 DEG C -950 DEG C, be incubated 10-15h, cooling After obtain product.
2. the method as described in claim 1, it is characterised 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.
CN201710687163.5A 2017-08-11 2017-08-11 A kind of preparation method of the sulphur lithium anode material of carbon silicon cladding Pending CN107492646A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108346785A (en) * 2018-01-19 2018-07-31 王顺良 A kind of preparation method of lithium ion conductor cladding phosphoric acid zirconium titanium sulphur lithium anode material
CN111233458A (en) * 2020-02-17 2020-06-05 西南科技大学 Titanium aluminum lithium phosphate solid electrolyte material and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106654216A (en) * 2017-01-06 2017-05-10 南京海泰纳米材料有限公司 Titanium zirconium phosphate-containing positive electrode material of lithium-sulfur battery and preparation method for positive electrode material
CN106784675A (en) * 2016-12-16 2017-05-31 无锡晶石新型能源有限公司 A kind of dry method method for coating of anode material of lithium battery
CN106784707A (en) * 2016-12-28 2017-05-31 江西正拓新能源科技股份有限公司 A kind of preparation method of nano-silicone wire/carbon composite lithium ion battery cathode material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784675A (en) * 2016-12-16 2017-05-31 无锡晶石新型能源有限公司 A kind of dry method method for coating of anode material of lithium battery
CN106784707A (en) * 2016-12-28 2017-05-31 江西正拓新能源科技股份有限公司 A kind of preparation method of nano-silicone wire/carbon composite lithium ion battery cathode material
CN106654216A (en) * 2017-01-06 2017-05-10 南京海泰纳米材料有限公司 Titanium zirconium phosphate-containing positive electrode material of lithium-sulfur battery and preparation method for positive electrode material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108346785A (en) * 2018-01-19 2018-07-31 王顺良 A kind of preparation method of lithium ion conductor cladding phosphoric acid zirconium titanium sulphur lithium anode material
CN111233458A (en) * 2020-02-17 2020-06-05 西南科技大学 Titanium aluminum lithium phosphate solid electrolyte material and preparation method thereof
CN111233458B (en) * 2020-02-17 2023-05-16 西南科技大学 Titanium aluminum lithium phosphate solid electrolyte material and preparation method thereof

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Application publication date: 20171219