CN108878844A - A kind of preparation method of lithium battery iron sulphur negative electrode material - Google Patents

A kind of preparation method of lithium battery iron sulphur negative electrode material Download PDF

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Publication number
CN108878844A
CN108878844A CN201810703805.0A CN201810703805A CN108878844A CN 108878844 A CN108878844 A CN 108878844A CN 201810703805 A CN201810703805 A CN 201810703805A CN 108878844 A CN108878844 A CN 108878844A
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iron sulphur
weight
sulphur compound
parts
iron
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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
    • 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
    • H01M4/58—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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/626—Metals
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of lithium battery preparation methods of iron sulphur negative electrode material, the method uses the ferrite hollow sphere with special micro-nano structure to prepare high-performance iron sulphur compound under suitably vulcanization sintering temperature, the higher iron sulphur compound of crystallinity can be obtained, is conducive to that storage lithium reaction occurs；The present invention is compound by carbon nitrogen, improves the electric conductivity of active material, in addition, the expansion of volume provides the useful space when cavity between the carbon-coating of N doping and iron sulphur compound is active material Li insertion extraction, it is therefore prevented that the dusting reunion of iron sulphur compound.

Description

A kind of preparation method of lithium battery iron sulphur negative electrode material
Technical field
The present invention relates to battery material fields, and in particular to a kind of preparation method of lithium battery iron sulphur negative electrode material.
Background technique
In recent years, domestic new-energy automobile industry development is rapid, and battery variety is rich and varied, demand of the market to battery and It is required that gradually increasing.Its most concerned key index is concentrated mainly on five broad aspects：Safety and stability performance, cycle life, resistance to width Warm nature, charging rate and energy density.
Now, effect of the lithium ion battery in social development is higher and higher.Therefore, high-performance, environmentally protective is developed Electrode material becomes the research hotspot of lithium ion battery.Lithium ion battery negative material is based on graphitized carbon material at present, but Carbon material has the following disadvantages：（1）SEI film is generated in discharge process for the first time, causes irreversible capacity loss, or even causes carbon electric Pole internal structure change and poor contact；（2）Because the decomposition of protective layer, leads to battery failure or cause safe sexual behavior when high temperature Therefore；（3）Unit volume capacity is relatively low.Since metal, metal oxide and its composite material have high specific capacity, They become the substitute of lithium ion battery negative material, have biggish development potentiality.
Metal sulfide pyrite（FeS2）With its energy density height（890mAh/g）, stable structure, safe and non-toxic no dirt It contaminates and cheap, receives the attention of researcher, be a kind of lithium cell cathode material of great application prospect.But iron There are self-conductance rates that polysulfide that is lower, being formed in cyclic process is easily soluble in electrolysis as negative electrode material for sulphur compound Liquid and volume increase the disadvantages of causing material structure seriously to destroy in charge and discharge process, cause the stability in cyclic process It is all poor with high rate performance, their applications in real life are hindered significantly.Nano material is because have special pattern With size and make it with special property, can solve above-mentioned iron sulphur compound conduct by some special structures designs The problem of negative electrode material faces.
Summary of the invention
The present invention provides a kind of preparation method of lithium battery iron sulphur negative electrode material, and the method, which uses, has special micro-nano The ferrite hollow sphere of structure suitably vulcanization sintering temperature under prepare high-performance iron sulphur compound, can obtain crystallinity compared with High iron sulphur compound is conducive to that storage lithium reaction occurs；The present invention is compound by carbon nitrogen, improves the conduction of active material Property, in addition, the expansion of volume provides when cavity between the carbon-coating of N doping and iron sulphur compound is active material Li insertion extraction The useful space, it is therefore prevented that the dusting of iron sulphur compound is reunited.
To achieve the goals above, the present invention provides a kind of preparation method of lithium battery iron sulphur negative electrode material, this method Include the following steps：
（1）Prepare iron sulphur compound material
Soluble ferric iron salt is dissolved in the mixed solution of alcohol and amine and obtains molysite mixed solution, wherein soluble ferric iron salt is iron chloride Or ferric sulfate, alcohol is ethylene glycol or propylene glycol in the mixed solution of alcohol and amine, in the mixed solution of alcohol and amine amine be ethylenediamine or Propane diamine, wherein the concentration of soluble ferric iron salt is 0.0015-0.002mmol/L in molysite mixed solution；
Molysite mixed solution is transferred in reaction kettle obtain having in 200-250 DEG C of progress solvent thermal reaction 10-24h it is special micro- Receive the ferrite mixture of hollow ball structure；
Ferrite mixture is centrifugated, obtains that there is the shallow of special micro-nano hollow ball structure after repeatedly being washed with organic solvent Green ferrite, then it is placed in drying in baking oven, wherein organic solvent is dehydrated alcohol, acetone, hexamethylene, dimethyl sulfoxide or tetrahydro One of furans is a variety of；
Ferrite after drying is placed in tube furnace, in sulfurous gas atmosphere or the mixed atmosphere of inert gas and sulfurous gas Under, 400-500 DEG C of reaction 4-6h is warming up to the heating rate of 5-8 DEG C/min, obtains iron sulphur compound after natural cooling；
（2）Prepare silica cladding iron sulphur compound presoma
By the iron sulphur compound of 60 parts by weight be dispersed in 150-180 parts by weight by ethylene glycol and water by volume 3:1 composition In mixed liquor, 10-60min is stirred by ultrasonic, 2-4 parts by weight ammonium hydroxide and 0.2-0.3 parts by weight then is being added just under agitation Tetraethyl orthosilicate continues to stir 8-14h, centrifugation, washing, i.e. acquisition silica coats iron sulphur compound presoma；
（3）The silica cladding iron sulphur compound presoma of acquisition is dispersed in 100 parts by weight of ethanol, 1-2 weight is then added The high molecular surfactant of part is measured, 20-30h, centrifugation, washing are stirred；
It disperses silica cladding iron sulphur compound presoma after washing in 80 parts by weight of deionized water, 0.3- is then added 0.35 parts by weight pyrrole monomer, ultrasonic 45-50min, then it is 20- that 50 parts by weight concentration are added dropwise under agitation The initiator solution of 25mmol/L, last polymerization reaction 4-12h, centrifugation, washing, drying；
（4）Product after the drying is placed in atmosphere of inert gases, is warming up to 570 with the heating rate of 5 DEG C -8 DEG C/min DEG C -630 DEG C, anneal 1-3h, and polypyrrole is made to be carbonized；
Product after the carbonization is put into alkaline solution and is performed etching, to remove SiO2To get arrive iron sulphur negative electrode material.
Preferably, the high molecular surfactant is poly amic acid, hydroxyethyl cellulose and polyoxyethylene copolymerization At least one of object；The initiator is at least one of ammonium persulfate, potassium bichromate and Potassiumiodate.
The invention has the advantages that and remarkable result：
（1）It is high that the method uses the ferrite hollow sphere with special micro-nano structure to prepare under suitably vulcanization sintering temperature Performance iron sulphur compound can obtain the higher iron sulphur compound of crystallinity, be conducive to that storage lithium reaction occurs；
（2）The present invention is compound by carbon nitrogen, improves the electric conductivity of active material, in addition, the carbon-coating of N doping and iron vulcanize The expansion of volume provides the useful space when closing the cavity between object as active material Li insertion extraction, it is therefore prevented that iron sulphur compound Dusting is reunited.
Specific embodiment
Embodiment one
Soluble ferric iron salt is dissolved in the mixed solution of alcohol and amine and obtains molysite mixed solution, wherein soluble ferric iron salt is chlorination Alcohol is ethylene glycol in the mixed solution of iron, alcohol and amine, and amine is ethylenediamine in the mixed solution of alcohol and amine, wherein molysite mixed solution The concentration of middle soluble ferric iron salt is 0.0015mmol/L；Molysite mixed solution is transferred in reaction kettle in 200 DEG C of progress solvents Thermal response 10h obtains the ferrite mixture with special micro-nano hollow ball structure.
Ferrite mixture is centrifugated, obtains that there is special micro-nano hollow ball structure after repeatedly being washed with organic solvent Light green color ferrite, then be placed in baking oven dry, wherein organic solvent is dehydrated alcohol.
Ferrite after drying is placed in tube furnace, in the mixing of sulfurous gas atmosphere or inert gas and sulfurous gas Under atmosphere, 400 DEG C of reaction 4h are warming up to the heating rate of 5 DEG C/min, obtain iron sulphur compound after natural cooling.
By the iron sulphur compound of 60 parts by weight be dispersed in 150 parts by weight by ethylene glycol and water by volume 3:1 composition In mixed liquor, 10min is stirred by ultrasonic, 2-4 parts by weight ammonium hydroxide and the positive silicic acid tetrem of 0.2 parts by weight are then added under agitation Ester continues to stir 8h, centrifugation, washing, i.e. acquisition silica coats iron sulphur compound presoma.
The silica cladding iron sulphur compound presoma of acquisition is dispersed in 100 parts by weight of ethanol, 1 weight is then added The high molecular surfactant of part stirs 20h, centrifugation, washing；Silica cladding iron sulphur compound presoma dispersion after washing In 80 parts by weight of deionized water, 0.3 parts by weight pyrrole monomer, ultrasonic 45min is then added, then add dropwise under agitation Enter the initiator solution that 50 parts by weight concentration are 20mmol/L, last polymerization reaction 4h, centrifugation, washing, drying；By the drying Product afterwards is placed in atmosphere of inert gases, is warming up to 570 DEG C with the heating rate of 5 DEG C/min, and anneal 1h, makes polypyrrole carbon Change；Product after the carbonization is put into alkaline solution and is performed etching, to remove SiO2To get arrive iron sulphur negative electrode material.
Wherein, the high molecular surfactant is poly amic acid, hydroxyethyl cellulose and polyoxyethylene analog copolymer At least one of；The initiator is at least one of ammonium persulfate, potassium bichromate and Potassiumiodate.
Embodiment two
Soluble ferric iron salt is dissolved in the mixed solution of alcohol and amine and obtains molysite mixed solution, wherein soluble ferric iron salt is sulfuric acid Alcohol is propylene glycol in the mixed solution of iron, alcohol and amine, and amine is propane diamine in the mixed solution of alcohol and amine, wherein molysite mixed solution The concentration of middle soluble ferric iron salt is 0.002mmol/L；Molysite mixed solution is transferred in reaction kettle in 250 DEG C of progress solvent heats Reaction obtains the ferrite mixture with special micro-nano hollow ball structure for 24 hours.
Ferrite mixture is centrifugated, obtains that there is special micro-nano hollow ball structure after repeatedly being washed with organic solvent Light green color ferrite, then be placed in baking oven it is dry, wherein organic solvent be dehydrated alcohol, acetone, hexamethylene, dimethyl sulfoxide or One of tetrahydrofuran is a variety of.
Ferrite after drying is placed in tube furnace, in the mixing of sulfurous gas atmosphere or inert gas and sulfurous gas Under atmosphere, 500 DEG C of reaction 6h are warming up to the heating rate of 8 DEG C/min, obtain iron sulphur compound after natural cooling.
By the iron sulphur compound of 60 parts by weight be dispersed in 180 parts by weight by ethylene glycol and water by volume 3:1 composition In mixed liquor, 60min is stirred by ultrasonic, 4 parts by weight ammonium hydroxide and the positive silicic acid tetrem of 0.3 parts by weight are then added under agitation Ester continues to stir 14h, centrifugation, washing, i.e. acquisition silica coats iron sulphur compound presoma.
The silica cladding iron sulphur compound presoma of acquisition is dispersed in 100 parts by weight of ethanol, 2 weight are then added The high molecular surfactant of part stirs 30h, centrifugation, washing；Silica cladding iron sulphur compound presoma dispersion after washing In 80 parts by weight of deionized water, it is then added 0.35 parts by weight pyrrole monomer, ultrasonic 50min, then under agitation dropwise The initiator solution that 50 parts by weight concentration are 25mmol/L, last polymerization reaction 12h, centrifugation, washing, drying is added；It will be described Product after drying is placed in atmosphere of inert gases, is warming up to 630 DEG C with the heating rate of 8 DEG C/min, and anneal 3h, makes polypyrrole Carbonization；Product after the carbonization is put into alkaline solution and is performed etching, to remove SiO2To get arrive iron sulphur negative electrode material.
Wherein, the high molecular surfactant is polyoxyethylene analog copolymer；The initiator is Potassiumiodate.
Using above-described embodiment one, two products therefrom materials as being used for cathode of lithium battery, with just extremely LiFePO 4 material The test battery pack of composition carries out cyclical stability test, and discharge capacity is respectively 1243mAh/g and 1207mAh/g for the first time, is followed Capacity is 1025mAh/g and 994mAh/g after ring 200 times, has good cyclical stability.

Claims (2)

1. a kind of lithium battery preparation method of iron sulphur negative electrode material, this method comprises the following steps：
（1）Prepare iron sulphur compound material
Soluble ferric iron salt is dissolved in the mixed solution of alcohol and amine and obtains molysite mixed solution, wherein soluble ferric iron salt is iron chloride Or ferric sulfate, alcohol is ethylene glycol or propylene glycol in the mixed solution of alcohol and amine, in the mixed solution of alcohol and amine amine be ethylenediamine or Propane diamine, wherein the concentration of soluble ferric iron salt is 0.0015-0.002mmol/L in molysite mixed solution；
Molysite mixed solution is transferred in reaction kettle obtain having in 200-250 DEG C of progress solvent thermal reaction 10-24h it is special micro- Receive the ferrite mixture of hollow ball structure；
Ferrite mixture is centrifugated, obtains that there is the shallow of special micro-nano hollow ball structure after repeatedly being washed with organic solvent Green ferrite, then it is placed in drying in baking oven, wherein organic solvent is dehydrated alcohol, acetone, hexamethylene, dimethyl sulfoxide or tetrahydro One of furans is a variety of；
Ferrite after drying is placed in tube furnace, in sulfurous gas atmosphere or the mixed atmosphere of inert gas and sulfurous gas Under, 400-500 DEG C of reaction 4-6h is warming up to the heating rate of 5-8 DEG C/min, obtains iron sulphur compound after natural cooling；
（2）Prepare silica cladding iron sulphur compound presoma
By the iron sulphur compound of 60 parts by weight be dispersed in 150-180 parts by weight by ethylene glycol and water by volume 3:1 composition In mixed liquor, 10-60min is stirred by ultrasonic, 2-4 parts by weight ammonium hydroxide and 0.2-0.3 parts by weight then is being added just under agitation Tetraethyl orthosilicate continues to stir 8-14h, centrifugation, washing, i.e. acquisition silica coats iron sulphur compound presoma；
（3）The silica cladding iron sulphur compound presoma of acquisition is dispersed in 100 parts by weight of ethanol, 1-2 weight is then added The high molecular surfactant of part is measured, 20-30h, centrifugation, washing are stirred；
It disperses silica cladding iron sulphur compound presoma after washing in 80 parts by weight of deionized water, 0.3- is then added 0.35 parts by weight pyrrole monomer, ultrasonic 45-50min, then it is 20- that 50 parts by weight concentration are added dropwise under agitation The initiator solution of 25mmol/L, last polymerization reaction 4-12h, centrifugation, washing, drying；
（4）Product after the drying is placed in atmosphere of inert gases, is warming up to 570 with the heating rate of 5 DEG C -8 DEG C/min DEG C -630 DEG C, anneal 1-3h, and polypyrrole is made to be carbonized；
Product after the carbonization is put into alkaline solution and is performed etching, to remove SiO2To get arrive iron sulphur negative electrode material.
2. the method as described in claim 1, which is characterized in that the high molecular surfactant is poly amic acid, hydroxyl second At least one of base cellulose and polyoxyethylene analog copolymer；The initiator is ammonium persulfate, potassium bichromate and Potassiumiodate At least one of.
CN201810703805.0A 2018-06-30 2018-06-30 A kind of preparation method of lithium battery iron sulphur negative electrode material Pending CN108878844A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112133919A (en) * 2020-09-23 2020-12-25 杭州怡莱珂科技有限公司 Sulfide-carbon in-situ composite material, electrode, preparation method of electrode and battery
CN113659135A (en) * 2021-08-11 2021-11-16 电子科技大学 Application of iron sulfide in lithium iron phosphate secondary battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106816595A (en) * 2017-03-09 2017-06-09 合肥工业大学 A kind of lithium ion battery coats di-iron trioxide negative material and preparation method thereof with nitrogen-doped carbon
CN106867263A (en) * 2017-03-24 2017-06-20 浙江师范大学 ZnFe2O4@SiO2@RGO wave absorbing agents and its preparation technology
CN106898770A (en) * 2017-03-28 2017-06-27 河南师范大学 The method that ferrite vulcanization prepares flower-shaped lithium cell cathode material iron sulphur compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106816595A (en) * 2017-03-09 2017-06-09 合肥工业大学 A kind of lithium ion battery coats di-iron trioxide negative material and preparation method thereof with nitrogen-doped carbon
CN106867263A (en) * 2017-03-24 2017-06-20 浙江师范大学 ZnFe2O4@SiO2@RGO wave absorbing agents and its preparation technology
CN106898770A (en) * 2017-03-28 2017-06-27 河南师范大学 The method that ferrite vulcanization prepares flower-shaped lithium cell cathode material iron sulphur compound

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112133919A (en) * 2020-09-23 2020-12-25 杭州怡莱珂科技有限公司 Sulfide-carbon in-situ composite material, electrode, preparation method of electrode and battery
CN113659135A (en) * 2021-08-11 2021-11-16 电子科技大学 Application of iron sulfide in lithium iron phosphate secondary battery
CN113659135B (en) * 2021-08-11 2023-02-03 电子科技大学 Application of iron sulfide in lithium iron phosphate secondary battery

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