CN109546128A - A kind of nanometer of ferrous sulfide/grapheme composite positive electrode material preparation method - Google Patents

A kind of nanometer of ferrous sulfide/grapheme composite positive electrode material preparation method Download PDF

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CN109546128A
CN109546128A CN201811430971.4A CN201811430971A CN109546128A CN 109546128 A CN109546128 A CN 109546128A CN 201811430971 A CN201811430971 A CN 201811430971A CN 109546128 A CN109546128 A CN 109546128A
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ferrous sulfide
graphene
positive electrode
nanometer
electrode material
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赵海雷
方节军
张子佳
李兆麟
陶昕
张运超
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • 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
    • H01M4/48—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
    • 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
    • H01M4/36—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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 nanometer of ferrous sulfide/grapheme composite positive electrode material preparation methods.Using ferroso-ferric oxide/graphene composite material as reaction product, sulphur source is introduced by chemical vapour deposition technique and prepares ferrous sulfide/graphene composite material.Ferrous sulfide particle is uniformly dispersed on the surface of graphene, and it combines and stablizes with graphene, so as to effectively prevent nano particle to reunite in charge and discharge process, buffer volumes expansion, inhibit the dissolution of reaction product in the electrolytic solution, it is final to guarantee that electrode structure is stablized in charge and discharge process；Meanwhile graphene provides good conductive network, accelerates electron-transport.Preparation process of the invention is simple, time-consuming short, at low cost, it is easy to accomplish industrialized production；Ferrous sulfide/graphene composite material that this method is prepared has excellent chemical property, is a kind of ideal anode material for lithium-ion batteries, can be widely applied to the fields such as portable electronic device electric car and aerospace.

Description

A kind of nanometer of ferrous sulfide/grapheme composite positive electrode material preparation method
Technical field
The invention belongs to new energy materials and electrochemical field, and in particular to it is a kind of it is novel can charging-discharging lithium ion battery receive The preparation method of rice ferrous sulfide/graphene (FeS/graphene) composite material.
Technical background
Current era, lithium ion battery is because having high reversible capacity, high voltage, high circulation performance, high-energy density, length to follow The advantages such as ring service life, small self-discharge rate and memory-less effect, in the digital electronic goods such as mobile phone, notebook and hybrid electrically The fields such as automobile are widely used.The battery performance requirements used in it are also got in the fast development of electronic digital product Come higher, is badly in need of that there is the lithium ion battery of high capacity, high-energy density to meet its market demand.Now, limiting lithium ion " bottleneck " of battery capacity is positive electrode.All the time, there is increase but no decrease in enthusiasm to this research by people.Sulfide positive electrode The advantages that with its high capacity, low cost, hypotoxicity, preferable cycle performance, becomes positive electrode most promising at present One of.On the basis of the problems such as solving the matching of electrolyte, inhibiting Li dendrite to generate and improve cycle performance, it is expected to such The energy storage material industrialization haveing excellent performance, therefore have very important significance for the research of such positive electrode tool.
FeS theoretical capacity is up to 609mAh/g, resourceful, and low toxicity, electric conductivity is preferable, receives researchers in recent years Extensive concern.But FeS during removal lithium embedded along with biggish volume change it is living so that dusting occurs for active particle Property substance and collector lose electrical contact or fall off from its surface, lead to the rapid decay of capacity.In addition, the electricity of FeS material Sub- conductance is poor, causes electrochemical reaction dynamics slow, high rate performance is poor.Currently, many researchs all attempt through various sides Method improves its chemical property, such as reduces particle size, synthesis special appearance etc..Another kind is effectively improved ferrous sulfide electrification The method for learning performance is to form compound with conductive carbon matrix material.
The research work of representative ferrous sulfide base electrode material includes: in document
(1) Mexico State University Hongmei Luo teaches research group with Fe (NO3)3·9H2O is source of iron, Na2S·9H2O is sulphur source, and ferrous sulfide/graphene composite material is prepared using coprecipitation, the electricity prepared with the material Pole, under the current density of 100mA/g, first discharge specific capacity is more than 1300mAh/g, and the specific discharge capacity after 40 circulations is 978mAh/g, coulombic efficiency is lower, and only 97%；With the increase of current density, capacity attenuation is accelerated.It can be found that the material Material is used as lithium ion battery electrode material, and cyclical stability and ladder high rate performance are poor.And the preparation method controllability compared with Difference is not easy to large-scale production (ACS applied materials&interfaces, 2013,5 (11): 5330-5335).
(2) China Science & Technology University Yan Yu teaches research group using PVA, PVP as surfactant, using solvent Thermal method has synthesized FeS/C/carbon cloth composite material, and is directly used in the electrode material of lithium ion battery.Electrochemistry Can test and show: under the low current density of 0.15C, electrode first discharge specific capacity reaches 699mAh/g, after recycling 100 times still Keep 420mAh/g；There is obvious decaying after recycling 200 times under the high current density of 1.2C.The preparation process is at high cost, energy consumption Greatly, low output (ACS applied materials&interfaces, 2015,7 (50): 27804-27809).
It is special that nanosizing, Composite and design are concentrated mainly on for the research of anode material of lithium battery ferrous sulfide at present Different pattern.The bright sulfur ferrous materia for preparing nanoscale, due to volume change biggish in charge and discharge process and poor Electronic conductance, and nano material is easy so that active ferrous sulphide is reunited in charge and discharge process, cyclical stability with It still needs further improvement for high rate performance；The ferrous sulfide for preparing special appearance uses organic formwork or organic surfactant mostly Agent, preparation process is complicated, low yield；It prepares ferrous sulfide/C compound and mostly uses solvent-thermal method and coprecipitation, but is such Preparation method technical process poor controllability, at high cost, energy consumption is high, is not easy to be mass produced.
Summary of the invention
The purpose of the present invention is to provide a kind of nanometer of ferrous sulfide/grapheme composite positive electrode material preparation methods.
The present invention provides a kind of preparation methods of lithium ion battery ferrous sulfide/grapheme composite positive electrode material, special Sign is to prepare ferrous sulfide/graphene with nanoscale using chemical vapour deposition technique.
The specific steps are that:
(1) ferroso-ferric oxide/graphene is prepared: by the graphene oxide powder ultrasonic disperse of 190mg in 100ml ethylene glycol In solvent, it is uniformly mixed；The ferric trichloride and sodium acetate that molar ratio is 1:7 is added, being stirred continuously dissolves it sufficiently, will obtain Solution pour into the water heating kettle of polytetrafluoroethyllining lining, react 6h in insulating box 200 DEG C；Obtained product is centrifuged Separation, it is multiple with deionized water and ethanol washing, powder is obtained after freeze-drying；
(2) ferrous sulfide/graphene is prepared: by powder that step (1) obtains and sulphur source by centainly rubbing in protective atmosphere Powder after mixing is placed in sealing device by you than being uniformly mixed；Wherein, ferroso-ferric oxide/graphene amount controls 1 × 10-4~3 × 10-2The amount of mol, sulphur source substance are controlled 1 × 10-3~1 × 10-1mol；By sealing device in tube furnace It is passed through the protective gas of certain flow, is heat-treated certain time under certain temperature；Gas flow control 10~ 100sccm, heat treatment time are controlled in 1~8h.
Wherein step (2) protective atmosphere is high-purity argon gas or high pure nitrogen；Sulphur source is sulphur powder, thiocarbamide or thio second Amide；Sealing device is stainless steel seal pipe or quartz glass seals pipe；The certain temperature refers to that the temperature of heat treatment is 400~900 DEG C.
The present invention introduces sulphur source, passes through chemical vapor deposition using ferroso-ferric oxide/graphene composite material as reaction product Method prepares ferrous sulfide/graphene composite material.Ferrous sulfide particle is uniformly dispersed on the surface of graphene, and and graphite Alkene, which combines, to be stablized, and so as to effectively prevent nano particle to reunite in charge and discharge process, buffer volumes expansion inhibits anti- The dissolution of product in the electrolytic solution is answered, it is final to guarantee that electrode structure is stablized in charge and discharge process；Meanwhile graphene provides well Conductive network, accelerate electron-transport.Preparation process of the invention is simple, time-consuming short, at low cost, it is easy to accomplish industrial metaplasia It produces；Ferrous sulfide/graphene composite material that this method is prepared has excellent chemical property, is a kind of ideal lithium Ion battery positive electrode can be widely applied to the fields such as portable electronic device electric car and aerospace.
Detailed description of the invention
Fig. 1 is ferrous sulfide/graphene composite material field emission scanning electron microscope picture of embodiment 1.
Fig. 2 is ferrous sulfide/graphene composite material circulation volume figure of embodiment 1.
Fig. 3 is ferrous sulfide/graphene composite material high rate performance figure of embodiment 1.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but is not limited to protection scope of the present invention:
Embodiment 1:
In an ar atmosphere by 0.05g ferroso-ferric oxide/graphene, 0.14g sulphur powder is uniformly mixed, by the powder after mixing Body is placed in stainless steel seal pipe.It is 40sccm's that stainless steel seal pipe obtained above, which is placed in tube furnace, and is passed through throughput Ar gas finally obtains ferrous sulfide/graphene composite material in 600 DEG C of heat treatment 2h；
The CMC of ferrous sulfide/graphene composite material of 70wt%, the acetylene black of 15wt%, 15wt% are uniformly mixed, Slurry is made, is coated uniformly on copper foil, circular electrode pole piece is stamped into after vacuum drying, is to electrode, 1mol/ with lithium metal L LiPF6/ EC+DEC+DMC (volume ratio 1:1:1) is electrolyte, and Celgard 2400 is diaphragm, is assembled into button cell. Constant current charge-discharge test is carried out to battery, charging/discharging voltage range is 1.0~3.0V, the results showed that, which shows preferably Chemical property: under the current density of 0.1A/g, first discharge specific capacity reaches 463mAh/g, still keeps after circulation 20 times The reversible specific capacity of 397mAh/g；Even if what composite material still showed 296mAh/g can under the high current density of 2A/g Inverse specific capacity, high rate performance are excellent.
Embodiment 2:
In an ar atmosphere by 0.1g ferroso-ferric oxide/graphene, 0.05g thioacetamide powder is uniformly mixed, and will mix it Powder afterwards is placed in stainless steel seal pipe.Stainless steel seal pipe obtained above is placed in tube furnace and is passed through throughput and is The Ar gas of 40sccm finally obtains ferrous sulfide/graphene composite material in 400 DEG C of heat treatment 1h；
The CMC of ferrous sulfide/graphene composite material of 70wt%, the acetylene black of 15wt%, 15wt% are uniformly mixed, Slurry is made, is coated uniformly on copper foil, circular electrode pole piece is stamped into after vacuum drying, is to electrode, 1mol/ with lithium metal L LiPF6/ EC+DEC+DMC (volume ratio 1:1:1) is electrolyte, and Celgard 2400 is diaphragm, is assembled into button cell. Constant current charge-discharge test is carried out to battery, charging/discharging voltage range is 1.0~3.0V, the results showed that, with poor electrification Learn performance: under the current density of 0.1A/g, first discharge specific capacity reaches 292mAh/g, after circulation 20 times only 103mAh/g can Inverse specific capacity；As current density increases, the decaying of electrode reversible specific capacity is very fast, and high rate performance is poor.
Embodiment 3:
In an ar atmosphere by 0.15g ferroso-ferric oxide/graphene, 0.41g thiocarbamide powder is uniformly mixed, by the powder after mixing Body is placed in stainless steel seal pipe.It is 40sccm's that stainless steel seal pipe obtained above, which is placed in tube furnace, and is passed through throughput Ar gas finally obtains FeS/rGO composite material in 900 DEG C of heat treatment 8h；
The CMC of the FeS/ graphene composite material of 70wt%, the acetylene black of 15wt%, 15wt% are uniformly mixed, are made Slurry is coated uniformly on copper foil, and circular electrode pole piece is stamped into after vacuum drying, is to electrode, 1mol/ with lithium metal LLiPF6/ EC+DEC+DMC (volume ratio 1:1:1) is electrolyte, and Celgard 2400 is diaphragm, is assembled into button cell.It is right Battery carries out constant current charge-discharge test, and charging/discharging voltage range is 1.0~3.0V, the results showed that, with poor electrochemistry Performance: under the current density of 0.1A/g, first discharge specific capacity reaches 356mAh/g, and only 192mAh/g's is reversible after circulation 20 times Specific capacity；As current density increases, the decaying of electrode reversible specific capacity is very fast, and high rate performance is poor.

Claims (5)

1. a kind of nanometer of ferrous sulfide/grapheme composite positive electrode material preparation method, it is characterized in that using vapor deposition legal system Standby ferrous sulfide out has nanoscale and particle is uniform, and ferrous sulfide is stablized in conjunction with graphene, specific process step are as follows:
(1) ferroso-ferric oxide/graphene is prepared: by the graphene oxide powder ultrasonic disperse of 190mg in 100ml ethylene glycol solvent In, it is uniformly mixed；The ferric trichloride and sodium acetate that molar ratio is 1:7 is added, being stirred continuously dissolves it sufficiently, molten by what is obtained Liquid pours into the water heating kettle of polytetrafluoroethyllining lining, reacts 6h in insulating box 200 DEG C；Obtained product carries out centrifugation point From, it is multiple with deionized water and ethanol washing, powder is obtained after freeze-drying；
(2) prepare ferrous sulfide/graphene: the powder and sulphur source for obtaining step (1) in protective atmosphere are by certain mol proportion It is uniformly mixed, powder after mixing is placed in sealing device；Wherein, the control of ferroso-ferric oxide/graphene amount 1 × 10-4~3 × 10-2The amount of mol, sulphur source substance are controlled 1 × 10-3~1 × 10-1mol；Sealing device is passed through in tube furnace The protective gas of certain flow is heat-treated certain time under certain temperature；Gas flow control is in 10~100sccm, heat Time control is handled in 1~8h.
2. according to claim 1 nanometer of ferrous sulfide/grapheme composite positive electrode material preparation method, feature exist In: protective atmosphere described in step (2) is high-purity argon gas or high pure nitrogen.
3. according to claim 1 nanometer of ferrous sulfide/grapheme composite positive electrode material preparation method, feature exist In: sulphur source described in step (2) is sulphur powder, thiocarbamide or thioacetamide.
4. according to claim 1 nanometer of ferrous sulfide/grapheme composite positive electrode material preparation method, feature exist In: sealing device described in step (2) is stainless steel seal pipe or quartz glass seals pipe.
5. according to claim 1 nanometer of ferrous sulfide/grapheme composite positive electrode material preparation method, feature exist In: certain temperature described in step (2) refers to that the temperature of heat treatment is 400~900 DEG C.
CN201811430971.4A 2018-11-28 2018-11-28 A kind of nanometer of ferrous sulfide/grapheme composite positive electrode material preparation method Pending CN109546128A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
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US20140294981A1 (en) * 2011-10-06 2014-10-02 Karlsruher Institut Fuer Technologie Carbon encapsulated transition metal oxide nanocomposite, a method for its preparation and its use in li-ion batteries
CN107230558A (en) * 2017-06-21 2017-10-03 太原理工大学 A kind of Fe3O4The preparation method of/graphene composite material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140294981A1 (en) * 2011-10-06 2014-10-02 Karlsruher Institut Fuer Technologie Carbon encapsulated transition metal oxide nanocomposite, a method for its preparation and its use in li-ion batteries
CN107230558A (en) * 2017-06-21 2017-10-03 太原理工大学 A kind of Fe3O4The preparation method of/graphene composite material

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Title
SEUNG YEON LEE等: "Sodium-Ion Storage Properties of FeS-Reduced Graphene Oxide Composite Powder with a Crumpled Structure", 《CHEMISTRY A EUROPEAN JOURNAL》 *
YUZHI JIAO等: "Improved electrochemical performance in nanoengineered pomegranate-shaped Fe3O4/RGO nanohybrids anode material", 《JOURNAL OF MATERIALS SCIENCE》 *
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Application publication date: 20190329