CN108288700A - A kind of preparation method of PEDOT@β-FeOOH/rGO array type lithium ion battery negative materials - Google Patents

A kind of preparation method of PEDOT@β-FeOOH/rGO array type lithium ion battery negative materials Download PDF

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CN108288700A
CN108288700A CN201810074265.4A CN201810074265A CN108288700A CN 108288700 A CN108288700 A CN 108288700A CN 201810074265 A CN201810074265 A CN 201810074265A CN 108288700 A CN108288700 A CN 108288700A
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pedot
feooh
rgo
ion battery
lithium ion
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CN108288700B (en
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曹丽云
马萌
齐慧
李嘉胤
黄剑锋
姚恺
陈文卓
吴桂娟
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Shaanxi University of Science and Technology
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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
    • H01M4/48—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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

Graphene oxide dispersion is obtained suspension A by a kind of preparation method of PEDOT β FeOOH/rGO array type lithium ion battery negative materials in deionized water；Soluble ferric iron salt, 3,4 ethene dioxythiophenes (EDOT) are added in suspension and are sufficiently mixed to obtain suspension B；Suspension B is poured into homogeneous hydrothermal reaction kettle, reaction kettle is then sealed, is put it into and is naturally cooled to room temperature after hydro-thermal reaction in homogeneous hydro-thermal reaction instrument and obtain product C；Product C is washed with washing, alcohol respectively, the product after washing is dispersed in water to obtain product D；Product D is freeze-dried to obtain PEDOT@β FeOOH/rGO self assembly blinds array type lithium ion battery negative materials.Redox graphene good conductivity has larger specific surface area and more surface functional group, and ferriferous oxide is compound with graphene, will significantly improve the dispersibility of ferriferous oxide, avoids reuniting.It is coated using conducting polymer PEDOT simultaneously, self assembly regulation and control are carried out to pattern, further improve the chemical property of product.

Description

A kind of preparation of PEDOT@β-FeOOH/rGO array type lithium ion battery negative materials Method
Technical field
The invention belongs to electrochemical technology fields, and in particular to a kind of PEDOT coating betas-FeOOH/rGO array type lithium ions The preparation method of cell negative electrode material.
Background technology
Lithium ion battery negative material is the important component of lithium ion battery, and the Nomenclature Composition and Structure of Complexes of negative material is to lithium The chemical property of ion battery has decisive impact.Transition metal composite has higher theoretical specific capacity mostly, Discharge potential platform is about between 1.0~2.0V；As lithium ion battery negative material, the reaction machine of transition metal composite Reason is reacted different from the embedding de- lithium of graphite material or the alloying reaction of Sn, Si class material, but a kind of reversible redox Reaction.
Due to the natural abundance and nontoxicity of iron, iron-based transition metal oxide material is always lithium ion battery (LIB) The promising negative material of electrode.β -- FeOOH is component part important in ferriferous oxide, due to its high power capacity (> 1200mAh/g), abundant natural resources, nontoxicity and low cost are also considered as the promising time of negative material of new generation Select object, but it is also the same with other transition metal oxides, there are poorly conductive, volume expansion is big the shortcomings of.It is main for it Disadvantage, its Material cladding or electrode design with high conductivity is improved their electrochemistry cycle performance by us.Oxygen reduction Graphite alkene good conductivity has larger specific surface area and more surface functional group, and ferriferous oxide is compound with graphene, will The dispersibility for significantly improving ferriferous oxide avoids reuniting.PEDOT has conductivity high, chemistry is steady as a kind of conducting polymer The advantages that qualitative high.Therefore this project is by regarding the graphene of good conductivity as the backing material in charge and discharge process, with β- Compound its electric conductivity of raising of FeOOH and structural stability, while it is coated using conducting polymer PEDOT, to pattern Self assembly regulation and control are carried out, the chemical property of product is further improved.Zhang Meng et al. (Journal of Alloys and Compounds, 2015,648,134-138) 4h is reacted under 80 DEG C of hydrothermal conditions as reactant using iron chloride and urea to obtain FeOOH, material conductivity is poor, and specific capacity needs to be further increased；Zhai Yan person of outstanding talent et al. (Journal of Power Sources, 2016,327,423-431) using iron chloride and cerous nitrate as raw material, PVP etc. is surfactant, is mixed on FeOOH Miscellaneous Ce improves the cycle performance of material.
Invention content
The purpose of the present invention is to provide one kind improving β-by lamella rGO supports, conducting polymer PEDOT claddings The structural stability and electric conductivity of FeOOH materials, the PEDOT@β-FeOOH/rGO array type lithium-ion electrics for improving chemical property The preparation method of pond negative material.
In order to achieve the above objectives, the technical solution adopted by the present invention is：
1) commercially available graphene oxide is dispersed in the solution that 1~5mg/mL is configured in 25~50mL deionized waters, so Finely dispersed graphene oxide suspension A is formed using ultrasonic generator afterwards；
2) analytically pure soluble ferric iron salt is added in above-mentioned suspension A, under agitation be added dropwise 0.01~ 0.05mLEDOT, after be sufficiently stirred and keep iron salt dissolved, EDOT evenly dispersed, be configured to molysite and graphene oxide, EDOT it is mixed Solution is closed, then mixed solution is disperseed suspended by wherein a concentration of 0.05~0.5mol/L of molysite using ultrasonic generator Liquid B；
3) the suspension B of above-mentioned preparation is poured into homogeneous hydrothermal reaction kettle polytetrafluoroethyllining lining, then sealing reaction Kettle, after put it into homogeneous hydro-thermal reaction instrument and to carry out hydro-thermal reaction at 50~150 DEG C, naturally cool to room temperature after reaction Obtain product C；
4) product C is washed with washing, alcohol respectively, the product after washing is dispersed in water to obtain product D；
5) product D is freeze-dried at -20~-50 DEG C, holding vacuum degree is 10~60Pa, and the sample after drying is PEDOT@β-FeOOH/rGO self assembly blinds array type lithium ion battery negative materials.
The power of step 1) the excusing from death generator is 300W, and ultrasonic time is 1~3h.
Step 2) the soluble ferric iron salt is in Iron(III) chloride hexahydrate, green vitriol, Fe(NO3)39H2O It is a kind of.
Step 2) the mixing speed is 200~400rad/min, and mixing time is 2~5h.
The power of step 2) the excusing from death generator is 300W, and ultrasonic time is 2~5h.
Step 3) the hydrothermal reaction kettle compactedness is 30%~80%.
Step 3) the hydro-thermal reaction time is 2~5h.
The washing of the step 4) is washed respectively using centrifuge, alcohol is washed 3 times, each 1~4min of centrifugation time, and centrifugation turns Speed is 3000~9000rpm.
Step 5) the drying time is 10~20h.
Due to redox graphene good conductivity, there is larger specific surface area and more surface functional group, iron oxygen Compound is compound with graphene, will significantly improve the dispersibility of ferriferous oxide, avoids reuniting.PEDOT as a kind of conducting polymer, Have many advantages, such as that conductivity height, chemical stability are high.Therefore, we are using the graphene of good conductivity as in charge and discharge process Backing material, and compound its electric conductivity of raising of β-FeOOH and structural stability, while using conducting polymer PEDOT to its into Row cladding carries out self assembly regulation and control to pattern, further improves the chemical property of product.It is effectively solved by three's recombination energy The problem of β-FeOOH poorly conductives, and volume expansion can be inhibited, so that battery structure is more stablized, to improve the cycle of battery Stability.
Beneficial effects of the present invention are embodied in：
1) present invention for the purpose of alleviating volume expansion, and then is prepared for PEDOT@β-to improve the electric conductivity of product FeOOH/rGO self assembly blinds array type lithium ion battery negative materials.
2) present invention combines ultrasonic wave added method and homogeneous hydro-thermal method, utilizes the coordination of molysite and graphene oxide, EDOT Polymerization etc. realizes PEDOT and is given birth to the self assembly of the uniform cladding and β-FeOOH nanometer rods of β-FeOOH on the surface of graphene It is long, and then PEDOT@β-FeOOH/rGO self assembly blinds array type lithium ion battery negative materials are formed, experimental method is simple, It is of low cost, it is easy to accomplish.
Description of the drawings
Fig. 1 is that product particles prepared by the embodiment of the present invention 1 are analyzed with Rigaku D/max2000PCX- x ray diffractometer xs Sample drawing；
Fig. 2, Fig. 3 and Fig. 4 are that sample prepared by the embodiment of the present invention 1 is scanned with the JSM-6700F types that Japanese firm produces Electron micrograph.
Specific implementation mode
Invention is further described in detail below in conjunction with the accompanying drawings.
Embodiment 1：
1) commercially available graphene oxide is dispersed in the solution for being configured to 1mg/mL in 25mL deionized waters, is then used The ultrasonic generator of 300W disperses 1h, forms finely dispersed graphene oxide suspension A；
2) analytically pure soluble ferric iron salt Iron(III) chloride hexahydrate is added in above-mentioned suspension A, under agitation 0.01mLEDOT is added dropwise, after be sufficiently stirred and keep iron salt dissolved, EDOT evenly dispersed, be configured to molysite and graphene oxide, EDOT Mixed solution, the wherein a concentration of 0.05mol/L of molysite, then by mixed solution using 300W ultrasonic generator disperse 2h Obtain suspension B；
3) the suspension B of above-mentioned preparation is poured into homogeneous hydrothermal reaction kettle polytetrafluoroethyllining lining, compactedness 30%, Then seal reaction kettle, after put it into homogeneous hydro-thermal reaction instrument and to carry out hydro-thermal reaction 5h at 50 DEG C, it is natural after reaction It is cooled to room temperature and obtains product C；
4) product C is washed 3 times with washing, alcohol respectively, each centrifugation time 1min, centrifugal rotational speed 3000rpm will be washed Product afterwards is dispersed in water to obtain product D；
5) product D is freeze-dried at -20 DEG C, holding vacuum degree is 10Pa, and the sample after dry 20h is PEDOT@ β-FeOOH/rGO self assembly blinds array type lithium ion battery negative materials.
Product is β-FeOOH, card serial number PDF#34-1622 as seen from Figure 1.
It can be seen that made PEDOT@β-FeOOH/rGO self assembly blinds array type lithium-ion electrics by Fig. 2, Fig. 3 and Fig. 4 Pond negative material pattern is：The nanometer rods for being about 150nm, radial dimension about 50nm are uniformly arranged, and compact growth is in graphene film Layer surface, this self-assembled growth characteristics of nanometer rods are exactly caused by the polymerization by EDOT.
Embodiment 2：
1) commercially available graphene oxide is dispersed in the solution for being configured to 2mg/mL in 30mL deionized waters, is then used The ultrasonic generator of 300W disperses 3h, forms finely dispersed graphene oxide suspension A；
2) analytically pure soluble ferric iron salt Iron(III) chloride hexahydrate is added in above-mentioned suspension A, under agitation 0.02mLEDOT is added dropwise, after be sufficiently stirred and keep iron salt dissolved, EDOT evenly dispersed, be configured to molysite and graphene oxide, EDOT Mixed solution, the wherein a concentration of 0.3mol/L of molysite, then by mixed solution using 300W ultrasonic generator disperse 3h Obtain suspension B；
3) the suspension B of above-mentioned preparation is poured into homogeneous hydrothermal reaction kettle polytetrafluoroethyllining lining, compactedness 80%, Then seal reaction kettle, after put it into homogeneous hydro-thermal reaction instrument and to carry out hydro-thermal reaction 4h at 70 DEG C, it is natural after reaction It is cooled to room temperature and obtains product C；
4) product C is washed 3 times with washing, alcohol respectively, each centrifugation time 4min, centrifugal rotational speed 4000rpm will be washed Product afterwards is dispersed in water to obtain product D；
5) product D is freeze-dried at -20 DEG C, holding vacuum degree is 60Pa, and the sample after dry 15h is PEDOT@ β-FeOOH/rGO self assembly blinds array type lithium ion battery negative materials.
Embodiment 3：
1) commercially available graphene oxide is dispersed in the solution that 5mg/mL is configured in 35mL deionized waters, then using super Acoustic generator disperses 2h, forms finely dispersed graphene oxide suspension A；
2) analytically pure soluble ferric iron salt green vitriol is added in above-mentioned suspension A, under agitation 0.025mLEDOT is added dropwise, after be sufficiently stirred and keep iron salt dissolved, EDOT evenly dispersed, be configured to molysite and graphene oxide, EDOT Mixed solution, the wherein a concentration of 0.5mol/L of molysite, then by mixed solution using 300W ultrasonic generator disperse 4h Obtain suspension B；
3) the suspension B of above-mentioned preparation is poured into homogeneous hydrothermal reaction kettle polytetrafluoroethyllining lining, compactedness 60%, Then seal reaction kettle, after put it into homogeneous hydro-thermal reaction instrument and to carry out hydro-thermal reaction 3h at 150 DEG C, it is natural after reaction It is cooled to room temperature and obtains product C；
4) product C is washed 3 times with washing, alcohol respectively, each centrifugation time 2min, centrifugal rotational speed 5000rpm will be washed Product afterwards is dispersed in water to obtain product D；
5) product D is freeze-dried at -50 DEG C, holding vacuum degree is 25Pa, and the sample after dry 20h is PEDOT@ β-FeOOH/rGO self assembly blinds array type lithium ion battery negative materials.
Embodiment 4：
1) commercially available graphene oxide is dispersed in the solution that 3mg/mL is configured in 50mL deionized waters, then using super Acoustic generator disperses 3h, forms finely dispersed graphene oxide suspension A；
2) analytically pure soluble ferric iron salt Fe(NO3)39H2O is added in above-mentioned suspension A, is dripped under agitation Add 0.05mLEDOT, after be sufficiently stirred and keep iron salt dissolved, EDOT evenly dispersed, be configured to molysite and graphene oxide, EDOT Then mixed solution, the wherein a concentration of 0.1mol/L of molysite are obtained mixed solution using the ultrasonic generator dispersion 5h of 300W Suspension B；
3) the suspension B of above-mentioned preparation is poured into homogeneous hydrothermal reaction kettle polytetrafluoroethyllining lining, compactedness 80%, Then seal reaction kettle, after put it into homogeneous hydro-thermal reaction instrument and to carry out hydro-thermal reaction 2h at 100 DEG C, it is natural after reaction It is cooled to room temperature and obtains product C；
4) product C is washed 3 times with washing, alcohol respectively, each centrifugation time 1min, centrifugal rotational speed 9000rpm will be washed Product afterwards is dispersed in water to obtain product D；
5) product D is freeze-dried at -40 DEG C, holding vacuum degree is 40Pa, and the sample after dry 10h is PEDOT@ β-FeOOH/rGO self assembly blinds array type lithium ion battery negative materials.

Claims (9)

1. a kind of preparation method of PEDOT@β-FeOOH/rGO array type lithium ion battery negative materials, it is characterised in that：
1) commercially available graphene oxide is dispersed in the solution for being configured to 1~5mg/mL in 25~50mL deionized waters, is then adopted Finely dispersed graphene oxide suspension A is formed with ultrasonic generator；
2) analytically pure soluble ferric iron salt is added in above-mentioned suspension A, 0.01~0.05mL is added dropwise under agitation EDOT, after be sufficiently stirred and keep iron salt dissolved, EDOT evenly dispersed, be configured to the mixed solution of molysite and graphene oxide, EDOT, Then mixed solution is disperseed to obtain suspension B by wherein a concentration of 0.05~0.5mol/L of molysite using ultrasonic generator；
3) the suspension B of above-mentioned preparation is poured into homogeneous hydrothermal reaction kettle polytetrafluoroethyllining lining, then seals reaction kettle, after It puts it into and carries out hydro-thermal reaction in homogeneous hydro-thermal reaction instrument at 50~150 DEG C, naturally cooling to room temperature after reaction must produce Object C；
4) product C is washed with washing, alcohol respectively, the product after washing is dispersed in water to obtain product D；
5) product D is freeze-dried at -20~-50 DEG C, holding vacuum degree is 10~60Pa, and the sample after drying is PEDOT@β-FeOOH/rGO self assembly blinds array type lithium ion battery negative materials.
2. the preparation method of PEDOT@β-FeOOH/rGO array type lithium ion battery negative materials according to claim 1, It is characterized in that：The power of step 1) the excusing from death generator is 300W, and ultrasonic time is 1~3h.
3. the preparation method of PEDOT@β-FeOOH/rGO array type lithium ion battery negative materials according to claim 1, It is characterized in that：Step 2) the soluble ferric iron salt is in Iron(III) chloride hexahydrate, green vitriol, Fe(NO3)39H2O One kind.
4. the preparation method of PEDOT@β-FeOOH/rGO array type lithium ion battery negative materials according to claim 1, It is characterized in that：Step 2) the mixing speed is 200~400rad/min, and mixing time is 2~5h.
5. the preparation method of PEDOT@β-FeOOH/rGO array type lithium ion battery negative materials according to claim 1, It is characterized in that：The power of step 2) the excusing from death generator is 300W, and ultrasonic time is 2~5h.
6. the preparation method of PEDOT@β-FeOOH/rGO array type lithium ion battery negative materials according to claim 1, It is characterized in that：Step 3) the hydrothermal reaction kettle compactedness is 30%~80%.
7. the preparation method of PEDOT@β-FeOOH/rGO array type lithium ion battery negative materials according to claim 1, It is characterized in that：Step 3) the hydro-thermal reaction time is 2~5h.
8. the preparation method of PEDOT@β-FeOOH/rGO array type lithium ion battery negative materials according to claim 1, It is characterized in that：The washing of the step 4) is washed respectively using centrifuge, alcohol is washed 3 times, each 1~4min of centrifugation time, from Heart rotating speed is 3000~9000rpm.
9. the preparation method of PEDOT@β-FeOOH/rGO array type lithium ion battery negative materials according to claim 1, It is characterized in that：Step 5) the drying time is 10~20h.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110061220A (en) * 2019-04-28 2019-07-26 西安交通大学 A kind of FeOOH/ graphene active material and preparation method thereof, lithium sulfur battery anode material and preparation method thereof
CN111640927A (en) * 2020-06-17 2020-09-08 中国人民解放军国防科技大学 Graphene-bridged polythiophene-coated germanium nanoparticle composite material and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN101423256A (en) * 2008-11-04 2009-05-06 扬州大学 Method for preparing beta-FeOOH nano granule suspension solution
CN102443251A (en) * 2011-09-21 2012-05-09 中国科学院理化技术研究所 Preparation method of iron oxide/poly (3, 4-dioxoethyl) thiophene composite nanorods
CN103165888A (en) * 2013-03-02 2013-06-19 合肥国轩高科动力能源股份公司 Preparation method of ferric three fluoride (FeF3) nanorod with embedded lithium activity
CN106356525A (en) * 2016-08-25 2017-01-25 陕西科技大学 Method for preparing graphene in-situ growth FeOOH nano array lithium ion battery cathode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101423256A (en) * 2008-11-04 2009-05-06 扬州大学 Method for preparing beta-FeOOH nano granule suspension solution
CN102443251A (en) * 2011-09-21 2012-05-09 中国科学院理化技术研究所 Preparation method of iron oxide/poly (3, 4-dioxoethyl) thiophene composite nanorods
CN103165888A (en) * 2013-03-02 2013-06-19 合肥国轩高科动力能源股份公司 Preparation method of ferric three fluoride (FeF3) nanorod with embedded lithium activity
CN106356525A (en) * 2016-08-25 2017-01-25 陕西科技大学 Method for preparing graphene in-situ growth FeOOH nano array lithium ion battery cathode material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110061220A (en) * 2019-04-28 2019-07-26 西安交通大学 A kind of FeOOH/ graphene active material and preparation method thereof, lithium sulfur battery anode material and preparation method thereof
CN111640927A (en) * 2020-06-17 2020-09-08 中国人民解放军国防科技大学 Graphene-bridged polythiophene-coated germanium nanoparticle composite material and preparation method and application thereof
CN111640927B (en) * 2020-06-17 2021-10-01 中国人民解放军国防科技大学 Graphene-bridged polythiophene-coated germanium nanoparticle composite material and preparation method and application thereof

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