CN104916824A - Tin/oxidized graphene anode material for lithium battery and preparation method thereof - Google Patents
Tin/oxidized graphene anode material for lithium battery and preparation method thereof Download PDFInfo
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
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- 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
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- 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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- 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
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention discloses a tin/oxidized graphene anode material for a lithium battery and a preparation method thereof. The composite anode material is formed by uniformly adhering nanosized tin to the surface of oxidized graphene. The preparation method comprises the following steps: ultrasonically dispersing oxidized graphene powder into a mixed solution of water and ethylene glycol to obtain a dispersion solution, adding nanosized tin and a dispersing agent in the dispersion solution until the nanosized tin is completely dispersed through ball-milling, and drying to obtain the composite anode material in which the flaky nanosized tin is uniformly adhered to the surface of the oxidized graphene. The composite material can be used for preparing the lithium ion battery with the characteristics of high specific discharge capacity, excellent rate performance, long cycle life and the like; and the preparation method is simple, reliable, good in process repeatability, high in operability and low in cost, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of tin for lithium ion battery/graphene oxide negative material and preparation method thereof, belong to field of lithium ion battery.
Background technology
Since nineteen ninety Sony corporation of Japan take the lead in succeeding in developing lithium ion battery and by its commercialization since, lithium ion battery obtains fast development.Nowadays lithium ion battery has been widely used in civilian and military every field.Along with the continuous progress of science and technology, the performance of people to battery proposes more higher requirements: the miniaturization of electronic equipment and individualized development, and the specific energy needing battery to have less volume and Geng Gao exports; Aero-Space energy requirements battery has cycle life, the security performance of better low temperature charge-discharge performance and Geng Gao; Electric automobile needs the battery of Large Copacity, low cost, high stability and security performance.
The negative material of lithium ion battery has material with carbon element, intermetallic compound, tin-based composites etc.What current commercial Li-ion battery negative material adopted is graphite-like material with carbon element, and having lower lithium embedding/deintercalation current potential, suitable reversible capacity and aboundresources, the advantage such as cheap, is more satisfactory lithium ion battery negative material.But its theoretical specific capacity only has 372mAh/g, thus limit the further raising of lithium ion battery specific energy, the demand of growing high-energy Portable power source can not be met.The storage lithium principle of kamash alloy is similar to silicon-base alloy, utilizes tin and lithium to form alloy.The highest component can reach Li
4.4the level of Sn, theoretical capacity 994mAh/g.But same, after embedding Li in Sn, volumetric expansion is to original 358%, causes alloying pellet to break, electrode performance fails.
Graphene is that the thinnest (0.335nm) is the hardest nano material also in the world at present, it is almost completely transparent, absorptivity is only 2.3%, conductive coefficient is up to 5300 W/mK, higher than the material with carbon element such as carbon nano-tube and diamond, the electron conduction of Graphene is good, and under normal temperature, its electron mobility is higher than 15000cm2/Vs, and resistivity is only 10-6 Ω cm, it is the material that resistivity is minimum in the world at present.
Connection in Graphene between each carbon atom is very pliable and tough, and when applying external mechanical force, carbon atom face with regard to flexural deformation, thus makes carbon atom need not rearrange to adapt to external force, also just maintains Stability Analysis of Structures.The research group of Columbia Univ USA is through lot of experiments, find that Graphene is the material that intensity is maximum in the world up to now, if make according to measuring and calculating Graphene the film (thickness about 100 nanometer) that thickness is equivalent to bread and cheese plastic packaging bag thickness, so it can bear the pressure of about two tons of heavy articles, and be unlikely to fracture.Meanwhile, Graphene is the material that mankind's known strength is the highest, also harder than diamond, taller upper 100 times of the iron and steel that strength ratio is best in the world.
Graphene, as a kind of novel two-dimension nano materials, is the Two Dimensional Free state atomic crystal of the unique existence found at present.Since finding from 2004, Graphene not only receives very big concern in pure science, and the nanostructure special due to it and the physical and chemical performance of excellence and show at electronics, optics, magnetics, biomedicine, catalysis, energy storage and sensor numerous areas and have huge application potential, cause showing great attention to of scientific circles and industrial circle.Countries in the world one after another using Graphene and application technology thereof as long-range strategy developing direction, to being active and first chance in the new round Industrial Revolution caused by Graphene.
At present, effectively slowing down tin as the method for capacity rapid decay during negative material is generally active material and other basis material are carried out compound or synthesizes the active material of specific morphology.And up to the present, also without any technology composite material being prepared by graphene oxide and Sn compound, more there is no related compound material as the relevant report of lithium cell cathode material.
Summary of the invention
For the defect that existing lithium ion battery material exists, the object of the invention is to be to provide a kind of structure of nanometer tin uniform adsorption in surface of graphene oxide with sheet-like morphology, can be used for preparing the tin/graphene oxide anode material of the lithium ion battery with features such as high specific discharge capacity, excellent high rate performance and long circulation lifes.
Another object of the present invention is that to be to provide a kind of technique simple, reproducible, with low cost, the eco-friendly method preparing tin/graphene oxide anode material.
The invention provides a kind of tin for lithium ion battery/graphene oxide anode material, this composite material is made up of in surface of graphene oxide nanometer tin uniform adsorption.
In preferred tin/graphene oxide anode material, the quality of nanometer tin accounts for 5 ~ 15% of nanometer tin and graphene oxide gross mass.
In preferred tin/graphene oxide anode material, nanometer tin pattern is sheet, and lamellar spacing is 5 ~ 20nm.The pattern of nanometer tin is even, and thickness can regulate and control in suitable scope.
In preferred tin/graphene oxide anode material, nanometer tin is adsorbed on surface of graphene oxide by the mode of ball milling to obtain further.
Preferred tin/graphene oxide anode material specific area is 200 ~ 600m
2/ g.
Present invention also offers a kind of method preparing tin/graphene oxide anode material, the method is by graphene oxide powder and nanometer tin by a certain percentage, adds solvent and dispersant, pass through ball milling, disperse completely to nanometer tin, centrifugal solid-liquid is separated, and is drying to obtain.
The method preparing tin/graphene oxide anode material of the present invention also comprises following preferred version:
In preferred scheme, the mass ratio of tin and graphene oxide is 0.05 ~ 0.5:1.
In preferred scheme, solvent is the mixed solution of water and ethylene glycol further.
In preferred scheme, dispersant is at least one in softex kw (CTAB), dodecyl sodium sulfonate lithium (PVP), polyvinylpyrrolidone (SDS) further.
Most preferred scheme is: graphene oxide powder ultrasonic disperse standby for the Hummers legal system of improvement is obtained dispersion liquid in the mixed solution of water and ethylene glycol, add in gained dispersion liquid dispersant, nanometer tin and ball milling mixing 10 ~ 24h, centrifugal solid-liquid is separated, then, after drying, tin/graphene oxide composite material is obtained.
In preferred scheme, drying is dry in the vacuum drying chamber of 60 ~ 90 DEG C further.
Graphene oxide of the present invention is that the Hummers method by improving prepares: flaky graphite purity being not less than 99.5% joins in the mixed solution of the concentrated sulfuric acid and phosphoric acid, after abundant dispersion, maintain mixed solution temperature between 0 ~ 5 DEG C, divide many batches and add potassium permanganate, and stir 2 ~ 4h, at room temperature stir 12 ~ 24h again, at 75 ~ 85 DEG C, stir 0.5 ~ 1h further, obtain mixture; Under condition of ice bath, slowly add deionized water and dilute, carry out oxidation reaction simultaneously in mixture, add hydrogen peroxide removing potassium permanganate after having reacted, Separation of Solid and Liquid, drying, namely obtain graphene oxide powder.
Described flaky graphite and the mass ratio of potassium permanganate are 1:1 ~ 6.
The described concentrated sulfuric acid and the volume ratio of phosphoric acid are 7 ~ 5:1.
Described flaky graphite and the solid-to-liquid ratio of the concentrated sulfuric acid are 1 ~ 5g:100 ~ 350mL.
Described hydrogen peroxide and the mass ratio of potassium permanganate are 0.5:1.
The tin that the present invention obtains/graphene oxide negative material prepares negative pole: tin/graphene oxide negative material and conductive black conductive agent and PVDF binding agent and a small amount of water are thoroughly mixed to form uniform pastel through grinding, to be coated on Copper Foil matrix as test electrode, to make button cell using lithium metal as to electrode.
Beneficial effect of the present invention: nanometer tin is adsorbed on surface of graphene oxide by first passage physics ball-milling method of the present invention, form composite material, in this composite material, the pattern of tin is uniform sheet, and thickness is controlled, can be used for preparing the lithium ion battery with high specific discharge capacity, excellent high rate performance and long circulation life.Hinge structure, the beneficial effect that technical solution of the present invention is brought:
The preparation method of 1, tin/graphene oxide anode material is simple, is synthesized by ball-milling method, reproducible, with low cost, and environmental friendliness is applicable to suitability for industrialized production;
2, using the graphene oxide of high conductivity and mechanical strength, bigger serface agent and porosity as basis material, due to dispersion and the carrying effect of graphene oxide, tin is uniformly dispersed, there is laminated structure, and thickness is 5 ~ 20nm, the laminated structure of suitable thickness makes composite material have higher specific area, can provide larger reaction interface, the volumetric expansion of material can be alleviated again simultaneously, thus effectively improve its cyclical stability in charge and discharge process;
3, the graphene oxide of layer structure and tin perfect adaptation, the special construction of graphene oxide effectively can alleviate the change in volume of composite material in charge and discharge process caused by tin negative pole, composite electrode capacity attenuation can be avoided too fast, simultaneous oxidation Graphene can increase material conductivity, compensate for the deficiency of single tin electrode;
4, tin/graphene oxide anode material, during as lithium ion battery negative material, has high specific discharge capacity and good cycle performance.
Embodiment
Following examples are intended to be described in further details content of the present invention; And the protection range of the claims in the present invention does not limit by embodiment.
Embodiment 1
Take the flaky graphite of 5g purity 99.5%, join containing 350mL mass fraction be 98% the concentrated sulfuric acid and 50mL mass fraction be in the mixed solution of the phosphoric acid of 85%, add 30g potassium permanganate to be oxidized in batches, this mixed solution is remained on 0 DEG C, stir 2h, then at room temperature stirring in water bath 12h, stirs 0.5h further, obtains mixture at 80 DEG C.In mixture, 350mL deionized water is slowly added under condition of ice bath.After 15min, then add 15g hydrogen peroxide removing potassium permanganate, mixture color becomes glassy yellow afterwards, suction filtration, then with the watery hydrochloric acid that concentration is 10% wash 3 times, suction filtration, namely obtain graphene oxide (GO) at 60 DEG C of vacuumize 48h.
Take 0.3g GO, add 20mL deionized water and 40mL ethylene glycol ultrasonic disperse 3h formation dispersion liquid, then under agitation, add 0.170g CTAB successively, 0.015g Sn, then ball milling mixing 24h, obtain black solid, after suction filtration cleaning, the drying box being put in 60 DEG C is dried, and can obtain tin of the present invention/graphene oxide negative material.
Take the above-mentioned obtained tin/graphene oxide anode material of 0.4g, add 0.05g conductive black as conductive agent, 0.05gPVDF is as binding agent, add a small amount of NMP and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using lithium metal as to electrode, its electrolyte is the LiPF6/EC+DMC+EMC (v/v=1:1:1) of 1mol/L, and test charging and discharging currents density is 500mA/g.
Adopt the electrode that tin/graphene oxide anode material is made, at room temperature when 500mA/g constant-current discharge, circulation 200 circle specific capacity still can remain on 430mAh/g, shows good cycle performance.
Embodiment 2
Take the flaky graphite of 3g purity 99.5%, join containing 350mL mass fraction be 98% the concentrated sulfuric acid and 50mL mass fraction be in the mixed solution of the phosphoric acid of 85%, add 18g potassium permanganate to be oxidized in batches, this mixed solution is remained on 0 DEG C, stir 2h, then at room temperature stirring in water bath 12h, stirs 0.5h further, obtains mixture at 80 DEG C.In mixture, 350mL deionized water is slowly added under condition of ice bath.After 15min, then add 9g hydrogen peroxide removing potassium permanganate, mixture color becomes glassy yellow afterwards, suction filtration, then with the watery hydrochloric acid that concentration is 10% wash 3 times, suction filtration, namely obtain graphene oxide (GO) at 60 DEG C of vacuumize 48h.
Take 0.3g GO, add 40mL deionized water and 80mL ethylene glycol ultrasonic disperse 3h formation dispersion liquid, then under agitation, add 0.170g CTAB successively, 0.045g Sn, then ball milling mixing 12h, obtain black solid, after suction filtration cleaning, the drying box being put in 60 DEG C is dried, and can obtain tin of the present invention/graphene oxide anode material.
Take the above-mentioned obtained tin/graphene oxide anode material of 0.35g, add 0.1g conductive black as conductive agent, 0.05gPVDF is as binding agent, add a small amount of NMP and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using lithium metal as to electrode, its electrolyte is the LiPF6/EC+DMC+EMC (v/v=1:1:1) of 1mol/L, and test charging and discharging currents density is 500mA/g.The electrode of lithium cell adopting the present embodiment to prepare and lithium sheet are assembled into button cell, and at room temperature when 500mA/g constant-current discharge, circulation 200 circle specific capacity still can remain on 510mAh/g.Show good cycle performance.
Embodiment 3
Take the flaky graphite of 5g purity 99.5%, join containing 300mL mass fraction be 98% the concentrated sulfuric acid and 50mL mass fraction be in the mixed solution of the phosphoric acid of 85%, add 30g potassium permanganate to be oxidized in batches, this mixed solution is remained on 0 DEG C, stir 2h, then at room temperature stirring in water bath 12h, stirs 0.5h further, obtains mixture at 80 DEG C.In mixture, 350mL deionized water is slowly added under condition of ice bath.After 15min, then add 15g hydrogen peroxide removing potassium permanganate, mixture color becomes glassy yellow afterwards, suction filtration, then with the watery hydrochloric acid that concentration is 10% wash 3 times, suction filtration, namely obtain graphene oxide (GO) at 60 DEG C of vacuumize 48h.
Take 0.1g GO, add 30mL deionized water and 60mL ethylene glycol ultrasonic disperse 3h formation suspension-turbid liquid, then under agitation, add 0.100g PVP successively, 0.015g Sn, then ball milling mixing 24h, obtain black solid, after suction filtration cleaning, the drying box being put in 60 DEG C is dried, and can obtain tin of the present invention/graphene oxide anode material.
Take the above-mentioned obtained tin/graphene oxide anode material of 0.35g, add 0.1g conductive black as conductive agent, 0.05gPVDF is as binding agent, add a small amount of NMP and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using lithium metal as to electrode, its electrolyte is the LiPF6/EC+DMC+EMC (v/v=1:1:1) of 1mol/L, and test charging and discharging currents density is 500mA/g.The electrode of lithium cell adopting the present embodiment to prepare and lithium sheet are assembled into button cell, and at room temperature when 500mA/g constant-current discharge, circulation 200 circle specific capacity still can remain on 480mAh/g.Show good cycle performance.
Embodiment 4
Take the flaky graphite of 5g purity 99.5%, join containing 350mL mass fraction be 98% the concentrated sulfuric acid and 50mL mass fraction be in the mixed solution of the phosphoric acid of 85%, add 30g potassium permanganate to be oxidized in batches, this mixed solution is remained on 0 DEG C, stir 2h, then at room temperature stirring in water bath 12h, stirs 0.5h further, obtains mixture at 80 DEG C.In mixture, 350mL deionized water is slowly added under condition of ice bath.After 15min, then add 15g hydrogen peroxide removing potassium permanganate, mixture color becomes glassy yellow afterwards, suction filtration, then with the watery hydrochloric acid that concentration is 10% wash 3 times, suction filtration, namely obtain graphene oxide (GO) at 60 DEG C of vacuumize 48h.
Take 0.2g GO, add 40mL deionized water and 80mL ethylene glycol ultrasonic disperse 3h formation dispersion liquid, then under agitation, add 0.170g SDS successively, 0.05g Sn, then ball milling mixing 24h, obtain black solid, after suction filtration cleaning, the drying box being put in 60 DEG C is dried, and can obtain tin of the present invention/graphene oxide anode material.
Take the above-mentioned obtained tin/graphene oxide anode material of 0.4g, add 0.05g conductive black as conductive agent, 0.05gPVDF is as binding agent, add a small amount of NMP and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using lithium metal as to electrode, its electrolyte is the LiPF6/EC+DMC+EMC (v/v=1:1:1) of 1mol/L, and test charging and discharging currents density is 500mA/g.The electrode of lithium cell adopting the present embodiment to prepare and lithium sheet are assembled into button cell, and at room temperature when 500mA/g constant-current discharge, circulation 200 circle specific capacity still can remain on 420mAh/g.Show good cycle performance.
Embodiment 5
Take the flaky graphite of 5g purity 99.5%, join containing 350mL mass fraction be 98% the concentrated sulfuric acid and 50mL mass fraction be in the mixed solution of the phosphoric acid of 85%, add 30g potassium permanganate to be oxidized in batches, this mixed solution is remained on 0 DEG C, stir 2h, then at room temperature stirring in water bath 12h, stirs 0.5h further, obtains mixture at 80 DEG C.In mixture, 350mL deionized water is slowly added under condition of ice bath.After 15min, then add 15g hydrogen peroxide removing potassium permanganate, mixture color becomes glassy yellow afterwards, suction filtration, then with the watery hydrochloric acid that concentration is 10% wash 3 times, suction filtration, namely obtain graphene oxide (GO) at 60 DEG C of vacuumize 48h.
Take 0.3g GO, add 20mL deionized water and 40mL ethylene glycol ultrasonic disperse 3h formation dispersion liquid, then under agitation, add 0.15g CTAB successively, 0.036g Sn, then ball milling mixing 12h, obtain black solid, after suction filtration cleaning, the drying box being put in 60 DEG C is dried, and can obtain tin of the present invention/graphene oxide anode material.
Take the above-mentioned obtained tin/graphene oxide anode material of 0.4g, add 0.05g conductive black as conductive agent, 0.05gPVDF is as binding agent, add a small amount of NMP and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using lithium metal as to electrode, its electrolyte is the LiPF6/EC+DMC+EMC (v/v=1:1:1) of 1mol/L, and test charging and discharging currents density is 500mA/g.
The electrode of lithium cell adopting the present embodiment to prepare and lithium sheet are assembled into button cell, and at room temperature when 500mA/g constant-current discharge, circulation 200 circle specific capacity still can remain on 460mAh/g, shows good cycle performance.
Claims (7)
1., for tin/graphene oxide anode material of lithium battery, it is characterized in that, be made up of in surface of graphene oxide nanometer tin uniform adsorption.
2. tin according to claim 1/graphene oxide anode material, is characterized in that, the quality of described nanometer tin accounts for 5 ~ 15% of nanometer tin and graphene oxide gross mass.
3. tin according to claim 1/graphene oxide anode material, is characterized in that, described nanometer tin pattern is sheet, and lamellar spacing is 5 ~ 20nm.
4. tin according to claim 3/graphene oxide anode material, is characterized in that, described nanometer tin is adsorbed on surface of graphene oxide by the mode of ball milling to obtain.
5. tin according to claim 1/graphene oxide anode material, is characterized in that, the specific area of described tin/graphene oxide composite material is 200 ~ 600m
2/ g.
6. prepare the method for the tin/graphene oxide anode material described in any one of Claims 1 to 5, it is characterized in that, by graphene oxide powder and nanometer tin by a certain percentage, add solvent and dispersant, by ball milling, disperse completely to nanometer tin, centrifugal solid-liquid is separated, and is drying to obtain.
7. method according to claim 6, is characterized in that, described solvent is the mixed solvent of water and ethylene glycol, and its volume ratio is 1:2 ~ 4; The mass ratio of tin and graphene oxide is 0.05 ~ 0.5:1; Described dispersant is at least one in softex kw, dodecyl sodium sulfonate lithium, polyvinylpyrrolidone.
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| CN201510332627.1A CN104916824A (en) | 2015-06-13 | 2015-06-13 | Tin/oxidized graphene anode material for lithium battery and preparation method thereof |
| PCT/CN2016/082875 WO2016202141A1 (en) | 2015-06-13 | 2016-05-20 | Tin/graphene oxide negative-electrode material for lithium batteries and preparation method therefor |
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| WO2016202141A1 (en) * | 2015-06-13 | 2016-12-22 | 田东 | Tin/graphene oxide negative-electrode material for lithium batteries and preparation method therefor |
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- 2016-05-20 WO PCT/CN2016/082875 patent/WO2016202141A1/en active Application Filing
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016202141A1 (en) * | 2015-06-13 | 2016-12-22 | 田东 | Tin/graphene oxide negative-electrode material for lithium batteries and preparation method therefor |
| CN105702922A (en) * | 2016-01-22 | 2016-06-22 | 浙江极力动力新能源有限公司 | Zinc oxide modified graphene negative electrode paste of lithium ion battery and preparation method of negative electrode paste |
| CN111707725A (en) * | 2020-07-13 | 2020-09-25 | 重庆文理学院 | Preparation and application of nano metallic tin/sulfonated graphene modified electrode |
| CN111707725B (en) * | 2020-07-13 | 2022-02-11 | 重庆文理学院 | Preparation and application of nano metallic tin/sulfonated graphene modified electrode |
| CN114005988A (en) * | 2021-11-01 | 2022-02-01 | 安徽华铂再生资源科技有限公司 | Preparation method of novel lithium ion battery negative electrode material |
| CN114975936A (en) * | 2022-06-06 | 2022-08-30 | 浙江大学 | Reduced graphene oxide loaded nano tin composite material and preparation method and application thereof |
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