CN110323440A - A kind of preparation method of graphene/carbon-silicon nano composite anode material - Google Patents
A kind of preparation method of graphene/carbon-silicon nano composite anode material Download PDFInfo
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- CN110323440A CN110323440A CN201910610780.4A CN201910610780A CN110323440A CN 110323440 A CN110323440 A CN 110323440A CN 201910610780 A CN201910610780 A CN 201910610780A CN 110323440 A CN110323440 A CN 110323440A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M10/052—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
- 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
A kind of preparation method of graphene/carbon-silicon nano composite anode material, comprising the following steps: (1) be dispersed in water graphene oxide is sonicated, obtain graphene oxide aqueous dispersions；(2) pitch and nano silicon particles are added into graphene oxide dispersion, is dispersed with stirring uniformly, forms mixed solution；(3) by the spray-dried processing of mixed solution, the nanometer silicon composite material of the pitch with chondritic and graphene oxide cladding is obtained；(4) composite material is heat-treated in an inert atmosphere, obtains graphene/silicon-carbon compound cathode materials.Gained negative electrode material specific discharge capacity of the invention is high, and charge-discharge characteristic is good, and cyclical stability is higher, and process flow is simple, easily implements and is suitble to large-scale production.
Description
Technical field
The present invention relates to a kind of preparation methods of negative electrode for lithium ion battery composite material, and in particular to and a kind of graphene/
Carbon-silicon nano composite anode material preparation method.
Background technique
Lithium ion battery becomes just due to having the characteristics that high voltage, high-energy-density, long circulation life and environmentally friendly
Take the mating power supply of ideal of formula electronic product, mobile product, electric car.Due to portable electronic device, mobile product, electronic
The fast development of automobile, needs the new type lithium ion battery of high-energy density, height ratio capacity in a hurry, and the lithium ion of Development of Novel
Cell negative electrode material is crucial.The theoretical capacity of conventional graphite cathode only has 372 mAh g-1, seriously constrain entire lithium
The development of ion battery industry.Silicon (Si) negative electrode material has high theoretical capacity, discharge plateaus, resourceful and security performance
The advantages that good, theoretical capacity can achieve 3579 mAh/g, be a kind of great possible electrodes for replacing commercialization graphite cathode
Material.Therefore by silica-base material as concern of the cathode increasingly by numerous researchers of lithium ion battery.
But Si negative electrode material acute variation of lattice in charge and discharge process hinders the use of pure Si: in Li+With Si
Negative electrode material occurs to will lead to negative electrode material reexpansion when alloying process and shrink, and volume increases nearly 300%.By volume
The stress that variation generates can cause the structure of Si phase to change and destroy solid electrolyte interface (SEI) film, for commercial cells
For cycle life, the presence of SEI film is most important.Si contraction in removal alloying step makes SEI film be easy to rupture and shell
It falls, the electrical contact between active material and current-collector is destroyed, so as to cause electrode rapid failure.In view of the above-mentioned problems, research
Persons explore a variety of methods for improving silicium cathode material circulation performance, such as reduce silicon materials grain diameter, form porous material
Material, silicon thin film material, silicon nanowires, silicon composite etc..Wherein relatively effective method is to be prepared into silicon based composite material
Alleviate the volume expansion in charge and discharge process, the method has been widely used for the study on the modification of lithium ion battery negative material
In.
CN108565451A discloses a kind of preparation method of silicon-carbon cathode material: using agraphitic carbon and graphite to silicon
Grain is coated, and improves the electric conductivity of battery material and the cycle performance of battery, but the method still cannot protect well
The dusting of silicon nanoparticle is protected, and the material morphology made is irregular.
CN105024076A discloses a kind of lithium ion battery negative material and its preparation method and application, and material is divided into two
Layer: carbon core layer and silicon clad can effectively alleviate the expansion of silicon materials, to improve the cyclicity of battery material
Can, but simple carbon coating is to improving the ability of conductivity of composite material or limited.
The process described above cannot fundamentally solve silicon materials negative electrode lithium ion battery body in charge and discharge process
Long-pending sharply expansion issues.
Summary of the invention
The technical problem to be solved by the present invention is to, overcome drawbacks described above of the existing technology, provide a kind of graphene/
Carbon-silicon nano composite anode material preparation method, graphene/carbon-silicon composite cathode material of this method preparation, can be from basic
It is upper solve silicon materials negative electrode lithium ion battery volume in charge and discharge process sharply expansion issues, thus improve silicium cathode lithium from
The efficiency for charge-discharge of sub- battery, prolongs the service life.
The further technical problems to be solved of the present invention are to overcome drawbacks described above of the existing technology, provide a kind of stone
The preparation method of black alkene/carbon-silicon nano composite anode material, comprising the following steps:
(1) graphene oxide is carried out ultrasonic treatment to be dispersed in water, obtains graphene oxide aqueous dispersions；
(2) pitch and nano silicon particles are added into the resulting graphene oxide aqueous dispersions of step (1), are stirred, disperse
Uniformly, mixed solution is obtained；
(3) mixed solution obtained by step (2) is subjected to spray drying treatment, obtains pitch and graphene oxide with chondritic
The nanometer silicon composite material of cladding；
(4) in an inert atmosphere that the nano-silicon of the pitch obtained by step (3) with chondritic and graphene oxide cladding is multiple
Condensation material is heat-treated, and graphene/carbon-silicon composite cathode material is obtained.
Further, in step (1), the concentration of the graphene oxide dispersion is the mg/mL of 0.01mg/mL~2.
Further, in step (2), the particle size range of the nano silicon particles is the nm of 5 nm~100；The pitch contains
Carbon amounts is 30% ~ 50%
Further, in step (2), the stirring is magnetic agitation.
Further, in step (2), the range of the ratio between the pitch and nano silicon particles and graphene oxide is 50~
150: 5~50: 1.
Further, in step (3), the atomisation pressure range of the spray drying is 0.1MPa~1MPa.
Further, in step (3), the inlet temperature of the spray drying is 110 DEG C~300 DEG C.
Further, in step (3), the flow velocity of the spray drying is 300 mL/h~1000mL/h.
Further, in step (4), the temperature of the high-temperature heat treatment is 500 DEG C ~ 950 DEG C；The time of high-temperature heat treatment is
1h~6h；
Further, in step (4), the inert atmosphere is at least one of nitrogen, argon gas or helium.
Beneficial effects of the present invention are as follows: (1) using a kind of carbon materials or carbon materials and organic mixture or conduct
Carbon source carries out high temperature pyrolysis carbon coating to silicon particle.The grain diameter formed after cladding is 500 ~ 600nm, is conducive to be electrolysed
Liquid is effectively contacted with negative electrode material, can shorten transmission path of the lithium ion in negative electrode material, and can be in charge and discharge process
Rock-steady structure is kept, is conducive to lithium ion in the shuttle of charge and discharge process, so that be able to maintain can in a height for electrode reaction
Inverse state；(2) graphene/carbon-silicon composite in the present invention is assembled into battery, in 0.01~1V voltage range,
Under the current density of 2A/g, after 200 circle of circulation, specific discharge capacity is up to 695.8mAh/g, coulombic efficiency base in cyclic process
This holding >=98.5%, illustrates the stable structure of material, and charge-discharge performance is good；(3) raw material cost is low for the method for the present invention, is suitable for
In industrialized production.
Detailed description of the invention
Fig. 1 is silicon/carbon graphite alkene composite negative pole material SEM electron microscope prepared by the embodiment of the present invention 1.
Fig. 2 is silicon/carbon graphite alkene composite negative pole material of the preparation of the embodiment of the present invention 1 in 2A g-1Following under current density
Ring performance curve.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Chemical reagent used in the embodiment of the present invention is obtained by routine business approach unless otherwise specified.
Embodiment 1
The present embodiment the following steps are included:
(1) 20mg graphene oxide powder is well dispersed in 100ml deionized water by ultrasonic treatment, obtains graphite oxide
Alkene aqueous dispersions；
(2) 2g pitch and 0.25g nano silicon particles (20nm ~ 60nm) are added into obtained graphene oxide aqueous dispersions, and
2h is stirred in magnetic stirring apparatus, obtains mixed solution；
(3) it is 260 DEG C, atomisation pressure 0.2MPa, flow velocity 600ml/h in outlet temperature for mixed solution to be done by spraying
Dry processing obtains the nanometer silicon composite material of the pitch with chondritic and graphene oxide cladding；
(4) by obtained silicon composite in argon atmosphere in 750 DEG C of progress high-temperature heat treatment 2h, obtain spherical graphite
Alkene/carbon-silicon composite cathode material.
The SEM electron microscope of the resulting graphene/carbon-silicon composite cathode material of the present embodiment, as shown in Figure 1.It can be in figure
Observe graphene, the mixing of nano Si uniform particle, amorphous carbon links together silicon nanoparticle well, and graphite
Alkene and agraphitic carbon have good cladding to nano Si particle.
Battery assembly: by graphene/carbon-silicon composite cathode material and polyvinyladine floride and acetylene black according to 8: 1: 1 matter
Amount forms the composite material of consistency of thickness than being coated in together after mixing on copper foil, and dries in 120 DEG C of vacuum ovens
Dry, slice forms electrode slice.Using the electrode slice of carrying active material as working electrode in the closed glove box of applying argon gas, with
Microporous polypropylene membrane is as diaphragm, 1.0 M LiPF6Be dissolved in volume ratio be 1: 1 ethylene carbonate (EC) and carbonic acid diformazan
Ester (DMC) mixed solvent is used as electrolyte, metal lithium sheet to electrode, is assembled into CR2025 button cell.Battery is existed
In 0.01~1 V voltage range, its charge-discharge performance is tested.Graphene/carbon-silicon composite cathode material cycle performance curve,
As shown in Fig. 2, in 2 A g-1Circulating current under, first discharge specific capacity 800mAh/g, charge and discharge cycles 200 times, still
The specific capacity of 695.8mAh/g is maintained, capacity retention ratio 87% illustrates this 3 SiC 2/graphite alkene/carbon-silicon composite cathode material tool
There is good stability.
Embodiment 2
The present embodiment the following steps are included:
(1) 10mg graphene oxide powder is well dispersed in 100ml deionized water by ultrasonic treatment, obtains graphite oxide
Alkene aqueous dispersions；
(2) 1g pitch and 0.25g nano silicon particles (30nm ~ 70nm) are added into obtained graphene oxide aqueous dispersions, and
2h is stirred in magnetic stirring apparatus, obtains mixed solution；
(3) it is 200 DEG C, atomisation pressure 0.25MPa, flow velocity 500ml/h in outlet temperature for mixed solution to be done by spraying
Dry processing obtains the nanometer silicon composite material of the pitch with chondritic and graphene oxide cladding；
(4) by obtained silicon composite in Ar gas atmosphere in 650 DEG C of progress high-temperature heat treatment 2h, obtain spherical graphite
Alkene/carbon-silicon composite cathode material.
In the SEM electron microscope of the resulting graphene/carbon-silicon composite cathode material of the present embodiment it is observed that graphene,
The mixing of nano Si uniform particle, amorphous carbon links together silicon nanoparticle well, and graphene and agraphitic carbon
There is good cladding to nano Si particle.
Battery assembly: by graphene/carbon-silicon composite cathode material and polyvinyladine floride and acetylene black according to 8: 1: 1 matter
Amount forms the composite material of consistency of thickness than being coated in together after mixing on copper foil, and dries in 120 DEG C of vacuum ovens
Dry, slice forms electrode slice.Using the electrode slice of carrying active material as working electrode in the closed glove box of applying argon gas, with
Microporous polypropylene membrane is as diaphragm, 1.0 M LiPF6Be dissolved in volume ratio be 1: 1 ethylene carbonate (EC) and carbonic acid diformazan
Ester (DMC) mixed solvent is used as electrolyte, metal lithium sheet to electrode, is assembled into CR2025 button cell.Battery is existed
In 0.01~1 V voltage range, its charge-discharge performance is tested.Graphene/carbon-silicon composite cathode material cycle performance curve can
Know, in 2 A g-1Circulating current under, first discharge specific capacity 1076.3mAh/g charge and discharge cycles 200 times, is still maintained
There is the specific capacity of 708mAh/g, it is good to illustrate that this 3 SiC 2/graphite alkene/carbon-silicon composite cathode material still has for capacity retention ratio 66%
Good stability.
Embodiment 3
The present embodiment the following steps are included:
(1) 5 mg graphene oxide powders are well dispersed in 100ml deionized water by ultrasonic treatment, obtain graphite oxide
Alkene aqueous dispersions；
(2) 0.5 g pitch and 0.25g nano silicon particles (30nm ~ 80nm) are added into obtained graphene oxide aqueous dispersions,
And 2h is stirred in magnetic stirring apparatus, obtain mixed solution；
(3) it is 280 DEG C, atomisation pressure 0.3MPa, flow velocity 800ml/h in outlet temperature for mixed solution to be done by spraying
Dry processing obtains the nanometer silicon composite material of the pitch with chondritic and graphene oxide cladding；
(4) by obtained silicon composite in Ar gas atmosphere in 550 DEG C of progress high-temperature heat treatment 2h, obtain spherical graphite
Alkene/carbon-silicon composite cathode material.
In the SEM electron microscope of the resulting graphene/carbon-silicon composite cathode material of the present embodiment it is observed that graphene,
The mixing of nano Si uniform particle, amorphous carbon links together silicon nanoparticle well, and graphene and agraphitic carbon
There is good cladding to nano Si particle.
Battery assembly: by graphene/carbon-silicon composite cathode material and polyvinyladine floride and acetylene black according to 8: 1: 1 matter
Amount forms the composite material of consistency of thickness than being coated in together after mixing on copper foil, and dries in 120 DEG C of vacuum ovens
Dry, slice forms electrode slice.Using the electrode slice of carrying active material as working electrode in the closed glove box of applying argon gas, with
Microporous polypropylene membrane is as diaphragm, 1.0 M LiPF6Be dissolved in volume ratio be 1: 1 ethylene carbonate (EC) and carbonic acid diformazan
Ester (DMC) mixed solvent is used as electrolyte, metal lithium sheet to electrode, is assembled into CR2025 button cell.Battery is existed
In 0.01~1 V voltage range, its charge-discharge performance is tested.Graphene/carbon-silicon composite cathode material cycle performance curve can
Know, in 2 A g-1Circulating current under, first discharge specific capacity 1487mAh/g charge and discharge cycles 200 times, there remains
It is preferable to illustrate that this 3 SiC 2/graphite alkene/carbon-silicon composite cathode material has for the specific capacity of 745.8mAh/g, capacity retention ratio 50%
Stability.
Claims (10)
1. a kind of graphene/carbon-silicon nano composite negative pole material preparation method, which comprises the following steps:
(1) graphene oxide is carried out ultrasonic treatment to be dispersed in water, obtains graphene oxide aqueous dispersions；
(2) pitch and nano silicon particles are added into the resulting graphene oxide aqueous dispersions of step (1), are stirred, disperse
Uniformly, mixed solution is obtained；
(3) mixed solution obtained by step (2) is subjected to spray drying treatment, obtains pitch and graphene oxide with chondritic
The nanometer silicon composite material of cladding；
(4) in an inert atmosphere that the nano-silicon of the pitch obtained by step (3) with chondritic and graphene oxide cladding is multiple
Condensation material is heat-treated, and graphene/carbon-silicon composite cathode material is obtained.
2. graphene/carbon according to claim 1-silicon nano composite anode material preparation method, it is characterised in that: step
Suddenly in (1), the concentration of the graphene oxide dispersion is the mg/mL of 0.01mg/mL~2.
3. graphene/carbon according to claim 1 or 2-silicon nano composite anode material preparation method, feature exist
In: in step (2), the particle size range of the nano silicon particles is the nm of 5 nm~100；The phosphorus content of the pitch be 30% ~
50%。
4. graphene/carbon described according to claim 1~one of 3-silicon nano composite anode material preparation method, feature
Be: in step (2), the stirring is magnetic agitation.
5. graphene/carbon described according to claim 1~one of 4-silicon nano composite anode material preparation method, feature
Be: in step (2), the range of the ratio between the pitch and nano silicon particles and graphene oxide is 50~150: 5~50: 1.
6. graphene/carbon described according to claim 1~one of 5-silicon nano composite anode material preparation method, feature
Be: in step (3), the atomisation pressure range of the spray drying is 0.1MPa~1MPa.
7. graphene/carbon described according to claim 1~one of 6-silicon nano composite anode material preparation method, feature
Be: in step (3), the inlet temperature of the spray drying is 110 DEG C~300 DEG C.
8. graphene/carbon described according to claim 1~one of 7-silicon nano composite anode material preparation method, feature
Be: in step (3), the flow velocity of the spray drying is 300 mL/h~1000mL/h.
9. graphene/carbon described according to claim 1~one of 8-silicon nano composite anode material preparation method, feature
Be: in step (4), the temperature of the high-temperature heat treatment is 500 DEG C~950 DEG C；The time of high-temperature heat treatment is 1h~6h.
10. graphene/carbon described according to claim 1~one of 9-silicon nano composite anode material preparation method, special
Sign is: in step (4), the inert atmosphere is at least one of nitrogen, argon gas or helium.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111435736A (en) * | 2019-12-31 | 2020-07-21 | 蜂巢能源科技有限公司 | Silicon-carbon negative electrode material, preparation method and lithium ion battery |
| CN112047323A (en) * | 2020-09-01 | 2020-12-08 | 四川大学 | Carbonized grapefruit pulp @ silicon @ rGO natural electromagnetic shielding material and preparation method and application thereof |
| CN112736231A (en) * | 2021-01-12 | 2021-04-30 | 杭州新川新材料有限公司 | Preparation method of silicon monoxide negative electrode material of lithium ion battery |
| CN114906834A (en) * | 2022-05-09 | 2022-08-16 | 北京化工大学 | Preparation method and energy storage application of silicon carbon/graphene composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050666A (en) * | 2012-12-12 | 2013-04-17 | 中南大学 | Preparation method of silicon and carbon-coated graphene composite cathode material |
| CN105576203A (en) * | 2015-12-23 | 2016-05-11 | 厦门大学 | Graphene/silicone/carbon nano tube composite material and preparation method and application thereof |
| CN107611406A (en) * | 2017-09-21 | 2018-01-19 | 中南大学 | A kind of preparation method of silicon/graphene/carbon composite negative pole material |
| CN109873152A (en) * | 2019-02-27 | 2019-06-11 | 陕西煤业化工技术研究院有限责任公司 | A kind of lithium ion battery graphene-silicon substrate composite negative pole material and preparation method thereof |
-
2019
- 2019-07-08 CN CN201910610780.4A patent/CN110323440A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050666A (en) * | 2012-12-12 | 2013-04-17 | 中南大学 | Preparation method of silicon and carbon-coated graphene composite cathode material |
| CN105576203A (en) * | 2015-12-23 | 2016-05-11 | 厦门大学 | Graphene/silicone/carbon nano tube composite material and preparation method and application thereof |
| CN107611406A (en) * | 2017-09-21 | 2018-01-19 | 中南大学 | A kind of preparation method of silicon/graphene/carbon composite negative pole material |
| CN109873152A (en) * | 2019-02-27 | 2019-06-11 | 陕西煤业化工技术研究院有限责任公司 | A kind of lithium ion battery graphene-silicon substrate composite negative pole material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111435736A (en) * | 2019-12-31 | 2020-07-21 | 蜂巢能源科技有限公司 | Silicon-carbon negative electrode material, preparation method and lithium ion battery |
| CN111435736B (en) * | 2019-12-31 | 2022-05-27 | 蜂巢能源科技有限公司 | Silicon-carbon negative electrode material, preparation method and lithium ion battery |
| CN112047323A (en) * | 2020-09-01 | 2020-12-08 | 四川大学 | Carbonized grapefruit pulp @ silicon @ rGO natural electromagnetic shielding material and preparation method and application thereof |
| CN112736231A (en) * | 2021-01-12 | 2021-04-30 | 杭州新川新材料有限公司 | Preparation method of silicon monoxide negative electrode material of lithium ion battery |
| CN114906834A (en) * | 2022-05-09 | 2022-08-16 | 北京化工大学 | Preparation method and energy storage application of silicon carbon/graphene composite material |
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Application publication date: 20191011 |