CN107069004A - A kind of preparation method of the lithium ion battery negative material of three-dimensional porous structure - Google Patents
A kind of preparation method of the lithium ion battery negative material of three-dimensional porous structure Download PDFInfo
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- CN107069004A CN107069004A CN201710230908.5A CN201710230908A CN107069004A CN 107069004 A CN107069004 A CN 107069004A CN 201710230908 A CN201710230908 A CN 201710230908A CN 107069004 A CN107069004 A CN 107069004A
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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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- 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
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- 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
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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
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
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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
Abstract
The invention discloses a kind of preparation method of the lithium ion battery negative material of three-dimensional porous structure.First, tin ash/glycan compound cluster is prepared using hydro-thermal method, then these clusters are dissolved in the mixed solution of water and ethanol, and sodium carboxymethylcellulose and polyvinyl alcohol are sequentially added thereto, add the graphene oxide water solution of low concentration after well mixed thereto again, and in being continuously stirred at 50~70 DEG C 12 hours.Finally, the solution stirred is instilled in silica gel mould, is freezed from top to bottom with liquid nitrogen, be placed in freeze drying box and thoroughly freeze after sample is stripped, products therefrom is calcined 2~4 hours at 350~550 DEG C.Product amorphous carbon/tin ash/graphene nanocomposite material of the present invention shows as three-dimensional porous structure, when as lithium ion battery negative material, due to its excellent architectural characteristic, the gram volume of superelevation, remarkable high rate performance and cyclical stability are shown.
Description
Technical field
The present invention relates to a kind of technology of preparing of three-dimensional porous structure material, belong to the technology neck of nano composite material preparation
Domain.
Background technology
Lithium ion battery has turned into mobile phone, notes so that its open-circuit voltage is high, energy density is big, the advantages of have extended cycle life
The main power source of the portable sets such as this computer.In recent years, developing rapidly with the extensive energy storage device such as electric automobile, right
The performance of lithium ion battery proposes higher requirement.Negative pole as lithium ion battery an important component, to battery
Performance plays the effect of key.Current commercialized lithium ion battery is due to its structure mostly using graphite as negative pole
Limitation, its theoretical lithium storage content is only 372mAh/g, it is difficult to meet the requirement of extensive energy storage device, and this just promotes people to seek
The high specific energy negative material of graphite can be substituted by looking for.
Tin ash is due to its higher theoretical capacity (782mAh/g), relatively low cost, abundant reserves and nontoxic
The advantages of be considered as one of most promising lithium ion battery negative material of future generation, with good development potentiality and application before
Scape.Although tin ash has above-mentioned advantage, it is due to its huge Volume Changes in charge and discharge process, causes electrode
Efflorescence, capacity declines rapidly, and electrode surface is the problems such as form unstable solid electrolyte membrane (SEI), seriously limits
Its practical application.In order to alleviate the Volume Changes of tin ash, improve the electrical contact between active material, by tin ash and
It is a kind of effective means that carbon material is compound, and this can not only suppress the Volume Changes of tin ash, can also improve leading for electrode
Electrically.In the present invention, we can be formed using sodium carboxymethylcellulose polymer with tin ash/glycan and graphene oxide
The characteristic of hydrogen bond, the two is closely linked together, and by adjusting the ratio of tin ash/glycan and graphene oxide, is adopted
Amorphous carbon/tin ash/graphene nanocomposite material of three-dimensional porous structure, this structure are prepared for freeze-drying
There is substantial amounts of hole and inner space, add amorphous carbon and the good pliability of graphene, restrained effectively titanium dioxide
The Volume Changes of tin, and this loose structure is conducive to the infiltration of electrolyte, shortens lithium ion diffusion length, while graphite
Alkene forms three-dimensional continuous conductive network, drastically increases the electric conductivity of electrode.In addition, amorphous carbon and graphene are wrapped in
Around tin ash, it is to avoid it is directly exposed in electrolyte, therefore stabilizes SEI.When it is used as negative electrode of lithium ion battery
When, drastically increase capacity, cyclical stability and high rate performance.
The content of the invention
Technical problem：It is an object of the invention to provide a kind of system of the lithium ion battery negative material of three-dimensional porous structure
Preparation Method.When the material is used as negative electrode of lithium ion battery, the problem of tin ash capacity attenuation is very fast is solved, is improved simultaneously
The electric conductivity of electrode.Realize the targets such as electrode material high power capacity, long circulating, high magnification.
Technical scheme：The present invention a kind of three-dimensional porous structure lithium ion battery negative material preparation method include with
Lower step：
Step 1: glucose, potassium stannate are added sequentially to fill in the container of deionized water, it is then that above-mentioned mixing is molten
Liquid is stirred 0.5~1.5 hour, and the mass ratio of glucose and potassium stannate is 2:1~3:1；Obtained colourless solution is loaded into hydro-thermal
In reactor, seal, and reactor is placed in heating 4~8 hours in 160~180 DEG C of drying box, question response will production after terminating
Thing is centrifuged, and outwells supernatant, and sediment thoroughly cleaning is clean, will be obtained tin ash/glycan sepia solid and is placed in 60
Dried 8~12 hours in~80 DEG C of vacuum drying chamber；
Step 2: the product obtained in step one is added in the container of the mixed solution of the water filled and ethanol, surpass
The volume ratio of sonication 0.5~1.5 hour, its reclaimed water and ethanol is 2:3~3:2, state in mixed solution and add successively then up
Sodium carboxymethylcellulose and polyvinyl alcohol, are stirred 5~20 minutes, then that concentration is water-soluble for 1~3mg/mL graphene oxide
Liquid is added in above-mentioned solution, and container was placed at 50~70 DEG C and continuously stirred 8~12 hours after 0.5~1.5 hour by ultrasound,
The solution stirred is instilled in silica gel mould, from top to bottom freezed it completely with liquid nitrogen, is freezed after sample is stripped dry
Dry 48~72 hours；
Step 3: the product obtained in step 2 to be carried out to the temperature of calcination processing, wherein calcination processing in tube furnace
For 350~550 DEG C, heating rate is 3~5 DEG C/min, and soaking time is 2~4 hours, obtain three-dimensional porous amorphous carbon/
Tin ash/graphene nanocomposite material lithium ion battery negative material.
Wherein：
The condition that sediment thoroughly cleaning is clean described in step one is to be washed respectively using deionized water and absolute ethyl alcohol
Wash three times.
Described in step 2 with liquid nitrogen from top to bottom by the condition that it is freezed completely be cooling time at least 10 minutes with
On, it is ensured that exist without liquid phase.
The pressure of calcination processing described in step 3 is normal pressure, and atmosphere is argon gas.
The viscosity of the sodium carboxymethylcellulose is more than 1.9 pascal seconds, and the molecular weight of polyvinyl alcohol is 89 000~98
Between 000, the mass ratio of sodium carboxymethylcellulose and polyvinyl alcohol is 1:1~1:2.
Beneficial effect：
1st, the present invention does solvent, environmental protection using water and ethanol solution.Tin ash/glycan is prepared using hydro-thermal method multiple
Compound cluster, three-dimensional porous structure is prepared with freeze-drying, and technical process is easy to control, and the material property of preparation is good, cost compared with
It is low.
2nd, product of the present invention is three-dimensional porous structure, possesses abundant hole and inner space, restrained effectively dioxy
Change Volume Changes of the tin in cyclic process, while substantially increasing the contact area of active material and electrolyte, and then contract
Short diffusion length of the lithium ion in electrode material, this structure is conducive to improving the cyclical stability of material and forthright again
Energy.
3rd, product of the present invention is a kind of amorphous carbon/tin ash/graphene nanocomposite material, amorphous carbon and graphite
Alkene can not only alleviate the Volume Changes of tin ash, but also greatly improve the electric conductivity of whole electrode.
Brief description of the drawings
Fig. 1 is that the amorphous carbon/tin ash/graphene nano for the three-dimensional porous structure that the embodiment of the present invention 1 is obtained is multiple
X-ray diffraction (XRD) collection of illustrative plates of condensation material.
Fig. 2 is that the amorphous carbon/tin ash/graphene nano for the three-dimensional porous structure that the embodiment of the present invention 1 is obtained is multiple
The photomacrograph of condensation material and the scanning electron microscopic picture of low range.
Fig. 3 is that the amorphous carbon/tin ash/graphene nano for the three-dimensional porous structure that the embodiment of the present invention 1 is obtained is multiple
The high magnification scanning electron microscopic picture and transmission electron microscope picture of condensation material.
Fig. 4 is that the amorphous carbon/tin ash/graphene nano for the three-dimensional porous structure that the embodiment of the present invention 1 is obtained is multiple
Condensation material is used as cyclic voltammetry curve during negative electrode of lithium ion battery.
Fig. 5 is that the amorphous carbon/tin ash/graphene nano for the three-dimensional porous structure that the embodiment of the present invention 1 is obtained is multiple
Condensation material is used as cycle performance figure during negative electrode of lithium ion battery.Test condition is first to circulate 20 under current density 100mA/g
It is secondary, then circulated under current density 1A/g 680 times, voltage range is 0.01~3V.By 700 circulations, specific capacity is maintained at
1458.8mAh/g, coulombic efficiency is close to 100%, and capability retention is up to 98.8%.
Embodiment
Embodiment 1：
In the container that the potassium stannate of 8.87g glucose and 3.93g is added sequentially to to fill 70mL deionized waters, then
Above-mentioned mixed solution is stirred 1 hour, the mass ratio of glucose and potassium stannate is 2.25:1.Obtained colourless solution is loaded into water
In thermal response kettle, seal, and reactor is placed in heating 4 hours in 180 DEG C of drying box.Question response terminate after by product from
The heart, outwells supernatant, and sediment thoroughly cleaning is clean, and obtained sepia solid (tin ash/glycan) is placed in into 80
DEG C vacuum drying chamber in dry 12 hours；
In the container that 100mg tin ash/glycan is added to the mixed solution of the water for filling 10mL and ethanol, ultrasound
The volume ratio of processing 1 hour, its reclaimed water and ethanol is 1:1.State then up in solution adds 17.5mg to enter carboxymethyl cellulose successively
Plain sodium and 25mg polyvinyl alcohol, is stirred 10 minutes, and the mass ratio of sodium carboxymethylcellulose and polyvinyl alcohol is 7:10.Then will be dense
The graphene oxide water solution spent for 2mg/mL is added in above-mentioned solution, and container was placed at 50 DEG C and connected after 0.5 hour by ultrasound
Continuous stirring 12 hours.The solution stirred is instilled in silica gel mould, from top to bottom freezed it completely with liquid nitrogen, by sample
It is freeze-dried 72 hours after the demoulding；
Dried product is subjected to calcination processing in tube furnace, the wherein temperature of calcination processing is 550 DEG C, heating speed
Rate is 3 DEG C/min, and soaking time is 4 hours, obtains three-dimensional porous amorphous carbon/tin ash/graphene nano composite wood
Expect lithium ion battery negative material.
X-ray diffraction point is carried out to three-dimensional porous amorphous carbon/tin ash/graphene nanocomposite material of preparation
Analysis, as shown in figure 1, product is tin ash, the diffraction maximum of graphene is not observed, and this is probably the diffraction maximum because graphene
Caused by being overlapped with the diffraction maximum of tin ash.
Three-dimensional porous amorphous carbon/tin ash/graphene nanocomposite material is taken a picture and entered under low range
Row ESEM is characterized, and as a result as shown in Fig. 2 visible product is three-dimensional porous structure, tin ash is in graphene nanometer sheet
Distribute very evenly.
Electricity is scanned to three-dimensional porous amorphous carbon/tin ash/graphene nanocomposite material under high magnification
Mirror and transmission electron microscope are characterized, as seen from Figure 3, and amorphous carbon and graphene nanometer sheet are closely wrapped in tin ash cluster week
Enclose, the cluster diameter is about 70~80nm, and the tin dioxide nano-particle by many particle diameters in 5~8nm is constituted.
Electrode is made in three-dimensional porous amorphous carbon/tin ash/graphene nanocomposite material and button is assembled into
Battery, sweep speed be 2mV/s under carry out cyclic voltammetry, as a result as shown in figure 4, first circulate after, cyclic voltammetric
Curve is almost overlapped, and shows that battery invertibity and repeatability are good.
The battery is circulated 20 times under current density 100mA/g, then 680 are then circulated under current density 1A/g
Secondary, as shown in figure 5, after 700 times circulate, capacity is maintained at 1458.8mAh/g, coulombic efficiency is close to 100%, capability retention
Up to 98.8%.
Embodiment 2：
In the container that the potassium stannate of 7.86g glucose and 3.93g is added sequentially to to fill 80mL deionized waters, then
Above-mentioned mixed solution is stirred 1.5 hours, the mass ratio of glucose and potassium stannate is 2:1；Obtained colourless solution is loaded into water
In thermal response kettle, seal, and reactor is placed in heating 6 hours in 170 DEG C of drying box；Question response terminate after by product from
The heart, outwells supernatant, and sediment thoroughly cleaning is clean, will obtain sepia solid (tin ash/glycan) and is placed in 70 DEG C
Vacuum drying chamber in dry 10 hours；
In the container that 200mg tin ash/glycan is added to the mixed solution of the water for filling 20mL and ethanol, ultrasound
The volume ratio of processing 1.5 hours, its reclaimed water and ethanol is 3:2；State then up in solution adds 20mg to enter carboxymethyl cellulose successively
Plain sodium and 28.6mg polyvinyl alcohol, is stirred 20 minutes, and the mass ratio of sodium carboxymethylcellulose and polyvinyl alcohol is 7:10；Then will
Concentration is added in above-mentioned solution for 3mg/mL graphene oxide water solution, and container was placed at 60 DEG C and connected after 1 hour by ultrasound
Continuous stirring 10 hours, the solution stirred is instilled in silica gel mould, from top to bottom freezed it completely with liquid nitrogen, by sample
It is freeze-dried 60 hours after the demoulding；
Dried product is subjected to calcination processing in tube furnace, the wherein temperature of calcination processing is 450 DEG C, heating speed
Rate is 5 DEG C/min, and soaking time is 2 hours, obtains high performance amorphous carbon/tin ash/graphene nanocomposite material
Lithium ion battery negative material.
Embodiment 3：
In the container that the potassium stannate of 11.79g glucose and 3.93g is added sequentially to to fill 80mL deionized waters, so
Above-mentioned mixed solution is stirred 0.5 hour afterwards, the mass ratio of glucose and potassium stannate is 3:1；Obtained colourless solution is loaded
In hydrothermal reaction kettle, seal, and reactor is placed in heating 8 hours in 160 DEG C of drying box；Question response terminate after by product from
The heart, outwells supernatant, and sediment thoroughly cleaning is clean, will obtain solid (tin ash/glycan) body of sepia and is placed in 60 DEG C
Vacuum drying chamber in dry 8 hours；
In the container that 50mg tin ash/glycan is added to the mixed solution of the water for filling 15mL and ethanol, ultrasound
The volume ratio of processing 1.5 hours, its reclaimed water and ethanol is 2:3；State then up in solution adds 15mg to enter carboxymethyl cellulose successively
Plain sodium and 21.4mg polyvinyl alcohol, is stirred 20 minutes, and the mass ratio of sodium carboxymethylcellulose and polyvinyl alcohol is 7:10；Then will
Concentration is added in above-mentioned solution for 1mg/mL graphene oxide water solution, and container is placed at 70 DEG C by ultrasound after 1.5 hours
Continuously stir 8 hours, the solution stirred is instilled in silica gel mould, from top to bottom freezed it completely with liquid nitrogen, by sample
It is freeze-dried 48 hours after pint mould；
Dried product is subjected to calcination processing in tube furnace, the wherein temperature of calcination processing is 350 DEG C, heating speed
Rate is 4oC/min, and soaking time is 3 hours, obtains high performance amorphous carbon/tin ash/graphene nanocomposite material
Lithium ion battery negative material.
Claims (5)
1. a kind of preparation method of the lithium ion battery negative material of three-dimensional porous structure, it is characterised in that this method is included such as
Lower step：
Step 1: glucose, potassium stannate are added sequentially to fill in the container of deionized water, then above-mentioned mixed solution is stirred
Mix 0.5~1.5 hour, the mass ratio of glucose and potassium stannate is 2:1~3:1；Obtained colourless solution is loaded into hydro-thermal reaction
In kettle, sealing, and by reactor be placed in 160~180 DEG C of drying box heat 4~8 hours, question response terminate after by product from
The heart, outwells supernatant, and sediment thoroughly cleaning is clean, will obtain tin ash/glycan sepia solid and is placed in 60~80
DEG C vacuum drying chamber in dry 8~12 hours；
Step 2: the product obtained in step one is added in the container of the mixed solution of the water filled and ethanol, at ultrasound
The volume ratio of reason 0.5~1.5 hour, its reclaimed water and ethanol is 2:3~3:2, state add carboxylic first in mixed solution successively then up
Base sodium cellulosate and polyvinyl alcohol, stir 5~20 minutes, then add concentration for 1~3mg/mL graphene oxide water solution
Enter into above-mentioned solution, container was placed at 50~70 DEG C and continuously stirred 8~12 hours, will stir after 0.5~1.5 hour by ultrasound
Mix uniform solution to instill in silica gel mould, it is freezed completely from top to bottom with liquid nitrogen, 48 are freeze-dried after sample is stripped
~72 hours；
Step 3: the product obtained in step 2 is carried out into calcination processing in tube furnace, the wherein temperature of calcination processing is 350
~550 DEG C, heating rate is 3~5 DEG C/min, and soaking time is 2~4 hours, obtains three-dimensional porous amorphous carbon/titanium dioxide
Tin/graphene nanocomposite material lithium ion battery negative material.
2. the preparation method of the lithium ion battery negative material of three-dimensional porous structure according to claim 1, its feature exists
In the condition that sediment thoroughly cleaning is clean described in step one is to wash three respectively using deionized water and absolute ethyl alcohol
It is secondary.
3. the preparation method of the lithium ion battery negative material of three-dimensional porous structure according to claim 1, its feature exists
In, described in step 2 with liquid nitrogen from top to bottom by the condition that it is freezed completely be cooling time at least more than 10 minutes, really
Protect and exist without liquid phase.
4. the preparation method of the lithium ion battery negative material of three-dimensional porous structure according to claim 1, its feature exists
In the pressure of calcination processing described in step 3 is normal pressure, and atmosphere is argon gas.
5. the preparation method of the lithium ion battery negative material of three-dimensional porous structure according to claim 1, its feature exists
Be more than 1.9 pascal seconds in the viscosity of, the sodium carboxymethylcellulose, the molecular weight of polyvinyl alcohol 89 000~98 000 it
Between, the mass ratio of sodium carboxymethylcellulose and polyvinyl alcohol is 1:1~1:2.
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| CN108346789A (en) * | 2018-02-05 | 2018-07-31 | 东南大学 | Multiconductor nucleocapsid cavity structure anode material of lithium-ion battery and preparation method thereof |
| CN108447695A (en) * | 2018-02-02 | 2018-08-24 | 北京理工大学 | A kind of preparation method of folding paper substrate micro super capacitor |
| CN108717974A (en) * | 2018-06-07 | 2018-10-30 | 深圳市梅莎新能源科技有限公司 | A kind of preparation method of lithium ion battery material |
| CN109037611A (en) * | 2018-07-03 | 2018-12-18 | 上海交通大学 | Graphene-based flexible self-supporting binder free electrode composite material and preparation method thereof |
| CN109817944A (en) * | 2019-02-18 | 2019-05-28 | 山东星火科学技术研究院 | Lithium ion battery cathode silica/graphene nano material preparation method |
| CN110391419A (en) * | 2019-07-26 | 2019-10-29 | 广东工业大学 | A kind of porous carbon and its application in lithium-sulphur cell positive electrode |
| CN111115618A (en) * | 2019-12-02 | 2020-05-08 | 深圳石墨烯创新中心有限公司 | Graphene/carbon/tin oxide nano composite material and preparation method and application thereof |
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| CN108447695A (en) * | 2018-02-02 | 2018-08-24 | 北京理工大学 | A kind of preparation method of folding paper substrate micro super capacitor |
| CN108346789A (en) * | 2018-02-05 | 2018-07-31 | 东南大学 | Multiconductor nucleocapsid cavity structure anode material of lithium-ion battery and preparation method thereof |
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| CN109037611A (en) * | 2018-07-03 | 2018-12-18 | 上海交通大学 | Graphene-based flexible self-supporting binder free electrode composite material and preparation method thereof |
| CN109037611B (en) * | 2018-07-03 | 2021-11-09 | 上海交通大学 | Graphene-based flexible self-supporting adhesive-free electrode composite material and preparation method thereof |
| CN109817944A (en) * | 2019-02-18 | 2019-05-28 | 山东星火科学技术研究院 | Lithium ion battery cathode silica/graphene nano material preparation method |
| CN110391419A (en) * | 2019-07-26 | 2019-10-29 | 广东工业大学 | A kind of porous carbon and its application in lithium-sulphur cell positive electrode |
| CN110391419B (en) * | 2019-07-26 | 2022-07-05 | 广东工业大学 | Porous carbon and application thereof in lithium-sulfur battery anode |
| CN111115618A (en) * | 2019-12-02 | 2020-05-08 | 深圳石墨烯创新中心有限公司 | Graphene/carbon/tin oxide nano composite material and preparation method and application thereof |
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