CN110323443A - A kind of spherical N doping redox graphene material and its application - Google Patents
A kind of spherical N doping redox graphene material and its application Download PDFInfo
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- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
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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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of spherical N doping redox graphene material and its applications, belong to battery material field.The material passes through spray-dried processing obtains spherical graphene oxide powder again after the ultrasonic Homogenization Treatments of graphene oxide water solution dilution；Then it is obtained with nitrogen source ground and mixed and after 600~1200 DEG C of 0.5~6h of heat preservation.The spherical N doping redox graphene material has both satisfactory electrical conductivity and high fold, bigger serface and hierarchical porous structure, and adulterates nitrogen-atoms and can introduce functional group abundant, avoid graphene serious stacking and its caused by adverse effect.Uses the material and sulphur are compound as lithium sulfur battery anode material, not only may be implemented active material it is evenly dispersed, improve and carry sulfur content, but also electrode conductivuty can be improved and mitigate " shuttle effect ", the chemical property of final raising sulphur anode.
Description
Technical field
The present invention relates to a kind of spherical N doping redox graphene material and its applications, belong to battery material neck
Domain.
Background technique
It is constantly progressive with the development of science and technology with human society, the global energy systems based on fossil energy are in ring
Border deteriorates and energy shortage aspect makes us increasingly worrying, and pushes the fast development of new energy and renewable energy, lithium-ion electric
Pond is recycled type energy storage device as the green in new energy field, has technical maturity, the small, longevity of service of self discharge etc. excellent
Point has been widely used in the industries such as mobile electronic device, New-energy electric vehicle and energy storage, but is limited to electrode
The theoretical specific capacity (< 300mAh/g) of material, energy density are difficult to meet current and future society increasingly higher demands,
Therefore, new high specific discharge capacity is found, the electrode active material having extended cycle life, which becomes, develops the secondary electricity of next-generation high specific energy
The key in pond.
In many battery systems, lithium-sulfur cell has high-energy density, in addition, active material sulphur nature reserves are rich
It is rich, environmentally friendly, cheap, become one of the new secondary battery system being concerned.But sulphur simple substance poorly conductive,
Reaction front and back volume expansion is easily destroyed electrode structure integrality, and the more lithium sulfides of reaction intermediate are soluble in electrolyte formation and wear
Shuttle effect leads to specific capacity rapid decay.Graphene has bigger serface and satisfactory electrical conductivity, is a kind of good for sulphur anode
Good modified material.However, graphene film tends to be formed irreversible in graphene preparation and subsequent electrode production
Aggregate or even stacks again by Van der Waals interaction and forms graphite, cause specific surface area and Surface accessible active
Site is reduced, this is unevenly distributed uniform reduce to the adsorption capacity of polysulfide for cause active material.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of spherical N doping redox graphene material and its answering
With using spray drying in conjunction with the spherical N doping redox graphene material of high temperature reduction building, redox graphene
Spherical structure can prevent lamella from stacking, be conducive to the evenly dispersed of active material, hetero atom N doping combination porosity
Be conducive to enhance the adsorption capacity to more lithium sulfides；Melting constructs spherical N doping redox graphene composite sulfur after carrying sulphur
Anode realizes sulphur anode good chemical property while improving and carrying sulfur content.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of spherical N doping redox graphene material, the material are prepared by the following method to obtain:
(1) graphene oxide water solution of 0.5~12mg/mL is diluted into 4~16h of ultrasonic Homogenization Treatments, then through spraying
Mist obtains spherical graphene oxide powder after being dried；Wherein, inlet temperature is 120~180 DEG C in spray drying treatment,
Outlet temperature is 80~140 DEG C, and charging peristaltic pump flow set is 200~1000mL/h, and cleansing pin frequency is set as 2~6s/ times；
Preferably, graphene oxide water solution described in step (1) is prepared by improving Hummers method.
Preferably, the processing time of ultrasonic homogenation described in step (1) is 7~16h, and temperature is 10~40 DEG C.
Preferably, inlet temperature is 150~170 DEG C in spray drying treatment described in step (1), feeds wriggling pump discharge
It is set as 400~800mL/h, cleansing pin frequency is set as 2~4s/ times.
(2) it by spherical graphene oxide powder and nitrogen source ground and mixed, is then heated under argon gas or nitrogen atmosphere
600~1200 DEG C of 0.5~6h of heat preservation, obtain a kind of spherical N doping redox graphene material；Wherein, nitrogen source and class ball
Shape graphene oxide powder mass ratio is 10~1:1, and the nitrogen source is one in melamine, urea and polyvinylpyrrolidone
Kind or more.
Preferably, agate mortar is used in step (2) when grinding.
Preferably, heating temperature described in step (2) is 800~1000 DEG C, and soaking time is 1~3h.
A kind of application of spherical N doping redox graphene material, by the material with sulphur is compound obtains a type
The spherical compound sulfur materials of N doping redox graphene, use as lithium sulfur battery anode material.
Preferably, by the spherical N doping redox graphene material and sulphur powder close full of argon gas or nitrogen
It is mixed in envelope kettle, is then transferred to Muffle furnace with 1~3 DEG C/min and is heated to 100~130 DEG C of 1~4h of heat preservation, then with 0.5~5
DEG C/min be heated to 150~160 DEG C heat preservation 12~for 24 hours, 220~300 DEG C of 1~6h of heat preservation are finally heated to 1~10 DEG C/min,
Obtain a kind of spherical compound sulfur materials of N doping redox graphene；The wherein spherical N doping reduction-oxidation graphite
Alkene material and sulphur powder mass ratio are 1:1.5~10.
Preferably, 110~120 DEG C of 1~3h of heat preservation are heated to 1~2 DEG C/min, are then heated to 0.5~2 DEG C/min
154~156 DEG C of 12~16h of heat preservation are finally heated to 220~250 DEG C of 1~3h of heat preservation with 5~10 DEG C/min.
Preferably, the seal pot is polytetrafluoroethyllining lining stainless steel cauldron.
Beneficial effect
1, the present invention by by certain density graphene oxide water solution ultrasonic homogenation processing after again by doing by spraying
Dry processing, controls out temperature and spherical graphene oxide powder is prepared in charging rate, and simple process is controllable, environmentally friendly
Pollution-free, high production efficiency, yield are big.The spherical graphene oxide powder of gained has bigger serface, high degree of folding, multistage
Pore structure and abundant functional group avoid lamella during sequential reduction and stack the damage for causing specific surface area and active site
It loses.
2, the present invention constructs spherical N doping redox graphene material by step thermal reduction, while realizing oxidation
Graphene partial reduction and N doping, method simplicity, N doping amount and structure-controllable, the spherical N doping oxygen reduction fossil
Black alkene material has satisfactory electrical conductivity and maintains high degree of folding, bigger serface and hierarchical porous structure, and doping nitrogen-atoms draws
Enter functional group abundant, avoid redox graphene it is serious stacking and its caused by adverse effect.
3, the present invention avoids electrode and prepared by constructing the spherical compound sulfur materials of N doping redox graphene
The loss of specific surface area and active site caused by journey redox graphene piece stacks, and sulphur heating speed is carried by regulation
Degree, reduces the viscosity of molten sulfur, realizes the evenly dispersed of active material, improves and carries sulfur content and improve sulphur positive conductive, porous
Structure has buffer function to the volume expansion in reaction process, protects the integrality of electrode structure, cooperates abundant functional group
Presence physical chemistry synergistic sorption effect can be realized to more lithium sulfides, mitigate the shuttle effect of more sulphions, improve lithium sulphur
The chemical property of battery sulphur anode.
Detailed description of the invention
Fig. 1 is the X of spherical graphene oxide powder and spherical N doping redox graphene material in embodiment 1
X ray diffraction tests (XRD) figure；
Fig. 2 is scanning electron microscope (SEM) figure of spherical graphene oxide powder in embodiment 1；
Fig. 3 is the SEM figure of spherical N doping redox graphene material in embodiment 1；
Fig. 4 is the SEM figure of the spherical compound sulfur materials of N doping redox graphene in embodiment 1；
Fig. 5 is the spherical compound sulfur materials of N doping redox graphene in Examples 1 and 2 as lithium-sulphur cell positive electrode
The material loop test curve (1C=1675mA/g) at 1.5-2.8V, 0.5C and 0.2C multiplying power respectively.
Specific embodiment
Further description is made to the present invention below with reference to embodiment and attached drawing.
In following embodiment:
(1) XRD is tested: X-ray diffractometer model UltimaIV-185 used, voltage 40kV, electric current 100mA, test
5~85 ° of range, 0.02 ° of step-length, 8 °/min of scanning speed, Cu target, K alpha ray,
(2) SEM is tested: Scanning Electron microscope model Hitachi S-4800, electron accelerating voltage 20kV used,
Conductive tape surface is directly anchored to after sample drying.
(3) cycle performance is tested: by lithium sulfur battery anode material, conductive carbon black Super P and Kynoar (PVDF)
Binder 8:1:1 in mass ratio prepares uniform sizing material in N-Methyl pyrrolidone (NMP), is coated on aluminium foil, is transferred to 60
It is dried in DEG C baking oven, is cut into diameter 11mm disk as anode using slitter, lithium foil is cathode, and electrolyte is using 1mol/L's
LiTFSI/ (DME+DOL, v:v=1:1)+0.2mol/L LiNO3, diaphragm Celgard2300, in the glove box for being full of argon gas
In be assembled into CR2025 type button cell.Using the blue electric battery test system of CT2001Aland model in the section 1.5~2.8V
It is interior, test loop performance under 0.5C multiplying power.
Embodiment 1:
(1) it improves Hummers method: at room temperature, 4g graphite being added in the 160mL concentrated sulfuric acid (96wt%) and stirs 12h, with
After 5gNaNO is added3It is uniformly mixed, then 18g potassium permanganate powder is slowly added in above-mentioned mixed solution in 2h, utilize
Temperature controlled water baths are 7 DEG C, and 300mL hydrogen peroxide solution (10wt%) and 100mL hydrochloric acid solution (10wt%) is added after standing 4 days
It stirs evenly, then obtains the faintly acid graphene oxide water solution (centrifugation that concentration is 6mg/mL with deionized water dilution centrifugation
Machine model H/T16MM, revolving speed control be 10000rpm, 5min/ times)；
(2) by graphene oxide water solution continuous ultrasound homogenize process 7h (ultrasonic machine model KQ-300DE, ultrasonic function
Rate setting 100%, control temperature are lower than 40 DEG C), it is handled by BILON-6000Y type spray dryer, inlet temperature is set as
170 DEG C, outlet temperature is set as 80 DEG C, and charging peristaltic pump flow set is 400mL/h, and cleansing pin frequency is set as 2s/ times, obtains
The porous spherical graphene oxide powder (GO) of high fold and abundant oxygen-containing functional group；Temperature will affect material when spray drying
Rate of drying then influences product morphology, and charging rate influences spray drying synthetic product particle size, and charging rate gets over abortion
Object partial size is smaller, on the contrary then partial size is bigger.
(3) by 2.5g melamine and the spherical graphene oxide powder of 0.5g, mixed grinding is uniform in the agate mortar,
It is subsequently transferred in SK-G06123K model vacuum tube furnace be warming up to 800 DEG C of heat preservation 1h under an argon atmosphere with 5 DEG C/min, obtain
Obtain high fold, aperture 5.4nm, specific surface area 362.4m2The spherical N doping oxygen reduction fossil of/g and itrogen content of getter with nitrogen doped 4.57at%
Black alkene material (NRGO)；
(4) spherical N doping redox graphene material is uniformly mixed to be placed in sulphur powder 1:1.5 in mass ratio and is filled
In the seal pot (polytetrafluoroethyllining lining stainless steel cauldron) of full argon gas, it is then transferred to SX-G04133 model Muffle furnace, with
1 DEG C/min is warming up to 115 DEG C of heat preservation 1h, is then heated to 155 DEG C of heat preservation 12h with 0.5 DEG C/min, finally with 5 DEG C/min heating
To 220 DEG C of heat preservation 2h, the spherical compound sulfur materials of N doping redox graphene for carrying sulphur 70.2wt% are obtained, as lithium sulphur
Cell positive material uses.
XRD test result: obtained in spherical graphene oxide powder (GO) and step (3) obtained in step (2)
The XRD curve of spherical N doping redox graphene material (NRGO) as shown in Figure 1, the characteristic peak of GO and NRGO respectively about
For 11.2 ° and 25.5 °, the interplanar distance according to Bragg equation 2dsin θ=n λ, available GO and NRGO is respectively
0.76nm and 0.35nm proves that graphite oxidation is removed to obtain the widened graphite oxide of interplanar distance compared to the 0.34nm of graphite
Alkene, and spherical N doping redox graphene material is obtained by spherical graphene oxide powder partial reduction.
SEM test result: Fig. 2 is the SEM figure of spherical graphene oxide powder obtained by step (2), and Fig. 3 is step (3)
The SEM of resulting spherical N doping redox graphene material schemes, Fig. 4 be step (4) resulting spherical N doping also
The SEM of the former compound sulfur materials of graphene oxide schemes.As can be seen from the figure spherical N doping redox graphene material and
Spherical graphene oxide powder appearance structure is similar, and molten sulfur infiltrates through spherical N doping redox graphene material
Between fold；It is evenly dispersed that this structure is conducive to sulfur materials, improves and carries sulfur content, improves positive conductive, alleviates volume expansion, protection
Electrode structure integrality improves sulphur anode chemical property.
Cycle performance test result: cyclic curve is as shown in figure 3, first can obtain 1040.7mAh/g specific discharge capacity, coulomb in week
Efficiency is 98.1%, and after 100 weeks circulations, capacity retention ratio 83.1% shows good electrochemical cycle stability.
Embodiment 2:
(1) it improves Hummers method: at room temperature, 3g graphite being added in the 150mL concentrated sulfuric acid (96wt%) and stirs 16h, with
After 4gNaNO is added3It is uniformly mixed, then 16g potassium permanganate powder is slowly added in above-mentioned mixed solution in 2h, utilize
Temperature controlled water baths are 5 DEG C, stand 4 days and 500mL hydrogen peroxide solution (3wt%) and 200mL hydrochloric acid solution (5wt%) is then added
Stir evenly, then with deionized water dilute be centrifuged, obtain concentration be 0.5mg/mL faintly acid graphene oxide water solution (from
Scheming model H/T16MM, revolving speed control be 8000rpm, 15min/ times)；
(2) by graphene oxide water solution continuous ultrasound homogenize process 4h (ultrasonic machine model KQ-300DE, ultrasonic function
Rate setting 100%, control temperature are lower than 40 DEG C), it is handled by BILON-6000Y type spray dryer, inlet temperature setting 150
DEG C, outlet temperature is set as 80 DEG C, feeds peristaltic pump flow set 800mL/h, and cleansing pin frequency is set 4s/ times, obtains with rich
The spherical graphene oxide powder of rich oxygen-containing functional group；
(3) by 2.5g melamine and the spherical graphene oxide powder of 0.5g, mixed grinding is uniform in the agate mortar,
It is subsequently transferred in SK-G06123K model vacuum tube furnace be warming up to 800 DEG C of heat preservation 1h under an argon atmosphere with 5 DEG C/min, obtain
Obtain high fold, aperture 5.2nm, specific surface area 314.5m2The spherical N doping oxygen reduction fossil of/g and itrogen content of getter with nitrogen doped 4.49at%
Black alkene material；
(4) spherical N doping redox graphene material is uniformly mixed to be placed in sulphur powder 1:4 in mass ratio and is full of
In the seal pot (polytetrafluoroethyllining lining stainless steel cauldron) of argon gas, be transferred to SX-G04133 model Muffle furnace, with 1 DEG C/
Min is warming up to 115 DEG C of heat preservation 1h, is then heated to 155 DEG C of heat preservation 12h with 0.5 DEG C/min, is finally heated to 220 with 5 DEG C/min
DEG C heat preservation 2h, obtain carry sulphur 75.4wt% the spherical compound sulfur materials of N doping redox graphene, as lithium-sulfur cell
Positive electrode uses.
XRD and SEM test result are similar to Example 1.
Cycle performance test result: cyclic curve passes through as shown in figure 3, first can obtain 1012.3mAh/g specific discharge capacity week
After 100 weeks circulations, specific discharge capacity is maintained at 722.4mAh/g, and average coulombic efficiency is 99.12%, shows good electrification
Learn performance.
Embodiment 3:
(1) it improves Hummers method: at room temperature, 4g graphite being added in the 150mL concentrated sulfuric acid (96wt%) and stirs 16h, with
After 4gNaNO is added3It is uniformly mixed, then 16g potassium permanganate powder is slowly added in above-mentioned mixed solution in 2h, utilize
Temperature controlled water baths are 10 DEG C, stand 4 days and 500mL hydrogen peroxide solution (3wt%) and 200mL hydrochloric acid solution is then added
(10wt%) is stirred evenly, and is then diluted and is centrifuged with deionized water, and the faintly acid graphene oxide water that concentration is 12mg/mL is obtained
Solution (centrifuge model H/T16MM, revolving speed control be 10000rpm, 10min/ times)；
(2) by graphene oxide water solution continuous ultrasound 10h (ultrasonic machine model KQ-300DE, ultrasonic power setting
100%, control temperature is lower than 40 DEG C), it is handled by BILON-6000Y type spray dryer, inlet temperature sets 170 DEG C, out
Mouth temperature is set as 140 DEG C, feeds peristaltic pump flow set 600mL/h, and cleansing pin frequency is set 2s/ times, and acquisition, which has to enrich, to be contained
The spherical graphene oxide powder of oxygen functional group；
(3) by 5g melamine and the spherical graphene oxide powder of 0.5g, mixed grinding is uniform in the agate mortar, with
After be transferred in SK-G06123K model vacuum tube furnace 1000 DEG C of heat preservation 2h be warming up to 8 DEG C/min under an argon atmosphere, obtain
Obtain high fold, aperture 4.3nm, specific surface area 373.6m2The spherical N doping oxygen reduction fossil of/g and itrogen content of getter with nitrogen doped 5.53at%
Black alkene material；
(4) spherical N doping redox graphene material is uniformly mixed to be placed in sulphur powder 1:9 in mass ratio and is full of
In the seal pot (polytetrafluoroethyllining lining stainless steel cauldron) of argon gas, be transferred to SX-G04133 model Muffle furnace, with 2 DEG C/
Min is warming up to 115 DEG C of heat preservation 1h, is then heated to 155 DEG C of heat preservation 16h with 1 DEG C/min, is finally heated to 250 with 10 DEG C/min
DEG C heat preservation 1h, obtain carry sulphur 85.3wt% the spherical compound sulfur materials of N doping redox graphene, as lithium-sulfur cell
Positive electrode uses.
XRD and SEM test result are similar to Example 1.
Cycle performance test result: 1301.3mAh/g specific discharge capacity, coulombic efficiency 98.61%, performance can be obtained first week
Good chemical property out.
Above-described specific descriptions have carried out further specifically the purpose of invention, technical scheme and beneficial effects
It is bright, it should be understood that the above is only a specific embodiment of the present invention, the protection model being not intended to limit the present invention
It encloses, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the present invention
Protection scope within.
Claims (10)
1. a kind of spherical N doping redox graphene material, it is characterised in that: the material is prepared by the following method
It obtains:
(1) graphene oxide water solution of 0.5~12mg/mL is diluted into 4~16h of ultrasonic Homogenization Treatments, then through spraying dry
Spherical graphene oxide powder is obtained after dry processing；Wherein, inlet temperature is 120~180 DEG C in spray drying treatment, outlet
Temperature is 80~140 DEG C, and charging peristaltic pump flow set is 200~1000mL/h, and cleansing pin frequency is set as 2~6s/ times；
(2) by spherical graphene oxide powder and nitrogen source ground and mixed, then it is heated to 600 under argon gas or nitrogen atmosphere~
1200 DEG C of 0.5~6h of heat preservation, obtain a kind of spherical N doping redox graphene material；Wherein, nitrogen source and spherical oxygen
Graphite alkene powder quality ratio is 10~1:1, the nitrogen source be one of melamine, urea and polyvinylpyrrolidone with
On.
2. a kind of spherical N doping redox graphene material as described in claim 1, it is characterised in that: step (1)
Described in graphene oxide water solution by improve Hummers method be prepared.
3. a kind of spherical N doping redox graphene material as described in claim 1, it is characterised in that: step (1)
Described in ultrasonic homogenation processing the time be 7~16h, temperature be 10~40 DEG C.
4. a kind of spherical N doping redox graphene material as described in claim 1, it is characterised in that: step (1)
Described in spray drying treatment inlet temperature be 150~170 DEG C, charging peristaltic pump flow set is 400~800mL/h, logical
Needle frequency is set as 2~4s/ times.
5. a kind of spherical N doping redox graphene material as described in claim 1, it is characterised in that: step (2)
Agate mortar is used when middle grinding.
6. a kind of spherical N doping redox graphene material as described in claim 1, it is characterised in that: step (2)
Described in heating temperature be 800~1000 DEG C, soaking time be 1~3h.
7. a kind of application of the spherical N doping redox graphene material as described in claim 1~6 any one,
Be characterized in that: by the material with sulphur is compound obtains a kind of spherical compound sulfur materials of N doping redox graphene, as
Lithium sulfur battery anode material uses.
8. a kind of application of spherical N doping redox graphene material as claimed in claim 7, it is characterised in that: will
The spherical N doping redox graphene material mixes in the seal pot full of argon gas or nitrogen with sulphur powder, then turns
It moves to Muffle furnace and 100~130 DEG C of 1~4h of heat preservation is heated to 1~3 DEG C/min, then 150 are heated to 0.5~5 DEG C/min~
160 DEG C of heat preservations 12~for 24 hours, 220~300 DEG C of 1~6h of heat preservation are finally heated to 1~10 DEG C/min, obtain a kind of spherical nitrogen
Adulterate the compound sulfur materials of redox graphene；The wherein spherical N doping redox graphene material and sulphur powder quality
Than for 1:1.5~10.
9. a kind of application of spherical N doping redox graphene material as claimed in claim 8, it is characterised in that: with
1~2 DEG C/min is heated to 110~120 DEG C of 1~3h of heat preservation, is then heated to 154~156 DEG C of heat preservations 12 with 0.5~2 DEG C/min
~16h is finally heated to 220~250 DEG C of 1~3h of heat preservation with 5~10 DEG C/min.
10. a kind of application of spherical N doping redox graphene material as claimed in claim 8, it is characterised in that:
The seal pot is polytetrafluoroethyllining lining stainless steel cauldron.
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| CN110642546A (en) * | 2019-10-25 | 2020-01-03 | 菲大装配式建筑工程(重庆)有限责任公司 | Graphene aerated concrete additive, preparation method thereof and graphene aerated concrete |
| CN111653777A (en) * | 2020-05-20 | 2020-09-11 | 佛山科学技术学院 | Graphene/sulfur porous microsphere composite material used as lithium-sulfur battery anode and preparation method thereof |
| CN111933948A (en) * | 2020-08-18 | 2020-11-13 | 武汉先见科技有限公司 | Lithium-sulfur battery, lithium-sulfur battery positive electrode material, lithium-sulfur battery negative electrode material and preparation method of lithium-sulfur battery positive electrode material |
| CN113955745A (en) * | 2021-10-20 | 2022-01-21 | 昆明云大新能源有限公司 | Nitrogen-doped graphene and preparation method and application thereof |
| CN114556623A (en) * | 2020-01-03 | 2022-05-27 | 株式会社Lg新能源 | Positive electrode for lithium secondary battery and lithium secondary battery comprising same |
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| CN113955745A (en) * | 2021-10-20 | 2022-01-21 | 昆明云大新能源有限公司 | Nitrogen-doped graphene and preparation method and application thereof |
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